JP2655544B2 - Thermal transfer recording material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermal transfer recording material such as a thermal transfer ribbon and a thermal transfer sheet used for a thermal recording device such as a thermal printer.

<Prior Art and Problems to be Solved by the Invention> Generally, the thermal transfer recording material is formed by thermally transferring a heat-fusible ink layer, a heat sublimable ink layer, or the like onto a surface of a support layer made of a resin film, glassine paper, or the like. It is constituted by laminating ink layers having properties. In this thermal transfer recording material, the ink layer is brought into close contact with the surface of a recording medium such as a receiving paper (receiving paper), and the ink is applied from the back side of the support layer by a thermal head or thermal pen of a thermal recording apparatus. When the layer is heated, the ink is transferred to the surface of the recording medium.

In the thermal transfer recording material, the support layer is fused to a thermal head or a thermal pen during thermal transfer.
In order to prevent the so-called "stick", and to improve the lubricity of the thermal transfer recording material conveyed at high speed when contacting with the thermal recording device and the releasability, a back layer containing a lubricant is used as the backing layer of the support layer. Lamination is carried out on the back surface, or the above-mentioned lubricant is contained in the support layer.

As the lubricant, metal soaps such as metal stearate are usually used. For example, aluminum stearate, magnesium stearate, and calcium stearate have poor sticking prevention effect (hereinafter referred to as "stick resistance"). Although zinc stearate has excellent stick resistance, it has problems such as poor lubricity.

Therefore, relatively high melting point, stick resistance, lubricity,
Attempts have been made to use sodium stearate and calcium stearate which have excellent mold release properties.

However, since the thermal transfer recording material is heated to 450 ° C. or more for a very short time (about several ms to several tens of ms) at the time of transfer, the sodium stearate and potassium stearate are thermally decomposed, and Releases ions and potassium ions, thermal head, thermal pen, electrode,
It has been found that a new problem of corroding metals of the thermal recording device, such as lead wires, is caused.

The present invention has been made in view of the above circumstances, and has as its object to provide a thermal transfer recording material that is excellent in stick resistance, lubricity, and releasability, and that does not adversely affect a thermal transfer device. .

<Means for Solving the Problems> In order to solve the above problems, the thermal transfer recording material according to the invention according to claim 1 is a thermal transfer recording material having at least a thermal transferable ink layer on the surface of a support layer. An organic phosphorus compound represented by the following general formula (I) and / or general formula (II) (hereinafter referred to as “specific organic phosphorus compound”) is provided on the back surface of the support layer at a ratio of 0.01 to 15% by weight of a binder resin. The thermal transfer recording material according to claim 2, wherein a back layer dispersed therein is formed, wherein the thermal transfer recording material includes at least a thermal transferable ink layer on the surface of a support layer. The support layer is characterized in that the specific organic phosphorus compound is contained in a ratio of 0.01 to 15% by weight.

(In the above formula, R represents an alkyl group having 8 or more carbon atoms,
M represents zinc, and m represents the same integer as the valency of M) In the thermal transfer recording material having the above-mentioned structure, the specific organic compound represented by the above general formula (I) and / or the general formula (II) as a lubricant is used. Phosphorus compounds have excellent stick resistance, lubricity, and mold release properties, as well as excellent heat resistance, and do not contain alkali metals that corrode metals in the molecule, which adversely affects the thermal transfer device. Nothing.

As the support layer, various materials usually used for the support layer of the thermal transfer recording material can be used, and a preferable material is polyethylene terephthalate (PE).
Examples thereof include polyester films such as T), resin films such as polyimide films, and papers such as glassine paper and capacitor paper.

The thickness of the support layer depends on the material of the support.
It is preferable that the thickness be within a range of from about 10 μm to several tens μm.

As the thermal transfer ink layer laminated on the surface of the support layer, in addition to the hot-melt ink layer and the thermal sublimation ink layer, a solid ink layer corresponding to low-smooth paper, a multi-type ink capable of performing multiple printings And the like.

The thickness of the heat transferable ink layer can be optimally set in the range of thickness depending on the type of the above-described various ink layers.

The heat transferable ink layer is formed on the surface of the support layer by an appropriate method according to the type. For example, the hot-melt ink layer is formed on the surface of the support layer by a coating method such as hot melt coating, solvent coating, or emulsion coating.

In the thermal transfer recording material according to the present invention, the back surface containing the specific organic phosphorus compound is provided on the back surface of the support layer, that is, on the surface of the support layer opposite to the side on which the thermal transfer ink layer is formed. A layer is formed.

As the specific organic phosphorus compound, the compound represented by the general formula (I)
And / or zinc salts of alkyl phosphate diesters represented by the general formula (II). In both the above formulas, the alkyl group represented by R must have 8 or more carbon atoms. If the number of carbon atoms is less than 8, lubricity is insufficient and it is difficult to improve stick resistance and the like.

The specific organophosphorus compound is represented by the general formula (I)
And / or various compounds corresponding to the general formula (II) can be used. In particular, lauryl phosphate (dodecyl phosphate), cetyl phosphate (hexadecyl phosphate), stearyl phosphate (octadecyl phosphate) Acid esters) and zinc salts of phosphates such as tricosyl phosphate.

The specific organophosphorus compound has higher lubricity as the number of carbon atoms in the alkyl group is larger.However, in consideration of the supply amount and price, the number of carbon atoms is preferably 23 or less. Salts of acid esters are most preferably used.

The back layer is formed by dispersing the specific organic phosphorus compound in a binder resin.

The thickness of the resin-dispersed back layer is preferably in the range of 0.01 to 10 μm. If the film thickness is less than 0.01 μm,
If the stick resistance, lubricity, and mold release properties cannot be sufficiently exhibited, and if the thickness exceeds 10 μm, not only will the coating cost increase, but also the back layer will peel off due to friction with the mechanical part of the thermal recording device. It will be easier.

Further, the content ratio of the specific organic phosphorus compound in the back layer needs to be in the range of 0.01 to 15% by weight. If the content is less than 0.01% by weight, the specific organic phosphorus compound necessary for sufficiently exhibiting the stick resistance, lubricity, and releasability during thermal transfer of the thermal transferable ink layer is leached from the back layer. If it exceeds 15% by weight, the specific organic phosphorus compound excessively exudes from the back layer during thermal transfer,
The thermal recording device or the like may be soiled, or scum may easily accumulate on the thermal head.

As the binder resin, silicone resin, epoxy resin,
Melamine resin, phenolic resin, thermosetting resin such as fluororesin; hydroxyethylcellulose, ethylcellulose, methylcellulose, carboxymethylcellulose,
Polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, starch and its derivatives, casein,
Resin materials excellent in stick resistance, which are usually used as a binder resin for the back layer, such as gelatin, shellac, and water-soluble resins such as styrene-maleic anhydride copolymer can be used. Further, the binder resin may contain a conventionally known plasticizer, stabilizer, filler and the like.

The back layer is formed by applying a coating solution containing the above components to the back surface of the support layer by a conventional coating method such as a spray coating method, a roller coating method, or a blade coating method.

In forming the back layer, in order to improve the adhesion to the support layer and to further strengthen the back layer, prior to the application, the surface of the support layer is subjected to a corona discharge treatment or the like. Pretreatment is preferably performed.

In the thermal transfer recording material according to the second aspect of the present invention, the support layer itself contains the above-mentioned specific organic phosphorus compound, and the back layer becomes unnecessary. Excellent mechanical strength.

The content ratio of the specific organic phosphorus compound in the support layer needs to be in the range of 0.01 to 15% by weight. If the content is less than 0.01% by weight, the specific organic phosphorus compound necessary for sufficiently exhibiting the stick resistance, lubricity, and releasability during thermal transfer of the thermal transferable ink layer is leached from the back layer. If it exceeds 15% by weight,
The specific organophosphorus compound excessively oozes out of the back layer, and contaminates the thermal recording device or the like, and scum easily accumulates on the thermal head.

To produce a support layer containing a specific organic phosphorus compound, for example, when the support layer is a resin film,
When producing a film in various conventionally known film production methods, it is preferable to mix a specific organic phosphorus compound in the raw material resin, when the support layer is paper,
A method of impregnating the paper after papermaking with a specific organic phosphorus compound is preferred.

<Example> Hereinafter, the present invention will be described based on examples and comparative examples.

Example 1 13.5 parts by weight of zinc stearyl phosphate (a mixture of diester and monoester in a molar ratio of 1: 2)
Polyvinyl alcohol (Kuraray Co., trade name PVA-110)
A coating liquid for a back layer composed of 99.0 parts by weight and 150.0 parts by weight of water was prepared, and this coating liquid was applied to the surface of a PET film having a thickness of 4 μm by a roller coating method, and was then dried and solidified to a thickness of about 1 μm. Back layer was formed. The content ratio of the stearyl phosphate zinc salt in the formed back layer was 12% by weight.

Next, a hot-melt ink layer comprising 20.0 parts by weight of carbon black as a pigment, 60.0 parts by weight of carnauba wax as a binder, 10.0 parts by weight of stearic acid as a softener, and 10.0 parts by weight of additives such as a stabilizer. The composition was melt-coated using a hot-melt coater and cooled to form a hot-melt ink layer having a thickness of about 1 μm.

Then, the PET film was cut into a width of 6.35 mm to produce a thermal transfer ribbon.

(Comparative Example 1) A thermal transfer ribbon was produced in the same manner as in Example 1 except that potassium stearate (13.5 parts by weight) was used instead of stearyl phosphate zinc salt (13.5 parts by weight). The content ratio of potassium stearate in the back layer was 12% by weight.

(Comparative Example 2) A thermal transfer ribbon was prepared in the same manner as in Example 1 except that the stearyl phosphate zinc salt was not added to the back layer coating solution.

(Practical test) The thermal transfer ribbons produced in Example 1 and Comparative Examples 1 and 2 were loaded into a thermal printer to perform continuous printing, and the presence or absence of a stick or the like when printing a total of 30 km of ribbon was observed. However, in the thermal transfer ribbon of Comparative Example 2 which does not contain a lubricant, defective ribbon feeding in the stick and other mechanical parts frequently occurred. However, in the thermal transfer ribbon of Example 1 and Comparative Example 1, both defective stick and ribbon feeding occurred. Did not.

In addition, when the thermal printer was inspected after printing for 30 km of the thermal transfer ribbon, the thermal printer using the thermal transfer ribbon of Comparative Example 1 showed a thermal head made of titanium nitride and electrodes made of tin disposed around the thermal head. Corrosion was observed on aluminum lead wires and the like, but no corrosion was observed on the thermal printer using the thermal transfer ribbon of Example 1.

From the above, it was found that the thermal transfer ribbon of Example 1 was excellent in stick resistance, lubricity and releasability, and did not adversely affect the thermal transfer device.

<Effect of the Invention> The thermal transfer recording material according to the present invention is configured as described above and uses a specific organic phosphorus compound as a lubricant, so that it has excellent stick resistance, lubricity, and releasability, and
This has no adverse effect on the thermal transfer device.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Tsujimoto 5-1 Ebisshima-cho, Sakai City, Osaka Prefecture Inside Sakai Chemical Industry Co., Ltd. (72) Inventor Yoshio Naruki 5-1 Ebisshima-cho, Sakai City, Osaka Sakai Chemical (72) Inventor Noriko Yamazaki 5-11, Ebisshima-cho, Sakai City, Osaka Sakai Chemical Industry Co., Ltd. (72) Inventor Chie Kajima 5-1-1, Ebisshima-cho, Sakai City, Osaka Sakai Chemical (56) References JP-A-61-118291 (JP, A) JP-A-61-14992 (JP, A) JP-A-62-56193 (JP, A) JP-A-62-95289 (JP, A A)

Claims (2)

(57) [Claims] 1. A thermal transfer recording material comprising at least a thermal transferable ink layer on the surface of a support layer, wherein the back surface of the support layer has the following general formula (I) and / or general formula (II):
A thermal transfer recording material comprising a back layer in which an organic phosphorus compound represented by the formula (1) is dispersed in a binder resin at a ratio of 0.01 to 15% by weight. (In the above formula, R represents an alkyl group having 8 or more carbon atoms,
M represents zinc, and m represents the same integer as the valence of M) 2. A thermal transfer recording material comprising at least a thermal transferable ink layer on the surface of a support layer, wherein the support layer is an organic phosphorus compound represented by the following general formula (I) and / or general formula (II): Is a thermal transfer recording material containing 0.01 to 15% by weight. (In the above formula, R represents an alkyl group having 8 or more carbon atoms,
M represents zinc, and m represents the same integer as the valence of M)