JP5492474B2 - Patterned paper - Google Patents

Description

  The present invention relates to a patterned paper such as cloud dragon paper in which a rayon fiber is mixed with pulp fibers to form a Japanese paper-like texture on the surface of the paper, and more particularly to a patterned paper having high slip resistance.

  Patterned paper obtained by mixing rayon fibers with pulp fibers is usually called pattern paper, and is marketed under names such as bill paper, Yunlong paper, and hooks. Among them, Yunryu paper, which has a gentle Japanese paper-like texture, aggregates rayon fibers to form a dragon pattern on the surface. It is used for a wide variety of packaging paper such as insoles, liquor, tea, rice, noodles, and laver.

  Such patterned paper has slippery properties because the low-friction rayon fibers are fixed to the paper surface because the rayon fibers are mixed with the pulp fibers. The inconvenience resulting from the property that the patterned paper is slippery is particularly noticeable when it is used for a heavy bag such as a rice bag, and slipping and collapse of the rice bag are likely to occur. Further, even in the manufacturing stage of this rice bag or the like by a machine, there is a disadvantage that the manufacturing efficiency is lowered due to the slipperiness of the surface.

  As a means for solving the problem of slipperiness of the paper surface, a method of applying a slip preventive agent (water repellent, etc.) to the paper surface is generally developed (for example, JP-A-2006-161180). (See publications). However, unlike the case where anti-slip agent is applied to paper such as general printing paper, wrapping paper, and paperboard, when anti-slip agent is applied to pattern paper, the anti-slip material has a pattern made of rayon fibers. In order to coat, there is a disadvantage that the texture of Japanese paper is lowered or sufficient slip resistance is not exhibited. In addition, there is a disadvantage that the printability of the paper surface is lowered by application of the anti-slip agent.

  Moreover, as a technique regarding the slip resistance of the pattern paper which mix | blended the rayon fiber, the pattern paper by which the surface of the rayon fiber is coat | covered with a small amount of natural pulp can be considered (for example, refer Unexamined-Japanese-Patent No. 2003-293285 etc.). With this technology, by covering the surface of the rayon fiber with natural pulp, in addition to firmly bonding the pulp layer to the rayon fiber, the friction force on the paper surface can be improved because the rayon fiber is coated. Be expected. However, even by this means, rayon fibers are not completely covered with pulp fibers, and sufficient anti-slip properties cannot be exhibited.

JP 2006-161180 A JP 2003-293285 A

  The present invention has been made in view of these disadvantages, and an object of the present invention is to provide a patterned paper excellent in slip resistance, smoothness and printability while maintaining a Japanese paper-like texture.

The invention made to solve the above problems is
A base layer and a pattern layer scattered on the surface of the base layer;
The base layer has natural pulp fiber, rayon fiber, binder and sizing agent,
The patterned layer is a patterned paper having a rayon fiber aggregate and a binder,
The blending amount of the natural pulp fiber with respect to the total amount of the base layer is 65% by mass or more and 90% by mass or less, the blending amount of the binder is 0.3% by mass or more and 6% by mass or less, and the sizing agent with respect to the total amount of the base layer. The content of is 0.1% by mass or more and 1% by mass or less,
The fineness of the rayon fiber of the base layer is 0.2 dtex or more and 8 dtex or less, and the fiber length is 2 mm or more and 8 mm or less,
The base layer contains inorganic particles having an average particle diameter of 0.2 μm or more and 8 μm or less and a Mohs hardness of 3 or more and 6 or less,
Basis weight of the pattern layer is less than 0 g / ^{m 2} Ultra 3.0 g / ^{m 2,}
Ash content is 1% or more and 4.5% or less,
It appears coated paper, characterized in that the amount of active ingredient is dried by a Yankee dryer coated with 0.05 g / m ² or more 1 g / m ² or less of a release agent.

  In the case of the patterned paper, since the base layer contains inorganic particles as a filler, the inorganic particles adhere to natural pulp fibers and rayon fibers, and are fixed by a binder, so that the inorganic particles are uneven on the fiber surface. And the anti-slip property of the surface is improved. In addition, since the patterned paper has an appropriate hardness of 3 to 6 in terms of the Mohs hardness of the contained inorganic particles, the inorganic particles are exposed when the patterned paper surface overlaps with other paper or the like and pressure is applied. Since it becomes a wedge without breaking its shape and can enter the inside of the surface layer of other paper or the like, excellent slip resistance is exhibited. Furthermore, since the inorganic paper contained in the patterned paper has a predetermined hardness, the anti-slip function is maintained without being crushed by pressing when the shape of the inorganic particles is used as a rice bag, etc. In this case, the inorganic particles are not finely pulverized, and a predetermined particle shape necessary for anti-slip properties can be maintained. Moreover, since the hardness of the contained inorganic particle is not too high if it is the said pattern processed paper, the damage | damage of the apparatus in a manufacturing process can be prevented because an inorganic particle is grind | pulverized to some extent in a manufacturing process.

  In the case of the patterned paper having an average particle size of 0.5 μm or more and 8 μm or less, the inorganic particles having such an average particle size have a texture of Japanese paper on the surface of natural pulp fiber and rayon fiber and It can be suitably adhered and fixed without reducing smoothness. In the case of a patterned paper containing inorganic particles of such a size, the presence of inorganic particles is held in a wedge shape on the fiber surface when the paper surface comes into contact with other paper when used as a rice bag or the like. And sufficient anti-slip properties are exhibited.

  The inorganic particles are preferably hydroxyapatite. As described above, since the inorganic particles are hydroxyapatite, the particles can have a suitable hardness and can be easily formed in the above-mentioned size, so that the anti-slip property can be preferably improved and the pattern processing with high anti-slip property can be achieved. Paper can be industrially mass-produced.

  If the textured paper has an ash content of 1% or more and 4.5% or less, the content of the inorganic particles is adjusted so that the ash content is within the above range. The slip resistance of the surface can be further improved without lowering. This ash content is measured according to JIS-P8251 (2003) “Paper, paperboard and pulp-ash content test method—525 ° C. combustion method”.

  If the patterned paper contains a sizing agent in the base layer of the patterned paper, the inorganic particles adsorbed between the fibers can be effectively prevented from being taken by the Yankee dryer in the drying process. The slip resistance can be improved, and the slip resistance can be maintained for a long time.

  The slip angle of the patterned paper surface is preferably 25 degrees or more and 40 degrees or less. If it is the said pattern-processed paper whose surface slip angle is the said range, it has required slip resistance and can exhibit the outstanding printability.

  As described above, with the patterned paper of the present invention, the smoothness and printability can be improved and the slip resistance can be improved while maintaining the texture of Japanese paper. As a result, the pattern-processed paper of the present invention can be suitably used for food packaging materials, particularly heavy-weight packaging materials such as rice bags.

2 is an electron micrograph showing the patterned paper obtained in Example 1. FIG. 2 is an electron micrograph showing the patterned paper obtained in Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail.
The patterned paper of the present invention includes a base layer and a patterned layer laminated in a scattered manner on the surface of the base layer.

[Base layer]
The base layer contains natural pulp fibers as raw pulp, rayon fibers, a binder, and inorganic particles.

[Natural pulp fiber]
Examples of the natural pulp fibers contained in the base layer include chemical pulps such as softwood kraft pulp, hardwood unbleached kraft pulp (LUKP), and hardwood bleached kraft pulp (LBKP); thermomechanical pulp (TMP), pressurized stone ground Mechanical pulp such as pulp (PGW); chemical pulp such as dingping pulp (DIP) and waist pulp (WP), waste paper pulp derived from mechanical pulp, and the like can be used, but conifer kraft pulp is preferably used.

  As softwood kraft pulp, both softwood unbleached kraft pulp (NUKP) and softwood bleached kraft pulp (NBKP) can be used. And can be preferably used in the present invention from the viewpoint of becoming a flexible paper. Moreover, you may use together conifer kraft pulp and the other natural pulp mentioned above.

  As a minimum of the compounding quantity of the said natural pulp fiber, 65 mass% is preferable among base layer total amount, and 70 mass% is especially preferable. On the other hand, the upper limit of the blending amount of natural pulp fibers is preferably 95% by mass, particularly preferably 90% by mass, based on the total amount of the base layer. When the blending amount of the natural pulp fiber is smaller than the above lower limit, the texture becomes rough due to the effect of the blended rayon fiber, so that the smoothness of the surface is lowered and the printability is lowered. On the contrary, if the blending amount of natural pulp fibers exceeds the above upper limit, the blending of rayon fibers to be added is reduced, and the texture of Japanese paper is lowered.

[Rayon fiber]
The rayon fiber, which is the main raw material for the patterned paper of the present invention, gives a Japanese paper-like texture to the patterned paper. Known rayon fibers are used. As a minimum of the fineness of this rayon fiber, 0.3 dtex is preferable and 0.4 dtex is especially preferable. On the other hand, the upper limit of the fineness of the rayon fiber is preferably 8 dtex, particularly preferably 7.7 dtex. If the fineness of the rayon fiber is smaller than the above lower limit, the rayon fiber is thinned and the texture of the Japanese paper is deteriorated. On the contrary, when the fineness of the rayon fiber exceeds the above upper limit, the printability is deteriorated due to the thickening of the fiber.

  The lower limit of the fiber length (average fiber length) of the rayon fiber is preferably 2.5 mm, particularly preferably 3 mm. On the other hand, the upper limit of the fiber length (average fiber length) of the rayon fiber is preferably 8 mm, particularly preferably 7 mm. If the fiber length of the rayon fiber is smaller than the above lower limit, the texture of the Japanese paper becomes worse. On the contrary, when the fiber length of the rayon fiber exceeds the above upper limit, the fibers are bound to each other and the printability is deteriorated.

  As a minimum of the compounding quantity with respect to the base layer total amount of rayon fiber, 4 mass% is preferable and 5 mass% is especially preferable. On the other hand, the upper limit of the amount of the rayon fiber is preferably 35% by mass, particularly preferably 25% by mass. When the blending amount of the rayon fiber is smaller than the lower limit, the texture of Japanese paper is lowered. On the other hand, when the blending amount of the rayon fiber exceeds the above upper limit, the blending amount of the natural pulp fiber is reduced, so that the printability is lowered.

〔binder〕
The shape of the binder is preferably a fibrous shape so that it can be uniformly mixed with the rayon fiber. Since rayon fibers have the property of being difficult to fibrillate, they are not easily bonded by entanglement with pulp fibers and other rayon fibers. However, by blending the binder, it becomes possible to strongly combine the rayon fibers with each other and the rayon fibers and the pulp fibers. In particular, when drying with a Yankee dryer in the manufacturing process of the patterned paper of the present invention, if the surface temperature of the Yankee dryer is set slightly higher than the melting point of the binder to be blended, the binder is thermally melted and is the main raw material Natural pulp and rayon fiber can be strongly heat-bonded.

  The raw material of the binder is not particularly limited, but polyvinyl alcohol, viscose, vinylon, etc. are used, and vinylon having a melting point of about 80 ° C., which is lower than the surface temperature 105 ° C. of the Yankee dryer used in a normal drying process. Is preferred. If it is a binder which has such melting | fusing point, the heat melting of the binder by the heating of a Yankee dryer will advance easily, and a rayon fiber and a natural pulp can be adhere | attached firmly.

  As a minimum of the compounding quantity with respect to the base total amount of a binder, 0.3 mass% is preferred and 0.5 mass% is especially preferred. On the other hand, as an upper limit of the compounding quantity of a binder, 6 mass% is preferable and 5 mass% is especially preferable. When the blending amount of the binder is smaller than the above lower limit, the fiber-to-fiber bond becomes weak and the rayon fiber may fall off. On the other hand, if the blending amount of the binder exceeds the above upper limit, the sticking to the dryer becomes strong, and there is a possibility that the inorganic filling amount is dropped and the smoothness is lowered.

[Inorganic particles]
The base layer contains inorganic particles. By containing the inorganic particles as filler, the inorganic particles adhere to the natural pulp fiber and rayon fiber, so that the inorganic particles become uneven on the fiber surface and function as a wedge, improving the anti-slip property of the surface. The The base layer containing inorganic particles has a pattern layer coated on the surface, but the pattern layer does not cover the entire base layer, and a part of the base layer surface is exposed to the surface. ing. Therefore, since the inorganic particles are in a state of being fixed to the surface of the patterned paper, it becomes a wedge and can contribute to the improvement of the slip resistance.

  Specific examples of the inorganic particles include zeolite, silicon oxide, titanium oxide, calcium carbonate, barium carbonate, barium sulfate, calcium sulfate, zinc sulfate, tin oxide, calcium carbide, calcium phosphate, zinc oxide, bentonite, smectite, and silica. And anhydrous silicic acid. These may have a crystal structure or an amorphous structure. Furthermore, these can be used individually or in combination of 2 or more types. Among the above inorganic substances, calcium phosphate is preferably used. If calcium phosphate is used, particles can be easily formed to a predetermined size, and since it has an appropriate hardness, slip resistance can be suitably increased, and industrially mass-produced patterned paper with high slip resistance. be able to.

Calcium phosphate is an inorganic compound having calcium ions and a phosphate group (PO ₄ ³⁻ ) or a pyrophosphate group (P ₂ O ₇ ⁴⁻ ). Specific examples of calcium phosphate particles include amorphous calcium phosphate, fluorapatite, chlorine apatite, hydroxyapatite, octacalcium phosphate, tricalcium phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate, and the like. . Among these, hydroxyapatite, octacalcium phosphate, tricalcium phosphate and calcium hydrogen phosphate are preferable from the viewpoint of high composition stability, and hydroxyapatite (3Ca ₃ (PO ₄ ) ₂ · Ca (OH) ₂ : Mohs Hardness 5) is particularly preferred.

  When the inorganic particles have a crystal structure, the crystal lattice is preferably orthorhombic, hexagonal, trigonal, tetragonal or hexagonal, and particularly preferably hexagonal or cubic. Since the inorganic particles have such a highly symmetric crystal lattice, the area in contact with the fiber surface increases, the inorganic particles can be fixed with high stability, and effectively function as a wedge. Can be made.

  The inorganic particles are preferably aggregates in which fine particles are aggregated. The inorganic particles are composed of an aggregate of fine particles, and thus can be appropriately pulverized by dissociation of a part of the bonding portion in the aggregate during the manufacturing process of the patterned paper. That is, if it is the said inorganic particle, the grinding | pulverization of the inorganic particle in a manufacturing process will be considered, and the aggregate particle larger than the inorganic particle finally fixed to the fiber surface can be mix | blended with a raw material. This improves the efficiency of fixing the inorganic particles to the fiber surface in the paper making stage, and the inorganic particles are pulverized in the subsequent process, so that the inorganic particles having the required particle size are present in the final patterned paper. Can be made. That is, from the beginning of blending, when inorganic particles having a small particle size (having a target particle size) are blended, since the particle size is small, the number of particles passing between the fibers increases, so the adhesion rate of the inorganic particles decreases. However, if it is the said means, the adhering rate of an inorganic particle can be improved by mix | blending the aggregate which has a fixed particle diameter.

  The lower limit of the average particle diameter of the inorganic particles fixed to the fiber surface is preferably 0.5 μm, and particularly preferably 1 μm. On the other hand, the upper limit of the average particle diameter of the inorganic particles is preferably 8 μm, and particularly preferably 5 μm. The inorganic particles having such an average particle diameter can be suitably attached and fixed on the surfaces of natural pulp fibers and rayon fibers while having a Japanese paper-like texture and smoothness. Also, if it is a patterned paper containing inorganic particles of such a size, when used as a rice bag or the like, when the paper surface comes into contact with other paper or the like, the surface is optimal as a wedge due to the presence of inorganic particles. Size irregularities are formed, and a sufficient anti-slip function is exhibited. When the average particle size of the inorganic particles is smaller than the above lower limit, the anti-slip property on the surface is lowered. On the other hand, if the average particle diameter of the inorganic particles exceeds the above upper limit, there is a risk of damaging a mechanical device or the like in the production process, and printability and Japanese paper-like texture are reduced.

  In the present invention, the average particle size of the inorganic particles means an average of the particle sizes of 30 particles randomly extracted from particles observed with an electron microscope having a magnification of 1000 times. The particle diameter is defined by the ferret diameter (interval when the projected image is sandwiched between parallel lines in a certain direction).

  In addition, since it is necessary to contain particles having the above average particle size in the final product, in the raw material adjustment stage, particles having an average particle size larger than the above range are taken into consideration that the particles are crushed in the production process. It is good to mix.

  The lower limit of the Mohs hardness of the inorganic particles is 3, and 4 is preferable and 4.5 is particularly preferable. On the other hand, the upper limit of the Mohs hardness of the inorganic particles is set to 6, and 5.5 is particularly preferable. When the inorganic particles have a hardness in the above range, when the surface of the patterned paper is overlapped with other paper or the like and the pressure is applied, the inorganic particles become a wedge without breaking the shape, and the surface layer of the other paper or the like Since it can enter the inside, the slip resistance of the patterned paper is improved. When the Mohs hardness of the inorganic particles is smaller than the above lower limit, the particles do not have sufficient hardness against the friction acting on the surface and the anti-slip property is not improved, and the particles are pulverized during the manufacturing process. It becomes difficult to fix inorganic particles having a constant particle size in the patterned paper. On the other hand, if the Mohs hardness of the inorganic particles exceeds the above upper limit, it has sufficient hardness for exhibiting anti-slip properties, but there is a risk of damaging the production equipment during papermaking.

  The Mohs hardness is a numerical value for hardness based on how the standard material is scratched. Standard materials from 1 to 10 are specified in order from soft to soft. As specific reference materials, Mohs hardness 1 is talc, 2 is gypsum, 3 is calcite, 4 is fluorite, and 5 is phosphorus. Ashite, 6 is plagioclase, 7 is quartz, 8 is topaz, 9 is corundum, and 10 is diamond. For example, if the sample is scratched with fluorite of standard material 4 and the sample is not scratched, and the sample is scratched with apatite of standard material 5, this sample is harder than 4 and softer than 5. And expressed as “4.5” as the Mohs hardness. In addition, when the sample and the fluorite are scratched by scratching with the fluorite of the standard material 4, the sample has the same hardness as the standard material 4 and expressed as “4” as the Mohs hardness. The value of Mohs hardness is a relative value, not an absolute value.

  The blending amount of the inorganic particles may be adjusted so as to be 1% to 4.5%, preferably 1.5% to 4% as the ash content of the patterned paper. If it is the said pattern-processed paper in which content of the inorganic particle was adjusted so that it might become the ash content of the said range, surface slip resistance can be improved further, without reducing smoothness and printability. This ash content is measured according to JIS-P8251 (2003) “Paper, paperboard and pulp-ash content test method—525 ° C. combustion method”. When the ash content is less than the above range, the slip resistance is reduced. On the other hand, when the ash content exceeds the above range, the content of the inorganic particles is excessive, and the smoothness and printability are deteriorated.

  In order for the pattern-processed paper to have the above ash content, it varies depending on papermaking conditions. For example, the blending amount of inorganic particles is 2.5% by mass or more and 7.0% with respect to the total amount of natural pulp fiber, rayon fiber and binder. It is good to mix it by mass% or less.

[Size agent]
The base layer of the patterned paper of the present invention preferably further contains a sizing agent. If the patterned paper containing the sizing agent, inorganic particles adsorbed between the natural pulp can be effectively prevented from being taken by the Yankee dryer in the drying process. Furthermore, the anti-slip property can be maintained for a long time.

  Examples of the sizing agent that is internally added to the patterned paper include rosin sizing agent for acidic papermaking, modified rosin sizing agent for neutral papermaking, alkenyl succinic acid-based sizing agent, alkyl ketene dimer (AKD) -based size. Agent, alkenyl succinic anhydride (ASA) sizing agent, wax sizing agent, styrene resin sizing agent, olefin resin sizing agent, styrene-acrylic resin sizing agent, higher fatty acid sizing agent, cationic polymer Mold sizing agent, oxidized starch, etc. are included, but in order not to deteriorate over time, further, deterioration of printability due to excessive sticking of patterned paper to the Yankee dryer in the drying process is prevented, and inorganic particles are removed. AKD can prevent Sizing agent and a neutral sizing agent such as ASA-based sizing agent is preferably used.

  As a minimum of content to the base layer total amount of the sizing agent, 0.2 mass% is preferred and 0.4 mass% is especially preferred. On the other hand, the upper limit of the content of the sizing agent is preferably 1% by mass, particularly preferably 0.5% by mass. If the content of the sizing agent is smaller than the above lower limit, the inorganic particles are taken out by the Yankee dryer, or the inorganic particles fall off due to friction during printing, and the slip resistance is not improved. On the other hand, when the content of the sizing agent exceeds the above upper limit, the improvement of the anti-slip property does not appear and the production cost increases. In addition, the paper may float from the Yankee dryer, causing problems in drying, leading to a decrease in printability.

  The patterned paper becomes a highly slip-resistant patterned paper by adding a sizing agent, but by applying a release agent to the surface of the Yankee dryer, the patterned paper is more effective. It can be.

[Pattern layer]
The pattern layer scattered on the surface of the base layer contains rayon fiber aggregates and a binder, and the rayon fiber aggregates form a dragon pattern. The patterned layer does not cover the entire surface of the base layer, and most of the base layer is exposed to the surface. The surface area of the pattern layer is preferably 3.0 g / m ² or less. If it exceeds 3.0 g / m ² , most of the base layer having inorganic particles is covered, resulting in poor slip resistance.

[Rayon fiber aggregate]
As the rayon fibers constituting the dragon pattern in the pattern layer, known ones can be used. The lower limit of the fineness of the rayon fiber is preferably 1.5 dtex, particularly preferably 2.2 dtex. On the other hand, the upper limit of the fineness of the rayon fiber is preferably 4.4 dtex, and particularly preferably 3.3 dtex. If the fineness of the rayon fiber constituting the dragon pattern is smaller than the above lower limit, the rigidity of the fiber becomes low, so that bundling occurs, the surface is likely to be uneven, and the texture of Japanese paper may be impaired. On the other hand, if the fineness of the rayon fiber exceeds the above range, the rigidity becomes too high, the fibers are not entangled, and it becomes difficult to obtain a soft pattern with a Japanese paper-like texture.

  The lower limit of the fiber length (average fiber length) of the rayon fiber is preferably 15 mm, and particularly preferably 20 mm. On the other hand, the upper limit of the fiber length (average fiber length) of the rayon fiber is preferably 30 mm, and particularly preferably 25 mm. When the fiber length of the rayon fiber is smaller than the lower limit, natural fiber entanglement is lost and the texture of the dragon pattern is lowered. On the other hand, if the fiber length of the rayon fiber exceeds the above upper limit, excessive fiber entanglement may occur and the surface may be uneven.

  In the case of ordinary rayon-blended paper, fineness of 0.5 to 7.7 dtex and fiber length of 2.5 to 7 mm are sufficient, but in the case of a patterned paper having a dragon pattern with a more Japanese paper texture, In order to further fix the pattern layer to the base layer, it is necessary to use one having a fineness and a long fiber length.

  The lower limit of the amount of the rayon fiber in the pattern layer is preferably 70% by mass and particularly preferably 80% by mass in the total amount of the pattern layer. On the other hand, the upper limit of the amount of the rayon fiber is preferably 95% by mass, particularly preferably 90% by mass. If the amount of rayon fiber is less than the above lower limit, it is difficult to obtain a sufficient aggregate of rayon fibers. On the other hand, when the blending amount of the rayon fiber exceeds the above upper limit, a sufficient binder for retaining the base layer and the pattern layer cannot be added, and the pattern layer is easily peeled off from the base layer.

〔binder〕
Similarly to the base layer, the pattern layer also contains a binder in addition to the rayon fiber. The binder preferably has a fibrous shape so that it can be uniformly mixed with the rayon fiber. Since rayon fibers have the property that they are not easily fibrillated, they are not easily bonded by entanglement with pulp fibers and other rayon fibers. However, by blending the binder, it becomes possible to strongly bond the rayon fibers and the rayon fibers and the pulp fibers. In particular, when drying with a Yankee dryer in the manufacturing process of the patterned paper of the present invention, if the surface temperature of the Yankee dryer is set slightly higher than the melting point of the binder contained in the base layer and the pattern layer, the binder is heated. The dragon pattern which is the aggregate of rayon fibers in the pattern layer and the natural pulp and rayon fibers which are the base layer raw materials can be firmly heat-bonded.

  The raw material of the binder is not particularly limited, but polyvinyl alcohol, viscose, vinylon, etc. are used, and vinylon having a melting point of about 80 ° C., which is lower than the surface temperature 105 ° C. of the Yankee dryer used in a normal drying process. Is preferred. If the binder has such a melting point, it is easy for the binder to be melted by heating of the Yankee dryer in the drying step, and the rayon fiber aggregate of the pattern layer can be firmly adhered to the base layer.

  As a minimum of the compounding quantity of the binder in a pattern layer, 3 mass% is preferable with respect to the pattern layer total amount, and 5 mass% is especially preferable. On the other hand, the upper limit of the amount of the binder is preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the blending amount of the binder in the pattern layer is smaller than the above lower limit, it becomes difficult to obtain strong adhesion. On the other hand, if the blending amount of the binder in the pattern layer exceeds the above upper limit, the addition of rayon fibers is reduced, making it difficult to obtain the desired rayon fiber aggregate. On the other hand, if the blending amount of the binder exceeds the above upper limit, paper sticking to the dryer tends to occur due to the addition of a large amount of the binder, resulting in a problem that the papermaking property is lowered.

  In other words, in this patterned paper, by adding a binder to both the base layer and the pattern layer, the thick and firm dragon pattern can be kept firmly by bonding the binder from both the base layer and the pattern layer. It is possible to achieve a good fiber-to-fiber bond.

[Flocculant]
It is preferable to mix a cationic flocculant and an anionic flocculant in the pattern layer. By these, rayon fiber aggregates can be formed efficiently. The types of the cationic fiber aggregating agent and the anionic fiber aggregating agent are not particularly limited as long as they are generally used in papermaking applications. However, the cationic aggregating agent is not limited to the yield of fine fibers in the paper layer. Aluminum sulfate having effective characteristics is preferable, and the anionic flocculant is preferably a polyacrylamide resin that exhibits a cohesive strength of light in water.

  As a minimum of the addition amount of a cationic flocculant, 0.01 mass% is preferable with respect to a pattern layer total amount, and 0.05 mass% is especially preferable. On the other hand, the upper limit of the addition amount of the cationic flocculant is preferably 0.3% by mass, particularly preferably 0.2% by mass, based on the total amount of the pattern layer. Moreover, as a minimum of the addition amount of an anionic flocculant, 0.5 mass% is preferable with respect to the pattern layer total amount, and 1 mass% is especially preferable. On the other hand, the upper limit of the addition amount of the anionic flocculant is preferably 5% by mass, and particularly preferably 3% by mass. When the addition amount of the cationic flocculant and the anionic flocculant is smaller than the lower limit, the rayon fibers are not sufficiently agglomerated and it is difficult to obtain a sufficiently large dragon pattern. On the other hand, if the addition amount exceeds the above upper limit, there is a possibility that operational inconveniences such as fouling the blanket / system due to the addition of an excessive flocculant may occur.

〔paint remover〕
A release agent is preferably applied to the patterned paper of the present invention. This release agent is applied by transfer when the patterned paper is dried with a Yankee dryer having a release agent applied to the surface. In the case of the patterned paper, when the surface is dried with a Yankee dryer, the release from the surface of the patterned paper is improved by applying a release agent to the surface of the Yankee dryer, so that the inorganic particles in the patterned paper are improved. Detachment is prevented.

The lower limit of the coating amount of the release agent applied to the Yankee dryer surface, the amount of the active ingredient is preferably ^{0.05g / m 2, 0.1g / m} 2 is particularly preferred. In contrast, the upper limit of the coating amount of the release agent, the active ingredient amount of preferably ^{1g / m 2, 0.4g / m} 2 is particularly preferred. This solid component refers to the main component in the release agent that remains on the patterned paper after drying and exhibits releasability. If the coating amount of the release agent is smaller than the lower limit, the coating amount is small and the releasability from the Yankee dryer is not improved, so the inorganic particles in the patterned paper adhere to the Yankee dryer surface and remain in the patterned paper. The amount of inorganic particles decreases, and as a result, the slip resistance of the patterned paper decreases. On the other hand, when the coating amount of the release agent exceeds the above upper limit, the coating amount is too large, so that the paper floats from the Yankee dryer, causing problems in drying, which may lead to a decrease in printability.

  As this release agent, erucylamide, stearoamide, calcium stearate, zinc stearate, stearic acid, montanic acid, montanic acid ester, montanate, oleic acid, palmitic acid, paraffin wax, polyethylene wax, polypropylene wax, carnauba wax, A material such as glycerol monostearate or glycerol roll stearate is used, and polyethylene wax is particularly preferably used from the viewpoints of releasability from a Yankee dryer and coating workability on the patterned paper surface.

〔Production method〕
Next, the manufacturing method of the patterned paper of this invention is demonstrated.

  The patterned paper of the present invention is a layer having a process of making a pattern layer, which is a layer in which a pattern formed by agglomerating rayon fibers is scattered, and natural pulp fibers, rayon fibers, and the like with respect to the pattern layer. It can manufacture by the process of making paper so that a base layer may be bonded together. In the step of making the pattern layer, it is preferable to use a short net paper machine in order to form a dragon pattern by agglomerates of rayon fibers. In the step of making the base layer, it is preferable to use a circular net paper machine.

  Below, the more specific embodiment of the manufacturing method of the pattern processed paper of this invention is demonstrated.

  (1) First, a rayon fiber and a binder fiber are prepared as a raw material for the pattern layer, and this is disaggregated with a fiber disaggregator. ) Of the rayon slurry.

  (2) A cationic flocculant and an anionic flocculant are added to the rayon slurry to form an aggregate of rayon fibers.

  (3) On the other hand, natural pulp fiber, rayon fiber and binder fiber are prepared as the base layer raw material, and this is disaggregated by a fiber disaggregator, and a sizing agent and inorganic particles are blended. A slurry of 0.0 to 2.5 mass% (absolute dry mass) is prepared.

  (4) A certain amount of the rayon fiber aggregate is supplied to a short net paper machine to form a dragon pattern on the short net. At this time, a small amount of the base layer raw material may be supplied onto the short net from the base layer raw material chest. Thus, by adding a predetermined amount of base layer raw material, the base layer raw material fills the gaps in the concave and convex portions of the dragon pattern formed on the paper machine. It is possible to form a pattern layer with a small amount, that is, a high smoothness.

  (5) Thereafter, the pattern layer formed by the short net paper machine is transferred to the circular net paper machine, and the base layer raw material is paper-made so that the circular net paper machine is bonded to the back side of the dragon pattern of the pattern layer. And a base layer is formed.

(6) The wet paper of the patterned paper thus formed is dried by a Yankee dryer whose surface is coated with a release agent. At this time, when the thermal melting of the binder contained in the base layer proceeds, the fiber bond of the insertion becomes stronger. At the time of this drying, in order to improve the smoothness of the patterned paper surface and improve the printability, it may be pressed with a predetermined pressure. The pressure of this Yankee dryer is preferably 2.0 kg / cm ² or more and 7.0 kg / cm ² . When the pressure of the Yankee dryer is less than 2.0 kg / cm ² , since the pressure applied is weak, the pattern-processed paper is poorly dried, resulting in poor printability and blocking. On the other hand, when the pressure of the Yankee dryer exceeds 7.0 kg / cm ² , the smoothness is excessively improved, so that the slip resistance is lowered.

  The patterned paper manufactured in the above-described process having such a configuration has a sliding angle measured by a method according to the JIS-P8147 (1994) tilt method, which is 28 degrees or more and 40 degrees. Compared to the above, it has extremely high slip resistance.

  Further, the patterned paper has a surface smoothness measured by a method according to the JIS-P8119 smoothness test method of preferably 20 seconds or more and 70 seconds or less. The patterned paper has sufficient printability by having such surface smoothness. In addition, smoothness is adjusted with the compounding quantity of natural pulp fiber, a filler, a sizing agent, etc.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, Examples 2, 3, 5, 6, 10, 11, 14, 15, 19, 23, 27, 31, 36, and 37 in the following shall be read as reference examples.

Example 1
(Base material adjustment)
NBKP 72.6 mass%, rayon fiber (fineness 3.0 dtex x average fiber length 5.0 mm) 24.2 mass%, vinylon binder fiber (fineness 1 dtex x average fiber length 3 mm) 3.2 mass% mixed as base layer raw material By doing so, the cellulosic raw material slurry was adjusted. With respect to this raw material slurry, 4.5% by mass of hydroxyapatite particles (3Ca ₃ (PO ₄ ) ₂ .Ca (OH) ₂ : Mohs hardness 5) as inorganic particles of the filler, AKD sizing agent (AD1602 manufactured by Seiko PMC) ) 0.4% by mass.

(Adjustment of pattern layer material)
10% by weight of Ohmy Kenshi Rayon Hope (fineness 3.3 dtex × average fiber length 20 mm) 90% by mass and Unitika vinylon binder (fineness 1.2 dtex × average fiber length 5 mm, melting point 80 ° C.) A slurry having a water dispersion concentration of 0.19% by mass (absolute dry mass) was prepared while circulating disaggregation and injection.

  Next, 1.5% by mass of pamuol (manufactured by Meisei Chemical Co., Ltd.) as an anionic flocculant as a solid content is added to the above circulating slurry, and after stirring for several minutes, a sulfuric acid band (Sumitomo Chemical Industries, Ltd.) 0.12% by mass as a solid content, and a rayon aggregate (raw layer material) containing a vinylon binder was transferred to a short net paper machine.

(Paper)
The raw material of the pattern layer was continuously supplied to the bat of the short net paper machine so that the rice basis weight of the pattern layer was 1.0 g / m ² . Then, the paper was made so that the base layer raw material was bonded to the back side of the pattern layer transferred to the circular paper machine. The patterned paper of Example 1 was obtained by drying with a Yankee dryer (surface temperature 105 ° C.) having a release agent applied to the surface at 0.2 g / m ² . When the surface of the patterned paper was observed with an electron microscope, the average particle diameter of 30 calcium phosphate particles observed was 1.1 μm.

(Example 2)
A patterned paper of Example 2 was obtained in the same manner as Example 1 except that no sizing agent was added and no release agent was applied.

(Example 3)
A patterned paper of Example 3 was obtained in the same manner as Example 1 except that the sizing agent was not blended.

(Example 4)
A patterned paper of Example 4 was obtained in the same manner as Example 1 except that the blending amount of the sizing agent was 0.1% by mass.

(Example 5)
A patterned paper of Example 5 was obtained in the same manner as in Example 1 except that the blending amount of the sizing agent was 1.1% by mass.

(Example 6)
A patterned paper of Example 6 was obtained in the same manner as Example 1 except that the release agent was not applied.

(Example 7)
A patterned paper of Example 7 was obtained in the same manner as in Example 1 except that the coating amount of the release agent was 0.1 g / m ² .

(Example 8)
A patterned paper of Example 8 was obtained in the same manner as Example 1 except that the coating amount of the release agent was 0.5 g / m ² .

Example 9
A patterned paper of Example 9 was obtained in the same manner as in Example 1 except that the coating amount of the release agent was 1.0 g / m ² .

(Example 10)
A patterned paper of Example 10 was obtained in the same manner as Example 1 except that the coating amount of the release agent was 1.1 g / m ² .

(Example 11)
A patterned paper of Example 11 was obtained in the same manner as in Example 1 except that the blending amount of NBKP in the base layer was 75.6% by mass and the blending amount of the binder was 0.2% by mass.

(Example 12)
A patterned paper of Example 12 was obtained in the same manner as in Example 1 except that the amount of NBKP in the base layer was 75.5% by mass and the amount of binder was 0.3% by mass.

(Example 13)
Example 13 was performed in the same manner as in Example 1 except that the amount of NBKP in the base layer was 73.0% by mass, the amount of rayon fiber was 22.0%, and the amount of binder was 6.0% by mass. Pattern processed paper was obtained.

(Example 14)
Example 14 was carried out in the same manner as in Example 1 except that the amount of NBKP in the base layer was 73.0% by mass, the amount of rayon fiber was 21.5%, and the amount of binder was 6.5% by mass. Pattern processed paper was obtained.

(Example 15)
Implemented in the same manner as in Example 1 except that the amount of NBKP in the base layer was 63.0% by mass, the amount of rayon fiber was 36.0% by mass, and the amount of binder fiber was 1.0% by mass. The patterned paper of Example 15 was obtained.

(Example 16)
Implemented in the same manner as in Example 1 except that the amount of NBKP in the base layer was 65.0% by mass, the amount of rayon fiber was 34.0% by mass, and the amount of binder fiber was 1.0% by mass. The patterned paper of Example 16 was obtained.

(Example 17)
Implemented in the same manner as in Example 1 except that the amount of NBKP in the base layer was 95.0% by mass, the amount of rayon fiber was 4.0% by mass, and the amount of binder fiber was 1.0% by mass. The patterned paper of Example 17 was obtained.

(Example 18)
Implemented in the same manner as in Example 1 except that the amount of NBKP in the base layer was 96.0% by mass, the amount of rayon fiber was 3.0% by mass, and the amount of binder fiber was 1.0% by mass. The patterned paper of Example 18 was obtained.

(Example 19)
Implemented in the same manner as in Example 1 except that the amount of NBKP in the base layer was 63.0% by mass, the amount of rayon fiber was 32.0% by mass, and the amount of binder fiber was 5.0% by mass. The patterned paper of Example 19 was obtained.

(Example 20)
A patterned paper of Example 20 was obtained in the same manner as in Example 1 except that the fineness of the rayon fiber in the base layer was 0.2 dtex.

(Example 21)
A patterned paper of Example 21 was obtained in the same manner as in Example 1 except that the fineness of the rayon fiber in the base layer was 0.5 dtex.

(Example 22)
Other than that the fineness of the rayon fiber in the base layer is 8.0 dtex, the amount of NBKP is 82.0% by mass, the amount of rayon fiber is 16.0% by mass, and the amount of binder is 2.0% by mass. Obtained the processed paper of Example 22 in the same manner as in Example 1.

(Example 23)
Other than that the fineness of the rayon fiber in the base layer is 9.0 dtex, the amount of NBKP is 82.0% by mass, the amount of rayon fiber is 16.0% by mass, and the amount of binder is 2.0% by mass. Obtained a patterned paper of Example 23 in the same manner as in Example 1.

(Example 24)
A patterned paper of Example 24 was obtained in the same manner as in Example 1 except that the average fiber length of the rayon fibers in the base layer was 2.0 mm.

(Example 25)
A patterned paper of Example 25 was obtained in the same manner as in Example 1 except that the average fiber length of the rayon fibers in the base layer was 3.0 mm.

(Example 26)
A patterned paper of Example 26 was obtained in the same manner as in Example 1 except that the average fiber length of the rayon fibers in the base layer was 8.0 mm.

(Example 27)
A patterned paper of Example 27 was obtained in the same manner as in Example 1 except that the average fiber length of the rayon fibers in the base layer was 9.0 mm.

(Example 28)
A patterned paper of Example 28 was obtained in the same manner as in Example 1 except that the amount of the hydroxyapatite particles was 2.0% by mass.

(Example 29)
A patterned paper of Example 29 was obtained in the same manner as in Example 1 except that the amount of the hydroxyapatite particles was 2.5% by mass.

(Example 30)
A patterned paper of Example 30 was obtained in the same manner as in Example 1 except that the amount of the hydroxyapatite particles was 7.0% by mass.

(Example 31)
A patterned paper of Example 31 was obtained in the same manner as in Example 1 except that the amount of the hydroxyapatite particles was 7.5% by mass.

(Example 32)
A patterned paper of Example 32 was obtained in the same manner as in Example 1 except that the average particle diameter of the hydroxyapatite particles was 0.2 μm.

(Example 33)
A patterned paper of Example 33 was obtained in the same manner as in Example 1 except that the average particle diameter of the hydroxyapatite particles was 0.5 μm.

(Example 34)
A patterned paper of Example 34 was obtained in the same manner as in Example 1 except that the average particle diameter of the hydroxyapatite particles was 4.4 μm.

(Example 35)
A patterned paper of Example 35 was obtained in the same manner as in Example 1 except that the average particle diameter of the hydroxyapatite particles was 8.0 μm.

(Example 36)
A patterned paper of Example 36 was obtained in the same manner as in Example 1 except that the average particle diameter of the hydroxyapatite particles was 10.0 μm.

(Example 37)
A patterned paper of Example 37 was obtained in the same manner as in Example 1 except that the pattern area was 3.0 g / m ² .

(Example 38)
A patterned paper of Example 38 was obtained in the same manner as in Example 1 except that the inorganic particles of the filler were calcium sulfate particles (Mohs hardness 3).

(Example 39)
A patterned paper of Example 39 was obtained in the same manner as in Example 1 except that the inorganic particles of the filler were calcium carbonate particles (Mohs hardness 4).

(Example 40)
A patterned paper of Example 40 was obtained in the same manner as in Example 1 except that the inorganic particles of the filler were titanium oxide particles (Mohs hardness 6).

(Comparative Example 1)
A patterned paper of Comparative Example 1 was obtained in the same manner as Example 1 except that the filler inorganic particles were not blended.

(Comparative Example 2)
Patterned paper of Comparative Example 2 was obtained in the same manner as in Example 1 except that talc particles (Mohs hardness 1) were blended as inorganic particles of the filler.

  About the pattern processed paper manufactured in Examples 1-40 and Comparative Examples 1-2, performance evaluation was performed by the following reference | standard. Table 1 shows the blending amounts of the examples and comparative examples and the evaluation results.

[Evaluation]
(1) Sliding angle Using a sliding angle measuring instrument (manufactured by Toyo Seiki Co., Ltd.), the coating surface and the flow direction (vertical) are measured with each other according to the method according to JIS-P8147 (1994), and the average value of 5 times. Rounded.

(2) Beck smoothness The surface was measured according to JIS-P8119 “Paper and paperboard—Smoothness test method using Beck smoothness tester”.

(3) Printability The surface was printed using a K printing proofer manufactured by PK Print Coat Instruments. As the ink, DANEC3-indigo manufactured by Toyo Ink was used, and the amount of ink was 5 ml. Evaluation was performed according to the following criteria.
A: Uneven coloring of ink, poor transfer of ink, etc. cannot be visually observed.
○: Ink coloring unevenness, ink transfer failure, etc. are slightly visible.
Δ: Ink coloring unevenness, ink transfer failure, etc., but no problem in practical use.
X: There are many uneven coloring of ink, poor transfer of ink, and the like.

(4) Ash content Measured according to JIS-P8251 (2003) “Paper, paperboard and pulp—ash content test method—525 ° C. combustion method”.

  From Table 1, it turned out that the pattern processed paper manufactured in Examples 1-40 has high slip resistance, while providing the outstanding smoothness and printability. On the other hand, the patterned paper of Comparative Example 1 to which inorganic particles were not added was shown to have low slip resistance. Further, in the patterned paper of Comparative Example 2 using talc having a Mohs hardness of 1 as a filler, since the talc particles are finely crushed in the manufacturing process and the like, the particles in the patterned paper are too small and the slip resistance is not improved. I understand that. In Examples 38 and 39, when inorganic particles with low Mohs hardness are blended, the particle size becomes small in the manufacturing process and the amount of adhering particles decreases (decrease in ash content). Increased the amount. As a result, it was confirmed that the amount of remaining inorganic particles could be increased, and that a certain amount of ash and high slip resistance were maintained.

  When the surface of the patterned paper of Example 1 is observed with an electron microscope, the hydroxyapatite particles as filler are dispersed and fixed on the pulp fiber as shown in the electron micrograph of FIG. Was confirmed. The main hydroxyapatite particles fixed are shown circled in FIG. The maximum particle diameter in FIG. 1 is about 6 μm, but it is confirmed that there are many particles of 1 μm or less that are not surrounded by a circle. On the other hand, since the patterned paper of Comparative Example 1 does not contain inorganic particles as a filler as shown in the electron micrograph of FIG. 2, only fibers are confirmed.

Claims (3)

A base layer and a pattern layer scattered on the surface of the base layer;
The base layer has natural pulp fiber, rayon fiber, binder and sizing agent ,
The patterned layer is a patterned paper having a rayon fiber aggregate and a binder,
The blending amount of the natural pulp fiber with respect to the total amount of the base layer is 65% by mass or more and 90% by mass or less, the blending amount of the binder is 0.3% by mass or more and 6% by mass or less, and the sizing agent with respect to the total amount of the base layer. The content of is 0.1% by mass or more and 1% by mass or less,
The fineness of the rayon fiber of the base layer is 0.2 dtex or more and 8 dtex or less, and the fiber length is 2 mm or more and 8 mm or less,
The base layer contains inorganic particles having an average particle diameter of 0.2 μm or more and 8 μm or less and a Mohs hardness of 3 or more and 6 or less ,
Basis weight of the pattern layer is less than 0 g / ^{m 2} Ultra 3.0 g / ^{m 2,}
Ash content is 1% or more and 4.5% or less,
Pattern coated paper, characterized in that the amount of active ingredient is dried by a Yankee dryer coated with 0.05 g / m ² or more 1 g / m ² or less of a release agent.   The patterned paper according to claim 1, wherein the inorganic particles are hydroxyapatite. The patterned paper according to claim 1 or 2, wherein the slip angle of the surface is 25 degrees or more and 40 degrees or less.