JP2015167902A - Manufacturing method of design sheet having pigment fastened onto inorganic solidification layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a design sheet which has an inorganic solidification layer as a printing layer, can express color and glossiness of a region incapable of being provided according to an inkjet printing after performing the printing with an inkjet printer and can materialize low cost with a simple method.SOLUTION: A lamination sheet made by laminating a base material sheet, an inorganic solidification layer and a nonwoven fabric cloth in the order is formed, the nonwoven fabric cloth is removed, thereafter, an image is printed on the inorganic solidification layer by means of an inkjet printer, a pigment of which the average particle size is a half or less of an average fiber diameter of fibers constituting the nonwoven fabric cloth is applied onto the printed inorganic solidification layer, thereafter, excessive pigment is removed and the pigment on the inorganic solidification layer is solidified.

Description

  The present invention relates to a method for producing a design sheet comprising an inorganic solidified layer, and a pigment fixed on the surface of the inorganic solidified layer.

  With the spread of personal computers and digital cameras to general households, inkjet printers capable of printing clear full-color images are widely used due to their low cost. As recording paper for printing used in inkjet printers, it is difficult to use ordinary high-quality paper and copy paper in terms of performance. Ink adhering to the paper surface is quickly absorbed inside, and ink droplets on the paper surface There are demands for characteristics such as spreading and blurring being suppressed, a clear image being formed, and the resulting image being excellent in fastness that does not cause color fading over a long period of time.

  In order to impart such characteristics to the printed surface (paper surface), it has been proposed to form an inorganic solidified layer in which various inorganic solid substances are applied to the paper surface together with a binder. Document 1 proposes a printing sheet comprising a base sheet and a printing layer (inorganic solidified layer) formed on the surface of the base sheet and containing semi-solidified plaster.

  When the printing sheet proposed in Patent Document 1 is printed on the surface of the printing layer by an ink jet printer or the like, the carbonization of the stucco progresses after printing, and solidifies into calcium carbonate. It has the property that the image is firmly held on the printing surface. In addition, the printed image formed is not only a rugged image and a robust image with a painting-like depth, but also the ink components forming the image are protected from ultraviolet rays and ozone. Is also excellent in terms of long-term storage.

WO2008 / 013294

  By the way, in the printing sheet as described above, when printing is performed by inkjet using pigment-based or dye-based ink, the color gamut of the image obtained by printing is limited by the ink used for inkjet. . That is, in an image printed by inkjet, even if an image with a black density of 100%, that is, whiteness = 0 is printed, an image with a black density of 100% actually obtained by printing is measured with a spectroscopic difference meter. The ISO whiteness becomes around 20%, and the whiteness cannot be lowered any more.

  In addition, when printing an image set to 100% whiteness, an image with 100% whiteness obtained by actual printing is not printed because white ink is not mounted on the inkjet printer, and the white color of the print sheet itself is not printed. Can not be whiter than the degree.

  Furthermore, in inkjet printing, it is difficult to sufficiently express an image having a pearly luster.

  Therefore, an object of the present invention is to provide an inorganic solidified layer as a printing layer, and can express the color and gloss of an area that cannot be obtained by inkjet printing after printing, and a simple method. And it is providing the manufacturing method of the design sheet | seat which can implement | achieve cost reduction.

  As a result of many experiments and studies on the influence of the surface state of the inorganic solidified layer formed on the design sheet on the fixation of the pigment, the present inventors have found that the base sheet and the inorganic solidified layer laminated thereon And after printing an image with an ink jet printer on the inorganic solidified layer formed when the nonwoven fabric is peeled off from the surface of the inorganic solidified layer from the laminated sheet having the nonwoven fabric adhered to the surface of the inorganic solidified layer, It has been found that a pigment or a pearl pigment can be fixed to the part, and the present invention has been completed.

That is, according to the present invention,
(1) The process of forming the lamination sheet formed by laminating | stacking a base material sheet, an inorganic solidified layer, and a nonwoven fabric in this order,
(2) removing the nonwoven fabric;
(3) A step of printing an image with an inkjet printer on the inorganic solidified layer (4) A step of applying a pigment on the inorganic solidified layer,
(5) removing excess pigment; and
(6) A method for producing a design sheet comprising a step of fixing a pigment on an inorganic solidified layer is provided.

  As a further feature of the method for producing a design sheet of the present invention, it is preferable that the average particle diameter of the pigment is not more than one-half of the average fiber diameter of the fibers constituting the nonwoven fabric.

  According to the method for producing a design sheet of the present invention, by fixing a pigment to an image printed on an inorganic solidified layer by an ink jet printer, an image having a color gamut wider than that obtained by ink jet printing can be easily obtained. And the design sheet | seat with which manufacturing cost was suppressed can be obtained.

It is a figure which shows the cross-section of the design sheet | seat of this invention with a nonwoven fabric. It is an electron micrograph (magnification 100 times) of the surface for transfer of the nonwoven fabric shown in FIG. It is an electron micrograph (100-times multiplication factor) of the surface (printing surface) of the inorganic solidified layer shown by FIG.

  The design sheet of the present invention forms a laminated sheet composed of an inorganic solidified layer laminated on the surface of a substrate sheet and a nonwoven fabric in close contact with the inorganic solidified layer, and is formed on the surface of the inorganic solidified layer immediately before printing with an inkjet printer. The non-woven fabric adhered is peeled off, an image is printed by an ink jet printer, the pigment is applied to the image portion, the excess pigment is removed, and then the pigment remaining in the inorganic solidified layer is fixed.

  The present invention will be described below with reference to the drawings.

(Method for forming laminated sheet)
The laminated sheet 1 for forming the design sheet of the present invention has a structure in which the inorganic solidified layer 3 is laminated on the base sheet 5, and the surface 3 a of the inorganic solidified layer 3 has a mold material sheet. A peelable non-woven fabric 7 that functions as is provided in close contact. That is, as shown in FIG. 1, the laminated sheet 1 is stored in a form in which a nonwoven fabric 7 is provided on the inorganic solidified layer 3, and the nonwoven fabric 7 is pulled from the surface of the inorganic solidified layer 3 during ink jet printing. The surface 3a (that is, the printing surface) of the peeled and exposed inorganic solidified layer 3 is printed.

  In the laminated sheet 1, the inorganic solidified layer 3 is held in a state where it is not completely solidified, and is an inorganic layer that is printed in this state and solidifies completely after printing, such as gypsum. It can also be formed from those that solidify due to moisture in the air, but using a layer containing plaster in a semi-solidified state as an inorganic solidified layer increases the friction resistance and UV resistance of the printed image, It is optimal for forming a robust and stable printed image.

  Hereinafter, the case where such a semi-solidified layer containing plaster is used as the inorganic solidified layer 3 will be described as an example.

  That is, the inorganic solidified layer 3 as described above is formed in a kneaded product layer formed by coating a hydrophilic surface of the base sheet 5 with a kneaded product of slaked lime (calcium hydroxide) powder and water, and drying. It is formed by removing the moisture. In such a layer, a part of slaked lime (calcium hydroxide) reacts with carbon dioxide in the air during the drying process to become a semi-solidified plaster precursor (mixture of slaked lime and calcium carbonate). If left untreated, the slaked lime remaining in the semi-solidified plaster precursor reacts with carbon dioxide in the air to produce calcium carbonate, further solidifying to form plaster. That is, a layer including a semi-solidified plaster precursor in which a part of slaked lime is carbonated and calcium carbonate is present is provided on the surface of the base sheet 5 as the inorganic solidified layer 3.

  Such an inorganic solidified layer 3 may include a semi-solidified plaster precursor before the calcium hydroxide (slaked lime) is completely carbonated and completely solidified, but preferably the plaster precursor. The calcium hydroxide therein is at least 10% by weight, preferably 15% by weight or more. That is, when the content of calcium hydroxide is less than the above range, the fastness of the image tends to decrease and color fading tends to occur. In addition, when printing is performed by applying the printing ink to the surface 3a of the inorganic solidified layer 3, the amount of calcium hydroxide that elutes in the printing ink and moves to the surface is reduced, so that the protective effect of the printed image is reduced. In addition, there is a disadvantage that the effect of suppressing deterioration of the printed image due to ultraviolet rays or the like is reduced.

  Further, the amount of calcium hydroxide in the inorganic solidified layer 3 is preferably as large as possible to achieve the above-mentioned purpose. However, if it is too large, the hardness of the inorganic solidified layer 3 becomes insufficient, and the inorganic solidified layer 3 is insufficient during the printing process. It becomes easy to produce damage etc. Therefore, the amount of calcium hydroxide in the inorganic solidified layer 3 is preferably suppressed to 90% by weight or less, and preferably 80% by weight or less.

  The amount of calcium hydroxide in the inorganic solidified layer 3 can be confirmed by differential thermal analysis.

  In addition, the content of calcium hydroxide in the inorganic solidified layer 3 is determined by the carbonation rate of the calcium hydroxide used to form this layer (the amount of calcium carbonate produced relative to the weight of slaked lime used in the slurry preparation described above). Weight ratio) and the ratio of additives such as binder materials, inorganic fine aggregates, and liquid-absorbing inorganic powders to be described later.

  Among the above adjustment methods, when the method of adjusting the carbonation rate of calcium hydroxide is employed, the upper limit of the carbonation rate is desirably 80%, particularly 40%. That is, when the carbonation proceeds excessively, the surface 3a of the inorganic solidified layer 3 is densified and the permeability of the printing ink tends to decrease.

  By leaving the inorganic solidified layer 3 as described above in the air after printing an image, the plaster precursor in the layer is carbonated and finally becomes plaster. The toughness of such an inorganic solidified layer 3 In order to improve this, it is preferable that this layer contains a solid emulsion of a polymer as a binder material. Such polymer emulsions are those in which monomers, oligomers or polymers thereof are dispersed in an aqueous medium, such as acrylic resins, styrene-acrylic resins, vinyl acetate resins, polyurethanes, styrene / butadiene rubbers and the like. Mention may be made of polymer emulsions. In such an emulsion, the medium (water) evaporates and the polymer component in the emulsion remains in the inorganic solidified layer 3 in the drying step. However, if the solid content (that is, the polymer) of such an emulsion is excessively present, the permeability of the printed image (printing ink) into the inorganic solidified layer 3 tends to be reduced. In order to increase and ensure ink permeability, generally the solids content of the polymer emulsion in this layer 3 is preferably in the range of 3 to 50% by weight.

  In addition to the above emulsion, the inorganic solidified layer 3 may contain various additives for adjusting physical properties, such as various fiber materials, inorganic fine aggregates, liquid-absorbing inorganic powders, and the like. . These additives improve physical properties such as strength of the inorganic solidified layer 3 that functions as a printing layer.

  Examples of the fiber material include glass fiber, vinylon fiber, polypropylene fiber, polyester fiber, polyethylene terephthalate fiber, acrylic fiber, aramid fiber, carbon fiber, metal fiber, and the like. Further, as the shape of the fiber, those of short fiber, long fiber, woven fabric, non-woven fabric, etc. can be used. Among these, the short fiber is particularly effective for improving the toughness and cutting workability of the inorganic solidified layer 3. . The length and diameter of such a short fiber are not particularly limited, but the length is 1 mm to 10 mm, particularly 2 mm to 6 mm, and the diameter is 5 to 50 μm, particularly 10 to 30 μm. It is suitable for further improving toughness and, in some cases, excellent cutting workability.

  The inorganic fine aggregate is an inorganic granular material having an average particle diameter in the range of about 0.01 to 2 mm, and has an average particle diameter of 1/4 or less of the thickness of the printing layer 3 within this range. Specific examples thereof include silica sand, cold water sand, mica, glazed silica sand, glazed mica, ceramic sand, glass beads, perlite, and calcium carbonate.

Furthermore, in order to avoid a decrease in affinity with the hydrophilic ink by blending the polymer emulsion in the inorganic solidified layer 3, and to compensate for the liquid absorbency that decreases with the progress of carbonation of calcium hydroxide, It is preferable to mix a liquid-absorbing inorganic powder in the solidified layer 3. This liquid-absorbing inorganic powder is porous and has a high oil absorption of 100 ml / 100 g or more, and is a fine inorganic powder, for example, an average particle diameter (D ₅₀ ) in terms of volume measured by a laser diffraction scattering method. For example, alumina powder and zeolite powder of 0.5 μm or less.

  That is, the polymer emulsion described above is effective for improving toughness and further increasing the bonding strength between the base sheet 5 and the inorganic solidified layer 3, but on the other hand, it reduces the hydrophilicity of the inorganic solidified layer 3. For example, when printing is performed using hydrophilic ink, the ink may be repelled and the printed image may be blurred. However, the use of the above-described liquid-absorbing inorganic powder improves the absorbability of the printing ink, and thus can effectively prevent the above disadvantages. In particular, the liquid-absorbing inorganic powder is preferably blended in the inorganic solidified layer 3 containing stucco in an amount of about 0.5 to 10% by weight.

  In addition to the above, various additives known per se can be blended in the inorganic solidified layer 3 in accordance with the purpose, either alone or in combination of two or more. It should be blended in such an amount that does not impair the penetration and fixation of the inorganic solidified layer 3, for example, the content of calcium carbonate formed by carbonation of slaked lime (that is, carbonation when the carbonation rate is 100%) In the range where the calcium content is maintained at 50% by weight or more, various additives are desirably blended.

  The thickness of the inorganic solidified layer 3 as described above is set to an appropriate range in which printing is possible, but in general, a range of about 0.05 to 0.3 mm, particularly about 0.1 to 0.25 mm is preferable. It is. That is, if this thickness is excessively thin, there is a risk that when an image is printed, the image fixability due to the penetration of the printing ink is deteriorated, or the depth of the image expressed by unevenness is impaired. Further, if it is too thick, there is a possibility that the printer used for printing may be restricted, such as being disadvantageous economically or being likely to form a fold by bending.

  As the base material sheet 5 supporting the inorganic solidified layer 3 as described above, for example, any material can be used as long as the inorganic solidified layer 3 can be formed by applying a slurry containing a stucco precursor on the surface thereof. Instead, it may be made of any material.

  Suitable examples thereof include wood pulp paper, 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. Examples of the various resin sheets or resin films can be given. Further, it may be a woven fabric or a non-woven fabric made of a fibrous material such as glass fiber, vinylon fiber, polypropylene fiber, polyester fiber, polyethylene terephthalate fiber, acrylic fiber, aramid fiber, carbon fiber, etc. Or a sheet may be sufficient.

  Moreover, the suitable base material sheet 5 has flexibility, and has moderate waist strength. In the base material sheet 5 having such properties, it is difficult to form a crease even when it is bent, and it is possible to effectively suppress inconveniences such as formation of a crack in the inorganic solidified layer 3 provided on the base material sheet 5. Because it can. The material of the base sheet 5 is considerably limited, but generally, pulp paper is preferably used. Pulp paper is generally available paper, has flexibility and bending strength, and can have good adhesion to the inorganic solidified layer 3. In addition to such pulp paper, synthetic paper mixed with pulp paper using chemical fibers such as glass fibers, polyvinyl acetate fibers, polyester fibers, and vinylon fibers as binder fibers can be used.

  In addition, the surface of the base material sheet 5 may be subjected to corona treatment or the like to improve the hydrophilicity, whereby the bonding strength between the inorganic solidified layer 3 and the base material sheet 1 can be improved.

  Moreover, the thickness of the base material sheet 5 is set to a suitable range according to the use, and is normally 0.02-0.5 mm. When this printing sheet is used as a recording material for a printer, the thickness of the base sheet 5 is set so that the printing sheet can be easily passed through the printer.

  Such a design sheet 1 of the present invention applies an inorganic slurry for forming the inorganic solidified layer 3, for example, a slurry for forming a stucco, to one surface of the base sheet 5, and further adheres a nonwoven fabric 7. The inorganic solidified layer 3 is formed by drying appropriately.

  The slurry for forming the plaster is obtained by blending the aforementioned binder material and various additives into a kneaded product of slaked lime powder and water.

  The slaked lime powder used for the preparation of such a slurry contains, for example, fine particles having a particle size of 5 μm or less in an amount of 20 to 80% by weight and coarse particles having a particle size of 10 to 50 μm in an amount of 10 to 40% by weight. It is preferable to use what is. That is, the fine particle component imparts shape retention and strength of the inorganic solidified layer 3, while the coarse particle component is useful for ensuring the permeability of the image. By using the slaked lime powder containing the above in an amount ratio as described above, it is extremely suitable for forming a stucco layer having good strength and durability without impairing the permeability of the image. For example, when slaked lime powder consisting only of the fine particle components as described above is used, the ink permeability may be impaired, and the fastness of the printed image may be reduced.

  In addition, in this slurry, a surfactant for uniformly dispersing various compounding agents and a thickener are appropriately blended so as not to cause dripping when coating the kneaded product. It is preferable that the viscosity is adjusted. Slurry coating can be performed by bar coater, roll coater, flow coater, knife coater, comma coater, spray, dipping, discharge, mold material transfer, etc. A shaft press or the like can be employed.

  The application thickness of the slurry as described above is set so that the thickness after drying becomes the thickness of the inorganic solidified layer 3 described above. Moreover, what is necessary is just to perform the drying after slurry application to such an extent that the water content of the stucco-containing inorganic solidified layer 3 is 5% or less. If the moisture content is too high, the layer form cannot be maintained, or if printing is performed with the moisture content maintained at a high level, ink bleeding or the like is likely to occur. is there. Drying is performed by heating the slurry coating layer to about 40 to 150 ° C. by blowing hot air or the like. At this time, if the heating temperature is increased more than necessary, the base sheet 5 and the nonwoven fabric 7 are deformed by heat, so care must be taken.

  In addition, the carbonation reaction of calcium hydroxide (slaked lime) proceeds by contact with carbon dioxide gas. However, as long as the slurry described above is stored in a non-breathable bag or container in a sealed state, a predetermined carbonic acid is obtained. Therefore, there is no problem in maintaining the conversion ratio and maintaining the calcium hydroxide amount in the printing layer 3 within a certain range.

  In the present invention, as shown in FIG. 1, a non-woven fabric 7 is provided in close contact on the inorganic solidified layer 3 of the laminated sheet 1, and the non-woven fabric 7 is peeled off during printing. 3 is printed.

  That is, since the surface 3a of the inorganic solidified layer 3 is not completely solidified and is in a semi-solidified state, the surface of the inorganic solidified layer 3 that has penetrated into the inside from the transfer surface 7a of the nonwoven fabric 7 by peeling off the nonwoven fabric 7 The portion is dropped or destroyed together with the nonwoven fabric 7, and as a result, the transfer surface 7 a of the nonwoven fabric 7 is transferred to the surface 3 a of the inorganic solidified layer 3.

  Such a nonwoven fabric 7 naturally also has a function as a protective sheet for protecting the surface of the inorganic solidified layer 3. That is, since the inorganic solidified layer 3 is formed from inorganic particles (for example, calcium hydroxide or calcium carbonate particles), the inorganic solidified layer 3 is relatively fragile and is damaged by external pressure or the surface falls off. However, since the nonwoven fabric 7 as described above is provided from immediately after the production of the laminated sheet 1 to immediately before printing, such an inconvenience can be effectively prevented.

  The present invention makes use of the fact that the transfer surface 7a of the nonwoven fabric 7 is transferred to the surface 3a of the inorganic solidified layer 3, and makes this surface 3a a printing surface excellent in printing suitability.

  For this reason, as said nonwoven fabric 7, it is a nonwoven fabric sheet which consists of a heat-fusible fiber, and what was adjusted so that the surface excellent in printability might be transcribe | transferred by the crimping process by a heat roll.

  That is, as shown in FIG. 2, the transfer surface 7a of the nonwoven fabric 7 used in the present invention is observed with an electron micrograph at a magnification of 100 times, and a continuous flat surface and an irregularity surrounded by the flat surface are observed. The surface is a mix of regular recesses. That is, in FIG. 2, a region surrounded by a circle with low whiteness, that is, a black region, is observed as an irregular recess A (that is, a gap between fibers), and a portion with high whiteness around the recess A is flat. It is a surface.

In the present invention, in such a transfer surface 7a, a flat surface is present at a ratio of 70 to 90% per unit area, and the major axis is 1 mm ² so as to be surrounded by the flat surface. In order to make the surface 3a of the inorganic solidified layer 3 a printing surface excellent in printability, it is preferable that the number of recesses A having a size of 10 to 300 μm is observed in the number of 45 to 250. That is, by laminating the transfer surface 7a of the nonwoven fabric 7 in close contact with the surface 3a of the inorganic solidified layer 3, the inorganic solidified material on the surface portion of the inorganic solidified layer 3 enters the irregular recess A of the transfer surface 7a. To do. Therefore, when the nonwoven fabric 7 is peeled off, the portion that has entered the recess A of the transfer surface 7a is broken, and as a result, the surface 3a of the inorganic solidified layer 3 corresponds to such an irregular recess A. An irregular convex part will be formed. Since a predetermined number of irregular recesses A having the above size are formed on the transfer surface 7a, the irregular projections having a predetermined size and a rough surface are correspondingly formed. Part is formed on the surface 3a of the inorganic solidified layer 3, and as a result, the presence of such convex portions increases the penetration speed of the printing ink into the inorganic solidified layer and is effective in preventing bleeding of the printed image. A printing surface suitable for obtaining a clear printed image is formed. Further, such irregularly shaped convex portions are also effective in giving a printed image a three-dimensional effect, a sense of depth, or a natural texture.

  Accordingly, in order to form the irregular recesses A having the above-mentioned sizes at a predetermined ratio, usually, a nonwoven fabric sheet made of heat-fusible fibers is used, and this nonwoven fabric sheet is pressure-bonded with a heating roll. The thing is used as a nonwoven fabric 7. That is, by pressing with a heating roll, the fiber surface can be made flat and the recess A can be clearly present.

  For example, when a woven sheet is used instead of a non-woven sheet, when heat sealing is performed, the transfer surface 7a becomes a flat surface, and the uneven surface becomes the surface 3a of the inorganic solidified layer 3. It can no longer be formed. Even if the concave portions can be clearly present, since the fibers are regularly woven, it becomes a surface in which the regular concave portions are regularly arranged, and printing is performed on the surface of the inorganic solidified layer 3. The characteristic peculiar to the laminated sheet 1 to be given will be impaired. Furthermore, the concave portions cannot be present in a sufficient area ratio, and therefore, the generation of the convex portions as the printing surface becomes insufficient, making it difficult to effectively suppress the blurring of the printed image, and clear printing. I can't get a statue.

  By using a non-woven sheet that has been heat-sealed, a part of the fiber does not adhere to the surface of the inorganic solidified layer 3 when peeled off, and the printability can be improved, and the fiber surface Since it is crushed by heat, the concave portion A can be clearly present. For this reason, the convex portion transferred to the surface 3a of the inorganic cured product layer 3 is stabilized and effectively prevents bleeding of the printed image. Therefore, it is possible to obtain a printing surface capable of stably forming a clear printed image.

  Furthermore, in the present invention, the nonwoven fabric sheet is preferably formed of heat-fusible core-sheath fibers (the core material is a high-melting fiber and the sheath is a low-melting fiber). For example, a nonwoven fabric sheet made of a commercially available core-sheath fiber having polypropylene as a core material and polyethylene as a sheath is preferably used. That is, by using a nonwoven fabric composed of such core-sheath fibers, the low melting point fibers of the sheath part are melted without melting the core part by the pressure-bonding treatment with a hot roll, and the fiber form remains while the fiber form remains. Flattening is performed at the same time as fusion between the two, thereby forming the above-described flat portion and the irregular recess A (that is, the gap between the fibers).

  In addition, pressure bonding with a hot roll is performed by adjusting temperature, time, and roll pressure so as not to crush a concave portion that becomes a gap between fibers. For example, when a non-woven fabric of core-sheath fibers as described above is used. It is preferable to perform the pressure-bonding treatment at a temperature equal to or higher than the melting point of the low-melting fiber serving as the sheath and lower than the melting point of the core high-melting fiber. In this case, it is desirable to perform the pressure bonding process at a temperature of about 90 to 150 ° C.

Moreover, the fiber which comprises a nonwoven fabric, and its fabric weight are set so that the flat part and the recessed part A of a predetermined size may be formed in the ratio mentioned above. For example, in the above-described core-sheath fiber (polypropylene fiber / polyethylene fiber), a long fiber having a fiber diameter of about 10 to 50 μm is preferable, and the basis weight is preferably set to about 30 to 120 g / m ^2. With this, for example, the nonwoven fabric 7 can be held in close contact with the surface of the inorganic solidified layer 3 with an appropriate peel strength, and a stable transfer effect and protective effect can be exhibited.

  A non-woven sheet having a transfer surface 7a that has been subjected to pressure-bonding treatment with a heat roll as described above and that satisfies a predetermined condition is used as the non-woven cloth 7, and is provided in close contact with the surface of the inorganic solidified layer 3 and peeled off. Thereby, the surface 3a of the inorganic solidified layer 3 can be made into the surface excellent in printability.

  The surface 3a of the inorganic solidified layer 3 as described above is a surface in which a continuous flat surface C and an irregular convex portion B surrounded by the flat surface are mixed, as observed with an electron micrograph of 100 times magnification. It has become. For example, in FIG. 3, a region surrounded by a circle and having a high whiteness is an irregular convex portion B, and this convex portion B is the concave portion A (gap between fibers) of the transfer surface 7 a of the nonwoven fabric 7 described above. ), And a portion with low whiteness around the convex portion B is a flat surface C.

  That is, in the laminated sheet 1 of the present invention, by removing the nonwoven fabric, the irregular recess A of the transfer surface 7a of the nonwoven fabric 7 is transferred to the surface 3a of the inorganic solidified layer 3 to form the irregular projection B. However, since the convex portion B is formed by peeling, the surface of the convex portion B becomes a considerably rough surface, and as a result, the printing ink adhering to this portion penetrates quickly into the printing layer, which is This is one of the factors that prevent bleeding.

In the present invention, when observed with an electron micrograph at a magnification of 100 times, the irregular convex portion B exists at a rate of 10 to 30% per unit area, and is 1 mm ² as the irregular convex portion B. Hits having a major axis of 10 to 300 μm are observed in the number of 50 to 300. That is, a lot of irregular fine convex portions B are randomly present between the flat surfaces C with a constant balance, and printing ink adheres to the flat surfaces C and convex portions B and penetrates into the inside. By doing so, bleeding of the printed image is effectively prevented, and a clear printed image can be formed.

  Moreover, the natural texture peculiar to the printing surface formed using an inorganic solidified layer is not impaired by the printed image formed. That is, in addition to effectively suppressing ink bleeding, a large number of irregularly shaped convex portions B that are not fixed in shape and have a certain size are randomly formed between the flat portions C. Therefore, a particularly clear image quality can be effectively projected without impairing the natural texture. For example, even if a large number of convex portions are formed, if the shape of the convex portions is a regular shape such as a circle or a square, or is regularly arranged, the naturalness is impaired, and mechanically It will give a synthesized impression.

  Furthermore, the surface 3a of such an inorganic solidified material 3 has no adhesion of fibers and the like, and deterioration of image quality due to fiber marks or the like is effectively prevented.

(Process to remove non-woven fabric)
In the present invention, after forming the laminated sheet 1 as described above, the nonwoven fabric 7 is removed prior to printing. In addition, when taking time between formation of a lamination sheet and printing, it is preferable to store in the state of a lamination sheet and to remove the nonwoven fabric 7 just before printing.

  As a method of removing such a nonwoven fabric 7, it is common to carry out by hand. In other words, the nonwoven fabric 7 is pierced and peeled off with a sharp needle or a thousand sheets in the cross section of the nonwoven fabric at the end of the laminated sheet 10. Or if the lamination sheet 10 is roll shape, it is also possible to remove the nonwoven fabric 7 continuously using a winder.

  By removing the nonwoven fabric 7, irregularities derived from the fiber structure of the nonwoven fabric are generated on the surface 3 a of the inorganic solidified layer 3.

(Process of printing an image on an inorganic solidified layer with an inkjet printer)
In the present invention, an image or the like is printed on the surface 3 a of the inorganic solidified layer 3 obtained by removing the nonwoven fabric 7 from the formed laminated sheet 1.

  As a method of printing an image or the like on the surface 3a of the inorganic solidified layer 3, printing is performed by an ink jet printer using ink in which a predetermined pigment or dye is dispersed or dissolved. Any known inkjet printer can be used without any particular limitation. As the ink to be used, a hydrophilic ink in which a water-soluble dye is dissolved or a pigment is dispersed in water (or a water / alcohol mixed solvent) with a surfactant or the like is most preferable. When such hydrophilic ink is used, a sharp image can be formed on the inorganic solidified layer 3 without bleeding and stably maintained. In particular, in the present invention, an ink using a pigment is preferably used.

(Method of applying pigment on inorganic solidified layer)
In the present invention, after an image is printed on the surface 3a of the inorganic solidified layer 3 by an ink jet printer, a pigment is applied to the surface of the printed image or the like. In order to apply the pigment, a method of applying the pigment in a powder state is recommended. That is, in the case of a dispersion liquid in which a pigment is dispersed in water or a solvent, there is a risk of affecting an image printed by an ink jet printer. When a dispersion containing pigment is applied, the water or solvent in the dispersion swells the pigment forming the image printed by the inkjet printer, and the image is blurred or the color density of the image is reduced. This is because the image is not clear due to a problem such as a malfunction.

  In the present invention, the pigment is applied in a predetermined color to the surface 3a of the inorganic solidified layer 3 on which an image or the like has been printed with an ink jet printer using a fibrous material such as a brush, brush, absorbent cotton, or cloth. It is desirable.

  As a pigment used for this invention, it is suitable that the average particle diameter is 1/2 or less of the average fiber diameter of the fiber which comprises a nonwoven fabric. That is, when the average particle diameter of the pigment is smaller than half of the average fiber diameter of the fibers constituting the nonwoven fabric, the pigment can sufficiently enter the concave portions of the surface 3a of the inorganic solidified layer 3 formed by removing the fibers. Can do. Further, when the average particle diameter of the pigment is smaller than one half of the average fiber diameter of the fibers constituting the nonwoven fabric, the coarse particles prevent fine particles from entering the recesses on the surface 3a of the inorganic solidified layer 3. Less likely to occur.

  The pigment in the present invention is not particularly limited. As pigments, yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navelous yellow, naphthol yellow S, Hanser yellow G, Hansar yellow 10G, benzidine yellow G, benzidine yellow GR , Quinoline yellow lake, permanent yellow NCG, tartrazine lake, and other color pigments, such as titanium oxide, zinc oxide, carbon black, iron black, aniline black, benzidine orange, chrome vermilion, cadmium orange , Permanent Orange GTR, First Orange Lake, Lake Red C, Petite, Watching Red, Brilliant Carmine 6B, Permanent Red F5R, Permanent Red 2B, Permanent Red FRLL, C Mine rake, quinacridone red, methyl violet lake, first violet B, quinacridone violet, indanthrene violet, phthalocyanine blue, first sky blue, bitumen, ultramarine, cobalt blue, Victoria blue lake, phthalocyanine green, marker light green lake, pigment green B, Inorganic pigments, organic pigments, inorganic pigments, metal powder pigments and the like of various colors represented by viridian, schenner, amber, aluminum powder, bronze powder and the like can be used. In addition, colored processed powders and fluorescent pigments in which dyes and pigments are combined with resin powders, natural mica surfaces coated with metal oxides, synthetic mica surfaces coated with metal oxides, pearl pigments, Further, extender pigments such as aluminum hydroxide, calcium carbonate, barium sulfate, and calcium sulfate can be used.

  In the present invention, among the above-mentioned pigments, inorganic pigments, pearl pigments, metal powder pigments, extender pigments and the like are suitable. In the case of an organic pigment, characteristics such as weather resistance, heat resistance, strength, and the like are deteriorated, and the advantages of the present invention may not be sufficiently exhibited. Moreover, the pigment mentioned above can be used individually by 1 type or in combination of 2 or more types according to the target hue.

(Step of removing excess pigment)
In the present invention, pigments other than the loosely fixed pigment are removed by entering the concave portion of the surface 3 a of the inorganic solidified layer 3. The removal of the excess pigment applied on the surface 3a of the inorganic solidified layer 3 is not only the suction of the excess pigment, but also the adhesion of the excess pigment by fibers such as brushes, brushes, absorbent cotton, cloth, etc. It can be carried out by attaching excess pigment with a tape, or blowing off excess pigment by blowing air.

  With such a method, it is possible to remove the excess pigment with an arbitrary removal amount relatively easily without damaging the image printed by the ink jet printer.

(Step of fixing the pigment on the inorganic solidified layer)
If the pigment is applied onto the surface 3a of the inorganic solidified layer 3, the particles constituting the pigment enter the recesses formed on the surface 3a of the inorganic solidified layer 3 and cannot be easily removed. By applying to the surface 3a of the inorganic solidified layer 3 to which the pigment has been applied, the pigment can be firmly fixed.

  In the present invention, the solvent-based resin includes one or more solvents such as methanol, ethanol, propanol, butanol, dimethylformamide (DMF), methyl ethyl ketone (MEK), toluene, cyclohexane, butyl acetate, urethane resin, acrylic resin, vinyl chloride. What melt | dissolved resin etc. is suitable.

  It is appropriate to contain 0.1 to 10.0% by weight of this resin component. If it is less than 0.1% by weight, stable coating becomes difficult and the pigment cannot be fixed. Moreover, when it exceeds 10.0 weight%, a resin layer will be formed thick and will interfere with carbonation of the uncured plaster (calcium hydroxide) of an inorganic solidified layer. The method for coating the solvent-based resin is not particularly limited, but a method in which the solvent-based resin is soaked in a brush or a roller brush and applied to the surface 3a of the inorganic solidified layer 3, or the solvent-based resin is applied to the inorganic solidified layer 3 by spraying. For example, a method of spraying on the surface 3a and a method of continuously applying a solvent-based resin to the surface 3a of the inorganic solidified layer 3 with a gravure printing machine or the like are used.

  When the inorganic solidified layer 3 is a layer containing plaster, when the design sheet 1 is produced as described above, by leaving it in the atmosphere (usually about 2 to 30 days), carbonic acid in the atmosphere Absorbs gas, carbonation of the remaining calcium hydroxide progresses, and solidification progresses to plaster, and in particular, the image penetrates and is fixed to uneven porous plaster and becomes a wall painting, photographic image, etc. Is a deeper one. In addition, the formed image is excellent in fastness, does not cause color fading even if it is rubbed, and can protect the ink component from ultraviolet rays and the like, and is stably maintained for a long time. .

  The design sheet 1 of the present invention has a large number of irregularly shaped convex portions having a certain size on the surface 3a of the inorganic solidified layer 3 on which a printed image is formed, regardless of whether or not it contains plaster. In particular, it is possible to display an image that requires fineness, such as a human image or a still-life image, without impairing the three-dimensional effect or the deeply painting style.

  Moreover, since the manufacturing method of this design sheet 1 is excellent in weather resistance etc., it is very useful especially for the use as an inkjet recording material used for an inkjet printer.

  The excellent effect of the present invention will be described in the following experimental example.

The test methods and materials used in the experimental examples are shown below.
(1) Method for measuring the number of concave or convex portions of an inorganic solidified layer or nonwoven fabric:
Using an electron microscope (manufactured by EFI, Qanta200. Genesis 2000 type), the surface of the inorganic solidified layer or the surface image of the nonwoven fabric at a magnification of 100 was taken as a digital image. The obtained digital image data was binarized by a discriminant analysis method using image processing software (manufactured by Digital Being Kids Co., Ltd., “Pop Imaging 4.00”) to clearly distinguish the concave and convex portions. Furthermore, the total number of concave portions or convex portions per unit area and the area ratio were measured by the image measurement function of the image processing software.
(2) Printing with an inkjet printer:
An image having a black density of 100% is formed on a laminated sheet (A4 size) produced under the conditions shown in each Example and Comparative Example using an inkjet printer (product name: PRO-1, water-based ink in which pigment is dispersed) manufactured by Canon. Printed.
(A) Substrate sheet:
Pulp paper: Fuji Kyowa Paper's inkjet base paper “FK Slat R-IJ” (trade name) (thickness 0.17 mm, basis weight 160 g / m ² )
(B) Calcium hydroxide:
Slaked lime: "High-purity slaked lime CH" (trade name) manufactured by Ube Materials
(C) Inorganic powder:
Calcium carbonate: Yakusen Lime “White 7” (trade name)
(D) Aqueous acrylic resin emulsion:
Polytron: “Polytron A1480” (trade name) manufactured by Asahi Kasei Corporation (acrylic copolymer latex, solid content 40% by weight)
(E) Liquid-absorbing inorganic powder Alumina fine powder: Average particle diameter (D50) 0.05 μm, Oil absorption 180 ml / 100 g
(F) Nonwoven fabric sheet Nonwoven fabric A: Shinwa Co., Ltd. core (polypropylene) sheath (polyethylene) fiber nonwoven fabric (fiber diameter 0.02 mm, thickness 0.12 mm, basis weight 60 g / m ² )
Nonwoven fabric B: Hirose Paper Co., Ltd. core (polypropylene) sheath (polyethylene) fiber nonwoven fabric “HOP-30H” (trade name) (fiber diameter 0.02 mm, thickness 0.09 mm, basis weight 30 g / m ² )
(Production Examples 1-4)
Non-woven fabric A and non-woven fabric B were subjected to thermal calendering to obtain non-woven fabrics α to δ shown in Table 1, respectively. The total number per unit area and the area ratio of the concave portions of these nonwoven fabrics were measured by the above measuring method. The results are shown in Table 1.

  Next, it knead | mixed by the compounding ratio of 100 weight part of slaked lime, 60 weight part of water-based acrylic resin emulsion, 20 weight part of water, and 5 weight part of liquid absorbing inorganic powder (alumina fine powder), and obtained the slaked lime slurry. Pulp paper (300 × 300 mm) is used as a base sheet, and the obtained slaked lime slurry is applied to the surface with a bar coater. Immediately after that, nonwoven fabrics α to δ shown in Table 1 are pressure-bonded to the surface of the slurry, In the dryer for 30 minutes. The nonwoven fabric adhered to the surface of the obtained laminate was peeled off to obtain laminated sheets A to D. Moreover, there was no adhesion of fiber on the surface of the inorganic solidified layer after peeling off the nonwoven fabrics α to δ. Next, the total number per unit area of the convex portions on the surface of the inorganic solidified layer of the design sheets A to D and the area ratio of the concave portions were measured by the above measuring method. The results are shown in Table 2.

(Examples 1-4)
An image having a black density of 100% was printed on the surface of the inorganic solidified layer of the laminated sheet obtained in Production Examples 1 to 4 using an inkjet printer. After drying at room temperature for 5 hours, ISO whiteness was measured. The results are shown in Table 3.

  Next, a small amount of carbon black (manufactured by Mitsubishi Chemical Co., Ltd., brand name: # 30) was taken with a No. 5 brush (acrylic hair 100%), applied to a 100% black image of the laminated sheet, and carbon black was put in the recesses. Thereafter, excess carbon black was removed with a No. 6 brush (100% acrylic hair).

  Subsequently, an acrylic resin (manufactured by Sekisui Chemical Co., Ltd., ESREC BM-1) was dissolved in isopropanol (IPA), and a solvent-based resin adjusted to a concentration of 6% by weight was applied to the image coated with carbon black by spraying. And dried for 1 hour at room temperature and measured for ISO whiteness. The results are shown in Table 3.

(Comparative Example 1)
A laminate having an inorganic solidified layer (printing layer) using a slurry having the same composition except that a polyethylene sheet (material: polyethylene, thickness 0.05 mm) is used instead of the nonwoven fabric used in the above production example. Got. In the obtained laminate, when the polyethylene sheet adhered to the surface of the inorganic solidified layer was peeled off, the total number of convex portions was 4/1 mm ² and the concave area ratio was 98%.
Next, the surface of the inorganic solidified layer obtained by peeling off the polyethylene sheet was printed at a black density of 100% as in the example, dried at room temperature for 5 hours, and then measured for ISO whiteness, it was 5.9%. It was.

  Subsequently, carbon black was applied to the surface of the inorganic solidified layer printed at a black density of 100% in the same manner as in the example, and the excess carbon black was removed. As a result, the carbon black remained very little because the surface was smooth. It was.

  Furthermore, the acrylic resin was sprayed in the same manner as in Example, dried at room temperature for 1 hour, and measured for ISO whiteness, it was 5.2%.

1: Laminated sheet design sheet 3: Inorganic solidified layer 5: Base sheet 7: Non-woven fabric

Claims (2)

(1) The process of forming the lamination sheet formed by laminating | stacking a base material sheet, an inorganic solidified layer, and a nonwoven fabric in this order,
(2) removing the nonwoven fabric;
(3) A step of printing an image with an inkjet printer on the inorganic solidified layer (4) A step of applying a pigment on the inorganic solidified layer,
(5) removing excess pigment; and
(6) A method for producing a design sheet comprising a step of fixing a pigment on an inorganic solidified layer.   The method for producing a design sheet according to claim 1, wherein the average particle diameter of the pigment is not more than one-half of the average fiber diameter of the fibers constituting the nonwoven fabric.

Images