JPS609154B2 - Transfer sheet for knitted fabrics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer sheet for transfer printing a knitted fabric (hereinafter abbreviated as woven fabric) used as a textile material.

The inventors first took a flexible substrate with a removable layer thereon containing a dye and/or pigment and a film-forming polymer base (which layer, when heated, Press this layer onto the fabric while heating (becoming more adhesive enough to adhere to the fabric under the action of pressure) and remove the flexible layer leaving a layer that will adhere to the fabric. The fabric is then subjected to a fixation treatment (this process fixes the dye or pigment to obtain a solid product and causes thermal decomposition of the film, so the presence of the residue may affect the material properties of the fabric or the fastness of the colored product). We have discovered a transcription method that is characterized by having no effect on sex.

．． According to the present invention, there is provided a transfer material primarily for use in transferring textiles, which has the advantage of being very short and producing efficient transfer of removable layers with very short contact times, A base of plastic film-forming polymeric material and a pigment, a crosslinking agent capable of crosslinking the thermoplastic polymer, a thermally activated catalyst to promote this crosslinking reaction, a high temperature plasticizer and optionally an initially flexible polymer. Features a flexible substrate having a removable layer of other materials to assist in applying the removable layer to the substrate.

The removable layer may contain more than one pigment,
The pigment may be inert or capable of reacting with the polymer and/or crosslinking agent.

Said material is subjected to a fixing treatment (this treatment) in which the material is brought into contact with the material to be transferred, usually a textile, under heat and pressure in order to bond together the removable pigment-containing layer and the material to be transferred. is used by fixing the pigment on the material and applying it to the material (which usually dissolves the transferred layer so that the presence of the residue does not significantly modify the properties of the material).

The use of a thermally activated catalyst makes it possible to use sufficient heat and pressure to initiate fixation, which then transfers the material to be transferred, using techniques described in more detail below. It can be completed in just a few days, for example during storage. The flexible substrate can be removed before or after the fixation process. Generally, higher temperature and pressure combinations are required in the initial contact treatment when removing after fixation than when removing a flexible substrate before fixation. In some circumstances it is advantageous to remove the soft matrix after the fixing process to minimize the risk of contamination of machine parts with pigment and removable layer material. The initial heat and pressure contact is very brief and sustained with one pass through a heated noprolle, i.e. applying heat and pressure on the order of 10-2 or 10-3 seconds. This may make it possible to achieve transfer and optionally also immobilization. Suitable polymers when forming the base of the removable layer are polyvinyl acetals, such as polyvinyl butyral and polyvinyl formal.

They can be used alone or in acrylic acid polymers, polyamides,
It can also be used in mixtures with other polymers containing polyvinyl acetate or polyvinyl alcohol. Suitable crosslinking agents that can be used include dialdyhydes such as glyoxal, epoxy resin monomers and aminoplasts.

Of particular value are methylolated aminofs. Last monomers such as dimethylol urea, dimethylol dihydroxyethylene urea, dimethylol cyclic ethylene urea or their methyl esters such as methylolated melamine and trimethoxymethyl melamine. Catalysts that can be used include zinc nitrate, sodium dihydrogen phosphate, bromosuccinic acid.

As mentioned above, the catalyst used to promote crosslinking is thermally activated.

This means that they are ineffective at normal ectotherms and
Therefore, there is no tendency for cross-linking during the manufacture and storage of the polymeric compound of the transfer material, which means giving this material a longer life. The temperature at which the catalyst may be activated may vary, but is preferably 10,000 or higher. Activation can take place by heat treatment after or simultaneously with the transfer of the removable layer to the material to be decorated. Suitable temperature-activated catalysts are the so-called "protected" amine or ammonium salts of strong acids, such as the ethanolamine or jetanolamine salts of mineral acids, and ammonium salts such as ammonium chloride, nitric acid, phosphoric acid and sulfate. It is a catalyst.

The activity of the amine or ammonium salt is reduced by dissociation of the salt. The catalyst has no significant effect in the removable film until a critical temperature is reached. The catalysts suggested in our previously mentioned co-pending applications exhibit initiation even at very low temperatures, such as 50 to 60 degrees centigrade or even lower. The use of thermally activated catalysts increases the temperature. The amine salts of p-toluenesulfonic acid are particularly valuable in this respect, making it possible to raise the critical onset temperature to as high as 120 °C and correspondingly improving the thermal stability of the reproduceable layer, the layer during transfer. flow and the degree of thermal decomposition during transfer and heat fixation. Amine compounds suitable for combination with p-toluenesulfonic acid include S-carbazide, mono- and jetanolamines. It is particularly desirable to utilize catalyst/crosslinking agent combinations that provide precise temperatures for crosslinking.

For example, during the formation of a removable layer on a flexible substrate by coating or printing, it may be necessary to heat the paper to remove the solvent; such heating may speed up the cross-linking reaction. It is important that it is not started. During the transfer process, when heat and pressure are applied, there should initially be enough for the material of the removable layer to flow easily; However, at the end of the transfer process, heat and pressure may be increased to activate the catalyst. High temperature plasticizers constitute a special subgroup of enabling agents and have the property of lowering the temperature of the rubber/melt transition.

They may or may not also have the properties of common plasticizers, ie, the ability to lower the temperature of the glass/rubber transition to yield relatively soft films. Since the cosmetic process does not require that the continuity of the transferred film continues to be maintained during the fixing process, common plasticizers do not have a significant role to play. However, high temperature plasticization improves the degree of penetration of the releasable film into the substrate during transfer and the persistence of this process during the subsequent fixation process. Materials suitable for use as high temperature plasticizers include fatty acids such as palmitic or stearic acid, esters of palmitic or stearic acid with polyethylene glycol or glycerol, paraffin waxes, stearamides or finely dispersed polyethylene. . The removable layer may be a continuous layer of one color or a decorative layer.
It may be a separate layer in the form of a ve pa ratio, etc.

Said separate layers are conveniently produced by printing, and another aspect of the invention provides a printing ink consisting of the components of said layers dissolved or dispersed in a suitable solvent.
In particular, the ink according to the invention comprises a thermoplastic polymeric film-forming material capable of cross-linking, a cross-linking agent capable of cross-linking the polymeric film-forming material, pigment(s). It features an ink medium consisting of a catalyst and a high temperature plasticizer (as described above) to promote the reaction.

Said ink can be formulated according to common ink manufacturing practices and its consistency can be adjusted to the particular application required. avoid heating the
It is also important to avoid the use of acidic materials as additives for the same reason. The removable layer may be a simple single layer or may consist of several partial layers.

An essential aspect of the removable layer is that it contains the components mentioned above as necessary components of the removable layer, either throughout the entirety or in at least one of its sublayers or in a combination of said sublayers. The use of multiple sublayers may be particularly advantageous in some circumstances when it is desirable to use special printing methods. For example, printing by lithography may Achieving a balance of the above properties requires that the ink has special properties with respect to its physical reaction with the lithography.Achieving a balance of the above properties requires that the ink also contain substances with the properties discussed. coating or printing using any suitable method with a releasable film comprising all of the ingredients required for the present invention, drying the coated substrate, and then injecting it with a conventional lithographic ink. A thinner transfer material can be established by printing with some lithographic inks than the first one printed on to achieve the best transferability and fastness. It may be advantageous to apply another coating similar in composition to a thermoplastic base material such as that provided by ultraviolet curing inks based on glycidyl methacrylate when lithographic inks are used. Similarly, in gravure printing, the production of good images depends on the receptivity of the ink-receiving surface of the ink in the engraved cells and the co-flowing of the printed dots to cover the entire range. In order to aid this process in the removable layer system of the present invention it may be advantageous to pre-coat the flexible support with a full removable coating of a similar composition. In producing transfer materials by any conventional printing technique, colored transfers are established by successive printings using different colors, and mixed shades are obtained by overlaying one printed coating on another. ``In any multicolor printing process, the formation of multiple layers is unavoidable.''

In printing by any method, and especially when multiple layers are involved, it is important to avoid the use of drying temperatures that may initiate t-crosslinking reactions or cause high temperature plasticizers to take effect. The first is that cross-linking may proceed for some period after heating is stopped, resulting in a paper with poor storage stability, and the second is that ``in a roll of printed paper separate sheets or This results in a sticky paper that cannot be stacked without layer sticking.The flexible substrate is such that the surface inherently has the necessary release properties between the substrate and the removable layer. A wide variety of materials can be selected that have been or have been surface treated to produce the desired effect.

Self-supporting films of cellulose acetate and nitrocellulose or foils of aluminum and other metals can be used as such, or alternatively, for example "waxes, nitrocellulose, silicone or rubbery coatings of e.g. polybutadiene" can be used. Suitable papers may be used which are coated with a surface having a fertile surface; silicone coated paper, wax coated paper or acrylic or methacrylic acid cross-linked by ultraviolet irradiation in the presence of a suitable catalyst. Thermoplastic coated paper, such as that provided by unsaturated esters, is a preferred flexible substrate. Certain paper forms can be used as is, ie, without foil coating. When the transfer material of the invention is used, the removable layer must first be transferred to the fabric to be transferred. This may be done by using the thermoplastic properties of this removable layer and then applying a suitable fixation to this layer. This is done by subjecting the thermoplastic material to crosslinking and forming a discontinuous matrix which fixes the pigment to the material to be transferred.A clearly removable layer is removed as a layer during said processing. If they remain, the feel and appearance of the fabric after transfer is seriously affected.

It is therefore essential to use a removable layer formulation that decomposes upon heating to yield a discontinuous non-external layer and to use transfer conditions that allow this process to occur. Preferred transfer conditions are therefore such that the high temperature plasticizer in the removable layer becomes active and the pressure used promotes proper flow of the fluidized bed into the transferring fabric. The temperature at which the removable layer is raised during the transfer process may be such that the cross-linking reaction is initiated by activation of the catalyst and, if this is done, the pigment is then heated and heated. No need for fixation, fixation up to full fastness,
For example, this occurs automatically over 10 to 20 field hours. We achieve sufficient absorption of the removable layer into the material of the textile by choosing appropriate pressures and temperatures for the initial application of the transfer material according to the invention to the textile to be transferred. It has been found that this allows for less or no adhesion to remain between the fabric and the flexible substrate. In these environments, when using certain mechanical molds for the immobilization process, it may be advantageous to protect the mechanical parts from contamination by leaving the complex unseparated during immobilization. There is. Satisfactory transfer of the removable layer to the fabric to be universalized is obtained using a calender with one or two heated rollers. The inventors found that 80-1
It has been found that a temperature of 0°C and a pressure of 40 to 200 pounds per inch of loaf width produces a satisfactory result. Best results are obtained when the transfer paper reaches a temperature during the nip at which the high temperature plasticizer becomes active. The plasticizer is selected such that the normal operating roller temperature is between 80°C and 120°C. The operating speed, combined with the fact that the contact time is on the order of 10-2 seconds or less,
It may be as slow as, for example, 5 to 10 meters, or even faster, and it is desirable to obtain a suitable transfer paper temperature in this short time. If relatively high pressures are used, the degree of transfer into the interstices of the fabric is very high and the ideas described above apply. Since the thickness, density, compressibility, etc. of the fabric all affect the degree of thermal film transfer into the fabric under heat and pressure conditions, the nature of the fabric to be transferred will affect the transfer conditions and therefore the conditions should be strictly controlled. cannot be specified. For example, it is possible to use a static press, although transfer using a very short, sustained heat/pressure treatment during a calendar is preferred. Usually this involves the application of high pressure, e.g. 800 psi, to obtain satisfactory results;
The transfer process lasts longer than when using a calendar, but
Much shorter than usual, when using a static press to get transfer makeup. When using the material of the present invention, it is usually 5~
Requires 8 seconds of static pressure. This can be contrasted, for example, with the period of 6-day sand used during sublimation transfer printing (see Defago et al. US Pat. No. 3,782,899).
Textiles that can be transferred using the material of the invention are:
Fibrous, e.g. cotton, viscose rayon, purinose (
polyamides such as nylon 66 or nylon 6, polyesters, mixtures of fibers such as polyester/cotton or wool/cotton blends, coated fibers such as polyvinyl chloride coated cotton fabrics, It may be an aluminum coated fabric.

The following examples illustrate the invention. EXAMPLE 1 Paper coated with a silicone release layer is printed with an ink containing each of the following in 100 ta to give a 3 micron thick dry film.

Copper phthalocyanine pigment
Company) 15% Stearyl alcohol-ethylene oxide condensate 6% Dimethylol dihydroxy cyclic ethylene urea in 20% aqueous solution 3% Ammonium nitrate 1% 640p ethanol 73% The printed paper was brought into contact with mercerized cotton fabric and 100 pounds per inch of nip was added. Pass it between two rollers adjusted so that a pressure of .

The upper roller is made of steel and is heated to 11,000°C to force the textile paper composite through the nip at 6 yards per minute. The composite is then fed onto a 165° oil heated drum under a felt blanket used to aid contact. The fabric is in contact with the heated surface and the contact time is 3 seconds. After this heat treatment, the paper is removed and the touch is printed with a glossy blue design that has high fastness to washing and light. Its look and feel is that of substantially unprinted fabric. If the nip pressure is reduced by 10 pounds per inch of nip and the same operation is used, the transferred design is clearly present on the fabric surface.

Similarly, if the paper is removed before passing around the oil-heated drum, the transferred film is observed to mark the blanket, although the design is no longer superficially fixed. EXAMPLE 2 Silicone was printed on delamination coated paper by screen printing using inks containing 100% of each of the following to obtain a 6 micron thick dry film.

Color Index Pigment Yellow No. 1 2 Polyvinyl butyral (Boutvuar 98 - Monsanto Company) 15 Stearyl alcohol-ethylene oxide condensate 8 20% solution of trimethylolmelamine in water 2 Ammonium sulfate 1 Ethyl cellosolve 40 640 p Ethanol 33 The printed paper is brought into contact with the cotton laminate and passed between two rollers adjusted to produce 150 pounds per inch of nip pressure.

The top (steel) roller is heated to 125 qo and the fabric/paper composite is passed through the nip at 5 yards per minute. Next, this mixture was fed into a garment press adjusted to a temperature of 165°C for 3 inkstone sands, and then the paper was removed. The fabric is printed in a deep yellow shade with high wash and light fastness.

The texture of the fabric is excellent and the fabric material properties are not impaired. Example 3 The paper of Example 1 was used to print fabrics made from a 67-33 polyester uniform blend, a 50/5 Buta Ryoichi polyamide blend, and viscose; similar results were obtained.

EXAMPLE 4 Silicone was coated with a second full coating of delamination coated paper using a solution containing 100% of each of the following to obtain a 6 micron thick dry layer.

16 parts polyvinyl butyral (Butovuar 98 - Monsanto Company) 8 parts stearyl alcohol ethylene monoxide condensate 3 parts dimethylol dihydroxy cyclic ethylene urea 19 parts ammonium nitrate 72 parts 64 op ethanol 100 parts each on this double-coated paper. Using an ink containing a medium, such as a brush or felt pad'
Design from here.

Color of the 5th evening.

Index Pigment Red No. 6 10 days of polyvinyl alcohol 85 days of water After drying, the paper is contacted with a 50/5 female curtain-polyester blend fabric and then processed as in Example 2.

The design is perfectly transferred to the fabric to obtain a green color scheme and a red color scheme with excellent fastness to light. Example 5 An ink is prepared containing the following in 10 parts each.

Pigments selected from the list below 5 parts stearyl alcohol ethylene monoxide condensate 1 o trimethoxymethylmelamine (40% aqueous solution) 2 parts ammonium sulfate 1.5 parts polyvinyl petyral 1.5 parts 640P ethanol 33.5 parts toluene 33. Silicone release paper or wax is printed by Ikarito screen printing.
Print this ink on the Hina paper.

The design can be transferred to cotton-polyester or cotton fabric by contacting the printed side of the paper with the fabric and heating the composite for 0.03 seconds at 125 qo under pressure (400 pounds per square inch). The composite is then heated to a temperature of 3 to 16 yo under irradiation or without pressure. The paper is then removed and the printed design remains on the fabric, providing a wash-resistant transfer. Alternatively, the paper may be removed from the fabric after the first heat treatment and before the second heat treatment.

Some pigments that can be used in the ink in this example are shown below.

Copper Phthalocyanine (Blue Tint) Carbon Black (Ash Tint) (Red Tint) (Yellow Tint) (Purple Tint) Example 6 Fine Carbon Black Pigment 2 Polyvinyl Butyral (Butovuar 98 - Monsanto Company) 159 Stearyl Alcohol 10 parts of ethylene monoxide condensate, 2 parts of trimethoxymethylmelamine, 1 part of the mo/ethylamine salt of tap-toluenesulfonic acid, 2 parts of pentonite, in a mixture with 5 parts of polyethylene glycol and 18 parts of diacetone alcohol. It is dispersed to produce screen printed matter.

Silicone coated paper as used in Example 1 is printed with this ink by screen printing and dried at 75q0. The printed paper was then placed in contact with the fabric and the nip was operated at a pressure of 70 pounds per inch and
This paper is used to transfer onto a cotton fabric by passing it through a heated calendar roller heated to a temperature of 95°C. The feed rate is 20 meters per minute. The paper is then removed from the cotton fabric, leaving behind the printed design. The fabric is then heated in a 140 oo oven for 3 hours. After this heat treatment, the fabric is imprinted with a robust black design. The fastness improves to a higher standard with standing, giving excellent fastness to the iS04 wash test. Example 7 In Example 6, the carbon black pigment was replaced with a red pigment (color).

When replacing with index pigment (red No. 6) and printing a design on wax-coated paper by screen printing. Excellent transfer to the rayon fabric is achieved by increasing the calender pressure to 115 pounds per inch and increasing the heated roller temperature to 110°C. The fastness of the transfer after heat treatment as described in Example 6 is excellent. Example 8 An ink formulated as shown in Example 6 is applied to wax-coated paper by screen printing.

The paper is then heated in a calender at a pressure of 100 pounds per inch of nip (one loaf is 190 pounds).
qo and the operating speed is 1 yard per minute). Next, remove the paper from the fabric. After 7 days of storage, the fastness of the transfer is much improved from that observed immediately after paper removal and is equal to that observed for the mold produced by the transfer and fixation conditions used in Example 5.

Example 9 Polyvinyl butyral i5 in 85 parts of n-propanol
The coating solution in which the solution is dissolved is applied to paper that has been coated with an ultraviolet radiation cured butyl methacrylate composition containing a suitable photochemical initiator.

The polyvinyl butyral coating is applied to a wet thickness of 6 mm. The coated paper is printed with a conventional lithographic ink containing steel phthalocyanine pigments using conventional operations and then coated again with a solution containing:
Dry at 5000C.

Polyvinyl butyral 15 parts Stearyl alcohol
1 part trimethoxymethylmelamine 2 parts jetanolamine salt of P-toluenesulfonic acid
One part was dissolved in 72 rings of n-butanol.

The wet thickness of the second coating is 6 mm. The printed paper is then brought into contact with the fabric and the cotton/polyester blend shirting fabric is dressed by passing the composite through a heated calendar adjusted to a pressure of 70 pounds per inch and a heated roller temperature of 10,000 degrees.

After sending it to a calendar and removing the paper, the transferred design remains on the fabric. The latter is then heated to 135 oo for 45 seconds to obtain a blue transfer with very high fastness to severe washing and light. Example 10 A gravure printing ink is produced by dispersing 61 parts of 640p ethanol in 61 parts of copper phthalocyanine pigment, 8 parts of polyvinyl butyral, 15 parts of stearyl alcohol monoxide Cechley condensate, 12 parts of trimethylolmelamine, 2 parts of ammonium nitrate.

The design is then applied to ultraviolet radiation cured butyl methacrylate coated paper as used in Example 8 by gravure printing using a force of 9k9-1 and a running speed of 20 skin-1. The printed paper is then transferred to a cotton fabric using the procedure described in Example 6.

Claims (1)

[Claims] 1. A thermoplastic film-forming polymer, a pigment, a cross-linking agent capable of cross-linking the polymer, and a thermally activated catalyst promoting the cross-linking reaction on a flexible sheet-like substrate. and a high-temperature plasticizer, and is provided with a removable layer in which the matrix portion becomes discontinuous when heat and pressure are applied during the transfer operation and, if necessary, a heat setting treatment is performed. 2. The removable layer contains one or more pigments,
The transfer sheet according to claim 1, at least some of which can react with a polymer and/or a crosslinking agent. 3. The transfer sheet according to claim 1 or 2, wherein the thermoplastic film-forming polymer material is polyvinyl butyral. 4. The transfer sheet according to any one of claims 1 to 3, wherein the thermoplastic film-forming polymer material is made of one or more of polyvinyl acetal, acrylic polymer, polyamide, polyvinyl acetate, and polyvinyl alcohol. . 5. The transfer sheet according to any of the preceding claims, wherein the crosslinking agent is one or more dialdehydes. 6. The transfer sheet according to any one of claims 1 to 4, wherein the crosslinking agent is a methylolated aminoplast monomer. 7 The crosslinking agent is dimethylol urea, dimethylol dihydroxyethylene urea, dimethylol cyclic ethylene urea,
The transfer sheet according to claim 6, which is selected from methylolated melamine and trimethoxymethylmelamine. 8. A transfer sheet according to any of the preceding claims, wherein the catalyst is selected from amine and ammonium salts of strong mineral acids. 9. The transfer sheet according to any one of claims 1 to 7, wherein the catalyst is an amine salt of p-toluenesulfonic acid.
10. Transfer according to any of claims 1 to 9, wherein the high temperature plasticizer is selected from high molecular weight fatty acids, esters of high molecular weight fatty acids with polyethylene glycol or glycerol, parf-in waxes, suaric acid amides and polyethylene. sheet. 11. A transfer sheet 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 transfer sheet according to any of claims 1 to 10, wherein the removable layer is present as a continuous coating over the flexible substrate. 13. The transfer sheet according to any one of claims 1 to 12, wherein the removable layer is composed of a plurality of partial layers. 14. The removable layer comprises a first partial layer containing the components (excluding pigments) as defined in claim 1, printed thereon in one or more colors and containing an ink. Transfer according to any one of claims 1 to 12, consisting of a lithographic image printed from a pigment and a second partial layer having a similar composition to the first partial layer on the lithographic image. sheet. 15. The transfer sheet according to any one of claims 1 to 14, wherein the flexible substrate is cellulose acetate or nitrocellulose film, aluminum foil, or surface-treated paper. 16. The transfer sheet according to any one of claims 1 to 14, wherein the flexible substrate is a silicone release coated paper. 17. The transfer sheet according to any one of claims 1 to 14, which is a flexible substrate or wax-coated paper. 18. Any one of claims 1 to 14, wherein the flexible substrate is paper coated with a thermoplastic coating formed from a mixture of unsaturated esters of acrylic acid or methacrylic acid cross-linked by ultraviolet radiation. transfer sheet. 19 A thermoplastic film-forming polymer, a pigment, a crosslinking agent capable of crosslinking the polymer, a thermally activated catalyst promoting the crosslinking reaction, and a high temperature plasticizer are placed on a flexible sheet-like substrate. , placing a removable layer of a transfer sheet on a knitted fabric, which is provided with a removable layer in which the matrix portion becomes discontinuous when heat and pressure are applied during the transfer operation and a heat setting treatment is performed as necessary; A transfer method for knitted fabrics characterized by fixing pigments in a removable layer by applying heat and pressure. 20. The method of claim 19, wherein the flexible substrate is removed from the fabric prior to fixing. 21 Transfer the transfer sheet and knitted fabric to 4 per inch of roller width.
21. A method as claimed in claim 19 or 20, comprising combining between heated calender rolls under a line pressure of 0 to 200 pounds. 22 Claim 1, in which the knitted fabric and the transfer sheet are passed through a heated calendar roll at a speed of at least 5 m per minute.
22. The method according to any one of items 9 to 21. 23. The method of any of claims 19-22, wherein the heat and pressure are sufficient to activate the catalyst and initiate the immobilization reaction.