JPH0528678B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a thermal transfer ink ribbon used in the production of dry transfer materials. It is possible to transfer and print even on surfaces with poor peelability and strong peelability, and the transferred image (ink image) obtained by thermal transfer can be effectively pressure-sensitively retransferred onto the target transfer object using pressure. The present invention relates to an ink ribbon for producing a dry transfer material, which can be used for printing.

(Prior art and its problems) In recent years, thermal transfer printers, typewriters, word processors, and other printing devices have been developed and are now widely used for everything from small personal use to business use. . Printing using this thermal transfer method involves supporting the thermal transfer ribbon by bringing the thermal transfer ink ribbon into close contact with a predetermined printing paper using a thermal head, and by causing a desired heating element among the many heating elements of the thermal head to generate heat. Melts the heat-melting ink part that is in contact with the heating element through the body,
This is done by transferring it onto printing paper.

By the way, this type of thermal transfer ribbon has conventionally been made by simply coating a heat-melting ink consisting of a colorant and a binder agent on a predetermined support, and the binder agent is mainly composed of wax. It was meant to be. Moreover, this type of thermal transfer ribbon was only intended for use with ordinary paper as the transfer material.

On the other hand, recently, with the spread of thermal transfer methods, there has been a demand for improved transferability to rough paper (paper with low smoothness), and various patent applications related to this have been filed. Various technologies have also been proposed, such as multi-time ribbons that enable multiple transfers and printing with the same ink ribbon, and collectable ribbons that can erase and correct typos.

However, to the best of our knowledge, there are no thermal transfer ink ribbons to date that are intended to enable transfer and printing on surfaces with poor wettability and good releasability and peelability. However, no reports have been made. Moreover, since the thermal transfer method has not been adopted at all as a method for manufacturing dry transfer materials for instant lettering, the thermal transfer ink ribbon used to manufacture dry transfer materials for instant lettering is No proposals have been made so far.

(Object of the Invention) The present invention has been made against this background, and its first object is to provide a thermal transfer ink ribbon for producing a dry transfer material. It is in.

A second object of the present invention is to provide an ink ribbon for producing dry transfer materials that has improved heat-sensitive transferability to surfaces with poor wettability.

Furthermore, the third object of the present invention is to transfer an ink image (transfer image) onto a basic sheet by heat-sensitivity.
To provide a heat-sensitive transfer ribbon that can easily and completely pressure-sensitively transfer the following information to a target object by applying pressure from behind a base sheet.

(Solution Means) In order to achieve the above object, the present invention configures an ink ribbon for dry transfer material production so as to have the following features. In other words, dry transfer is a method for retransferring an ink image thermally transferred onto a basic sheet using a thermal transfer method onto an arbitrary transfer object by applying pressure from the surface of the basic sheet opposite to the ink image transfer side. In an ink ribbon for manufacturing a dry transfer material used when manufacturing a material, (a) it is provided on one side of a predetermined film-like ribbon base material and is composed of a colorant, a binder agent, and a pressure-sensitive adhesive. an ink layer; (b) provided on the ink layer, an ethylene-vinyl acetate copolymer, a polyvinyl acetate, an ionomer, an acrylic polymer, an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer; One or more heat-sensitive adhesive resins selected from the group consisting of vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyamide, and ethyl cellulose;
The ink layer contains one or more tackifying resins selected from the group consisting of petroleum resin, rosin, hydrogenated rosin, rosin ester, ketone resin, and phenolic resin, and has a viscosity lower than that of the ink layer. The transfer property adjustment layer has high heat-sensitive adhesive properties, hardness, and cohesive force.

(Specific structure and operation) By the way, in the thermal transfer ink ribbon according to the present invention, as shown in FIG. A layer 12 is formed, and a transferability adjusting layer 13 is further formed thereon to a predetermined thickness. Note that an anti-staking layer 14 made of a heat-resistant resin such as a silicone resin is provided on the surface of the ribbon base material 11 opposite to the surface coated with the ink layer 12.

In such a thermal transfer ink ribbon 10 for producing a dry transfer material, the film-like ribbon base material 11 that supports the ink layer 12 may be any of various materials conventionally used as a base material for thermal transfer ink ribbons. can be used, but
In particular, since the ink ribbon is brought into contact with a thermal head (printing device) for thermal transfer, polyester, polyimide, polycarbonate, polysulfon, polyether sulfon, polyphenylene sulfate, etc. with a heat resistance temperature of 150°C or higher are recommended. A resin film made of fiber, etc., or paper such as capacitor paper or glassine paper is used as a suitable material, and its thickness will be determined appropriately depending on the type of material, but generally it is 3 to 20 μm. It is desirable to use a material with a thickness in the range of .

Further, the ink layer 12 mainly includes a colorant, a binder agent, and a pressure-sensitive adhesive.
As the coloring agent, a pigment such as carbon black is mainly used, but an appropriate dye may be added as necessary to adjust the color tone.

The binder agent constituting this ink layer 12 is mainly Candelilla wax,
Vegetable waxes such as carnauba wax, rice wax, and wood wax; Animal waxes such as beeswax, lanolin, and spermaceti; Mineral waxes such as Montan wax and ceresin; Petroleum waxes such as paraffin wax and microcrystalline wax. Waxes consisting of one or more of the above and an adhesion agent such as petroleum resin, rosin resin, ketone resin, polyamide resin, or phenol resin are used. In addition, as the above-mentioned waxes, resin-based waxes such as α-olefin-maleic anhydride copolymer can also be used.
In addition, tackifiers improve the adhesion and hardness of ink,
It functions to impart cohesive force, adhesive force, and tackiness to pressure-sensitive adhesives. Further, the wax and the tackifying agent constituting the binder agent are generally mixed in a ratio of about 15:1 to 3:2 on a weight basis.

Further, as the pressure-sensitive adhesive constituting the ink layer 12, polyvinyl chloride, polyacrylic ester, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer,
Ethyl acrylate copolymer, polyvinyl acetate,
Vinyl polymers such as polyvinyl ether, polyvinyl acetal, and polyisobutylene; fiber polymers such as ethyl cellulose, nitrocellulose, and cellulose acetate; and one or more combinations of rubber polymers such as chlorinated rubber and natural rubber. It is used.

In addition, the above-mentioned colorant, binder agent, and pressure-sensitive adhesive that constitute the ink layer 12 are generally mixed in a ratio of 5 to 30:40.
The ink composition is blended in a ratio of about 93:2 to 30, and provides an ink composition having a viscosity of less than 3000 centipoise, particularly about 200 to 1000 centipoise, preferably at a temperature of 95°C. Further, such an ink composition is dissolved or dispersed in an appropriate solvent to form an ink liquid, or heated and mixed to form an ink, and then applied onto the intended film-shaped ribbon substrate 11 using a known method. Accordingly, coating or hot melt coating is applied.

On the other hand, the transferability adjusting layer 13 as a top coat layer formed on the ink layer 12 has a higher viscosity (under thermal transfer conditions) and has greater heat-sensitive adhesiveness, hardness, and cohesive force than the ink layer 12. Since it is configured as a layer, the transferability adjustment layer 13 has a strong adhesive force during thermal transfer, which improves thermal transferability to surfaces with poor wettability, and prevents cohesion. Because the force, viscosity, and hardness are increased, transfer defects such as crushing and spreading can be effectively improved, and the ink can also be effectively prevented from being scraped by the head of the printing device. . In addition, during pressure-sensitive transfer, in which pressure is applied from behind the basic sheet of the dry transfer material to transfer the ink image (transfer image) created by thermal transfer to the transferred object,
The transferability adjusting layer 13 has high cohesive force and hardness, so that it can integrally transfer a predetermined ink image from the basic sheet without residual ink, and the transferred ink This makes it possible to obtain a beautiful image with no distortion, and at the same time protects and strengthens the transferred image.

By the way, such a transferability adjusting layer 13 is made of a resin having high film-forming properties and high heat-sensitive adhesive properties, specifically, ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, and ethylene-vinyl acetate copolymer. Ethyl acrylate copolymer, ethylene-
One or more of acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyamide, ethyl cellulose, and a resin with high cohesive force and tack imparting properties, specific It is mainly composed of one or a mixture of two or more of petroleum resin, rosin, hydrogenated rosin, rosin ester, ketone resin, phenol resin, etc. The heat-sensitive adhesive resin and the adhesion-imparting resin are mixed in a ratio of 0.5 to 10 parts by weight, preferably 0.8 to 7 parts by weight, of the latter to 1 part by weight of the former. becomes.

The heat-sensitive adhesive resin with high film-forming properties constituting the transferability adjusting layer 13 is either incompatible with the ink layer 12 or is difficult to mix with the ink layer 12 even if it is compatible with the ink layer 12 . The other adhesion-imparting resin forms a highly heat-sensitive adhesive film on the film-forming resin and the ink layer 1.
It is added to improve the adhesion with No. 2, increase cohesive force, hardness, and tackiness, and adjust heat-sensitive transferability.

The composition comprising the heat-sensitive adhesive resin with high film-forming properties and the tackifying resin can be prepared in the form of an aqueous solution or aqueous dispersion, or in the form of a general-purpose organic solvent that does not attack the ink layer 12. In the form of a solution or dispersion, it is coated on the ink layer 12 to a predetermined thickness according to a normal coating method, and the transferability adjusting layer 13 formed in this way is , which has a higher viscosity than the ink layer 12 under thermal transfer conditions and generally includes:
The layer has a viscosity of 3,000 centipoise or more, preferably 10,000 centipoise or more at a temperature of 95°C.

In addition, the transferability adjusting layer 13 formed in this manner is further coated with kaolin and talc in order to adjust the film strength and obtain a sharp printed image, and to prevent staining and blocking. , bentonite, titanium oxide, and other fillers, and organic or inorganic powders such as metal soaps such as zinc stearate and aluminum stearate, in a proportion not exceeding 20% by weight, and present in the transferability adjusting layer 13. It is also possible to force it.

Then, using the ink ribbon 10 obtained in this way, the head heating element shape, head heating element position, head installation angle, head pressing pressure, winding torque, head applied energy, printing speed, etc. are adjusted. By setting the dry transfer material in a printing device such as a thermal transfer printer, and performing printing and thermal transfer, the desired dry transfer material can be advantageously manufactured.

That is, by using such an ink ribbon 10, even if a transfer image such as a desired character or figure is thermally printed on a film (basic sheet) having a surface with poor wettability, it will not spread, collapse, shading, or It is possible to realize a good printed image without causing any problems such as scraping by the head, stringiness, yuzu skin, or insufficient transfer.

Furthermore, even if the image printed in this way is pressure-sensitively transferred onto the target material such as paper, plastic, or metal by applying pressure from the back side of the film (basic sheet), the film There is no residual ink on the surface, and the transferred image can be a good, firmly adhered image that does not collapse, spread, or become brittle.

(Examples) Some examples of the present invention will be shown below to clarify the present invention more specifically, but the present invention is not limited in any way by such descriptions. It goes without saying that it is nothing.

In addition to the following examples and the above-mentioned specific description, the present invention includes various changes, modifications, and changes based on the knowledge of those skilled in the art, as long as they do not depart from the spirit of the present invention. It should be understood that improvements and the like may be made.

Example 1 In order to form the ink layer 12 and the transferability adjustment layer 13, an ink and a coating liquid for forming the transferability adjustment layer were prepared as follows. Note that the viscosity of the ink layer 12 formed with this ink is
270 centipoise (95°C), and the viscosity of the transferability adjusting layer 13 formed with this coating liquid is 5.
It was between 10,000 and 70,000 centipoise (95°C). Ink layer 12 Composition Weight parts α-olefin-maleic anhydride copolymer [Diakarna 30 manufactured by Mitsubishi Chemical Industries, Ltd.] 2 Candelilla wax [Candelilla wax 2698 manufactured by Chukyo Yushi Co., Ltd.] 3 Microcrystalline wax [Manufactured by Nippon Seiro Co., Ltd.]
Hi-MiC 1045] 9 Rosin ester [Superester A-100 manufactured by Arakawa Chemical Co., Ltd.] 2 Ethylene-vinyl acetate copolymer [EVA210 manufactured by Mitsui DuPont Polychemical Co., Ltd.] 2 Carbon black [Mitsubishi Chemical Industries, Ltd.] MA- manufactured by Co., Ltd.
7] 2 Methyl isobutyl ketone (solvent) 100 Transferability adjustment layer 13 Composition Polymerization part Ethylene-vinyl acetate copolymer [EVA210 manufactured by Mitsui Dupont Polychemical Co., Ltd.] 1 Petroleum resin [HiResin manufactured by Toho Oil Resin Co., Ltd. #90]
5 Methyl isobutyl ketone (solvent) 54 Then, using a 3.5 μm polyethylene terephthalate (PET) film as the ribbon base material 11, ink having the above composition was applied onto the film to a dry film thickness of 6 to 7 μm. After forming the ink layer 12 by processing and drying,
Furthermore, a coating liquid for forming a transferability adjustment layer having the above composition is applied thereon to a dry film thickness of 1 to 2 μm,
By drying, the desired ink ribbon 10 was obtained.

Next, using the thus obtained ink ribbon, it was set in a controlled thermal transfer type writer (EP-43 manufactured by Brother Industries, Ltd.), and a polyethylene film coated with silicone resin (thickness: When printed on 100 μm),
Therefore, a beautiful printed image of good quality could be obtained. Furthermore, by rubbing the printed polyethylene film from the back side and applying pressure, the printed image was pressure-sensitively transferred onto the desired surface of paper, plastic, or metal, and the quality was sufficiently good. I was able to complete the statue.

Example 2 An ink ribbon 10 was prepared in the same manner as in Example 1 using an ink and a coating liquid that gave the following composition of the ink layer 12 and transferability adjustment layer 13.
As a result of thermal transfer experiments, we were able to obtain beautiful printed images of good quality, and we were able to transfer such printed images as good quality images onto the desired transfer material using pressure-sensitive transfer. I was able to coerce him. The viscosity of the ink layer 12 formed using the ink having the composition shown below is 700 centipoise (95°C), and the viscosity of the transferability adjusting layer 13 formed using the coating liquid shown below is 50,000 centipoise. ~70,000 centipoise (95
℃). Ink layer 12 Composition Weight parts α-olefin-maleic anhydride copolymer [Diakarna 30 manufactured by Mitsubishi Chemical Industries, Ltd.] 8 Candelilla wax [Candelilla wax 2698 manufactured by Chukyo Yushi Co., Ltd.] 5 Rosin ester [Arakawa Superester A-100 manufactured by Kagaku Kogyo Co., Ltd.] 2 Ethylene-vinyl acetate copolymer [EVA210 manufactured by Mitsui Dupont Polychemicals Co., Ltd.] 3 Carbon black [MA- manufactured by Mitsubishi Chemical Industries, Ltd.]
7] 2 Methyl isobutyl ketone (solvent) 100 Transferability adjustment layer 13 Composition Polymerization part Ethyl cellulose [Reagent manufactured by Kanto Kagaku Co., Ltd., 10 cps]
1 Hydrogenated rosin [Hyperel manufactured by Arakawa Chemical Industry Co., Ltd.] 5 Isopropyl alcohol (solvent) 54 Example 3 As an ink for forming the ink layer 12,
An ink ribbon was prepared in the same manner as in Example 1, using the same composition as in Example 1, and a coating liquid for forming a transferability adjustment layer having the following composition. As a result of conducting tests and pressure-sensitive transfer tests, good results were obtained. Note that the transferability adjusting layer 13 was formed using a coating liquid having the following composition.
had a viscosity of 50,000 to 70,000 centipoise (95°C). Transferability adjusting layer 13 Composition: Part by weight Polyamide [Sanmide manufactured by Sanwa Kagaku Kogyo Co., Ltd.
615A] 1 Ketone resin [Ketone Resin K manufactured by Arakawa Chemical Industry Co., Ltd.
-90] 1 Toluene 38 Comparative Examples 1 to 3 An ink ribbon using the ink of Example 1 but without forming the transferability adjustment layer 13 (Comparative Example 1),
While using the ink of Example 2, transferability adjustment layer 1
A transfer test similar to that in Example 1 was conducted using an ink ribbon that did not form No. 3 (Comparative Example 2) and a commercially available wax-type thermal transfer ink ribbon [manufactured by Fuji Kagaku Paper Industries Co., Ltd.] (Comparative Example 3). However, both heat-sensitive transferability and pressure-sensitive transferability were insufficient.
Specifically, regarding pressure-sensitive transfer properties, problems include insufficient transferability due to insufficient adhesive strength, spreading and crushing of transferred prints due to insufficient cohesive force, viscosity, and hardness, scraping of prints by the head, shading of prints, and yuzu skin. It was recognized that such problems would occur. In addition, regarding pressure-sensitive transferability, the final transferred printed image may be crushed or spread due to insufficient pressure-sensitive adhesive strength, insufficient adhesion strength, insufficient cohesive force, viscosity, and even hardness, insufficient strength, and poor integral transfer, which are the basics of the film. Problems such as residual ink remaining on the sheet occurred.

(Effects of the Invention) As is clear from the above description, according to the present invention, on the ribbon base material (support) of the ink ribbon,
Along with the ink layer, a transfer adjustment layer with heat-sensitive adhesive properties, high hardness, viscosity, and cohesive force is provided as a top coat layer to form a two-layer structure, and the ink layer has pressure-sensitive adhesive properties to improve wettability. The heat-sensitive transfer properties to the bad surface of the paper were significantly improved, and the pressure-sensitive transfer properties of the printed image formed by heat-sensitive transfer to other materials using pressure were also advantageously improved. The great industrial significance of the present invention lies in the fact that it has become possible to advantageously produce a dry transfer material having the following properties.

[Brief explanation of drawings]

FIG. 1 is an explanatory cross-sectional view showing an example of a thermal transfer ink ribbon for producing a dry transfer material according to the present invention. 10: Thermal transfer ink ribbon, 11: Ribbon base material, 12: Ink layer, 13: Transferability adjustment layer, 1
4: States king prevention layer.

Claims (1)

[Claims] 1. An ink image thermally transferred onto a basic sheet by a thermal transfer method is retransferred to an arbitrary transfer object by applying pressure from the surface of the basic sheet opposite to the ink image transfer side. An ink ribbon for dry transfer material production used in the production of dry transfer material for printing, which is provided on one side of a predetermined film-like ribbon base material and contains a colorant, a binder agent, and a pressure-sensitive adhesive. an ink layer formed on the ink layer, an ethylene-vinyl acetate copolymer, polyvinyl acetate, an ionomer, an acrylic polymer, an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer, One or more heat-sensitive adhesive resins selected from the group consisting of vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyamide, and ethyl cellulose, petroleum resin, rosin, and hydrogenated resin. It is composed of one or more tackifying resins selected from the group consisting of rosin, rosin ester, ketone resin, and phenolic resin, has a higher viscosity than the ink layer, and has heat-sensitive adhesive properties. An ink ribbon for producing a dry transfer material, characterized by having a transfer property adjusting layer having high hardness and cohesive force. 2. The dry transfer according to claim 1, wherein the ink layer has a viscosity of less than 3000 centipoise at 95°C, and the transferability adjustment layer has a viscosity of 3000 centipoise or more at 95°C. Ink ribbon for material manufacturing.