JPH05294078A - Ink ribbon for producing dry transfer material - Google Patents

Abstract

PURPOSE:To markedly enhance the thermal transfer properties to a surface inferior to wettability by providing a transfer adjusting layer having high thermal adhesiveness, high hardness, high viscosity and strong flocculation force on an ink layer as a topcoat layer to form a two-layered structure and providing pressure-sensitive adhesiveness to the ink layer. CONSTITUTION:An ink ribbon 10 for producing a dry transfer material is obtained by forming an ink layer 12 on one surface of a film like ribbon base material (support) 11 and further forming a transfer adjusting layer 13 on the ink layer 12 in a predetermined thickness. If necessary, a sticking preventing layer 14 composed of a heat-resistant resin such as a silicone resin is provided to the surface on the side opposite to the coating surface of the ink layer 12 of the ribbon base material 11. The ink layer 12 contains a colorant, a binder and a pressure-sensitive adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer ink ribbon used in the production of a dry transfer agent, and in particular, using a heat-sensitive transfer type printer, typewriter, word processor, etc. Transfer to strong surface,
Manufacturing of a dry transfer agent which is printable and enables a transfer image obtained by heat-sensitive transfer to an object to be transferred to be effectively pressure-transferred onto a second target object to be transferred by pressure. The present invention relates to an ink ribbon.

[0002]

2. Description of the Related Art In recent years, printers such as printers, typewriters, and word processors of the thermal transfer type have been developed and are widely used for 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 predetermined heating element among a large number of heating elements included in the thermal head is heated to support the thermal transfer ribbon. By melting the heat-meltable ink part that is in contact with the heating element through the body,
It is performed by transferring it to a printing paper.

By the way, a thermal transfer ribbon of this type has heretofore been prepared by simply coating a predetermined support with a hot-melt ink composed of a colorant and a binder agent thereof, and the binder agent is a wax. Was the main component. Moreover, this type of thermal transfer ribbon only targets normal paper as a transfer target.

On the other hand, recently, with the spread of the heat-sensitive transfer method, improvement in transferability to rough paper (paper with low smoothness) has been required, and various patent applications related to this have been made. In addition, various technologies such as a multi-type ribbon that enables transfer and printing with the same ink ribbon many times and a collectable ribbon that can erase and correct erroneous characters have been proposed.

[0005]

However, as far as the inventors of the present invention are aware, it is an object of the present invention to make it possible to perform transfer and printing on a surface having a good releasability, a good releasability, and a release surface because of poor wettability. So far, no report has been made on the thermal transfer ink ribbon. Moreover, as a method for producing a dry transfer material for instant lettering, since a thermal transfer method has not been adopted at all so far, the thermal transfer ink ribbon used for producing a dry transfer material for instant lettering is also No proposal has been made so far.

Therefore, the present invention adopts the following configuration in order to solve the above problems.

[0007]

SUMMARY OF THE INVENTION That is, the gist of the present invention is to provide an ink ribbon for producing a dry transfer material, which converts a transferred material into a dry transfer material by thermal transfer, on one side of a film ribbon base material. An ink layer provided with a colorant and an adhesive, and a thermal transferability adjustment provided on the ink layer and containing a heat-sensitive adhesive resin, a tackifying resin and a heat sensitivity improving agent. An ink ribbon for producing a dry transfer material, comprising:

Here, as illustrated in FIG. 1, in the ink ribbon 10 for producing a dry transfer material, an ink layer 12 is formed on one surface of a film-shaped ribbon base material (support) 11, and further thereon. In addition, the transferability adjusting layer 13 is formed with a predetermined thickness. A sticking prevention 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 coated surface of the ink layer 12, if necessary.

In such a thermal transfer ink ribbon 10 for producing a dry transfer material, the film-shaped ribbon base material 11 for supporting the ink layer 12 has been conventionally used as a base material of the thermal transfer ink ribbon. Although any of the above can be used, polyester, polyimide, polycarbonate, polysulfone, which has a heat-resistant temperature of 150 ° C. or higher, since a thermal head (printing device) comes into contact with the ink ribbon particularly for thermal transfer.
Plastic film made of polyether sulfone or polyphenylene sulfide, or condenser paper,
Paper such as glassine paper is used as a suitable material, and polyester, polycarbonate, and polyphenylene sulfide are particularly preferable from the viewpoint of heat resistance. Also its thickness,
Although it will be appropriately determined depending on the type of material, it is generally desirable to use a tape having a thickness in the range of 3 to 20 μm from the viewpoint of various requirements as a tape.

The ink layer 12 is mainly composed of a coloring material, a binder agent and a pressure sensitive adhesive.

As the colorant, a pigment such as carbon black is mainly used, and an appropriate dye is added, if necessary, for adjusting the color tone.

Examples of the binder agent forming the ink layer 12 include (A) a plant wax such as candelilla wax, carnauba wax, rice wax, and wax.
Animal waxes such as beeswax, lanolin and whale wax, mineral waxes such as montan wax and ceresin, petroleum waxes such as paraffin wax and microcrystalline wax, synthetic waxes such as polyethylene wax, and α-olefin-maleic anhydride. A wax composed of one or more resin waxes such as copolymers;
(B) A petroleum resin, a rosin, a hydrogenated rosin, a rosin ester, a ketone resin, a phenol resin, or a tackifier composed of one or more of them is used. This tackifier functions to improve the adhesion of the ink, the hardness, the cohesive force, the tackiness, and the pressure-sensitive adhesive. In particular, as the tackifier, petroleum resin,
Rosin, hydrogenated rosin and rosin ester are preferable from the viewpoint of tackiness. In addition, the wax and the tackifier which compose the binder agent are generally in a weight ratio of 15: 1 to 1: 1.
It is mixed in a ratio of about 3: 2.

Further, as the pressure-sensitive adhesive forming the ink layer 12, polyvinyl chloride, polyacrylic acid ester,
Ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl acetate, polyvinyl ether, polyvinyl acetal, vinyl-based polymers such as polyisobutylene, fiber-based polymers such as ethyl cellulose, nitrocellulose, cellulose acetate, chloride One type or a combination of two or more types of rubber polymers such as rubber and natural rubber is used. Particularly, polyacrylic acid ester, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and polyvinyl acetate are preferable from the viewpoint of adhesiveness.

The colorant forming the ink layer 12,
Binders and pressure sensitive adhesives are generally 5-30: 40.
It is an ink composition which is blended in a ratio of about 93: 2 to 30 and preferably gives a viscosity of less than 2500 centipoise, particularly about 100 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, which is formed on the target film-shaped ribbon base material 11 by a known method. It is coated or hot melt coated according to.

On the other hand, formed on the ink layer 12,
The transferability adjusting layer 13 as a top coat is formed as a layer having a higher viscosity and a higher heat-sensitive adhesiveness, hardness and cohesive force under the conditions of thermal transfer than the ink layer 12. The transferability adjusting layer 13 has improved adhesiveness at the time of heat-sensitive transfer to a basic sheet as a transfer target, so that the heat-sensitive transfer property to a surface having poor wettability is improved, and the cohesive force, viscosity, and Since the hardness is increased, transfer defects such as crushing and spreading are effectively improved, and the ink has a function of effectively preventing the ink from being scratched by the head of the printing apparatus. Further, when pressure is applied from behind the basic sheet of the dry transfer agent to transfer the image of the ink (transfer image) produced by thermal transfer to the second transfer target, the transferability adjusting layer 13 is Since the cohesive force and hardness are increased, it is possible to transfer a predetermined ink image from the basic sheet together without residual ink, and it spreads to the transferred ink, and is beautiful without leaks. It makes it possible to obtain a solid image and at the same time protects the transferred image to make it strong.

The transferability adjusting layer 13 includes (1) a first resin having a large film-forming property and a large heat-sensitive adhesive property, such as ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer. , Ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl pyrrolidone,
One or more of polyvinyl alcohol, polyamide, ethyl cellulose and the like, and (2) a second resin having a large cohesive force and tackifying property, for example, petroleum resin, rosin, hydrogenated rosin, rosin ester, ketone resin. (A) candelilla wax, carnauba wax, rice wax, wax, etc. as a thermal sensitivity improving agent for adjusting the melting point and the melt viscosity to improve the thermal sensitivity with one or more kinds of phenol resin, etc. Vegetable wax, beeswax, lanolin, animal wax such as whale wax, montan wax,
Mineral wax such as ceresin, paraffin wax, petroleum wax such as microcrystalline wax, synthetic wax such as polyethylene wax, and resin wax such as α-olefin-maleic anhydride copolymer
Or waxes consisting of two or more kinds, (B) phosphates such as tributyl phosphate and triphenyl phosphate, phthalates such as dimethyl phthalate and di-n-octyl phthalate, fats such as butyl oleate Group 1 monobasic acid esters, dibasic dibutyl adipates and other dibasic acid esters, diethylene glycol dibenzoates and other dihydric alcohol esters, and plasticizers comprising one or more of them, (C) flaxseed oil, tung oil Such as dry oil, soybean oil, cottonseed oil, rapeseed oil and other semi-dry oil, peanut oil, olive oil,
Vegetable and animal oils such as camellia oil and non-drying oil such as castor oil,
Fats and / or oils consisting of one or more of fatty acids such as palmitic acid, stearic acid, oleic acid and behenic acid, higher alcohols and polyhydric alcohols,
(D) one or more selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants and other surfactants consisting of one or more, and
It is mainly composed of

The above-mentioned heat sensitivity improvers (A) to (D) also have the effect of controlling the film strength and the like and preventing thread pulling. Among them, the (D) surfactants improve the wettability, so that the transferability to the transferred material becomes particularly good.

The above-mentioned first resin is more preferably ethylene-vinyl acetate copolymer, polyamide, or ethyl cellulose from the viewpoints of film-forming property, heat-sensitive adhesive property, etc., and the second resin is petroleum resin, rosin, Hydrogenated rosin and rosin ester are more preferable from the viewpoint of cohesive force, tackifying property and the like.

Ratio of the sum of the compounding amounts of the first resin and the second resin to the compounding amounts of (A) waxes, (C) fats and / or oils, and (D) surfactants. Is preferably 100: 2 to 50 on a weight basis. If the latter is less than 2, the effect is low, and if it exceeds 50, the adhesive strength is reduced.

The ratio of the sum of the compounding amounts of the first resin and the second resin to the compounding amount of the (B) plasticizer is 1 on a weight basis.
00: 2-30 is preferable. If the latter is less than 2, the effect is low, and if it exceeds 30, the adhesive strength is reduced.

Among these, the first resin and the second resin are preferably 1: 0.5 to 10 on a weight basis, and particularly 1: 1:
0.8 to 7 is preferable in terms of performance balance.

The first resin is incompatible with the ink layer 12 or hardly mixes even if it is compatible, and forms a film having a large heat-sensitive adhesive property on the ink layer 12. The other second resin is added for improving the adhesiveness between the first resin and the ink layer 12, increasing cohesive force, hardness and tackiness, and adjusting the heat-sensitive transferability. It is a thing. Further, the thermal sensitivity improver adjusts the melting point and the melt viscosity of the transferability adjusting layer 13 mainly composed of the composition of the first resin and the second resin, improves the thermal sensitivity, and improves the transfer performance by the thermal transfer printer. Improve.

The composition comprising the first resin, the second resin and the thermal sensitivity improver is in the form of an aqueous solution or an aqueous dispersion, or a solution or dispersion of a general-purpose organic solvent which does not attack the ink layer 12. In the form of a liquid, it is applied to the ink layer 12 in a predetermined thickness according to a usual application method. The transferability adjusting layer 13 thus formed has a viscosity higher than that of the ink layer 12 under a thermal transfer condition, and generally has a viscosity of 2,500 centipoise or more, preferably 8,000 centipoise or more at a temperature of 95 ° C. Layered.

The transferability adjusting layer 13 thus formed is further adjusted in its film strength so as to obtain a sharp and sharp printed image and to prevent stains and blocking. It is also possible to add fillers such as talc, bentonite, and titanium oxide, and organic or inorganic powders such as metal soaps such as zinc stearate and aluminum stearate in a proportion not exceeding 20% by weight.

Ink ribbon 10 thus obtained
A film with poor wettability in a thermal transfer printer in which the head heating element shape, head heating element position, head mounting angle, head pressing pressure, winding torque, head applied energy, printing speed, etc. are adjusted using When the transfer image of the desired character or figure is printed on the top with heat, it spreads.
Crushing, shading, scraping by head, stringing, citron skin,
Good printed images can be realized without causing problems such as insufficient transfer.

Further, even if the image printed in this way is pressure-sensitively transferred onto the target transfer material such as paper, plastics, metal or the like by applying pressure from the back side of the film sheet, the image is transferred onto the film. There is no residual ink, and the transferred image can be a good image with strong adhesion without being crushed, spread or brittle.

[0027]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto, and various modes can be adopted without departing from the scope of the invention.

The following ink layer formulation and transferability adjusting layer formulation were prepared.

Ink layer formulation-1 parts by weight α-olefin-maleic anhydride copolymer 2 [Dyakarna 30 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.] Candelilla wax 3 [Candelilla wax 2698 manufactured by Chukyo Yushi Co., Ltd.] ] Microcrystalline wax 9 [Hi-Mic1045 manufactured by Nippon Seiro Co., Ltd.] Rosin ester 2 [Super ester A-100 manufactured by Arakawa Chemical Industry Co., Ltd.] Ethylene-vinyl acetate copolymer 2 [Mitsui DuPont Polychemicals Co., Ltd. ) EVA210] Carbon black 2 [MA-7 manufactured by Mitsubishi Kasei Co., Ltd.] Methyl isobutyl ketone 100 Ink layer formulation-2 parts by weight α-olefin-maleic anhydride copolymer 8 [Mitsubishi Kasei Co., Ltd.] Dyakarna 30 manufactured by Candelilla Wax 5 [Candelilla wax 2698 manufactured by Chukyo Yushi Co., Ltd.] Rosin ester 2 [Arakawa Chemical Industry Co., Ltd. Super ester A-100 manufactured by Mfg. Co., Ltd. Ethylene-vinyl acetate copolymer 3 [EVA 210 manufactured by Mitsui DuPont Polychemical Co., Ltd.] Carbon black 2 [MA-7 manufactured by Mitsubishi Kasei Co., Ltd.] Methyl isobutyl ketone 100 Transferability adjusting layer formulation-1 part by weight Ethylene-vinyl acetate copolymer 1 [EVA210 manufactured by DuPont Mitsui Polychemicals Co., Ltd.] Petroleum resin 4 [High resin # 90 manufactured by Toho Petroleum Resin Co., Ltd.] Paraffin wax 1 [Japan Seisei Wax Co., Ltd., Benzene 15] Methyl isobutyl ketone 54 Transferability adjustment layer formulation-2 parts by weight Ethyl cellulose 1 [Kanto Chemical Co., Inc. reagent 10 cps] Hydrogenated rosin 4 [Arakawa Chemical Co., Ltd. high pal] Microcrystalline Wax 1 [Hi-Mic1045 manufactured by Nippon Seiro Co., Ltd.] Isopropyl alcohol 54 Blending of transferability adjusting layer-3 parts by weight Polya Mido 5 [Versamid 940 manufactured by Henkel Hakusui Co., Ltd.] Hydrogenated rosin 5 [High pale manufactured by Arakawa Chemical Co., Ltd.] Polyethylene wax 1 [Mitsui High Wax 4202E manufactured by Mitsui Petrochemical Co., Ltd.] Isopropyl alcohol 99 Transferability Adjustment layer formulation-4 parts by weight Ethylene-vinyl acetate copolymer 10 [EVA210 manufactured by Mitsui DuPont Polychemical Co., Ltd.] Petroleum resin 47 [High resin # 90 manufactured by Toho Petroleum Resin Co., Ltd.] Tricresyl phosphate (phosphate ester) 3 [Kyowa Fermentation Co., Ltd.] Methyl isobutyl ketone 540 Transferability adjusting layer formulation-5 parts by weight Ethyl cellulose 10 [Kanto Chemical Co., Ltd. reagent 10 cps] Hydrogenated rosin 47 [Arakawa Chemical Co., Ltd. high pail] ] Di-2-ethylhexyl malate (aliphatic dibasic acid ester) 3 [Kyowa Fermentation Co., Ltd.] Isopropyl LUCOL 540 Blending of transferability adjusting layer-6 parts by weight Polyamide 11 [Versamid 940 manufactured by Henkel Hakusui Co., Ltd.] Hydrogenated rosin 10 [High pale manufactured by Arakawa Chemical Industry Co., Ltd.] Dibutyl phthalate 1 [Dainippon Ink and Chemicals Inc. Made] Isopropyl alcohol 99 Blending of transferability adjusting layer-7 parts by weight Ethylene-vinyl acetate copolymer 5 [EVA210 manufactured by Mitsui DuPont Polychemical Co., Ltd.] Petroleum resin 14 [High resin # 90 manufactured by Toho Petroleum Resin Co., Ltd.] Glycerin monostearate (nonionic surfactant) 1 [Rheodol MS-60 manufactured by Kao Corporation] Methyl isobutyl ketone 180 Transferability adjusting layer formulation-8 parts by weight Ethylcellulose 4 [Reagent 10 cps manufactured by Kanto Chemical Co., Inc.] Hydrogenated rosin 15 [High-palle manufactured by Arakawa Chemical Industries, Ltd.] Stearic acid 1 Isopropyl alcohol 180 Transferability adjusting layer formulation-9 parts by weight Polyamide 9 [Versamid940 manufactured by Henkel White Water Co., Ltd.] Hydrogenated rosin 10 [High pale manufactured by Arakawa Chemical Industry Co., Ltd.] Rapeseed oil 1 [Reagent manufactured by Kanto Chemical Co., Ltd.] Isopropyl Alcohol 180 Using 18 combinations of the ink layer composition of the above 2 examples and the transferability adjusting layer composition of the above 9 examples, an ink layer having a dry film thickness of 6 to A coating thickness of 7 μm was formed, and then a transferability adjusting layer was formed so as to have a dry film thickness of 1 to 2 μm to obtain an ink ribbon. A thermal transfer typewriter (EP43 manufactured by Brother Industries, Ltd.) adjusted using this ink ribbon was used to print on a polyethylene film of 100 μm as a transfer target coated with a silicone resin.

For all combinations, the printed images were sufficiently clean and of good quality. By rubbing from the back of the polyethylene film while applying pressure, the printed image on the polyethylene film is pressure-sensitively transferred to paper, plastic, or metal as the second transfer target, and an image of sufficiently good quality is obtained. I was able to form. Also, other combinations of the present invention gave similar good results.

The viscosity of each ink layer formulation and each transferability adjusting layer formulation at 95 ° C. after drying was 200 to 1000 centipoise for the ink layer formulation and 30,000 to 70,000 centipoise for the transferability adjusting layer formulation.

[0032]

[Comparative Example] An ink layer was formed with either of the ink layer formulations 1 and 2 and a transferability adjusting layer was not formed, and a commercially available wax type thermal transfer ink ribbon was used, and the same procedure as in the example was performed. When a transfer test was conducted, both the heat-sensitive transferability and the pressure-sensitive transferability were insufficient. Specifically, regarding heat-sensitive transferability, transferability is insufficient due to insufficient adhesion, cohesive force, viscosity, spread of transfer printing due to insufficient hardness, crushing,
There were problems such as scraping of prints by the head, shading of prints, and citron skin. Regarding pressure-sensitive transferability, insufficient transfer due to insufficient pressure-sensitive adhesive force, insufficient adhesive force, cohesive force and viscosity,
Furthermore, the crushing and spreading of the final transfer print image due to insufficient hardness,
There were problems such as insufficient strength and poor integrated transfer, and residual ink was recognized on the basic film sheet.

[0033]

As described above, the present invention provides a two-layer structure in which a transferability adjusting layer having high heat-sensitive adhesiveness, hardness, viscosity and cohesive force is provided as a top coat layer on the ink layer as described above to form a two-layer structure. By providing the pressure-adhesive property, the heat-sensitive transfer property to the surface having poor wettability is remarkably improved, and further the pressure-sensitive transfer property to another substance due to the pressure of the printed image provided by the heat-sensitive transfer is also advantageous. At the same time, the addition of a heat sensitivity improver such as wax to the transferability adjusting layer improves the heat sensitivity and enables transfer with low energy. Further, there is an effect that the melting point, the melt viscosity, the film strength and the like can be adjusted according to the energy, the stringing is prevented, and the cutting is improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional explanatory view showing an example of an ink ribbon for producing a dry transfer agent according to an embodiment of the present invention.

[Explanation of symbols]

 10 Ink Ribbon for Manufacturing Dry Transfer Material 11 Ribbon Substrate 12 Ink Layer 13 Transferability Adjusting Layer

Claims (5)

[Claims] 1. An ink image thermally transferred onto a basic sheet by a thermal transfer system is pressed from the surface of the basic sheet opposite to the ink image transfer side, whereby the ink image is transferred onto an arbitrary transfer target. An ink ribbon for the production of a photosensitive transfer material, which is used when manufacturing a dry transfer material for retransfer, which is provided on one side of a film-shaped ribbon base material, and is made of vinyl resin, acrylic resin, polyolefin, or fiber-based material. One or more pressure-sensitive adhesives selected from molecules and rubber-based polymers, and one or more adhesives selected from petroleum resins, rosins, hydrogenated rosins, rosin esters, ketone resins and phenol resins An ink layer comprising a imparting agent, a colorant, and a wax and having a pressure-sensitive adhesive property, provided on the ink layer, an ethylene-vinyl acetate copolymer, polyvinyl acetate, One selected from onomer, acrylic copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyamide and ethyl cellulose. Alternatively, a transferability adjusting layer composed of two or more heat-sensitive adhesive resins and one or more heat sensitivity improvers selected from waxes, plasticizers, oils and fats, oil agents and surfactants. An ink ribbon for producing a dry transfer material, which is characterized by being provided. 2. The heat sensitivity improver is a vegetable wax,
The ink ribbon for producing a dry transfer material according to claim 1, wherein the ink ribbon comprises one or more waxes selected from animal waxes, mineral waxes, petroleum waxes, synthetic waxes, and resin waxes. 3. The thermal sensitivity improver is a phosphoric acid ester,
The ink ribbon for producing a dry transfer material according to claim 1, comprising one or more plasticizers selected from phthalic acid esters, aliphatic dibasic acid esters and dihydric alcohol esters. 4. The ink ribbon for producing a dry transfer material according to claim 1, wherein the thermal sensitivity improver comprises one or more selected from oils and fats and oils consisting of animal and vegetable oils. 5. The thermal sensitivity improver comprises one or more surfactants selected from anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. An ink ribbon for producing a dry transfer material according to claim 1.