JPH0378077B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the Invention] (Industrial Application Field) The present invention relates to a thermal transfer material. More specifically, the present invention relates to a thermal transfer sheet used for thermal recording, which is provided with an abrasion-resistant and heat-resistant protective layer to prevent the base film from fusing to the thermal head. With the development of thermal heads, thermal recording methods have been incorporated into facsimile machines and printers. This method uses paper called thermosensitive recording paper, which generally has a structure in which a thermosensitive coloring layer in which two components emitted when heated are dispersed is provided on a base material. This paper has drawbacks such as poor storage stability, easy tampering after recording, and poor solvent resistance.Therefore, thermal transfer recording sheets that have improved these drawbacks are known. This is a method in which a heat-melting ink layer is provided on a support, and this is layered with, for example, plain paper, and the ink is transferred from the thermal transfer recording sheet to the plain paper using heat from a thermal head to perform recording. be. According to this method, it is possible to record on plain paper, thereby eliminating the drawbacks of conventional thermal recording methods. (Prior Art) In this recording method, the heat generated from the thermal head passes through the support and melts the thermal transfer ink, thereby transferring the ink onto plain paper.
It is necessary to melt the ink layer but not the support (base film), which is generally a plastic film. However, since it is necessary to increase the amount of heat applied to the thermal head in order to speed up recording, the amount of heat applied to the base film increases, and as a result, the base film is melted. As a result, if the molten support adheres to the thermal head, satisfactory recording will not be possible, and troubles such as damage to the head will occur, making normal recording impossible. Such a phenomenon is generally called a stick phenomenon. Conventionally, in order to improve this sticking phenomenon, it has been known to apply a heat-resistant resin or the like to the lower surface of the base film, as shown in Japanese Patent Publication No. 58-13359 and Japanese Patent Application Laid-open No. 56-187396. is not satisfactory. (Problems to be Solved by the Invention) As a result of intensive research into methods to improve the above-mentioned drawbacks, the present inventors have found that even if the amount of heat applied to the thermal head is increased, the base film does not melt, and furthermore, the heat applied to the ink layer does not melt. We have completed a thermal transfer material that does not impede conduction. [Structure of the Invention] (Means for Solving the Problems) That is, the present invention provides a thermal transfer material in which a heat-melting ink layer is provided on a support (base film), and a titanium alkoxide layer is provided on the back surface of the base film. , titanium chelate, zircon alkoxide,
This is a heat-sensitive transfer material comprising a metal crosslinking agent selected from zircon chelate, zircon soap, or aluminum chelate, and a protective layer of a resin having a hydroxyl group, a carboxyl group, a sulfone group, or an amino group that reacts with the metal crosslinking agent. What is the resin containing a metal crosslinking agent in the present invention (1)
Metal-based cross-linking agents such as organic compounds or chelate compounds of titanium, zirconium, or aluminum, and mixtures thereof; (2) resins having hydroxyl groups, carboxyl groups, sulfonic groups, or amino groups that react with the metal-based cross-linking agents during chemical reaction; (3) ) If necessary, a resin that does not contain such reactive substituents but is compatible with the above resin; Consists of powder. Examples of metal crosslinking agents include (1) titanium alkoxides such as tetra-i-propoxytitanium, tetra-n-butoxytitanium and tetrastearoxytitanium, (2) di-i-propoxy-bis(acetylacetonato) titanate, dihydroxy - β such as bis(lactate) titanate and di-i-propoxy-bis(ethyl acetoacetate) titanate.
-Titanium chelates with diketones, ketoesters, hydroxycarboxylic acids or their esters and salts, ketoalcohols, aminoalcohols, enolic active compounds, etc. as ligands, (3) tri-n-butoxytitanium monostearate and i-propoxy Titanium acylates such as titanium dimethacrylate-i-stearate, (4) tetra-t-butoxyzirconate, tetra-n-propoxyzirconate, tetra(2-methyl)butoxyzirconate and tetra-n-octyloxyzirconate. (5) β-diketones such as zirconium tetraacetylacetonate,
Chelates of keto esters, keto alcohols, amino alcohols and enolic active hydrogen compounds, (6) zircon soaps such as zirconium naphthenate and zirconium stearate, (7) zirconium acetate, (8) aluminum-sec-butyrate, aluminum, Aluminum alkoxides such as isopropylate, (9) enolic active compounds such as aluminum tris(ethylacetoacetate), aluminum mono-acetylacetonate bis(ethylacetoacetate), aluminum oxide octoate, keto alcohols, amino alcohols, hydroxy Carboxylic acids or their esters and salts, aluminum chelates such as β-diketones and ketoesters, ethyl silicate,
Examples include alkyl silicate compounds such as butyl silicate. In addition, the resin that reacts with the crosslinking agent during chemistry is
Resins having reactive groups such as hydroxyl groups, carboxyl groups, and sulfone groups, specifically acrylic resins,
Polyester resin, melamine resin, epoxy resin, ketone resin, rosin resin, alkyd resin,
Phenol resin, silicone resin, cellulose resin such as cellulose acetate butyrate, nitrocellulose, cellulose acetate, fluorocarbon resin such as vinylidene fluoride, polyvinyl alcohol resin, urethane resin, polyacetal resin, polycarbonate resin, polyimide resin, polyvinyl carbazole resin, etc. It is. In addition to the above resins, resins that do not contain reactive groups include rubber resins such as chlorinated rubber and cyclized rubber. Also, if necessary,
Inorganic extender pigments such as silicon oxide, barium sulfate, and calcium carbonate may also be added. The resin layer as described above can be formed by coating a base film by a conventionally known method and drying it. Drying conditions may be normal coating conditions and no special high temperature treatment is required. The metal-based crosslinking agent and the resin are crosslinked through a conventionally known reaction. For example, in the case of tetraalkoxytitanium, it is known that cellulose is crosslinked according to the following reaction formula. As the support used in the present invention, a conventionally known base film can be used. Examples include polyester films (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide films (nylon, etc.), polyolefin films (polypropylene, etc.), cellulose films (triacetate, etc.), polycarbonate films, and the like. Polyester film is most preferred because of its excellent heat resistance, mechanical strength, tensile strength, and tensile stability. The thinner the support, the better the thermal conductivity, but from 3 μm to 3 μm due to strength and ease of applying the ink layer.
50μ is most preferred. Furthermore, conventionally known inks can be used as they are for the ink layer. Examples of such inks include paraffin wax, carnauba wax,
Ink colored with dyes or pigments can be used using waxes such as wood wax and beeswax as a binder. According to the present invention, an abrasion-resistant and heat-resistant protective layer is provided on the back surface of the base film provided with the ink layer. This protective layer has a thickness of about 0.01μ to several μ,
Preferably it is 0.1μ to 5μ. Hereinafter, the present invention will be explained in detail with reference to Examples. Note that "parts" in the examples are "parts by weight." (Example) Example 1 6μ polyester film (base film)
A resin solution with the following composition is applied to the surface using a gravure coater to a dry thickness of approximately 1μ, and on the back side, an ink layer containing carnauba wax as the main component and colored with carbon black is applied using a bar coater. It was applied while heating. The thickness of the ink layer was 3.2μ. On the other hand, a thermal transfer sheet without a protective layer was also prepared in the same manner. Resin solution A Acrylic resin (Hitaroid 2605 Hitachi Chemical Co., Ltd.)
Co., Ltd.) 20 parts Tetra-i-propoxy titanium 5 parts Toluene 22 parts Methyl ethyl ketone 5 parts A printing test was conducted using a thermal head using these two transfer sheets. Printability was observed by changing the energy applied to the thermal head. Transfer sheet with protective layer starts from 1.00mj/dot
Even when the energy was increased to 1.70mj/dot, the printing was not disturbed at all. No fusion of the base film to the thermal head was observed. Furthermore, no melting and damage of the base phenol was observed. On the other hand, with the thermal transfer sheet without a protective layer, printing began to become distorted at 1.2 mj/dot, and at 1.3 mj/dot, the base film fused to the thermal head, and the base film was also damaged and melted. Hereinafter, the following protective layer was formed on the base material in the same manner as in Example 1, and a thermal transfer sheet provided with an ink layer was similarly prepared and compared with a thermal transfer sheet without a protective layer. The printing test was conducted continuously for 10 minutes at constant energy. The energy level can be changed from 1.3 mj/dot by changing the voltage applied to the thermal head and the pulse width.
It went up to 1.7mj/dot. In all of the examples, the thermal transfer material provided with the protective layer was significantly superior to the thermal transfer material provided with no protective layer in terms of printing performance, sticking phenomenon to the thermal head, melting of the base film after printing, and damage state. Resin solution composition of protective layer *Kanhyo resin solution B Polyester resin (Tokuseal 4310-60, manufactured by Tokushima Essential Oil Co., Ltd.) 25 parts Dihydroxybis(lactate) titanate
10 parts Xylene 20 parts Methyl ethyl ketone 45 parts Resin solution C Ketone resin (Hiraku 222, manufactured by Hitachi Chemical Co., Ltd.)
30 parts Nitrocellulose 10 parts Tetol-t-butoxyzirconate 5 parts Toluene 55 parts Resin solution D Phenol resin (Hitanol 271A, manufactured by Hitachi Chemical Co., Ltd.) 40 parts Aluminum-sec-butyrate 1 part Ethyl silicate 5 parts Toluene 54 parts Resin solution E Rosin resin (Bencel KK, manufactured by Arakawa Chemical Co., Ltd.)
10 parts dihydroxybis(lactate) titanate
1 part Tetra-isopropoxy titanate 8 parts Toluene 81 parts Resin solution F Alkyd resin (Phthalkyd D615, manufactured by Hitachi Chemical Co., Ltd.) 30 parts Metal alkoxide (hydrolyzed to ZrO ₂ SiO ₂
Metal alkoxide, manufactured by Nichiita Research Institute Co., Ltd.) 10 parts Toluene 60 parts Resin solution G Melamine resin (Tesmin 250-60, Tokushima essential oil)
(manufactured by Amino Alkyd Co., Ltd.) 10 parts Amino alkyd resin (Amino alkyd resin)
425, manufactured by Tokushima Essential Oil Co., Ltd.) 30 parts Zirconium tetraacetylacetonate
3 parts Toluene 57 parts Resin solution H Polyester polyol (Tesla Tsuk)
UD2256, manufactured by Tokushima Essential Oil Co., Ltd.) 20 parts Butylated melamine resin (Tesmin 251-60,
Tokushima Essential Oil Co., Ltd.) 5 parts Zirconium stearate 1 part Toluene 74 parts Resin solution I Urethane resin (Desmodeur N-75)
8.2 parts Polyol part resin (Hitaloid 3004, manufactured by Hitachi Chemical Co., Ltd.) 60 parts Aluminum tris (ethyl acetoacetate) 1 part Xylene 30.8 parts (Effects of the invention) The thermal transfer material of the present invention increases the amount of heat of the thermal head. Since the base film does not melt and there is almost no heat loss due to the protective layer, clear printing can be obtained even at high printing speeds, making it possible to handle high-speed printing. .

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Claims (1)

[Claims] 1. In a thermal transfer material in which a heat-melting ink layer is provided on a base film, on the back side of the base film,
A metal crosslinking agent selected from titanium alkoxide, titanium chelate, zircon alkoxide, zircon chelate, zircon soap, or aluminum chelate, and a hydroxyl group that reacts with the metal crosslinking agent;
A heat-sensitive transfer material comprising a protective layer of a resin having a carboxyl group, a sulfone group, or an amino group.