JPH03219995A - Sublimation transfer image receiving medium - Google Patents

Abstract

PURPOSE:To enhance releasability and to perform recording with high image density by adding a vinyl chloride type resin containing an OH group, an isocyanate compound and waxes to a receiving layer as main components. CONSTITUTION:A dye receiving layer based on a vinyl chloride type resin containing an OH group, an isocyanate compound and waxes is provided on a support. As the OH group-containing vinyl chloride resin, for example, a polyvinyl alcohol modified vinyl chloride/vinyl acetate copolymer is used and, as the isocyanate compound, various isocyanate compounds such as tolylene dissocyanate or the like are used. The use ratio of the OH group-containing vinyl chloride type resin and the isocyanate compound is pref. 0.2 - 2.0 in a NCO/OH mol. ratio. A dyeing resin, for example, a polyester resin and waxes such as silicone wax or polyethylene wax are used in the dye receiving layer. Characteristics excellent in dyeing properties, releasability, light fastness and preservability are imparted according to the vinyl chloride type resin and releasability is further enhanced by the curing reaction of an OH group and the isocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image receiving medium for sublimation transfer used in combination with a thermal transfer recording medium having a transfer layer containing a sublimable dye.

[Prior Art] In recent years, the demand for full-color printers has increased year by year, and the recording methods for these full-color printers include electrophotography,
There are inkjet methods, thermal transfer methods, etc., but among these, the thermal transfer method is often used because it is easy to maintain and produces no noise.

This thermal transfer method uses 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 placed on the ink layer surface, and thermal energy controlled by an electric signal from a laser or a thermal head is applied from the recording medium side to heat-melt transfer or sublimation the ink in that area onto the image-receiving sheet. This is a recording method that forms an image by transferring the image.

This thermal transfer recording method is roughly divided into a heat-melting transfer type and a sublimation transfer type depending on the type of recording medium used.The latter, in principle, uses dyes that respond to heat energy from a thermal head, etc. Since it sublimates in a monomolecular form, it has the advantage that intermediate tones can be easily obtained and the gradation can be controlled at will, and is considered to be the most suitable method for full-color printers.

However, this sublimation type thermal transfer recording method uses a color ink sheet as a recording supply and selectively performs heating recording based on image signals. This method has the drawback that running costs are high because one ink sheet is used, and even if there is an unused portion, it is discarded.

In order to improve this drawback, in recent years a 0x mode method has been used in which the speed of the image receiving sheet is set to n times the speed of the ink sheet (n>1) and printing is repeated while both sheets are running. . In this 0x mode method, printing is performed multiple times using a relative speed method in which the overlap between the previously used portion of the ink layer and the later used portion is shifted little by little.

[Problems to be Solved by the Invention] Conventionally, in the sublimation transfer recording method, a dye receiving layer made of a thermoplastic polyester resin or the like that exhibits strong dyeability against sublimation dyes is used as an image receiving sheet on a substrate (paper, synthetic paper, Plastic films, etc.) have been used. However, conventional image-receiving sheets do not have sufficient releasability, and especially in the 0x mode method, strong frictional force is applied between the ink sheet and the image-receiving sheet, which may cause fusion or damage to the sheet during recording. There were times when I would do something like that.

Therefore, the present invention provides an image receiver for sublimation transfer that has excellent releasability and is capable of recording high image density, which can be used even in the 0x mode method, which requires even higher releasability than the normal sublimation thermal transfer recording method. The purpose is to provide a medium.

[Means for Solving the Problems] According to the present invention, in an image receiving medium having a dye receiving layer on a substrate to which a sublimation dye can be dyed, the receiving layer is made of a vinyl chloride resin containing an OH group and an isocyanate compound. An image receiving medium for sublimation transfer is provided, which is characterized by containing wax as a main component.

That is, the image receiving medium for sublimation transfer of the present invention has OH
Since it has a structure in which a dye-receiving layer is mainly composed of a vinyl chloride resin containing groups and an isocyanate compound,
The vinyl chloride resin has excellent properties in dyeability, releasability, light resistance, and storage stability, and further, the releasability is further improved due to the curing reaction between the OH group and the isocyanate compound. Generally, with a hardened receptor layer, the sensitivity decreases and the image density of the recorded image is not sufficient, but in the present invention, since the receptor layer contains polycaprolactone, the image density is increased, and the effect of the hardened receptor layer is Does not damage.

Examples of vinyl chloride resins containing OH groups used in the dye-receiving layer of the present invention include vinyl chloride/vinyl acetate copolymers modified with polyvinyl alcohol, and commercially available products include, for example, Union Carbide Co., Ltd. Made by VAGH.

VROH etc. and Denkabinir 1000 manufactured by Denki Kagaku Kogyo Co., Ltd.
Examples include GKT, 100OGK, 100OGKs, and the like. In addition, as isocyanate compounds, tolylene diisocyanate, hexamethylene diisocyanate),
Various isocyanate compounds such as 4.4-diphenylmethane diisocyanate and triphenylmethane triisocyanate are used, and adducts of these with hexanetriol and the like can also be used. Note that the ratio of the vinyl chloride resin containing an OH group to the isocyanate compound is preferably in the range of 0.2 to 2.0 in molar ratio of N G Olo H.

Furthermore, the dye-receiving layer of the present invention may contain conventionally known dyeable resins such as polyester resins, polycarbonate resins,
Styrene resin, vinyl chloride resin, silicone resin, etc. can be contained.

Examples of waxes used in the present invention include silicone wax, polyethylene wax, carnauba wax, paraffin wax, Sasol wax, microcrystal wax, castor wax, lanolin wax, montan wax, and candelilla wax.

Among these, silicone wax is preferred, and reactive groups (e.g. -〇H, -NH
2, unsaturated bonded gold groups, epoxy-derived groups), and copolymers formed after these are reacted with other compounds.

Specific examples include silicone steryl alcohol wax, methylstyrene-modified silicone wax, olefin-modified silicone wax, polyether-modified silicone wax, amino-modified silicone wax, alcohol-modified silicone wax, mercapto-modified silicone wax, and waxes with trifluoroalkyl groups in the molecule. The first targets include, but are not limited to, fluorine-modified silicone waxes with fluorine-modified silicone waxes, hydrophilic silicone waxes into which hydrophilic groups have been introduced, higher fatty acid-modified silicone waxes, carnauba-modified silicone waxes, carboxyl-modified silicone waxes, and amide-modified silicone waxes.

In addition, silicone waxes with reactive groups (e.g. -〇H, -NH2, unsaturated bonded gold groups, epoxy-derived groups) introduced at the molecular chain ends of these silicone waxes, and those formed after they react with other compounds. It may also be a copolymer.

The content of waxes is 5 to 80% by weight based on the dyeing resin.
is preferred.

Further, in the present invention, a release agent such as amino-modified silicone, epoxy-modified silicone, alkyd-modified silicone, etc. can be contained in the dye-receiving layer. In particular, a reaction product of epoxy-modified silicone and alcohol-modified silicone is preferred. Use of these silicones further improves the effect of preventing heat fusion with the transfer recording medium.

The amount added is preferably 10% by weight or less based on the amount of resin in the receiving layer.

Incidentally, a filler can also be contained in the dye-receiving layer. Examples of the filler include white pigments such as silica, titanium oxide, and calcium carbonate, and the amount added thereof is preferably 5 to 60% by weight based on the amount of resin in the receiving layer. In addition, the dye-receiving layer may contain a surfactant, an ultraviolet absorber, an antioxidant, etc. as appropriate.

Further, as the substrate in the image receiving medium of the present invention, synthetic paper,
Art paper, high-quality paper, coated paper, gravure paper, baryta paper, cellulose fiber paper, plastic film, etc. are preferably used alone or in a laminate thereof.

The amount of the dye-receiving layer coated on the substrate is preferably 0.1 to 20 geI12 in terms of solid content.Examples Next, the present invention will be explained in more detail with reference to Examples. Note that all parts shown below are based on weight.

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

[Liquid A] Vinyl chloride/vinyl acetate/vinyl 10 parts alcohol copolymer (trade name: VAG; H.

Union Carbide Co., Ltd.) Isocyanate (Product name: Coronate L; 5 parts, manufactured by Nippon Polyurethane Industries, Ltd.) Silicone wax (Product name: Q5 10158A, manufactured by Toshi Silicone Co., Ltd.) 3 parts Alcohol-modified silicone (Product name: 0.5 parts 5F-84)
27. Epoxy-modified silicone (manufactured by Toshi Silicone Co., Ltd.)
Product name 0.5 part 5F-8411, Toshi Silicone Co., Ltd.) Toluene 40
40 parts methyl ethyl ketone Next [
[Liquid A] was applied onto synthetic paper with a thickness of approximately 150μ (trade name: Yupo FP -150, manufactured by Tamago Yuka Synthetic Paper Co., Ltd.) using a wire bar, and dried for 1 minute at a drying temperature of 75°C. After forming a dye-receiving layer with a thickness of about 5μ, it was further heated at 80°C for 3
The image-receiving medium of the present invention was prepared by storing and curing for a period of time.

On the other hand, as a sublimation transfer recording medium, a silicone cured resin film (thickness approximately 1μ11) was provided as a back layer with a thickness of 6μ.
A coating liquid for an ink layer (that is, a dye transfer layer) [liquid B] having the following formulation was applied to a thickness of about 2 μI on a PET film of 100 mm to obtain a transfer recording medium.

[Liquid B] Polyvinyl butyral 10 parts (trade name BX-1, manufactured by Sekisui Chemical Co., Ltd.) Sublimation disperse dye for cyan 6 parts (trade name Kayaset 714; manufactured by Nippon Kayaku Co., Ltd.) Polyethylene wax 3 parts (320P; manufactured by Mitsui Petrochemical Co., Ltd.) ) Methyl ethyl ketone 45 parts Toluene 45 parts The obtained transfer recording medium and image receiving medium were superimposed so that the ink layer of the transfer recording medium and the dye receiving layer of the image receiving medium faced each other,
Images were recorded from the back side of the transfer recording medium by changing the heating energy using 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 is 12 dots/
mm, and the recording output was 0.16 W/dot.

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

[Liquid C] Vinyl chloride/vinyl acetate/vinyl 7 parts alcohol copolymer (product name VAGH; manufactured by Union Carbide) Vinyl chloride/vinyl acetate copolymer 7 parts (product name v
YHH; manufactured by Union Carbide) Isocyanate (trade name Coronate L, 3 parts manufactured by Nippon Polyurethane Industries) Silicone wax (trade name Q5-O158A, manufactured by Toshi Silicone) 4 parts Amino-modified silicone 0.5 parts (trade name 5F8417; Toshi Silicone Co., Ltd.) Epoxy modified silicone 0.5 part (Product name 5F8411)
, manufactured by Toshi Silicone Co., Ltd.) Toluene
40 parts methyl ethyl ketone
Subsequently, 40 copies of the image were recorded in the same manner as in Example 1.

Comparative Example 1 Except for using the following [Liquid D] as the coating liquid for the dye-receiving layer,
An image receiving medium for comparison was prepared in the same manner as in Example 1, and images were recorded.

[Liquid D] Polyester resin 10 parts (trade name Byron 200, manufactured by Toyobo Co., Ltd.) Amino-modified silicone 0.1 part (trade name 5F8417, manufactured by Toshi Silicone Co., Ltd.) Epoxy-modified silicone
0.1 part (product name 5F8411; manufactured by Toshi Silicone Co., Ltd.) Toluene 40
Part Methyl Ethyl Ketone 40 Parts Comparative Example 2 An image receiving medium was prepared in the same manner as in Example 1 except that it did not contain silicone wax, and further image recording was performed.

The results of the above image recording are shown in the table below.

[Results] [Effects of the Invention] As described above, the image receiving medium for sublimation transfer of the present invention is characterized by high image density and recording with excellent peelability without fusion even when printing by the n-fold mode method.

Claims (1)

[Claims] (1) In an image-receiving medium having a dye-receiving layer on a substrate that can be dyed with a sublimation dye, the receiving layer is mainly composed of a vinyl chloride resin containing an OH group, an isocyanate compound, and waxes. Characteristic image receiving medium for sublimation transfer.