JP2571769B2 - Thermal transfer material and thermal transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention uses a heat-sensitive transfer material suitable for dyeing a substrate such as cotton and cotton-polyester fiber and a film, and uses the transfer material. The present invention relates to a thermal transfer method.

(Prior Art) Conventionally, a method of forming a pattern on a paper backing sheet using a sublimable ink by a known printing technique, and then transferring the pattern to a cloth or a fiber by heat and pressure is well known. Using this technology, T-
Methods of decorating shirts and clothing are in practical use. Since this method is a method of printing a sublimable ink on a sheet by a gravure printing machine or the like, it is advantageous for producing the same pattern in large quantities, but disadvantageous for producing different patterns in small quantities. In addition, it is mainly used only for cloths and fibers mainly composed of polyester and has a drawback that it cannot be transferred well to other materials.

(Problems to be Solved by the Invention) The present inventors have intensively studied to improve the above-mentioned drawbacks. As a result, a heat-sensitive transfer material and a transfer material capable of forming a pattern easily and inexpensively even in a small amount of production have been developed. Invented the thermal transfer method used. In addition, the present invention has succeeded in transferring and printing cloths, fibers and films other than polyester.

[Configuration of the invention]

That is, in the first invention of the present application, the thermal transfer material and the transfer receiving sheet are overlapped, the ink is transferred to the transfer receiving sheet by the first thermal energy to form a desired pattern, and then the pattern is formed. Used in a thermal transfer method in which a transfer receiving sheet and a substrate are superimposed and the pattern is transferred to the substrate by a second thermal energy and pressure. The heat-sensitive transfer material is characterized in that a color layer containing a heat transferable dye and a heat-meltable layer mainly containing waxes are sequentially provided.

Further, the second invention of the present application relates to a heat-meltable layer mainly composed of waxes on a support, a colored layer containing a resin as a vehicle and containing a heat transferable dye, and a heat-meltable layer mainly composed of waxes. A heat-sensitive transfer material, which is sequentially provided with a transfer receiving sheet, and the ink is transferred to the transfer receiving sheet by the first thermal energy to form a desired pattern, and then the transfer receiving sheet formed with the pattern is formed. A heat transfer method wherein the pattern is transferred to the substrate by second heat energy and pressure.

The heat-sensitive transfer material according to the present invention comprises a heat-meltable layer mainly composed of a heat-meltable vehicle, a resin as a vehicle, and a resin.
A coloring layer containing a heat-transferable dye and a heat-meltable layer mainly containing a heat-meltable vehicle are sequentially provided. Using this transfer material, a first heat-transfer printer or the like on a receiving sheet such as paper is used. After forming a character or pattern with energy, the formed character or pattern is overlaid with a cloth or fiber and the dye is transferred by a second heat energy such as a conventionally known heating roll to convert the character or pattern into cloth or fiber. , Film, etc.

As the heat transferable dye used in the present invention, disperse dyes, basic dyes and leuco dyes conventionally used for dyeing fibers by sublimation transferability can be used. As sublimable dyes
A dye that sublimates at 100 to 400 ° C is preferable, and a dye that sublimates at too low a temperature is sublimated when a thermal transfer material is superimposed on a transfer receiving sheet and a pattern is formed using first thermal energy such as a thermal head. The dye gradually sublimates and fades during storage of the thermal transfer material. Dyes that sublimate at too high a temperature may have low transfer efficiency or require a high transfer temperature when re-transferred by the second heat energy and pressure when the patterned sheet is superimposed on a substrate such as cloth or fiber. I do. These dyes include dyes used in thermal transfer printing, such as disperse dyes, cationic dyes and oil-soluble dyes,
There are dyes known as color formers (eg leuco dyes).

Examples of disperse dyes include CI Disperse Yellow 1, 3,
7,9,13,16,23,42,54,60 etc., CI Disperse Orange
3,7,15,21 etc., CI Disperse Red 1,4,9,11,13,1
5,21,41 etc., CI Disperse Violet 1,4,9,12,1
8,27 etc., CI Disperse Blue 1,3,5,14,24,26,58 etc., CI Solvent Red 23,24,25 etc., CI Basic Yellow 11,13,29 etc., CI Basic Orange 21 etc. C.
I. Basic Red 13, CI Basic Green 1,4
N- (1,2-dimethyl-3-yl) is a colorless dye for color formers such as CI Basic Blue 5.
Methylidene-2,4-dimethoxyaniline (colored yellow), 4- (5-chloro-1,3,3-trimethyl-isoindolino) methyl-7- (N-methyl-N-phenyl) amino-5-chloro -1 ', 3', 3 ',-Trimethyl-spiro [2H-1-benzopyran- (2H) -indole] (developed in magenta), 3,7-bis-diethylamino-10-trichloroacetyl-phenoxazine ( Cyan color)
Is an example.

Waxes provided on a support such as a polyester film or condenser paper by using an ink made by kneading the dye having heat transferability with the resin at the time of hot melting or kneading the resin and the dye in the presence of an organic solvent. The present invention comprises providing a colored layer by applying under heating, if necessary, on a heat-meltable layer mainly composed of, and further providing a heat-meltable layer mainly composed of waxes on the colored layer. Can be produced. When characters or patterns are formed on a receiving sheet such as general paper using a thermal transfer material by using thermal energy of a thermal transfer printer or the like, and then the characters or patterns are retransferred to cloth or fiber by a conventionally known heating roll or the like. In addition, if a thermal transfer material is used in which an ink obtained by kneading a heat transferable dye and a resin is directly applied to a support, the dye may remain on a receiving sheet on which characters or patterns are formed, or may migrate to the back surface of the receiving sheet. And the proportion of dyes dyed on fabrics and fibers is reduced. On the other hand, when the thermal transfer material having the three-layer structure of the present invention is used, the transfer efficiency of cloth, fiber and film is high. The reason is that a heat-meltable layer, a colored layer, and a heat-meltable layer are formed in this order from the receiving sheet surface, and if this is used, the dye can be prevented from migrating to the receiving sheet during retransfer. Also, it is considered that the transfer efficiency to the fiber increases.

In the heat-sensitive transfer material having a three-layer structure of the present invention, the wax used for the heat-meltable layer in close contact with the substrate and the wax used for the heat-meltable layer on the colored layer need not necessarily be the same. The colored layer is preferably as thin as possible, and desirably 0.1 to 3 μm or less. Of the two heat-meltable layers, it is better to make the layer in contact with the substrate thinner, but if it is too thin, characters and patterns cannot be formed accurately with a thermal printer.
0.3-1 μm is most preferred. If the heat-meltable layer on the colored layer is too thin, it will sublime to the receiving sheet side during dyeing,
If the thickness is too large, accurate characters and patterns cannot be obtained with a thermal printer or the like.

The heat-meltable layer of the present invention is made of waxes used in conventionally known heat-melt transfer materials, for example, natural waxes such as candelilla wax, carbana wax, rice wax,
Vegetable waxes such as wood wax and jojoba oil; animal waxes such as beeswax, lanolin, and whale wax; petroleum waxes such as montan wax and petrolatum; Waxes, such as wax, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, hydrogenated waxes such as hardened castor oil, hardened castor oil derivatives, lauric acid,
Fatty acids such as palmitic acid, mystolic acid, stearic acid, 12-hydroxystearic acid, and waxes such as fatty acid amide are the main components. Acrylic, styrene, ester, rosin, vinyl, acetal,
It is an ink containing rubber and other resins, fillers such as calcium carbonate, precipitated barium sulfate and silicon dioxide, and other additives. The ink can be applied at room temperature using a coating machine. Hot melt coating, gravure It can also be applied by hot lacquer coating such as a method. In other methods except hot melt coating, the ink is applied with a diluting solvent.

In order to make transfer material that can be obtained in multi-colored characters and patterns, when dyeing fabrics and fibers, ink using a sublimable dye that dyes yellow, red, indigo, and black inks by a printing machine or coating machine This can be done by painting in a line-sequential or line-sequential manner. In general, coating can be performed with a printing machine or a coating machine. However, coating at a normal temperature is preferable for coating a hot-melt layer on a colored layer. It is not preferable because the adhered heat-meltable layer is melted.

For the coloring layer, inks such as gravure inks, flexo inks, and offset inks, which are conventionally known as inks containing a resin and a heat transfer dye as main components, can be used. Gravure inks can be used in both aqueous and solvent systems. As a resin in the coloring layer, an acrylic resin, a styrene resin, an ester resin, a rosin resin, a vinyl resin, an acetal resin, a rubber resin, or the like is used. The content of the dye or pigment in the colored layer is usually about 2 to 70% by weight. In addition, if necessary, a plasticizer may be added to the colored layer.
Surfactants, calcium carbonate, precipitated barium sulfate, silicon dioxide, and the like can be added, and in some cases, a wax can be used in combination.

Examples of the heat-meltable ink base material used in the present invention include papers such as condenser paper, heat-resistant films such as polyester and polyimide, and films provided with a heat-resistant coat layer.

A receiving sheet on which a pattern is formed using a thermal transfer material can be accurately recorded, and is preferably a sheet or a film having good heat resistance and heat conductivity and low ink absorption, and is preferably a general paper, a condenser paper, a parchment paper, a paper. Racing paper, paraffin paper, heat-resistant synthetic resin film and the like are used.

When the condenser paper is used for the receiving sheet, the efficiency of retransfer of the dye to the cloth and fiber when heated by a hot roll or the like is improved as compared with the case where ordinary paper is used. It is also recognized that the reason for this is that the rate of sublimation of the dye on the back of the receiving paper coated with the ink layer through the receiving paper is lower than that of ordinary paper.

However, when used as a receiving sheet, condenser paper lacks the accuracy of recording such as letters and patterns when used as a receiving sheet, so letters such as names and numbers can be dyed on cloth and fibers, but delicate patterns It is preferable to use general paper when dyeing is used. When the general paper is used as the receiving sheet, as described above, when the three-layered thermal transfer material of the present invention is used, it is possible to form a high-density delicate pattern with high dye retransfer efficiency, which is very advantageous. .

The substrate to be retransferred is cloth, fiber, film, or the like. When a color former is used as a dye, a developer must be contained in the substrate. These materials include not only polyester but also natural fibers such as cotton and wool, and synthetic and semi-synthetic fiber films such as polyamide, polyacrylonitrile, polyurethane, and cellulose.

What can be retransferred to many types of substrates as described above is
Unlike the sublimation transfer method conventionally used, it is considered that the dye is dispersed in the heat-meltable vehicle, and the vehicle melted by the thermal energy at the time of retransfer becomes the carrier. Upon retransfer, these molten vehicles penetrate the substrate or remain on the surface. Among the materials remaining on the surface, those materials having a sufficient adhesive force remain on the substrate surface as they are, but those that do not are easily peeled off. At the time of retransfer, these heat-meltable vehicles are very small and pose little problem in operation.

The thermal transfer material obtained according to the present invention can form characters and patterns on a receiving sheet such as paper by heat energy of a thermal printer or the like, and then form the characters and patterns on a cloth or a fiber film with a hot roll. It is possible to record the name, number, address, etc. on the film to prevent tampering, and to record characters on cloth or textile,
It is industrially advantageous because it can be used for applications different from conventional dry sublimation printing, such as the application of making an arbitrary pattern by a thermal printer or the like and transferring it to a fiber such as a T-shirt.

 Hereinafter, the present invention will be described in detail with reference to examples.

 All “parts” in the examples are “parts by weight”.

Example 1 Each of the following compositions precondensed in a 5 liter sand mill filled with 60% by volume of glass beads having an average particle size of 1.5 mm was charged by a gear pump at a rate of 2 liter / min, and the sand mill was charged at 10 m / min. Kneading by rotating at a speed of 5 seconds
By repeating the process twice, inks for the heat-meltable layer and the inks for the colored layers having the following compositions were produced.

(Heat-melting layer ink-A) Carbana wax aqueous dispersion (Note 1) (solid content 20%)
5 parts Aqueous acrylic resin (Riocryl AP-2 manufactured by Toyo Ink Mfg. Co., Ltd., solid content 27%) 0.5 parts Water 1 part Isopropyl alcohol 1 part (Note 1) Heat carbana wax with a melting point of 83-84 ° C to 100 ° C An aqueous dispersion obtained by gradually adding to warm water of 90 ° C. with vigorous stirring and cooling to room temperature.

[Colored layer ink]

(Yellow ink composition-No.1) Aqueous acrylic resin (Ryocryl AP-2 manufactured by Toyo Ink Manufacturing Co., Ltd.) 5 parts CI Disperse Yellow 1 0.2 parts Water 1 part Isopropyl alcohol 1 part (Red ink composition-No.2 9) 0.24 part of Disperse Red was used in place of Disperse Yellow 1 having a yellow ink composition.

(Composition of Indigo Ink-No. 3) Disperse Blue 1 (0.18 parts) was used in place of Disperse Yellow 1 of the yellow ink composition.

Each of the obtained inks was coated as follows. Using a gravure printing machine for color printing, perform solid printing using a gravure printing plate to a thickness of 0.5 μm (when dry) on a 6 μm polyester film with ink A using a hot-melt layer. 0.8 μm of red ink and indigo ink
Were applied to a predetermined size in a thickness (at the time of drying). Further, a hot-melt layer was solid-printed thereon so as to have a thickness of 1.5 μm (when dried). This process was performed continuously using a gravure printing machine to obtain three-color heat-sensitive transfer materials.

This transfer sheet was recorded on ordinary paper with a normal color thermal printer, and the resulting recorded material was placed on a polyester roll of white paper and placed in a hot roll (at 190 ° C). Obtained.

Example 2 In the same manner as in Example 1, the following inks for a heat-meltable layer and inks for a colored layer were trial-produced.

(Heat-melting ink-B) Carbana wax toluene dispersion (Note 2) (solid content 23%)
Acrylic resin (Hitaloid 100 manufactured by Hitachi Chemical Co., Ltd.)
5, solid content 40%) 0.5 part Toluene 1 part Ethyl acetate 0.5 part Methyl ethyl ketone 0.5 part (Note 2) Carbanana wax having a melting point of 83-84 ° C at 100 ° C
And slowly added to 90 ° C. toluene with vigorous stirring, and cooled to room temperature to obtain a toluene dispersion.

[Ink for coloring layer]

Yellow ink No.1, red ink No.2, indigo ink No.3 of Example 1
Was used.

The obtained ink was applied in the same manner as in Example 1 as follows. 3.5μ using a gravure printing machine for color printing
0.8μm using Ink-B on polyester film
m (dry) to form a hot-melt layer, and yellow ink No. 1, red ink No. 2, and 0.8 μm thick (dry) on top of it. The indigo ink No. 3 was solid-printed to a certain size in a face-to-face fashion. 1.0 on it
A heat fusible layer having a thickness of μm was formed.

This transfer sheet was recorded with an ordinary color thermal printer on a paper in the same manner as in Example 1, and the recorded matter was superimposed on a polyester film (10 μm) and placed on a heating roll (temperature: 160 ° C.). A color record was obtained. The recorded matter never disappeared even if it was rubbed violently with an eraser or the like.

Examples 3 to 11 Using the same sand mill as in Example 1, inks having the following compositions were charged and kneaded to produce prototype inks. For the colored ink, solid printing of only the color was performed, and the application of three colors was omitted.

[Heat-melting layer ink-C]

1 part of pulverized paraffin wax (Nippon Seiro Co., Ltd., paraffin wax 155, melting point 70 ° C) 1 part Rosin-modified maleic resin isopropyl alcohol 30
% Solution (Arokawa Chemical Industries, Ltd., Marquid 3002 isopropyl alcohol solution) 0.5 parts Isopropyl alcohol 3 parts Methyl ethyl ketone 0.5 parts [Heat-fusible layer ink-D] Xylene solution of rosin-modified phenolic resin (Arosawa Chemical Co., Ltd., rosin-modified) Phenolic resin Tamanol 135-5
6% synthetic wax (Diacarna 3 manufactured by Mitsubishi Chemical Industry Co., Ltd.)
0) 3 parts montan wax (Hoechst wax E manufactured by Hoechst)
1 part Polyamide resin (Versamide 33 manufactured by Henkel Hakusui Co., Ltd.)
5) 1 part silicon oxide (Aerosil 30 manufactured by Nippon Aerosil Co., Ltd.)
0) 0.5 parts Toluene 3 parts Isopropyl alcohol 1 part (Indigo ink for coloring layer No.4) Cyclic rubber (Thermolite N manufactured by Seiko Chemical Co., Ltd.) 3 parts CI Basic Blue 5 0.8 parts Toluene 1 part Ethyl acetate 0.5 parts Methyl 0.5 parts of isobutyl ketone (Red ink No.5 for colored layer) Cyclic rubber (Thermolite N manufactured by Seiko Chemical Co., Ltd.) 3 parts CI Solvent Red 23 0.9 parts 1 part of toluene 0.5 parts of ethyl acetate 0.5 parts of methyl isobutyl ketone (coloring Indigo ink for layer No. 6) (color develops into indigo) Cyclic rubber (Thermolite N manufactured by Seiko Chemical Co., Ltd.) 3 parts 3,7-bis-diethylamino-10-trichloroacetyl-phenoxazine 0.7 parts toluene 1 part Ethyl acetate 0.5 part Methyl isobutyl ketone 0.5 part A thermal transfer material was experimentally produced in the same manner as in Example 1 using the above ink.

 Table 1 shows the structure of the prototype transfer material.

When the heat-sensitive transfer materials of Examples 3 to 11 were recorded by a usual thermal printer, the obtained recordings were transferred to a substrate. As a result, excellent recordings having good washing fastness and abrasion resistance were obtained.

〔The invention's effect〕

As described above, according to the thermal transfer material and the thermal transfer method of the present invention, an arbitrary pattern can be formed on a cloth, a fiber or a film very easily, and the pattern can be formed with thin lines,
Subtle characters and the like can be formed accurately.

In the conventional sublimation transfer method, a pattern having a sufficient density cannot be obtained except for polyester fibers. However, according to the present invention, a pattern having a sufficient density can be formed other than polyester fibers. In addition, the receiving sheet used to form the picture can be made of general paper as well as paraffin paper, condenser paper and tracing paper, and when a general paper is used, a fine picture can be formed. is there.

Claims (2)

(57) [Claims] 1. A heat-sensitive transfer material and a transfer receiving sheet are stacked and
After the ink is transferred to the transfer receiving sheet by the heat energy to form a desired pattern, the transfer receiving sheet on which the pattern is formed and the substrate are overlapped, and the pattern is formed by the second heat energy and pressure. Used in the thermal transfer method of transferring to a substrate, a heat-meltable layer containing wax as a main component on a support, a resin as a vehicle, a colored layer containing a thermopolychromatic dye, and a wax as a main component. The above-mentioned heat-sensitive transfer material, wherein a heat-fusible layer is sequentially provided. 2. A heat-fusible layer mainly composed of waxes, a colored layer containing a heat-transferable dye, and a heat-meltable layer mainly composed of waxes are successively provided on a support. A heat-sensitive transfer material, and a transfer receiving sheet are superimposed on each other, and the ink is transferred to the transfer receiving sheet by the first thermal energy to form a desired pattern, and then the transfer receiving sheet having the pattern formed thereon is formed. A thermal transfer method, wherein a sheet and a substrate are overlapped and the pattern is transferred to the substrate by a second heat energy and pressure.