JPS591829B2 - How to decorate woven fabrics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for decorating fabrics, particularly textile fabrics.

Although the following description refers throughout to the treatment of textile fabrics, the term should be construed to include any flexible substrate that needs to be decorated, such as textiles.

Various methods of decorating textile fabrics have been known for a long time. Decorating methods that involve printing designs directly onto the fabric require a lot of complex equipment and the fabric is generally not particularly dimensionally stable, so
gister) Medium multicolor designs are difficult to print. Recently, methods of transferring printed designs onto fabrics have been developed, and paper with designs printed with sublimation dyes has come to be used. If the printed paper and a suitable fabric are pressed together and heated at a temperature of 200-260°C, the dye will sublimate and re-deposit onto the fabric to create the desired pattern. This method is known as sublimation. This is time consuming and requires high temperatures so that the paper substrate is unusable after the design has been removed from it, while the fabric is also often damaged by the heat. Also, because the dye does not transfer from the paper to the fabric, a lot of waste is produced. According to the present invention, a new method for decorating textile fabrics is provided.

Thus, the present invention provides a flexible transfer material comprising a film substrate and a removable layer comprising dyes and/or pigments on the film substrate and a film-forming polymer, wherein the film-forming polymer is typically does not exhibit pressure-sensitive tack when heated, but has sufficient tack to cause the removable layer to adhere to textile substrates under the action of pressure even more strongly than it does to film substrates. Polyvinyl butyral, polyvinyl acetate, or polyvinyl butyral and polyvinyl acetate, which naturally forms discontinuous deposits on the textile material as a transfer target when heated.
A flexible transfer material, which is a mixture of polyvinyl alcohol, cellulose nitrate or ethyl cellulose, is used; the removable layer of the transfer material is pressed onto a textile substrate as a recipient while heating; the film substrate is removed; The removable layer of the transfer material is transferred onto a textile fabric while being adhered to the textile fabric; the textile fabric with the removable layer is then heat treated leaving the film-forming polymer in the layer intact to inject the dye onto the textile fabric. and/or fixing the pigment and leaving the film-forming polymer as discontinuous deposits on the textile fabric soil. Methods of decorating textile fabrics by transfer from transfer materials were well known prior to the present invention, but prior art techniques of this type could in principle fall into one of three different categories:

(a) Sublimation transfer using a heat-volatile dye (the sublimation transfer method described above).

(b) Solvent transfer, in which a solvent is used to spread the printed design on a support onto a textile substrate.

(c) Melt transfer, in which heat and pressure are used to melt the design on the transfer material and press it onto the textile substrate as the transferee.

The method and disadvantages of Da) above are as described above.

The solvent transfer method (b) above avoids one of the significant limitations associated with the sublimation transfer method (a) above, namely the need for sublimable dyes and the limitations on the fabrics that can be printed with such dyes. There is. While vapor phase transport is not required, this solvent method fills the space between the transfer material and the textile material with a solvent in which the dye is dissolved, allowing the dye to diffuse between them. Various solvent transfer methods have been proposed, but all suffer from slow transfer, poor fastness of the final product, and the need to remove (e.g., wash away) unfixed dye and processing solutions. There was a trend. On the other hand, in the above-mentioned melt transfer method (c), a transfer material consisting of a film substrate (for example, paper) and a design layer is brought into contact with a textile material under heat and pressure, and the design layer is inserted into the gap between the textile materials. be pushed into.

Regarding this method, especially regarding the composition of the design layer,
Although various proposals have been made, the fundamental drawback of most of these methods is that the decorated design leaves some continuous film on the final woven fabric, which creates a film-like appearance on the decorated woven fabric. It has a negative effect on the texture and the hand of the textile fabric.
The present invention relates to the improvement of the above-mentioned melt transfer method αc), and according to the present invention, the original softness, texture and feel of the textile fabric are substantially retained even after the decoration layer is transferred using the transfer material. be able to.

This is achieved by using selected film-forming polymers with certain specific properties as raw materials for the removable layer (decoration layer) of the transfer material. These film-forming polymers do not exhibit pressure-sensitive tack under normal conditions, but when heated, under the action of pressure, the above-mentioned removable layer adheres more strongly to a textile substrate as a substrate. However, upon heating after transfer, it physically disintegrates, leaving only discontinuous deposits on the textile material to be transferred. Accordingly, the present invention provides a removable layer comprising such a film-forming polymer (
When the decoration layer) is transferred to a woven fabric, the result is a decorated woven fabric that has the softness, handle and feel of the original woven fabric before decoration, without the filmy feel; Easy to wash and has excellent durability. The present invention will be explained in more detail below.

According to the invention, the transfer of the removable layer from the film substrate to the textile fabric can be accomplished at relatively low temperatures, for example at temperatures of 50 to 60°C, without damaging either the film substrate or the textile fabric.

The film substrate can therefore be reused. After transfer, the fabric is heated to, for example, 100-200°C for a sufficient time to fix the dye and/or pigment therein. In the case of sublimable dyes, this time may be 5 to 30 seconds. In the case of a film substrate, the film-forming polymer in the removable layer material transferred to the textile fabric remains on the textile fabric as discontinuous deposits due to this heating, which is detrimental to the feel and other properties of the textile fabric. It has no effect. It is possible with appropriate selection of the ingredients to ensure that the temperatures required to transfer the removable layer to the textile fabric are low, so that the raw materials treated according to the invention can be treated with ease. There is no need to heat set the soil prior to this treatment.

If a heat setting step is required, this can be done at the same time as the heat treatment required to fix the dye in the fabric. The method of the invention can be used to treat both hydrophilic or hydrophobic synthetic and natural fibers. Wool and cotton fabrics can also be processed without difficulty. Fabrics made from wool and some various synthetic polymers, in particular polyethylene terephthalate and polypropylene fibers, can also be successfully processed, for example mixed fabrics with different fibers such as polyester/cotton can also be processed. The various components of the flexible transfer material used in the method are defined in detail below and the steps are considered individually.

Flexible Transfer Material The flexible transfer material used in the method of the invention consists of a film substrate and a removable layer overlying the film substrate.

(A) Film Substrate In order to successfully transfer the removable layer containing the dye and/or pigment and the film-forming polymer from the film substrate to the textile fabric, there is a hydrophilic/removable layer between the film substrate and the removable layer. Preferably there is a hydrophobic control.

This aids in clean and complete transfer of the removable layer.
Thus, the film substrate can itself have a hydrophobic or hydrophilic surface, or alternatively it can include a base sheet with a hydrophobic or hydrophilic surface. A hydrophilic or hydrophobic removable layer is applied to this hydrophobic or hydrophilic surface, respectively. The film substrate naturally has a hydrophilic or hydrophobic surface and can be, for example, a plastic film or a metal foil.

Alternatively, the film substrate may consist of a flexible base sheet, such as paper, with a suitable coating. Typical film substrates are high quality paper coated on one side with synthetic polybutadiene rubber, wax or a suitable silicone.
The hydrophilic removable layer applied to the surface of such a coating film can be easily peeled off and transferred to the transfer target (textile material).
transcribed into. Transfer is also successful using cellulose acetate as the film substrate instead of paper.

Such cellulose acetate film substrates include nitrocellulose-coated cellulose acetate films (e.g., TransparcntPap, Bury. Lancs.).
ers Ltd. ) which can be used in place of polybutadiene rubber coated paper.

The cellulose acetate system requires the use of slightly higher transfer temperatures than the control paper system. S) Removable Layer The removable layer used in the method of the invention comprises dyes and/or pigments and film-forming polymers.

This film-forming polymer exhibits no pressure-sensitive adhesive properties under normal conditions at 0.degree. C., but when heated, it adheres well to textile fabrics under the influence of pressure and physically disintegrates under heating.
The removable layer containing the design to be applied to the textile fabric as a decoration can be applied as a layer to the film substrate in a conventional manner. Obviously coating systems may be used for designs such as small pieces, but printing may be used for commonly multicolored designs. The removable layer includes a film-forming polymeric substrate and dyes as well as materials such as optical brighteners and other adjuvants to improve the appearance of the fabric. The removable layer on the film substrate may be continuous, discontinuous, or in many segments. If desired, the layers on the film substrate can be continuous layers of only a single color: similar systems are known for sublimation printing, where uniformly printed monochrome sheets are used.

This is used when it is necessary to make small amounts of colored fabric without using complicated dyeing methods. This type of system has the advantage over conventional dyeing that a better uniform dyeing can be obtained between different batches of fabric. If the method of the present invention is thus used as an alternative to dyeing, the storage of the dyed fabric can be very small, in addition, since the additional dyeing is very easy and fast: the method can be easily carried out in 2-3 hours. I can do it. This is an advantage compared to the practice of sending items for dyeing, which is expensive to transport and takes several weeks. In order to successfully apply a removable layer by printing methods, it is necessary to formulate the components of the layer to be sufficiently printable and to work satisfactorily across the two methods described above.

For the above purpose, the ink used for printing consists of particles of a film-forming polymer, pigment or dye, and one or more solvents or thinners, in a concentration suitable for printing. preferable.

The solvent or thinner for the ink must, of course, sufficiently dissolve the film-forming polymer.

Single solvents or mixed solvents may be used, but the special formulation methods are similar to those used in the production of printing inks for other purposes. Suitable solvents include lower alcohols, ethanol/toluene mixtures, and the solvents may also contain small amounts of water. The strength of the printed ink film or removable layer must, of course, be strong enough to maintain the removable layer in one cohesive layer during transfer from the film substrate to the textile substrate.

The strength of this removable layer depends on the choice of film-forming polymer used, but also on the content of plasticizer used and the thickness of the layer. The thickness itself depends on the viscosity of the Printyquik and the printing method used. Solids such as dyes added to the print film (removable layer) should be finely divided if possible, since large particles tend to create breakage nuclei that cause film failure. Because of this, it must be remembered that for some dyes, the particle size in the layer after printing may be changed by aging. This may therefore result in undesirable layer weakening. The removable layer can be printed or coated onto the film substrate.

Convenient printing methods include, for example, screen printing, lithography, gravure or flexography.
Ograph) printing is used. The particular printing method chosen will depend both on the nature of the design being printed and the desired thickness of the film. The softening point of the printed ink layer (removable layer) must not be too close to room temperature, otherwise when the print is rolled up, the printed material will tend to stick to the back side of the next wrap. be.

Before applying the dye- or pigment-containing layer (removable layer) to a film substrate with a hydrophobic or hydrophilic surface, a sublayer of a film-forming polymer having hydrophilic or hydrophobic properties, respectively, is applied, which is thermally heated. Particularly good transfer of the printed design is obtained if it is non-degradable and can be made sufficiently tacky by heating to adhere to the textile fabric more strongly than under pressure so that it adheres to the surface of the film substrate.

Thus, a film substrate that can have a hydrophobic or hydrophilic non-removable coating (1) has a hydrophilic or hydrophobic continuous film-forming polymer sublayer (2) and a film with dyes and/or pigments. It can have hydrophobic or hydrophilic sublayers containing forming polymers. The effect of the continuous removable sublayer (2) is to increase the accuracy and efficiency of the transfer of the dye- or pigment-containing material layer to the textile substrate.

The polymeric material in the sublayer (2) and that in the third layer (3) need not be the same, although both layers need to be hydrophilic or hydrophobic with respect to the non-removable coating (1).
i) Film-forming polymers The film-forming polymers used according to the invention do not exhibit pressure-sensitive tack in their normal state, but when heated, a removable layer adheres to the film substrate under the action of pressure. Furthermore, it has sufficient adhesiveness to strongly adhere to a textile material as a transfer target.

Furthermore, this film-forming polymer forms discontinuous deposits on a textile material as a transfer medium when heated. Suitable film-forming polymers for use in the removable layer are polyvinyl butyral, polyvinyl acetate or mixtures of polyvinyl butyral with polyvinyl acetate, polyvinyl alcohol, cellulose nitrate or ethylcellulose.

A typical hydrophilic film-forming polymer used in the removable layer is polyvinyl butyral. Such removable layers may contain paraffin waxes and other waxy substances, solvent plasticizers such as tricresyl phosphate, dioctyl phthalate, and condensates of fatty alcohols and ethylene oxide to adjust their properties. But that's fine. A further film-forming polymer that can be used in the removable layer is polyvinyl acetate.

It has the advantage of higher water absorption in a steam bath than other vinyl polymers, such as polyvinyl butyral. In printing water-soluble dyes using vapor fixation, dye release from the removable layer is therefore greatly enhanced. At the same time, the importance of molecular weight in the polymer is emphasized by our results with polyvinyl acetate, which will be discussed later. The higher hydrophilicity of polyvinyl acetate releases it more easily from polybutadiene coated paper than polyvinyl butyral, so no plasticizer is needed. In fact, the use of excess plasticizer reduces the adhesion of the removable layer to the film substrate below practical levels. Hydrophilic film-forming polymers which can be used in the removable layer, particularly on a film substrate of cellulose acetate, are, for example, polyvinyl butyral and/or polyvinyl acetate.

Generally any of these polymers alone will give satisfactory results. However, while polyvinyl butyral generally produces films with excellent release properties when used with water-soluble dyes that require steam fixation, this relatively hydrophobic removable layer (compared to polyvinyl acetate) Absorption is less than necessary and dye transfer from the film to the fabric is slow or inadequate. Polyvinyl acetate, on the other hand, produces a removable layer with adequate but generally unsatisfactory release properties and is somewhat sticky to the touch. If used with water-soluble dyes, its more hydrophilic nature provides better dye transfer than commonly seen with polyvinyl butyral. Mixtures of these two polymers provide the advantages of each. The proportion of polyvinyl butyral in the mixture is O
By varying between % and 100%, the properties of the removable layer can be varied continuously as required. Mixtures of polyvinyl acetate and 5% to 50% polyvinyl butyral together with water-soluble dyes are particularly advantageous as they offer easy release, good dye fixation and the possibility of incorporating relatively high solids contents in the removable layer. .

The production of satisfactory printed fabrics relies on the removable layer material being transformed into a distinct shape during the fixing step, which shape is not easily discernible by hand or eye, unless of course a certain effect is desired.

During the fixing step, the film-forming polymer physically disintegrates, leaving a discontinuous residue on the fabric. In order to collapse into discontinuous deposits in this manner, it is desirable that the polymer soften and flow during fixation to create discontinuous deposits. Using polyvinyl butyral we have a molecular weight of 18000027
3000034000 compared to substances in the range 0000
We have found it very advantageous to use materials such as

Of course, the former also has practical effects. The thermal strain temperature of polyvinyl butyral in these molecular weight ranges is 4
5 to 55°C and 56 to 60°C, and the flow temperature (
1000p. s. i) is 105 to 11'C and 14
The temperature is 5 to 155°C. The viscosity of the molten polymer also appears to have an important influence. Polyvinyl acetate having a molecular weight of 50,000-60,000 has desirable properties as described above, although it can sometimes result in a hard finish if too thick a removable layer is used. For any given system, a single run indicates the optimal molecular weight, flow temperature, and melt viscosity correlation for best results.
The range of optimal properties can be defined as those properties that, if made into a polymer, would give the polymer excellent effects. Preferably, the film-forming polymer should not lose its continuous film form upon heating to 180 DEG to 220 DEG C. and should not leave behind any residual material that would adversely affect the properties of the fabric.

In some cases, i.e. when using special dyes or pigments or special film substrates, it is advantageous for the film-forming polymer to have one or both of the following properties: (1) the dye can migrate into the textile fabric; (2) The polymer should release the dye in the ink during processing after drying or wetting so that it remains intact during washing, despite destruction of the original continuous film configuration.
In the transfer of pigment printing, the removable layer should have the property of physically binding the pigments present in the ink to the textile fabric so that the dyeing is not abrasive and dry-cleanable to textiles or other materials. It plays a dual role.

First it becomes a medium for mechanically transferring the printed design onto the fabric. It is then heated to melt and bind the pigments into the fabric, giving it a durable print in the wash. When using sublimable disperse dyes or fixing soluble dyes by steam treatment, certain considerations arise in the transfer of pigment printing, since the pigment does not migrate. The nature of the polymer is particularly important because as the film melts into the fabric it must be non-uniform over the printed area. Inks need to be formulated accordingly. It is desirable to incorporate a plasticizer into the ink to aid in the release of the removable layer during the transfer process and to improve the properties of the removable layer material during the fixing process.

Examples of solvent plasticizers that can be mixed into inks include: dibutyl phthalate tricresyl phosphate halomityl alcohol sodium ricinoleate stearate palmitate stearyl alcohol polyethylene monoxide condensate stearamide, polyethylene fine powder It improves fluidity and fabric permeability and acts as a secondary solvent.

The incorporation of higher aliphatic alcohols, such as octadecanol, and especially condensates of such alcohols with polyethaneoxy polymers, such as stearyl alcohol ethylene monoxide condensates, in the ink produces good quality prints. It is especially useful.

)) Dyes and/or Pigments Dyes that can be added to the ink include, for example, dispersion, reaction, direct, acid, acid milling, butt, metal complex and yarn-dyed dyes, sublimation dyes, dyes used in thermosol processes.

Pigments that can be used include organic and inorganic pigments and fine metal powders. All kinds of dyes and pigments can be used, including nitro, azo, stilbene, di- and triarylmethane, acridine, quinoline, methine and polymethine,
Thiazole, indamine and indophenol, oxine, oxazine, thiazine, sulfur, aminoketone,
There are anthraquinone, indigoid, and phthalocyanine dyes. For many dye applications, the presence of dyeing aids such as acids, alkaline solubilizers, etc. aids in dye fixation.

For example, with the most common fiber-reactive dyes for cellulose, the presence of alkali is required during fixation. Acid dyes used on wool and nylon wear out more quickly in the presence of acid. Solubilizing agents such as urea are often added to textile printing to aid in fixing dyes with a wide range of dyes. In the method of the present invention, such adjuvants can be added to the ink to form a transferable film, thus eliminating the need for a pre-impregnation step or a post-printing step. Specific examples of dyes and pigments that can be mixed into the ink are: Dispersol Yellow-D-7G (IC
I) Dispersol Yellow-C-4R (ICI) Dispersol Blue D-2R (IC) Dispersol Navy P-R (ICI) Azolodine 2G (SandO2
) Prodione Blue HA (ICI) Ciba-Geigy GC (Ciba-Geigy) Sabra Print Blue 70032 (L,.BlHOll
lday&CO. Ltd. ) Lumogen Red RF (
BASF) Phthalogen Brilliant Blue 1F3G (FarbenfabrikenBayer) Carbon Black Bronze Powder Monastrol Fast Blue B (ICI) Examples of dye fixing aids that can be mixed with inks include:
Sodium Lactate Bisulfite Sodium Diotinate Sodium Carbonate Urea and Thiourea 1 Dyes and/or pigments can be mixed into the ink used to apply the removable layer, depending on the type of fabric to be transferred.

For example, for polyether/cotton fabrics, mixtures of disperse dyes and reactive dyes may be used, or mixtures of disperse dyes and pigments may also be used. Fixation aids are chosen according to the type of dye used.

For example, reactive dyes used on cellulose substrates usually require the presence of alkali and in some cases urea for subsequent fixation. Vat dyes require an alkali 2 and a reducing agent such as sodium formaldehyde sulfoxylate. Although the choice of plasticizer is generally not influenced by the choice of dye, it has been found that when pigments are used, aliphatic alcohols or aliphatic alcohol-polyethaneoxy condensates 2 generally give good looking prints.

The proportions of ingredients in the ink (excluding solvent and thinner) can obviously be varied depending on the strength of the dye or pigment added.

Generally, the plasticizer component is varied between 20 and 100% of the polymerization amount and the dye component is varied between 0 and 100% of the polymerization amount. When pigments are used, it is desirable to include a cross-linking agent in the ink that binds the pigment to the fabric to improve the washability and solvent fastness of the final print.

3 Examples of such materials are dialdehydes such as cryoxal, epoxy resin monomers and aminoplasts.

When the polymeric material forming the film is polyvinyl butyral, the preferred cross-linking agent is methylolated aminoplus monomers such as dimethylol urea, dimethylol dihydroxyethylene urea, dimethylol cyclic ethylene urea or methylol melamine. It is. The use of such cross-linking agents will make the final fabric feel rough, and to avoid this, a softener may be added or a cross-linking agent may be used.
Solvent plasticizers, such as stearamides, are preferably selected which act as compensators by interaction with the solvent. In some cases, excellent wash fastness properties are obtained if, in addition to the crosslinker and other additives, an acid or an acid generating catalyst such as zinc nitrate is present. The washing fastness of the final pigmented fabric is determined by
For example, improvements can be made using inherently colored thermoplastics.

Typical ink formulations are, for example, as follows: 5-Method Details Heating the removable layer onto a woven fabric can be accomplished by any of a number of commonly known methods.

For example, steam or superheated steam heating or infrared heating is possible.
Hot air may be passed through the dough, or the dough may be passed over a hot plate. Microwave heating may also be used. It has been found advantageous to cool the fabric, the design-containing removable layer material, and the film substrate as a whole prior to separation of the film substrate.

The bond between the fabric and the removable layer material needs to be stronger than that between the removable layer material and the film substrate.
The temperature point at which this occurs and the time at which adhesion is ensured depends on the composition of the film substrate and removable layer material and the textile fabric. Generally, it is preferable to formulate the ink so that it exhibits sufficient performance after cooling for 2 to 20 seconds at room temperature. Example 4 below also describes the cooling stage. Apparatus for carrying out the invention may vary widely.

A flat bed press of the type commonly used for transfer printing is used in the first step of the process and the fabric then proceeds to a fixing step. However, a preferred device is a pair of adjacent rollers, at least one of which is heated, and a film carrying the textile material and pattern (removable layer) to be decorated is fed through a nip between the rollers. equipment to
It consists of a guide device for advancing the fabric and substrate together along the cooling path and a device for separating the fabric and substrate. Such devices generally consist of an entire framework or base supporting various rollers and guides and suitable feeding and winding devices for fabrics and substrates. roller drive means;
For example, it is provided with an electric motor and combined with adjustment means. The detailed construction of such machines is generally known and will not be described further. The cooling path may be a space through which the dough and substrate can easily pass.

There may also be cooling devices such as fans or cooling surfaces or rollers. The heating temperature of the rollers may be variable, and the rollers may be driven at variable speeds.

Optimal decoration can be achieved by adjusting the speed and temperature of the rollers. Due to different fabrics, nip pressure should be adjustable if possible. It is generally desirable to be able to adjust the nip pressure from 5 to 50 pounds per lineal inch (ie, from 250 to 2500 pounds for a 50 inch wide roller). Preferably, the heated rollers are heated so that the fabric and flexible substrate in the nip reach a temperature of 100-220°C.

The contact time between the substrate or fabric and one of the heated rollers can be adjusted, for example from 30 to 18'C, by varying the degree of contact of that roller with the fabric or substrate.
90 to 180°C at the substrate/fabric interface in the nip
It can be adjusted to raise the temperature. In the subsequent cooling pass, the temperature is reduced to 60-80°C while the adhesion between the decoration on the substrate and the fabric is complete.

The fabric and substrate are then peeled off. The device has one or more processing stages to which it is further guided after the fabric has been removed.

For example, the decoration may be fixed by steam or other treatment and known suitable treatment steps may be conveniently constructed. A suitable device is illustrated by way of example in Figures 1 and 2, both of which are schematic side drawings.

Figure 1: A machine that decorates one side of fabric.

Figure 2: A machine that decorates both sides of the fabric at the same time. In both figures, the heating roller coated with metal or rubber is 1
, 2 and the fabric to be printed comes from roll 3.

The pre-printed decoration web also comes from roll 4. The guide roll 5 can adjust the change in contact with the heating rollers 1 and 2, and 6 indicates a cooling path. At the end of pass 6, the fabric and web pass through a nip formed between a pair of rollers 7 and are separated. The used web is wound onto a take-up roll 8, while the fabric is further processed in step 9. It will be seen that the method of the present invention has many advantages when compared to the sublimation method described above.

When using Sublistatic systems, there is a tendency for the fabric to harden and/or yellow and/or become glassy; these do not occur with the method of the present invention. The total transfer of dye in the method of the invention provides the possibility of creating deeper, more opaque colorations without the unavoidable waste of sublistatic printing. When used for sub-static printing, it is preferable to heat and fix the dough in advance, but this is not necessary if the method of the present invention is used. Compared to substatic printing, the speed can be increased step by step and the temperature can be lowered, for example from 30 seconds at 250°C to 5 to 10 seconds at 200'C. Although the equipment required for substatic printing is complex and specialized, it may be simple equipment for use with the present invention, or standard equipment may be readily adapted. This has to do with the fact that subristographic printing requires very close contact between the fabric and the preprinted design. The method of the invention does not require this. The variety of fabrics that can be decorated using the method of the invention is very wide. All kinds of synthetic and natural fiber fabrics can be decorated satisfactorily. Improvements have been made in sub-static printing, but only because the length of the polyester fabric is easy enough to work with. The tendency of fabric to shrink during sub-static printing is also not experienced in the method of the present invention which provides highly accurate print registration and pattern repetition. Ultimately, the dyes used in sublistatic printing have the desired sublimation properties and are subject to various other conditions (COlOurS).
eleetiOnfOrTransferPrint
rlgE. C. Vellns. ．． BritishKn
IttIngIndustryl, April 972).

A wide variety of dyes can be used in the present invention providing a wide range of shades, flexibility and precision in color formulation. The possibility of using dyes other than sublimation dyes depends on the quality of the dyed product,
It allows for an overall improvement, especially with respect to the stiffness criteria. Various variations in details are possible in the particular components of the materials used in the method of the invention, and in particular circumstances the particular formulation will depend on the type of material to be decorated and the type of dye used.

Care must be taken in the use of disperse dyes or pigments to ensure that they are sufficiently pulverized in the coating, otherwise poorly pulverized particles will tend to form crack nuclei and cause the film matrix to form on the fabric. This will result in incomplete transfer of the removable layer from the substrate. Importantly, compared to conventional fabric dyeing and printing methods, the method of the present invention causes less or no environmental pollution.

In particular, a large amount of waste water used for dyeing is eliminated. Also, due to the low temperature and short processing time, the energy requirements of this method are lower than conventional methods. The following examples illustrate the invention. Example 1 Eleven sheets of paper were coated with a solution of polybutadiene in benzene (5% W/V) and dried.

Appropriate designs were printed on the coated side of the paper with ink of the following formulation or all over. The dye was dispersed in a solution of other ingredients dissolved in ethanol for ink production.

After printing, the patterned or colored paper was dried. The paper was dried at 80°C with one uncolored side of the paper in contact with a heated surface, and a small piece of fabric woven from polyethylene terephthalate fibers was pressed onto the paper for 5 seconds.

When the cloth and paper were separated, the pattern was completely transferred to the cloth. The cloth was then placed between two metal plates at 200° C. and heated for 10 seconds to produce a red colored cloth with good washing fastness. The polymer was converted into discrete layers.

Dyeing of good quality can be achieved by using other dyes in place of Dispersol Stretch R used in the above method.

For example, L.B.
Sabra Print Yellow 70 manufactured by ay&COLtd)
001, Sabra Print Red 70027, and Sabra Print Blue 70032 can be used to produce yellow, red or blue dyeings, respectively. Similar good results can be obtained by replacing the tricresyl phosphate used with dibutyl phthalate or triphenyl phosphate. Example 2 Example 1 was repeated using a fabric made of nylon instead of the polyethylene terephthalate fabric.

Good coloring was obtained by a second heat treatment carried out at a temperature of 190°C.

When the fabric was placed on a mixture of polyethylene terephthalate or nylon fibers and cotton or viscose fibers, coloring was obtained, but the cellulose fibers were hardly dyed.

Example 3 Sodium carbonate solution (2
0y/. A cotton fabric was impregnated with e) and dried.

A sheet of paper was treated as in Example 1 except that the dye used in the layer was a water-soluble dye, namely Prodione Blue H-4.
R (ICI Organics) was used.

When the paper was heated to 80°C and pressed onto the treated cotton fabric for 5 seconds and then removed, the layer remained on the cotton fabric.

The dough was then steam treated at 100° C. for 10 minutes. After washing with hot water, the cotton fabric was dyed blue and was found to have strong washing fastness. Example 4 A design was printed on paper coated with a 5% (w/v) polybutadiene solution in benzene and dried with an ink of the following formulation: dye and trisodium phosphate were dispersed in an ethanolic solution of the polymer.

After printing, the paper was dried. The unprinted side of the paper was brought into contact with a heated surface of 130° C. and the cotton fabric was pressed against the paper, and the printed pattern was transferred to the overlapping pieces of cotton fabric. After cooling for 15 seconds, the paper was removed from the fabric, leaving a pattern behind.

The fabric was then steam treated at 102°C for 300 seconds and thoroughly washed with hot water. The fabric was printed with a dark blue pattern and showed good fastness when washed. The polymer was in discrete deposits. The dye used was Prodionelet H-8BN (IC
l), Cibacron Brilliant Yellow 2G-P (Ci
ba-Geigy) Reva Fix Violet P-4R
It can be replaced by any one or a mixture of a number of fiber-reactive dyes for cellulose, such as (FarbenBayer) (which produces red, yellow and purple prints, respectively).

Example 5 A design was printed on a sheet of paper coated with polybutadiene as in Example 4 with ink of the following formulation: Dyes etc. were dispersed as above.

After printing on paper, let it dry. As mentioned above, the dye film was transferred to nylon 66 fabric at 150°C, and the dye was applied at 100°C.
Steam fixation was carried out for 10 minutes at °C. The polyvinyl acetate layer is a discrete deposit. After the steam treatment, the dyed fabric was thoroughly washed and dried. The fabric had a bright red color and exhibited light and washing fastness. Example 6 The ink of Example 5 was changed to the following formulation.

Vat dye, potassium carbonate, and sodium formaldehyde sulfoxylate were dispersed in the ethanolic solution of the polymer. The dye film was transferred to a cotton fabric at 140°C as in Example 5 and then steamed at 102°C for 5 minutes. The bat dye was converted to soluble lyuco salt during steam treatment and absorbed by the cotton. The cotton fabric is removed from the steamer, washed with water to remove any unfixed dye, treated with an oxidizing solution for 5 minutes, or exposed to air to convert the vat dye back into the insoluble quinonoid form, washed with water and treated for 5 minutes. Treated in boiling detergent solution. Post-steaming processing is a common method for printing and dyeing vat dyes. The cotton was colored bright orange and showed strong fastness to washing and light. The polyvinyl acetate layer was discontinuous.

The butt dye used in the above examples was Durindon Pink F.
F fine powder (ICI) was substituted to produce a dark pick color, Caledon Green BN3OO fine powder (ICI) was substituted to produce a dark green color, and Ciba-Niero 1 GC powder (Ciba-G
eigy) can produce a deep yellow color.

Example 7 Paper was coated with a 5% (w/v) polybutadiene solution in benzene and dried.

An appropriate design or the entire surface of the paper was printed using ink of the following composition. The dye and tricresyl phosphate were dispersed in the ethanolic solution of the polymer.

After printing, the paper was dried. The unprinted side of the paper was brought into contact with a heating surface at 130° C., and the cotton fabric was pressed onto the paper, and the printed pattern was transferred to the small piece of cotton fabric by doubling it. The latter was allowed to cool for 15 seconds and the paper was removed from the fabric, leaving a pattern behind. The fabric was then steam treated at 102° C. for 300 seconds and thoroughly washed in hot water to remove any unfixed dye. The cloth was printed with a dark red pattern and showed strong fastness against washing. The polymer layer is a discontinuous deposit and does not retain a film feel. Example 8 An appropriate design or the entire surface of a cellulose acetate film coated with a nitrocellulose film (obtained from Transparent Paper Co., Barley, Lux) was printed with an ink of the following formulation.

To make the ink, the dye was dispersed in a solution of other ingredients dissolved in ethanol.

After printing, the patterned or colored film was dried. The cellulose acetate was heated to 110° C. by contacting the uncolored side of the cellulose acetate with a heated surface and a small piece of fabric made of polyethylene terephthalate fibers was pressed against it for 5 seconds.

When the cloth and cellulose acetate were peeled off, the pattern was completely transferred to the cloth. The fabric was then heated between two metal plates at 200° C. for 10 seconds to produce a red colored fabric: it showed good washing fastness. The polymer layer was in discrete deposits.

Dispersol Stretch R used in the above method can be substituted with other dyes to produce a quality dyeing.

For example, Sabra Print Yellow 70001 Sabra Print Red 70027 and Sabra Print Blue 70032 manufactured by L.B. Holiday may be used for yellow, red and blue dyeing, respectively. Similar good results can be obtained by using dibutyl phthalate or triphenyl phosphate in place of tricresyl phosphate.

Example 9 A sheet of paper was coated with a 5% (W/) solution of polybutadiene in benzene and dried.

A design was printed on the coated side of the paper using ink of the following formulation. The pigment was dispersed in an ethanol solution of the other ingredients. The non-printed side of the paper was brought into contact with a heated surface at 150° C., and the cotton fabric was pressed against the paper, doubling to transfer the printed pattern onto the small piece of cotton fabric. The double product was cooled and the paper was removed to leave a pattern. The fabric was then heated to 180°C for 10 seconds. It was printed with a bright red design and showed excellent fastness to washing. When the cotton used in the above examples was replaced with acrylic fiber fabric, a durable fluorescent red print was obtained.

The pigment used can be replaced with Lumogen Orange RF (BASF) or Lumogen RT Green (BASF) to give orange or green prints respectively. Example 10 Film weight 57 per square meter of paper when dried with a 5% polybutadiene (W7V) solution in cyclohexane
It was coated on a sheet of paper to a thickness such that

The dry coated paper was then coated with 3% (w/v) tricresyl phosphate.
A 3% (W7V) solution of polyvinyl butyral polymer (molecular weight approximately 34,000) in ethanol containing:

A suitable design was printed on the coated side of the paper with an ink of the following formulation: the dye was dispersed in an ethanolic solution of the other ingredients.

After printing, the patterned paper was dried. When dried, the weight of the film is 1.57/M2 for the continuous coating and 27/M2 for the dye-containing coating when two layers containing polyvinyl petitral are dried.
It was adjusted so that it became Trl. The paper was heated to 120°C and the fabric made from polyethylene terephthalate was brought into contact with light pressure for 3 seconds to overlap the paper.

When the composite was allowed to cool for 5 seconds and the paper was removed from the fabric, the pattern was completely transferred to the fabric. A cloth with a red pattern was made by heating the cloth at 200°C for 25 seconds.

It showed good washing fastness. The polymer had become discontinuous deposits. It has been found that if the initial polyvinyl butyral/tricresyl phosphate coating is completely eliminated, the transfer of the printed pattern to the fabric is not very good.

Dyes can be replaced with pigments such as Lumogen Orange RF (BASF), which produces a fast orange color, and Monolite Fast Blue I-V (ICI), which produces a timeless blue color.

When such pigments are used, patterns can be transferred to cotton or cotton/polyester blend fabrics, resulting in printed fabrics with good fastness. When the fabric to be printed is cotton, the dyes used can be replaced with Prodionelet H-8BN (ICI) 27 and sodium carbonate 5y. After the pattern was transferred to the cotton, the fabric was steamed at 100° C. for 10 minutes. After rinsing with water to remove unfixed dye, the cotton developed a timeless red pattern. Example 11 An ink was prepared containing in 100 parts by weight: The ink was used to print a design on polybutadiene coated paper and dry.

The design was transferred to the fabric by heating the paper at 155° C. for 8 seconds in contact with a piece of cotton fabric and then separating the resulting duplex. The fabric was heated to 190° C. for 30 seconds and dyed a deep red color, which showed strong fastness to washing and dry cleaning solvents. If dimethylol dihydroxycyclic ethylene urea is not included, the decoration will be difficult to wash, e.g. S.
O. The fastness of the dyeing gradually deteriorates in response to the black 3 washing test.

Example 12 A sheet of siliconized paper (“Slik” siliconized vegetable parchment: P.
N. l2 Messars Leonard Staith Co., Ltd. (Mess
rslLeOnardStaceLtd. ) was coated with a solution having the following composition.

The thickness of the applied film was 17 microns as a dry film.

The coated paper was printed with an ink of the following composition: The ink was screen printed to a dry ink layer thickness of 4 microns. The printed paper was heated at 165°C for 5 seconds at 10p. s.
The product was heated in contact with a cotton cloth at a pressure of 1, then cooled for 5 seconds, separated, and the design was transferred to the cloth.

The fabric was then heated to 185°C for 45 seconds. The polymer layer was in discrete deposits.

The fabric was printed yellow and was found to be very durable in washing and abrasion treatments.

C. I. C. instead of pigment Yellow-1. I. pigment red 6
If you use , you can get a red color that won't fade.

Also C. ．． Pigment Yellow-3 and C. I. The same goes for the mixture of 2 parts each of Pigment Blue 15. Example 13 The siliconized paper used in Example 12 was coated with a solution of the following composition.

The coating weight in wet condition using silk screen is 247.
It was m-2.

This paper was dried. "PIOLOFORMBNl8" is polyvinyl butyral 76-80% (W/W), polyvinyl acetate 1-2% (W/W), polyvinyl alcohol 1
The mixture contains 8-22%. The coated paper was brought into contact with the cotton fabric, and the weight was 30 kg/? At a speed of 15 m/min under a pressure of
It was passed through a heated roller at 120°C.

The design was transferred from paper to textile. The fabric was heated to 175°C.
After heating for 0 seconds, the polyvinyl alcohol layer became discontinuous deposits and the fabric took on a red color with excellent washing fastness. Example 14 An aqueous solution of a Warner chromium complex of myristic acid and polyvinyl alcohol was applied to drifted kraft paper using a bar coater to form a wax-like film, which was then dried.

This paper was printed with ink having the following composition using a silk screen and dried. This paper is brought into contact with a polyamide fabric for 35 minutes.
It was passed between rollers at 130°C at a speed of 4 m/min under a pressure of k9/CTn.

The design was transferred from paper to textile. Then 1 at 102℃
Steam heated for 5 minutes. The unfixed dye was washed out with warm water to obtain a polyamide fabric with a strong red design. Example 15 An ink having the following components was applied to the same siliconized paper as used in Example 12 using a bar coater and dried.

This paper was brought into contact with polyester fabric and 25k9/CT
It was passed through a heated roller at 135° C. at a speed of 12 m/min under a pressure of n.

The design was transferred from paper to fabric. 205℃
When heated for 30 seconds, a strong red color appeared. The polymer had become discontinuous and the refilm feeling had disappeared. Example 16 Bleached kraft paper was bleached to 36μ using a solution with the following ingredients:
It was coated to a thickness of 100 ml and dried.

was dissolved in 50 parts of diacetone alcohol and 17 parts of polyethylene glycol 100.

The dry film thickness of the printing ink layer was 12-15 microns. This decorative paper is brought into contact with a cotton fabric, and 3-4 p.m. s
．． The sample was placed in a transfer printing press operating at 195-200° C. for 35 seconds at a plate pressure of 1. The black design transferred almost completely from the paper to the fabric, resulting in a soft, transparent decoration with remarkable resistance to light, washing and cracking. During the transfer process, the ink film was transferred to the fabric and easily peeled off from the substrate.

[Brief explanation of the drawing]

The accompanying drawing is a schematic side view of an apparatus suitable for carrying out the invention.

Claims (1)

[Claims] 1. A flexible transfer material consisting of a film substrate and a removable layer on the film substrate comprising dyes and/or pigments and a film-forming polymer, the film-forming polymer being polyvinyl butyral, polyacetic acid, etc. A flexible transfer material, which is a mixture of vinyl or polyvinyl butyral and polyvinyl acetate, polyvinyl alcohol, cellulose nitrate or ethyl cellulose, is used; the removable layer of the transfer material is applied while heating to a textile fabric as the transferee. the film substrate is removed and the removable layer of the transfer material is transferred onto the textile fabric; and the textile fabric with the removable layer is left with the film-forming polymer in the layer. A method for decorating textile fabrics, characterized in that the dyes and (or pigments) are fixed on the textile fabric by heat treatment and the film-forming polymer is left on the fabric as discontinuous deposits.