JP2714670B2 - Sublimation transfer recording method - Google Patents

Description

The present invention relates to a heat transfer recording medium having a dye transfer layer containing a sublimable dye, and a dye receiving layer capable of dyeing a sublimable dye, which is n-fold. The present invention relates to a sublimation transfer recording method for forming an image by a mode method.

[Conventional technology]

In recent years, the demand for full-color printers has been increasing year by year, and the recording methods of these full-color printers include an electrophotographic method, an ink jet method, and a thermal transfer method. Of these, the thermal transfer method is often used because of easy maintenance and no noise. Used.

This thermal transfer method is based on a thermal transfer recording medium (color ink sheet) in which a colorant is dispersed in a heat-fusible substance or an ink layer in which a sublimable dye is dispersed in a resin binder is provided on a substrate. An image receiving medium (image receiving sheet) is superimposed on the ink layer surface, and thermal energy controlled by an electric signal of a laser, a thermal head, or the like is applied from the recording medium side, and the ink in that portion is thermally melt-transferred or sublimated onto the image receiving sheet. This is a recording method for forming an image by shifting.

The thermal transfer recording method is roughly classified into a heat-melt transfer type and a sublimation transfer type according to the type of recording medium to be used. Has the advantage of being able to easily obtain a halftone because of sublimation in a monomolecular state and to be able to control the gradation at will, and is considered to be the method most suitable for a full-color printer.

However, in this sublimation type thermal transfer recording system, a color ink sheet is used as a recording supply, and heat recording is selectively performed by an image signal. In order to obtain one full-color image, yellow, magenta, cyan, (black) )
This method has a drawback that the running cost is high because the ink sheets are used one by one and discarded even if there is an unused portion thereafter.

Therefore, in order to improve this drawback, an n-times mode method in which the speed of the image receiving sheet is set to n times (n> 1) the speed of the ink sheet and printing is repeated while both sheets are running has been performed in recent years. . In the n-times mode method, printing is performed a large number of times by a relative speed method in which an overlap between a used portion of the ink layer before and a used portion of the ink layer is gradually shifted.

[Problems to be solved by the invention]

In the conventional sublimation transfer recording method, a dye receiving layer made of a thermoplastic polyester resin or the like having a strong dyeing property to a sublimation dye is formed on a substrate (paper, synthetic paper, plastic film, etc.) as an image receiving sheet. Things have been used. However, the conventional image receiving sheet does not have sufficient releasability from the ink sheet, and particularly in the n-times mode method, a strong frictional force is applied between the ink sheet and the image receiving sheet.
At the time of recording, fusion was sometimes caused or the sheet was sometimes damaged.

Accordingly, an object of the present invention is to provide a sublimation transfer image receiving medium which is particularly excellent in releasability, and to provide a sublimation transfer recording method by the n-fold mode method using the same.

[Means for solving the problem]

The present inventors have obtained an image receiving sheet having a layer mainly composed of a vinyl chloride resin containing an OH group and an isocyanate compound,
It has been found that it is effective as an image receiving medium in a sublimation transfer recording method by an n-fold mode method. The present invention has been made based on this.

Therefore, according to the present invention, an image receiving medium having a dye receiving layer capable of dyeing a sublimation dye containing a vinyl chloride resin containing an OH group and an isocyanate compound as main components on a substrate, and a sublimable A transfer recording medium having a dye transfer layer containing a dye as a main component is overlapped so that the dye receiving layer of the image receiving medium and the dye transfer layer of the transfer recording medium face each other, and the speed of the image receiving medium is set to the transfer speed. N times the speed of the recording medium (n>
In 1), while the image receiving medium and the transfer recording medium are running, heat energy is applied from the substrate surface side of the transfer recording medium to transfer the sublimable dye of the transfer recording medium to the dye receiving layer of the image receiving medium. A sublimation transfer recording method is provided, wherein a dye image is formed by sublimation transfer, and this image formation is performed many times.

 Hereinafter, the present invention will be described in more detail.

The image-receiving medium for sublimation transfer used in the method of the present invention has a structure in which a vinyl chloride resin containing an OH group and a dye receiving layer mainly containing an isocyanate compound are provided on a substrate. Thereby, it has properties excellent in dyeing property, peeling property, light resistance and storage stability, and further has improved peelability by a curing reaction between an OH group and an isocyanate compound.

Examples of the vinyl chloride resin containing an OH group used in the dye receiving layer include, for example, a vinyl chloride / vinyl acetate copolymer modified with polyvinyl alcohol, and commercially available products such as Union Carbide Co., Ltd.
VAGH, VROH etc. and Denka Vinyl 1000 manufactured by Denki Kagaku Kogyo Co., Ltd.
GKT, 1000GK, 1000GKS and the like. As the isocyanate compound, various isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, and triphenylmethane triisocyanate are used, and an adduct thereof with hexanetriol or the like may be used. it can. Incidentally, the use ratio of the vinyl chloride resin containing an OH group and the isocyanate compound is 0.2 to 0.2 mol / mol of NCO / OH.
A range of 2.0 is preferred.

Further, the dye receiving layer has a conventionally known dyeing resin,
For example, a polyester resin, a polycarbonate resin, a styrene resin, a vinyl chloride resin, a silicon resin, or the like can be occupied. Of these, vinyl chloride resins are particularly preferably used, and commercially available products include, for example, VYHH, VYNS, VYHD, and VYLF manufactured by Union Carbide, and Denka Vinyl 1000MT, 1000A, 1000L manufactured by Denki Kagaku Kogyo.
1000D, MHE100, ME120 and the like. The amount of these resins used is 0.1% based on the vinyl chloride resin containing OH groups.
A range of 10 to 10 times is preferable.

In the present invention, a release agent such as an amino-modified silicone, an epoxy-modified silicone or an alkyd-modified silicone can be contained in the dye receiving layer. By using these silicones, the effect of preventing thermal fusion with the transfer recording medium is further improved. The addition amount is preferably 10% by weight or less based on the resin amount of the receiving layer.

Note that a filler can be contained in the dye receiving layer. Examples of the filler include white pigments such as silica, titanium oxide, and calcium carbonate. The amount of the filler is preferably 5 to 60% by weight based on the resin amount of the receiving layer. In addition, the dye receiving layer may appropriately contain a surfactant, an ultraviolet absorber, an antioxidant, and the like.

As the substrate in the image receiving medium, synthetic paper, art paper, high-quality paper, coated paper, gravure paper, baryta paper, cellulose fiber paper, plastic film, and the like are preferably used alone or in a laminate thereof.

The coating amount of the dye receiving layer on the substrate is preferably 0.1 to 20 g / m ² in terms of solid content.

On the other hand, the transfer recording medium used in the method of the present invention is conventionally known, and includes a substrate having an ink layer formed on the surface of a substrate.

Using these image receiving medium and transfer recording medium, an image is formed by the n-times mode method.

〔The invention's effect〕

The sublimation transfer recording method according to the n-fold mode method of the present invention employs OH on a substrate as an image receiving medium for sublimation transfer used therein.
Because it was configured to have a dye receiving layer containing vinyl chloride resin containing a group and an isocyanate compound as main components,
It is extremely excellent in releasability, does not cause fusing, sheet breakage, and the like even during recording by the n-fold mode method, can sufficiently withstand use, and can provide a large number of high-quality images.

〔Example〕

Next, the present invention will be described in more detail with reference to examples. All parts shown below are on a weight basis.

Example 1 A mixture having the following composition was sufficiently mixed and dispersed to prepare a dye receiving layer coating solution [Solution A].

[A liquid]

Vinyl chloride / vinyl acetate / vinyl alcohol copolymer 10
Part (VAGH; manufactured by Union Carbide) Isocyanate (brand name: Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 5 parts Amino-modified silicone 0.5 part (brand name: SF-8417; manufactured by Toray Silicone Co., Ltd.) Epoxy-modified silicone 0.5 part (product Name SF-8411; manufactured by Toray Silicone Co., Ltd.) Toluene 40 parts Methyl ethyl ketone 40 parts Next, [solution A] was applied to a thickness of about 150 μm using a wire bar.
m on synthetic paper (trade name: Yupo FPG-150; manufactured by Oji Yuka Synthetic Paper Co., Ltd.) and dried at a drying temperature of 75 ° C. for 1 minute to form a dye receiving layer having a thickness of about 5 μm. Further, the mixture was stored at 80 ° C. for 3 hours and cured to prepare an image receiving medium used in the present invention.

On the other hand, as a sublimation transfer recording medium, a 6 μm thick silicone cured resin film (about 1 μm thick) was provided as a back layer.
On a PET film, a coating solution [solution B] for an ink layer (ie, a dye transfer layer) having the following formulation was applied to a thickness of about 2 μm,
A transfer recording medium was obtained.

[Solution B] Polyvinyl butyral (trade name BX-1; manufactured by Sekisui Chemical Co., Ltd.) 10
Part Sublimation disperse dye for cyan (Kayaset 714, trade name; manufactured by Nippon Kayaku Co., Ltd.) 6 parts Methyl ethyl ketone 45 parts Toluene 45 parts The obtained transfer recording medium and image receiving medium are combined with the ink layer of the transfer recording medium and the dye receiving of the image receiving medium. The layers were superposed so that they faced each other, and image recording was performed by changing the heating energy from the back surface of the transfer recording medium with a thermal head. Here, recording was performed under the condition that the speed ratio between the transfer recording medium and the image receiving medium was n = 10. The recording density of the thermal head was 6 dots / mm, and the recording output was 0.42 W / dot.

Example 2 In Example 1, instead of [Solution A], the following [Solution C] was used.
An image receiving medium used in the present invention was prepared in the same manner as in Example 1 except that was used.

[Liquid C]

Vinyl chloride / vinyl acetate / vinyl alcohol copolymer 7
Part (trade name VAGH; manufactured by Union Carbide) 7 parts of vinyl chloride / vinyl acetate copolymer (trade name: VYHH; manufactured by Union Carbide) isocyanate (trade name: Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 3 parts Amino-modified silicone ( 0.5 part of epoxy-modified silicone (trade name: SF8417; manufactured by Toray Silicone Co., Ltd.) 0.5 part (trade name: SF8411; manufactured by Toray Silicone Co., Ltd.) Toluene: 40 parts Methyl ethyl ketone: 40 parts Subsequently, an image was recorded in the same manner as in Example 1.

Comparative Example 1 A comparative image-receiving medium was prepared in the same manner as in Example 1 except that the following [Solution D] was used as the coating solution for the dye-receiving layer.
In addition, an image was recorded.

[D liquid]

Polyester resin (trade name Byron 200; manufactured by Toyobo Co., Ltd.)
10 parts Amino-modified silicone (trade name: SF8417; manufactured by Toray Silicone Co., Ltd.) 0.1 part Epoxy-modified silicone 0.1 part (trade name: SF8411; manufactured by Toray Silicone Co., Ltd.) Toluene 40 parts Methyl ethyl ketone 40 parts Comparative Example 2 [Compound D] An image receiving medium for comparison was prepared and an image was recorded in the same manner as in Comparative Example 1, except that the following [Solution E] was used instead of.

[E liquid]

Vinyl chloride / vinyl acetate copolymer 10 parts (trade name: VYHH; manufactured by Union Carbide) Amino-modified silicone (trade name: SF8417; manufactured by Toray Silicone Co.) 0.1 part Epoxy-modified silicone 0.1 part (trade name: SF8411; manufactured by Toray Silicone Co., Ltd.) Toluene 40 parts Methyl ethyl ketone 40 parts or more The surface of the transfer recording medium and the image receiving medium after image recording was visually observed. Table 1 shows the results.

From Table 1, in the sublimation transfer recording method of the present invention,
By using a specific sublimation transfer image receiving medium, when recording is performed by the n-fold mode method, fusion with the ink sheet or damage to the ink sheet does not occur, and the sublimation transfer image receiving medium used in the present invention is extremely low. It can be seen that the releasability is excellent, and that a large number of high quality images can be obtained.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hidehiro Mochizuki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (56) References JP-A-63-231986 (JP, A) JP-A Sho JP-A-6-132387 (JP, A) JP-A-2-594 (JP, A) JP-A-61-262189 (JP, A) JP-A-63-104880 (JP, A) JP-A-1-160681 (JP, A) A) International Publication 90/1419 (WO, A1)

Claims (1)

(57) [Claims] 1. An image receiving medium having a dye receiving layer capable of dyeing a sublimation dye containing a vinyl chloride resin containing an OH group and an isocyanate compound as main components on a substrate, and a sublimation dye on another substrate. A transfer recording medium having a dye transfer layer as a component is superimposed such that the dye receiving layer of the image receiving medium and the dye transfer layer of the transfer recording medium face each other, and the speed of the image receiving medium is reduced. At a speed n times (n> 1), heat energy is applied from the substrate surface side of the transfer recording medium while the image receiving medium and the transfer recording medium are running, and the sublimable dye of the transfer recording medium is removed. A sublimation transfer recording method, wherein a dye image is formed by sublimation transfer to a dye receiving layer of an image receiving medium, and this image formation is performed many times.