JPS62292483A - Thermal transfer recording method - Google Patents

Abstract

PURPOSE:To obtain favorable gradation properties and image quality, by using a mixed wave having a melting point in a specified temperature range for each ink layer of a thermal transfer recording ink ribbon, and using an image- receiving paper coated with polyvinylidene chloride, polyethylene and an ink obtained by removing a dye or pigment from a mixed ink for transfer. CONSTITUTION:A set of ink layers comprising a dye or pigment added to a mixed wax comprising a wax having a melting point of 45-70 deg.C and a heat- fusible substance having a melting or softening point of 100-200 deg.C are provided on a sheet member by sequential repeated coating to obtain a thermal transfer recording ink ribbon. An image is recorded by sequentially thermally transferring the ink layers of the ink ribbon to an image-receiving paper obtained by coating a base with polyvinylidene chloride, polyethylene and one of inks obtained respectively by removing the dye or pigment from the ink layers. By using the mixed wax comprising the wax and the heat-fusible substance, gradation properties are greatly enhanced.

Description

[Detailed description of the invention] 3. Detailed description of the invention (Industrial application field) The present invention relates to a thermal transfer recording method.

(Prior Art) Conventional thermal transfer methods are generally known as thermal sublimation transfer methods and thermal melt transfer methods. Among these, the thermal sublimation transfer method is expected to be used as a full-color recording method because of its good image gradation.

However, the thermal sublimation transfer method requires a large amount of sublimation energy, so it takes a long time to create an image using a printer, and there are problems with the storage stability of the obtained image. Therefore, as a method to improve this, a method has been proposed in which the sublimation energy is reduced by developing color on receiver paper after sublimation transfer, but problems still remain in the storage stability of the image. . From this point of view, a thermal melt transfer method that requires low transfer energy and has good storage stability has recently been studied.

(Problems to be Solved by the Invention) However, the thermal melt transfer method has a problem in that it is inferior to the thermal sublimation transfer method in terms of gradation and image quality. Therefore,
Various heat-melting transfer methods have been studied to improve gradation and image quality, but so far nothing has been achieved that is equivalent to or better than heat-sublimation transfer methods in terms of gradation and image quality. do not have.

(Means for Solving the Problems) The thermal transfer recording method of the present invention comprises a wax having a melting point in the range of 45 to 70°C and a heat-melting substance having a melting point or softening point in the range of 100 to 200°C. A thermal transfer recording ink ribbon is used, in which a plurality of ink layers are prepared by adding dyes and pigments to a mixed wax containing wax, and a set of ink layers are sequentially and repeatedly coated on a sheet member. , polyethylene, and ink obtained by removing dyes and pigments from each of the above-mentioned ink layers, and image-forming by sequentially thermally transferring each ink layer of the ink ribbon for thermal transfer recording onto an image-receiving paper coated on a base. It is.

(Example) The present invention will be explained in detail below.

The present invention is characterized by the distribution of waxes and resins used in each ink layer, including wax TFIA having a melting point in the range of 45 to 70°C and wax having a melting point in the range of 100 to 200°C.
At least one type of wax is selected from among the heat-melting substances B having a melting point or softening point within the range of 1 and 2 and is used as a mixed wax. In this way, by using a mixture of waxes A and heat-melting substance B, waxes A or heat-melting substance B can be mixed and used.
It has been found that the gradation during transfer is much improved compared to when used alone. This point is clarified by the comparative test examples described below. In addition, it is also possible to use waxes other than waxes A and heat-melting substance B together with waxes A and heat-melting substance B in the mixed wax, and even in this case, the gradation was in very good condition.

Waxes A and heat-melting substances B used in the present invention
Typical examples are shown below.

Examples of waxes belonging to waxes A include paraffin wax 5P-0110, paraffin wax 115, paraffin wax PF-4015, and PF-
5025, paraffin wax 120.125,135
, 130, 140, 150° 155, paraffin wax PR-0120, paraffin wax 5C-5025
, paraffin wax PF-4025, paraffin wax 5P-1030, 5p-1035, 5p-3035
゜5P-3040, 5P-6145, Paraffin Wax Candle 35, Himic 2045, 1045, Volume) 1025. 1135.8025, Neo Barax 2845, 2545.2745, Palpax 13
35,1330,1430°1425, Bontex 0
100, 1033, Cartowax 2225, 3020
,3025,3030.3036,3135,3635
．． 3640, NPS8070. 8020. 8135
．． 9125, Bisen 0453 Nippon Oil paraffin wax 130, 135, 140° 145,
Eye size 1 candle, eye size 2 candle, soft wax 512 Paranok 103, 104. 303, 201
, 202, 203, Special Paraffin ESSO Petroleum Paraffin Wax 130, 135.135SPL, Nislax 132, 142, 152 M0B I L Petroleum Paraffin Wax 130, 135.1353PL, Wax Rex 140.155 Taniguchi Oil Paraffin Wax 100. L-3B, SB.

AS-130, 130 flakes, 135 Varico Petrolite WB-16, Hyper 260, Hyper 2
53, Piper 5013 Allied AC polyethylene #430 Hoechst wax ■ Nikko Fine Ceresin wax 7101 Ozoke Ceresin Noda Wax unbleached beeswax high acid, unbleached beeswax low acid, deodorized beeswax high acid, bleached beeswax high acid, deodorized beeswax low Acid, bleached beeswax Low acid Kato Yoko pure white bleached (high acid), semi-bleached, pure white bleached (low acid) Miki Chemical deodorized dark blue bleached beeswax, navy seal bleached beeswax, refined beeswax, deodorized red seal bleached beeswax, red seal bleached It includes beeswax and other heat-melting substances with melting points of 45 to 70°C.

Examples of thermofusible substances B include Bontex 1066.2222.2244 manufactured by Nippon Seiro, Baranok 101 manufactured by Nippon Oil, Petrolite C-7500 manufactured by Varico, and Polywax 655.85.
0.1000,2000. E1040°E2070. E
2020 Cheap Crude Oil Neowax H, M, Clearon P-105゜P-11
5, P-125, M-105, M-115 Allied AC polyethylene #617. #6. #7. #612, #
615. #625. #635. #8. #9, #820.
#840. #656. #401゜#580. #629.
#655. #540. #680, #392. #316 Bastman Evolen C-15, C-10, C-16, N-11, C
-13,N-10,N-14,N-12゜N-45,E
-15, E-14, Evolen E-11°F-12, E-
45, E-43 BASFAM3. manufactured by Badische. AM6. A, AF, Al1 1゜AH
6, AHIO Mitsui Petrochemical High Wax ll0P, 220P, 220MP.

320P, 320MP, 210P, 210MP.

410P, 310MP, 405MP, 200P.

00P Manufactured by Sanyo Chemical Sunwax 161P, 17IP, 165P.

151P, 131P Hoechst PE520. PE130. PE190, Hoechst DED522. DED521. DEDI21, DED
153, Hoechst wax UPC3S, OP, X55,
Hoechst Wax Special, Hoechst Wax C,
There are O, PL, R21, Hoechstwasox, and in addition to these, there are also others with melting points or softening points of 100 to 200
Contains heat-melting substances at °C.

As for the usage ratio of waxes A and heat-melting substance B, wax mA is used in an amount of 1 to 40% by weight, heat-melting substance B is used in an amount of 1 to 60% by weight, and the remainder is other waxes. This was done to compensate.

An example of waxes other than wax HA and thermofusible substance B, which are used in combination with wax A and thermofusible substance B, is shown below.

Synthetic waxes include paraffin wax, microcrystalline wax,
Oxidized paraffin wax, chlorinated paraffin wax,
Plant-based waxes such as ricinoleic acid amide, lauric acid amide, erucic acid amide, valmitic acid amide, oleic acid amide, 12-hydroxystearic acid, distearyl ketone, and ethylene bisstearic acid amide include rice wax, wood wax, and cane. Animal-based waxes such as Delilah wax and carnauba wax include larinone, beeswax, and shellac wax; mineral-based waxes include montan wax; higher fatty acids include palmitic acid and stearic acid; and higher alcohols include palate. Methyl alcohol, stearyl alcohol, ceryl alcohol, etc. Metallic soaps include sodium stearate, sodium palmitate, potassium laurate, potassium myristate, calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, lead stearate,
Examples of synthetic polyalcohols such as dibasic barium stearate include polyethylene glycol and polypropylene glycol.

It was confirmed that by using a wax mixture of wax A and 1 MB of heat-melting material, the gradation was greatly improved compared to when wax A or heat-melting material B was used alone. did.

Incidentally, it is preferable that the total amount of wax HA and heat-fusible substance B is adjusted to be 60ffi% or more of the entire mixed wax used. This point is also clarified by the comparative test examples described later.

Furthermore, it has been found that by adding polystyrene resin to this mixed wax, the mechanical strength of the ink is improved and the gradation properties are further improved. The amount of polystyrene resin added is 0.01 to 50% by weight,
Preferably, it is used in an amount of 5 to 20% by weight. however,
The resin added to wax mA and thermofusible substance B is not limited to polystyrene resin.

Sufficient gradation can be obtained by performing thermal transfer onto image receiving paper (substrate) using the ink ribbon for thermal transfer recording produced in this way, but the present inventors have attempted to further improve density and image quality. In order to achieve this goal, we also considered the image receiving paper (substrate). The results are shown in Table 1.

(Margin below) [Table 1] As is clear from Table 1, polyvinylidene chloride, polyethylene, and ink obtained by removing dyes and pigments from the mixed ink used for transfer were applied to a smooth surface such as paper or polyester film. As a result of using the coated material as image receiving paper,
It was confirmed that the density was higher and the image quality was also improved.

That is, by using an ink ribbon for thermal transfer recording prepared by mixing waxes as described above and an image receiving paper whose surface is coated with the resin described above, the ink ribbon for thermal transfer recording is placed on the image receiving paper. Each ink layer (yellow, magenta, cyan, black, etc.) is transferred to obtain a full-color image. The resins coated on the image-receiving paper were highly effective in improving image quality when transferring color ink. It was also confirmed that the images obtained by this method are comparable to those obtained by sublimation transfer.

Typical colored dyes and pigments used in the present invention are shown below.

Examples of colored dyes and pigments include azo pigments (monoazo, bisazo, condensed azo pigments), dyeing lake pigments (acid dye lake, basic dye lake, mordant dye lake pigment), nitro pigments, nitrone pigments, phthalocyanine pigments, and high-grade pigments ( Examples include vat dye-based inks, metal complex pigments, perylene pigments, isoindolinone pigments, and quinacrine pigments). To give a more specific example, the azo pigment is Hansa Yellow (C, 1,
11680 (hereinafter in parentheses indicates C, 1, Na), Hansa Yellow R (12710), Pyrazolone Red B (2
1120), Permanent Red R (12085), Lake Red C (15585), Brilliant Carmine 6
B (15850), Permanent Emin FB (1
2490) (monoazo pigments), Benzidine Yellow 〇 (21090), Benzidine Yellow GR (21100)
, Permanent Yellow NCR (20040) (all bisazo pigments), Chromophthal Yellow, and Chromophthal Red (all condensed azo pigments). Dyeing lake pigments include quinoline yellow lake (47005), eosin lake (45380), and alkali blue lake (427).
50A, 4277OA) (more than acid dye lake pigment),
Rhodamine Lake B (45170), Methyl Violet Lake (42535), Victoria Blue Lake (4
4045), malachite green lake (42000)
(the above basic dye lake pigments), alizarin lake (5
8000) (mordant dye lake pigment). Naphthol Yellow B (10316) as a nitro pigment, Pigmezotogeline B (10006) and Naphthol Green B (10020) as a nitro pigment, and metal-free phthalocyanine blue (74100) as a phthalocyanine pigment.
, phthalocyanine blue (74160), and phthalocyanine green (74260).

High-grade pigments include Anthrapyrimidine Yellow (68420), Indanthrene Brilliant Orange GK (59305), Indanthrene Brilliant Orange GK (59305), Indanthrene Blue R3 (69800), Thioindigo Red B (73300) (vat dye pigments), and Nickel Azo. Yellow (12775) (metal complex pigment), Perylene Red (71140), Perylene Scarlet (711
37) (perylene pigments), isoindolinone yellow (isoindolinone pigments), quinacridone left Y (4
6500) and quinacridone magenta (73915).

In addition, carbon black (C) is used as a black pigment.

1.77265).

Examples of disperse dyes include aminoazo or aminoanhraquinone dyes, nidroarylamine dyes, and the like.

To give more specific examples, examples of aminoazo dyes include Disbirds xo-3 (C, 1,11855 and below the brackets indicate C, 1, llh), Disbirds Orange 3 (1
1005), Disperse Red 1 (11110), Disperse Violet 24 (11200), Disperse Blue 44, etc. As an aminoanthraquinone dye, Diverse Orange l 1 (60700
), Disperse Red 4 (60755), Disperse Violet 1 (61100), Disperse Blue 3 (61505), etc. Disverse Yellow 1 (10345) is a nidroarylamine dye.
and 42 (10338).

Examples of oil-soluble dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, and phthalocyanine dyes. To give a more specific example, the azo dye is Solvent Yellow 2 (C, 1, 11020; hereinafter, the numbers in parentheses are C, 1
, Nll), Solvent Orange 1 (11920
), Solvent Red 24 (26105), Solvent Brown 3 (11360), etc.; as azo metal complex dyes, Solvent Yellow 19 (13900A),
Solvent Orange 5 (18745A), Solvent Red 8 (12715), Solvent Brown 37, and Solvent Black 123 (12195) are used as anthraquinone dyes.
60725), Solvent Blue 11 (61525),
Solvent Green 3 (61565) is a phthalocyanine dye such as Solvent Blue 25 (743).
50) etc.

Water-soluble dyes include nitroso dyes, azo dyes (mono, bis, tris, and tetrakisazo dyes), stilbene azo dyes, ketoimine (diphenylmethane) dyes, triphenylmethane dyes, xankene dyes, acridine dyes, quinoline dyes, methine dyes, Polymethine dye, thiazole dye, indamine dye 1. Examples include azine dyes, thiazine dyes, oxyketone dyes, anthraquinone dyes, and phthalocyanine dyes. To give a more specific example, the nitroso dye is mordant geline 4 (C, 1, 10005
(Hereinafter, the numbers in parentheses indicate C, 1, Nll), the azo dye is Direct Red 28 (22120), the stilbene azo dye is Direct Orange 71 (4Q
205), as a ketoimine dye, Hesic Ero-2
(41000),) Basic Blue 1 (42025) as a liphenylmethane dye, Acid Red 52 (45100) as a xanthine dye, and Basic Orange 23 (46075) as an acridine dye.
, Acid Yellow 2 (47010) is a quinoline dye.
), Direct Yellow 59 (4
9000), Acid Blue 59 (
50315), Mordand Blue 10 (51Q30) as an oxazine dye, Basic Blue 9 (52015) as a thiazine dye, Acid Blue 45 (63010) as an anthraquinone dye, and Direct Blue 86 (74180) as a phthalocyanine dye.
and so on.

The pigments and dyes described above are not limited to these, and sublimation dyes may also be used.

Materials used for the sheet-like member of the ink ribbon for thermal transfer recording and the image receiving paper include, for example, thin paper such as capacitor paper, typewriter paper, tracing paper, synthetic paper, cellophane paper, polyester film, polypropylene film, Examples include polyvinyl chloride film, polyimide film, polyethylene film, polycarbonate film, polystyrene film, and Teflon film.

(Comparative Test Example) First, the amounts of dyes and pigments shown in Table 2, polystyrene resin, and dispersant were added to a solution of 10 parts of toluene, and then dispersed in a ball mill for 24 hours. Heat-melting substance B was added and dissolved by heating, and the mixture was coated on a polyester film and dried to prepare five types of color ink samples.

Using each of the samples thus prepared, a transfer test was conducted on image receiving paper by varying the energy of the thermal head, and the test results shown in Table 3 were obtained.

The test results were measured using RD918 manufactured by Maches.

The image receiving paper was prepared by coating polyvinylidene chloride (Flehalon Latex RA) on a polypropylene film, and by dissolving and dispersing polyethylene in 10 parts of toluene (5%
) and 1 part of a polystyrene solution (11.8%), a dispersant, 11 parts of wax neck AO, and 8006 parts of a heat-melting substance were added to 10 parts of toluene and dissolved by heating (hereinafter referred to as colorless ink). Each was applied to a polypropylene film and used.

(The following is a blank space) Awesome 2] As is clear from the results in Table 3, in the combination of color ink and image receiving paper according to the present invention, as the energy of the thermal head increases, the optical properties of the image change more linearly and gradually from the low energy side. The density rises and a wide gradation range is obtained. Moreover, the maximum density was 1.25 or more, which was comparable to that of the thermal sublimation transfer method.

On the other hand, in order to compare with this test result, color ink containing only wax IA, color ink containing only heat-melting substance B, color ink containing both wax r4A and heat-melting substance B, resins, etc. Table 4 shows the results of a transfer test conducted in the same manner as above in combination with an uncoated image receiving paper. The test results are for RD9 made by Maches.
The values measured by No. 18 are shown.

(The following is a margin) As is clear from Table 4, the optical density of the image-receiving paper not coated with resin or the like is extremely low, and the gradation cannot be said to be sufficient.

Next, Table 5 shows the results of a transfer test performed on image-receiving paper coated with acrylic resin while varying the ratio of waxes A and heat-fusible substance B to the total mixed wax.

(Margins below) As is clear from Table 5, when the ratio of A+B is less than 60% by weight, for example, when it is 57% by weight, the gradation width is in the range of 0.264 to 0.594 in terms of the energy width of the thermal head. Yes, but not enough. However, in the case of 60% by weight or more, for example, 62.5% by weight, the gradation width is 0.264 to 0.79 based on the energy width of the thermal head.
2, which was sufficient.

(Effects of the Invention) As explained above, according to the thermal transfer recording method of the present invention, each ink layer of the ink ribbon for thermal transfer recording has a
a thermofusible substance having a melting point in the range of 100 to 20 °C;
By using a mixed wax containing waxes having a melting point in the range of 0°C, and using an image receiving paper coated with ink made by removing dyes and pigments from polyvinylidene chloride, polyethylene, and a mixed ink for transfer, It is possible to obtain extremely good gradation and image quality that is comparable to images obtained by thermal sublimation transfer.

Claims (1)

[Claims] 1) A mixed wax containing a wax having a melting point in the range of 45 to 70°C and a heat-melting substance having a melting point or softening point in the range of 100 to 200°C is used and dyed. Using an ink ribbon for thermal transfer recording in which a plurality of ink layers to which pigments have been added are made into a set and the set of ink layers are repeatedly coated on a sheet member, polyvinylidene chloride, polyethylene, and each of the above-mentioned ink layers are used. A thermal transfer recording method comprising sequentially thermally transferring each ink layer of the ink ribbon for thermal transfer recording onto an image-receiving paper coated with one of the inks from which dyes and pigments have been removed to form an image. 2) Claim 1, wherein the sum of waxes having a melting point in the range of 45 to 70°C and heat-melting substances having a melting point or softening point in the range of 100 to 200°C is 60% by weight or more. The thermal transfer recording method described.