JP2621738B2 - Thermal transfer ink ribbon for dry transfer material production - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer ink ribbon used in the production of a dry transfer agent, and particularly to a thermal transfer type printer, typewriter, word processor, etc. It is possible to transfer and print on the basic sheet surface such as a strong film, and the transfer image obtained by thermal transfer to the basic sheet surface is effectively pressure-sensitive re-transfer onto the target transfer object by pressure. The present invention relates to an ink ribbon for producing a dry transfer material which can be used.

[0002]

2. Description of the Related Art In recent years, printing apparatuses such as printers, typewriters, and word processors using a thermal transfer system have been developed, and have been widely used from small personal use to business use. In the printing by the thermal transfer method, the thermal transfer ink ribbon is brought into close contact with a predetermined printing paper by a thermal head, and a required heating element among a large number of heating elements of the thermal head is heated to support the thermal transfer ribbon. This is performed by melting a heat-meltable ink portion that is in contact with the heating element through the body and transferring the melted ink portion to printing paper.

The inventors of the present invention have developed a heat-sensitive transfer ink ribbon for transferring and printing a film or the like having good wettability and good releasability and releasability onto a basic sheet surface. First, Japanese Patent Application No. 61-275538
No., Japanese Patent Application No. 61-275538 and Japanese Patent Application No. 62-85.
No. 350, and an ink ribbon aimed at improving the thermal sensitivity is also disclosed in Japanese Patent Application No. 62-80126.
Issue. In general, an ink ribbon has a diameter of about 15 mm and a width of about 8 mm.
The ink surface and the rear surface of the ink ribbon can be brought into close contact with each other with a strong force, since the ink ribbon and the ink ribbon are wound around a length of about 100 m and handled. Therefore, for example, if such an ink ribbon is stored for 24 hours at a temperature of about 55 ° C. in a slightly high-temperature environment, the ink ribbon is strongly adhered due to the effect of components such as wax which become soft at a temperature of 55 ° C. There is a problem that the force for laterally releasing the applied force acts, the overlapping ink ribbons are shifted little by little, the ribbon spool jumps out of the winding, and the winding is disturbed.

[0004]

However, no report has been made so far on an ink ribbon which simultaneously solves such a problem of storage stability.

The present invention has been made in view of such circumstances, and a first object of the present invention is to improve heat transferability to a basic sheet surface such as a film having poor wettability. It is an object of the present invention to provide an ink ribbon for producing a dry transfer material, and a second object of the present invention is to provide
A heat-sensitive transfer ribbon that can easily and completely transfer the ink image (transferred image) transferred onto the base sheet by heat with pressure from the back of the base sheet to the target object. Is to provide.

It is a third object of the present invention to provide an ink ribbon for producing a dry transfer material which has good storage stability and does not cause winding disturbance of a ribbon spool even under a slightly high temperature environment.

[0007]

According to the present invention, in order to achieve the above object, an ink ribbon for producing a dry transfer material has the following features. That is, an ink layer is formed on the surface of a predetermined film-shaped ribbon substrate, and a transferability adjusting layer including a heat-sensitive adhesive resin and a tackifying resin is formed on the ink layer. A thermal transfer ink ribbon, wherein the ink layer comprises a colorant, a binder containing wax as a main component, and a pressure-sensitive adhesive, and 80% by weight or more of the wax in the binder. The thermal transfer ink ribbon for dry transfer agent production is formed so that the penetration at 55 ° C. is 50 or less.

[0008]

In the thermal transfer ink ribbon according to the present invention as described above, for example, as shown in FIG. 1, an ink layer 12 is formed on one surface of a film-like ribbon substrate (support) 11. And further thereon a transferability adjusting layer 13
Is formed with a predetermined thickness. In addition, on the surface of the ribbon base material 11 opposite to the coating surface of the ink layer 12,
The anti-sticking layer 14 made of a heat-resistant resin such as a silicone resin is provided.

In such a thermal transfer ink ribbon 10 for producing a dry transfer agent, a film-shaped ribbon substrate 11 for supporting the ink layer 12 is conventionally used as a substrate for a thermal transfer ink ribbon. Any of various types can be used, but since the thermal head (printing device) is brought into contact with the ink ribbon particularly for thermal transfer, the heat resistant temperature is 150 ° C.
Above, polyester, polyimide, polycarbonate, polysulfone, polyethersulfone, resin film made of polyphenylene sulfide, etc., or capacitor paper, paper such as glassine paper is used as a suitable material, and even if the thickness, the material The thickness is appropriately determined depending on the type, but it is generally preferable to use one having a thickness in the range of 3 to 20 μm.

The ink layer 12 is mainly composed of a colorant, a binder, and a pressure-sensitive adhesive. As the colorant, a pigment such as carbon black is mainly used, and an appropriate dye may be added as needed for color tone adjustment.

[0011] The binder agent constituting the ink layer 12 is mainly a vegetable wax such as candelilla wax, carnauba wax, rice wax, or wood wax; an animal wax such as beeswax, lanolin, or whale wax; Mineral waxes such as montan wax and ceresin;
A wax comprising one or more of petroleum waxes such as paraffin wax and microcrystalline wax, and a tackifier such as a petroleum resin, a rosin-based resin, a ketone resin, a polyamide resin, and a phenol resin. It is used. However, at least 80% by weight or more of the wax has a penetration at 55 ° C of 50%.
It will be composed of the following wax. A part of candelilla wax, carbana wax, paraffin wax and the like correspond to this.

As the above waxes, resin waxes such as α-olefin-maleic anhydride copolymers can be used.
It functions to improve hardness, impart cohesion, impart adhesive strength, and impart pressure-sensitive adhesive. Further, the wax and the tackifier constituting the binder agent are generally mixed in a ratio of about 15: 1 to 3: 2 on a weight basis.

Further, the pressure-sensitive adhesive constituting the ink layer 12 includes polyvinyl chloride, polyacrylate, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl acetate, polyvinyl ether, and the like. Vinyl polymers such as polyvinyl acetal and polyisobutylene; fibrous polymers such as ethyl cellulose, nitrocellulose and cellulose acetate; and one or more rubber polymers such as chlorinated rubber and natural rubber are used in combination. It is.

The colorant, the binder and the pressure-sensitive adhesive constituting the ink layer 12 are generally 5 to 30:40.
~ 93: It is compounded at a ratio of about 2 to 30,
Preferably, the ink composition gives a viscosity of less than 3000 centipoise, particularly about 200 to 1000 centipoise at a temperature of 95 ° C. In addition, such an ink composition is dissolved or dispersed in an appropriate solvent to form an ink liquid, or is heated and mixed to form an ink, and is formed on a target film-shaped ribbon base material 11 by a known method. Is applied or hot melt 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) than the ink layer 12 and has a heat-sensitive adhesiveness, hardness and hardness. Since it is constituted as a layer having a large cohesive force, the transferability adjusting layer 13
During thermal transfer, the adhesive force is strengthened to improve thermal transferability to poorly wettable surfaces, and the cohesion, viscosity, and hardness are increased, resulting in crushing, spreading, etc. This has the effect of effectively improving the transfer failure of the ink and effectively preventing the ink from being scraped by the head of the printing apparatus. Further, at the time of pressure-sensitive transfer in which pressure is applied from the back of the basic sheet of the dry transfer agent to transfer the image (transferred image) of the ink produced by the thermal transfer onto the material to be transferred, the transferability adjusting layer 13 has a cohesive force. Because the hardness is increased, from the basic sheet,
Without residual ink, it is possible to transfer a predetermined ink image integrally, and the transferred ink spreads, making it possible to obtain a beautiful image without crushing, and at the same time, transfer the transferred image They are protected and strong.

Incidentally, the transferability adjusting layer 13 as described above is used.
Has a large film-forming property and a large heat-sensitive adhesive resin, for example, ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, One or more of vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyamide, ethyl cellulose and the like, and a resin having a large cohesive force and a tackifying property such as petroleum resin, rosin, hydrogenation It is mainly composed of one or a mixture of two or more of rosin, rosin ester, ketone resin, phenol resin and the like. The heat-sensitive adhesive resin and the tackifying resin are in the ratio of 0.5 to 10 parts by weight of the former to 1 part by weight of the former, preferably 0.8 to 7 parts by weight. It will be blended.

The heat-sensitive adhesive resin having a large film-forming property and constituting the transferability adjusting layer 13 is made of the ink layer 1
2, which are incompatible with or hardly mixed with each other, form a large heat-sensitive adhesive film on the ink layer 12, and have the other tackifying resin as described above. By improving the adhesion between the resin having a large film forming property and the ink layer 12,
It is added in order to increase cohesion, hardness and tackiness and adjust thermal transferability.

The composition comprising the heat-sensitive adhesive resin having a large film-forming property and the tackifying resin may be used in the form of an aqueous solution or aqueous dispersion, or the ink layer 1
2 in the form of a solution or dispersion of a general-purpose organic solvent that does not attack the ink layer 1 according to a usual coating method.
The transferability adjusting layer 13 formed in this manner has a higher viscosity than the ink layer 12 under thermal transfer conditions, and generally has a temperature of 95 ° C. At a temperature of 3,000 centipoise or more, preferably 10,000 centipoise or more.

Further, the transferability adjusting layer 13 thus formed is further adjusted for its film strength to obtain a sharp printed image with good sharpness, and to prevent dirt and blocking. Fillers such as kaolin, talc, bentonite, and titanium oxide, and organic or inorganic powders such as metal soaps such as zinc stearate and aluminum stearate are blended at a ratio not exceeding 20% by weight, and the transferability adjusting layer 13 is mixed. It is also possible to make it exist inside. Further, the transferability adjusting layer 13 has good ribbon running properties without ribbon meandering and slippage, and also has good storage properties without blocking and turbulence even when stored at a temperature of 55 ° C. , A fluoropolymer,
Compound a polymer surface modifier such as a silicone polymer, a higher alcohol, a glycerin ester, a sorbitan ester, a fatty acid, a polyhydric alcohol, a monoamide, a bisamide, a lubricant such as a fat wax in a ratio not exceeding 10% by weight, It is also possible to make it exist in the transferability adjusting layer 13.

Then, using the ink ribbon 10 obtained in this manner, the ink ribbon 10 is formed into a head heating element shape, a head heating element position, a head mounting angle, a head pressing pressure, a winding torque, a head marking processing energy, and a printing. Set it on a printing device such as a thermal transfer printer with adjusted speed, etc.
By performing printing and thermal transfer, the desired dry transfer material can be advantageously produced.

In other words, by using such an ink ribbon 10, even if a desired character or figure is transferred to a film (basic sheet) having a surface having poor wettability by thermal printing, the image spreads and collapses. A good printed image can be realized without causing any problems such as shading, head scraping, stringing, citron skin and insufficient transfer.

Further, the image printed in this way can be pressure-sensitively transferred onto a target transfer object such as paper, plastics, metal or the like by applying pressure from the back side of the film (basic sheet). There is no residual ink on such a film, and even after transfer, it is possible to form a firmly bonded good image without crushing, spreading, and brittleness.

Also, such an ink ribbon 10
It was recognized that no problems such as blocking and turbulence of the ribbon spool occurred at all even when stored at 55 ° C. for 24 hours. There is no problem such as slip, etc., and printing and thermal transfer can be performed to the end of the ribbon. In these developments, 80% by weight or more of a wax having a composition having a penetration at 55 ° C. of 50 or less is contained in the wax which is a main component of the binder agent in the ink layer. This is probably due to the rise in heat softening temperature.

[0024]

EXAMPLES Hereinafter, some examples of the present invention will be shown to clarify the present invention more specifically. However, the present invention is not limited by such description. That goes without saying.

The present invention may be modified in various ways based on the knowledge of those skilled in the art, in addition to the following embodiments, in addition to the above-described specific description, without departing from the spirit of the present invention. , Modifications, improvements, etc.
It should be understood.

Incidentally, the value of the penetration in the examples is based on JIS-K
This is a measured value according to −2235.

Example 1 In order to form an ink layer (12) and a transferability adjusting layer (13), an ink having the following composition and a transferability adjustment layer were formed.
Use coating liquid was prepared. The viscosity of the ink layer (12) formed by this ink is 250 centipoise (95 ° C.), and the viscosity of the transferability adjusting layer (13) formed by such a coating liquid is 50,000 to 70,000. It was centipoise (95 ° C.). In the wax, which is the main component of the binder agent in the ink layer (12), the proportion of wax having a penetration 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 [Diacarna 30 of Mitsubishi Kasei Kogyo Co., Ltd.] Penetration (55 ° C.): 10 or less 3 [Candelilla wax 2698, manufactured by Chukyo Yushi Co., Ltd.] Penetration (55 ° C): about 10 Paraffin wax ... 9 [HNP manufactured by Nippon Seiro Co., Ltd.] -10] Penetration (55 ° C.): about 20 Rosin ester ······ 2 [Superester A-100 manufactured by Arakawa Chemical Industry Co., Ltd.] Ethylene-vinyl acetate copolymer ······· 2 EVA210 manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.] Carbon black ........ 2 [MA-7 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.] Methyl isobutyl ketone (solvent)... 100 transferability adjusting layer (13) ) Composition The amount of the polyamide ..... 4 [Sanwa Chemical Industry Co., Ltd. Sanmide 615A] hydrogenated rosin ----- 5 [Arakawa Chemical Industrial Co., Ltd. Haiperu] Talc ..... 1 [ Reagent manufactured by Kanto Chemical Co., Ltd.] Isopropyl alcohol 90 toluene 100 A 3.5 μm polyethylene terephthalate (PET) film is used as the ribbon substrate (11), and on the film Then, the ink having the above composition was dried with a film thickness of 6 to
An ink layer (12) was formed by applying the solution to a thickness of 7 μm and drying to form a coating liquid for forming a transferability adjusting layer having the above composition on the ink layer (12).
And dried to obtain the target ink ribbon (10).

Next, using the thus obtained ink ribbon, the ink ribbon was set on a regulated thermal transfer type typewriter (EP-43 manufactured by Brother Industries, Ltd.), and a polyethylene film coated with a silicone resin ( (Thickness: 100 μm), a sufficiently beautiful printed image of good quality could be obtained. Also,
By rubbing such a printed polyethylene film from the back side and applying pressure, such a printed image was pressure-sensitively transferred onto a desired surface of paper, plastics or metal, and an image of sufficiently good quality was obtained. Was completed. Further, a storage test was conducted at 55 ° C. for 24 hours, but there was no problem such as winding disorder.

Example 2 As an ink for forming the ink layer (12),
Using the same composition as in Example 1, but forming a transferability adjusting layer
As the solution coating solution, the one having the following composition was used.
An ink ribbon was made in the same manner as in Example 1, and a thermal transfer test was performed.
Experience, ribbon storage test, ribbon running test and a pressure-sensitive transfer test
As a result, good results were obtained as in Example 1.
Incidentally, the transferability adjusting layer (1) formed with a coating solution having the following composition:
3) has a viscosity of 50,000 to 70,000 centipoise (95 ° C)
Was to do.

Composition of transferability adjusting layer (13) : parts by weight Polyamide 91 [Sunmide 615A manufactured by Sanwa Chemical Industry Co., Ltd.] Hydrogenated rosin 91 [Arakawa Chemical Industry Co., Ltd.] Hyper] Titanium oxide 18 [ Taipe A-100 manufactured by Ishihara Sangyo Co., Ltd.] Isopropyl alcohol 3800 Comparative Example 1 Implemented as ink for forming ink layer (12)
Using the same composition as in Example 1, but forming a transferability adjusting layer
As the solution coating solution, the one having the following composition was used.
An ink ribbon was made in the same manner as in Example 1, and a thermal transfer test was performed.
Test, ribbon storage test, ribbon running test and pressure-sensitive transfer test
As a result of printing, the printed image is slightly
Except for the occurrence of
Good results were obtained as in Example 1. In addition, the following composition
The transferability-adjusting layer (13) formed by the working liquid is 50,000 to 7
It has a viscosity of 10,000 centipoise (95 ° C).
Was.

Composition of transferability adjusting layer (13): parts by weight ethylene-vinyl acetate copolymer EVA210 manufactured by DuPont-Mitsui Polychemicals Co., Ltd. Petroleum resin 5 Toho Petroleum Resin High Resin # 90 manufactured by Co., Ltd.] Methyl isobutyl ketone (solvent) 54 Comparative Example 2 Composition and transferability adjusting layer (1) of ink layer (12) as described below
3) using in click and coating solution gives the composition of Example 1
In the same manner as above, make an ink ribbon (10)
Results in a beautiful and good quality printed image
And such a printed image can be transferred by pressure-sensitive transfer.
Transfers a good quality image onto the desired transfer object
I was able to do it. Also, as a result of the ribbon running test,
There are no problems such as snaking, slipping, etc.
Storage test for 24 hours at 55 ° C as in 1
However, there was no problem such as turbulence. However,
As in Comparative Example 1, the printed image was slightly cut
Staining occurred and slight blocking was observed.

It should be noted that the ink was formed with the following ink composition.
The ink layer (12) has a viscosity of 500 centipoise (9
5 ° C) and transferability formed with the following coating liquid
The viscosity of the adjustment layer (13) is 50,000 to 70,000 centipoise (95
° C). Also, a binder agent in the ink layer (12)
The penetration at 55 ° C of the wax which is the main component of
The proportion of waxes of 50 or less was 92% by weight.

Composition of ink layer (12) : parts by weight paraffin-based wax 4 [HNP-14 manufactured by Nippon Seiro Co., Ltd.] Penetration (55 ° C.): about 20 to 25 α-olefin-anhydrous maleic acid ----- 5 copolymer [Mitsubishi Kasei DIACARNA 30 industrial Corporation] penetration (55 ° C.): 10 or less candelilla wax ..... 3 [Chukyo Yushi Co., Ltd. Candelilla wax 2698] Penetration (55 ° C): about 10 microcrystalline wax ··· 1 [HNP-10 manufactured by Nippon Seiro Co., Ltd.] Penetration (55 ° C): about 150 rosin ester · ... 2 [ Superester A-100 manufactured by Arakawa Chemical Industry Co., Ltd.] Ethylene - vinyl acetate copolymer ........... 2 [EVA210 manufactured by Mitsui DuPont Polychemicals Co., Ltd.] Carbon black ... ... 2 [three Chemical Industry Co., Ltd. MA-7] methyl isobutyl ketone (solvent) ----- 100 transferable adjusting layer (13) Parts by weight ethyl cellulose ..... 1 Kanto Chemical Co. reagent, [ 10cps] hydrogenated rosin ···· 5 [Hyper manufactured by Arakawa Chemical Industries Co., Ltd.] oleic acid amide ··· 0.18 [ Amide 0 manufactured by Kao Corporation] isopropyl alcohol (solvent) ··· ... 54 Comparative Example 3 Performed as ink for forming ink layer (12)
Using the same composition as in Example 1, but forming a transferability adjusting layer
As the coating liquid for use, the one having the following composition was used.
An ink ribbon was made in the same manner as in Example 1, and a thermal transfer test was performed.
Test, ribbon storage test, ribbon running test and pressure-sensitive transfer test
As a result of printing, the printed image is slightly
Except for the occurrence of
Good results were obtained as in Example 1. In addition, the following composition
The transferability-adjusting layer (13) formed by the working liquid is 50,000 to 7
It has a viscosity of 10,000 centipoise (95 ° C).
Was.

Composition of transferability controlling layer (13) Composition by weight Polyamide [ ... ] [ Sunmide 615A manufactured by Sanwa Chemical Industry Co., Ltd.] Ketone resin [ ... ] [ 1 ] [Arakawa Chemical Industry Co., Ltd.] Ketone Resin K-90] Polymer Surface Modifier 0.06 [Demoiper F-100 manufactured by NOF CORPORATION] Toluene 38 Comparative Examples 4 to 6 On the other hand, transferability adjusting layer (13)
Ink ribbon in which no ink was formed (Comparative Example 4 ), Comparative Example 2
While an ink ribbon (Comparative Example 5 ) in which the transferability adjusting layer (13) was not formed and a commercially available wax-type thermal transfer ink ribbon (manufactured by Fuji Chemical Paper Industries, Ltd.) (Comparative Example 6 ) were used. When a transfer test similar to that of Example 1 was performed, both the heat transfer property and the pressure transfer property were insufficient. Specifically, regarding pressure-sensitive transferability, insufficient transferability due to insufficient adhesive force, cohesive force, viscosity, spread of transferred print due to insufficient hardness, crushing, scraping of print by head,
Then, it was recognized that problems such as shading of printing and citron skin occurred. Regarding pressure-sensitive transferability, film transfer was insufficient due to insufficient pressure-sensitive adhesive force, insufficient fixation, cohesive strength and viscosity, and the final transfer print image was crushed, spread, lacked strength, and insufficient transfer due to insufficient hardness. There were problems such as residual ink remaining on the sheet.

Comparative Example 7 The paraffin-based wax of the entire ink in Example 1 was a beeswax [manufactured by Kato Yoko Co., Ltd.] (penetration was 45 to 45 ° C. at 40 ° C.).
A storage test similar to that of Example 1 was performed using the ink ribbon changed to 50 or more than 50 at 55 ° C.). As a result, the ink ribbon became unusable due to blocking or winding disorder.

[0037]

As is apparent from the above description, the thermal transfer ink ribbon according to the present invention comprises a ribbon base material (support), a coloring agent, a binder agent mainly composed of wax, and a pressure-sensitive transfer agent. And a transferability-adjusting layer is further formed on the ink layer. The wax in the binder agent of the ink layer has a penetration at 55 ° C. of 50 or less. Is contained in an amount of 80% by weight or more, the thermal softening temperature rises, and even in a slightly high temperature environment (about 55 ° C.), the winding of the ribbon spool is not disturbed, and good storage stability is obtained. You get it.

Further, a transferability adjusting layer having a large heat-sensitive adhesiveness, hardness, viscosity, and cohesive force is provided as the top coat layer, and the ink layer is provided with pressure-sensitive adhesiveness so that a film having poor wettability can be obtained. The heat transferability to the basic sheet surface was remarkably improved, and the pressure transferability to another substance due to the pressure of the print image provided by the heat transfer could be advantageously improved, and similarly excellent characteristics were obtained. This is where the present invention has great industrial significance where a dry transfer material can be advantageously produced.

[Brief description of the drawings]

FIG. 1 is an explanatory sectional view showing an example of a thermal transfer ink ribbon for producing a dry transfer material according to the present invention.

[Explanation of symbols]

 Reference Signs List 10 Thermal transfer ink ribbon 11 Ribbon base material 12 Ink layer 13 Transferability adjusting layer 14 Sticking prevention layer

Claims (1)

(57) [Claims] An ink image thermally transferred on a base sheet by a thermal transfer method is pressed from a surface opposite to a surface on which the ink image on the base sheet is heat-transferred.
A thermal transfer ink ribbon for dry transfer material production used when producing a dry transfer material for retransferring the ink image to any receiver, formed on the surface of a predetermined film-shaped ribbon base material, An ink layer comprising a colorant, a binder containing wax as a main component, and a pressure-sensitive adhesive, wherein 80% by weight or more of the wax in the binder has a penetration of 50 or less at 55 ° C .; Formed on the ink layer, ethylene-vinyl acetate copolymer, polyvinyl acetate ionomer, acrylic polymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer One or more heat-sensitive adhesives selected from, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyamide, ethyl cellulose And of resin,
One or more tackifying resins selected from petroleum resin, rosin, hydrogenated rosin, rosin ester, ketone resin, phenolic resin, and one or two selected from kaolin, talc, bentonite titanium oxide A heat-sensitive transfer ink ribbon for producing a dry transfer material, comprising: a transferability-adjusting layer comprising the above-mentioned filler for preventing blocking.