JP4498201B2 - Recording method using receptor for thermal transfer recording, receptor for thermal transfer recording, and recording medium - Google Patents

Description

  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording method using a silver thermal transfer recording receptor, a thermal transfer recording receptor, and a recording body, and more specifically, a thermal transfer recording receptor in which a transferred image formed on the receiver is excellent in solvent resistance and friction resistance. The present invention relates to a recording method using a recording medium, a thermal transfer recording receptor, and a recording medium.

A method for forming an image by heating a thermal transfer recording medium with a thermal head and transferring ink to a receptor is generally known, and is used for producing labels such as nameplates.
When such a label is used in an environment using an organic solvent such as MEK, it is required that the image transferred to the label is not erased by such an organic solvent.

  Examples of the receptor excellent in ink transfer property and chemical resistance include Japanese Patent Application Laid-Open No. 4-115995 in Patent Document 1, Japanese Patent Application Laid-Open No. 5-286227 in Patent Document 2, Japanese Patent Application Laid-Open No. 8-43994 in Patent Document 3, and Japanese Patent Application Laid-Open No. 8-58250 of Patent Document 4 discloses a receptor using an ethylene ionomer resin for a receiving layer. Japanese Patent Application Laid-Open No. 2002-113959 of Patent Document 5 shows a coating layer made of an unsaturated carboxylic acid olefin copolymer and an ethyleneimine adduct of a polyimine polymer. However, it cannot be said that the solvent resistance of the image formed on the receiving layer or coating layer is sufficient.

Furthermore, in order to obtain the solvent resistance of the transferred image, it has been devised to add the same kind of resin having excellent solvent resistance to the ink and the receiving layer. For example, Japanese Patent No. 2533456 of Patent Document 6 shows that a specific polyolefin is used for the ink resin and the receiving layer. Japanese Patent Application Laid-Open No. 4-347688 of Patent Document 7 and Japanese Patent Application Laid-Open No. 2001-199171 of Patent Document 8 show that nylon is added to the ink layer and the receiving layer.
Japanese Patent Laid-Open No. 4-115995 Japanese Patent Laid-Open No. 5-286227 JP-A-8-43994 JP-A-8-58250 JP 2002-113959 A Japanese Patent No. 25333456 JP-A-4-347688 JP 2001-199117 A

  However, even with these methods, it is not possible to obtain an image that can withstand extremely severe use conditions that satisfy the solvent resistance.

  In a recording method of printing on a thermal transfer recording medium using a thermal transfer recording medium in which a release layer containing a wax and an ink layer containing a colorant are sequentially laminated on a support, the ink layer comprises an ethylene-methacrylic acid copolymer. A thermal transfer recording receptor comprising a coalesced metal salt, wherein the thermal transfer recording receptor is provided with a receiving layer on a roughened surface of a plastic film having a roughened surface on at least one side, There is provided a recording method using a thermal transfer recording receptor, wherein the receiving layer is a metal layer.

  The smoothness of the receiving layer surface according to JIS P-8119 is preferably 150 to 500 seconds.

The recording material on which an image is formed on a receptor by the recording method of the thermal transfer recording receptor or claim 1 used in the recording method according to claim 1 is provided.

  As described above, in the thermal transfer recording receptor in which the receiving layer is provided on the plastic film whose surface is roughened, the receiving layer is a metal layer. By transferring the image, it is possible to obtain a recording material having excellent resistance to a solvent such as MEK.

The present invention is described in detail below. As described above, the recording method of the present invention is a recording method for printing on a thermal transfer recording receiver using a thermal transfer recording medium in which a release layer containing a wax and an ink layer containing a colorant are sequentially laminated on a support. The ink layer contains a metal salt of an ethylene-methacrylic acid copolymer, and the thermal transfer recording receiver has a receiving layer on a roughened surface of a plastic film on which at least one surface is roughened. It is a thermal transfer recording receptor provided, and is characterized by using a thermal transfer recording receptor characterized in that the receiving layer is a metal layer.
That is, in such a thermal transfer recording receptor, an image transferred onto the thermal transfer recording receptor has excellent resistance to a solvent such as MEK. It also has excellent friction resistance.

In the recording method for printing an image from a thermal transfer recording medium on the thermal transfer recording receiver of the present invention, a release layer containing a wax, a colorant and an ink layer containing a salt of an ethylene-methacrylic acid copolymer are formed on a support. Sequentially laminated thermal transfer recording media are used.
Ethylene ink layer - salt of methacrylic acid copolymer, ethylene - salt of methacrylic acid copolymer is part of the methacrylic acid Na, K, Ca, crosslinked with between molecular chains by Z n of which cations Take the structure. Among these, those containing at least one of Na, K, and Zn are preferable. Examples of such a salt of an ethylene-methacrylic acid copolymer include Chemipearl S-650 and S-659 manufactured by Mitsui Chemicals.

In addition to the metal salt of the ethylene-methacrylic acid copolymer, other resins may be added to the ink layer of the thermal transfer recording medium as necessary.
For example, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, polyvinyl alcohol such as polyvinyl alcohol modified with carboxyl group, sulfonic acid Na group, acetoacetyl group, cationic group, starch and derivatives thereof, methoxycellulose, hydroxy Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, polyacrylic acid, sodium polyacrylate, polyvinylpyrrolidone, acrylamide-acrylic acid ester copolymer, acrylamide-acrylic acid ester-methacrylic acid terpolymer, styrene- Water soluble maleic anhydride copolymer alkali salt, isobutylene-maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, etc. Resin, polyvinyl acetate, polyurethane, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene-acrylic copolymer, polyacrylic acid, polyacrylic ester, polymethacrylic ester, vinyl chloride-acetic acid Vinyl copolymer, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic acid copolymer, ethylene-vinyl acetate-acrylic acid copolymer, urethane-modified polyethylene, styrene-acrylic acid ester copolymer, ethylene-propylene copolymer Examples thereof include emulsions such as polymers, ethylene-vinyl chloride copolymers, vinyl acetate-ethylene-vinyl chloride copolymers, polyesters, and water dispersions.

  As the colorant used in the ink layer, an appropriate one can be selected from carbon black, organic pigments, inorganic pigments or various dyes according to the required color tone.

A release layer is provided between the support and the ink layer. The release layer preferably contains a resin and a wax as main components. A release layer containing resin and wax as main components facilitates the release of the ink from the support when heat energy is applied from the thermal head, and improves the thermal sensitivity. In the transferred image, the release layer is positioned on the ink layer to protect the ink layer from the solvent.

  As binders to be added to the release layer, ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetal, cellulose derivatives, polyvinyl chloride, polyvinylidene chloride, isoprene rubber, butadiene rubber, ethylene propylene rubber, Butyl rubber, nitrile rubber or the like is used.

  Examples of the wax added to the release layer include beeswax, whale wax, wood wax, rice bran wax, carnauba wax, candelilla wax, montan wax, paraffin wax, polyethylene wax, oxidized polyethylene wax, acid-modified polyethylene wax, and micro wax. Crystalline wax, acid wax, ozokerite, ceresin, ester wax, margaric acid, lauric acid, myristic acid, palmitic acid, stearic acid, furonic acid, behenic acid, stearyl alcohol, behenyl alcohol, sorbitan, stearamide, And oleic acid amide.

  For the support, a known film or paper may be used as it is. For example, a plastic film having relatively high heat resistance such as polyester such as polyethylene terephthalate, polycarbonate, triacetyl cellulose, nylon, polyimide, cellophane, sulfate paper, etc. Preferably used.

  The thermal transfer recording medium may be provided with a protective layer on the back surface of the support, if necessary. The protective layer is a layer to protect the support from high temperature when heat is applied by the thermal head. In addition to high heat resistance thermoplastic resin and thermosetting resin, UV curable resin and electron beam curable resin can also be used. It is. In addition, resin suitable for protective layer formation is a fluororesin, a silicone resin, a polyimide resin, an epoxy resin, a phenol resin, a melamine resin, etc., What is necessary is just to use these resin in a thin film form. Further, since the heat resistance of the support can be remarkably improved by installing the protective layer, a support that has been conventionally unsuitable by installing the layer can also be used.

  The thermal transfer layer described in detail above can be provided by laminating on a support by a hot melt coating method, a coating method using a solvent, or the like. What is the thermal transfer layer provided by such a coating method? The total thickness may be 0.1 to 10 μm, preferably 0.5 to 6.0 μm. The thickness of each layer is 0.5 to 6.0 μm, preferably 0.8 to 3 μm, and the release layer is 0.2 to 3.0 μm, preferably 1.0 to 2.0 μm. .

  In the present invention, a plastic film having a roughened surface is used as a base material for a thermal transfer recording receptor. The unevenness formed by roughening the surface protects the transferred image and improves the solvent resistance.

  Examples of the forming material include polyester, polyethylene, polypropylene, polyvinyl chloride, polyethersulfone, polyphenylene sulfide, polyetherimide, polyetheretherketone, polyimide, nylon, vinylon and other plastic films, and polyolefin and polyester synthetic paper. Used. By providing a metal layer on a plastic film having a roughened surface, the solvent resistance is further improved.

  An embossing method in which a plastic film is processed with an embossing roller (the roughness can be adjusted by the roughness of the embossing roller). There is a sandblasting process in which a large amount of fine particles are sprayed onto a plastic film to form a mat (the roughness can be adjusted by changing the size and amount of the particles to be sprayed). A kneaded mat film in which a matting agent is kneaded in the process of producing a plastic film can also be used.

In the present invention, a metal layer is provided on the roughened surface of the support. The metal salt of the ethylene-methacrylic acid copolymer contained in the ink layer is excellent in adhesion to metal. Therefore, if the receiving layer is a metal layer, the fixability of the image is improved and the solvent resistance is improved.
The metal layer is made of a metal such as aluminum, silver, or zinc. It is preferable to use aluminum.

  As a method of providing the metal layer, plating methods such as electroplating and chemical plating. Physical vapor deposition methods such as vacuum deposition, ion plating, sputtering, and beam method. There are chemical vapor deposition methods such as thermal CVD, plasma CVD, photo CVD, and laser CVD. The thickness of the metal layer is about 0.001 to 10 μm, preferably about 0.01 to 1 μm. The smoothness (JIS P-8119) of the receiving layer surface is preferably 150 to 500 seconds. If it is less than 150 seconds, the fineness of the image is lowered, and if it exceeds 500 seconds, the solvent resistance of the image is lowered.

  In the present invention, the receptor can be processed into a label that can adhere to the adherend by sequentially laminating an adhesive layer and release paper on the opposite side of the receptor on which the receptor layer is provided. .

  In this invention, it is preferable that it is 40-250 micrometers as the whole thickness of a support body, a receiving layer, and the adhesive layer provided as needed. If the thickness is less than 40 μm, the strength of the receptor is lowered and is easily broken, and if it exceeds 250 μm, it is caught when it is attached to an adherend as a label and is easily dropped.

  Next, the present invention will be described more specifically with reference to examples. In addition, a part here is a solid content weight reference | standard.

[Example 1]
(1) Preparation of thermal transfer recording medium As a support, a polyethylene terephthalate film having a thickness of 4.5 μm is prepared, and silicone rubber (SD7226 manufactured by Toray Dow Corning Silicone Co., Ltd.) is provided on the side opposite to the side on which the thermal transfer recording layer is applied. After drying, it was applied and dried so that the coating amount was 0.35 g / m ² to prepare a support having a heat-resistant slip layer.

Formulation of release layer forming coating solution Carnauba wax toluene dispersion (solid content 10%) 90 parts Ethylene-vinyl acetate copolymer resin (vinyl acetate amount 28 wt% MFR (melt flow rate) 15 dg / min) in toluene solution (10% solid content) 10 parts

  The release layer-forming coating solution having the above-described formulation was applied to the thermal transfer recording layer side of the support so that the release layer had a thickness of about 1.0 μm and dried to provide a release layer.

Formulation of coating liquid for forming ink layer Ethylene-methacrylic acid copolymer salt (Mitsui Chemicals, Chemipearl S-650: (solid content 27%) 62 parts Carbon black aqueous dispersion (solid content 38%) 22 parts 16 parts of water

An ink liquid having the above composition was applied onto the release layer so as to have a thickness of about 0.8 μm and dried to provide an ink layer, thereby preparing a thermal transfer recording medium.

(2) Preparation of Thermal Transfer Recording Receptor Aluminum was vapor-deposited on one side of a 50 μm thick polyester film that had been sandblasted to provide a metal layer. The smoothness of the receiving layer surface was 200 seconds when the smoothness shown in JIS P-8119 was measured.

[Example 2]
A receptor for thermal transfer recording was prepared in the same manner as in Example 1 except that a polyester kneaded mat film was used as the receptor substrate in Example 1. The smoothness of the receiving layer surface was 250 seconds when the smoothness shown in JIS P-8119 was measured. The same thermal transfer recording medium as in Example 1 was used.

[Comparative Example 1]
A receptor was prepared in the same manner as in Example 1 except that the metal layer was not provided in Example 1. The smoothness of the receiving layer surface was 190 seconds. The same thermal transfer recording medium as in Example 1 was used.

[Comparative Example 2]
A 50 μm thick aluminum vapor-deposited polyester film (Metal Me S50 manufactured by Toyo Metallizing Co., Ltd.) that was not roughened was used as a receptor. The smoothness of the metal layer surface was 30000 seconds when the smoothness shown in JIS P-8119 was measured. The same thermal transfer recording medium as in Example 1 was used.
Using the thermal transfer recording medium and the thermal transfer recording receptor obtained as described above, an evaluation test was conducted by the following method. Printing was evaluated under the following conditions.

(Printing conditions)
Printer: 96XiIII manufactured by Zebra
Printing speed: 2 inches / second Printing energy: Tone 26

The various characteristics evaluated are as follows.
Solvent resistance After applying a 0.5 cc solvent to a cotton swab and applying it to a transfer image, the sample was rubbed 30 times with a load of 100 g / Cm ² , and the image was observed and evaluated according to the following five criteria. MEK was used as the solvent.
5 As a result of the love test, there is no change from before the test.
4 As a result of the love test, the image can be read but slightly damaged.
3 As a result of the love test, the image can be read but can be damaged.
2 As a result of the love test, the image remains but cannot be read.
1 The image is erased as a result of the love test.
The above evaluation results are shown in Table 1.

Claims (3)

A method of recording on a thermal transfer recording receptor using a thermal transfer recording medium,
The thermal transfer recording medium, which has sequentially stacked and exfoliation layer and an ink layer on a support, wherein the release layer is one containing wax contains no coloring material, the ink layer of wax Not containing a colorant and a metal salt of an ethylene-methacrylic acid copolymer,
The receiver for thermal transfer recording is provided with a receiving layer on at least one side of a plastic film, and the surface of the plastic film on which the receiving layer is provided is roughened by embossing, sandblasting or kneading of a matting agent, A recording method using a thermal transfer recording receptor, wherein the surface of the receptor layer has a smoothness according to JIS P-8119 of 150 to 500 seconds, and the receptor layer is a vapor-deposited metal layer. A thermal transfer recording receptor used in the recording method according to claim 1. A recording material having an image formed on a receptor by the recording method according to claim 1.