JP2584517B2 - Thermal transfer material - 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, by providing a protective layer on a thermal transfer sheet used for thermal recording,
The present invention relates to a heat-sensitive transfer material having improved abrasion resistance and heat resistance, and improved transferability of a silicone compound used for imparting lubricity to a hot-melt ink surface and improved adhesion to a film substrate.

(Prior Art) With the development of office automation, thermal transfer recording systems have been adopted in various terminal devices such as facsimile machines and printers. In this recording method, a hot-melt transfer material coated with hot-melt ink or a transfer material coated with a thermo-sublimable dye are superimposed on recording paper, such as plain paper, and transferred by heating from a thermal head. The recording is performed by transferring ink or the like from the material to the recording paper. There are known ones that use recording needles instead of a thermal head (for example, JP-A-58-220793) and those that use electrode terminals (for example, JP-A-55-17521).

In the recording method using a thermal head, the heat generated from the thermal head melts the thermal transfer ink through the support and transfers the ink to plain paper, etc., so the ink layer melts, but the support such as a plastic film is used. (Base film) must not melt. However, to speed up the recording,
The amount of heat and pressure applied to the base film is significantly increased by increasing the amount of heat applied to the thermal head, increasing the applied pressure, and making the thermal head more protruding in order to record on recording paper with a rough surface. And eventually the base film is damaged. As a result, if the damaged support adheres to the thermal head, satisfactory recording cannot be performed, and troubles such as breakage of the head occur, and normal recording cannot be performed. Such a phenomenon is generally called a stick phenomenon.

In the method using recording needles and electrode terminals instead of the thermal head, remarkable heat is not applied to the base film unlike the thermal head, but a remarkable impact is applied by a discharge or a current flowing phenomenon, so that there is a possibility of breakage.

To improve this stick phenomenon,
As disclosed in JP-A-13359 and JP-A-58-187396, a method of applying a heat-resistant resin or the like to the lower surface of a base film is disclosed in JP-A-56-155794, JP-A-59-196291 and JP-A-59-196291. Japanese Unexamined Patent Publication No. 57-74195 discloses a method in which a lubricant or a surfactant is mixed with a photocurable resin and coating is performed, but the method is not satisfactory. When recording for a long period of time, lubricant or surfactant adheres to the thermal head, and when the thermal transfer material is stored under high temperature and high humidity, the lubricant or surfactant is transferred to the ink layer, resulting in normal recording. Troubles such as not being able to do.

(Problems to be Solved by the Invention) The present inventors have conducted intensive studies on a method for improving the above-mentioned drawbacks. As a result, there was no occurrence of trouble that the base film was damaged during recording, and foreign matter remained on the thermal head even during long-term recording. A heat-sensitive transfer material that does not adhere, withstands storage under high temperature and high humidity, and that does not hinder the thermal conductivity of the ink layer by the stick prevention layer has been completed.

[Configuration of the invention]

(Means for Solving the Problems) That is, the present invention relates to a heat-sensitive transfer material having a heat-transferable ink layer provided on a support (film substrate), wherein the heat-sensitive transfer material has (A) a reactive group on the back surface of the film substrate. A heat-sensitive transfer material provided with a cured resin film containing a resin, (B) a silicone compound having a functional group capable of reacting with the reactive group (A), and (C) an aziridine-based cross-linking agent.

Further, a resin having a reactive group having an active hydrogen such as a carboxyl group, an amino group or a hydroxyl group or a resin having a reactive group such as an epoxy group and an isocyanate group (A), a silicone compound having a functional group capable of reacting with the reactive group The cured film obtained by (B) and the aziridine-based cross-linking agent (C) serves as a stick prevention layer.

Examples of the resin (A) of the present invention include resins having a reactive group such as a carboxyl group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, and a mercapto group. Examples of the resin include an acrylic resin, a polyester resin, a melamine resin, an epoxy resin, and a ketone. Resins, rosin resins, maleic acid resins, fumaric acid resins, alkyd resins, phenolic resins, urethane resins, cellulose resins such as cellulose acetate butyrate, nitrocellulose, cellulose acetate, fluorine resins, polyvinyl alcohol resins, polyacetal resins,
Examples include a polycarbonate resin, a polyimide resin, and a polyvinyl carbazole resin.

Examples of the silicone compound (B) of the present invention include functional groups at one end, both ends, and side chains of amino-modified silicone compounds, epoxy-modified silicone compounds, hydroxy-modified silicone compounds, mercapto-modified silicone compounds, and carboxyl-modified silicone compounds. There are silicone compounds that have

As the aziridine-based crosslinking agent in the present invention, tri-
1-aziridinylphosphine oxide, N, N-hexamethylene-1,6-bis (1-aziridinecarboxamide),
N, N-diphenylmethane-4,4-bis (1-aziridinecarboxamide), trimethylolpropane-tri-beta-aziridinylpropionate, tetramethylolmethane-tri-beta-aziridinylpropionate,
N, N-toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-
Methylaziridine) phosphine and mermethylolpropane-tri-beta- (2-methylaziridine) propionate.

The protective layer of the present invention is obtained by applying a coating liquid containing the resin (A), the silicone compound (B) and the aziridine-based cross-linking agent (C) on a support, and heating at room temperature if necessary. The curing reaction proceeds to obtain a cured film.

The protective layer has a thickness of about 0.01 μm to several μm, preferably
1 μ to 5 μ.

As the support used in the present invention, a conventionally known base film can be used. For example, there are 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 films are most preferred because of their excellent heat resistance, mechanical strength, tensile strength, tensile stability and the like. The thinner the support, the better the thermal conductivity. However, from the viewpoint of the strength and the ease of coating the ink layer, the thickness is most preferably 3 μm to 50 μm.

In the ink layer, a conventionally known ink can be used as it is. As an example of such an ink, an ink colored with a dye or pigment using waxes such as paraffin wax, carnauba wax, wood wax and beeswax as a binder agent can be used.

 Hereinafter, the present invention will be described in detail with reference to examples.

 In the examples, "parts" is "parts by weight".

(Example) Example 1 A 6 μm polyester film (base film) was coated with a coating solution A having the following composition by a gravure coater to a dry film thickness of 0.
Apply to a thickness of 2 μm, heat and dry at 60 ° C for 30 seconds, and apply a thermal transfer ink consisting of 30 parts of carnauba wax, 30 parts of paraffin wax, 20 parts of carbon black, and 20 parts of dispersant on the back of the coating. It was applied with a hot melt coater so as to have a thickness of μm. Then, it was aged at 40 ° C for one week.

Half of the solution 1 having the following composition was charged into a flask, and the remaining half was reacted dropwise under reflux.

[Solution 1: Resin having a reactive group] Methyl methacrylate 20 parts Acrylic acid 8 parts 2-hydroxyethyl methacrylate 2 parts Methyl ethyl ketone 100 parts Azobisisobutyronitrile 3 parts [Coating liquid A] The above solution 1 9 parts X- 22-3701E (Shin-Etsu Chemical Co., Ltd., carboxyl group-containing silicone compound) 1.5 parts PZ-33 (Nippon Shokubai Chemical Co., Ltd. trifunctional aziridine-based crosslinking agent) 0.5 parts Toluene 40 parts Methyl ethyl ketone 44 parts Example 2 HDU ( Dissolve 1 part of trifunctional aziridine-based crosslinking agent (manufactured by Nippon Shokubai Chemical Co., Ltd.) with toluene to a solid content of 10%.
The flask was charged in advance, and then a solution of X-22-3701E (15 parts) in toluene having a solid content of 10% was dropped and stirred at 90 ° C. After completion of the reaction, the mixture was reacted at 100 ° C. for 1 hour and then under reflux for 3 hours. This is designated as solution 2.

Using this solution 2, a coating liquid B having the following composition was prepared, and a thermal transfer sheet was prepared in the same manner as in Example 1. And
Aged at 40 ° C for 1 week.

[Coating liquid B]

Solution 1 (Example 1) 9 parts Solution 2 10 parts PZ-33 0.5 part Toluene 40 parts Methyl ethyl ketone 40 parts Example 3 Solution 1 of Example 1 was treated with methyl ethyl ketone / toluene =
Example 2 Dissolved to a solid content of 10% with 1/1 solvent
Solution 2 was dropped and stirred at 90 ° C., and after the completion, reacted at 100 ° C. for 1 hour and then under reflux for 3 hours. This is designated as solution 3.

Using this solution 3, a coating solution C having the following composition was prepared, and a thermal transfer sheet was prepared in the same manner as in Example 1. And
Aged at 40 ° C for 1 week.

[Coating liquid C]

Solution 3 100 parts PZ-33 0.5 part Example 4 The following composition was charged into a flask, dropped at 90 ° C., and stirred at 100 ° C.
For 1 hour and then 3 hours under reflux. This is referred to as solution 4.

[Solution 4] X-22-3701E 9 parts HDU 1 part Toluene 40 parts Methyl ethyl ketone 50 parts Using this solution 4, a coating liquid D having the following composition was prepared, and a thermal transfer sheet was prepared in the same manner as in Example 1. . And
Aged at 40 ° C for 1 week.

[Coating liquid D]

Solution 4 100 parts PZ-33 0.5 part Example 5 Half of the following composition was charged into a flask, and the other half was dropped and reacted under stirring and reflux. This is designated as solution 5.

[Solution 5] Methyl methacrylate 20 parts Glycidyl methacrylate 12 parts 2-hydroxyethyl methacrylate 3 parts Methyl ethyl ketone 100 parts Azobisisobutyronitrile 4 parts Using this solution 5, the following composition was charged into a flask, and
The reaction was carried out at 1 ° C. for 1 hour and then under reflux for 3 hours.

[Solution 6] X-22-3701E 9 parts HEA (2- (hydroxyethyl) manufactured by Wako Pure Chemical Industries, Ltd.)
Aziridine)) 0.1 part Toluene 40 parts Methyl ethyl ketone 50 parts Using this solution 6, a coating liquid D having the following composition was prepared, and a thermal transfer sheet was prepared in the same manner as in Example 1. And
Aged at 40 ° C for 1 week.

[Coating liquid E]

Solution 6 100 parts PZ-33 0.5 part Example 6 Half of the following composition was charged into a flask, and the other half was dropped and reacted under reflux with stirring. This is designated as solution 7.

[Solution 7] Methyl methacrylate 20 parts Isocyanate ethyl methacrylate 16 parts 2-hydroxyethyl methacrylate 3 parts Methyl ethyl ketone 100 parts Azobisisobutyronitrile 4 parts Using this solution 7, the following composition was charged into a flask, and
The mixture was dropped and stirred at 100 ° C., and reacted at 100 ° C. for 1 hour and then under reflux for 3 hours.

[Solution 8] Solution 7 9 parts X-22-3701E 1 part HEA 0.1 part Toluene 40 parts Methyl ethyl ketone 50 parts Using this solution 8, a coating liquid F having the following composition was prepared, and subjected to thermal transfer in the same manner as in Example 1. Created a sheet. And
Aged at 40 ° C for 1 week.

[Coating liquid F]

Solution 8 100 parts PZ-33 0.5 part Comparative Example 1 A coating solution G having the following composition was prepared in the same manner as in Example 1 to prepare a thermal transfer sheet.

[Coating liquid G]

Solution 1 9 parts X-22-3701E 1 part Toluene 40 parts Methyl ethyl ketone 50 parts Using the thermal transfer sheets of Examples 1 to 6 and Comparative Example 1, a printing test was performed using a thermal head.

The printing test was carried out for 10 minutes at a constant energy for 10 minutes, with 10 minutes pause as one cycle. The energy level is changed by changing the voltage and pulse width applied to the thermal head.
I went from 1.3mj / dot to 3.0mj / dot.

The thermal transfer material sheets provided with the protective layers of Examples 1 to 6 were 1.
Printing was not disturbed at all even if the energy was increased from 0 mj / dot to 3.0 mj / dot. In addition, a 10-cycle printing test
Even at an energy of 3.0 mj / dot, no fusion of the base film to the thermal head or attachment of foreign matter was observed at all. Of course, no breakage of the base phenol was found at all. On the other hand, in the thermal transfer sheet of Comparative Example 1, printing began to be disturbed at 1.1 mj / dot,
At 1.3 mj / dot, fusion to the thermal head occurred. on the other hand,
The test for the transfer of the silicone compound was carried out by superposing the heat-resistant protective layer of the heat-sensitive transfer sheets of Examples 1 to 6 and Comparative Example 1 on a 6 μm polyethylene terephthalate film coated with nothing and applying a pressure of 500 g / cm ² to 40 g. After aging at 48 ° C. for 48 hours, a wettability test was performed on the surface of the polyethylene terephthalate film superimposed on the surface of the heat-resistant protective layer. For the wettability test, a wetting index standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

Table 1 shows the results of the printing test and the migration test of the silicone compound.

Claims (1)

(57) [Claims] 1. A heat-sensitive transfer material comprising a heat-sensitive transfer recording layer provided on one side of a film substrate and a protective layer provided on the other side, wherein the protective layer comprises (A) a resin having a reactive group,
(B) A heat-sensitive transfer material comprising a cured resin film containing a silicone compound having a functional group capable of reacting with the reactive group of (A) and (C) an aziridine-based crosslinking agent.