Heat meltable ink image-receiving sheet and image forming method using the same

BACKGROUND OF THE INVENTION

[0001] The present invention relates to a heat meltable ink image-receiving sheet used in an image forming method wherein a thermal transfer sheet with a heat meltable ink on a substrate is brought into contact with the ink-receiving layer of the image-receiving sheet so as to face the ink side of the thermal transfer sheet, and the ink is melted with heat given by a printing head of a thermal transfer printer from the back side of the thermal transfer sheet and penetrated into pores of the ink-receiving layer, and an image forming method using the image-receiving sheet.

[0002] In forming a high-definition image using a thermal transfer printer, a method forming a color image wherein an image-receiving sheet with a porous ink-receiving layer was used and a melting transfer from thermal transfer sheets in yellow, magenta and cyan (black etc. if required) was performed by penetrating heat meltable inks in a molten state into pores of the porous ink-receiving layer was already reported in ITE (The Institute of Image Information and Television Engineers) Technical Report, Vol. 17, No. 27 (May, 1993), pages 19-24.

[0003] Furthermore, as methods for forming a porous layer, the following methods are known:

[0004] a wet coagulation method, wherein a sheet coated with a solution of a resin in dimethylformamide is dipped in water and the dimethylformamide is replaced with water to form a porous layer (JP, B, 49-25430 and JP, A, 5-155163);

[0005] a mechanical agitation foaming method, wherein after a resin is mechanically agitated to be foamed and the foamed resin is applied onto a sheet to form a porous layer (JP, A, 7-32753 and JP, A, 7-309074);

[0006] a pigment addition method, wherein a porous layer of a resin is formed by utilizing oil absorbing property of a porous pigment incorporated in the resin (JP, A, 3-98333 and Japanese Patent No. 2,535,371);

[0007] a solvent dissolving method or a dry method, wherein a resin is dissolved into a mixture of a good solvent with a lower boiling point and a poor solvent with a higher boiling point, and the resultant solution is applied onto a sheet and then dried to form a porous layer with a porous structure composed of pores resulting from the poor solvent with a slower rate of drying (JP, A, 4-82790, and JP, A, 6-166283);

[0008] a foaming agent method, wherein a porous layer of a resin is formed by incorporating into the resin a foaming agent that generates a gas upon heating, and then foaming the resin (JP, A, 2-3396); and

[0009] a soluble particles-dissolving-off method, wherein a resin containing soluble particles is formed into a film and the soluble particles contained in the film are dissolved off by washing to form a porous layer (JP, A, 6-171250).

[0010] However, in all the above-described porous layer forming methods, it is difficult to control the state of a porous structure which is recognized to be the most important factor in a thermal transfer involving penetrating ink into pores of the porous ink-receiving layer, and as a result there are problems such as that because the number of minute pores in the receiving layer is small, enough penetration is not achieved, and that the pore size is large, causing an adverse effect on transfer of minute dots.

[0011] Among the above-described porous layer forming methods, the wet coagulation method is a method that can relatively easily form a large number of minute pores in the ink-receiving layer. As for this method, various types of methods have been examined. Particularly, methods of incorporating a filler component in a resin component to improve a film strength are reported in JP, B, 49-25430 (a wet coagulation method using a mixture of a styrene resin, a plasticizer and a filler), and JP, B, 5-18332 (a wet coagulation method using a mixture of a polyester resin, a plasticizer and a filler). However, also in porous layers formed by these methods, the pore size in the porous layer is large and the porous structure is in a coarse state. Consequently, in a thermal transfer printing, it is difficult to form dots in a uniform shape because of an insufficient ink penetration. Especially in the case of printing a full-color image, a transfer failure of a second color or subsequent colors to be superimposed on a first color occurs, and hence it is difficult to form a high-definition image.

[0012] The present inventors have carried out evaluation of various porous sheets prepared according to these known technologies as a porous image-receiving sheet. The characteristics of respective porous sheets prepared by the mechanical agitation foaming method and the wet coagulation method, among the above-described methods, which are considered to be extensively improved in the formation of a high-quality image as compared with the conventional image-receiving sheets, are summed as follows:

[0013] In the case of an image-receiving sheet having a porous ink-receiving layer formed by the mechanical agitation foaming method, a water based coating can be used and an image-receiving sheet can be produced only by drying process after coating process. Therefore, it is possible to use a paper sheet as a substrate and there is an advantage of a wide selection of substrates for the image-receiving sheet. On the other hand, the obtained porous ink-receiving layer has a wide variation of open pore diameter and a high proportion of pores with large diameter. As a result, there are the following disadvantages: It is difficult to obtain sharp dots. Grainy appearance of small dots is conspicuous in a highlight region. A maximum density (saturated density) of a high level is difficult to be obtained. The gloss of the image obtained is poor.

[0014] On the other hand, in the case of an image-receiving sheet having a porous ink-receiving layer formed by the wet coagulation method, pure paper cannot be used as a substrate because of its manufacturing process and the cost is high. From the viewpoint of formation of a high-definition image, however, the porous ink-receiving layer has a narrow variation of open pore diameter and a low proportion of pores with large diameter as compared with the porous ink-receiving sheet prepared by the mechanical agitation foaming method, resulting in sharply improved performances. However, in order to obtain an image quality comparable to or superior to the image quality achieved by a sublimation transfer method, it must be improved still more. Furthermore, the present inventors have conducted an evaluation for superimposing performance of a second color and subsequent colors by using an image-receiving sheet having a porous ink-receiving layer formed by the wet coagulation method disclosed in JP, A, 62-197183 in the image forming method disclosed in JP, A, 6-286181. The results show such defect that a lot of ink flows and dot lacks are observed especially in a region from intermediate tone to shadow tone in the resultant image. In order to obtain a high-definition color image, not only the performance of a first color but also the superimposing performance of a second color or subsequent colors is significantly important. However, in the prior art, no disclosures mentioning to such importance are found, as far as the present inventors know.

[0015] The water vapor permeability of an ink image-receiving sheet is described in Japanese Patent No. 2,966,901. However, this patent mentions to only that writing property with writing devices such as a pencil and various pens is improved by limiting a thickness of a porous ink-receiving layer to a range of 3 to 50 μm and a water vapor permeability to a range of 1,000 to 9,000 g/(m2·hour). Moreover, the patent does not mention to the production of an image-receiving sheet which is used in an image formation method using a heat-meltable ink, the transfer of which is performed by melting the heat-meltable ink with heat provided from a printer head in thermal transfer to penetrate the ink into a porous structure of the receiving sheet, and which is superior in dot shape reproducibility and gradation reproducibility including variable printing performance, and color clearness, especially, dot reproducibility of second color and subsequent color in a color image, which is the object of the present invention.

[0016] Furthermore, although the patent mentions to the improvement in the writing property with writing devices such as a pencil and a pen, no description is given as to hardness of the pencil used. The inventors have performed experiments based on this patent. With respect to writing property with a pencil on an ink-receiving layer formed according to the patent, the experiments confirm good writing property in a writing using pencils with relatively low hardness from 2B to 6B. However, when a writing was performed with generally used pencils with relatively high hardness of HB or harder, the surface of the ink-receiving layer was scraped off or depressed with the pencil since the hardness of the ink-receiving layer was insufficient due to the high water vapor permeability layer of the porous layer which constitutes the ink-receiving layer (i.e., a high content of pores in the layer). Thus, it was recognized that the ink-receiving layer had insufficient writing property. With respect to the writing property with a water based ball pen or an oil based ball pen, a good result was obtained in the beginning of writing, but a drawback that a bleeding of written characters caused by diffusion of ink with time tends to occur because of the existence of open pores in the porous layer was observed. Moreover, when an image was formed using an image-receiving sheet having a porous ink-receiving layer with a water vapor permeability prescribed in the patent and a heat meltable ink which can be transferred by penetration, the ink-receiving layer itself could not restored to its original state after being pressed with a thermal transfer printer head in printing because the strength of the ink-receiving layer itself was low. Consequently, especially in the case of printing a second color or subsequent color, when a thermal transfer sheet for a second color or subsequent color was pressed against the ink-receiving layer with the thermal transfer printer head from the back side of the thermal transfer sheet, the thermal transfer sheet could not be brought into close contact with the ink-receiving layer and the heat-meltable ink was not sufficiently melted, and as a result it was difficult to form uniform dots, especially in a low density region. Furthermore, since the adhesion force of the porous ink-receiving layer to a substrate was poor, some disadvantages were observed, for example, that the ink-receiving layer was removed from the substrate by weak frictional force.

[0017] In view of the foregoing, an object of the present invention is to provide an ink image-receiving sheet used in a melting type thermal transfer recording method which has excellent ink-receiving property and writing property, and is capable of forming a high-definition, high-quality recorded image excellent in dot reproducibility and gradation reproducibility especially in a full-color printing.

[0018] Another object of the present invention is to provide a method for forming an image using foregoing ink image-receiving sheet which is capable of forming an image excellent in dot reproducibility and gradation reproducibility, especially excellent in dot reproducibility of a second color or subsequent color in color image formation.

[0019] These and other objects of the present invention will become apparent from the description hereinafter.

SUMMARY OF THE INVENTION

[0020] The present invention provides the following ink image-recieving receiving sheet and image forming method:

[0021] (1) A heat meltable ink image-receiving sheet used in an image forming method comprising the steps of: bringing a thermal transfer sheet with a heat meltable ink on a substrate into contact with an image-receiving sheet to face the ink side of the thermal transfer sheet, and melting the ink with heat given by a printing head of a thermal transfer printer from the back side of the thermal transfer sheet to transfer the ink onto a surface of the image-receiving sheet, thereby forming an image,

[0022] the heat meltable ink image-receiving sheet comprising a sheet substrate and a porous ink-receiving layer comprising a resin formed on at least one side of the sheet substrate, the porous ink-receiving layer having a thickness of 3 to 50 μm and a water vapor permeability (JIS L 1099) of not less than 300 g/(m2·hour) and less than 1,000 g/(m2·hour).

[0023] (2) The heat meltable ink-receiving sheet according to (1) above, wherein the resin of the porous ink-receiving layer comprises a polyurethane resin.

[0024] (3) The heat meltable ink-receiving sheet according to (2) above, wherein the polyurethane resin has a softening point of not less than 100° C.

[0025] (4) The heat meltable ink-receiving sheet according to any of (2) or (3) above, wherein the porous ink-receiving layer further comprises a particulate component with an oil absorption of not less than 50 ml/100 g (JIS K 5101), and a weight ratio of the polyurethane resin and the particulate component is in a range of 70:30 to 35:65.

[0026] (5) The heat meltable ink-receiving sheet according to (4) above, wherein the particulate component is a light calcium carbonate.

[0027] (6) The heat meltable ink image-receiving sheet according to any of (1) to (5) above, wherein the sheet substrate comprises a plastic material or a paper material.

[0028] (7) The heat meltable ink image-receiving sheet according to any of (1) to (6) above, wherein the porous ink-receiving layer is a layer with a porous structure formed by a wet coagulation method.

[0029] (8) A method for forming an image comprising the steps of:

[0030] providing a heat meltable ink image-receiving sheet comprising a sheet substrate and a porous ink-receiving layer comprising a resin formed on at least one side of the sheet substrate, the porous ink-receiving layer having a thickness of 3 to 50 μm and a water vapor permeability (JIS L 1099) of not less than 300 g/(m2·hour) and less than 1,000 g/(m2·hour),

[0031] bringing a thermal transfer sheet with a heat meltable ink on a substrate into contact with the ink-receiving layer of the image-receiving sheet to face the ink side of the thermal transfer sheet, and melting the ink with heat given by a printing head of a thermal transfer printer from the back side of the thermal transfer sheet to penetrate the ink into pores of the ink-receiving layer, thereby forming an image.

DETAILED DESCRIPTION

[0032] By using the heat-meltable ink image-receiving sheet of the present invention in the image formation method wherein a heat-meltable ink is penetrated into pores of an image-receiving sheet having a porous layer, as reported in the above-described ITE (The Institute of Image Information and Television Engineers) Technical Report, Vol. 17, No. 27 (May, 1993), pages 19-24, etc., it has been made possible to form an image excellent in gradation reproducibility and dot reproducibility including variable printing performance, and a color clearness.

[0033] A degree of penetration of a heat meltable ink into pores of the porous ink-receiving layer is determined by (1) a diameter of pores opening in the surface of the ink-receiving layer; (2) a ratio of the total area of all pore openings to the whole surface area of the ink-receiving layer; and (3) a ratio of the number of open pores to the number of all pores contained in the ink-receiving layer. These items can be evaluated easily by measuring the water vapor permeability (JIS L 1099) of the porous ink-receiving layer itself.

[0034] In the present invention, an ink image-receiving sheet having a porous ink-receiving layer that has a thickness of 3 to 50 μm and a water vapor permeability of not less than 300 g/(m2·hour) and less than 1,000 g/(m2·hour) as a measurement of the porous ink-receiving layer itself is used, and a heat meltable ink is melted with heat provided by a thermal transfer printer head and penetrated into the porous structure of the ink image-receiving sheet. By such method, the ink can be sufficiently penetrated into the porous structure even in printing a second color or subsequent color, and a jump-up of density in the vicinity of a saturated density is not observed in a high density region and a reproduction of a uniform minute dots can be performed even in a low density region. As a result the present invention provides an image with a rich gradation representation and a high definition that could not be reproduced by the conventional area gradation method.

[0035] Furthermore, in a preferred embodiment of the present invention, a particulate component with an oil absorption of not less than 50 ml/100 g (JIS K 5101) is blended with a resin component as a constituent of the porous ink-receiving layer to improve its layer strength and increase its oil absorption capacity. As a result the writing property with writing devices such as a pencil, and a water based ball pen or an oil based ball pen is improved.

[0036] The ink image-receiving sheet of the present invention is composed of a sheet substrate and a porous ink-receiving layer comprising a resin formed on at least one side of the sheet substrate. The thickness of the porous ink-receiving layer is 3 to 50 μm and the water vapor permeability (JIS L 1099) of the porous ink-receiving sheet itself is not less than 300 g/(m2·hour) and less than 1,000 g/(m2·hour), and preferably from 300 g/(m2·hour) to 900 g/(m2·hour). If the water vapor permeability is lower than the foregoing range, an heat meltable ink cannot be sufficiently penetrated into pores of the porous ink-receiving layer, resulting in degraded gradation reproducibility and dot reproducibility including variable printing performance, and also especially degraded dot reproducibility and color clearness of a second color and subsequent color in forming a color image. When the water vapor permeability is higher than the foregoing range, the ink-receiving layer itself cannot be restored to its original state after being pressed with a thermal transfer printer head in printing because the strength of the ink-receiving layer itself is low. Consequently, especially in the case of printing a second color or subsequent color, when a thermal transfer sheet for a second color or subsequent color is pressed against the ink-receiving layer with a thermal transfer printer head from the back side of the thermal transfer sheet, the thermal transfer sheet cannot be brought into close contact with the ink-receiving layer and the heat meltable ink is not sufficiently melted, and as a result it is difficult to form uniform dots, especially in a low density region. Furthermore, since the adhesion force of the porous ink-receiving layer to the substrate is poor, the ink-receiving layer is removed from the substrate by weak frictional force. If the thickness of the porous ink-receiving layer is smaller than the foregoing range, since the amount of the heat-meltable ink penetrated in the porous ink-receiving layer is small, a degradation tends to be obseved in gradation reproducibility and dot reproducibility including variable printing performance, and especially in dot reproducibility of a second color or subsequent color and color clearness in forming color image. Moreover, if the thickness of the porous ink-receiving layer is larger than the foregoing range, the writing property tends to be degraded due to its excessive elasticity.

[0037] There is a term “voidage” as a physical property showing the characteristics of a porous layer but a voidage value does not reflect the above-described factors; (1) a diameter of pores opening in the surface of the ink-receiving layer; (2) a ratio of the total area of all pore openings to the whole surface area of the ink-receiving layer; and (3) a ratio of the number of open pores to the number of all pores contained in the ink-receiving layer, which determine a degree of penetration of a heat meltable ink into pores of the porous ink-receiving layer. In the present invention, the water vapor permeability is used as a physical property reflecting the factors (1), (2) and (3). The limitation of the water vapor permeability to the above-described range enables to form an image with excellent gradation reproducibility and dot reproducibility including variable printing performance, and color clearness in an image forming method wherein the heat meltable ink is penetrated into the pores of the image-receiving sheet having the porous layer.

[0038] In the present invention, the porous ink-receiving layer can be formed by general methods for forming a porous layer. However, a wet coagulation method and a porous layer forming method using a water-in-oil type polyurethane emulsion are preferred. A wet coagulation method is especially preferred, because it is easy to form pores along the thickness direction of the ink-receiving layer, and when the penetration transfer of a heat meltable ink into the resultant image-receiving sheet is performed, uniform dots are easily reproduced (namely, the molten ink does hardly diffuse in the planar direction of the ink-receiving layer).

[0039] In a wet coagulation method, a coating liquid for ink-receiving layer in which a resin is dissolved in an organic solvent is applied onto a substrate, and then the coated substrate is introduced into a bath containing a treating liquid that is compatible or miscible with the aforesaid organic solvent and does not dissolve the aforesaid resin. Since the organic solvent in the receiving layer coating liquid is highly compatible with the treating liquid in the bath, they are replaced mutually, i.e., the organic solvent in the coated layer flows out into the bath, and at the same time the treating liquid of the bath penetrates into the coated layer. Consequently, the resin in the coated layer is coagulated because it is insoluble in the treating liquid. Thereby the portions in the coated layer from which the organic solvent has flowed out becomes pores to form a porous layer (refer to JP, B, 49-25430 and JP, A, 5-155163). In a receiving layer coating liquid, minute particles may be added as a third component as shown in JP, B, 49-25430 and JP, B, 5-18332. Moreover, two or more kinds of resins with mutually low miscibility may be used in combination as a resin component as shown in JP, B, 5-87311.

[0040] In a porous layer forming method using a water-in-oil type polyurethane emulsion, a water-in-oil type polyurethane emulsion wherein a suitable amount of water is emulsified into a polyurethane solution prepared by dissolving and/or dispersing a polyurethane resin into an organic solvent with a low boiling point, is applied onto a substrate and dried. In the process of drying, pores are formed in the portions where the water with a slower drying rate has remained, giving a porous layer (refer to JP, A, 4-82790 and JP, A, 6-166283).

[0041] In the present invention, it is preferable that the pores contained in the porous ink-receiving layer are open pores because an image is formed by penetration-transfer of a heat meltable ink into pores of the porous ink-receiving layer. Furthermore, the thickness of the porous ink-receiving layer is preferably decided to have pores which can contain the whole quantity of the transferred ink, within the range of 3 to 50 μm. Practically, for example, when a transfer is performed using four thermal transfer sheets having respective different color heat meltable ink layers of yellow, magenta, cyan and black, each ink layer having a thickness of 2 μm, it is preferable that the thickness is 16 μm or more for a porous ink-receiving layer with a voidage of 50%. Herein, the voidage means a ratio of the total volume occupied by voids in the formed porous layer. The voidage is obtained by the following equation:

Voidage (%)=(1-w/dh)×100

[0042] wherein

[0043] w: the weight of a porous layer (g/m2)

[0044] d: the true specific gravity of a porous layer (g/cm3)

[0045] h: the thickness of a porous layer (μm)

[0046] In the case of the wet coagulation method, the receiving layer coating liquid used in the present invention is composed of a resin component and a solvent. The resin component is preferably composed of a polyurethane resin as a main component. In the case of a method using a water-in-oil type polyurethane emulsion, the receiving layer coating liquid is composed of an oil phase comprising of a polyurethane resin and an organic solvent, and an aqueous phase comprising water as a main component and a surface active agent if required.

[0047] Examples of polyurethane resins which can be used in the present invention are polyester based polyurethanes, polyether based polyurethane, polyamide based polyurethanes and polycarbonate based polyurethanes. It is preferable to use polyester based polyurethanes in a wet coagulation method. It is preferable to use polyether based polyurethanes in a water-in-oil polyurethane emulsion method.

[0048] The porous layer is preferably composed of a resin component as a main component, preferably a polyurethane resin as a main component, having a softening point of more than the softening point of a heat meltable ink, typically a softening point of not less than 100° C., by which the penetration of the heat meltable ink into the porous layer is secured even in a transfer of a second color or subsequent color. When the softening point of the resin component as a main component is less than 100° C., there is a possibility that the porous structure is fractured in a thermal transfer of the heat meltable ink, and as a result the ink penetration of a second color or subsequent color is hindered, resulting in failure to form an image formation with high quality.

[0049] Furthermore, in the present invention, a particulate component may be incorporated in the ink-receiving layer. By the incorporation of the particulate component in the ink-receiving layer, minute pores can be stably formed in forming a porous structure, and a dot thickening resulting from spreading of a heat meltable ink in the plane direction can be prevented in a penetration transfer of the heat meltable ink. Furthermore, the incorporation of the particulate component increases the strength of the receiving layer and reduces the coefficient of friction on a surface of the receiving layer, resulting in an improvement of a conveyance property of the image-receiving sheet within a printer. Moreover, due to the strength of the receiving layer increased by the incorporation of the particulate component, a writing property with writing devices, especially pencils with a relatively high hardness, for example, a usually used hardness ranging from HB to H, is improved. In addition, the ink of a water based ball pen, an oil based ball pen or the like can absorbed more quickly to more satisfactorily prevent bleeding of written characters by using a particulate component having an oil absorption of not less than 50 ml/100 g (JIS K 5101).

[0050] Moreover, a weight ratio of a resin component and a particulate component is preferably in a range of 70:30 to 35:65. If the proportion of the resin component is more than this range, a favorable effect of the particulate component on formation of a porous structure, especially on formation of pores in a surface layer of an ink-receiving layer, tends to become inadequate, so that a penetration of a heat meltable ink becomes difficult and a dot shape becomes non-uniform in printing with the heat meltable ink. If the proportion of the particulate component is more than this range, a surface strength of the receiving layer tends to decrease, so that particles drop out even with a weak frictional force, causing degradation of a writing property.

[0051] As the particulate component to be incorporated, a light calcium carbonate, particularly an aragonite type light calcium carbonate is preferable. It is preferable that a particulate component is ground until its agglomeration structure is broken and uniformly dispersed in a resin component, particularly a polyurethane resin. The particulate component dispersed preferably has an average particle size of not more than 2.5 μm, more preferably not more than 1.5 μm. In the case where the agglomeration structure is not fully broken, a secondary agglomeration appears on the receiving layer surface formed and a satisfactory surface smoothness is not obtained. Consequently, uniform dots cannot be formed and a grainy appearance occurs in a highlight region due to dropout portions in minute dots and lack of minute dots. Thus it is difficult to form a high-definition image.

[0052] As substrates for the image-receiving sheet, commonly used plastic films or sheets, white films or sheets in which a white pigment or the like is incorporated in plastic material, foamed plastic films or sheets, and paper sheets with water resistance such as synthetic paper sheets or laminated paper sheets can be used. Moreover, when a porous layer is formed using a water-in-oil type polyurethane emulsion, non-coated paper sheets such as high-quality paper sheets and PPC paper sheets, and coated paper sheets such as art paper sheet, can be used besides the foregoing substrates with water resistance. Furthermore, a primer layer, an antistatic treatment or a corona treatment may be applied onto the foregoing substrates to improve adhesion with an ink-receiving layer. In addition, a lubricating layer or an antistatic layer may be applied onto the back side of the substrate and/or onto an ink-receiving layer if required.

[0053] In the present invention, a receiving layer coating liquid may be applied using various known methods such as a reverse roll coating method, an air knife coating method, a gravure coating method, a blade coating method, a comma coating method and a rod coating method.

[0054] Next, the thermal transfer sheet used in the image formation method of the present invention will be explained. In the present invention, a thermal transfer sheet that has on a support a heat meltable colored ink layer composed of a wax as a main component, which ink layer can be melted with heat provided by a printer head and penetrated into the porous structure of the ink-receiving layer of the aforesaid image-receiving sheet, can be used.

[0055] Colored ink layers of a plurality of colors, for example, yellow, magenta and cyan, and optionally black, are used for the formation of a multi- or full-color image. Colored ink layers of a plurality of colors may be sequentially arranged in a side-by-side relation on a single support, or the respective colored ink layers may be provided on separate supports.

[0056] In the case of forming a multi- or full-color image according to the image formation method of the present invention, for example, colored inks of a first color, a second color, a third color and if required further subsequent colors (fourth color, and so on) are subsequently penetrated into the pores of an ink-receiving layer of an image-receiving sheet to form a multi- or full-color image including regions developing a color resulting from superimposed inks in the pores. Herein, a color transferred first on the image-receiving sheet is referred to as a first color; a color transferred second as a second color; a color transferred third as a third color; and a color transferred fourth as a fourth color; and so on. Usually, a first color, a second color and a third color are selected from yellow, magenta and cyan which are primary colors for subtractive color mixture, and if required, black is used as a fourth color.

[0057] In the image formation method of the present invention, after an image is formed on an image-receiving sheet, if required, a transparent overcoat layer may be thermally transferred onto the foregoing image for the purpose of imparting a gloss to the image and/or of protecting the image surface. This overcoat layer may be sequentially arranged with the colored ink layers on the same support of the thermal transfer sheet or may be provided on a support which is independent of the thermal transfer sheet.

[0058] The present invention will be described in more detail by way of Examples. It is to be understood that the present invention will not be limited to the Examples, and various changes and modifications may be made in the invention without departing from the spirit and scope thereof. The term “part” in Examples and Comparative Examples represents “part by weight”.

[0059] Manufacturing of image-receiving sheet

EXAMPLE 1

[0060] A liquid composition with the following Composition-1 underwent a grinding/dispersing treatment so that the light calcium carbonate had an average particle size of 1.0 μm, yielding a receiving layer coating liquid. The receiving layer coating liquid was applied onto one side of a polyethylene terephthalate film with a thickness of 100 μm, and the resultant coated film was dipped in water at 20° C. for 60 seconds and then in hot water at 80° C. for 10 seconds. After the moisture of the coated film was fully removed, the coated film was dried for one minute in a hot air dryer at 85° C. to form a porous ink-receiving layer with a thickness of 15.0 μm and a voidage of 61%.

1ComponentPartPolyester based polyurethane resin60.0(softening point: 215° C., 100% modulus: 4.4 MPa)Polyester based polyurethane resin40.0(softening point: 215° C., 100% modulus: 10.6 MPa)Light calcium carbonate30.0(oil absorption: 60 ml/100 g)N,N-dimethylformamide150.0 Hydrophilic surface active agent 3.0

COMPARATIVE EXAMPLE 1

[0061] A coating liquid with the following Composition-2 was applied onto one side of a polyethylene terephthalate film with a thickness of 100 μm, and the resultant coated film was dipped in water at 20° C. for 60 seconds and then in hot water at 90° C. for 5 seconds. After the moisture of the coated film was fully removed, the coated film was dried for one minute in a hot air dryer at 50° C. to form a porous ink-receiving layer with a thickness of 18.0 μm and a voidage of 39%.

[0062] Composition-2

2ComponentPartPolyether based polyurethane resin160.0(softening point: 120° C., 100% modulus: 12.4 MPa)N,N-dimethylformamide640.0

EXAMPLE 2

[0063] A coating liquid with the following Composition-3 (water-in-oil type polyurethane emulsion) was applied onto one side of a polyethylene terephthalate film with a thickness of 100 μm, and the resultant coated film was dried for 120 seconds in an oven at 80° C. and then for 120 seconds in an oven 130° C. to form a porous ink-receiving layer with a thickness of 21 μm and a voidage of 46%.

[0064] The water-in-oil type polyurethane emulsion was prepared as follows: A polyether based polyurethane resin was dissolved into a mixed solvent of methyl ethyl ketone/toluene to prepare a polyurethane solution (liquid A). On the other hand, an isocyanate was dispersed in water to prepare an isocyanate dispersion (liquid B). The liquid B was added in five portions into the liquid A with stirring at 1,200 rpm to obtain a water-in-oil type polyurethane emulsion.

[0065] Composition-3

3ComponentPartLiquid APolyether based polyurethane resin100.0(softening point: 170° C., 100% modulus: 3.5 MPa)Methyl ethyl ketone100.0Toluene 20.0Liquid BWater 50.0Isocyanate 2.0

COMPARATIVE EXAMPLE 2

[0066] A coating liquid with the following Composition-4 (water-in-oil type polyurethane emulsion) was applied onto one side of a polyethylene terephthalate film with a thickness of 100 μm, and the resultant coated film was dried for 120 seconds in an oven at 60° C. and then for 120 seconds in an oven at 125° and aged at 40° C. for one week to form a porous ink-receiving layer with a thickness of 15 μm and a voidage of 83%.

[0067] The water-in-oil type polyurethane emulsion was prepared as follows: A polyether based polyurethane resin was dissolved into methyl ethyl ketone to prepare a polyurethane solution (liquid C). On the other hand, an isocyanate solution was prepared by mixing a 50% by weight isocyanate solution in methyl ethyl ketone with a mixed solvent of methyl ethyl ketone/toluene. Water was emulsified into the isocyanate solution in the presence of an emulsifier to prepare an emulsion (liquid D). The liquid D was added into the liquid C with stirring at 1,200 rpm to obtain a water-in-oil type polyurethane emulsion.

[0068] Composition-4

4ComponentPartLiquid CPolyether based polyurethane resin30.0(softening point: 170° C., 100% modulus: 3.5 MPa)Methyl ethyl ketone70.0Liquid DMethyl ethyl ketone30.0Toluene30.050% by weight isocyanate solution in10.0methyl ethyl ketoneEmulsifier 5.0Water60.0

[0069] Manufacturing of thermal transfer sheet

[0070] Each of the colored inks shown below was applied by a hot melt coating method onto one side of a 4.5 μm-thick polyethylene terephthalate film which had a 0.1 μm-thick sticking prevention layer composed of a modified silicone resin on the other side to form a colored ink layer having a thickness of 2.0 μm. Thus, four thermal transfer sheets in yellow, magenta, cyan and black were obtained.

5ComponentPartYellow inkYellow pigment (C.I.P.Y.14)15.0Paraffin wax60.0Carnauba wax20.0Ethylene-vinyl acetate copolymer 5.0Magenta inkMagenta pigment (C.I.P.R.57:1)15.0Paraffin wax60.0Carnauba wax20.0Ethylene-vinyl acetate copolymer 5.0Cyan inkCyan pigment (C.I.P.B.15:3)15.0Paraffin wax60.0Carnauba wax20.0Ethylene-vinyl acetate copolymer 5.0Black inkCarbon black15.0Paraffin wax60.0Carnauba wax20.0Ethylene-vinyl acetate copolymer 5.0

[0071] Evaluation method

[0072] (1) Water vapor permeability

[0073] Each porous ink-receiving layer formed on the polyethylene terephthalate film with a thickness of 100 μm in the aforesaid Examples 1 and 2 and Comparative Examples 1 and 2 was carefully removed off so that the porous layer was not be broken. According to A-1 method (calcium chloride method) prescribed in JIS L 1099, the water vapor permeability was determined based on an increase in weight of the calcium chloride after one hour. The results are shown in Table 1.

[0074] (2) Writing property

[0075] (2-1) Pencil writing property

[0076] Letters were written on the surface of each porous ink-receiving layer formed on the polyethylene terephthalate film with a thickness of 100 μm in the aforesaid Examples 1 and 2 and Comparative Examples 1 and 2, using a pencil with hardness of HB, and a degree of damage of the surface of the receiving layer was evaluated according to the following criteria. The results are shown in Table 1. A practically acceptable level is Grade 3 or more.

[0077] 5: The written part suffers no damage.

[0078] 4: The surface of the written part is a little depressed.

[0079] 3: The surface of the written part is depressed.

[0080] 2: A portion of the surface of the written part is scraped off to suffer damage to a degree that reading of the letters is difficult.

[0081] 1: The surface of the written part is scraped off to suffer damage to a degree that reading of the letters is impossible.

[0082] (2-2) Writing property with water based ball pen or oil based ball pen Letters were written on the surface of each porous ink-receiving layer formed on the polyethylene terephthalate film with a thickness of 100 μm in the aforesaid Examples 1 and 2 and Comparative Examples 1 and 2, using a water based ball pen or an oil based ball pen, and bleeding in the written letters was evaluated according to the following criteria. The results are shown in Table 1. A practically acceptable level is Grade 3 or more.

[0083] 5: No bleeding occurs in letters of the written part.

[0084] 4: A little bleeding occurs in letters of the written part.

[0085] 3: A little thickening of line occurs in letters of the written part due to bleeding of ink.

[0086] 2: Thickening of line occurs in letters of the written part due to bleeding of ink to a degree that reading of letters is difficult.

[0087] 1: Reading of letters in the written part is impossible due to bleeding of ink.

[0088] (3) Minimum dot diameter, minimum dot shape and number of gradations in density gradation representation

[0089] A 256-gradation pattern was printed with black color by means of a variable dot type thermal transfer color printer (dot density: 300 dpi, maximum printing energy: 0.12 mJ/dot, printing speed: 10 msec/line) using each ink image-receiving sheet and black color thermal transfer sheet obtained above. A minimum dot diameter and a minimum dot shape and a number of gradations in density gradation representation were determined as described below. The results are shown in Table 1.

[0090] (3-1) Minimum dot diameter

[0091] Printing was performed using the aforesaid printer by changing a printing energy in 256 levels to form an image, and the diameter of a colored ink dot (the length of the long side) that could be transferred with a minimum energy among the printed dots in the image was measured by a microscope.

[0092] (3-2) Minimum dot shape

[0093] Printing was performed in the same manner as in (3-1) above to form an image. The shape of a colored ink dot that could be transferred with a minimum energy among the printed dots in the image was observed by a microscope and evaluated according to the following criteria. A practically acceptable level is Grade 4 or more.

[0094] 5: Dots in the same optical density region are reproduced in a uniform shape without any dropout portion or void.

[0095] 4: Dots in the same optical density region are reproduced in an almost uniform shape, although a dropout portion or void occurs in some of dots.

[0096] 3: A dropout portion or void in dot and dot lack occur in some of dots in the same optical density region.

[0097] 2: A dropout portion or void in dot and dot lack occur in a lot of dots in the same optical density region.

[0098] 1: A dropout portion or void in dot and dot lack occur in dots in the same optical density region to a degree that a grainy appearance is conspicuous as an image.

[0099] (3-3) Number of gradations in density gradation representation

[0100] Printing was performed using the aforesaid printer by changing a printing energy in 256 levels wherein an energy difference between adjacent energy levels was set constant to form respective images corresponding to the energy levels. The number of energy levels giving images between which a significant difference in reflective optical density (OD value) was observed, i.e. number of gradations, were determined. A practically acceptable level is Grade 4 or more.

[0101] 5: 96 gradations or more

[0102] 4: 64 to 95 gradations

[0103] 3: 32 to 63 gradations

[0104] 2: 16 to 31 gradations

[0105] 1: 15 gradations or less

[0106] (4) Ink penetration

[0107] Using the aforesaid printer, a solid printing was successively performed with yellow ink (first color ink), magenta ink (second color ink) and cyan ink (third color ink) in this order on each image-receiving sheet, and then a 256-gradation pattern was printed with black ink (fourth color ink). A deformation degree of dot shape of black dots in the printed image was observed by a microscope and penetration of inks into the ink-receiving layer was evaluated according to the following criteria. A practically acceptable level is Grade 4 or more.

[0108] 5: Dots of the first color ink to the fourth color ink have a uniform shape.

[0109] 4: Dots of the first color ink to the third color ink have a uniform shape and a part of only the fourth color ink is not penetrated into pores and is flowed out of pores.

[0110] 3: Dots of the first color ink to the third color ink have a uniform shape and only the fourth color ink is not penetrated into pores and flowed out of pores.

[0111] 2: Dots of the first color ink and the second color ink have a uniform shape and a part of the third color ink and the fourth color ink are not penetrated into pores and flowed out of pores.

[0112] 1: Dots of the first color ink and the second color ink have a uniform shape and the third color ink and fourth color ink are not penetrated into pores and flowed out of pores.

6TABLE 1Water vaporMinimum dotWriting propertyProductionpermeabilityDiameterNumber ofInkHBWater basedOil basedmethod(m2 · hour)(μm)Shapegradationspenetrationpencilball penball penEx. 1Wet73015555544coagulationmethodEx. 2Emulsion38020544434methodCom.Wet25020222434Ex. 1coagulationmethodCom.EmulsionNote50215222Ex. 2methodNote: Measurement of water vapor permeability was impossible because the porous layer was broken when it was removed from the substrate.

[0113] With respect to the ink penetration, the same good results as in Examples 1 and 2 were obtained even when the yellow ink, magenta ink and cyan ink were transferred in an order other than that defined above (i.e. the transfer of the yellow ink, magenta ink and cyan ink in this order).

[0114] An image with excellent gradation reproducibility and dot reproducibility including a variable printing performance and color cleanness can be formed by using the ink image-receiving sheet of the present invention. Furthermore the ink image-receiving sheet of the present invention has excellent writing property with a pencil and a pen.

Heat meltable ink image-receiving sheet and image forming method using the same

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