JP3209285B2 - Sublimation transfer receiver - Google Patents

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, so that the sublimable dye is transferred onto a dye receiving paper, which is in contact with the thermal transfer sheet, and printed. It is for obtaining an image.
As the dyeing resin used in the dyeing layer of the above-mentioned sublimation transfer image receiving paper, there are conventionally known dyes described in JP-A-57-107885 and JP-A-6
As disclosed in JP-A-64-899, JP-A-61-258790 and JP-A-62-105689, those containing a saturated polyester as a main component are known. Also,
Japanese Patent Application Laid-Open No. Hei.
No. 96 is known.

[0003]

Heretofore, 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 state of the dye, and due to the study of the resin design for the dyeing layer, although there are some points that are not as good as silver halide color photographs, they reach a level where image storability can be obtained considerably I've been. However, when compared with silver halide color photographs, in the present method in which the dye image-receiving layer is exposed to the surface, there is a fundamental problem in long-term storage in terms of image disorder. As an example of improving the problem, when using a resin for a dyeing layer that emphasizes storability, a problem occurs in that an image having low dyeing sensitivity occurs, and it is difficult to achieve both dyeing sensitivity and storability. there were. Another object of the conventional multilayer laminate is to improve the peeling of the thermal head by preventing thermal fusion due to heating.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a sublimation transfer image receptor in order to solve the above-mentioned problems. As a result, the image receptor having the following structure has a reduced dyeing sensitivity. The present invention was found to be excellent in image durability without performing, and reached the present invention. That is, the present invention provides a sublimation transfer image receiving body comprising a substrate, a dyeing layer provided on the substrate, and at least one image protective layer on the surface of the dyeing layer. Is an aqueous dispersion of polyester resin
Or coated in the form of an aqueous solution (no solvent)
And the dyeable resin mainly composed of the dyed layer of the sublimation transfer image receptor is a polyester resin.

[0005] In the composition of the dyeing resin forming the dyeing layer of the sublimation transfer image receiving body in the present invention, the polyester resin which characterizes the present invention is a polyester having the following composition and a polyurethane made from these. , 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, an aromatic glycol or the like 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, aliphatic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid Dicarboxylic acid, fumaric acid, maleic acid, tetrahydrophthalic acid, tricyclodecanedicarboxylic acid, 1,
Examples include unsaturated aliphatic and alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, and tri- and tetracarboxylic acids such as trimellitic acid and pyromellitic acid. Desirable 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.

[0007] Glycol components which can be used in the present invention include, for example, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, tripropylene glycol, 2,3,4-trimethylol-1. , 3-pentanediol, 1,6-hexanediol, tricyclodecane dimethylol, 1,4-
Cyclohexane dimethanol, ethylene oxide adduct of bisphenol A, ethylene oxide and / or propylene oxide adduct of hydrogenated bisphenol A, 2,2-diethyl-1,3-propanediol,
-N-butyl-2-ethyl-1,3-propanediol, spiroglycol and the like. Of these, neopentyl glycol, ethylene glycol, polyethylene glycol, propylene glycol,
Tricyclodecane dimethylol, 1,4-cyclohexanedimethanol, an ethylene oxide adduct of bisphenol A, spiro glycol, and propylene glycol.

[0008] 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 in combination with the chain extender.

The organic diisocyanate compound (b) used for such a 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-diisocyanatomethylcyclohexane, 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'-biphenylenediisocyanate,
4,4'-diisocyanate diphenyl ether, 1,
5'-naphthalenediisocyanate and the like. 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-cyclohexane dimethanol, bisphenol A ethylene oxide adduct, 1,4-cyclohexane dimethanol, and the like. Among the above chain extenders, more preferred ones are
Neopentyl glycol, ethylene glycol, polyethylene glycol, diethylene glycol, bisphenol A ethylene oxide adduct, tricyclodecane dimethylol, and 1,4-cyclohexanedimethanol.

The polyurethane resin is produced in a known manner, for example, in a solvent at a reaction temperature of 20 ° C. to 150 ° C. in the presence or absence of a catalyst. As a solvent used at this time, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used as a catalyst for promoting a reaction. Examples thereof include amines and organotin compounds.

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

The method of coating the polyester resin used in the dyeing layer of the present invention is generally carried out by dissolving the polyester resin and the polyurethane resin in a solvent, or using a non-aqueous dispersion or an aqueous dispersion. Alternatively, it can be used in the form of an aqueous solution (no solvent). The solid concentration is generally used at 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 from 1,000 to 100,000.
Is 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 reduced. On the other hand, if it exceeds 100,000, the solution viscosity becomes too high and handling becomes difficult, which is not preferable.

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

The resin mainly composed of at least one image protective layer on the surface of the dyeing layer of the present invention includes, for example,
Examples include hydrophilic resins, oil-repellent resins, and resins that are hardly soluble in organic solvents. Further, a sensitizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a heat releasing agent, and the like 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 is used in the form of an aqueous dispersion or aqueous solution (solvent-free) of a hydrophilic resin, an oil-repellent resin, and a resin insoluble in an organic solvent. The solid content can be used at about 5 to 70% by weight.

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

[0018]

EXAMPLES Hereinafter, the present invention will be described with reference to production examples and examples in order to specifically explain the present invention. 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. These results are shown in Table 1. The measurement methods for the dyeing concentration, light resistance, heat resistance, plasticizer resistance, and fingerprint resistance are as described below, and the evaluation results are shown in Table 2.

(1) Production example of polyester for dyeing layer In an autoclave equipped with a thermometer and a stirrer, 388 parts of dimethyl terephthalate and 376 parts of dimethyl isophthalate were added.
Parts, 12 parts of trimellitic anhydride, 541 parts of neopentyl glycol glycol, 706 parts of tricyclodecane dimethylol, and 0.5 part of tetrabutoxytitanate, and heated at 150 to 220 ° C. for 240 minutes to perform transesterification. The temperature of the reaction system was raised to 250 ° C. in 10 minutes, and the pressure of the system was gradually reduced.
The reaction was continued for further 60 minutes under these conditions to obtain a pale yellow transparent polyester A for a 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, ethylene glycol 224 parts and 0.5 part of tetrabutoxytitanate were charged and heated at 150 to 220 ° C. for 240 minutes to carry out transesterification.
The temperature was raised to 50 ° C., and the pressure of the system was gradually reduced. After 25 minutes, the pressure was reduced to 0.3 mmHg or less. The reaction was continued for further 60 minutes under these conditions to obtain a pale 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 3 to 4 at 85 ° C.
Stir for a while to obtain a uniform white aqueous polyester resin X-1.
I got Table 1 shows Resin Y-1 obtained by the same method.

(3) Method for Evaluating Density of Printed Image The image receiving sheet and the thermal transfer sheet are overlapped so that the dyeing layer (dye receiving layer) and the color material layer are in contact with each other, and a thermal head is provided from the base side of the thermal transfer sheet. By heating at a head output of 0.7 W / dot, a head heating time of 8 mS, and a dot density of 3 dots / mm, the cyan dye in the color material layer was transferred to the dye layer. The resulting transferred image density was measured with a reflection densitometer (DM-600, manufactured by Dainippon Screen Co., Ltd.).

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

(5) Evaluation method of heat resistance (dark fading rate) The image receiving body to which the cyan dye has been transferred is left for 168 hours in an environment of 60 ° C. in a dark place, aged, and subjected to aging to determine the density before the heat resistance test. And the dye concentration retention rate (%) in the comparison of.

(6) Evaluation method of plasticizer resistance The thickness of 80 μm is applied to the surface of the image receiving body onto which the cyan dye has been transferred.
A 1 cm @ 2 film of vinyl chloride was applied, and a load of 5 g was applied on the vinyl chloride film. The film was allowed to stand at 40 DEG C. for 24 hours to remove the color of cyan dye.
I saw traces of the film. After aging, those having no change such as color omission without a film mark on the image receiving layer surface were evaluated as ○, those with no change in color but film marks remained as Δ, and those with changed color and film marks remained as X. .

(7) Fingerprint resistance evaluation method Thumbs are strongly pressed against the surface of the image receiving body onto which the cyan dye has been transferred so that the fingerprints remain on the image surface, and are left under an environment of 40 ° C. for 48 hours. Aggregation, color loss, and fingerprint traces of the cyan dye were observed. After aging, the sample having no color change on the surface of the image receiving layer and having no change in color was evaluated as ○, the sample with no color change but with fingerprint trace remaining was evaluated as △, and the sample in which the dye aggregated on the image surface was evaluated as ×.

Example 1 Polyester A for the receiving layer was diluted with a mixed solvent of toluene: methyl ethyl ketone = 50: 50 to obtain a 20% solution. An 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 based on the above resin. Was applied so that a dry coating film of 7 μm was obtained. The sheet was dried in an atmosphere at 120 ° C. for 30 minutes to obtain a dyeing layer (dye receiving layer). Next, X-1 diluted with a mixed solution of isopropanol: water = 60: 40 was applied onto the obtained dyeing layer, and the dried image protective layer was coated with a coating having a thickness of 0.5.
It was applied with a bar coater so as to have a thickness of about 5 μm. This solution was mixed with a modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount of 8% by weight based on the resin for the image protective layer. Drying is 10
Performed at 0 ° C. for 20 minutes. The adhesion between the obtained image protective layer and the dyeing layer was very good.

Example 2 An image receiving member was provided in the same manner as in Example 2 by using the resin B for the dyeing layer of the present invention and the resin Y-1 for the image protective layer.

Comparative Example 1 Comparative Example 1 was prepared by using resin A and providing only a dyeing layer in the same manner as in Example 1.

COMPARATIVE EXAMPLE 2 Comparative Example 2 was made by using resin B and providing only a dyeing layer in the same manner as in Example 1.

COMPARATIVE EXAMPLE 3 Comparative Example 3 was carried out by using the resin X-1 for the image protective layer and directly coating the substrate without providing a dyeing layer in the same manner as in Example 1.

COMPARATIVE EXAMPLE 4 Comparative Example 4 was carried out using resin Y-1 for an image protective layer and directly coating the substrate without providing a dyeing layer in the same manner as in Example 1.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

As described above, the sublimation type thermosensitive recording image receiver having the dyeing layer of the present invention and at least one image protective layer on the surface thereof has high dyeing sensitivity, and the obtained image is It has excellent durability and storage stability and is industrially useful.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-294595 (JP, A) JP-A-63-30293 (JP, A) JP-A-64-30792 (JP, A) JP-A-1- 269589 (JP, A) JP-A-2-92592 (JP, A) JP-A-1-264896 (JP, A) JP-A-64-78882 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (1)

(57) [Claims] 1. A sublimation transfer image receiving body comprising a base material, a dyeing layer provided on the base material, and at least one image protective layer on the surface of the dyeing layer. Is
Aqueous dispersion or aqueous solution of ester resin (no solvent)
Of are those coated with the form, and sublimation transfer image receiver of dyeable resin is characterized in that it is a polyester resin constituting the dyeing layer of the sublimation transfer image receiver mainly.