JP2547401B2 - Thermal transfer recording method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermal transfer recording method.

(Prior Art) As a conventional thermal transfer method, a thermal melting transfer method of a thermal sublimation transfer method is roughly classified. Of these, the thermal sublimation transfer method is expected as a full-color recording method because it has good image gradation. However, the thermal sublimation transfer method requires a long time to create an image on a printer due to a large amount of sublimation energy, and has a problem in storability of the obtained image. So, as a way to improve this,
Although a method of reducing the sublimation energy by performing color development on an image receiving paper after sublimation transfer has been proposed, a problem still remains in the storage stability of the image. From such a point, recently, a thermal fusion transfer method, which has a low transfer energy and excellent storage stability, has been studied.

(Problems to be Solved by the Invention) However, there is a problem that the thermal fusion transfer method is inferior to the thermal sublimation transfer method in terms of gradation and image quality. Therefore, various thermal fusion transfer methods have been studied with the aim of improving gradation and image quality. Has not been done.

(Means for Solving 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-fusible substance having a melting point or a softening point in the range of 100 to 200 ° C. A mixed wax containing 60% by weight or more of the total of these waxes and the heat-fusible substance is used, and a plurality of ink layers in which dyes and pigments are added are set as one set, and the one set of ink layers is formed on the sheet member. Using a thermal transfer recording ink ribbon which is sequentially and repeatedly coated on polyvinylidene chloride, polyethylene, and the above-mentioned image-receiving paper coated with any one of the inks obtained by removing dyes and pigments from the ink layers described above. The ink layers of the thermal transfer recording ink ribbon are sequentially thermally transferred to form an image.

(Example) Hereinafter, the Example of this invention is described.

The present invention is characterized by the distribution of waxes and resins used in each ink layer. Waxes A having a melting point in the range of 45 to 70 ° C and melting point or softening in the range of 100 to 200 ° C. At least one wax is selected from the hot-melting substance B having dots and is used as a mixed wax. As described above, by using the waxes A and the heat-melting substance B as a mixture, the gradation at the time of transfer is significantly improved as compared with the case of using the waxes A or the heat-melting substance B alone. That is what I found. This point is clarified by a comparative test example described later. As the mixed wax, waxes other than the waxes A and the heat-meltable substance B are used.
It is also possible to mix and use the waxes A and the heat-meltable substance B, and even in this case, the gradation is very good.

Typical waxes A and heat-fusible substances B used in the present invention are shown below.

Examples of waxes belonging to the waxes A include paraffin wax SP-0110 and paraffin wax 11 manufactured by Nippon Seiro Co., Ltd.
5, paraffin wax PF-4015, PF-5025, paraffin wax 120, 125, 135, 130, 140, 150, 155, paraffin wax PR-0120, paraffin wax SC-5025, paraffin wax PF-4025, paraffin wax SP-1030, S
P-1035, SP-3035, SP-3040, SP-6145, Paraffin wax candle 35, Hymic 2045, 1045, Polute 1
025,1135,8025, Neo-Parax 2845,2545,2745, Palbucks 1335,1330,1430,1425, Bontex 0100,1033,
Cart wax 2225,3020,3025,3030,3036,3135,3635,3
640, NPS8070,8020,8135,9125, Bisen 0453 Nippon Oil paraffin wax 130,135,140,145, Nisseki No. 1 candle, Nisseki No. 2 candle, Soft wax 51, Paranock 103,104,303,201,202,203, Special paraffin ESSO Petroleum paraffin wax 130,135,135SPL, Eslux 13
2,142,152 MOBIL Petroleum paraffin wax 130,135,135 SPL, Wax Rex 140,155 Taniguchi Petroleum paraffin wax 100, L-SB, SB, AS-130,130 flakes, 135 Varico Petrolite WB-16, Viver 260, Viver 253, Viver 5013 Allied AC Polyethylene # 430 Hoechst Hoechst Wax V Nikko Fine Ceresin Wax 710, Ozoque 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 Made by Yoko Kato Pure self-bleached (high acid), semi-bleached, pure white bleached (low acid) Deodorized dark beeswax beeswax, dark blue beeswax beeswax, purified beeswax, made by Miki Kagaku
There are deodorized red-marked beeswax and red-marked beeswax, and in addition to these, it also contains heat-meltable substances with a melting point of 45 to 70 ° C.

Examples of substances that belong to the heat-melting substance B include Bontex 1066,2222,2244 made by Japanese wax, Paranock 101 made by Nippon Oil, Petrolite C-7500 made by Barico, and polywax 655,850,1000,2.
000, E1040, E2070, E2020 Yasuhara Yushi Neowax H, M, Clearon P-105, P-115, 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 Eastman Epollen C-15, C-10, C-16, N-11, C-13, N-10, N-
14, N-12, N-45, E-15, E-14, Epolene E-11, F-12, E
-45, E-43 Badische BASF AM3, AM6, A, AF, AL61, AH6, AH10 Mitsui Petrochemical High Wax 110P, 220P, 220MP, 320P, 320MP, 210P, 210M
P, 410P, 310MP, 405MP, 200P, 400P Sanyo Kasei Sun Wax 161P, 171P, 165P, 151P, 131P Hoechst Hoechst PE520, PE130, PE190, Hoechst DED522, DED52
1, DED121, DED153, Hoechst wax UPCSS, OP, X55, Hoechst wax special, Hoechst wax C, O, F
L, R21 and Hoechst wax are included, and in addition to these, heat-meltable substances with a melting point or softening point of 100 to 200 ° C are included.

As for the use ratio of waxes A and heat-melting substance B, 1 to 40% by weight of waxes A and 1 to 60% by weight of heat-melting substance B are used, and the rest is other waxes. It was designed to be supplemented with.

An example of waxes other than the waxes A and the heat-meltable substance B, which are used by mixing with the waxes A and the heat-meltable substance B, is shown below.

Synthetic waxes include paraffin wax, microcrystalline wax, oxidized paraffin wax, chlorinated paraffin wax, ricinoleic acid amide, lauric acid amide, erucic acid amide, valmitic acid amide, oleic acid amide, 12-hydroxystearic acid, distearyl ketone. , Ethylenebisstearic acid amide, etc. as plant wax, rice wax, wood wax, candelilla wax, carnauba wax, etc., animal wax as larinone, beeswax, shellac wax, mineral wax as montan wax Higher fatty acids such as wax, palmitic acid, stearic acid, etc., Higher alcohols: palmityl alcohol, stearyl alcohol, ceryl alcohol, etc. As I, sodium stearate, sodium palmitate,
Potassium laurate, potassium myristate, calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, lead stearate, barium dibasic stearate, etc.Synthetic polyalcohols include polyethylene glycol and polypropylene glycol. Can be mentioned.

It was confirmed that the use of the mixed wax of the waxes A and the heat-melting substance B in this way greatly improves the gradation as compared with the case where the waxes A or the heat-melting substance B is used alone. did.

The total of the waxes A and the heat-fusible substance B is preferably adjusted to be 60% by weight or more of the total mixed wax used. This point is also clarified by a comparative test example described later.

Further, it was found that adding polystyrene resin to this mixed wax improves the mechanical strength of the ink and at the same time improves the gradation. The polystyrene resin is added in an amount of 0.01 to 50% by weight, preferably 5 to 20% by weight. However, as the resin added to the wax A and the heat-meltable substance B,
It is not limited to polystyrene resin.

Although sufficient gradation can be obtained by performing thermal transfer on the image receiving paper (base) using the thermal transfer recording ink ribbon thus produced, the present inventors further improved density and image quality. In order to achieve this, we also examined the image receiving paper (base). Table 1 shows the results.

As is clear from Table 1, polyvinylidene chloride, polyethylene, and ink mixed with the dyes used for transfer, with the dyes and pigments removed, are applied to the surface of a paper or polyester film having a smooth surface as an image receiving paper. As a result of using it, it was confirmed that the density was high and the image quality was also good.

That is, the thermal transfer recording ink ribbon prepared by blending the waxes as described above and the image receiving paper coated with the resin as described above are used to form the thermal transfer recording ink ribbon on the image receiving paper. The respective ink layers (yellow, magenta, cyan, black, etc.) are transferred to obtain a full-color image. The resins coated on the image-receiving paper were very effective in improving the image quality when transferring color ink. It was also confirmed that the image obtained by this method is comparable to the image obtained by sublimation transfer.

Typical examples of 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), dyed lake pigments (acid dye lakes, basic dye lakes, mordant dye lake pigments), nitro pigments, nitrone pigments, phthalocyanine pigments, high-grade pigments ( Vat dye pigments, metal complex pigments, perylene pigments, isoindolinone pigments, quinacdone pigments) and the like. More specifically, as an azo pigment, Hansa Yellow G (CI1168
0, hereinafter brackets indicate CI No.), Hansa Yellow R
(12710), Pyrazolone Red B (21120), Permanent Red R (12085), Rake Red C (15585), Brilliant Carmine 6B (15850), Permanent Carmine F
B (12490) (above monoazo pigment), benzidine yellow G
(21090), benzidine yellow GR (21100), permanent yellow NCR (20040) (above bisazo pigment), chromophthal yellow, chromophthal red (above condensed azo pigment). Dyeing lake pigments include quinoline yellow lake (47005), eosin lake (45380), alkaline blue lake (42750A, 42770A) (above acidic dye lake pigment), rhodamine lake B (45170), methyl violet lake (42535), Victoria blue. Rake (4
4045), malachite green lake (42000) (basic dye lake pigment), alizarin lake (58000)
(Mordant dye lake pigment), etc. Naphthol yellow B (10316) as nitro pigment, pygmezoto green B (10006), naphthol green B (1
[0020] As the phthalocyanine pigment, metal-free phthalocyanine blue (74100), phthalocyanine blue (7416)
0) and phthalocyanine green (74260).

High-quality pigments include anthra virimidine yellow (68420), indanthrene brilliant orange GK (59305), indanthrene blue RS (69800), thioindigo red B (73300).
(The above are vat dye pigments), nickel azo yellow (1277
5) (metal complex salt pigment), perylene red (71140), perylene scarlet (71137) (above perylene pigment), isoindolinone yellow (isoindolinone pigment), quinacridone red Y (46500), quinacridone magenta (7)
3915) and so on.

As a black pigment, carbon black (CI7726
There is 5).

Examples of disperse dyes include aminoazo or aminoanraquinone dyes and nitroarylamine dyes. More specifically, as an aminoazo dye, Disperse Yellow 3 (CI11855 or less indicates CI No. in parentheses), Disperse Orange 3 (11005), Disperse Red 1 (11110), Disperse Violet 24 (11200),
There are Disperse Blue 44 and others. Examples of amino anthraquinone dyes include Dispers Orange 11 (60700), Dispers Red 4 (60755), Dispers Violet 1 (61100), and Disperse Blue 3 (61505). Nitroarylamine dyes include Disperse Yellow 1 (10345) and 42 (10338).

Oil-soluble dyes include azo dyes, azo metal complex dyes, anthraquinone dyes,
And phthalocyanine dyes. More specifically, examples of the azo dye include Solvent Yellow 2 (CI11020, hereinafter, the parentheses indicate CI No.),
Solvent Orange 1 (11920), Solvent Red 24
(26105), Solvent Brown 3 (11360), etc., Solvent Yellow 19 (13900) is an azo metal complex salt dye.
A), Solvent Orange 5 (18745A), Solvent Red 8 (12715), Solvent Brown 37, Solvent Black 123 (12195), etc., as anthraquinone dyes, Solvent Violet 13 (60725), Solvent Blue 11 (61525), Solvent Green 3 (61565)
And phthalocyanine dyes such as Solvent Blue 25 (74350).

Water-soluble dyes include nitroso dyes, azo dyes (mono, bis, tris, tetrakisazo dyes), stilbene azo dyes, ketoimine (diphenylmethane) dyes, triphenylmethane dyes,
Xanthene dye, acridine dye, quinoline dye, methine dye, polymethine dye, thiazole dye, indamine dye, azine dye, thiazine dye, oxyketone dye,
Examples include anthraquinone dyes and phthalocyanine dyes. More specifically, as a nitroso dye, Mordant Green 4 (CI10005, hereinafter in parentheses indicates CI No.), as an azo dye, Direct Red 28 (22120), and as a stilbene azo dye, Direct Orange 71 (40205). ), Basic yellow 2 (41000) as ketoimine dye, basic blue 1 (42025) as triphenylmethane dye, acid red 52 (45100) as xanthene dye, basic orange 23 (46075) as acridine dye, quinoline dye Acid Yellow 2 (47010) as a methine dye, Direct Yellow 59 (49000) as a methine dye, Acid Blue 59 (50315) as an azine dye, Mordant Blue 10 (51030) as an oxazine dye, and Basic Blue 9 as a thiazine dye. (52015), as anthraquinone dye Blue 45 (63010), Direct Blue 86 as the phthalocyanine dye (74180)
and so on. The pigments and dyes described above are not limited to these, and sublimation dyes may also be used.

Examples of materials used for thermal transfer recording ink ribbon sheet members and image receiving paper include thin paper such as capacitor paper, typewriter paper, tracing paper, synthetic paper, cellophane paper, and also polyester film, polypropylene film, poly There are vinyl chloride film, polyimide film, polyethylene film, polycarbonate film, polystyrene film, Teflon film and the like.

(Comparative Test Example) First, after adding the dye and pigment and the polystyrene resin and the dispersant in the amounts shown in Table 2 to a solution of 10 parts of toluene, dispersion was carried out in a ball mill for 24 hours, and then waxes A and The heat-meltable substance B was added and heated and melted, and the polyester film was coated and dried to prepare five types of color ink samples.

Then, using each of the samples thus produced, a transfer test was conducted on the image receiving paper while changing the energy of the thermal head, and the test results shown in Table 3 were obtained. The test results are the values measured by RD918 manufactured by Macbeth.

As the image-receiving paper, polyvinylidene chloride (Flehalon latex RA) was applied on a polypropylene film, and polyethylene was dissolved and dispersed in 10 parts of toluene (5%).
And 10 parts of toluene, 1 part of a polystyrene solution (11.8%), 1 part of a dispersant, 0.1 parts of waxes A, and 0.6 parts of a heat-meltable substance B were dissolved by heating (hereinafter referred to as colorless ink). ) Each of which was applied to a polypropylene film was used.

As is clear from the results in Table 3, in the combination of the color ink and the image receiving paper according to the present invention, the optical density of the image rises linearly and gradually from the low energy side as the energy of the thermal head increases, and a wide gradation range is obtained. Has been obtained. Moreover, the maximum density was 1.25 or more, which was almost comparable to the thermal sublimation transfer method.

On the other hand, for comparison with the test results, waxes A
A combination of a color ink containing only the heat-melting substance B, a color ink containing only the heat-melting substance B, and a color ink containing both the waxes A and the heat-melting substance B with an image-receiving paper not coated with a resin or the like. Table 4 shows the results of the transfer test performed as described above. Test results are Macbeth RD918
The value measured by

As is clear from Table 4, the image-receiving paper on which the resin or the like is not coated has an extremely low optical density and cannot be said to have sufficient gradation.

Next, Table 5 shows the results of a transfer test conducted on image-receiving paper coated with an acrylic resin by changing the ratio of the waxes A and the heat-meltable substance B in the total mixed wax.

As is clear from Table 5, in the case where the proportion of A + B is less than 60% by weight, for example, 57% by weight, the gradation width is the energy width of the thermal head in the range of 0.264 to 0.594,
Not enough. However, with 60% by weight or more, for example, 62.5% by weight, the gradation width was in the range of 0.264 to 0.792 in the energy width of the thermal head, which was sufficient.

(Effect of the Invention) As described above, according to the thermal transfer recording method of the present invention, 45 to 70 ° C. is applied to each ink layer of the thermal transfer recording ink ribbon.
A mixed wax containing a heat-melting substance having a melting point in the range of 100 to 200 ° C. and a wax having a melting point in the range of 100 to 200 ° C. and having a total of 60% by weight or more of these waxes and the heat-melting substance. In addition, by using an image-receiving paper coated with polyvinylidene chloride, polyethylene, and a dye-pigment-extracted ink from a mixed ink for transfer, as the energy of the thermal head increases, the image becomes linear and gentle from the low-energy side. The optical density rises, a good image having a wide gradation range can be obtained, and an image having a maximum density of 1.25 or more, which is almost comparable to the thermal sublimation transfer method, can be obtained. Also, the total amount of waxes and heat-meltable substances is 60% by weight or more, for example 62.5% by weight.
As a result, the gradation width is in the range of 0.264 to 0.792 in the energy width of the thermal head, and a sufficient gradation width can be obtained. That is, according to the thermal transfer recording method of the present invention, it is possible to obtain extremely good gradation and image quality comparable to those obtained by the thermal sublimation transfer method.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-25787 (JP, A) JP-A-60-104391 (JP, A) JP-A-58-201693 (JP, A) JP-A-61- 51385 (JP, A) JP 59-198196 (JP, A) JP 54-121139 (JP, A) JP 61-8386 (JP, A) JP 61-79695 (JP, A) JP-A-60-234889 (JP, A) JP-A-61-79696 (JP, A)

Claims (1)

(57) [Claims] 1. A wax containing a wax having a melting point in the range of 45 to 70 ° C. and a heat fusible substance having a melting point or a softening point in the range of 100 to 200 ° C. An ink ribbon for thermal transfer recording in which a mixed wax having a total amount of 60% by weight or more is used, and a plurality of ink layers obtained by adding dyes and pigments to the set are formed as a set, and the set of ink layers is sequentially and repeatedly coated on a sheet member. Each of the ink layers of the thermal transfer recording ink ribbon is sequentially thermally transferred onto an image receiving paper coated with one of the polyvinylidene chloride, polyethylene, and the ink obtained by removing the dye / pigment from each of the above-mentioned ink layers. A thermal transfer recording method characterized in that the image is formed by forming the image.