JP5652797B2 - Printed matter printed by cellulose microfiber and production method - Google Patents

Description

  The present invention relates to a printed matter in which significant information such as designs and characters are printed with cellulose microfibers, and a manufacturing method.

  Normally, when printing significant information such as designs and characters on paper, a solvent such as varnish is added to color materials such as pigments and dyes to make ink, and the ink is printed on paper by various printing means. . Ink and paper are compatible, and there are good and bad combinations. For this reason, in order to improve the acceptability of the ink to the paper, contrivances have been devised in the contents and the compounding method at the time of inking. Acceptability refers to the ease with which ink is deposited on paper.

  On the other hand, in order to improve the acceptability of ink on paper, a technique for processing paper not on the ink side is also disclosed. As a general paper processing technique conventionally used, there is a technique for improving the ink acceptability of a paper by applying a paint composed of a white pigment and a binder on the paper. In recent years, as an example of a new technique, a cellulose-based raw material is oxidized, and the oxidized cellulose is subjected to wet atomization to produce nanofibers (hereinafter referred to as “cellulose microfibers”). Printing papers that improve the air resistance and smoothness of paper by coating or impregnating paper additives with papermaking additives and are excellent in ink acceptability and prevention of back-through are disclosed (for example, patents) Reference 1).

  Thus, in recent years, technological advances have been remarkable, and the creation of nanoscale products has become possible not only for synthetic materials but also for natural materials such as cellulose. The present applicant has also filed a paper or printed matter in which cellulose fine fibers are added to a part of the paper, which is characterized by being invisible visually under reflected light and transmitted light. It is a paper or printed matter for authenticity determination that can be read by color change after printing by printing ink on the paper (see, for example, Patent Documents 2 and 3).

JP 2009-263850 A JP2012-021235 JP2012-020403

  Normal inks include a type in which color material components such as pigments and dyes are fixed to paper by chemical bonding, but many types contain a binder component that allows the paper to accept ink. With regard to the acceptability, there is a problem that the acceptability is deteriorated unless components to be accepted (such as a binder and a color material to be directly bonded) are mixed into the ink.

  In addition, regarding the technique of Patent Document 1, the paper is intended to improve the smoothness, ink acceptability, glossiness, etc. of the paper by coating cellulose microfibers (or double coating) on the entire surface of the paper. A printed matter in which significant information such as symbols and characters intended by the present invention was printed with cellulose microfibers could not be produced.

  Further, Patent Documents 2 and 3 are characterized in that they can not be visually recognized under reflected light and transmitted light, but can be determined by machine reading or reading by color change after ink printing on the paper. In addition, a printed matter in which significant information such as symbols and characters that can be visually recognized, which is the object of the present invention, is printed with cellulose microfibers could not be produced.

  The present invention aims to solve the above-described problems, and is a technique for improving the fixing property of significant information such as symbols and characters formed on the paper, and significant information such as symbols and characters. The present invention relates to a printed material printed with cellulose fine fibers and a production method.

  The printed matter according to the present invention is characterized in that the printed matter has a first region in at least a part of the paper, and significant information is printed in the first region by cellulose microfibers having a color different from that of the paper. .

  The printed matter of the present invention is characterized in that the fiber length of the cellulose microfiber is larger than the particle diameter of the pigment for coloring the cellulose microfiber in a color different from that of the paper.

  In the present invention, a method for producing a printed matter in which significant information is printed by cellulose microfibers includes a step of preparing cellulose microfiber dispersion by dispersing cellulose microfibers in water, and printing the cellulose microfiber dispersion by a printing apparatus. And a step of performing.

  In the method for producing a printed matter according to the present invention, the step of printing by a printing apparatus is to supply a paper having a moisture content of less than 9%, and to use a screen printing machine, a flexographic printing machine, an inkjet printing machine, a gravure printing machine, an offset printing machine, a letterpress. Screen printing device, flexographic printing device, ink jet printing device, gravure printing device, offset printing device that prints using either printing machine or intaglio printing machine or is installed between the wire part and drying part of paper machine And a letterpress printing apparatus, and printing on a sheet having a water content of 9 to less than 85%.

  In the method for producing a printed matter according to the present invention, the step of printing by each printing machine is performed by impregnating or spraying water on a paper having a water content of less than 9% before printing the cellulose fine fiber dispersion on the paper. It is characterized by having a water content adjusting step of less than ~ 85%.

  The manufacturing method of the printed matter in which significant information is printed by the cellulose microfiber in the present invention further includes a coloring step of coloring the cellulose microfiber with a colorant before the step of preparing the cellulose microfiber dispersion. And

  Since the fibers of the paper and the cellulose microfibers are hydrogen-bonded, they are firmly fixed on the paper without the need for a binder component, and effective in preventing falsification of significant information.

It is a figure which shows the printed matter which printed the cellulose microfiber in this invention. It is a figure which shows the preparation methods by the screen printing system of the printed matter of this invention. It is a figure which shows the printed matter which printed the cellulose microfiber in Example 1,2. It is a figure which shows the printed matter which printed the cellulose microfiber in Example 3. FIG. It is a figure which shows the printed matter which printed the cellulose microfiber in Example 4. FIG. It is a figure which shows the preparation methods by the printing apparatus installed in the paper machine of the printed matter of this invention.

  DESCRIPTION OF EMBODIMENTS Embodiments for carrying out the present invention will be described with reference to the drawings. However, the present invention is not limited to the embodiments described below, and includes various other embodiments within the scope of the technical idea described in the scope of claims.

  First, the configuration of the printed material will be described.

  FIG. 1A shows a plan view of a printed material according to the present invention. The printed matter (1) according to the present invention has a first region (3) on the paper (2), and the first region (3) has significant information due to cellulose microfibers having a color different from that of the paper ( 4) is printed.

  Further, the shape of the significant information (4) includes a symbol shape (for example, a heavy circle) as shown in FIG. 1 (a), a character shape (for example, NPB) as shown in FIG. 1 (b), and FIG. ) (For example, “” symbol), and the shape is not particularly limited.

  Cellulose microfibers in the present invention are fibers mainly composed of cellulose, particularly those using plant-derived natural cellulose as a raw material, and those fibrillated into fine cellulose fibers having a fiber width of less than 2 nm to 10 μm. Say.

  The term “defibration” as used herein refers to unraveling cellulosic fibers up to several micro or nanofibrils. Usually, the cellulose fiber obtained from a plant is an aggregate of cellulose nanofibrils composed of 30 to 50 cellulose molecules and having a fiber width of about 2 to 5 nm. Cellulose microfibrils are firmly bonded by innumerable hydrogen bonds, but can be broken into several units of cellulose micro or nanofibrils while remaining in a fibrous state by applying physical or chemical treatment.

  When the fiber width of the cellulose fiber is 10 μm or more, it becomes the same order as 10 to 30 μm, which is the fiber width of a general pulp fiber, and characteristics specific to microfibers cannot be obtained. Therefore, the term “microfiber” as used herein refers to a fiber having a cellulose nanofibril unit of about 2 nm to less than 10 μm, particularly preferably 2 nm to less than 1 μm, and more preferably 2 nm to less than 100 nm.

  Further, the fiber means an elongated individual having an aspect ratio (fiber length / fiber width) of usually 100 to 1000 or more, but the cellulose microfiber in the present invention is basically a fiber whose aspect ratio falls within this range. It is. In particular, in the case of microfibers having a fiber width of less than 100 nm, the aspect ratio may be 10,000 or more.

  Regarding the fiber length, it is desirable that the length is included in this aspect ratio, but the maximum limit length differs depending on the printing method, and even if the aspect ratio is 100 or less, at least the fiber length is larger than the fiber width. It only needs to be large.

  However, when the aspect ratio is 1 or less, the particle shape is obtained, and the characteristics are close to those of spherical or polygonal pigment particles, and printing characteristics using fibers cannot be obtained. From this, the fiber length of the cellulose microfiber needs to be larger than the particle diameter of the coloring agent mentioned later.

  Cellulose microfibers are mainly composed of cellulose fibers, but the fibers composed of cellulose are not particularly limited, and include chemical pulps such as KP and SP made of various kinds of wood, GP, TMP, and CTMP. Pulp such as mechanical pulp and recycled paper recycled pulp can be appropriately selected and used. Powdered cellulose obtained by pulverizing them, microcrystalline cellulose purified by chemical treatment, and the like can also be used. In addition, non-wood such as kenaf, hemp, rice, bagasse, abaca, cotton, Mitsumata, bamboo and the like can also be used.

  Cellulose microfibers are white or yellowish white (the color of the raw material pulp), and are used as they are when printing on paper of a different color. When printing on the same color paper, colored cellulose microfibers are used.

  The paper (2) to be printed is preferably paper made of wood or non-wood pulp, synthetic fiber paper made of synthetic fiber having a hydroxyl group, or nonwoven fabric. This is because the cellulose microfibers are firmly fixed on the paper by hydrogen bonding. However, even in the case of a sheet-like base material having a water absorption property such as synthetic fiber paper, nonwoven fabric, and film made of synthetic fibers having no hydroxyl group, the cellulose microfiber dispersion is mixed with a binder component, etc. If the fiber can be fixed on the substrate, it can be used.

  As described above, the printed matter of the present invention is formed by fixing cellulose microfibers on the paper (2) by hydrogen bonding. Therefore, in order to more firmly fix the cellulose microfibers on the paper (2), it is preferable to print on the paper (2) having a high water content.

  Paper made of wood or non-wood pulp, or a non-woven fabric made of a synthetic fiber having a hydroxyl group and made wet is formed into a sheet by bonding the fibers by hydrogen bonding between the fibers. In the hydrogen bond, the bond between the hydroxyl groups of the cellulose fiber is the strongest, and the water bonding force is reduced by the water molecules entering between the hydroxyl groups.

  Therefore, when paper (2) with a high water content is used, many hydrogen molecules are present between the fibers, resulting in loose hydrogen bonding, and newly added cellulose microfibers and paper fibers are newly hydrogen bonded. The hydrogen bond between the cellulose microfiber and the paper (2) becomes stronger. Hereinafter, paper (2) with a high water content is called “wet paper”, completed through the drying process of the paper machine, and paper (2) is called “dry paper”. Is called "paper".

  As described above, by printing the cellulose microfibers on the paper, the print region (3) has a unique texture (feeling of touch, roughness, low gloss, etc.) that is different from the print region of normal ink, The printed matter of the present invention is a unique printed matter made of fibers, which is different from a printed matter made of ordinary ink.

  Next, a method for producing a printed material will be described.

  First, a method for producing cellulose microfiber will be described. Cellulose microfibers are produced by defibrating fibers made of cellulose.

  As a method of defibration, in the physical method, micronization or nanofibrillation is performed by mechanical shearing force using a grinder, refiner, high-pressure homogenizer, etc., or by adding an organic solvent to mechanical grinding by a dry ball mill, atomization treatment There are ways to do this. In addition, as a method by chemical treatment, there are a method of removing a non-crystalline portion of cellulose fiber by sulfuric acid treatment, a method of highly dispersing by introducing a carboxyl group only on the surface of crystalline cellulose nanofibrils by oxidation treatment, and the like. These methods are all known methods, and the defibration performed for producing the cellulose microfibers in the present invention is also performed by a known method.

  As a method for producing colored cellulose microfibers, the cellulose microfibers are produced and then colored with a colorant, or the raw material fibers are colored with a colorant and then fibrillated to produce cellulose microfibers. However, coloring non-uniformity is less when cellulose microfibers are colored after production.

  As the colorant, it is preferable to use a direct dye or a reactive dye that dyes cellulose fibers well, but other dyes or pigments may be used as long as they can color the cellulose fibers. When coloring, an auxiliary such as a fixing agent is appropriately used according to the coloring method and the type of the coloring agent.

  As a coloring method, coloring with a dye includes an immersion dyeing method in which heating is performed in water, the dye is adsorbed on a fiber, washed with water, and dried. In addition, coloring with a pigment includes a method in which a pigment and a dispersant are wet dispersed using a mill or the like to form a colorant and the colorant is colored. These methods are all known methods, and the coloring performed for producing the colored fiber in the present invention is also performed by a known method.

  Uncolored or colored cellulose microfibers are dispersed in water to prepare a cellulose microfiber dispersion. It is possible to add a dispersant, a water-soluble polymer, a water-soluble liquid that does not inhibit the dispersion state of cellulose microfibers, an organic solvent, powder, fine particles, or the like.

  In addition, the cellulose fine fiber dispersion needs to have a concentration such that the fibrillated microfibers do not immediately recombine by hydrogen bonding, and is preferably used at a solid content concentration of about 0.1 to 3%. . However, the microfibers can be re-separated by vigorously stirring the dispersion or adding a dispersing agent, and problems in the printing process such as passing through the screen mesh or transferring to a roll should occur on the printing device. For example, there is no problem even with a solid content concentration of about 3 to 35%.

  This is because, when the solid content concentration is 35% or higher, re-defining treatment may be necessary because recombination of the microfibers cannot be suppressed only by adding stirring or a dispersing agent. On the contrary, if the solid concentration is a low concentration of 0.1% or less, the amount of fibers is so small that a pattern may not be formed during printing. However, there is no particular limitation as long as these problems can be avoided by other means.

  The cellulose fine fiber dispersion thus prepared is printed on paper. Printing is performed by a printing method such as screen printing, flexographic printing, gravure printing, inkjet printing, offset printing, letterpress printing, or intaglio printing.

  As for printing, the cellulose fine fiber dispersion is transferred to paper for both wet paper and dry paper, and the printing means for forming significant information, and the cellulose fine fiber dispersion is supplied to the printing means. The printing is performed by using a printing apparatus configured by the supply unit and capable of performing the above-described printing method. For example, the printing is performed using a printing apparatus such as a screen printing machine, a flexographic printing machine, a gravure printing machine, an inkjet printing machine, an offset printing machine, a relief printing machine, an intaglio printing machine.

  The printing means is a printing plate surface in the form of significant information or a spout in an ink jet printing machine, and is appropriately selected according to the printing apparatus to be used. The supply means is means for supplying the cellulose fine dispersion to the printing means, and is an ink supply section or an ink tank in the printing apparatus. It should be noted that other printing methods are not particularly limited as long as microfibers can be printed on paper and a pattern can be formed.

  In each printing method, printing is performed by supplying the cellulose fine fiber dispersion to a portion (referred to as “supplying unit” in the present invention) where normal ink is supplied in a printing apparatus. When it is necessary to increase the viscosity of the cellulose fine fiber dispersion by a printing method, a water-soluble polymer or the like may be added as a thickener as appropriate. Further, when it is necessary to improve the plate surface transferability and drying property of the cellulose fine fiber dispersion by the printing method, an organic solvent such as ethers or alcohols may be added as appropriate, or may be replaced with water. .

  Depending on the printing method, the length of the cellulose microfiber is limited. The maximum limit length is, for example, less than the length that can pass through the screen mesh in the screen printing method, less than the length that can be transferred to the roll cell in the flexographic printing method, and less than the length that can be ejected from the ejection port in the inkjet printing method. Need to be. The minimum critical length is that the fiber length of wood or non-wood pulp is usually about 0.5 to 20 mm, so the length of the cellulose microfiber is less than this.

  The process of printing cellulose microfibers on paper by a printing device includes a step of printing using a printing device installed on a paper machine and a step of printing using a printing machine in the same manner as printing using ordinary ink. There are two ways.

  First, the process of printing using the printing apparatus installed on the paper machine will be described. A wire unit that forms a paper suspension on a paper machine into a sheet form of a screen printing device, flexographic printing device, inkjet printing device, gravure printing device, offset printing device, or letterpress printing device, which is a printing device. Then, the cellulose dispersion is supplied to the supply means of each printing apparatus.

  Next, the cellulose dispersion is supplied from the supply unit to the printing unit. Finally, the cellulose fine fiber dispersion is printed on the paper on the paper machine that has been dehydrated to a moisture content of less than 9 to 85% from the printing means.

By going through a drying process after dehydration, the moisture content of the paper is less than 9%. In the present invention, the paper after the drying process of the paper machine is called “dry paper”, and therefore, for a paper having a moisture content of less than 9%, printing is performed using a printing machine in the same manner as printing using ordinary ink. This will be described later.

  When the water content is 85% or more, the stock suspension is not in the form of a sheet on the paper machine, and the printed cellulose fine fiber dispersion and the stock suspension are mixed to print significant information. Can not.

  The ink in the ink pan (in the present invention, cellulose fine fiber dispersion) is applied to the wet paper on the paper machine using a printing device that consists of a plate, anilox roller, ink pan, etc., installed in the press section on the paper machine. The details of the printing method to be performed are described in Japanese Patent No. 2740765 “Wet paper printed matter, manufacturing method thereof and wet paper printing apparatus” previously filed by the present applicant.

  Next, the process of printing using a printing machine in the same way as printing using ordinary ink will be described. In the case of dry paper, a screen printer, which is a printing device of various methods, on paper having a moisture content of less than 9%, such as paper, synthetic fiber paper, non-woven fabric, and film, which has been completed through a paper machine drying process Cellulose microfibers are printed using a flexographic printing machine, an inkjet printing machine, a gravure printing machine, an offset printing machine, a letterpress printing machine, and an intaglio printing machine.

  When performing on wet paper, impregnate or spray water on paper (moisture content of less than 9%) such as paper, synthetic fiber paper, and nonwoven fabric that has been completed through the paper machine drying process. Then, after making the water content 9 to less than 85%, it can be created by printing the cellulose fine fiber dispersion using the above-described various types of printing apparatuses.

  It is also possible to print the cellulose fine dispersion by providing each printing device at a location where the water content of the paper is less than 9% on the paper machine, such as after the drying step. In that case, the printed matter obtained is the same as the printed matter obtained by printing the cellulose fine dispersion on dry paper.

  The cellulose fine fiber dispersion is transferred to paper by various printing methods and then dried. When moisture evaporates during drying, the cellulose microfibers are fixed on the paper and form a pattern by hydrogen bonding between the cellulose microfibers and the paper fibers. There is no need to add a binder component as in normal ink, and a strong bond is formed.

  Drying of the printed cellulose microfiber dispersion is evaporation-penetration-type drying by evaporation of moisture in the dispersion and permeation into the paper, for example, heat drying. Heat drying is preferably a non-contact drying method such as hot air drying. However, even with a contact-type drying method using a cylinder or the like, there is no problem as long as cellulose fine fibers can be prevented from transferring to the cylinder surface. Without heating and drying, the paper penetrates more than the water evaporates and tends to cause deformation such as paper curl. In addition, about a drying system, it is not necessary to be limited to heat drying, What is necessary is just a system which can dry the printed cellulose microfiber dispersion liquid.

  For example, FIG. 2 shows an example of a method for printing cellulose microfibers by screen printing. As shown in FIG. 2 (a), the cellulose fine fiber dispersion is supplied by supplying the cellulose fine fiber dispersion to the ink supply point (5) of the screen printing machine and operating the squeegee (6) or the plate surface (7). Passes through the pattern-shaped opening (8) on the screen plate surface and transfers to the paper to form a pattern.

  Then, as shown in FIG.2 (b), it heat-drys using a dryer (9), the moisture in a cellulose microfiber dispersion liquid is evaporated, and it dries. Due to hydrogen bonding between the cellulose microfibers and the paper fibers, the cellulose microfibers are fixed on the paper, and the printed material (1) is produced.

  Example 1 of the present invention will be described with reference to FIG. Fig.3 (a) shows the top view of the printed matter (1-1) which printed the cellulose microfiber in this invention. The printed matter (1-1) in the present invention has a first region (3-1) in which the sign-form significant information (4-1) is printed on the paper (2-1). The region (3-1) is formed by printing with cellulose microfibers. In the first embodiment, the sign shape significant information (4-1) is the shape of a heavy circle illustrated in the drawing.

  Cellulose microfibers were produced by mechanically defibrating abaca pulp using a grinder. The abaca pulp dispersion having a solid content concentration of 2% was passed through a grinder (Supermass colloider, manufactured by Masuko Sangyo Co., Ltd.) six times. The grindstone used was a standard grindstone for soft raw materials (MKE, 46 mesh). The produced cellulose microfibers had an average fiber length of about 0.2 mm and a fiber width of 20 to 100 nm.

  The produced cellulose fine fiber dispersion (solid content concentration: 2%) was subjected to a water content of 6% (23 ° C., 50% rh.) Using a flat bed screen printer (MF-250, manufactured by RNAS). Printed on black paper. As the screen printing plate, a piercing etching printing plate (opening 300 μm, pitch 500 μm, plate thickness 100 μm, manufactured by Takagi Engraving Co., Ltd.) was used.

  Immediately after printing, water in the cellulose fine fiber dispersion was evaporated and dried by a hot air drying method and dried. The cellulose microfibers were fixed by hydrogen bonding with the paper fibers to form a pattern.

  As described above, as shown in FIG. 3, significant information (4-1) represented by a white heavy circle pattern of cellulose microfibers is printed on the print region (3-1) of the black paper (2-1). Printed matter (1-1) was produced.

  Example 2 of the present invention will be described with reference to FIG. FIG.3 (b) shows the top view of printed matter (1-2) which printed the cellulose microfiber in this invention. The printed matter (1-2) in the present invention has a first region (3-2) on which the significant information (4-2) of the character shape is printed on the paper (2-2). The region (3-2) is printed with cellulose microfibers. In the second embodiment, the significant information (4-2) on the character shape is the shape of the English character (NPB) shown in the drawing.

  Cellulose microfibers used “Selish KY100G (trade name)” manufactured by Daicel Chemical Industries, Ltd. This was vigorously stirred and diluted to prepare a cellulose fine fiber dispersion having a solid concentration of 2%.

  This cellulose fine fiber dispersion (solid content concentration: 2%) was blacked with a water content of 6% (23 ° C., 50% rh) using a flatbed screen printer (MF-250, manufactured by RNAS). Printed on paper. As the screen printing plate, an 80 mesh lacquer printing plate (opening 247 μm, wire diameter 71 μm, plate thickness 119 μm, manufactured by Nippon Special Textile Co., Ltd.) was used. The pattern was English letters (NPB).

  Immediately after printing, water in the cellulose fine fiber dispersion was evaporated and dried by a hot air drying method and dried. The cellulose microfibers were fixed by hydrogen bonding with the paper fibers to form a pattern.

  Thus, as shown in FIG. 3, a printed matter (1-2) in which white English letters (4-1) made of cellulose microfibers were printed on black paper (2-2) was produced.

A third embodiment of the present invention will be described with reference to FIG. Fig.4 (a) shows the top view of the printed matter (1-3) which printed the cellulose microfiber in this invention. The printed matter (1-3) in the present invention has a first region (3-3) on which significant information (4-3) is printed on a sheet (2-3), and the first region (3) -3) is printed with cellulose microfibers. In a significant information (4-3) Example 3, was the shape of a double circle are illustrated in the drawings.

  Cellulose microfibers were produced by mechanically defibrating wood pulp (NBKP) using a grinder. A wood pulp dispersion having a solid content concentration of 2% was passed through a grinder (Supermass colloider, manufactured by Masuko Sangyo Co., Ltd.) three times. The grindstone used was a standard grindstone for soft raw materials (MKE, 46 mesh). The produced cellulose microfibers had an average fiber length of about 0.2 mm and a fiber width of 20 to 100 nm.

  The produced cellulose microfiber was colored with a direct dye (Sumilite Violet BB Conk, manufactured by Sumitomo Chemical Co., Ltd.). After the cellulose fine fiber dispersion was heated to 80 to 90 ° C., 4% by weight of the dye and a fixing agent were added and stirred, and the dye was fixed on the fiber and washed to color the cellulose fine fiber.

  Using a flat bed type screen printer (MF-250, manufactured by RNAS), a colored cellulose fine fiber dispersion (solid content concentration: 2%) has a water content of 6% (23 ° C., 50% rh). Printed on fine paper (white). As the screen printing plate, a piercing etching printing plate (opening 300 μm, pitch 500 μm, plate thickness 100 μm, manufactured by Takagi Engraving Co., Ltd.) was used.

  Immediately after printing, water in the cellulose fine fiber dispersion was evaporated and dried by a hot air drying method and dried. The cellulose microfibers were fixed by hydrogen bonding with the paper fibers to form a pattern.

  In this way, as shown in FIG. 4 (a), a printed matter (1-3) in which a purple double circular pattern (4-3) of cellulose microfibers colored on white paper (2-3) is printed. ) Was produced.

  FIG. 4B shows an example of a gift certificate using the printed matter (1-3) shown in FIG. The gift certificate is produced by further printing other information on the printed matter (1-3) produced by the method described above. As other information, the face value and the design of the gift certificate were used, and the design was printed by offset printing.

  A fourth embodiment of the present invention will be described with reference to FIGS. FIG. 5: shows the top view of the printed matter (1-4) which printed the cellulose microfiber in this invention. The printed matter (1-4) in the present invention has a first area (3-4) on which significant information (4-4) is printed on a paper (2-4), and the first area (3-4) -4) is printed with cellulose microfibers. In Example 4, the significant information (4-4) is the star shape shown in the drawing.

  Cellulose microfibers used “Selish KY100G (trade name)” manufactured by Daicel Chemical Industries, Ltd. This was vigorously stirred and diluted to prepare a cellulose fine fiber dispersion having a solid concentration of 2%.

  Cellulose microfibers were colored with a direct dye (Sumilite Spula Blue G manufactured by Sumitomo Chemical Co., Ltd.). After the cellulose fine fiber dispersion was heated to 80 to 90 ° C., 1% by weight of the dye and a fixing agent were added and stirred to color the cellulose fine fibers.

  The colored cellulose microfiber dispersion (solid content concentration 2%) was treated with a planetary ball mill (Pulverisette 5, manufactured by FRITSCH) to further reduce the size. The processing conditions were 150 rpm, 10 minutes × 5 sets, and beads having a diameter of 5 mm were used.

  A colored cellulose fine fiber dispersion (solid content concentration 2%) is provided between the press section (11) and the drying section (12) after the wire section (19) on the paper machine (10) shown in FIG. Printing was performed using a flexographic printing apparatus (13).

The cellulose microfiber dispersion is supplied to the flexographic ink supply section, which is the supply means (14) of the flexographic printing apparatus (13), and the flexographic printing apparatus (13) is operated so that the cellulose microfiber dispersion is anilox roll ( 15) and the flexographic printing plate as the printing means (16), transferred to abaca paper having a moisture content of 60% (23 ° C., 50% rh) on the paper machine (10) to form a pattern. An anilox roll having a line number of 40 lines / cm and a cell volume of 28 cm ³ / m ² was used. A photosensitive resin plate was used for the plate surface.

  Immediately after printing, the cellulose fine fiber printing part is pre-dried by the hot air drying pre-drying part (17) of the paper machine (10), and further the residual moisture in the cellulose fine fiber dispersion by the cylindrical dryer (18). And the moisture of the whole paper was evaporated and dried. The cellulose microfibers were fixed by hydrogen bonding with the paper fibers to form a pattern.

  In this way, as shown in FIG. 5, a printed matter (1-4) is produced in which a blue star pattern (4-4) is printed with the cellulose microfibers colored on the white paper (2-4). It was.

1, 1-1, 1-2, 1-3, 1-4 Printed matter 2, 2-1, 2-2, 2-3, 2-4 Paper 3, 3-1, 3-2, 3-3, 5-5 First area 4, 4-1, 4-2, 4-3, 4-4 Significant information 5 Ink supply location 6 Squeegee 7 Screen plate surface 8 Opening portion 9 on plate surface Dryer 10 Paper machine 11 Press portion DESCRIPTION OF SYMBOLS 12 Drying part 13 Printing apparatus 14 Supply means 15 Anilox roll 16 Printing means 17 Pre-drying apparatus 18 Drying apparatus

Claims (4)

Having at least a first area on the paper;
The printed matter, wherein the first region is printed with significant information using cellulose microfibers having a color different from that of the paper.   The printed matter according to claim 1, wherein a fiber length of the cellulose microfiber is larger than a particle diameter of a pigment for coloring the cellulose microfiber in a color different from that of the paper. A method for producing a printed matter in which significant information is printed by cellulose microfibers,
A step of dispersing the cellulose microfiber in water to prepare a cellulose microfiber dispersion;
i) Supplying a paper having a water content of less than 9% and applying the cellulose fine fiber dispersion to any one of a screen printing machine, flexographic printing machine, inkjet printing machine, gravure printing machine, offset printing machine, letterpress printing machine and intaglio printing machine Or print using or
ii) Using a screen printing device, a flexographic printing device, an ink jet printing device, a gravure printing device, an offset printing device, and a relief printing device installed between the wire unit and the drying unit of the paper machine, a water content of 9 to Printing the cellulose microfiber dispersion on less than 85% paper, printing with a printing device;
In the case of i), before printing the cellulose fine fiber dispersion on paper, water content is adjusted by impregnating or spraying water on the paper having a water content of less than 9% to make the water content less than 9 to 85%. And a process for producing the printed matter. The method for producing a printed matter according to claim 3, wherein the method for producing the printed matter further includes a coloring step of coloring the cellulose fine fibers with a colorant before the step of preparing the cellulose fine fiber dispersion. .

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