JP3441721B2 - Sublimation dyeing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for providing a full-color image on a film product having a resin layer on its surface.

[0002]

2. Description of the Related Art Conventionally, a polyester cloth and a transfer paper on which ink-jet printing (image printing) is image-wise formed by using a sublimation ink containing a sublimation dye as a coloring material are brought into close contact with each other and pressed, and a temperature of about 190 to 200 ° C. The so-called sublimation heat transfer dyeing method is used in which the polyester cloth is dyed by heating for 30 to 60 seconds. The temperature required for evaporating the fast-moving sublimable dye used at this time under atmospheric pressure is generally about 170 to 180 ° C or higher. As a development of this, for heat-resistant film products such as polyester film and polycarbonate film in roll form or sheet form, and film products in which a cross-linking type clear resin layer is laminated on a more general-purpose film product. Also, the transfer paper is vacuum-contacted, and 150 to 170
It is also practiced to heat the clear resin in the surface layer by heating at a temperature of about C for about 2 to 5 minutes. Incidentally, in many cases, these film products are provided with an adhesive treatment on the back surface in advance.

[0003]

The above-mentioned sublimation heat transfer dyeing method for a polyester cloth is carried out by heating a sublimation dye which is integrated with an ink solvent and permeated and dried on a transfer paper to form an agglomerated powder. Is evaporated to reach the contact surface with the polyester cloth, the degree of adhesion of which is increased by pressurization, and its vicinity, and the diffusion to the polyester fiber is performed. As described above, in the case of polyester cloth, a pressure of about 300 g / cm ² and a high temperature of about 190 ° C. or higher are essential. This is because the fabric is a woven structure and is a heat insulator containing a large amount of air. Therefore, it is necessary to eliminate the contained air to substantially raise the temperature of the contact surface of the fabric with the transfer paper. This is because it is necessary to raise the temperature of the sublimable dye to a gas state so that the sublimable dye reaches a portion that cannot be brought into contact with the transfer paper even by pressure. This is also because in the case of polyester fiber, the crystallinity increases due to the orientation in the spinning process, and it becomes difficult for the dye to enter, and higher temperature energy is required.

In the sublimation heat transfer dyeing method for a film product, when the adhesion between the transfer paper and the film product is increased by pressurization, the film product is in a softened state because heat is applied at the same time. The texture of the surface of the transfer paper, which is the surface, is transferred to the film product surface as an embossed pattern, greatly impairing the gloss initially held by the film product surface. For this reason, thermal transfer is performed by applying pressure at a vacuum adhesion level at most. However, even then, it is impossible to maintain the gloss that the original film product had. Even in the case of a film product with high heat resistance, it is not possible to perform perfect thermal transfer.Therefore, for a film product with low heat resistance, the transfer paper and the film product are also bonded. The sublimation heat transfer dyeing method cannot be carried out at all. Therefore, the first object of the present invention is to use an inkjet printer using a sublimation ink to provide a full-color image on an arbitrary film product having a resin layer on its surface while completely maintaining the original high gloss of the product. It is to provide a method of giving. In this case, the film product means a resin film or a resin film laminated on an arbitrary film-shaped support such as metal, paper or wood.

On the other hand, the film product is not limited to a product wound into a roll, but it is cut into a size standardized in the field of use such as an ID card or a photograph, or a standard size of A4 or A3. There are many products that are used in single sheets, such as products. In these cases, printing is performed once on the transfer paper, precisely aligned with the sheet of film product, placed on top of each other, and then heated in close contact. However, this method requires precise manual work for each sheet, and thus requires a great deal of labor when the number of sheets is large. In addition, the transfer paper is
Since the vertical and horizontal sizes fluctuate by several percent or more, there is also a problem that the image size of the film product after thermal transfer cannot be precisely maintained at a predetermined size. Therefore, the second object of the present invention is to
It is an object of the present invention to provide a simple and inexpensive method for imparting a full-color image of a predetermined size to a large number of sheet-shaped film products by using an inkjet printer using a sublimation ink.

[0006]

On the other hand, since the sublimable dye has a very small molecular weight of about 300 or less, it has the property of diffusing in the process of molecular migration inside the resin even if the evaporation temperature is not reached. . This phenomenon is a phenomenon that commonly appears in resins in general, although there is a difference in the level of ease of transition and difficulty of transition. The sublimation heat transfer dyeing method for the film product is below a general evaporation temperature 150.
It is considered that the reason why the efficient operation can be performed even at about ° C is that the diffusion action based on this property is involved to a considerable extent. This is not the rough surface contact between the transfer paper and the film product as mentioned above, but if the contact cross section is a continuous layer of resin even if it is between different resin materials, it will be compared by molecular migration. It means that the sublimable dye can be efficiently diffused at extremely low temperature. This is an ink-receiving film having a structure in which an ink-jet receiving layer containing a water-soluble resin as a main component is laminated on a film product having a resin layer without using a transfer paper, and the sublimation ink is directly printed on it. It can be realized by using the method. Generally, the thickness of the resin layer laminated as an inkjet receiving layer is as thin as about 20 μm or less, so that the sublimable dye can smoothly diffuse into the base resin layer without bleeding in the peripheral portion.
Moreover, the water-soluble resin has a low affinity for the sublimable dye, and when heated, most of the water-soluble resin is transferred to the resin layer of the film product without leaving the sublimable dye on its own, which is advantageous.

When ink-jet printing is performed on this ink-receiving film, the ink droplets penetrate into the deep part of the ink-jet receiving layer and reach the interface with the resin layer of the base or the vicinity thereof. When heating is performed in this state, the sublimable dye diffuses evenly on the surface of the resin constituting the inkjet receiving layer and the surface of the resin layer in continuous contact due to molecular migration. What is important here is that there is no need for pressurization since the ink jet receiving layer and the film product are originally in uniform and continuous contact by coating. It depends on the material properties and heat capacity of the film product, but when the heating method of leaving it in a temperature-controlled room is adopted, it takes about 1 minute at 200 ° C for 16 minutes.
The dyeing is completed in about 2 to 5 minutes in the case of 0 ° C. Then, the inkjet receiving layer may be peeled off from the film product as a film layer. As a result, since the dyeing is completed on the surface of the film product softened by heating without applying any pressure, the original gloss of the surface of the film product is not impaired at all.

As described above, since the concept of transfer paper does not exist in the first place in this system, the pressurization essential in the conventional sublimation heat transfer dyeing method is not essentially required. Therefore, the conventional large-scale thermal transfer machine required for applying a constant pressure to the entire transfer area is not required. Any method may be used as long as a certain amount of heating is uniformly applied, in which an ink receiving film having an inkjet receiving layer laminated on a film product is directly printed with a sublimation ink to develop a color of a fixed sublimable dye. For example, a non-contact heating method such as a method of leaving it in a constant temperature room for a certain time or a method of passing a printed ink receiving film through the constant temperature room at a constant speed is preferable from the viewpoint of product quality and cost. In the latter method, an apparatus integrated with the inkjet printer is also possible, in which the ink receiving film continuously output from the inkjet printer is passed through the apparatus in synchronization with it. As described above, according to the present invention, since there is no work of precisely aligning the transfer paper and the film product, almost no manpower is required in the heating step. Depending on the case, even in the case of a sheet-type film product, it is possible to design the entire process as an automated line. In addition, since the image after printing (printed image) is formed on the inkjet receiving layer that is temporarily integrated with the film product, the image is diffused as it is to the surface layer of the film product below by the heating process.
Images of a given size are always acquired, regardless of humidity.

Note that the non-contact heating method is not limited as long as the above-described film surface gloss maintenance is not concerned. It can be considered that the printed transfer paper and the film product are integrated from the beginning, and from this point of view, it is obvious that the conventional iron press type thermal transfer machine and rotary type thermal transfer machine can be used in the same manner. Even with such a usage method, it is not necessary to use the transfer paper, and the effect of reducing the cost is great from the viewpoint of the paper cost and the process rationalization.

After heating, the ink-jet receiving layer may be formed as a film layer that can be smoothly peeled off from the film product. This is a problem that depends on the chemical activity of the surface of the film product, or the chemical activity of the coating resin when a coating is applied thereon, and the adhesive strength of the resin constituting the inkjet receiving layer. However, at this time, since the ink jet receiving layer has undergone a heating process at about 160 ° C., it is in a dry state with a moisture content of zero, so that the adhesive force is very weak and the film property is enhanced.
Further, in the case of polyvinyl alcohol and the like, crystallization is promoted by heating, so that the film property is further enhanced. For these reasons, the inkjet receiving layer after heating can be easily peeled off as a film layer in many cases. Further, even when the film product is a very hard resin such as a polycarbonate resin or an acrylic resin, the adhesive strength of the inkjet receiving layer is weak and the film layer can often be peeled off smoothly. If peeling is difficult, the surface of the resin layer of the film product may be coated with a fluorine-based or silicone-based lubricant, a release agent, an antiblocking agent, or the like in advance. Generally, the film surface is a fluorine resin,
Almost any kind of inkjet receiving layer can be smoothly peeled off as a film layer as long as it is a chemically inert resin such as a silicone type resin or an olefin type resin.
Specifically, the fluorocarbon resin is a homopolymer of fluoroolefins, a copolymer of fluoroolefins,
Alternatively, it is a copolymer of fluoroolefins and monomers other than fluoroolefins. For example, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-perfluoroacryl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polychlorotriene Fluoroethylene and the like can be mentioned. Examples of the silicone-based resin include pure silicone resin and silicone-modified resin (alkyd, epoxy, phenol, urethane, acrylic, melamine). As olefin resin, polyethylene, polypropylene,
Examples thereof include polyvinyl chloride.

In this case, the inventor of the present invention used the "dyeing method" (Japanese Patent 2,847,588, US Patent 5,364,41).
As disclosed in 2), chemically inactive types of resins have no affinity for sublimable dyes at the same time, and resins having high affinity for sublimable dyes such as polyester resin and polyurethane resin. In the case where the two are simultaneously laminated, when the sublimable dye on the non-affinity resin is heated, most of it passes through the non-affinity resin layer and is fixed to the affinity resin layer. Therefore, in the case of carrying out the present invention, in the case where the film product to be used has the fluorine resin or the like laminated on the outermost layer, the affinity resin as described above is always present adjacent to the lower layer. It is important to be designed as.

The sublimation ink used in the present invention is an aqueous ink containing water as a solvent. Therefore, the resin forming the inkjet receiving layer is mainly composed of a water-soluble resin that can quickly absorb and receive the ink. Water-soluble resins are water-soluble or hydrophilic natural or synthetic polymers. For example, polyvinyl alcohol resin, polyvinyl acetal resin,
Polyvinyl methyl ether, vinyl methyl ether-maleic anhydride copolymer, polyvinyl pyrrolidone, vinyl pyrrolidone-styrene copolymer, vinyl pyrrolidone-vinyl acetate copolymer, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, etc. Water-soluble acrylic resin synthesized from monomers and other monomers,
Selected appropriately from vinyl resins such as polyacrylamide, synthetic resins such as polyethylene oxide and polyglutamic acid, semi-synthetic resins such as cellulose derivatives such as carboxymethyl cellulose and methyl cellulose, and natural resins such as chitin, chitosan, starch and gelatin. One kind or two or more kinds can be used. Polyacrylic acid, polyelectrolyte polyelectrolytes such as alkali metal salts such as polystyrene sulfonic acid, or polycation polyelectrolytes such as polyethyleneimine, polyvinylamine, polyallylamine, polyvinylalkylammonium halides, polyvinylbenzylalkylammonium halides, Alternatively, amphoteric polyelectrolytes can be used.

An overcoat layer made of a hydrophilic resin in which inorganic fine particles are dispersed may be provided on the ink jet receiving layer for the purpose of improving the drying property and blocking resistance of the ink. The hydrophilic resin is a resin that is insoluble in water at least at room temperature but has ink permeability. For example, polyvinyl formal, polyvinyl acetoacetal, polyvinyl acetal resins such as polyvinyl butyral, polyalkyl vinyl ethers such as polyvinyl isobutyl ether, hydrophilic acrylic resins synthesized from acrylic acid, methacrylic acid or their esters, and aqueous polyester resins. And so on. If the thickness of the inkjet receiving layer is too thin, the landing ink cannot be quickly absorbed, and the landed inks are united on the surface, so that a high quality image cannot be printed. On the other hand, if it is too thick, the sublimable dye diffuses from the ink jet receiving layer to the surface of the resin layer, and the reaching distance becomes too long, which is an obstacle to realizing high density and high resolution. Taking these into consideration, the film thickness is generally 3 to 20 μm, preferably 5 to 15 μm.

The sublimable dye used in the present invention may be any dye having a sublimable or evaporative function, and is preferably a dye that sublimates or evaporates at 70 to 260 ° C. under atmospheric pressure. . Examples of these dyes include azo, anthraquinone, quinophthalone, styryl, di- or triphenylmethane, oxazine, triazine,
Examples thereof include dyes having sublimation or evaporation properties such as xanthene, methine, azomethine, acridine, and diazine. In addition to these, 1,4-dimethylaminoanthraquinone,
Brominated or chlorinated 1,5-dihydrooxy-4,8-diaminoanthraquinone, 1,4-diamino-2,3-dichloro-anthraquinone, 1, amino-hydroxy-anthraquinone, 1-amino-4-hydroxy-2-
(Β-Methoxy-ethoxy) -anthraquinone, 1-amino-4-hydroxy-2-phenoxy-anthraquinone, methyl, ethyl, propyl or butyl ester of 1,4-diamino-anthraquinone-2-carboxylic acid, 1-amino- 4-anilide-anthraquinone, 1
-Amino-2-cyano-4-anilide (or cyclohexylamino) -anthraquinone, 1-hydroxy-
2- (p-acetamino-phenylazo) -4-methylbenzene, 3-methyl-4- (nitrophenylazo)-
Examples thereof include dyes such as pyrazolone and 3-hydroxy-quinophthalone. As the basic dye, for example, malachite green, methyl violet or the like can be used, and a dye modified with sodium acetate, sodium ethoxide, sodium methylate or the like can also be used.

[0015]

Example 1 On a support polyester film having a thickness of 50 μm, a polyurethane resin dye fixing layer and a fluoroolefin copolymer resin layer were coated in this order from the bottom to a thickness of 15 μm. To prepare a white glossy film for sublimation heat transfer (manufactured by Kiwa Chemical Industry Co., Ltd.), which was obtained by bonding an adhesive layer and a separator on the back surface of the film. A cross-linking urethane-based inkjet coating agent for ink jet "Pateracol IJ-50" (trademark, manufactured by Dainippon Ink and Chemicals, Inc.) was laminated thereon to a thickness of 8 microns to form an inkjet receiving layer. An ink jet printer "MJ-8000C" (trademark, manufactured by Seiko Epson) was used to discharge sublimation ink (manufactured by ECS) of four color sets to print a full-color image (color printing). This printed film was left in a thermostatic chamber at 160 ° C. for 4 minutes and then taken out. After the pressure-sensitive adhesive tape was pressed against the end of the film, the film was pulled at a right angle to the film surface, whereby the entire inkjet receiving layer could be easily peeled off as a film layer. As a result, the white glossy film had a high density and was dyed in a clear image. Moreover, the gloss of the film surface was as it was. Observation of the cross section of this film revealed that most of the sublimable dye had passed through the fluoroolefin copolymer resin layer and dyed the polyurethane resin dye fixing layer.

(Example 2) Instead of the Pateracol of Example 1, polyvinyl alcohol "PVA217" (trademark,
Polymerization degree of 1700, saponification degree of 88 mol%, manufactured by Kuraray Co., Ltd.) was used as the coating agent, and other conditions were the same as in Example 1, and similar results were obtained.

(Example 3) A styrene-quaternary ammonium salt copolymer "Gocefimer C-82" (trademark, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used instead of the Paterachol of Example 1.
Was used as the coating agent, and the other conditions were exactly the same as in Example 1, and similar results were obtained.

(Example 4) Instead of the white glossy film of Example 1, a polycarbonate film having a thickness of 100 microns "Polycaace ECG100" (trademark, manufactured by Tsutsunaka Plastic Industry Co., Ltd.) was used, and the others were completely the same as those of Example 1. Under the same conditions, lamination of the inkjet receiving layer, full-color image printing and heating were performed. After the pressure-sensitive adhesive tape was pressed against the edge of the film after heating, it was pulled at a right angle to the film surface, whereby the entire inkjet receiving layer could be easily peeled off as a film layer. As a result, the polycarbonate film had a high density and was dyed in a clear image. Moreover, the gloss of the film surface was as it was.

(Embodiment 5) The same results were obtained when the above PVA217 was used as the coating agent instead of the Paterachol of Embodiment 4, and the other conditions were the same as those of Embodiment 4.

(Example 6) The same results were obtained when the above-mentioned goosefimer was used as the coating agent instead of the Paterachol of Example 4, and the other conditions were the same as those of Example 4.

(Example 7) Instead of the white glossy film of Example 1, a transparent polyester film "Teijin Tetoron Film S6" (trademark, manufactured by Teijin Ltd.) having a thickness of 50 microns was used, and a silicone type anti-blocking agent "Cymac US" was used. -352 "(trademark, manufactured by Toagosei Co., Ltd.) was used, and the inkjet receiving layer was laminated, full-color image printing and heating were performed under exactly the same conditions as in Example 1 except that the film was coated to a thickness of 1 micron. After the pressure-sensitive adhesive tape was pressed against the end portion of the film after heating, it was pulled at a right angle to the film surface, whereby the entire inkjet receiving layer could be easily peeled off. As a result, the polyester film had a high density and was dyed in a clear image.
Moreover, the gloss of the film surface was as it was.

(Example 8) Instead of the Cymac coated polyester film of Example 7, the polyester film as it was before the Cymac coating was used as it was, and the PVA217 was used as the coating agent instead of Pateracol. The same results were obtained by carrying out the same conditions as in Example 7.

(Example 9) Instead of the Cymac coated polyester film of Example 7, the polyester film as it was before the Cymac coating was used as it was, and instead of Pateracol, the above Gocefimer was used as a coating agent. Was carried out under exactly the same conditions as in Example 7, and similar results were obtained.

(Example 10) Instead of the white glossy film of Example 1, a polyester plasticizer "ADEKA CIZER PN-170" (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) was used as a plasticizer to obtain a white and transparent film. A film was prepared by laminating various kinds of polyvinyl chloride resin by a casting film forming apparatus (manufactured by Asahi Chemical Industry Co., Ltd.) to a total thickness of 100 microns, 50 microns each. On the transparent film surface, the above-mentioned Pateracall was laminated to a thickness of 8 microns. After that, full-color image printing and heating were performed under exactly the same conditions as in Example 1. After the pressure-sensitive adhesive tape was pressed against the edge of the film after heating, it was pulled at a right angle to the film surface, whereby the entire inkjet receiving layer could be easily peeled off as a film layer. As a result, the transparent film of polyvinyl chloride resin was dyed in a clear and sharp image with a white film as the background. Moreover, the gloss of the transparent film surface was as it was.

(Embodiment 11) The same results were obtained when the above PVA217 was used as the coating agent instead of the Paterachol of Embodiment 10, and the other conditions were the same as those of Embodiment 10.

Example 12 The same results were obtained when the above Gocefimer was used as a coating agent in place of Paterachol of Example 10, and the other conditions were the same as in Example 10.

[0027]

INDUSTRIAL APPLICABILITY According to the present invention, an inkjet printer using a sublimation ink is used to impart a full-color image to an arbitrary film product having a resin layer on the surface while completely maintaining the original high gloss of the product. It became possible to do. Also, for sheet-shaped film products, there is no work of precise alignment between transfer paper and film products, so it is possible to apply full-color images of a predetermined size to a large number of lots with little human intervention. became.

Claims (6)

(57) [Claims] 1. An ink-receiving film comprising a resin-made film or a film-shaped support having a resin layer on the surface of which a resin-made ink-jet receiving layer is provided, and an ink containing a sublimable dye is used to color the ink by an inkjet method. A step of printing, a step of transferring the sublimable dye to a surface resin layer on the resin film or a support by heating the ink jet receiving layer to a uniform temperature, and a step of peeling the ink jet receiving layer as a film layer. And a sublimation dyeing method. 2. The surface resin layer on the resin film or film-like support comprises a resin having an affinity for a sublimable dye and a resin having no affinity for the sublimable dye thereon. The sublimation dyeing method according to claim 1, wherein a laminated resin is used. 3. The sublimation dyeing method according to claim 2, wherein the resin having no affinity for the sublimation dye is a fluorine resin, a silicone resin, or an olefin resin. 4. The sublimation dyeing method according to claim 1, 2 or 3, wherein the ink jet receiving layer is heated in a non-contact manner. 5. The sublimation dyeing according to claim 4, wherein the non-contact heating is performed by leaving the ink receiving film in a temperature-controlled room for a certain time or by passing the ink receiving film through the temperature-controlled room at a constant speed. Method. 6. The sublimation dyeing method according to claim 1, wherein the film-shaped support is made of a resin.