JPH0528995B2 - - 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 on basic sheet surfaces such as films that have poor peelability and strong peeling properties, and the transferred image (ink image) obtained by thermal transfer to the basic sheet surface can be transferred to the intended transfer target by pressure. The present invention relates to an ink ribbon for producing dry transfer materials that can be effectively pressure-sensitively retransferred onto objects.

(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 then generating heat from the required heating elements among the many heating elements that the thermal head has. 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, the present inventors have previously reported on a thermal transfer ink ribbon that is intended to enable transfer and printing onto basic sheet surfaces such as films that have poor wettability and good release and peelability. , special application 1986-
No. 275538, Patent Application No. 1983-275539, and Patent Application No. 1983-
No. 85350, and patent application No. 85350 was also filed for an ink ribbon aimed at improving thermal sensitivity.
This is reported as No. 80126.

Therefore, ink ribbons are generally
It is wound onto a ribbon spool with a diameter of about 15 mm and a width of about 8 mm, and is wound in a length of about 100 m.
Due to the way it is handled, the ink surface and back surface of the ink ribbon are brought into close contact with each other with strong force. Therefore, for example, such an ink ribbon may be stored in a slightly high temperature environment of about 55℃ for 24 hours.
If you store it for a while, the ink may block on the back side, and due to the influence of ingredients such as wax that soften at a temperature of 55℃, a force that tries to release the force of strong adhesion to the side works, causing the ink to overlap. This caused problems such as the ink ribbon being placed in the ribbon being shifted little by little, causing the ribbon spool to pop out of the winding, causing the winding to become disordered.

However, the reality is that to date, no reports have been made regarding ink ribbons that simultaneously solve these storage problems.

(Object of the Invention) The present invention has been made against the background of the above, and its first purpose is to perform thermal transfer onto the surface of a basic sheet such as a film with poor wettability. A second object of the present invention is to provide an ink ribbon for producing a dry transfer material with improved properties, and a second object of the present invention is to transfer an ink image (transfer image) thermally transferred onto a base sheet by transferring it to the base sheet. With pressure from behind, easily and completely,
It is an object of the present invention to provide a heat-sensitive transfer ribbon capable of pressure-sensitive transfer to a target object.

A third object of the present invention is to provide an ink ribbon for producing a dry transfer material that has good storage stability and does not cause the ribbon spool to become disordered even in a slightly high-temperature environment.

(Solution Means) In order to achieve the above object, the present invention configures an ink ribbon for producing a dry transfer material so as to have the following features. In other words, an ink image thermally transferred onto a basic sheet by a thermal transfer method is retransferred onto an arbitrary receptor by applying pressure from the opposite side of the basic sheet to the side on which the ink image was thermally transferred. In a thermal transfer ink ribbon for producing a dry transfer material used in producing a dry transfer material, (a) it is formed on the surface of a predetermined film-like ribbon base material, and contains a colorant, a binder agent mainly composed of wax, and (b) an ink layer comprising a pressure-sensitive adhesive and in which 80% by weight or more of the wax in the binder has a penetration degree of 50 or less at 55°C; - Vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinylpyrrolidone, polyvinyl One or more heat-sensitive adhesive resins selected from the group consisting of alcohol, polyamide, and ethyl cellulose, and selected from the group consisting of petroleum resins, rosins, hydrogenated rosins, rosin esters, ketone resins, and phenolic resins. and one or more types of tackifying resin, which has a higher viscosity than the ink layer, and has heat-sensitive adhesive properties.
It has a transferability adjusting layer with high 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. However, at least 80% by weight of the above-mentioned wax is composed of wax having a penetration degree of 50 or less at 55°C. This includes Candelilla wax, Carnauba wax, and some paraffin waxes. In addition, the above waxes include α-
Resin-based waxes such as olefin-maleic anhydride copolymer can also be used, and tackifiers such as
It functions to improve the adhesion and hardness of ink, impart cohesive force, impart adhesive strength, and impart tackiness to pressure-sensitive adhesives. Additionally, the wax and tackifier that make up this binder are generally 15:1 on a weight basis.
They will be blended in a ratio of about 3:2.

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 transfer property adjusting layer 13 is made of a resin having high film-forming properties and high heat-sensitive adhesive properties, specifically, ethylene-vinyl acetate copolymer, polypynylacetate, ionomer, acrylic polymer, 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, specifically Specifically, it is mainly composed of one or a mixture of two or more of petroleum resin, rosin, hydrogenated rosin, rosin ester, ketone resin, and phenol resin.
The heat-sensitive adhesive resin and the tack-imparting resin are 1 part by weight of the former to 1 part by weight of the latter.
It will be blended in a proportion of 0.5 to 10 parts by weight, preferably 0.8 to 7 parts by weight.

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 consisting of the heat-sensitive adhesive resin with a high film-forming property and the tack-imparting resin is 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 way 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 organic 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. Furthermore, the transferability adjusting layer 13 includes ribbon meandering,
In order to obtain good ribbon runability without slipping, etc., and good storage stability without blocking or disordered winding even when stored at a temperature of 55°C, we use a polymer surface such as fluorine-based polymer or silicone-based polymer. A lubricant such as a modifier, a higher alcohol, a glycerin ester, a sorbitan ester, a fatty acid, a polyhydric alcohol, a monoamide, a bisamide, or an oil-based wax is blended in a proportion not exceeding 10% by weight and is 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 shape of the head heating element, the position of the head heating element, the head installation angle, the head pressing pressure, the winding torque, the energy applied to the head, the 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.

Also, such an ink ribbon 10,
Even when stored for 24 hours at 55℃,
It was confirmed that problems such as blotting and ribbon spool winding did not occur at all.
Furthermore, regarding ribbon running properties, there are no problems such as meandering or slipping of the ribbon, and printing and thermal transfer can be performed to the end of the ribbon. These phenomena occur because 80% by weight or more of the wax, which is the main component of the binder in the ink layer, has a composition with a penetration value of 50 or less at 55°C. This seems to be due to an increase in the thermal softening temperature.

(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.

In addition, the values of penetration in the examples are JIS-K-
2235.

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
250 centipoise (95°C), and the viscosity of the transferability adjusting layer 13 formed with this coating liquid is 5.
70,000 to 70,000 centipoise (95℃), and
In the wax which is the main component of the binder agent in the ink layer 12, the proportion of wax having a penetration degree of 50 or less at 55° C. was 100% by weight.

Composition of ink layer 12 Parts by weight α-olefin-maleic anhydride...2 Copolymer [Diakaruna 30 manufactured by Mitsubishi Chemical Industries, Ltd.] Penetration (55°C): 10 or less Candelilla wax...3 [ Kyanderin Lalow 2698 manufactured by Chukyo Yushi Co., Ltd.] Penetration (55℃): Approx. 10 Paraffin wax...9 [HNP-10 manufactured by Nippon Seiro Co., Ltd.] Penetration (55℃): Approximately 20 Rosin ester...2 [Super Ester A-100 manufactured by Arakawa Chemical Co., Ltd.] Ethylene-vinyl acetate copolymer...2 [EVA210 manufactured by Mitsui DuPont Polychemical Co., Ltd.] Carbon black...2 [ MA-7 manufactured by Mitsubishi Chemical Industries, Ltd.] Methyl isobutyl ketone (solvent)...100 Composition of transfer adjustment layer 13 Parts by weight Ethylene-vinyl acetate copolymer ...1 [EVA210 manufactured by Mitsui Dupont Polychemical Co., Ltd.] ] Petroleum resin...5 [High Resin #90 manufactured by Toho Oil Resin Co., Ltd.] Methyl isobutyl ketone (solvent)...54 Then, a 3.5 μm polyethylene terephthalate (PET) film was used as the ribbon base material 11, and such a film was After forming the ink layer 12 by coating the ink having the above composition to a dry film thickness of 6 to 7 μm and drying,
Furthermore, a coating liquid for forming a transfer 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 adjusted 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),
A sufficiently beautiful and good quality printed image could be obtained. In addition, when such a printed polyethylene film was rubbed from the back side and pressure was applied, the printed image was pressure-sensitively transferred onto a desired surface of paper, plastic, or metal, and a sufficiently good quality was obtained. I was able to complete the statue. In addition, a 24-hour storage test was conducted at 55°C, and there were no problems such as disordered winding.

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. In addition, as a result of a ribbon running test, there were no problems such as ribbon meandering or slipping.Furthermore, a storage test was performed in which the ribbon was stored at 55°C for 24 hours as in Example 1, but there was no winding disorder. There were no such problems at all.

The viscosity of the ink layer 12 formed with the ink having the following composition is 500 centipoise (95°C).
The viscosity of the transferability adjusting layer 13 formed with the coating liquid shown below is 50,000 to 70,000 centipoise (95
℃). Further, in the wax which is the main component of the binder agent in the ink layer 12, the proportion of wax having a penetration degree of 50 or less at 55° C. was 92% by weight.

Composition of ink layer 12 Parts by weight Paraffin wax...4 [HNP-14 manufactured by Nippon Seiro Co., Ltd.] Penetration (55°C): Approx. 20-25 α-olefin-maleic anhydride...5 Copolymer [Diakaruna 30 manufactured by Mitsubishi Chemical Industries, Ltd.] Penetration (55℃): 10 or less Candelilla Wax...3 [Candelilla Low 2698 manufactured by Chukyo Yushi Co., Ltd.] Penetration (55℃): Approx. 10 Microcrystalline wax...1 [Hi-Mic 1045 manufactured by Nippon Seiro Co., Ltd.] Penetration (55℃): Approx. 150 Rosin ester...2 [Super Ester A- manufactured by Arakawa Chemical Co., Ltd.] 100] Ethylene-vinyl acetate copolymer...3 [EVA210 manufactured by Mitsui Dupont Polychemical Co., Ltd.] Carbon black...2 [MA-7 manufactured by Mitsubishi Chemical Industries, Ltd.] Methyl isobutyl ketone (solvent)... 100 Composition of transferability adjustment layer 13 Parts by weight Ethylcellulose...1 [Reagent manufactured by Kanto Kagaku Co., Ltd., 10 cps] Hydrogenated rosin...5 [Hyperel manufactured by Arakawa Chemical Co., Ltd.] Oleic acid amide...0.18 [Hanasei] Amide O Co., Ltd.] 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 the coating liquid for forming the transferability adjustment layer had the following composition, and was subjected to a thermal transfer test. As a result of conducting a ribbon storage test, a ribbon running test, and a pressure-sensitive transfer test, good results similar to those of Example 1 or 2 were obtained. The transferability adjusting layer 13 formed with a coating liquid having the following composition had a viscosity of 50,000 to 70,000 centipoise (95°C).

Composition of transferability adjustment layer 13 Parts by weight Polyamide...1 [Sanmide 615A manufactured by Sanwa Chemical Industry Co., Ltd.] Ketone resin [Ketone resin K-90 manufactured by Arakawa Chemical Industry Co., Ltd.] Polymer surface modifier ...0.06 [Modaiper F-100 manufactured by Nippon Oil Co., Ltd.] Toluene...38 Comparative Examples 1 to 3 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. Problems such as residual ink remaining on the sheet occurred.

Comparative Example 4 The paraffin wax of the ink layer in Example 1 was waxed with beeswax [manufactured by Kato Yoko Co., Ltd.] (penetration was 40°C).
A storage test similar to that in Example 1 was conducted using an ink ribbon whose temperature was changed to 45 to 50 at 55°C and over 50 at 55°C.
As a result, the ink ribbon became unusable due to blocking and irregular winding.

(Effects of the Invention) As is clear from the above explanation, the thermal transfer ink ribbon according to the present invention has a ribbon base (support)
An ink layer containing a colorant, a binder agent mainly composed of wax, and a pressure-sensitive adhesive is formed on top of the ink layer, and a transfer adjustment layer is further formed on the ink layer. Among the waxes in the binder agent, 80% by weight or more of waxes with a penetration degree of 50 or less at 55°C increase the heat softening temperature, resulting in a slightly higher temperature environment (55°C). Even when the ribbon spool is rolled up, the ribbon spool does not become disordered, and good storage stability can be achieved.

In addition, its top coat layer has heat-sensitive adhesive properties,
By providing a transferability adjusting layer with high hardness, viscosity, and cohesive force, and providing pressure-sensitive adhesive properties to the ink layer, the heat-sensitive transferability to the base sheet surface such as a film with poor wettability becomes extremely good. It was also possible to advantageously improve the pressure-sensitive transferability of the printed image formed by thermal transfer to other materials using pressure, and it became possible to advantageously produce a dry transfer material with excellent properties. This is why the present invention has great industrial significance.

[Brief explanation of the drawing]

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. DESCRIPTION OF SYMBOLS 10...Thermal transfer ink ribbon, 11...Ribbon base material, 12...Ink layer, 13...Transferability adjustment layer, 14...Stating prevention layer.

[Claims]

1 In a thermal transfer ribbon in which a thermal transfer ink layer is provided on a heat-resistant base material, the thermal sublimation ink layer, a linear saturated polyester resin formed by condensation polymerization of a dicarboxylic acid component and a diol component, and a glass transition point of 50 A thermal transfer characterized in that heat-melting transfer ink layers mainly composed of a thermoplastic resin made of acrylic resin with a temperature range of 110 degrees Celsius, a colorant, and a lubricant are alternately and repeatedly provided in the length direction of the ribbon. ribbon. 2. A claim characterized in that the heat-sublimable ink layer is sequentially painted in the length direction of the ribbon with heat-sublimable ink of three colors: yellow, magenta, and cyan, or four colors of heat-sublimable ink including ink. The thermal transfer ribbon according to item 1. 3. The thermal transfer ribbon according to claim 1, wherein the colorant of the heat-melting transfer ink layer is a pigment, or a pigment and a heat-sublimable dye. 4 Transfer the heat-sublimable ink of the transfer ribbon provided with the heat-sublimable ink layer onto the receiving layer of the transfer recording medium, which has a heat-sublimable dye receiving layer on its surface, using a thermal head or thermal printing plate. In an image forming method for recording gradation images, a heat sublimable ink layer, a linear saturated polyester resin formed by condensation polymerization of a dicarboxylic acid component and a diol component, and

Claims (1)

and a transferability adjustment layer which is composed of a tackifying resin, has a higher viscosity than the ink layer, and has greater heat-sensitive adhesiveness, hardness, and cohesive force. Thermal transfer ink ribbon.