具体实施方式：
[0035]Referring to FIG. 1, the printed makeup product of the present invention has on a base sheet 1 an inorganic solid layer 3 serving as a printing surface. On the surface of the inorganic solid layer 3, an ink-jet printed image (may hereinafter be referred to simply as a printed image) 5 is formed by ink-jet printing. Makeup is applied onto the printed image 5 to form a makeup layer 7, and a protective layer 9 is further provided, if necessary.
[0036]Such a printed makeup product is prepared, for example, using the printing sheet described in the aforementioned Patent Document 2. By reference to FIG. 2, such a printing sheet (indicated entirely at 20 in FIG. 2) is supplied in a state where a fiber sheet 10 is stuck onto and closely adhered onto a surface of an inorganic solid layer 3 formed on a base sheet 1. At the time of ink-jet printing, the fiber sheet 10 is peeled off from the inorganic solid layer 3, and ink-jet printing is performed on a surface 3a (i.e., printing surface) of the exposed inorganic solid layer 3.
<Printing Sheet 20>
[0037]In the above-mentioned printing sheet 20, the base sheet 1 supporting the inorganic solid layer 3 is not particularly limited, but may be formed from any material, if its surface can support the inorganic solid layer 3.
[0038]Suitable examples are wood pulp paper, and various resin sheets or resin films of vinyl resins such as polyvinyl alcohol and polyvinyl acetate, acrylic resins such as poly (meth) acrylate, polyolefin resins such as polyethylene and polypropylene, and polyester resins such as polyethylene terephthalate. There may also be used woven fabrics or nonwoven fabrics comprising fiber materials such as glass fiber, vinylon fiber, polypropylene fiber, polyester fiber, polyethylene terephthalate fiber, acrylic fiber, aramid fiber, and carbon fiber, as well as laminated films or sheets thereof.
[0039]The preferred base sheet 1 has flexibility and moderate nerve. Even if folded, the base sheet 1 having such properties minimally forms a crease, and can effectively suppress such an inconvenience that cracks are formed in the inorganic solid layer 3 provided on the base sheet 1. The materials for the base sheet 1 are considerably limited, but generally pulp paper is preferably used. Pulp paper is a generally available paper, has flexibility and bending strength, and enables adherability to the inorganic solid layer 3 to be satisfactory. In addition to the pulp paper, there can be used a synthetic paper prepared by mixing chemical fibers such as glass fibers, polypropylene fibers, polyethylene fibers, polyester fibers, or vinylon fibers, as binder fibers, with the pulp paper.
[0040]The surface of the base sheet 1 may be subjected to corona treatment or the like for improved hydrophilicity. This makes it possible to enhance joining strength between the inorganic solid layer 3 and the base sheet 1.
[0041]The thickness of the base sheet 1 is set at such a thickness that the printing sheet 20 can easily pass through an ink-jet printer. Usually, the thickness is set in a range of the order of 0.02 to 0.5 mm in conformity with the grade of the printer to be used.
[0042]In the above printing sheet 20, the inorganic solid layer 3 may be formed from various inorganic materials, for example, metal oxides such as silica, alumina and zirconia, and calcium salts such as calcium carbonate and gypsum (calcium sulfate), as long as it is a stable solid layer capable of undergoing ink-jet printing on its surface, and this surface is a rough surface as will be described later.
[0043]From the viewpoints that its surface is a rough surface as described later, the rub resistance and ultraviolet resistance of the printed image are enhanced, and a fast and stable printed image is formed, however, it is optimal for the inorganic solid layer 3 containing calcium hydroxide to be formed.
[0044]The inorganic solid layer 3 containing calcium hydroxide, as described in Patent Document 2 as well, is formed by coating the hydrophilic surface of the base sheet 1 with a kneaded product of a powder of calcium hydroxide and water, and removing water in the resulting kneaded product layer by drying or the like. During the drying step, some of calcium hydroxide in the layer reacts with a carbon dioxide gas in the air, whereby the calcium hydroxide partly turns into calcium carbonate to form a plaster precursor (a mixture of calcium hydroxide and calcium carbonate). If the plaster precursor is further allowed to stand in the air, calcium hydroxide remaining in the plaster precursor (the mixture of calcium hydroxide and calcium carbonate) reacts with the carbon dioxide gas in the air to form calcium carbonate, with the result that carbonation further proceeds to form plaster (calcium carbonate formed by carbonation of calcium hydroxide). In this manner, a layer containing the plaster precursor having calcium carbonate present upon carbonation of part of the calcium hydroxide is provided, as the inorganic solid layer 3, on the surface of the base sheet 1. Such a plaster precursor is lower in hardness than plaster having calcium hydroxide carbonated completely (calcium carbonate formed by carbonation of calcium hydroxide). Thus, when the fiber sheet 10 to be described later is peeled off, a predetermined rough surface is easily formed. Moreover, the fiber sheet 10 can be applied without the use of a particular adhesive.
[0045]Thus, the inorganic solid layer 3 containing the plaster precursor may be in a state before the complete carbonation of calcium hydroxide (namely, the state where calcium hydroxide is contained). Preferably, however, the calcium hydroxide in the plaster precursor (the mixture of calcium hydroxide and calcium carbonate) is contained in an amount of at least 10% by weight, preferably 20% by weight or more (the amount of calcium carbonate is 90% by weight or less, preferably 80% by weight or less). If the content of the calcium hydroxide is lower than the above range, the carbonation of the calcium hydroxide, which proceeds after formation of the ink-jet printed image 5 on the inorganic solid layer 3 to be described later, does not result in the formation of a fast plaster layer (calcium carbonate layer). In this case, when the makeup material is applied onto the ink-jet printed image 5, the possibility arises that the surface of the inorganic solid layer 3 will collapse, causing decreased utility of the makeup.
[0046]A larger amount of the calcium hydroxide in the inorganic solid layer 3 is desirable for attaining the aforementioned object. If its amount is too large, however, the hardness of the inorganic solid layer 3 is insufficient, and damage to the inorganic solid layer 3, for example, tends to occur during the printing step. Preferably, therefore, the amount of calcium hydroxide in the inorganic solid layer 3 is kept down to 90% by weight or less, preferably 80% by weight or less.
[0047]The amount of the calcium hydroxide in the inorganic solid layer 3 can be confirmed by differential thermal analysis.
[0048]The content of calcium hydroxide in the inorganic solid layer 3 can be adjusted based on the carbonation rate of calcium hydroxide for use in the formation of this layer (i.e., the weight ratio of the resulting calcium carbonate to the weight of the calcium hydroxide used for preparing the slurry) and the proportions of additives to be described later, such as a binder, an inorganic fine aggregate, and a liquid-absorbing inorganic powder.
[0049]After the image is printed, the above-described inorganic solid layer 3 is left to stand in the atmosphere, whereby calcium hydroxide in the layer is carbonated, and finally converted into plaster (calcium carbonate formed by carbonation of calcium hydroxide). In order to improve the toughness of the inorganic solid layer 3, it is preferred that a solid component of a polymer emulsion is contained as a binder in the layer. The polymer emulsion is a dispersion of a monomer, an oligomer or a polymer thereof in an aqueous medium. Examples of the polymer emulsion are emulsions of polymers, such as an acrylic resin, a styrene-acrylate resin, a vinyl acetate resin, polyurethane, and styrene/butadiene rubber. In the drying step, the solvent (water) in the emulsion evaporates, and the polymer component in the emulsion remains in the inorganic solid layer 3. If the solid component (i.e., polymer) is present in an excess amount in the emulsion, permeation of the printed image (printing ink) into the inorganic solid layer tends to decrease. To enhance the toughness of the inorganic solid layer 3 and ensure the permeation of the ink, therefore, it is generally preferred that the solids content of the polymer emulsion in the layer 3 is in a range of 3 to 50% by weight.
[0050]In addition to the above emulsion, the inorganic solid layer 3 may further incorporate various additives for adjusting physical properties, such as various fiber materials, an inorganic fine aggregate, a liquid-absorbing inorganic powder, etc. These additives act to improve the physical properties, such as strength, of the inorganic solid layer 3 functioning as the printing layer.
[0051]Examples of the fiber material include glass fiber, vinylon fiber, polypropylene fiber, polyester fiber, polyethylene terephthalate fiber, acrylic fiber, aramid fiber, carbon fiber, and metal fiber. In terms of its shape, the fiber can be used as a staple fiber, a filament, a woven fabric, or a nonwoven fabric. Of them, the staple fiber is particularly effective in improving the toughness and cutting workability of the inorganic solid layer 3. The length and diameter of the staple fiber are not particularly limited, but the length is 0.2 mm to 10 mm, particularly 0.5 to 5 mm, and the diameter is 2 to 50 μm, particularly 5 to 20 μm. These dimensions are preferred in order to further improve the toughness of the inorganic solid layer 3 and, in some cases, to impart excellent cutting workability to the inorganic solid layer 3.
[0052]The inorganic fine aggregate is an inorganic particulate material having an average particle size in a range of the order of 0.01 to 0.1 mm and, within this range, one having an average particle size which is a quarter or less of the thickness of the inorganic solid layer 3. Concrete examples include silica sand, powdered white limestone, mica, glazed silica sand, glazed mica, ceramic sand, glass beads, perlite, and calcium carbonate.
[0053]Further preferably, a liquid-absorbing inorganic powder is incorporated into the inorganic solid layer 3 in order to avoid a decline in the affinity for the hydrophilic ink caused by the incorporation of the polymer emulsion into the inorganic solid layer 3, and to compensate for the liquid-absorbing properties decreasing with the progress of carbonation of calcium hydroxide. The liquid-absorbing inorganic powder is a fine inorganic powder which is porous and whose oil absorption is as high as 100 ml/100 g or more, for example, an alumina hydrate powder, a zeolite powder or a silica powder having a volume-based average particle size (D50), as measured by a laser diffraction scattering method, of 0.5 μm or less.
[0054]The aforementioned polymer emulsion is effective in improving the toughness and enhancing the joining strength between the base sheet 1 and the inorganic solid layer 3. However, the polymer emulsion may cause inconveniences such as a decline in the hydrophilicity of the inorganic solid layer 3, resulting in a situation where when printing is performed using a hydrophilic ink, for example, the ink is repelled, and the printed image is blurred. Here, the use of the above-mentioned liquid-absorbing inorganic powder improves the absorbability of the printing ink, and can thus effectively prevent the above inconveniences. It is particularly preferred that the liquid-absorbing inorganic powder is incorporated, in an amount of the order of 1 to 20% by weight, into the inorganic solid layer 3 containing the plaster.
[0055]In addition to the above additives, one of, or a combination of two or more of, various publicly known additives can be incorporated in the inorganic solid layer 3, in accordance with an intended object. Anyway, the additives should be incorporated in such an amount as not to impair the permeation of the printing ink into the inorganic solid layer 3 or the fixing of the former to the latter. For example, it is desirable that various types of additives be incorporated in a range in which the content of calcium carbonate formed by the carbonation of calcium hydroxide (i.e., the content of the calcium carbonate when the carbonation rate is 100%) is maintained at 50% by weight or more.
[0056]The thickness of the inorganic solid layer 3 is set to be in a suitable range where printing is possible. Generally, the preferred thickness is 0.05 to 0.5 mm, particularly, a value of the order of 0.1 to 0.25 mm. If the thickness is too small, there is a possibility that image fixing properties upon permeation of the printing ink when the image is printed will decrease, or the depth of the developed image associated with ruggedness will be spoiled. Too large a thickness, on the other hand, causes an economic disadvantage, and is apt to form creases when bent, thus arousing possibilities of limitations on the printer to be used in printing.
[0057]The above inorganic solid layer 3 is prepared by coating one surface of the base sheet 1 with an inorganic slurry for forming the layer 3, for example, a calcium hydroxide slurry or a slurry of the aforementioned inorganic oxide particles such as silica particles, and further sticking the fiber sheet 10 onto the coating, followed by moderate drying (see FIG. 2).
[0058]The slurry for forming the inorganic solid layer containing calcium hydroxide is obtained by adding the aforementioned binder and various additives to the kneaded product of the powder of calcium hydroxide and water.
[0059]The calcium hydroxide powder for use in preparing such a slurry is preferably one containing fine particles with a particle size of 5 μm or less in an amount of 20 to 80% by weight, and coarse particles with a particle size of 10 to 50 μm in an amount of 10 to 40% by weight. The fine particle component is useful for imparting the shape retainability and strength of the inorganic solid layer 3, whereas the coarse particle component is useful for ensuring the permeation properties of the image. The use of the calcium hydroxide powder containing the fine particle component and the coarse particle component in the above amount ratio is very preferred for forming the plaster layer having satisfactory strength and durability without impairing the image permeation properties. For example, if the calcium hydroxide powder comprising the above fine particle component only is used, the permeation properties of ink may be impaired, the printed image may be blurred, or the fastness of the printed image may decrease.
[0060]Also preferably, the slurry incorporates a surfactant for uniformly dispersing various compounding ingredients, and incorporates a thickening agent or the like, as appropriate, to achieve a moderate viscosity so that the kneaded product will not drip during coating. The slurry can be applied using a bar coater, a roll coater, a flow coater, a knife coater, a comma coater, spraying, dipping, ejection, or mold material transfer. If necessary, a trowel holder, a cap squeezer, roller compaction, or a monoaxial press, for example, can be employed.
[0061]The thickness of the slurry coated is set so that the thickness after drying becomes the thickness of the inorganic solid layer 3. Drying after coating with the slurry may be performed to such a degree that the water content of the inorganic solid layer 3 is of the order of 5% or less. If the water content is too high, the shape of the layer cannot be maintained. If printing is done, with the high water content being maintained, bleeding of the ink or the like is apt to occur. Furthermore, when the fiber layer 10 is peeled off, a predetermined rough surface may fail to be formed. Alternatively, it may become difficult to stick the fiber sheet 10 to the inorganic solid layer 3. Of course, the fiber sheet 10 can be stuck using a pressure-sensitive adhesive or an adhesive. In this case, however, peeling off the fiber sheet 10 may be difficult.
[0062]The drying is performed by blowing hot air, for example, thereby heating the coated layer of the slurry to a temperature of the order of 40 to 150° C. Here, care should be taken, because if the heating temperature is higher than required, deformation of the base sheet 1 or the fiber sheet 10 due to heat occurs.
[0063]The carbonation reaction of calcium hydroxide proceeds upon contact with the carbon dioxide gas. As long as the slurry is preserved in a sealed state in an air-impermeable bag or a container, there is no problem in maintaining a predetermined carbonation rate and in keeping the amount of calcium hydroxide in the inorganic solid layer 3 in a certain range.
[0064]As shown in FIG. 2, the fiber sheet 10 is pasted onto the inorganic solid layer 3 of the printing sheet 20. With the fiber sheet 10 being tightly adhered, the printing sheet 20 is supplied and, at the time of ink-jet printing, the fiber sheet 10 is peeled off, whereupon ink-jet printing is performed on the surface 3a of the inorganic solid layer 3.
[0065]In detail, the surface 3a of the inorganic solid layer 3 has low surface hardness because of incorporation of some water or incomplete carbonation. When the fiber sheet 10 is peeled off, therefore, a surface portion of the inorganic solid layer 3, which has penetrated into the fiber sheet 10 through its transfer surface 10a, is detached together with the fiber sheet 10, or destroyed. As a result, the transfer surface 10a of the fiber sheet 10 is transferred to the surface 3a of the inorganic solid layer 3.
[0066]The fiber sheet 10 of the above configuration, needless to say, also functions as a protective sheet for protecting the surface of the inorganic solid layer 3. That is, the inorganic solid layer 3 is formed from inorganic particles (e.g., particles of calcium hydroxide or calcium carbonate, or particles of an inorganic oxide such as silica). Thus, the inorganic solid layer 3 is relatively brittle, and is apt to suffer inconvenience such that it is scarred by pressure from the outside, or that its surface falls off. However, the above fiber sheet 10, provided since immediately after the production of the printing sheet 20 until immediately before printing, can effectively prevent such inconvenience.
[0067]In the present invention, the transfer surface 10a of the fiber sheet 10 is transferred to the surface 3a of the inorganic solid layer 3. By using this surface 3a as a printing surface, therefore, makeup of the ink-jet printed image 5 to be described later can be done.
[0068]As the fiber sheet 10, therefore, one having depressions formed on its surface as will be mentioned later is used. In particular, use is made of a nonwoven fabric comprising heat-fusible fibers and adjusted so as to transfer predetermined depressions by pressure bonding using a heated roll.
[0069]That is, the transfer surface 10a of the fiber sheet 10 used in the present invention is a surface where a continuous flat surface and indefinitely shaped depressions surrounded by the flat surface are intermingled, upon observation in an electron micrograph at a magnification of 100, as shown in FIG. 3. That is, in FIG. 3, an encircled black region is observed as the indefinitely shaped depression A (i.e., a gap between fibers), and a high-contrast portion around the depression A constitutes the flat surface.
[0070]In the transfer surface 10a of the above configuration, settings are made such that the flat surface is present in a proportion of 70 to 90% per unit area, and 50 to 300 of the depressions A per mm2, whose major diameter is 10 to 300 μm, are observed so as to be surrounded with the flat surface. These features are important in the present invention in order to form the ink-jet printed image 5 excellent in makeup characteristics on the surface 3a of the inorganic solid layer 3. That is, the transfer surface 10a of the fiber sheet 10 is closely adhered to and laminated onto the surface of the inorganic solid layer 3, whereby the inorganic solid particles in the surface portion of the inorganic solid layer 3 enter the indefinitely shaped depressions A of the transfer surface 10a. Thus, when the fiber sheet 10 is peeled off, the parts entering the depressions A of the transfer surface 10a are ruptured. As a result, indefinitely shaped protrusions corresponding to the indefinitely shaped depressions A are formed in the surface 3a of the inorganic solid layer 3.
[0071]As noted above, a predetermined number of the indefinitely shaped depressions A of the above size are formed in the transfer surface 10a, so that the indefinitely shaped protrusions of a predetermined size are correspondingly transferred to the surface 3a of the inorganic solid layer 3. Thanks to the presence of such indefinitely shaped protrusions, the printed image 5 formed on the surface 3a of the inorganic solid layer 3 is meticulous in terms of a three-dimensional effect and a sense of depth. Besides, when a portrait photograph (face, in particular) is printed, for example, the surface of the print is visible in a state very akin to the human skin. Consequently, excellent makeup characteristics are exhibited.
[0072]To form the indefinitely shaped depressions A of the above size in the predetermined proportion, it becomes necessary to use a nonwoven fabric sheet comprising heat-fusible fibers, and pressure bond the nonwoven fabric sheet by means of a heating roll, followed by using it as a mold material sheet. That is, the surface of the fibers is turned into a flat surface by pressure bonding using the heating roll, whereby the depressions A can be allowed to exist clearly.
[0073]If a woven fabric sheet is used instead of the nonwoven fabric sheet, for example, heat fusion converts the transfer surface 7a into a flat surface, thus making it difficult to form a surface with irregularities in the surface 3a of the inorganic solid layer 3. Even if depressions can be provided clearly, there will be a surface where definitely shaped depressions are arranged regularly, because the fibers are woven regularly. This poses a possibility that the printed image formed on the surface of the inorganic solid layer 3 will be considerably different from the human skin, impairing the makeup characteristics.
[0074]Even when a nonwoven fabric sheet is used, some of the fibers deposit on the surface of the inorganic solid layer 3 when the sheet is peeled off, if the sheet has not been heat-fused. Consequently, printability will be impaired and, since the surface of the fibers has not been collapsed by heat, the depressions A cannot be existent clearly. Thus, the protrusions transferred to the surface 3a of the inorganic solid layer 3 are unstable, and a printing surface capable of imparting fine image quality stably cannot be formed.
[0075]Further, it is preferred that the nonwoven fabric sheet be formed from heat-fusible core-sheath fibers (high-melting fibers as a core material, and low-melting fibers as a sheath). For example, a nonwoven fabric sheet comprising commercially available core-sheath fibers having polypropylene as a core material and polyethylene as a sheath is used preferably. By using such a nonwoven fabric comprising the core-sheath fibers, the low-melting fibers of the sheath portion are fused, without fusion of the core portion, upon pressure bonding by the heated roll. Consequently, flattening can be performed simultaneously with fusion bonding of the fibers, with the shape of the fibers being retained, whereby the aforementioned flattened portion and the indefinitely shaped depressions A (i.e., gaps between the fibers) can be formed.
[0076]The pressure bonding by the heated roll is performed, with the temperature, time and roll pressure being adjusted so that the depressions as the gaps between the fibers will not be collapsed. When the nonwoven fabric of core-sheath fibers as mentioned above is used, for example, it is preferred that the pressure bonding be performed at a temperature which is equal to or higher than the melting point of the low-melting fibers as the sheath, but lower than the melting point of the high-melting fibers as the core. In the case of a nonwoven fabric sheet of core-sheath fibers having polypropylene as a core material and polyethylene as a sheath, for example, it is desirable to carry out the pressure bonding at a temperature of the order of 90 to 150° C.
[0077]The fibers constituting the nonwoven fabric, and the weight per unit area of the fibers are determined or set so that the flat portion and the depressions A of the predetermined size will be formed in the aforementioned proportions. With the above-mentioned core-sheath fibers (polypropylene fibers/polyethylene fibers), for example, filaments with a fiber diameter of the order of 10 to 50 μm are preferred, and their weight per unit area is preferably set at a value of the order of 30 to 120 g/m2. According to these features, for example, the fiber sheet 10 can be held closely adhered to the surface of the inorganic solid layer 3 at a suitable peel strength, so that a stable transfer effect and a protective effect can be exhibited.
[0078]As described above, the nonwoven fabric sheet having the transfer surface 7a undergoing pressure bonding by a heated roll and satisfying predetermined conditions is used as the fiber sheet 10. This fiber sheet 10 is provided so as to be closely adhered to the surface of the inorganic solid layer 3, and is then peeled off, whereby the surface 3a of the inorganic solid layer 3 is rendered a surface with excellent printability, and the printed image 5 having excellent makeup characteristics can be formed.
[0079]The above surface 3a of the inorganic solid layer 3 is a surface where the continuous flat surface and the indefinitely shaped depressions surrounded by the flat surface are intermingled, upon observation in an electron micrograph at a magnification of 100, as shown in FIG. 4. That is, in FIG. 3, the encircled black region is an indefinitely shaped protrusion B, this protrusion B is observed corresponding to the depression A (the gap between fibers) in the transfer surface 7a of the fiber sheet 10, and a low-contrast portion around the protrusion B constitutes the flat surface.
[0080]In the printing sheet 1 of the present invention, as shown in FIG. 3, the indefinitely shaped protrusions B are formed as a result of the transfer of the indefinitely shaped depressions A of the transfer surface 7a of the fiber sheet 10 to the surface 3a of the inorganic solid layer 3. Upon observation in an electron micrograph at a magnification of 100, the indefinitely shaped protrusions B are present in a proportion of 10 to 30% per unit area, and 50 to 300 of the indefinitely shaped protrusions B per mm2, whose major diameter is 10 to 300 μm, are observed. That is, fine protrusions of an indefinite shape are present numerously and randomly in the flat surface. Since a printing ink adheres to and penetrates into the flat surface and the protrusions B, a meticulous printed image 5 can be formed, without detriment to natural feelings such as a three-dimensional effect and a sense of depth. When such a printed image 5 is the face of a person in a portrait photograph, its surface is visually recognized as akin to the human skin. Consequently, excellent makeup characteristics are exhibited.
[0081]That is, the indefinitely shaped protrusions B having an amorphous shape and a certain size are formed randomly in large numbers between flat portions. Thus, particularly fine image quality can be effectively reflected, without impairment of natural feelings. If the protrusions are in a definite shape such as a round or square shape, or they are arranged regularly, even when the numerous protrusions are formed in large numbers, naturalness is lost, and the impression of the image being mechanically synthesized is given. Furthermore, one will have the impression that the printed image is entirely different from the human skin.
[0082]In addition, the surface 3a of the inorganic solid layer 3 is free from the deposition of fibers, and deterioration of image quality due to fiber marks or the like is also effectively prevented.
[0083]The above-described printing sheet 20 is commercially available in a form in which it has the fiber sheet 10 stuck thereto, as shown in FIG. 2. Usually, however, in order to maintain the inorganic solid layer 3 in a state where it has not been completely carbonated, or in a water-containing state where it contains some water, a bundle of the laminates 10 is packaged in a gas barrier resin film or the like for preservation. If a plaster-containing inorganic solid layer 3 is allowed to stand in the atmosphere, for example, carbonation of the plaster precursor proceeds, with the result that printability (e.g., permeation and fixability of the image), etc. decline. To avoid such an inconvenience, it is necessary to suppress carbonation up to a point in time at which printing is performed. For this purpose, packaging in a gas barrier resin film or the like is required.
[0084]It goes without saying that the printing sheet 20 cut to a suitable size is wound into a roll, and this roll can be packaged in a gas barrier film for preservation.
[0085]There is no particular limitation on the gas barrier film, and various resin films in general use as packaging films are used. From the viewpoint of cost, etc., however, a polyolefin film such as polyethylene film, polypropylene film or polyester film is preferred.
[0086]The printing sheet 20 marketed in the above manner is stripped of the packaging film, and then the fiber sheet 10 is peeled off to expose the surface 3a of the inorganic solid layer 3, whereafter printing is performed on this surface.
<Formation of Printed Image 5>
[0087]In the printed makeup product of the present invention, the surface 3a of the inorganic solid layer 3 exposed in the above manner is subjected to printing by an ink-jet printer using an ink-jet ink having a predetermined pigment or dye dispersed or dissolved therein, whereby the ink-jet printed image 5 is formed, as shown in FIG. 1. The most preferred ink-jet ink used is a hydrophilic ink having a water-soluble dye dissolved therein or a pigment dispersed in water (or a water-alcohol mixed solvent) with a surfactant or the like. When such a hydrophilic ink is used, a sharp ink-jet printed image 5 without bleeding and held stably can be formed on the inorganic solid layer 3. In the present invention, in particular, ink using a pigment can be used preferably.
[0088]If the inorganic solid layer 3 is a layer containing calcium hydroxide, upon printing of the printed image in the above manner, the inorganic solid layer 3 is allowed to stand in the atmosphere (usually for about 1 to 30 days), or it is allowed to stand in a constant temperature and humidity chamber (usually for about 12 to 100 hours) filled with a high concentration carbon dioxide gas. As a result, it absorbs the carbon dioxide gas, and carbonation of the remaining calcium hydroxide proceeds to form plaster (calcium carbonate formed by carbonation of calcium hydroxide). The printed image 5, in particular, permeates the porous plaster with irregularities, and becomes fixed there. Compared with a photographic image or the like, the printed image 5 is akin to a real thing. The resulting printed image 5 is excellent in fastness and, even if rubbed, it does not suffer a color loss or the like. Moreover, its ink components can be protected from ultraviolet rays, etc., and the printed image is held stable for a long period of time.
[0089]In the present invention, in particular, the indefinitely shaped protrusions of a certain shape are formed in large numbers on the surface of the inorganic solid layer 3. Particularly when a human figure, especially, a photograph of a face, is printed, therefore, the surface of the printed image 5 is in a state similar to a stereoscopic human skin, as stated earlier. The surface is thus optimal for application thereon of a makeup material to be described later.
<Formation of Makeup Layer 7>
[0090]With the printed makeup product of the present invention, after formation of the ink-jet printed image 5, a makeup material is applied a