JP3074774B2 - Dye thermal transfer image receiving sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye thermal transfer image receiving sheet. More specifically, the present invention relates to a dye thermal transfer image receiving sheet which transfers and dyes a dye from an ink sheet by sublimation or thermal diffusion, and particularly to a dye thermal transfer image receiving sheet having excellent storage stability against light of a recorded image. It is about a sheet.

[0002]

2. Description of the Related Art Today, the development of high-quality color hard copy using a thermal transfer recording system, particularly a printer of a dye thermal transfer system, is rapidly progressing. In the dye thermal transfer method, the transfer amount of the dye of each color is continuously controlled by continuously controlling the heating energy of a thermal head on an ink sheet having a sublimable dye layer of three colors of yellow, magenta and cyan. By changing it, a full-color density gradation image can be printed. In such a thermal transfer recording system, in order to obtain a high-quality recorded image on the dye thermal transfer image receiving sheet, there is no thermal fusion with the ink sheet,
There is a demand for an image-receiving layer having a high dye transfer rate, a high saturation density, and good storage stability against light and heat.

In particular, the dye thermal transfer image receiving sheet in the dye thermal transfer recording system has an image receiving layer containing a thermoplastic resin as a main component which is easily dyed by a dye transferred from the ink sheet by sublimation or diffusion.
The light fastness of the dye image received on such a thermoplastic resin was not always sufficient. Therefore, in order to improve the light fastness of a dyed image, for example, Japanese Patent Application Laid-Open No. 32789/1986 discloses a method in which an ultraviolet absorber absorbing ultraviolet rays of 300 to 400 nm is contained. JP-A-61-229594
Discloses a method of providing an image receiving layer containing at least one of an ultraviolet absorber and a light stabilizer. However, the light fastness of these conventional dye images is still insufficient, and in recent years, with the advancement of printers, high sensitivity, high density dyeing, and further recording to maintain high-clear images have been performed. It is desired to develop an image receiving sheet having improved storage stability against light of an image and improved image bleeding prevention during heat storage.

In general, the fading of a recorded image is significantly increased by light having a wavelength of 400 nm or less. Therefore, it has been attempted to prevent fading by blending an ultraviolet absorber into the image-receiving resin layer. Was not enough.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional dye thermal transfer image receiving sheet, enables high-speed printing, obtains a good recorded image, and further improves image storability. In particular, an object of the present invention is to provide a dye thermal transfer image receiving sheet having excellent storage stability (light resistance) against light.

[0006]

The present inventors have conducted intensive studies to obtain a dye thermal transfer image receiving sheet having excellent storage stability, that is, light resistance, of a recorded image with respect to light. And at least one selected from dialkyltin maleate polymer and dialkyltin-S, S'-bis (isooctylmercaptoacetate) as an image storage stabilizer together with The present inventors have found that the storage stability of the present invention can be remarkably enhanced, and completed the present invention.

The dye thermal transfer image receiving sheet of the present invention has a sheet-like support, and an image receiving resin layer formed on at least one surface of the support and made of a dye receptive resin material. (1) a resin component comprising at least one selected from a saturated polyester resin and a vinyl chloride copolymer resin; (2) an ultraviolet absorber; and (3) a dialkyltin maleate. A polymer and at least one stabilizer selected from dialkyltin-S, S'bis (isooctylmercaptoacetate), wherein the content of the stabilizer is 1 to 20 parts by weight per 100 parts by weight of the resin component Part.

As the sheet-like support used in the present invention, high-quality paper,
Paper supports such as coated paper, polyester films, various plastic films such as synthetic papers which are mono- or biaxially stretched films mainly composed of polyolefin and inorganic pigments,
Alternatively, a laminated sheet obtained by combining them, a laminated paper obtained by extruding and laminating a composition mainly containing a polyolefin resin and a pigment on the surface of a paper support, or a composite sheet thereof can be used. The support used in the present invention has a thickness of 20 to 250 μm and a basis weight of 20 to 250 g / m ^2.
It is preferred that

In the present invention, the dye-receiving resin material for forming the image-receiving resin layer contains a dye-receiving resin component, an ultraviolet absorber component, and a stabilizer component, as described above.

The dye-receiving resin component used in the present invention contains at least one selected from a saturated polyester resin and a vinyl chloride copolymer resin. Dye-receiving saturated polyester resin can be selected from known ones, for example, terephthalic acid, if necessary,
A dicarboxylic acid component including other aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid; ethylene glycol; and, if necessary, other diol compounds such as an ethylene glycol adduct of bisphenol A And a polycondensate with a diol component containing a propylene oxide adduct of bisphenol A and the like.

The vinyl chloride copolymer resin is selected from, for example, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, vinyl chloride-acrylic acid copolymer resin, and the like. be able to.

The dye-receptive resin component used in the present invention may contain a small amount (preferably 30% or less of the total weight of the dye-receptive resin) in addition to the polyester resin and the vinyl chloride copolymer resin. ) It may contain one or more kinds selected from polycarbonate resin, polyvinyl acetal resin, polyamide resin, polyacrylate resin and the like.

In the present invention, the dye-receiving resin component comprises:
The content is preferably 83% or more, more preferably 87-97%, based on the weight of the image receiving resin layer.

The ultraviolet absorber used in the present invention is 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-cumylphenyl) benzotriazole, 2- (2'-hydroxy-
Benzotriazole compounds such as 5'-octylphenyl) benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxycybenzophenone, and 2,2'-dihydroxy-4- Benzophenone compounds such as dimethoxybenzophenone, p-tert-butylphenyl salicylate, phenyl salicylate, p-
It is preferably selected from salicylic acid compounds such as octylphenyl salicylate. Other succinic acid dimethylate and 1-hydroxyethyl-4-hydroxy-2,
Hindered amines such as polycondensates with 2,6,6-tetramethylpiperidine, and light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate may be contained. .

In the image receiving resin layer of the present invention, a dialkyltin compound is contained as a sensitive recording image storage stabilizer together with an ultraviolet absorber in order to improve the storage stability of the recorded image against light. As the dialkyltin compound, a dialkyltin maleate polymer and dialkyltin-S, S'-bis (isooctylmercaptoacetate) are used. These dialkyltin compounds are
They may be used alone or in combination.

Among the dialkyltin compounds, examples of the dialkyltin maleate polymer include di-n-octyltin maleate polymer, di-n-butyltin maleate polymer bismaleate, and di-n-butyltin maleate polymer. Examples of the dialkyltin-S, S'-bis (isooctylmercaptoacetate) include di-n-octyltin-S, S'-bis (isooctylmercaptoacetate) and di-n-butyltin- S,
S'-bis (isooctyl mercaptoacetate) or the like can be used.

The blending ratio of the ultraviolet absorber in the dye-receiving resin material of the present invention is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the dye-receiving resin component.
More preferably, it is set to 〜15 parts by weight. If the amount of the ultraviolet absorber is less than 1 part by weight, the storage stabilizing effect of the recorded image may be insufficient, and if it exceeds 20 parts by weight, the dye receptivity of the obtained image-receiving resin layer may be reduced. May drop. In the dye-receiving resin material of the present invention, the compounding ratio of the dialkyltin compound stabilizer is the dye-receiving resin component 10
0 parts by weight, 1 to 20 parts by weight, and 3 to 15 parts by weight.
It is preferable to use parts by weight. If the amount of the dialkyltin compound stabilizer is less than 1 part by weight, the storage stabilizing effect of the recorded image becomes insufficient, and if it exceeds 20 parts by weight, the dye receptivity of the obtained image-receiving resin layer decreases. . The compounding ratio of the UV absorber and the dialkyltin compound stabilizer is 9
It is preferably 0:10 to 10:90.

In the present invention, a crosslinking agent may be added to the dye-receiving resin material in order to improve the heat resistance of the image-receiving resin layer and the heat resistance of the recorded image. Examples of such a crosslinking agent include polyisocyanate compounds having two or more isocyanate groups, for example, polyfunctional isocyanate compounds such as tolylene diisocyanate, triphenylmethane p, p ', p "-triisocyanate, and polymethylene polyisocyanate. In addition, a compound having an epoxy group, a methylol group, or the like may be used.The amount of the crosslinking agent to be added is 1 to 20% by weight, particularly preferably 1 to 10% by weight, based on the weight of the image receiving resin layer. If the amount of the agent exceeds 20% by weight, the resin is cured, and the sensitivity of the image receiving resin layer is lowered, and if the amount is less than 1% by weight, a sufficient heat resistance effect cannot be obtained.

Further, in order to enhance the heat-resistant fusing property at the time of printing the ink ribbon and the image receiving resin layer by heat, a release agent may be used by mixing with a dialkyltin compound.
Such release agents as paraffin, waxes such as polyethylene wax, metal soap, silicone oil,
An amino-modified silicone, an epoxy-modified silicone, an alcohol-modified silicone, a silicone resin, a silicone varnish, a fluorine-based activator, a fluorine-based resin, a phosphate ester, and the like can be added. It is desirable that the content be not more than weight%.

Low molecular organic compounds such as terpenes and substituted phenols may be blended as components of the image-receiving resin layer of the present invention for the purpose of preventing oxidation, absorbing ultraviolet light, sensitizing, and the like. In general, a white pigment used for improving the whiteness and opacity of the paint, a fluorescent dye for adjusting the color tone of the receiving layer, and a dye such as blue or violet may be added.

The above-mentioned white pigment, ultraviolet absorber, stabilizer,
It is convenient to coat a cross-linking agent or the like with the dye-receiving resin component, but for an ultraviolet absorber or the like, apply it as a separate coating layer on or under the image-receiving resin layer. Is also good.

Generally, the weight of the image receiving resin layer is 2 to 20 g.
Preferably / a m ^2, and more preferably a 4~10g / m ^2. If the image-receiving resin layer is too thin, the density and sensitivity of the image decrease, and the uniformity of the image deteriorates due to the limitation of coating accuracy. On the other hand, if it is too thick, its effect is saturated and not only is uneconomical, but also its own strength is reduced.

The dye thermal transfer image receiving sheet of the present invention contains an antistatic agent on at least one surface of the sheet-like support in order to prevent generation of static electricity when the image receiving sheet travels in the printer. May be provided.
Alternatively, an antistatic agent may be added in the image receiving resin layer. As such an antistatic agent, a cationic, anionic or nonionic activator or an antistatic polymer can be used.

[0024]

The present invention will be described in more detail with reference to the following examples.

Example 1 An image receiving sheet was prepared by the following steps. 150 g / m
^A sheet-like support obtained by laminating polyethylene of 30 μm on both sides of a high-quality paper ^{2 as} a sheet-like support, and a coating 1 having the following composition as a coating for forming an image-receiving resin layer of a sublimable dye on one side thereof, Was applied to a weight of 5 g / m ² and dried to form an image-receiving resin layer to produce an image-receiving sheet for a dye thermal transfer printer.

The paint -1 vinyl chloride - 100 parts by weight of vinyl acetate resin (trademark: # 1000LT _3, manufactured by Denki Kagaku Kogyo) di -n- octyl-tin maleate polymer 3 parts by weight (trademark: TVS # 8813, Nitto Kasei Co., Ltd., Melting point: 90-100 ° C) 2- (2'-hydroxy-3'-tert-10 parts by weight butyl-5'-methylphenyl) -5-chlorobenzotriazole (Trade name: Sumithorp 300, manufactured by Sumitomo Chemical) Toluene 200 parts by weight Parts 200 parts by weight methyl ethyl ketone

Using the image receiving sheet obtained as described above, its dye receptivity and storage stability were tested and evaluated by the following methods. Each of the evaluation results was classified into 5 grades: 5th grade: excellent grade, 4th grade: good grade, 3rd grade: general quality grade, 2nd grade: poor grade, 1st grade: seriously defective grade Displayed with.

1. Dye receptivity A step pattern is printed on an image receiving sheet using a commercially available sublimation transfer color video printer (manufactured by Sony Corporation: UP5000), and the maximum density and sensitivity of the obtained thermal transfer image are tested and evaluated. Indicates the dye receptivity. (1) Maximum density: The density of a thermal transfer image was measured using a Macbeth reflection densitometer (manufactured by Kollmorgen: RD-914).
2.1 or higher is 5th grade, 2.0 or more and less than 2.1 is 4th, 1.9 or more and 2.0.
Less than 0 is grade 3; 1.8 or more and less than 1.9 is grade 2; less than 1.8 is 1
The class was indicated. (2) Sensitivity: The transfer image density at low energy was measured with a Macbeth reflection densitometer.
Grade 0 to less than 1.1, Grade 3, 0.9 to less than 1.0, Grade 0.8
Above 0.9 was indicated as 2nd grade, and less than 0.8 as 1st grade.

2. Storage Stability of Recorded Image The light transfer and heat resistance tests and evaluations were performed using the above-mentioned thermal transfer image, thereby indicating the storage stability. (1) Light resistance Xenon fade meter at 50 ° C, 63% R
After exposing for 48 hours under the condition of H, the change in the image was visually evaluated. (2) Heat resistance After the heat transfer image was stored in a 60 ° C. blast dryer for 200 hours, changes in the image were visually observed and evaluated. Table 1 shows the test results.

Example 2 The same operation as in Example 1 was performed. However, Paint-2 having the following composition was used as the paint for forming the image receiving resin layer. Paint-2 Polyester resin (trademark: Byron 200, manufactured by Toyobo) 100 parts by weight Amino-modified silicone oil 1 part by weight (trademark: KF393, manufactured by Shin-Etsu Silicone) 3 parts by weight of di-n-octyltin-S, S'-bis ( Isooctyl mercaptoacetate) (trademark: TVS # 8831, manufactured by Nitto Kasei, viscosity 90 centipoise or less (30 ° C)) 2-hydroxy-4-n-octoxybenzophenone 5 parts by weight (trademark: DK-21, manufactured by Asahi Denka Kogyo) ) Isocyanate compound 5 parts by weight (trademark: Coronate L, manufactured by Nippon Polyurethane) 200 parts by weight of toluene 200 parts by weight of methyl ethyl ketone Table 1 shows the test results.

Example 3 The same operation as in Example 1 was performed. However, Paint-3 having the following composition was used as a paint for forming an image-receiving resin layer. Paint -3 vinyl chloride - 100 parts by weight of vinyl acetate resin (trademark: # 1000LT _3, manufactured by Denki Kagaku Kogyo) di -n- octyl-tin maleate polymer 3 parts by weight (trademark: TVS # 8813, Nitto Kasei Co., melting point: 90 100 ° C.) 2- (2′-hydroxy-3′-tert-10 parts by weight butyl-5′-methylphenyl) -5-chlorobenzotriazole (trade name: Sumithorp 300, manufactured by Sumitomo Chemical) Amino-modified silicone oil 1 weight Parts (trademark: KF393, manufactured by Shin-Etsu Silicone) Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight The test results are shown in Table 1.

Example 4 The same operation as in Example 1 was performed. However, Paint-4 having the following composition was used as a paint for forming an image-receiving resin layer. Paints -4 vinyl chloride - 80 parts by weight of vinyl acetate resin (trademark: # 1000LT _3, manufactured by Denki Kagaku Kogyo) Polyester resin (trademark: Byron 200, Toyobo Co., Ltd.) 20 parts by weight of di -n- octyl-tin maleate polymer, 3 parts by weight (Trademark: TVS # 8813, manufactured by Nitto Kasei, melting point: 90-100 ° C) 2- (2'-hydroxy-3'-tert-10 parts by weight butyl-5'-methylphenyl) -5-chlorobenzotriazole (trademark) : Sumithorp 300, manufactured by Sumitomo Chemical) Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight Table 1 shows the test results.

Example 5 The same operation as in Example 1 was performed. However, Paint-5 having the following composition was used as the paint for forming the image receiving resin layer. Paint -5 vinyl chloride - 100 parts by weight of vinyl acetate resin (trademark: # 1000LT _3, manufactured by Denki Kagaku Kogyo) di -n- octyl-tin maleate polymer 1.5 parts by weight (trademark: TVS # 8813, Nitto Kasei Co., Ltd., melting point : 90-100 ° C) 1.5 parts by weight of di-n-octyltin-S, S'-bis (isooctylmercaptoacetate) (trademark: TVS # 8831, manufactured by Nitto Kasei, viscosity of 90 centipoise or less (30 ° C)) 2- (2'-hydroxy-3'-tert-10 parts by weight butyl-5'-methylphenyl) -5-chlorobenzotriazole (trade name: Sumisorp 300, manufactured by Sumitomo Chemical) Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight

Comparative Example 1 The same operation as in Example 1 was performed. However, a coating material 6 having the following composition as a coating material for forming an image-receiving resin was applied so as to have a solid content of 5 g / m ² , and dried to form an image-receiving resin layer. The properties of the obtained image receiving sheet were tested and evaluated. Table 1 shows the test results. Paint -6 vinyl chloride - 100 parts by weight of vinyl acetate resin (trademark: # 1000LT _3, manufactured by Denki Kagaku Kogyo) amino-modified silicone oil 1 part by weight (trademark: KF393, produced by Shin-Etsu Silicone) 200 parts by weight Methyl ethyl ketone 200 parts by weight Test Result Toluene Are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was performed. However, Paint-7 having the following composition was used as the paint for forming the image receiving resin layer. Paint-7 Polyester resin (trademark: Byron 200, manufactured by Toyobo) 100 parts by weight Amino-modified silicone oil 1 part by weight (trademark: KF393, manufactured by Shin-Etsu Silicone) Isocyanate compound 5 parts by weight (trademark: Coronate L, manufactured by Nippon Polyurethane) Toluene 200 Parts by weight Methyl ethyl ketone 200 parts by weight Table 1 shows the test results.

Comparative Example 3 The same operation as in Example 1 was performed. However, Paint-8 having the following composition was used as a paint for forming an image receiving resin layer. Paint -8 vinyl chloride - 100 parts by weight of vinyl acetate resin (trademark: # 1000LT _3, manufactured by Denki Kagaku Kogyo) amino-modified silicone oil 1 part by weight (trademark: KF393, produced by Shin-Etsu Silicone) 2-hydroxy -4-n-octoxy Benzophenone 5 parts by weight (trademark: DK-21, manufactured by Asahi Denka Kogyo) 200 parts by weight of toluene 200 parts by weight of methyl ethyl ketone The test results are shown in Table 1.

Comparative Example 4 The same operation as in Example 1 was performed. However, Paint-9 having the following composition was used as the paint for forming the image-receiving resin layer. Paint-9 Polyester resin (trademark: Byron 200, manufactured by Toyobo) 100 parts by weight Amino-modified silicone oil 1 part by weight (trademark: KF393, manufactured by Shin-Etsu Silicone) 3 parts by weight of di-n-octyltin-S, S'-bis ( Isooctyl mercaptoacetate) (trademark: TVS # 8831, manufactured by Nitto Kasei; viscosity: 90 centipoise or less (30 ° C)) 5 parts by weight of isocyanate compound (trademark: Coronate L, manufactured by Nippon Polyurethane) 200 parts by weight of toluene 200 parts by weight of methyl ethyl ketone Test results Are shown in Table 1.

[Table 1]

[0038]

The dye thermal transfer image receiving sheet of the present invention has a good recording sensitivity, a high recording density, and can record a recorded image having excellent light resistance and heat resistance. It is extremely useful.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (1)

(57) [Claims] An image-receiving resin layer formed on at least one surface of the support and made of a dye-receiving resin material, wherein the dye-receiving resin material comprises: 1) a resin component comprising at least one selected from a saturated polyester resin and a vinyl chloride copolymer resin; (2) an ultraviolet absorber; (3) a dialkyltin maleate polymer and dialkyltin-S , S'-bis (isooctyl mercaptoacetate), wherein the content of the stabilizer is 1 to 20 parts by weight per 100 parts by weight of the resin component. Dye thermal transfer image receiving sheet.