JPH05338363A - Sublimation transfer image receiving material - Google Patents

Abstract

PURPOSE:To reconcile preservability and dyeing sensitivity in the title image receiving material used in combination with a sublimable dye-containing thermal transfer sheet by constituting the image receiving material by forming a dyeing layer based on a dyeing resin composed of a polyester resin on a substrate and further forming one or more image projecting layer thereon. CONSTITUTION:The dyeing layer constituting a sublimation transfer image receiving material is formed using a polyester resin as the base of a dyeing resin. This polyester resin is formed from polyester obtained from aromatic carboxylic acid and aliphatic glycol, polyurethane and polyester acrylate and the number average mol.wt. thereof is 1000-100000. One or more image protecting layer is formed on the surface of the dyeing layer. This image protecting layer is formed by applying a hydrophilic resin and an oil repelling resin in a form of an aqueous dispersion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sublimation transfer image receptor used in combination with a thermal transfer sheet containing a sublimation dye.

[0002]

2. Description of the Related Art Conventionally, in this method, a thermal transfer sheet coated with a sublimable disperse dye is heated by a thermal head or the like to transfer the sublimable dye onto a dye image-receiving paper, which is brought into contact with the thermal transfer sheet, to print. To get the image.
As the dyeing resin used in the dyeing layer of the sublimation transfer image-receiving paper, there are conventionally known dyeing resins of JP-A-57-107885 and JP-A-6-107858.
It is known to contain a saturated polyester as a main component as disclosed in 0-64899, JP-A-61-258790 and JP-A-62-105689. Also,
Japanese Patent Application Laid-Open No. 3-1368 discloses a device characterized by multi-layer lamination.
No. 96 is known.

[0003]

Conventionally, when a saturated polyester is used as a dyeing resin, a high-quality image having good color density, gradation and color reproducibility can be obtained. On the other hand, the recorded image is closely related to the storage condition of the dye, and although it is not as good as the silver salt color photograph due to the study of the resin design for the dyeing layer, it reached a level at which the image storability is considerably obtained. I've been However, in comparison with silver salt color photographs, this method in which the dye image-receiving layer is exposed to the surface has a fundamental problem in long-term storage in terms of image distortion. As an example of improving the problem, when using a resin for dyeing layer with an emphasis on storability, a problem occurs that the image has low dyeing sensitivity, it is difficult to achieve both dyeing sensitivity and storability. there were. Further, the conventional multi-layer laminate has a purpose of improving peeling for preventing thermal fusion due to heating of the thermal head.

[0004]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies on a sublimation transfer image receptor, and as a result, the image receptor having the following structure has a lower dyeing sensitivity. The present invention has been achieved by finding that the image durability is excellent. That is, the present invention comprises a sublimation transfer image receptor having a substrate, a dyeing layer provided on the substrate and an image protective layer consisting of at least one layer on the surface of the dyeing layer, and the sublimation transfer image receptor. In the sublimation transfer image receptor, the dyeing resin mainly composed of the dyeing layer is a polyester resin.

In the composition of the dyeing resin which forms the dyeing layer of the sublimation transfer image receptor in the present invention, the polyester resin which characterizes the present invention means a polyester having the following composition and a polyurethane made of these materials. , Polyester acrylate, polyurethane acrylate and the like.

That is, the polyester in the present invention is
It is obtained by reacting an acid component such as an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid or an aliphatic dicarboxylic acid with an aliphatic glycol, an alicyclic glycol or an aromatic glycol by an arbitrary method. Examples of the dicarboxylic acid that can be used in the polyester of the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 2,3-naphthalic acid, 1,1,3-trimethyl-3-phenylindene-4 ′, 5-dicarboxylic acid. , Aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic acids Dicarboxylic acid, fumaric acid, maleic acid, tetrahydrophthalic acid, tricyclodecanedicarboxylic acid, 1,
Unsaturated aliphatic and alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, and tri- and tetracarboxylic acids such as trimellitic acid and pyromellitic acid can be used. Preferred dicarboxylic acids include terephthalic acid, isophthalic acid, sebacic acid, 1,1,3-trimethyl-3-phenylindene-4 ′, 5-dicarboxylic acid,
5-sodium sulfoisophthalic acid and 1,4-cyclohexanedicarboxylic acid.

Examples of the glycol component which can be used in the present invention include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, tripropylene glycol, 2,3,4-trimethylol-1. , 3-Pentanediol, 1,6-hexanediol, tricyclodecanedimethylol, 1,4-
Cyclohexanedimethanol, bisphenol A ethylene oxide adduct, hydrogenated bisphenol A ethylene oxide and / or pyropyrene oxide adduct, 2,2-diethyl-1,3-propanediol, 2
Examples include -n-butyl-2-ethyl-1,3-propanediol, spiroglycol and the like. Of these, preferably neopentyl glycol, ethylene glycol, polyethylene glycol, propylene glycol,
Tricyclodecane dimethylol, 1,4-cyclohexane dimethanol, an ethylene oxide adduct of bisphenol A, spiro glycol, and propylene glycol.

Among the polyester resins shown in the present invention, the polyurethane resin can be obtained by using the polyester resin alone with the organic diisocyanate or / and by using it together with the chain extender.

The organic diisocyanate compound (b) used for such purpose includes hexamethylene diisocyanate, tetramethylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3-diisocyanate-methylcyclohexane, 1,4-diisocyanate methylcyclohexane, 4,4'-diisocyanate Dicyclohexane, 4,4'-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene Diisocyanate, 3,3'-
Dimethyl-4,4'-biphenylene diisocyanate,
4,4'-diisocyanate diphenyl ether, 1,
For example, 5'-naphthalene diisocyanate can be used. Of these, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate are preferred. Examples of the chain extender include ethylene glycol, propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, polyethylene glycol, diethylene glycol, polypropylene glycol, polytetramethylene glycol,
Examples include tricyclodecane dimethylol, 1,4-cyclohexanedimethanol, bisphenol A ethylene oxide adduct, 1,4-cyclohexanedimethanol, and the like. Among the above chain extenders, more preferable ones are
Neopentyl glycol, ethylene glycol, polyethylene glycol, diethylene glycol, bisphenol A ethylene oxide adduct, tricyclodecane dimethylol, 1,4-cyclohexane dimethanol.

The above polyurethane resin is produced by a known method, for example, in a solvent at a reaction temperature of 20 ° C. to 150 ° C. in the presence or absence of a catalyst. As the solvent used in this case, for example, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate can be used, and a catalyst for promoting the reaction. As such, amines, organic tin compounds and the like are used.

Further, the polyester acrylate and polyurethane acrylate shown in the present invention can be obtained by reacting the above polyester and polyurethane with the following (meth) acrylic acid derivative. Examples of (meth) acrylic acid derivatives include (meth) acrylic acid and other compounds such as (meth) acrylates of monoalcohols such as methanol, ethanol, isopropanol, and glycidol, and glycols such as ethylene glycol, diethylene glycol, and hexamethylene glycol. Mono (meth) acrylates of triol compounds such as mono (meth) acrylate, trimethylolpropane, glycerin, and trimethylolethane, and mono (meth) acrylates of dihydric or higher valent polyols such as di (meth) acrylate, pentaerythritol, and dipentaerythritol ( Acrylic compounds containing hydroxyl group such as (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, glycerin monoallyl ether, glycerin diallyl ether Isocyanate group-containing acrylic compounds such as cyano ether (meth) acrylate and the like.

In the method for coating the polyester resin used in the dyeing layer of the present invention, the above polyester resin and polyurethane resin are generally used by dissolving them in a solvent, or a non-aqueous dispersion or an aqueous dispersion is used. Alternatively, it can be used in the form of an aqueous solution (without solvent). It is customary to use a solid content concentration of about 5 to 70% by weight.

The number average molecular weight of the polyester resin used in the dyeing layer of the present invention is 1,000 to 100,000.
And preferably in the range of 2,000 to 50,000.
When the molecular weight is less than 1,000, the coating film strength of the dyeing layer is lowered. Further, when it exceeds 100,000, the solution viscosity becomes too high and the handling becomes difficult, which is not preferable.

It may be mixed with a resin other than the polyester resin used in the dyeing layer of the present invention. Examples of the mixed resin include polyvinyl resins, polycarbonate resins, polyacrylic acid resins, polymethacrylic acid resins, polyolefin resins, cellulose derivative resins, polyether resins, and polyester resins.

The resin mainly composed of at least one image protective layer on the surface of the dyeing layer of the present invention is, for example,
It is a hydrophilic resin, an oil repellent resin, an organic solvent hardly soluble resin, or the like. Further, a sensitizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a heat release agent, etc. can be blended in at least one of the dyeing layer and the image protective layer.

The coating method of the image protective layer according to the present invention can be generally used in the form of an aqueous dispersion of a hydrophilic resin, an oil repellent resin, a resin hardly soluble in an organic solvent or an aqueous solution (solventless). Alternatively, it is possible to use an organic solvent in a category that does not damage the dyeing layer. The solid content concentration is about 5 to 70% by weight.

The substrate used for the sublimation transfer image receptor is not particularly limited, and examples thereof include paper, synthetic paper, various films, various sheets, metal plates and glass plates.

[0018]

EXAMPLES In order to specifically describe the present invention, production examples and examples will be described below. In the Production Examples and Examples, "parts" means "parts by weight" and "%" means "% by weight". The number average molecular weight of the produced polymer was measured by GPC, and the glass transition temperature was measured by DSC. The results are shown in Table 1. The measuring methods for dyeing density, light resistance, heat resistance, plasticizer resistance, and fingerprint resistance are as follows, and the evaluation results are shown in Table 2.

(1) Production example of polyester for dyeing layer 388 parts of dimethyl terephthalate and 376 dimethyl isophthalate were placed in an autoclave equipped with a thermometer and a stirrer.
Parts, trimellitic anhydride 12 parts, neopentyl glycol glycol 541 parts, tricyclodecane dimethylol 706 parts, and tetrabutoxy titanate 0.5 parts were charged and heated at 150 to 220 ° C. for 240 minutes to perform transesterification, and then. The reaction system is heated to 250 ° C. in 10 minutes, the system pressure is gradually reduced, and after 25 minutes, 0.3 mmHg
The reaction was continued below for 60 minutes under these conditions to obtain a light yellow transparent polyester A for dyeing layer. The number average molecular weight of the obtained resin was 27,000. Table 1 shows polyester B obtained by the same production method.

(2) Production Example of Water-Dispersible Resin for Image Protective Layer In an autoclave equipped with a thermometer and a stirrer, 373 parts of dimethyl terephthalate, 24 parts of 5-sodium sulfoisophthalic acid, 116 parts of cyclohexanedimethanol, and ethylene glycol. 224 parts and 0.5 part of tetrabutoxy titanate were charged and heated at 150 to 220 ° C. for 240 minutes for transesterification, and then the reaction system was heated for 2 minutes in 2 minutes.
The temperature of the system was raised to 50 ° C., the system pressure was gradually reduced, and after 25 minutes, the pressure was reduced to 0.3 mmHg or less, and the reaction was continued for another 60 minutes under these conditions to obtain a light yellow transparent polyester X for an image protective layer. The number average molecular weight of the obtained resin was 23,000. 30 parts of polyester resin X, 15 parts of n-butyl cellosolve and 55 parts of water were charged into a container and the mixture was heated to 85 ° C for 3-4.
After stirring for a time, a uniform white aqueous polyester resin X-1
Got Resin Y-1 obtained by the same method is shown in Table 1.

(3) Method for evaluating density of printed image The image-receiving sheet and the thermal transfer sheet are superposed so that the dyeing layer (dye receiving layer) and the coloring material layer are in contact with each other, and the thermal head is located on the base side of the thermal head. The head output was 0.7 W / dot, the head heating time was 8 mS, and the dot density was 3 dots / mm, and the cyan dye in the color material layer was transferred to the dye layer. The obtained transferred image density was measured with a reflection densitometer (DM-600 manufactured by Dainippon Screen).

(4) Method of evaluating light fastness The energy given by the xenon lamp is 6 at 40 ° C. on the image-receiving sheet on which the cyan dye is transferred.
Irradiation was performed at 7.0 KJ / m ^2, and the dye density retention rate (%) was shown in comparison with the density before the light resistance test. Dye density retention rate (%) = (density after light resistance test / density before light resistance test) × 100

(5) Evaluation method of heat resistance (dark fading rate) The image receptor on which the cyan dye was transferred is allowed to stand for 168 hours in an environment of 60 ° C. in the dark and aged to obtain the density before the heat resistance test. The dye density retention rate (%) is shown in the comparison.

(6) Evaluation method of plasticizer resistance A thickness of 80 μm is formed on the surface of the image receptor on which the cyan dye is transferred.
1 cm2 of vinyl chloride film is attached, and a load of 5 g is further applied on the vinyl chloride film, and it is left for 24 hours in an environment of 40 ° C.
I saw the remnants of the film. After aging, there was no film mark on the surface of the image-receiving layer and there was no change such as color loss. ○, there was no change in color but film marks remained, and △, color changes and film marks remained. .

(7) Fingerprint resistance evaluation method The thumb was strongly pressed against the surface of the image receptor to which the cyan dye was transferred so that the fingerprint remained on the image surface, and the fingerprint was left in an environment of 40 ° C. for 48 hours, Agglomeration of cyan dye, color loss, and fingerprint residue were observed. After aging, the image having no fingerprint on the surface of the image-receiving layer and having no color change was evaluated as ◯, the image having no color change but leaving fingerprint marks was evaluated as Δ, and the dye agglomerated on the image surface was evaluated as x.

Example 1 Polyester A for the receptor layer was diluted with a mixed solvent of toluene: methyl ethyl ketone = 50: 50 to prepare a 20% solution. Epoxy-modified silicone oil (KF-102, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this solution in an amount of 10% by weight with respect to the above resin, and a synthetic paper having a thickness of 150 μm (Yupo PPG-150, manufactured by Oji Petrochemical Co., Ltd.) was used as a wire bar. Was used to obtain a dry coating film of 7 μm. The above sheet was dried in an atmosphere of 120 ° C. for 30 minutes to obtain a dyeing layer (dye receiving layer). Next, X-1 diluted on the obtained dyeing layer with a mixed solution of isopropanol: water = 60: 40 was used to prepare a dried image protective layer having a coating film thickness of 0.5.
It was applied with a bar coater so as to have a thickness of ˜5 μm. Silicone modified oil (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to this solution in an amount of 8% by weight based on the resin for the image protective layer. Dry 10
It was performed at 0 ° C. for 20 minutes. The adhesion between the resulting image protective layer and the dyeing layer was very good.

Example 2 Using the resin resin B for the dyeing layer of the present invention and the resin Y-1 for the image protective layer, an image receptor was provided in the same manner as in the example, and the respective examples were set as example 2.

Comparative Example 1 Resin A was used, and only a dyeing layer was provided in the same manner as in Example 1 to give Comparative Example 1.

Comparative Example 2 Comparative Example 2 was prepared by using Resin B and providing only the dyeing layer in the same manner as in Example 1.

Comparative Example 3 Using the resin X-1 for an image protective layer, a substrate was directly coated in the same manner as in Example 1 without providing a dyeing layer, to give Comparative Example 3.

Comparative Example 4 Using the resin Y-1 for the image protective layer, a substrate was directly coated in the same manner as in Example 1 without providing a dyeing layer, to give Comparative Example 4.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

The dye-receiving layer of the present invention and at least one image-protecting layer on the surface of the image-receiving body for sublimation-type heat-sensitive recording show high dyeing sensitivity, and the obtained image is It has excellent durability and storage stability and is industrially useful.

Claims (1)

[Claims] 1. A sublimation transfer image receptor comprises a substrate, a dyeing layer provided on the substrate, and an image protective layer consisting of at least one layer on the surface of the dyeing layer, and the sublimation transfer. A sublimation transfer image receptor, wherein the dyeing resin mainly composed of the dyeing layer of the image receptor is a polyester resin.