JPH05301465A - Sublimation type thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To inexpensively provide a sublimation type thermal transfer image receiving material capable of obtaining a printing image of high image quality and generating no curl. CONSTITUTION:A dye receiving layer 2 formed from a material based on an org. polymeric compd. whose modulus at 100% elongation due to JIS-K 6301 is 300kg/m<2> or less or a porous resin (pref., a microporous structure of a vinyl chloride/vinyl acetate copolymer) is provided on a substrate (pref. having density of 0.7g/cm<3> or more) composed of natural fiber paper, chemical fiber paper or a laminate of them.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sublimation type thermal transfer image receptor used in combination with a thermal transfer recording medium provided with a transfer layer containing a sublimable dye.

[0002]

2. Description of the Related Art As shown in FIG. 1, a sublimation type thermal transfer recording is a sublimation type thermal transfer image receiving having a dye receiving layer (dyeing resin layer) 2 on a substrate (printing base paper) 1 made of synthetic paper or plain paper. Body (image-receiving paper) 3 and thermal transfer body (transfer body for sublimation heat transfer) 6 having sublimable dye transfer layer 5 on base film 4
Are superposed on each other, and they are pressed together by the thermal head 7 and the platen roller 8, and the dye transfer layer 5 is heated and vaporized by the thermal head 7 to transfer the dye transfer layer 5 to the image receptor 3.

However, the conventional sublimation type thermal transfer image receptor using the substrate 1 made of synthetic paper or plain paper has the following problems. That is, synthetic paper is generally stretched to increase its strength, and when it is heated by the thermal head only on the side where the dye receiving layer is provided during printing, contraction occurs and distortion occurs on the front and back of the image receptor. There is a drawback that curling occurs, and synthetic paper is often wrinkled in images because wrinkles are generated in the image receiver due to significant static electricity generated due to friction with the thermal head during printing compared to cellulose fiber paper. Met. On the other hand, when a fiber paper made of natural fibers or chemical fibers is used, it has the advantage that curling does not occur after printing, but it has a lower color density than synthetic paper and the voltage of the thermal head must be increased. However, there are drawbacks such as non-uniformity in color density due to large unevenness on the surface of the fiber paper.

A more specific consideration of the drawbacks associated with the above fiber paper will be described below. The substrate of the image receiver (image receiving paper) 3 (print base paper)
When the fiber paper is used as No. 1, there are many irregularities on the surface, and when viewed as the whole paper, there are large wavy unevenness and dents, and the dye receiving layer (dyeing resin layer) is formed on this. If two layers are stacked, it is possible to smooth small irregularities, but it is extremely difficult to completely smooth large unevenness and dents. Even if smoothing is possible, the back surface of the substrate 1, that is, the platen roller 8 Since there are large and small irregularities as well as overall large thickness irregularities or dents on the surface in contact with, the image receptor 3 has considerable irregularities when pressed by the thermal head 7 and the plantain roller 8 during printing. Occurs. Furthermore, since the fiber paper is made of fibers, it is stiff and has poor followability with respect to the surface of the thermal head 7, that is, the surface of the thermal transfer member 6, resulting in poor adhesion. Therefore, it is considered that the diffusion of the sublimable dye is hindered and the color density is low as a whole, resulting in unevenness in the color density (such as lack of color in the todd or white spots).

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the problems in the case of using the above-mentioned substrate made of fiber paper, and the object thereof is to obtain a high color density of prints and to prevent uneven color density. It is an object of the present invention to provide a sublimation-type thermal transfer image receptor that is significantly reduced and does not curl with a simple structure at low cost.

[0006]

According to the present invention, in a sublimation type thermal transfer image receptor having a dye receiving layer capable of dyeing a sublimable dye on a substrate, the substrate is a natural fiber paper or a chemical fiber paper. , Or those obtained by laminating a resin on these papers by laminating or coating, and the dye receiving layer is 100 defined by JIS-K-6301.
There is provided a sublimation-type image receptor for thermal transfer characterized by containing an organic polymer compound having a% modulus of 300 kg / m ² or less as a main component, and in particular, it is specified in JIS-K-6301 of the organic polymer compound. The sublimation type thermal transfer image receptor is provided, wherein the 100% modulus is 200 kg / m ² or less, and the organic polymer compound is a thermoplastic elastomer.

Further, according to the present invention, in a sublimation type thermal transfer image receptor having a dye receiving layer on which a sublimable dye can be dyed, the substrate is a natural fiber paper or a chemical fiber paper, or A resin is laminated by laminating or coating on paper, and the dye receiving layer is provided with a sublimation type thermal transfer image receptor characterized by containing a porous resin as a main component, in particular, the dye receiving layer, There is provided the sublimation type thermal transfer image receptor characterized by comprising a fine porous structure of a vinyl chloride-vinyl acetate copolymer.

Further, according to the present invention, the layer thickness of the dye receiving layer of the sublimation type thermal transfer image receptor is 1 to 100 in dry coating amount.
g / m ^2, in particular a 10 to 100 g / m ^2, also substrates of the sublimable thermal transfer image receiving body, the density 0.7 g / cm ³
There is provided the sublimation type thermal transfer image receptor characterized by being the above paper.

In the present invention, any fiber paper that has been conventionally used as a substrate (print base paper) can be used. For example, plain paper such as high-quality paper and medium-quality paper, recycled fiber paper,
Chemical fiber paper such as semi-synthetic fiber paper, synthetic fiber paper, and inorganic fiber paper can also be used, and excellent image quality without missing dots or white spots in the image can be obtained. Further, the substrate is preferably used as a resin-coated laminate substrate by laminating a plastic film or coating a resin together with a pigment, a whitening agent and the like. The fiber paper of these substrates has a density of 0.7 g / c
m ³ or more is preferable, and smoothness of less than m ³ ,
It is not preferable in terms of uniformity and coatability.

On the other hand, it is needless to say that the dye receiving layer needs to have sufficient dyeing property to the sublimation dye, but the dye receiving layer of the present invention has a 100% modulus of 30.
It is formed of a material containing an organic polymer compound of 0 kg / m ² or less, particularly 200 kg / m ² or less as a main component, or a porous resin, and these dye receiving layers are provided. Makes the color density higher,
Prints with less uneven color density can be obtained.

Examples of such organic polymer compounds include covalent cross-linking type elastomers, thermoplastic elastomers which are plasticized at a high temperature and can be molded by a plastic processing machine, and some thermoplastics having a low elastic modulus. it can. Covalent bond cross-linking elastomers typified by natural rubber, butyl rubber, nitrile rubber, urethane rubber and the like are generally excellent in heat resistance, and conversely, thermoplastic elastomers are excellent in processability and easy to form into a thin film. Good results can be obtained as the material for forming the dye-receiving layer in.

The thermoplastic elastomer requires both a rubber component having entropy elasticity in the molecule and a high-speed molecular component for preventing plastic deformation. However, a styrene-based frozen phase, an olefin or an ester is used as a molecular constraint component. Good results can be obtained in all cases, such as those based on crystalline layers such as those of the system, those due to hydrogen bonds such as urethane, and those due to ionic crosslinking such as acryl. Specific examples include styrene type, olefin type, polyester type, urethane type, polyamide type, polybutadiene type, polyvinyl chloride type and fluorine type.

As the porous resin used in the present invention,
Known resins having dye-dyeability, for example, polyester, vinyl chloride resin, polypropylene, polyethylene,
Examples thereof include polyamide, polycarbonate, polystyrene, acrylic resin, phenol resin, polyurethane and epoxy resin. Of these, vinyl chloride-vinyl acetate copolymers are particularly preferable.

As a method for forming a fine porous structure,
It is possible to use a method of utilizing the difference in solubility and exhibitability of a solvent, a method of mixing a resin and an incompatible oil, or the like.

The layer thickness of the dye receiving layer is from 1 to 1 in dry coating amount.
00g / m ^2, preferably in the range of 10 to 100 g / m ^2, not sufficient adhesion is not obtained at less than 1 g / m ^2, the color density decreases. Even if the dry coating amount is more than 100 g / m ² , uneven color density does not occur, and good color density and image quality can be obtained, but such high color density and improvement in image quality are not seen, and the cost is reduced. Be at a disadvantage. The dye-receptive layer is about 8 when formed as a coating solution by dissolving it in a solvent during coating.
When forming a dye receiving layer of g / m ² or more, an excessive amount of solvent may remain in the dye receiving layer of the finished image receptor, and the residual solvent may cause image blurring and image density variations among the image receptors. Become. Therefore, since a solvent-free coating is desired for forming a dye-receiving layer of about 8 g / m ² or more, a thermoplastic elastomer that can be extrusion-coated is a particularly preferable material for forming the dye-receiving layer.

In order to adjust the processability, heat resistance, elasticity, weather resistance and strength of the dye receiving layer, conventionally known inorganic vulcanizing agents, organic vulcanizing agents, vulcanization accelerating aids, Surfactants, antiaging agents, ultraviolet absorbers, antioxidants, mastication accelerators, softening agents, reinforcing agents, fillers, resins and the like can be added as appropriate. Examples of the filler include white pigments such as silica, titanium oxide, and calcium carbonate, and the addition amount thereof is 5 to 60% by weight based on the amount of the organic polymer compound of the receiving layer, that is, the receiving layer forming resin. Is preferred.

Further, in order to prevent the heat transfer body and the image receiving body for heat transfer from being thermally fused or adhered at the time of printing, a release agent such as a silicone type or a fluorine type is contained in the dye receiving layer, or a dye is used. A layer of a release agent or a layer containing a release agent may be provided on the receiving layer.

The material for forming the dye-receptive layer as described above is dissolved in a suitable organic solvent or adjusted to a suitable viscosity as an emulsion solution, and then, for example, a roll coater, a kiss coater,
It is provided by coating and drying by any coating means such as a gravure coater, and extrusion coating such as accumulator is also used for the thermoplastic substance.

[0019]

In the image receptor for sublimation thermal transfer of the present invention, an elastic dye receiving layer, that is, JIS, is provided on the substrate of the image receptor.
-100% modulus specified in K-6301 is 30
By providing a dye receiving layer formed from a material containing an organic polymer compound of 0 kg / m ² or less as a main component, even if there is some unevenness or thickness unevenness on the surface of the substrate, these can be easily performed. The surface can be smoothed, and the surface of the thermal transfer member can be easily followed by the pressure of the thermal head to maintain excellent adhesion. Therefore, it is possible to prevent the conventional problems such as the decrease in color density and the occurrence of unevenness in color density due to poor adhesion.
When the above-mentioned dye receiving layer having a 100% modulus of more than 300 kg / m ² is provided, the effects of smoothing and improving the adhesiveness cannot be obtained. Particularly, when the 100% modulus is 200 kg / m ² or less, the effects of smoothing and improving the adhesion to the thermal transfer member during thermal transfer become remarkable. When a thermoplastic elastomer is used, a low modulus dye receiving layer can be formed without using a solvent. Further, when a layer formed of a porous resin is provided as the dye receiving layer, there is no white spot and it is possible to prevent a decrease in color density and uneven color density. Further when the film thickness of the dye receiving layer is 1 to 100 g / m ² on a dry coating amount enables good adhesion between the thermal transfer material at the time of thermal transfer, particularly when the coating amount is 10 to 100 g / m ^2, There is no waste of materials for forming the paint receiving layer. When a fibrous sheet having a density of 0.7 g / cm ³ is used as the substrate, a uniform and smooth dye receiving layer can be formed.

[0020]

Next, the present invention will be described in more detail with reference to Examples. In the examples, “part” means “part by weight”,
In addition, each physical property was measured by the following methods. <Color density> Thermal head recording condition 6 dots / mm, applied power 440 mW / dot, applied pulse width 3.5 ms
ec was printed with a color printer, and the reflection density was measured with a Macbeth reflection densitometer RD918. <Color Density Unevenness> In the above-mentioned printed image, the color densities were arbitrarily measured at 10 places, and the unevenness of the color density, that is, the difference between the maximum value and the minimum value of the color density was measured. <Curl> As described above, in the color printer, the image receiving paper 3 on which the gradation pattern is printed by changing the applied pulse width is shown in FIG.
Place it on the horizontal plate 9 as shown in Fig.
Was measured as the maximum value of. <Image storability> 2 at 40 ° C using printing under the above printing conditions
The recorded images were stored for a day, and the blurring of dots was visually evaluated.

Example 1 Thermal Transfer Material (Thermal Transfer Paper) Silicone Hardness Resin Film (Thickness: about 1 μm) as Back Layer
On a 6 μm-thick PET film (base film) provided with the above, about 2 parts of the ink layer application liquid [liquid B] having the following formulation was prepared.
The dye transfer layer was formed by applying the dye to a thickness of μm to obtain a heat-sensitive transfer paper. [Liquid B] Polyvinyl butyral resin 10 parts (Brand name BX-1; Sekisui Chemical Co., Ltd.) Sublimation disperse dye for cyan 6 parts (Brand name Kayaset 714; Nippon Kayaku Co., Ltd.) Methyl ethyl ketone 45 parts Toluene 45 parts Receiving paper Art paper (Basis weight 127.9 g / m ² , smoothness 2000
Seconds) and the following solution [solution A-1] is applied at a dry coating amount of 6 g / m.
^Then , it is coated with a roll coater so as to be ² and dried to form the dye-receiving layer of the present invention, which is dried at 80 ° C. for 1 minute, and further 5
An image receiving paper was prepared by aging it at 0 ° C. for 24 hours. [A-1 liquid] Polyurethane resin 10 parts (Nipporan 2301, manufactured by Nippon Polyurethane) Polyester-modified silicone resin 1 part (AY42-125, manufactured by Toray Dow Corning Silicone) Dimethylformamide (DMF) / methyl ethyl ketone (MEK) 90 parts (volume) Ratio 1: 1) Thermal head recording conditions 6 dots / mm, applied power 0.4 W /
When a gradation pattern was printed with a color printer while changing the pulse width with dots, the printing characteristics of the image receiving paper shown in Table 1 were obtained.

Example 2 In the same manner as in Example 1 except that [A-1 solution] was changed to [A-2 solution] described below, a dry coating amount of 6 g / g on art paper was obtained. When a dye receiving layer was formed by coating with a roll coater to obtain m ² and drying, an image receiving paper was prepared and a gradation pattern was printed with a color printer, the printing characteristics of the image receiving paper shown in Table 1 were obtained. .. [A-2 liquid] Thermoplastic elastomer 10 parts (Aron NP4000, manufactured by Toagosei Co., Ltd.) Polyester modified silicone resin 2 parts (AY42-125, manufactured by Toray Dow Corning Silicone) DMF / THF 80 parts (volume ratio 1: 1 )

Example 3 In Example 1, the [A-1 solution] was changed to the following [A-3 solution], and coating was carried out by extrusion coating so that the coating amount was 14 g / m ² to form a dye receiving layer. An image receiving paper was prepared in the same manner as in Example 1 except for the points described above, and a gradation pattern was printed with a color printer. The printing characteristics of the image receiving paper shown in Table 1 were obtained. [A-3 liquid] Thermoplastic elastomer 10 parts (Aron NP4000, manufactured by Toagosei Kagaku) Polyester-modified silicone resin 1 part (AY42-125, manufactured by Toray Dow Corning Silicone)

Example 4 In Example 3, [A-3 solution] was changed to [A-4 solution] described below, and the dry coating amount was 14 g / m ² on the art paper (described above).
An image receiving paper was prepared in the same manner as in Example 3 except that the image was coated and dried with a roll coater so that the gradation pattern was printed with a color printer. The printing characteristics of the image receiving paper shown in Table 1 were obtained. It was [A-4 liquid] Thermoplastic elastomer (Aron NP4000) 10 parts Polyester-modified silicone resin 1 part (AY42-125, manufactured by Toray Dow Corning Silicone) THF / DMF (volume ratio 1: 1) 90 parts

Comparative Example 1 An image receiving paper was prepared in the same manner as in Example 1 except that [A-1 solution] was changed to [A-5 solution] below, and a gradation pattern was formed with a color printer. Then, the printing characteristics of the image receiving paper shown in Table 1 were obtained. [A-5 liquid] Vinyl chloride / vinyl acetate / vinyl alcohol copolymer 20 parts (Denka vinyl # 1000GKT, manufactured by Denki Kagaku) Polyester-modified silicone resin 1 part (AY42-125, manufactured by Toray Dow Corning Silicone) Toluene / MEK (Volume ratio 1: 1) 80 parts

Comparative Example 2 An image receiving paper was prepared in the same manner as in Comparative Example 1 except that polypropylene synthetic paper (basis weight: 97 g / m ² , smoothness: 1000 seconds or more) was used in place of the art paper, and a color printer was used. When the gradation pattern was printed, the printing characteristics of the image receiving paper shown in Table 1 were obtained.

[0027]

[Table 1] (1) "M100 of resin" means 100% modulus defined by JIS-K-6301, and the unit is kg /
m ² . (2) * means that measurement is impossible.

From Table 1, in the present invention (Examples 1 to 3), the image receiving paper having high color density, small chromaticity unevenness, almost no curl, no blur, and excellent image storability. Further, in Example 3, the thickness of the dye-receptive layer was considerably increased to 14 g / m ² , but since it was formed by extrusion coating, blurring of the image did not occur. Further, in Example 4 in which the dye receiving layer having a large layer thickness is formed by using the solvent solution type coating liquid, it is found that the image is slightly blurred due to the residual solvent. On the other hand, in Comparative Example 1 in which the dye receiving layer was formed using an organic polymer compound having a high 100% modulus, the color density was low and the unevenness of the color density was large.
It can be seen that the degree of curl is high in Comparative Example 2 in which synthetic paper is used as the material of the substrate.

Example 5 A layer having a thickness of 3 μm was formed from the following [C liquid] on a bond paper (density 0.6 g / cm ³ ), and then a layer having a thickness of 3 μm was formed using [D liquid]. After that, the surface was treated with a hexane solution to remove the oil component to obtain an image receptor having a fine porous structure. [C liquid] Polyester resin (XA-7052, made by Unitika) 20 parts Methyl ethylene ketone 40 parts Toluene 40 parts [D liquid] Epoxy resin (Epicoat 828, Shell Chemical Co., Ltd.) 10 parts Triethylene tetramine 0.5 part Lanolin fatty acid oil 3 parts Methyl ethyl ketone 40 parts Toluene 20 parts

Example 6 An image receptor was obtained in the same manner as in Example 5 except that the substrate was coated paper (density 0.9 g / cm ³ ).

Example 7 An image receptor was obtained in the same manner as in Example 5 except that the substrate was gravure paper (density 1.2 g / cm ³ ).

Example 8 In Example 5, [C liquid] was replaced with [E liquid] below and [D]
Liquid] was changed to [F Liquid] below, and art paper (density 1.3 g /
An image receptor was obtained in the same manner as in Example 5 except that a 5 μm-thick receiving layer was provided on the (cm ³ ). [Liquid E] Polyester resin (Byron 200, manufactured by Toyobo) 20 parts Lanolin fatty acid oil 5 parts Methyl ethyl ketone 40 parts Toluene 40 parts [F liquid] Vinyl chloride-vinyl acetate copolymer 20 parts (VYHH, Union Carbide) Silicone oil (SF8418, Toray Silicone) 0.4 parts Methyl ethyl ketone 40 parts Toluene 40 parts

The sublimation-type thermal transfer image receivers obtained in Examples 5 to 8 were printed in the same manner as in Example 1, and the results are shown in Table 2.

[Table 2]

[0034]

As described above, in the image receptor having the dye receiving layer capable of dyeing the sublimable dye on the support, the substrate is made of natural fiber paper, chemical fiber paper, or laminated or coated on them. By comprising a laminate with a resin, and the dye receiving layer is made of a material whose main component is an organic polymer compound having a 100% modulus of 300 kg / m ² or less defined in JIS-K-6301, By improving the adhesion between the image receiving member and the thermal transfer member, eliminating the decrease in the color density of the transferred image, the unevenness of the color density, and the blurring of the image, there is almost no curl, and an image receiving member having excellent printing characteristics is provided. It can be manufactured at low cost. Further, when the modulus is 200 kg / m ² or less, more excellent printing characteristics can be obtained. When the organic polymer compound is a thermoplastic elastomer, a low-modulus dye-receiving layer is formed without using a solvent, which results from residual solvent when a dye-receiving layer having a large layer thickness is formed. It is possible to completely eliminate the problem of image blurring and image density variation among image receivers. Furthermore, when the dye-receptive layer is formed of a porous resin, whitening, a decrease in color density,
Unevenness can be prevented. Furthermore, when the layer thickness of the dye receiving layer is set so that the dry coating amount is 1 to 100 kg / m ² , the adhesion between the image receiving member and the thermal transfer member is improved, and 10 to 100 kg / m 2 is obtained.
^In the case of ^2, the adhesiveness is further improved, and the image receiving body has excellent printing characteristics, a high quality transferred image can be obtained, and the dye receiving layer can be economically formed. When a fibrous sheet having a density of 0.7 kg / m ² is used as the substrate, the receiving layer provided thereon is a uniform and smooth receiving layer.

[Brief description of drawings]

FIG. 1 is a schematic diagram for explaining the concept of sublimation type thermal transfer recording, and a sectional structure of a sublimation type thermal transfer image receptor and a thermal transfer member.

FIG. 2 is an explanatory cross-sectional view of a curl degree and a measuring method of a sublimation type thermal transfer image receptor on which a gradation pattern is printed.

[Explanation of symbols]

 1 Substrate (printing base paper) 2 Dye receiving layer (dyeing resin layer) 3 Sublimation type thermal transfer image receptor (image receiving paper) 4 Base film 5 Dye transfer layer 6 Thermal transfer body 7 Thermal head 8 Platen roller 9 Horizontal plate

Front page continued (72) Inventor Hiroki Kuboyama 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Yutaka Ariga 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Naoya Moroboshi 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd.

Claims (8)

[Claims] 1. A sublimation type thermal transfer image receptor having a dye receiving layer capable of dyeing a sublimable dye on a substrate, wherein the substrate is a natural fiber paper or a chemical fiber paper, or a laminate or coating on these papers. The resin is laminated, and the dye receiving layer is JIS-K-630.
100% modulus specified in 1 is 300 Kg / m ²
A sublimation-type thermal transfer image receptor, which contains the following organic polymer compound as a main component. 2. The organic polymer compound is JIS-K-
100% modulus specified by 6301 is 200 kg
/ M ² or less, the image receptor for sublimation thermal transfer according to claim 1. 3. The image receptor for sublimation thermal transfer according to claim 1, wherein the organic polymer compound is a thermoplastic elastomer. 4. A sublimation type thermal transfer image receptor having a dye receiving layer capable of dyeing a sublimable dye on a substrate, wherein the substrate is a natural fiber paper or a chemical fiber paper, or a laminate or coating on these papers. A sublimation-type image receptor for thermal transfer, characterized in that a resin is laminated, and the dye-receiving layer contains a porous resin as a main component. 5. The sublimation type thermal transfer image receptor according to claim 4, wherein the dye receiving layer is composed of a microporous structure of a vinyl chloride-vinyl acetate copolymer. 6. The sublimation type thermal transfer image receptor according to claim 1, wherein the layer thickness of the dye receiving layer on the substrate is 1 to 100 g / m ² in a dry coating amount. 7. The sublimation type thermal transfer image receptor according to claim 6, wherein the layer thickness of the dye receiving layer on the substrate is 10 to 100 g / m ² in a dry coating amount. 8. The sublimation thermal transfer image receptor according to claim 1, wherein the substrate is paper having a density of 0.7 g / cm ³ or more.