JPS59201895A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To enable to express gradation on an ordinary paper and obtain an image with high density, by setting the solubility of a colorant in a heat-fusible substance to be higher than that in a binder, in a thermal transfer recording medium comprising a colorant layer and a heat-fusible transfer layer. CONSTITUTION:A colorant layer consisting of 1-90% of a colorant, 10-70% of a heat-nonfusible binder and 0-70% of additives is provided on a base such as a paper or a resin film high in heat resistance and smoothness in a thickness of 0.5-20mum, and then a transfer layer consisting of 50-100% of a heat-fusible substance and 0-50% of additives is provided thereon. Any of various known dyes, color forming substances or the like may be used as the colorant, and the binder and the heat-fusible substance is so selected that the solubility of the colorant in the heat-fusible substance is higher than the solubility of the colorant in the binder. Concretely, the binder may be polyvinyl butyral, polyvinyl chloride or the like, while the heat-fusible substance may be a wax, a higher fatty acid ester or the like.

Description

[Detailed description of the invention] [Branch technology field] The present invention is capable of expressing gradations on plain paper, cannot be tampered with,
Moreover, the transfer recording surface Gg has a sufficiently high density of 13';
All good! ↑Regarding a heat-sensitive transfer recording medium that can be used for printing.

[Ctit technology] [lγ-Later, an image can be transferred and formed on plain paper using a thermal printer, thermal facsimile, etc.
・)、? , 'fi, transfer'qh Self-recording media are those in which a heat-melting substance containing pigment or sublimation dye is melted, sublimated, or volatilized on the transfer recording medium by heating to form an image. It has been known. There have also been reports of materials in which a color forming agent and a color developer are added to a heat-melting material to develop and transfer color when heated. However, when using a sublimable dye, the dye placement of the transferred image changes from time to time, not only before the era but also after recording due to the sublimation property of the dye.
Because of its high potency, it had the disadvantage of poor storage stability. The method of transferring by heating a heat-melting substance containing pigments, etc. has superior storage stability, but it also has the advantage of improving the optical reflection density of the transferred image based on changes in the amount of image-forming substance per unit area of transfer. The essential drawback is that it is not possible to express the entire gradation by changing it. JP-A-56-1.20393
Thermal transfer recording media containing color formers, color developers, etc. described in However, it has the disadvantages that it easily develops color due to pressure, etc., and has poor storage stability.

Akina Kika et al. investigated a thermal transfer recording medium capable of expressing gradation by overcoming the above-mentioned drawbacks, and as a result published a patent application in 1751-1985.
No. 33 and No. 57-218336, it was reported that this can be achieved by separately providing a dye layer and a transfer window on a support.However, even with these thermal transfer recording media, the transfer recording image The maximum concentration was still not always sufficient.

[Purpose of Tsutomachi]

The present invention has been made to eliminate the above-mentioned drawbacks, and its first object is to provide a phosphorescent transfer recording medium that can form a sufficiently high maximum density of a double-sided image on plain paper or the like. That's true.

Akira Sotoya's second objective is to provide a thermal transfer recording medium that can obtain an even increase in transferred recorded images.

The third purpose of the invention is to create a product that can control the density of the transferred recorded image by changing the heating temperature and produce a transferred recorded stone image with rich gradation reproduction that is impossible to make. The objective is to provide a daily photographic recording medium.

A fourth object of the present invention is to provide a thermal transfer recording medium that has good storage stability and does not generate unnecessary transferred images due to pressure or the like before thermal recording.

A fifth object of the present invention is to provide a heat-sensitive transfer recording medium with high sensitivity during transfer recording. In a thermal transfer recording medium having a colorant layer containing a binder and a heat-fusible transfer layer containing a heat-fusible substance, the solubility of the colorant in the heat-fusible substance is higher than the solubility of the colorant in the binder. The gist is that the binder and the heat-fusible substance are selected so that

The present invention will be explained in detail below.

[Colorant]

The nine color agent used in the colorant layer of the present invention is a substance that can be dissolved or dispersed in the heat-fusible substance of the transfer layer during heating recording, and is therefore a material that can be used quickly. The material may be a material that absorbs light at visible light wavelengths (400 to 800 nn) or a material that forms a material that absorbs light in the visible light range.

Synthetic pigments called dyes and pigments, which are generally collectively referred to as "white pigments" and are suitable for heat-sensitive transfer recording media, natural pigments called animal dyes or plant pigments, and the like are used. Specifically, various pigments known in the drawing industry (e.g., nidomiso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine color pigments, triphenylmethane dyes, xanthine dyes, acridine dyes, quinoline pigments, methine-polymethine slings) , thiazole dyes, indamine dyes, indophenol dyes, Asian dyes, oxazine color complexes, thiazine dyes, sulfur dyes, aminoketone dyes, ochinctone dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, etc.); dye,
In particular, color-forming substances that are colorless or light-colored (for example, triarylmethane compounds, nphenylmethane compounds, xanthine compounds, thiazine thread compounds, spiro compounds, etc.).

) and acidic substances that cause color development (e.g. phenol-visitors, aromatic carboxylic acids, etc.): sublimable (including those that melt or vaporize with dissolution) used for mordant dyeing; (For example, azo dyes, anthraquinone dyes, nitrodiphenylamine dyes, etc.); Substances that are not dyes but have light absorption in the visible light range (400 to 800 nm) and have melting points in the range of about 45 to 120 degrees Celsius (for example, are azobenzene derivatives, nitrobenzene derivatives, thiophenol derivatives, aniline conductors, etc.).

Among these, specific examples of those that are easy to handle in the market are as follows. That is, the yellow pigments include Kayalon Polyester Light Yellow 5G-S (Nippon Kayaku), Oil Yellow-S-7 (white clay), and Eisensviron GRH.
Special (Hodogaya), Sumiplast Yellow F5G (
Resident), Eisensbiron Yellow GRH (Hodogaya),
Hansa Yellow G (3), Taldrazine Lake, etc. are preferably used. Red dyes include Diaceritone Fast Trend R (Mitsubishi Kasei), Thai Anisox Brilliant Trend BS-E (Mitsubishi Kasei), and Sumiplus Trend F.
B (Shinkata), Sumiplast Tread HFG (Shinkata), Kayalon Polyester Pink RCL-E (Nikki Kayaku), Eisen Subiron Renodo GEH Special (Hodogaya), Brilliant Carmine FB-Pure, Brilliant Carmine 6B (Yamauchi dye), Alizarin Lake, etc. are suitably used. As the blue pigment, Diaceriton Fast Brilliant Dobe/1. -R (Mitsubishi Kasei), Thai Anisox Blue EB-E (Sani Kasei), Punoyalon Polyester Blue B-3F Conc (Japanese Mulberry), Steer "Last Blue 3R1 Mitomo), Sumifer Last Blue G, Cerulean Blue, Sumikabu)) Shito/Anin Blue GN
-0 (Shikata), phthalocyanine fruit, etc. are included in the Q-Rose commercial. As the black ink, carbon blank, oil blank, etc. can be used. Particularly clever ones are Sumifuru Last Yellow F5G and Sumipsyst Red FB.

Sumi Blast Blue 3R is mentioned.

Ci',, :s Nagisa cut] As the %'i *'l that can be found in the uninvented eyebrow ρ removal layer, hydrophilic 7i' is selected from among the hydrophilic conjugate 7i' and hydrophobic disinfectants, etc. , the colorant may be selected depending on the seed stone of the coloring agent that is required per month for the present invention.
It did not melt even after heating for 5 seconds. ) The heat-melting binder used in the present invention, which is preferably a madder molecular compound or a natural substance, is composed of polyvinyl chloride, polyvinyl acetate, polyvinyl fluoride, polyvinyl butyral, polyvinyl butyral, polyvinyl chloride, polyvinyl acetate, polyvinyl fluoride, polyvinyl butyral, Vinyl resins such as vinylidene chloride, polyvinylidene, polyvinyl alcohol, vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl chloride IJden copolymer; acrylic resins such as polyvinylidene acid ester, polymethacrylic acid ester, etc. Resins; resins such as ethyl cellulose and cellulose; other polymers such as polystyrene, d41J ethylene, polyethylene/vinyl acetate copolymer, polyamide, ABS resin, gelatin, gum arabic, etc. KotL
Our house, polyvinyl butyral, moon? IJ salt vinyl, polyvinyl chloride/vinyl acetate copolymer, and vinyl alcohol blue are preferably used in injections.

[Hot-fusible monolithic substance] The heat-fusible substance used in the R1 fusible transfer layer of Kikkore IJ is such that the solubility of the colorant in the substance is greater than the solubility of the colorant in the binder of the colorant layer. It is selected from materials that are thick and strong. That is, the solubility compound X is selected such that when
C is determined.

Here, molten degree of h color ill is 6 degrees as follows.
11].

1. I) 11 g of powder (fry the meltable material and binder at 140' CT and 9 times a day, while stirring, add a certain amount here) 1 color Qi j1 to 1
j11'i next time 5 power 11. Let the weight (measured in Durham) of the VC force addition J]-Tanoi1 color cutter (measured in Durham) be J + i + i' until the point when Numakisai 11 can no longer be completely melted.

Uninvented iFJ,,'L melt#,i□! Among the low melting point substances that can be used in the transfer layer to melt or disperse the heat when melting the bath, It is advisable to select one that satisfies the above solubility ratio.

[Example of heat-melting substance]

Specific examples include plant waxes such as carnauba wax, tree wax, auriculie wax, and nispar wax, animal waxes such as beeswax, insect wax, selan wax, and whale wax, paraffin wax, microcrystalline wax, ester wax, Petroleum wax such as oxidized wax, montane wax,
In addition to waxes such as mineral waxes such as osikerite and selenium; higher fatty acids such as valmitic acid, stearic acid, margaric acid, and behenic acid; Higher alcohols such as sil alcohol and eicosanol; cetyl rumitate,
Higher fatty acid esters such as myricyl valmitate, cecyl stearate, myricyl stearate; amides such as acetamide, propionic acid amide, valmitic acid amide, stearic acid amide, amide wax; ester gum, ρ zine maleate resin, rosin phenolic resin ,
Rosin derivatives such as hydrogenated rosin; polymeric compounds with a softening point of 50 to 120°C such as phenol resins, terbene resins, ncropentadiene resins, and aromatic resins; thread polyamines such as svaloamine, behenylamine, and valmitine amyl; polyethylene Examples include polyethylene oxide such as Glycol 4000 and polyethylene glycol 6000, which may be used alone or in combination. Among these, higher fumitates such as valmitic acid amide, stearic acid amide, oleic acid amide, and amitowasox, and higher fatty acids such as polyethylene glycol, stearic acid, and valmitic acid are preferable.

〔Additive〕

Various additives may be added to the colorant layer.

For example, 0.01 to 200 μm of heat-melting material, carbon blank, etc., which can also be used in the heat-melting transfer layer.
Fine particle size powder, oils such as olive oil, silicone oil, etc. can be added. However, when a heat-fusible substance is used, it is necessary that the colorant solubility of the components other than the dye in the hazardous agent layer be lower than that of the heat-fusible substance in the transfer layer. This colorant solubility ratio X is also desirably selected so that X≧2, particularly X≧5.

Among the above-mentioned heat-fusible substances, preferred ones for use as heat-fusible substances that can be added to the colorant layer include waxes such as vegetable waxes, animal waxes, petroleum waxes, and mineral waxes, and rosin derivatives.

〔Additive〕

The transfer layer of the present invention may contain various additives.

For example, adding a polymer substance as a thickener, or if the coloring agent contained in the coloring agent layer is a coloring agent, adding a substance (coloring agent) that reacts with the coloring agent to form a pigment as an additive. On the other hand, when the coloring agent in the coloring agent layer is a coloring agent, a coloring agent that reacts with the coloring agent to form a pigment may be added as an additive.

Any layer constituting the thermal transfer recording medium of the present invention may contain appropriate additives, such as antioxidants, ultraviolet absorbers, color tone conditioning agents, etc., in one or more layers. may be included.

The thermal transfer recording medium of the present invention may be provided with a known subbing layer, overcoat layer, etc. Moreover, an intermediate layer may be coated as necessary.

[Support]

As the support for the thermal transfer recording medium of the present invention, it is desirable that the support has heat-resistant strength and smoothness.

Heat resistance strength requires strength to maintain the toughness of the support without becoming soft or plasticized due to the heating temperature of a heat source such as a thermal head, and smoothness requires that the transfer layer on the support has good transfer properties. Sufficient smoothness is desired to indicate the ratio.

The flatness of steel is determined by the flatness test using a Beck tester (JIS P
8119), preferably 100 seconds or more, and 300 seconds or more.
When the transfer rate is sec or more, images with better transfer rate and reproducibility can be obtained. Examples of the material include papers such as plain paper, synthetic paper, laminated paper, coated paper, resin films such as polyethylene, polystyrene, polypropylene, and polyimide, paper-resin film substrates, and metal sheets such as aluminum foil. All of these are preferably used. The thickness of the support is usually about 6 mm for good thermal conductivity.
It is preferably 0 μm or less, particularly 3 to 40 μm. [Example of colorant layer composition] The composition of the colorant layer in the present invention is not limited, and generally the total composition is 100% (heavy percentage, the same applies hereinafter). In contrast, the proportions are 1 to 90% of the colorant, 10 to 70% of the heat-insoluble binder, and 0 to 70% of the additive. In addition, thermal non-fusible bond cutting is 7
If it exceeds 0%, the transfer efficiency decreases, which is not preferable.

The thickness of this colorant layer is not limited and is generally 0.5
The thickness is about 20 μm, preferably about 0.5 to 10 μm, particularly preferably about 0.5 to 5 μm.

[Transfer layer composition example]

The composition of the transfer layer in the present invention is not limited, and generally 50 to 100% of the heat-melting substance is added to 100% of the total acid content.
%, the proportion of the additive ranges from 0 to 50.

The thickness of such a transfer layer is not limited, but is generally 15μ.
m or less, preferably 0.5 to 5 μm. .

[Example of creating Q media]

Misfire 1"j]'s 4'・field"・,-"ih已ijJ The medium is made as follows)7)',-j-re (good for f2.

[4i1chi, Kifumei's L)'rk''h rZ: Sha M
+26. The g medium can be formed by coating a support with 0 (-1 less) 1, at least a colored 7jlJ layer and a transfer layer of each [Ii and F]. To apply the ice-shaving layer, fl
Is it colored in a solution containing the eyebrow shaver? 111);
1 or the dispersed liquid, Sebuko is Ni'1 without all the solvent J11? Heat and melt the mixture, add a coloring agent for 4 or 1 minute to make a liquid, and apply this liquid to a wire bar, brush, caulk, etc. (b) By applying Cp cloth on a support using a one-layer machine: r-if-<) can be obtained. At this time, the sentence J\T body "2 〃-1 (41, 1λL with deleting I 7i
It is also possible to apply a thinning layer on the first layer to make it good.

()CIi'C, this ;h village? When applying a heat-melting transfer layer on top of the il1 layer, it is commonly known as ζ1ri1 (state of heat 1?
, F AJ! Applying sexual substances directly or visually inspecting them in a high-grade medium (fF medium) This can be done by applying using a device.

[Recording method] One method of recording using the thermal transfer recording medium of the present invention is to apply a coloring agent layer on the support using a device that generates heat such as a thermal head, a thermal vane, or an iron. The heating is performed from the non-supporting side (211), that is, the support side, and as a heat source, a laser, a xenon lamp, etc. may also be used. Incidentally, the heating may be performed from the sheet support 111υ made of plain paper or the like.During this recording, the recording medium of the present invention and the 414 nail sheet made of plain paper or the like are overlapped.

In Kitsuhemei, the colorant moves from the colorant layer to the heat-fusible transfer layer due to the phenomenon of diffusion and elution in response to heating with thermal bene and heating time, but during this heating recording, the transfer layer The heat-melting substance contained in the liquid melts and dissolves or disperses the liquid. At this time, the amount of colorant bath 9.1 times is regulated as in the present invention, '? f6flr'j-Iif, no6selfi"l
': 1lIIIi': j Ka I 1 child power, ru. The transfer layer is from tb! Daito no Ki Q1! If you transfer it to a sheet and return it in a warm box of at least g7, it will become a solid or a semi-hard solid.

The heating temperature when applying thermal energy to the transfer recording medium in accordance with the information to be recorded on the transfer recording medium is determined by the relationship between the applied temperature and the time. The relationship, the melting point of the I'l'A melting substance used in the thermal transfer H1, the melting point of the colorant, 441 (f'fi 勺), determined by However, it is desirable that the Mu temperature is higher than that, and practically, it is desirable that the temperature be higher than 45°C.

[Effect of utterance [11]] Since the funeral invention FJ' lki nobutsu and the effect are the same, the above-mentioned Honjo, [↓! 1, 8 - The second and third objectives can be achieved, and high concentration of ε7 on plain paper can be achieved. ii!
ii) 1q is obtained, and a multi-order δl-J image can be obtained.1. Since it has a high E intensity, it is possible to save labor on thermal energy using thermal vane, etc., and it is also possible to record heating in a short time, and has good heat resistance.

[it, q force'i+i 4511] 71 below! The fruit of "Sr, I↓I"! Examples 3 and 11 are given below, but the present invention is not limited to this example.
Coating liquid 1 was obtained by adding 0.3 g of nt Blue 11.

On the other hand, add 8 g of Aramide O (manufactured by Lion) to the 5-layer S-
40 (Surfactant 1, manufactured by Nippon Oil & Fats Co., Ltd.) was added to an aqueous solution of lO- and dispersed in a ball mill to obtain Blood 2.

Apply the coating liquid I to the volume 1/nterephthalate film of &alEi+LOμm using a wire bar,
A colorant layer having a thickness of 2.9 μm after drying was provided.

Next, while keeping the temperature at 50° C., coating liquid 2 was spread on the coating agent layer with a wire bar to form a transfer layer having a thickness of 2.3 μm after drying. Obtained.

In the past, various heat-melting substances were substituted for Aramide O in the heat-sensitive transfer recording medium as shown in Table 1 below.
I1,1 ZoC- On the other hand, LLI! 'J11' was used instead of the alumite 0 of the recording medium 11αl as described above. I installed and obtained a transfer recording medium N [L5]. The coated surfaces of the Kr thermal transfer recording media were placed in close contact with each other on separate sheets of JIlj paper, and heated at 60°C.
0℃, 120℃ for 0.5 seconds at each temperature) 'When heated with an iron, the transfer calligraphy of 5\ color with no blemishes, 2''
・I was able to get the image Z on plain paper ~ these %E
'4'i' 1tj sweat: Optical reflection of the image 3 degrees with reflection density G1- (Konishi Rokusha-, +, manufactured by JW, Inc.) (
I made it a rule.

As is clear from Including 1, the thermal transfer recorder of the present invention (,?,
Comparison 211 when using ri1to (++llt~4)
As 7J<shita A・；north, ゛su1−:fuJ′1゜self(
, i, than when using the medium (t115), it is possible to make the transfer recording surface f', ``'' with a lower optical reflection density by 1](gamma, l11, !-i1) than when using the medium (t115). .It was higher when the maximum optical reflection was 6 degrees and 61 brightness.

Actual): lj%'12 2 g of holivinyl phthyral (softening A 120°C) and 2 g of Barafini/wax'f! c Methyl ethyl ketone 40
v:e K ('fj jU't C, I 5
3g of Olvent Blue 11 was added and 3tf+ was added to the f' row 15.

- Dissolve 8 g of aramide O in 5-40 5-cycle water Ia
Add 65% to torg and disperse with a whole mill? Ili 'iF'< 4 4C1 I'm deaf.

1i"'+ I+;-! Orchid blood 3 was applied to a 111 μm Holiegrain terephthalate film using a wire bar.
73 pieces of cloth, dried 1'□, and the thickness of the cloth is 3. Oti
M's Kumuiro△ri theory is 1st r no/ko.

Next, apply 2 q of RP cloth (14 with a wire bar) on the D76 colorant layer from 1〈ξh to 50"C.
♀-photograph R' with a print of 2.1 μm after drying, and the crotch are heat-sensitive 1st photographs of unhunted J (1, /lI, i4y IQ
6k (!+ ”-.

To-11-, l'l, call'+-11'-'・Hakuyu;
I;l, 8mm R-59''l photo shoot, 10 hours of paraffin wax instead of Amade O.
L Oshi 2nd place; Suyoku (...,, etc.) 1st wave 7~+1q of Table 2 L O's Ell-, heat transfer T7th place, and
'(1 blue body is also 11 noha ratio %:, as <young" earth mu is evil 1 heat transfer 1 life J, aphrodisiac Rn 6 armoid O
A colorant layer and a transfer layer were applied in the same manner as described above, except that paraffin wax was used instead of p, to obtain a thermal transfer recording medium NQII.

Further, by using the same method, a heat-sensitive transfer recording medium Ugly L2 was obtained using carnauba wax for the colorant layer and paraffin wax for the transfer layer.

The thread fabric surfaces of these thermal transfer recording media were brought into close contact with each other on separate plain paper surfaces, and heated at 60°C, 80°C, and 100°C.
℃, 120℃(r)'4r Temperature: 0.5
When heated with an iron, an even blue transfer image is created on plain paper? I was able to do 4 things. These transcripts ii! The optical reflection density of the u image was measured at the hth reflection.

As is clear from Table 2, when using the thermal transfer recording media Nα6 to tau lO of the uninvented invention, when using the comparative thermal transfer recording media N[LLL and 12, It is possible to see a transferred recorded image with a high optical reflection density. -i7'' The maximum value of optical reflection density was also higher in the case of the present invention.

Claims (1)

[Claims] In a thermal transfer recording medium having a colorant layer containing a colorant and a binder and a heat-fusible transfer layer containing a heat-fusible substance on a support, the solubility of the colorant in the binder is Also, 81 heat melt r1/cleaning agent solution Ji for stretchable materials
A thermal transfer recording medium in which the binder and the heat-melting substance are selected so that the irradiance is higher.