JPS60225793A - Thermal transfer recording method - Google Patents

Abstract

PURPOSE:To thermally transfer an intermediate transfer recorded image formed on an intermediate recording sheet onto a final recording sheet, by a method wherein thermal energy is supplied in accordance with image information to melt a heat-fusible substance in an image-receiving layer, and a non-sublimable coloring agent provided in a coloring material supplying layer is moved into the heat-fusible substance in the image-receiving layer. CONSTITUTION:The coloring material supplying layer comprises a non-sublimable coloring agent and a heat-fusible high molecular weight substance. The coloring agent moved (dissolved or dispersed) into the heat-fusible substance in the image-receiving layer at the time of thermal recording is a direct, acid, basic, disperse or oil-soluble metallic complex salt dye which is non-sublimable. The heat-fusible substance has a melting or softening point of 45-150 deg.C, and is preferably a combination of a hard wax and a soft wax, the amounts of which are preferably in a ratio of 2:8-8:2. A heating temperature for transfer recording of the thermal transfer recording medium is preferably not lower than 45 deg.C. After the movement of the coloring agent, the image-receiving layer provided with an intermediate recorded image and the final recording sheet are laminated on each other, followed by again supplying thermal energy, whereby the image can be transferred onto the final recording sheet.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is a method for transferring a recorded image onto plain paper or the like using a heat-sensitive transfer recording medium having one coloring material supply layer and an intermediate recording sheet having a heat-melting image receiving layer. In particular, the present invention relates to a thermal transfer recording method that uses a thermal transfer recording material that has excellent raw storage stability and that allows a transfer recorded image with good storage stability to be obtained on plain paper.

[Prior art] n-! 19! A technology in which dye is transferred from a thermal transfer recording medium onto a recording sheet to form a recorded image using a thermal recording device that has a heat source such as a thermal head composed of resistors, thin film resistors, or semiconductor resistors, or a heat source such as a laser or a xenon lamp. Various proposals have been made in the past, and some have been implemented as thermal printer and triple facsimile technologies.

For example, JP-A-54-68253, JP-A-57-1606
No. 91 publications disclose that images are transferred multiple times onto plain paper using a heat-sensitive transfer recording medium in which a microporous layer containing a resin component as a binder contains an ink component that melts when heated. However, this recording method has noticeable unevenness in the transferred recorded image and is not suitable for obtaining a so-called solid image.

On the other hand, JP-A-59-14994 and other documents describe a thermal transfer recording medium using a polymer composition with a melting point or softening point of 100° C. or higher together with a dye, which provides an even transferred recorded image. It has been disclosed that it is possible. However, since this recording technique uses a sublimable dye, not only is there a drawback that the thermal transfer recording medium has poor storage stability, but also the storage stability of the transferred recorded image obtained by thermal transfer is also poor.

Therefore, the present applicant first proposed the technology shown in the patent application filed on April 20, 1980. The previously proposed technology stacks the coloring material supply layer of the thermal transfer recording medium and the heat-melting image receiving layer of the recording sheet facing each other, and applies thermal energy to the image receiving layer according to the image information to be recorded. Heat-sensitive transfer, in which a non-sublimable colorant contained in the colorant supply layer is dissolved or dispersed in the meltable substance of the image-receiving layer to form a transferred recorded image on the recording sheet. This is a recording method in which a heat-sensitive transfer recording material with excellent raw storage stability can be used, and the transferred recorded image obtained by thermal transfer also has good storage stability. However, the previously proposed technique has the disadvantage that it is impossible to use plain paper as the recording sheet.

[Problems to be Solved by the Invention] The present invention has been made in view of the above, and it is possible to use a heat-sensitive transfer recording material that has excellent raw storage stability, and also improves the storage stability of transferred recorded images obtained by thermal transfer. in good condition,
The technical problem is to make it possible to obtain a transferred recorded image on plain paper.

[Means for Solving the Problems] - The technical means of the present invention for solving the above technical problem is to arrange the coloring material supply layer of the thermal transfer recording medium and the heat-melting image receiving layer of the intermediate recording sheet facing each other. The heat-melting substance contained in the image-receiving layer is melted by applying thermal energy according to the image information to be recorded, and the non-sublimable colorant contained in the colorant supply layer is transferred to the image-receiving layer. The intermediate recording image is transferred to the intermediate recording sheet by transferring the intermediate recording image into a heat-melting substance, and the intermediate recording image is thermally transferred to the final recording sheet.

In the present invention, the means for applying thermal energy according to the image information to be recorded may apply thermal energy from the support side of the intermediate recording sheet using a thermal recording device having a heat source such as a thermal head or a sabre pen. Alternatively, thermal energy may be applied from the support side of the thermal transfer recording medium.

Thermal energy may be applied from both the support side of the intermediate recording sheet and the support side of the thermal transfer recording medium.

In addition, the means for thermally transferring the intermediate transfer recorded image obtained on the intermediate recording sheet to the final recording sheet such as plain paper uses a heat source such as a hot roll or an electric iron to apply thermal energy from the support side of the intermediate recording sheet. Thermal energy may be applied from the side of the final recording sheet such as plain paper, or the thermal energy may be applied from both the support side of the intermediate recording sheet and the side of the final recording sheet such as plain paper. .

The present invention will be described in more detail below, but first, the thermal transfer recording medium used in the present invention will be explained.

The thermal transfer recording medium used in the present invention has at least one coloring material supply layer on the support. The colorant supply layer mainly contains a non-sublimable colorant and a thermoplastic polymeric substance.

[Colorant]

Non-sublimable colorants are non-sublimable substances that can migrate (dissolve or disperse) into the heat-fusible substance of the image-receiving layer during heating recording, and have a color. It may be a substance that absorbs light at a wavelength (400 nm to 800 nm) or a substance that forms a substance that absorbs light in the visible light range.It is generally referred to as a dye and is suitable for thermal transfer recording media. , synthetic pigments called dyes, natural pigments called animal pigments or plant pigments, etc., which are non-sublimable are used.

The non-sublimable coloring agent used in the present invention is a coloring agent excluding sublimable (including those that vaporize with melting or dissolution) used in mordant dyes and the like.

The sublimability of the colorant used in the present invention can be determined by a simple test as described below.

interposing a spacer between the colorant and the image-receiving layer;
That is, an air layer is provided between the colorant and the image-receiving layer so that they do not come into direct contact with each other. The spacer may be, for example, a thin, porous material such as tissue paper. The image-receiving layer at this time is selected from water-soluble polymers, oil-soluble polymers, paper, glass, waxy substances, and other solid materials in which the colorant can be adsorbed or dissolved. Then, a heating plate (for example, 100°C) is applied to the colorant to absorb thermal energy. Therefore, if the colorant is non-sublimable, -H
In this test, the image was not transferred to the image-receiving layer at all or completely, regardless of the properties of the image-receiving layer. On the other hand, in the case of sublimation, it is transferred.

Preferred non-sublimable colorants for the present invention include direct dyeing $'l,
Examples include non-sublimable dyes such as acid dyes, basic dyes, disperse dyes, and oil-soluble gold HF5 complex salt dyes, and these dyes may be pallasted.

The basic dye preferably used as the non-sublimable coloring agent of the present invention is, for example, crystal piolet (C, 1
, 42555), malachite green (c, r.

42000), methyl violet (C,1,'425
35), Victoria Blue (G, 1.44045)
, Mazienta ((1:, I.

triphenylmethane dyes such as 42510), diphenylmethane dyes such as auramine (C, 1,655),
Astrafuroxin FF (C, ■, 413070),
Crampons Cachiron Yellow 30LH (Hodogaya Chemical Industry Co., Ltd. product, G, 1°413055), Crampons Cachiron Yellow 30LH
6BH (C, t, 4802θ) Astrazone Golden Yellow 6L (Bayer product, C, 1,4805
4), methine and azamethine dyes such as Rhodamine B (C:, 1.45170), Rhodamine 6G (G
, 1.4511110), thiazole azo and triazole azo dyes such as Astragin Blue GL (C, 1, 11052), Astrazone Red F3BL (C, 1, 11055), Eisenki Chiron Blue, etc. -5GH (C, 1, 11085), quinoneimine dyes such as methylene blue (c, 1.52015), quinone imine dyes such as -5GH (C, 1, 11085),
．． 11085), Cevron Yellow 3RL (DuPont product, C, 1, 11087), Astrazone Blue F
Examples include insulating azo dyes and anthraquinone dyes having an onium group at the structural end, such as GL (G, 1.61512).

Oil-soluble metal complex dyes are 1, for example, symmetric l:2 type azo metal complex dyes, asymmetrical 1:2 type azo metal complex dyes, l
Examples include type 1 azo metal complex dyes, azomethine metal complex dyes, formazan metal complex dyes, metal phthalocyanine dyes, and organic base salts of these dyes. Specifically, Eisenspiron Yellow 3RH (Hodogaya Chemical Co., Ltd. product, C,1, Solvent Yellow 25)
, f Hon Fast Yellow R (BASF product, G,
1.18890), Eisens Viron Orange 2RH
(C, 1, Solvent Orange 40).

Pomelo Fast Scarlet B (G, 1.12783)
, Eisenspiron Red GEH ((:, 1. Solvent Red 84), Zapon Fast Red BE (c, 1.
．． t27t5), -: i Bonfast Violet BE (C, 1, 121θ6), Cyanine Blue BB (Sumitomo Chemical Co., Ltd. product, C, 1, ?41130), /Curifast Black Han 3804 (Orient Chemical Co., Ltd. product, C ，
1,12185), Isenspiron Yellow 3RH Special (C,1, Solvent Yellow 25:l),
Eizen Nobilon Orange 2RH Special ((:, 1
．． Solvent Orange 40:l), Eisenspiron Blue-28N)l (Ill;, I, Solvent Blue 117), Zapon Fast Blue) 1i (C, 1, ?4)
35(1), Eisenspiron Black B)l Special (f;,l, Solvent Bruk 22:l), and the like.

Acidic dyes include, for example, C,1, Acid Yellow 19,
C,1, Acid Red 37, C,T, Acid Blue-132, 0,1, Acid Orange 10. C, 1, Ashindo Pull -83, C1, Ashindo Black 01
etc.

Direct dyes are C, T, Direct Yellow 44, c, r
.

Direct Yellow 142. C,1, Direct Yellow 12, C,l, Direct Blue 15, C,1,
Direct Blue 25, C, 1, Direct Blue 24
9, C, 1, Direct Red 81. G.1. Direct Rend 8, C1, Dairef I Red 31. C,
Examples include 1, Direct Black 154, (', , ■, Direct Black 17, etc.).

The disperse dyes are C soil Disbo's Yellow 5, C1 ■, Disbo's Yellow 51. C, 1, Disbose Yellow 64, C:, 1. Disbors Red 43. C,
1, Disbose Red 54, C, 1, Disbose Red 135, C0l, Disbose Blue 56, C, 1
, disbose blue 3, C:, T, disbose 8
1st prize is mentioned.

The ballasting pigments used in the present invention include aso-dyes,
Dyes such as azomethine dyes, anthraquinone dyes, naphthoquinone dyes, sterine dyes, phthalo-phthalo dyes, and phthalocyanine dyes (those that are solid or semi-solid at room temperature and become migratory upon heating, and are non-sublimating or non-vaporizing are preferable) .) A dye having at least one ballast group in the mother nucleus and having a melting point of 300°C or less is preferable, and 250
Particularly preferred are those below .

The ballast group of the present invention is a group that is highly soluble in a heat-fusible substance, such as an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylsulfonylamino group, an alkylsulfonyl group, a hydroxylalkyl group, a cyanoalkyl group,
It is a group having an alkyl group or an alkylene group having 6 or more carbon atoms, such as an alkoxycarbonylalkyl group, an alkoxyalkyl group, or an alkylthio group. Especially the number of carbon atoms in the molecule is 6.
A ballast group having at least one of the above alkyl groups is preferred.

At the end of this specification, structural examples of palust dyes used in the present invention are listed, but the present invention is not limited thereto.

Examples of thermoplastic polymer substances contained in the coloring material supply layer include casein, gelatin (including derivative gelatin),
Polyvinyl alcohol, polyvinyl 2-butyral, methyl cellulose, gum arabic, polyvinyl sulfate such as polyethylene terephthalate, polyvinyl formal, polypropylene, polystyrene, polycarbonate, polyvinyl chloride, ethyl cellulose, acetyl cellulose, nylon, polyethylene, phenolic resin, polyacrylonitrile, polysulfone, etc. A thermally stable material is preferred. These may be used alone or in combination.

In the present invention, the image-receiving layer contains a heat-melting substance (low melting point substance) that can dissolve or disperse the colorant when melted. The heat-melting substance refers to a substance that has a melting point in the range of 45°C to 150°C (value measured by Yanagimoto MPJ-2 model), and within this temperature range JIS K253.
1 (195El) is also included. Specifically, vegetable waxes such as carnauba wax, wood wax, auriculie wax, Nispar wax, animal waxes such as beeswax, insect wax, shellac wax, spermaceti wax, paraffin wax, microcrystalline wax, ester wax, oxidized wax, etc. In addition to waxes such as mineral waxes such as petroleum wax, montan wax, osikelite, and ceresin, higher fatty acids such as palmitic acid, stearidiic acid, and margaric acid, and higher alcohols such as eicosanol,
Examples include higher fatty acid esters such as cetyl palmitate and myricyl palmitate, oleylamide, and stearylamide. Particularly preferred are oleylamide,
Examples include carnauba wax and ester wax, and these low melting point compounds may be used alone or in combination of two or more.

The heat-fusible substance used in the colorant rear layer of the present invention is particularly preferably a combination of hard wax and soft wax (one or more of each). Hard wax [25℃ (100g)
Penetration (according to JIS K 2530) is 8
Examples of natural ester waxes such as i-ester wax (Carnapa wax, Montanwa wax), and Hoechst
Wax E, F, KP, KPS, BJ, OP, OM,
Synthetic ester waxes such as X22゜IJ and θ),
・■ Oxidized wax (wax obtained by oxidizing wax such as paraffin wax and microcrystalline wax, NFS-9210, NPS-81 manufactured by Hiki Seiro Co., Ltd.)
15. PETR0NABA@C manufactured by Toyo Petrolite Co., Ltd.
CARDIS 314, etc.), 1) Low molecular weight polystyrene waxes (especially those with molecules fFc3oo to 1000, such as POLYWAX 500 and 655 manufactured by Toyo Petrolite), ■ Acid waxes (Hoech manufactured by Hoechst)
st Wax S and LP, etc.). In addition, as an example of a soft wax [waxes with a penetration degree (according to JIS K 2530) of 8 or higher at 25°C (IQQg)], microcrystalline wax (8 stone microwax 155.180 (manufactured by Nippon Oil Co., Ltd.) is used). ), old-MIG-1080, II-WIG-2
065j old-[-2095, old-MIC-1070,
Old - IC knee 1045. Hl-AIC-2045 (manufactured by Hiki Seirosha), 5TARWAX 100. BE 5Q
UARE175.185. VIGTORY, ULTR
(manufactured by AFLEX (Toyo PE CI), etc.), stearic acid, behenic acid, stearyl alcohol, white wax, beeswax, stearin M dodecyl, stearone, sorbitan monostearate, polyoxyethylene monostearate, or Diacarna. 30 and Diamond Karuna PA30L
(manufactured by Mitsubishi Kasei Corporation). In addition, when such hard wax and soft wax are used in combination, the weight ratio used may be 1:9 to 9:1 (more preferably 2:8 to 8:2).

The heating temperature when heating the heat-sensitive transfer recording medium of the present invention for transfer recording can be determined by taking into account the relationship with the heating time and the melting point of the substance used in the heat-melting image-receiving layer. (25°C) or less, more preferably about 45°C or more.

At least one of the supports of the recording medium and intermediate recording sheet of the present invention has the following thickness. It consists of a support in the X direction. When only one of the supports is made of a thin support, the other may be made of a less thin support as shown below.

[Thinner Support] As the support for the thermal transfer recording medium and/or intermediate recording sheet of the present invention, it is desirable to use a support that has heat-resistant strength, high dimensional stability, and high surface smoothness. As for heat resistance strength,
It requires strength and dimensional stability to maintain the toughness of a support that does not soften or plasticize due to the heating temperature of a heat source such as a thermal head, and the surface smoothness is required to be included in the coloring material supply layer on the support. Sufficient smoothness is desired for non-sublimable colorants to exhibit good transfer rates. The smoothness is 1oose in the smoothness test (JIS P 8119) using a Beck tester.
c or more is better, and if it is 300 sec or more, images with better transfer rate and reproducibility can be obtained. Materials include, for example, paper such as plain paper, synthetic paper, laminated paper, condenser paper, coated paper, or polyethylene.
Resin films such as polyethylene terephthalate, polystyrene, polypropylene, polyester, polyimide, paper-resin film composites, metal sheets such as aluminum foil, etc. are all suitably used. The thickness of the support is 201 Lm or less, especially 2 to 1O# in order to obtain good thermal conductivity.
Preferably it is L11.

[Support that is not thin] As the support for the heat-sensitive transfer recording medium and/or intermediate recording sheet of the present invention, a support that has heat-resistant strength and high smoothness is desirable. The heat-resistant strength and smoothness are the same as those described for the thinner support, and the specific examples of the material are also the same. Other specific examples of the material include ceramics, porcelain, glassware, and fibers such as cloth. The heat-melting image-receiving layer provided on the support may partially penetrate into the support.

A portion may soak in during heating recording.

[Method of retransfer] After applying thermal energy according to the image information to move the non-sublimable colorant from the coloring material supply layer to the heat-melting image receiving layer, the image receiving layer having the transferred intermediate recorded image and the final recording are transferred. By overlapping the sheets and applying thermal energy again, the image is transferred to the final recording sheet (plain paper, glass, metal, resin, rubber, polymer surface, etc.). Retransfer can be performed using an iron, a hot roll, a thermal head, etc., regardless of the image information, or by applying thermal energy to the area that requires retransfer.This transfer principle can be achieved using normal thermal transfer sheet transfer technology. can be used as a reference.

[Effects of the Invention] Since the present invention has the above-described structure and operation, it is possible to solve the technical problems of the present invention described above, and it is possible to obtain so-called solid images with high density and evenly, and to obtain character images that are easy to see. Moreover, since it is highly sensitive, it is possible to save the amount of thermal energy required by a thermal pen or the like, or it is possible to record heat in a short time. In particular, according to the present invention, by using a non-sublimable colorant, the heat-sensitive transfer recording medium used has good raw storage stability, and the recorded image obtained by thermal transfer also has excellent storage stability. Moreover, a recorded image (print) can be obtained on plain paper, and thermal transfer recording can be performed two or more times from the image-receiving layer onto the plain paper.

[Examples] Preferred examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 A liquid containing the colorant and thermoplastic polymer shown in Table 1 below was applied to a 5.81 Lm polyethylene terephthalate film support-F to a dry film thickness of 1. A coloring material supply layer was provided by coating using a wire parser so as to obtain OpLm. On another 5.81 Lm polyethylene terephthalate film support, an image-receiving layer having a dry film thickness of 4.0 pm and consisting of a heat-melting material shown in Table 1 was provided.

Immediately after producing each sample of the thermal transfer recording medium in this manner, the following thermal transfer recording test was conducted. That is, the prepared image-receiving layer and coloring material supply layer are stacked facing each other, and a thermal printer (heating element density: 8 dots) is applied from the support side of the image-receiving layer sheet.
Prototype machine equipped with /■■ thin film type line thermal head. ), the thermal transfer recording test was conducted twice in succession.

The recording conditions are as follows.

Recording conditions Applied force (w/dat) 0.5 Applied pulse period (us) 800 Applied pulse duty (%) 50 Line period (ms) 25 Paper feeding speed (+w/S) 7.7 Platen pressing pressure (Kg) 5 After recording, optical transmission density was measured. Note that Table 1 shows the compositions of the coloring material supply layer and image receiving layer, and Tables 2 and 3 show the results.

Table 1 , H1 to H3 were all set to 0.8.

Colorant A Non-sublimable basic dye Colorant B Eisenspiron Orange 2RH Non-sublimable oil-soluble metal complex dye Colorant C In addition, multiple sheets of each sample were stacked with the coloring material supply layer facing up,
Then, a load (3 g/cm'') was placed on it, and after it was left at 30°C for one month, it was transferred and recorded in the same manner as above.
Also listed in the table.

Table 2 Transmission Density (at 2, OmJ/dat) 2 The image-receiving layer of the one-time transfer was layered on plain paper (Beck smoothness 100 seconds) and transferred with an iron (150°C, 2 seconds), and the optical reflection was The concentration was measured. The results are shown in Table 3.

Table 3 Main reconversion etc. reflection density Example 2 A thermal transfer recording test was conducted in the same manner as in Example 1.

Table 4 shows the compositions of the coloring material supply layer and image receiving layer, and Tables 5 and 6 show the results.

Table 4 Intrinsic plastic polymer substance/colorant (weight ratio) for samples 4 to 7
It was set as 0.8 for all of the above.

Colorant D C.1, Solvent Blue 11? Non-sublimable oil-soluble metal complex dye colorant E c, r, Solvent Yellow 25:l Non-sublimable oil-soluble metal complex dye colorant F Colorant G Sublimable disperse dye Table 5 Transmission density (2, OmJ/dat In this example, the only difference was that the heating direction was performed from the support side of the coloring material supply layer, but the samples of the present invention obtained almost the same good results as the present example. Ta.

As is clear from the above examples, according to the present invention, it has excellent raw storage stability, has little loss of density even in the second printing, and can obtain a transferred image with non-sublimable dye on plain paper. I see that it is possible.

[Ballasted color house stop (1) OH3 (3) C, 8H35-OH-C! H2 1 OH3NHOOH @) 8C2H5CH2CH2NH302CH3 Patent applicant Konishi Roku Photo Industry Co., Ltd. agent Patent attorney Nobuaki Sakaguchi (and one other person) T-continued amendment form) August 28, 1980 Commissioner of the Patent Office Manabu Shiga Tono 1 Case Display of 1981 Patent Application No. 81688 2 Name of the invention Thermal transfer recording method 3 Relationship with the case of the person making the amendment Applicant name (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent
105 6 Number of inventions increased by amendment 7 Specification subject to amendment (detailed description of invention column) 8 Contents of amendment (1) Pages 27 to 29 of the specification will be amended as shown in the attached sheet.

(Example of ballasted pigment) NHOOO1,I-1゜ 0H3N)I OOH

Claims (1)

[Scope of Claims] (1) By stacking the coloring material supply layer of the thermal transfer recording medium and the heat-melting image receiving layer of the intermediate recording sheet facing each other, and applying thermal energy according to the image information to be recorded, The intermediate recording image is transferred to the intermediate recording sheet by melting the thermofusible substance contained in the image-receiving layer and moving the non-sublimable colorant contained in the colorant supply layer into the thermofusible substance of the image-receiving layer. A thermal transfer recording method in which the intermediate recording image is thermally transferred to a final recording sheet. (2) A patent claim characterized in that thermal energy is applied from the support side of the intermediate recording sheet in accordance with the image information to be recorded. The thermal transfer recording method according to claim 1. (3) The method according to claim 1, characterized in that thermal energy is applied from the support side of the thermal transfer recording medium in accordance with the image information to be recorded. Thermal transfer recording method. (4) The thermal transfer recording method according to claim 1, 2 or 3, wherein the final recording sheet is plain paper.