JP2018119220A - Processed paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processed paper which contains a fiber composite of a cellulose fiber and an inorganic particle and a production method thereof.SOLUTION: The processed paper contains a fiber composite of a cellulose fiber and an inorganic particle. The production method of the processed paper contains a step of synthesizing an inorganic particle in a solution in the presence of a fiber to prepare a fiber composite of the cellulose fiber and the inorganic particle, and a step of producing a processed paper containing the fiber composite of the cellulose fiber and the inorganic particle.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a processed paper containing a fiber composite of cellulose fibers and inorganic particles.

  Of processed paper such as release paper, moisture-proof wrapping paper, wallpaper, etc., wallpaper is used by sticking to a wall for a long period of time in general residences, hotels, hospitals, etc. to be beautiful. The wallpaper includes vinyl wallpaper, olefin wallpaper, textile wallpaper, paper wallpaper, inorganic wallpaper, etc. These wallpapers hold a decorative layer such as vinyl layer, olefin layer, textile layer, paper layer, inorganic layer, and the decorative layer. For the base paper.

  These wallpapers are pasted with starch or vinyl acetate resin water-based glue at the time of construction, but the base paper absorbs moisture in the glue in the gluing process, so the wallpaper becomes soft or the base paper grows due to increased water content. There is. Due to these problems, the wallpaper is curled, causing problems such as difficulty in sticking to the wall and the tendency for wrinkles to occur after sticking. Further, when the glue dries, the base paper contracts, so that there is a gap (opening) in the joint portion between the adjacently bonded wallpapers, and there is a problem that the designability after construction is impaired.

  As a method for improving the dimensional stability of the base paper, synthetic paper fibers such as base paper (Patent Documents 1, 2, and 3), polyolefins, polyesters, polyamides and the like containing inorganic fibers such as glass fibers that are less stretched by moisture are used. Blended base papers (Patent Documents 4, 5, and 6) are disclosed.

  These non-cellulosic fibers are effective in improving the dimensional stability of the base paper. There is a problem of operability such that a drop occurs in the synthetic fiber, and the synthetic fiber is fouled by melting with drying heat. For this reason, it is desirable to reduce the blending ratio of non-cellulose fibers as much as possible in order to perform more stable operation.

  Under such circumstances, a method for improving the dimensional stability of the base paper for wallpaper other than the blending of non-cellulose fibers is desired.

  On the other hand, as a wallpaper having functionality, for example, a base paper for deodorizing and humidity control wallpaper coated with zeolite is known (Patent Document 7). However, in order to impart functionalities such as deodorization to wallpaper, it is necessary to provide a coating layer on uncoated paper in the conventional method, and thus there is a problem that the manufacturing cost increases. Therefore, there is a demand for the development of wallpaper having functionality without providing a coating layer on the base paper for wallpaper.

The cellulose fibers _are used in the _(C 6 H ₁₀ O ₅₎ is a fiber composed of cellulose represented by _n, widely. Cellulose fibers such as pulp and cotton as well as rayon, lyocell, and nitrocellulose are widely used in clothes, films, paper, and the like. In recent years, cellulose nanofibers have attracted attention, and the range of use of cellulose fibers is extremely wide.

  Cellulose fibers exhibit various properties based on the hydroxyl groups on the surface, but depending on the application, it may be necessary to modify the surface, and so far, techniques for surface modification of cellulose fibers have been developed. Yes.

  For example, regarding a technique for depositing inorganic particles on cellulose fibers, Patent Document 1 describes a composite in which crystalline calcium carbonate is mechanically bonded onto fibers. Patent Document 2 describes a technique for producing a composite of pulp and calcium carbonate by precipitating calcium carbonate in a pulp suspension by a carbon dioxide method. Patent Document 3 discloses a method for improving the whiteness and cleanliness of waste paper fibers by adding a large amount of filler to the fibers for paper and paperboard, and sending the slurry of waste paper pulp to a gas-liquid contact device. On the other hand, a technique is described in which an alkali salt slurry is contacted in the direction of flow with pulp in the contact zone, and a suitable reactive gas is fed and mixed with the sedimentary filler to adhere the filler to the fiber surface.

  Patent Documents 4 and 5 disclose a technique for manufacturing a fiber web in which calcium carbonate is efficiently incorporated by precipitating calcium carbonate in a step of forming a fiber web (wet paper).

Japanese Examined Patent Publication No. 7-122236 JP-A-8-1000039 Japanese Patent Publication No. 8-26631 JP-A-5-59696 JP-A-5-59698 JP-A-5-59699 JP 2004-218176 A Japanese Patent Laid-Open No. 06-158585 US Pat. No. 5,679,220 US Pat. No. 5,665,205 Special table 2013-521417 gazette US Patent Publication No. 2011/000633

  The subject of this invention is providing the processed paper containing the fiber composite of a cellulose fiber and an inorganic particle, and its manufacturing method.

The present invention includes, but is not limited to, the following inventions.
(1) A processed paper containing a fiber composite of cellulose fibers and inorganic particles.
(2) The processed paper according to (1), wherein the processed paper is release paper, moisture-proof packaging, glass paper, or base paper for wallpaper.
(3) The processed paper as described in (2) whose water elongation shown to following formula 1 is 2.5% or less.
(Formula 1)
Elongation in water (%) = {(length after immersion in water for 2 hours) − (length before immersion in water)} / (length before immersion in water) × 100
(4) The processed paper according to any one of (1) to (3), wherein the fiber composite of the cellulose fiber and the inorganic particle is coated with inorganic particles at 15% or more of the surface of the cellulose fiber.
(5) The processed paper in any one of (1)-(4) whose weight ratio of a cellulose fiber and an inorganic particle is 5 / 95-95 / 5.
(6) In any one of (1) to (5), at least a part of the inorganic particles is a metal particle containing calcium, silicic acid, magnesium, barium or aluminum metal salt, or titanium, copper, or zinc. The processed paper as described.
(7) The processed paper according to any one of (1) to (6), wherein the cellulose fibers are cellulose fibers derived from wood.
(8) The processed paper according to any one of (1) to (7), wherein the cellulose fiber is a wood-derived pulp fiber.
(9) A method for producing the processed paper according to any one of (1) to (8),
The said method including the process of synthesize | combining an inorganic particle in the solution for the fiber composite_body | complex of the said cellulose fiber and an inorganic particle in presence of a fiber.

  ADVANTAGE OF THE INVENTION According to this invention, the processed paper which has the characteristic of the inorganic particle contained in the fiber composite_body | complex of a cellulose fiber and an inorganic particle which has dimensional stability can be obtained.

  That is, a fiber composite of cellulose fibers and inorganic particles has, for example, fire resistance, opacity (concealment), radiation shielding, adsorbability and antibacterial properties. The processed paper to be contained can impart these functionalities.

  Furthermore, since the fiber composite of cellulose fibers and inorganic particles adheres to the fibers, the dehydrating and drying properties are good, and there is little powder falling off, and post-processing such as ease is easy. Processed paper can be obtained.

FIG. 1 is a schematic view showing a reaction apparatus used for production of samples 1 and 2. FIG. 2 is a schematic view of an apparatus for producing the sample 3 (P: pump). FIG. 3 is an electron micrograph of a sample 1 (composite of calcium carbonate fine particles and cellulose fibers (magnification: left 3000 times, right 10,000 times). FIG. 4 is a sample 2 (electron micrograph of a composite of magnesium carbonate fine particles and cellulose fibers (magnification: left 3000 times, right 10,000 times). FIG. 5 is an electron micrograph of Sample 3 (composite of hydrotalcite and cellulose fiber (magnification: left 3000 times, right 10,000 times). FIG. 6 is an electron micrograph of Sample 4 (complex of barium sulfate particles and cellulose fibers (magnification: left 3000 times, right 10,000 times). FIG. 7 is a photograph showing the results of evaluation of powder falling in Example 1. FIG. 8 is a photograph showing the result of evaluation of powder falling in Comparative Example 2.

  The present invention relates to a processed paper (wall paper for wallpaper) containing a fiber composite of cellulose fibers and inorganic particles. In particular, the present invention relates to a processed paper (base paper for wallpaper) containing a fiber composite of cellulose fibers and inorganic particles in which 15% or more of the cellulose fiber surface is coated with inorganic particles, and a method for producing the same.

  The processed paper (paper base paper) of the present invention is characterized by using a fiber composite of cellulose fibers and inorganic particles.

The fibers constituting the cellulose fiber- fiber composite are not particularly limited as long as they are cellulose fibers. For example, natural cellulose fibers, but also regenerated fibers (semi-synthetic fibers) such as rayon and lyocell, and synthetic fibers are used without limitation. can do. Examples of cellulose fiber materials include pulp fibers (wood pulp and non-wood pulp), cellulose nanofibers, bacterial cellulose, seaweed and other animal-derived cellulose, and algae. Wood pulp can be produced by pulping wood materials. Good. Wood raw materials include red pine, black pine, todomatsu, spruce, beech pine, larch, fir, tsuga, cedar, hinoki, larch, shirabe, spruce, hiba, douglas fir, hemlock, white fur, spruce, balsam fur, cedar, pine, Coniferous trees such as Merck pine, Radiata pine, etc., and mixed materials thereof, beech, hippopotamus, alder tree, oak, tab, shii, birch, broadleaf tree, poplar, tamo, dragonfly, eucalyptus, mangrove, lawan, acacia, etc. Examples are materials.

  The method for pulping natural materials such as wood raw materials (woody raw materials) is not particularly limited, and examples thereof include pulping methods generally used in the paper industry. Wood pulp can be classified by pulping method, for example, chemical pulp digested by methods such as kraft method, sulfite method, soda method, polysulfide method; mechanical pulp obtained by pulping by mechanical force such as refiner, grinder; Semi-chemical pulp obtained by carrying out pulping by mechanical force after pretreatment by; waste paper pulp; deinked pulp and the like. Wood pulp may be unbleached (before bleaching) or bleached (after bleaching).

  Examples of the non-wood-derived pulp include cotton, hemp, sisal hemp, manila hemp, flax, straw, bamboo, bagasse, kenaf, sugar cane, corn, rice straw, straw, honey and so on.

The pulp fiber may be either unbeaten or beaten, and may be selected according to the physical properties of the composite sheet, but it is preferable to beaten. Thereby, improvement of sheet strength and promotion of fixing of inorganic particles can be expected.
Further, these cellulose raw materials are further processed to give finely pulverized cellulose, chemically modified cellulose such as oxidized cellulose, and cellulose nanofiber: CNF (microfibrillated cellulose: MFC, TEMPO oxidized CNF, phosphate esterified CNF, carboxy Methylated CNF, mechanically ground CNF, etc.). The finely pulverized cellulose used in the present invention includes both what is generally called powdered cellulose and the above mechanically pulverized CNF. As the powdered cellulose, for example, a machined pulverized raw pulp or a bar shaft produced by a method of purifying and drying an undegraded residue obtained after acid hydrolysis, crushing and sieving Crystalline cellulose powder having a certain particle size distribution may be used, or commercially available products such as KC Flock (manufactured by Nippon Paper Industries), Theolas (manufactured by Asahi Kasei Chemicals), Avicel (manufactured by FMC), etc. Good. The degree of polymerization of cellulose in powdered cellulose is preferably about 100 to 1500, the degree of crystallinity of powdered cellulose by X-ray diffraction is preferably 70 to 90%, and the volume average particle size by a laser diffraction type particle size distribution analyzer. Is preferably 1 μm or less and 100 μm or less. The oxidized cellulose used in the present invention can be obtained, for example, by oxidizing in water using an oxidizing agent in the presence of a compound selected from the group consisting of N-oxyl compounds and bromides, iodides or mixtures thereof. it can. As the cellulose nanofiber, a method of defibrating the cellulose raw material is used. As the defibrating method, for example, an aqueous suspension of chemically modified cellulose such as cellulose or oxidized cellulose is mechanically ground or beaten with a refiner, a high-pressure homogenizer, a grinder, a single or multi-screw kneader, a bead mill, or the like. A method of defibration can be used. Cellulose nanofibers may be produced by combining one or more of the above methods. The fiber diameter of the produced cellulose nanofiber can be confirmed by observation with an electron microscope, and is, for example, in the range of 5 nm to 1000 nm, preferably 5 nm to 500 nm, more preferably 5 nm to 300 nm. When producing the cellulose nanofiber, before and / or after the cellulose is defibrated and / or refined, an arbitrary compound may be further added and reacted with the cellulose nanofiber to modify the hydroxyl group. it can. As functional groups to be modified, acetyl group, ester group, ether group, ketone group, formyl group, benzoyl group, acetal, hemiacetal, oxime, isonitrile, allene, thiol group, urea group, cyano group, nitro group, azo group , Aryl group, aralkyl group, amino group, amide group, imide group, acryloyl group, methacryloyl group, propionyl group, propioyl group, butyryl group, 2-butyryl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group , Decanoyl group, undecanoyl group, dodecanoyl group, myristoyl group, palmitoyl group, stearoyl group, pivaloyl group, benzoyl group, naphthoyl group, nicotinoyl group, isonicotinoyl group, furoyl group, cinnamoyl group and other acyl groups, 2-methacryloyl Isocyanate groups such as oxyethylisocyanoyl group, methyl group, ethyl group, propyl group, 2-propyl group, butyl group, 2-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl Group, decyl group, undecyl group, dodecyl group, myristyl group, palmityl group, stearyl group and other alkyl groups, oxirane group, oxetane group, oxyl group, thiirane group, thietane group and the like. Hydrogen in these substituents may be substituted with a functional group such as a hydroxyl group or a carboxy group. Further, a part of the alkyl group may be an unsaturated bond. The compound used for introducing these functional groups is not particularly limited. For example, a compound having a phosphoric acid-derived group, a compound having a carboxylic acid-derived group, a compound having a sulfuric acid-derived group, or a sulfonic acid-derived compound And the like, compounds having an alkyl group, compounds having an amine-derived group, and the like. Although it does not specifically limit as a compound which has a phosphoric acid group, Lithium dihydrogen phosphate which is phosphoric acid and the lithium salt of phosphoric acid, Dilithium hydrogen phosphate, Trilithium phosphate, Lithium pyrophosphate, Lithium polyphosphate is mentioned. . Furthermore, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate and sodium polyphosphate which are sodium salts of phosphoric acid are mentioned. Furthermore, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate which are potassium salts of phosphoric acid are mentioned. Further, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate which are ammonium salts of phosphoric acid are included. Of these, phosphoric acid, sodium phosphate, phosphoric acid potassium salt, and phosphoric acid ammonium salt are preferred from the viewpoint of high efficiency in introducing a phosphate group and easy industrial application. Sodium dihydrogen phosphate Although disodium hydrogen phosphate is more preferable, it is not particularly limited. The compound having a carboxyl group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. . The acid anhydride of the compound having a carboxyl group is not particularly limited, but examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. It is done. Although it does not specifically limit as a derivative of the compound which has a carboxyl group, The derivative of the acid anhydride of the compound which has a carboxyl group and the acid anhydride imidation of a compound which has a carboxyl group are mentioned. Although it does not specifically limit as an acid anhydride imidation thing of a compound which has a carboxyl group, Imidation thing of dicarboxylic acid compounds, such as maleimide, succinic acid imide, and phthalic acid imide, is mentioned. The acid anhydride derivative of the compound having a carboxyl group is not particularly limited. For example, at least some of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group, such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. are substituted (for example, alkyl group, phenyl group, etc. ) Are substituted. Among the compounds having a group derived from a carboxylic acid, maleic anhydride, succinic anhydride, and phthalic anhydride are preferred because they are easily applied industrially and easily gasified, but are not particularly limited. Further, the cellulose nanofiber may be modified in such a manner that the compound to be modified is physically adsorbed on the cellulose nanofiber without being chemically bonded. Examples of the physically adsorbing compound include surfactants, and any of anionic, cationic, and nonionic may be used. When the above-described modification is performed before cellulose is defibrated and / or pulverized, these functional groups can be removed after defibrating and / or pulverization to return to the original hydroxyl group. By performing the modification as described above, it is possible to promote the defibration of the cellulose nanofiber or to easily mix it with various substances when the cellulose nanofiber is used.

  A composite fiber of a synthetic fiber and a cellulose fiber can also be used in the present invention. For example, a composite fiber of a polyester fiber, a polyamide, a polyolefin, an acrylic fiber, a glass fiber, a carbon fiber, various metal fibers, etc. and a cellulose fiber is also used. be able to.

  The fibers shown above may be used alone or in combination. Especially, it is preferable that wood pulp is included or the combination of wood pulp, non-wood pulp, and / or synthetic fiber is included, and it is more preferable that it is only wood pulp.

  In a preferred embodiment, the fibers constituting the composite of the present invention are pulp fibers. Further, for example, a fibrous substance recovered from the wastewater of a paper mill may be supplied to the carbonation reaction of the present invention. By supplying such a substance to the reaction vessel, various composite particles can be synthesized, and fibrous particles and the like can be synthesized in terms of shape.

  In the present invention, in addition to the fiber, a substance that is not directly involved in the carbonation reaction but is taken into the product inorganic particles to form composite particles can be used. In the present invention, fibers such as pulp fibers are used, but these substances are further incorporated by synthesizing inorganic particles in a solution containing inorganic particles, organic particles, polymers and the like. Composite particles can be produced.

  The fiber length of the cellulose fiber to be combined is not particularly limited. For example, the average fiber length may be about 0.1 μm to 15 mm, and may be 1 μm to 12 mm, 100 μm to 10 mm, 500 μm to 8 mm, and the like.

  Further, the concentration of the cellulose fiber in the present invention is preferably 5% by weight or less, more preferably 4% by weight or less, and still more preferably 0.1 to 3% by weight.

Inorganic particles In the present invention, the inorganic particles to be combined with the cellulose fiber are not particularly limited, but are preferably water-insoluble or hardly soluble inorganic particles. Inorganic particles may be synthesized in an aqueous system, and the composite may be used in an aqueous system. Therefore, the inorganic particles are preferably insoluble or hardly soluble in water.

The inorganic particle said here means a metal or a metal compound. The metal compound is a metal cation (for example, Na ⁺ , Ca ²⁺ , Mg ²⁺ , Al ³⁺ , Ba ²⁺ ) and an anion (for example, O ²⁻ , OH ⁻ , CO ₃ ²⁻ , PO ₄ ^{3). -} , SO ₄ ²⁻ , NO ₃ −, Si ₂ O ₃ ²⁻ , SiO ₃ ²⁻ , Cl ⁻ , F ⁻ , S ^2−, etc.), which are generally called inorganic salts Say. The method for synthesizing these inorganic particles may be either a gas-liquid method or a liquid-liquid method. An example of the gas-liquid method is a carbon dioxide gas method. For example, magnesium carbonate can be synthesized by reacting magnesium hydroxide and carbon dioxide gas. Examples of liquid-liquid methods include reacting an acid (hydrochloric acid, sulfuric acid, etc.) and a base (sodium hydroxide, potassium hydroxide, etc.) by neutralization, reacting an inorganic salt with an acid or base, And a method of reacting the For example, barium sulfate and sulfuric acid are reacted to obtain barium sulfate, aluminum sulfate and sodium hydroxide are reacted to obtain aluminum hydroxide, or calcium carbonate and aluminum sulfate are reacted to produce calcium and aluminum. Composite inorganic particles can be obtained. In addition, when synthesizing inorganic particles in this manner, any metal or metal compound can be allowed to coexist in the reaction solution. In this case, these metals or metal compounds are efficiently incorporated into the inorganic particles and are combined. Can be For example, when phosphoric acid is added to calcium carbonate to synthesize calcium phosphate, composite particles of calcium phosphate and titanium can be obtained by allowing titanium dioxide to coexist in the reaction solution.

It is an ionic crystalline compound composed of barium ions and sulfate ions represented by barium sulfate (BaSO ₄ ), and is often in the form of a plate or column and is hardly soluble in water. Pure barium sulfate is a colorless crystal, but when it contains impurities such as iron, manganese, strontium and calcium, it becomes yellowish brown or blackish gray and becomes translucent. Although it can be obtained as a natural mineral, it can also be synthesized by chemical reaction. In particular, synthetic products by chemical reaction are used not only for pharmaceuticals (X-ray contrast media) but also widely used in paints, plastics, storage batteries, etc. by applying chemically stable properties.

  In the present invention, a composite of barium sulfate and fibers can be produced by synthesizing barium sulfate in a solution in the presence of fibers. For example, a method of reacting an acid (such as sulfuric acid) and a base by neutralization, reacting an inorganic salt with an acid or a base, or reacting inorganic salts with each other can be mentioned. For example, barium hydroxide can be reacted with sulfuric acid or aluminum sulfate to obtain barium sulfate, or barium chloride can be added to an aqueous solution containing sulfate to precipitate barium sulfate. A composite of barium sulfate and fibers can be suitably used as a radiation shielding material.

  In one preferred embodiment, the composite of the present invention can be obtained by synthesizing inorganic particles in the presence of cellulose fibers. This is because the surface of the cellulose fiber is a suitable place for the precipitation of the inorganic particles, so that it is easy to synthesize a composite of the inorganic particles and the cellulose fiber.

  As one preferred embodiment, the average primary particle diameter of the inorganic particles in the composite of the present invention can be, for example, 1 μm or less, but the average primary particle diameter is 500 nm or less, and the average primary particle diameter is 200 nm or less. Inorganic particles having an average primary particle diameter of 100 nm or less, and inorganic particles having an average primary particle diameter of 50 nm or less can be used. Moreover, the average primary particle diameter of the inorganic particles can be 10 nm or more. The average primary particle diameter can be calculated from an electron micrograph.

  In addition, the inorganic particles in the composite of the present invention may take the form of secondary particles in which fine primary particles are aggregated, and secondary particles according to the application can be generated by an aging process, or by pulverization. Agglomerates can also be made fine. For grinding, ball mill, sand grinder mill, impact mill, high-pressure homogenizer, low-pressure homogenizer, dyno mill, ultrasonic mill, kanda grinder, attritor, stone mill, vibration mill, cutter mill, jet mill, breaker, beater Short shaft extruder, twin screw extruder, ultrasonic stirrer, household juicer mixer and the like.

  The composite obtained by the present invention can be used in various shapes, for example, powders, pellets, molds, aqueous suspensions, pastes, sheets, and other shapes. Moreover, it can also be set as molded objects, such as a mold, particle | grains, and a pellet, with a composite as a main component and other materials. There is no particular limitation on the dryer in the case of drying into a powder, but for example, an air dryer, a band dryer, a spray dryer or the like can be preferably used.

  The composite obtained by the present invention can be used for various applications, for example, paper, fiber, cellulosic composite material, filter material, paint, plastic and other resins, rubber, elastomer, ceramic, glass, tire. , Building materials (asphalt, asbestos, cement, board, concrete, brick, tile, plywood, fiberboard, etc.), various carriers (catalyst carrier, pharmaceutical carrier, agricultural chemical carrier, microbial carrier, etc.), adsorbent (impurity removal, deodorization) ), Anti-wrinkle agent, clay, abrasive, modifier, repair material, heat insulating material, moisture proof material, water repellent material, water resistant material, light shielding material, sealant, shield material, insect repellent, adhesive, ink, Cosmetics, medical materials, paste materials, anti-discoloring agents, food additives, tablet excipients, dispersants, shape retention agents, water retention agents, filter aids, essential oil materials, oil treatment agents, oil modifiers, radio wave absorption Materials, insulation materials, sound insulation materials, vibration insulation materials, semiconductor sealing materials, radiation shielding materials, cosmetics, fertilizers, feeds, fragrances, additives for paints and adhesives, flame retardant materials, sanitary products (disposable diapers, sanitary napkins , Incontinence pads, breast milk pads, etc.). Moreover, it can be used for various fillers and coating agents in the above applications. The composite of the present invention may be applied to papermaking applications, for example, printing paper, newspaper, ink jet paper, PPC paper, kraft paper, fine paper, coated paper, fine coated paper, wrapping paper, thin paper, and color fine paper. Paper, cast coated paper, non-carbon paper, label paper, thermal paper, various fancy papers, water-soluble paper, release paper, process paper, base paper for wallpaper, non-combustible paper, flame retardant paper, laminated base paper, printed electronics paper, battery Separator, cushion paper, tracing paper, impregnated paper, ODP paper, building paper, decorative paper, envelope paper, tape paper, heat exchange paper, synthetic fiber paper, sterilized paper, water resistant paper, oil resistant paper, heat resistant paper, photocatalyst Paper, decorative paper (grease paper, etc.), various sanitary paper (toilet paper, tissue paper, wipers, diapers, sanitary products, etc.), tobacco paper, paperboard (liner, Corrugating, etc. white paperboard), paper plates base paper cup base paper, baking paper, abrasive paper, and synthetic paper. That is, according to the present invention, a composite of inorganic particles and fibers having a small primary particle size and a narrow particle size distribution can be obtained, which is different from conventional inorganic fillers having a particle size of more than 1 μm. Can exhibit its characteristics. Furthermore, unlike the case where the inorganic particles are simply blended with the fibers, if the inorganic particles are combined with the fibers, the inorganic particles are not only easily retained on the sheet, but also a sheet in which the particles are uniformly dispersed without agglomeration. Can be obtained. In the preferred embodiment, the inorganic particles in the present invention are not only fixed on the outer surface of the fiber and the inner side of the lumen, but are also generated on the inner side of the microfibril.

  Moreover, when using the composite_body | complex obtained by this invention, the particle | grains generally called an inorganic filler and an organic filler, and various fibers can be used together. For example, as inorganic filler, calcium carbonate (light calcium carbonate, heavy calcium carbonate), magnesium carbonate, barium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, clay (kaolin, calcined kaolin, deramikaolin) ), Talc, zinc oxide, zinc stearate, titanium dioxide, silica made from sodium silicate and mineral acid (white carbon, silica / calcium carbonate composite, silica / titanium dioxide composite), white clay, bentonite, diatomaceous earth, Examples thereof include calcium sulfate, zeolite, an inorganic filler that regenerates and uses the ash obtained from the deinking process, and an inorganic filler that forms a complex with silica or calcium carbonate in the process of regeneration. As the calcium carbonate-silica composite, amorphous silica such as white carbon may be used together with calcium carbonate and / or light calcium carbonate-silica composite. Organic fillers include urea-formalin resin, polystyrene resin, phenol resin, fine hollow particles, acrylamide composites, wood-derived materials (fine fibers, microfibril fibers, powder kenaf), modified insolubilized starch, ungelatinized starch, etc. Is mentioned. Fibers include natural fibers such as cellulose, synthetic fibers that are artificially synthesized from raw materials such as petroleum, regenerated fibers (semi-synthetic fibers) such as rayon and lyocell, and inorganic fibers. Can be used. In addition to the above, the natural fibers include protein fibers such as wool, silk thread and collagen fibers, and complex sugar chain fibers such as chitin / chitosan fibers and alginic acid fibers. Examples of the cellulose-based raw material include pulp fibers (wood pulp and non-wood pulp), animal-derived cellulose such as bacterial cellulose and sea squirt, and algae. The wood pulp may be produced by pulping the wood raw material. Wood raw materials include red pine, black pine, todomatsu, spruce, beech pine, larch, fir, tsuga, cedar, hinoki, larch, shirabe, spruce, hiba, douglas fir, hemlock, white fur, spruce, balsam fur, cedar, pine, Coniferous trees such as Merck pine, Radiata pine, etc., and mixed materials thereof, beech, hippopotamus, alder tree, oak, tab, shii, birch, broadleaf tree, poplar, tamo, dragonfly, eucalyptus, mangrove, lawan, acacia, etc. Examples are materials. The method for pulping the wood raw material is not particularly limited, and examples thereof include a pulping method generally used in the paper industry. Wood pulp can be classified by pulping method, for example, chemical pulp digested by methods such as kraft method, sulfite method, soda method, polysulfide method; mechanical pulp obtained by pulping by mechanical force such as refiner, grinder; Semi-chemical pulp obtained by carrying out pulping by mechanical force after pretreatment by; waste paper pulp; deinked pulp and the like. Wood pulp may be unbleached (before bleaching) or bleached (after bleaching). Examples of the non-wood-derived pulp include cotton, hemp, sisal hemp, manila hemp, flax, straw, bamboo, bagasse, kenaf, sugar cane, corn, rice straw, straw, honey and so on. Wood pulp and non-wood pulp may be either unbeaten or beaten. Further, these cellulose raw materials are further processed to give finely pulverized cellulose such as powdered cellulose, chemically modified cellulose such as oxidized cellulose, and cellulose nanofiber: CNF (microfibrillated cellulose: MFC, TEMPO oxidized CNF, phosphoric acid esterified) CNF, carboxymethylated CNF, mechanically ground CNF). Synthetic fibers include polyester, polyamide, polyolefin, acrylic fiber, semi-spun fibers include rayon and acetate, and inorganic fibers include glass fiber, carbon fiber, and various metal fibers. About these, these may be used alone or in combination of two or more.

  The average particle diameter, shape, and the like of the inorganic particles constituting the composite of the present invention can be confirmed by observation with an electron microscope. Furthermore, by adjusting the conditions for synthesizing the inorganic particles, the inorganic particles having various sizes and shapes can be combined with the fiber.

The manufacturing method of the composite based on this invention makes it essential to synthesize | combine an inorganic particle in the solution containing a fiber. For example, a solution containing fibers and inorganic particle precursors may be stirred and mixed in an open reaction tank to synthesize a composite, or an aqueous suspension containing fibers and inorganic particle precursors may be reacted. You may synthesize | combine by injecting in a container. As will be described later, when an aqueous suspension of an inorganic precursor is injected into a reaction vessel, cavitation bubbles may be generated, and inorganic particles may be synthesized in the presence thereof.
When one of the precursors of the inorganic particles is alkaline, the fibers can be swollen if the fibers are previously dispersed in the alkaline precursor solution, so that a composite of inorganic particles and fibers can be obtained efficiently. Although the reaction can be started after promoting the swelling of the fibers by stirring for 15 minutes or more after mixing, the reaction may be started immediately after mixing. In addition, when a substance that easily interacts with cellulose, such as aluminum sulfate (sulfuric acid band, polyaluminum chloride, etc.) is used as part of the precursor of inorganic particles, the aluminum sulfate side should be mixed with the fiber in advance. In some cases, the proportion of the inorganic particles fixed to the fibers can be improved.

  In the present invention, the liquid may be ejected under conditions that cause cavitation bubbles in the reaction vessel, or may be ejected under conditions that do not cause cavitation bubbles. The reaction vessel is preferably a pressure vessel in any case. In addition, the pressure vessel in this invention is a container which can apply the pressure of 0.005 Mpa or more. In the condition that does not generate cavitation bubbles, the pressure in the pressure vessel is preferably 0.005 MPa to 0.9 MPa in static pressure.

(Cavitation bubbles)
When the composite according to the present invention is synthesized, inorganic particles can be precipitated in the presence of cavitation bubbles. In the present invention, cavitation is a physical phenomenon in which bubbles are generated and disappear in a short time due to a pressure difference in a fluid flow, and is also referred to as a cavity phenomenon. Bubbles generated by cavitation (cavitation bubbles) are generated with very small “bubble nuclei” of 100 microns or less existing in the liquid as the nucleus when the pressure in the fluid becomes lower than the saturated vapor pressure for a very short time.

  In the present invention, cavitation bubbles can be generated in the reaction vessel by a known method. For example, cavitation bubbles are generated by jetting fluid at high pressure, cavitation is generated by stirring at high speed in the fluid, cavitation is generated by causing explosion in the fluid, ultrasonic vibration It can be considered that cavitation is generated by a child (vibratory cavitation).

  In particular, in the present invention, since cavitation bubbles are easily generated and controlled, it is preferable to generate cavitation bubbles by ejecting a fluid at a high pressure. In this aspect, by compressing the jet liquid using a pump or the like and jetting it through a nozzle or the like at high speed, cavitation bubbles are generated at the same time as the liquid itself expands due to extremely high shearing force near the nozzle and sudden pressure reduction. . The method using a fluid jet has high generation efficiency of cavitation bubbles, and can generate cavitation bubbles having a stronger collapse impact force. In the present invention, controlled cavitation bubbles are present when synthesizing the inorganic particles, and are clearly different from cavitation bubbles that cause uncontrollable harm that naturally occurs in fluid machinery.

  In the present invention, cavitation can be generated by using a reaction solution such as a raw material as an injection liquid as it is, or cavitation bubbles can be generated by injecting some fluid into the reaction vessel. The fluid in which the liquid jet forms a jet may be any liquid, gas, solid such as powder or pulp, or a mixture thereof as long as it is in a fluid state. Further, if necessary, another fluid such as carbon dioxide can be added to the above fluid as a new fluid. The fluid and the new fluid may be uniformly mixed and ejected, but may be ejected separately.

  The liquid jet is a jet of a fluid or a fluid in which solid particles or gas are dispersed or mixed in the liquid, and refers to a liquid jet containing raw slurry or bubbles of pulp or inorganic particles. The gas referred to here may include bubbles due to cavitation.

  Since cavitation occurs when a liquid is accelerated and the local pressure is lower than the vapor pressure of the liquid, flow rate and pressure are particularly important. From this, the basic dimensionless number representing the cavitation state, the cavitation number σ is defined as the following formula 1 (Yoji Kato's new edition of cavitation, basics and recent progress, Kashiwa Shoten 1999).

  Here, a large number of cavitations indicates that the flow field is in a state where cavitation is difficult to occur. In particular, when cavitation is generated through a nozzle or orifice pipe such as a cavitation jet, the cavitation number σ is expressed by the following equation (2) from the nozzle upstream pressure p1, the nozzle downstream pressure p2, and the saturated water vapor pressure pv of the sample water. In the cavitation jet, the pressure difference between p1, p2, and pv is large and p1 >> p2 >> pv. Therefore, the cavitation number σ can be further approximated as in the following Expression 2. (H. Soyama, J. Soc. Mat. Sci. Japan, 47 (4), 381, 1998).

  The cavitation condition in the present invention is such that the above-described cavitation number σ is preferably 0.001 or more and 0.5 or less, preferably 0.003 or more and 0.2 or less, and 0.01 or more and 0.1 or less. It is particularly preferred that If the cavitation number σ is less than 0.001, the effect is small because the pressure difference with the surroundings when the cavitation bubbles collapse is low, and if it is greater than 0.5, the flow pressure difference is low and cavitation occurs. It becomes difficult to occur.

Further, when the cavitation is generated by injecting the injection liquid through the nozzle or the orifice pipe, the pressure of the injection liquid (upstream pressure) is desirably 0.01 MPa or more and 30 MPa or less, and 0.7 MPa or more and 20 MPa or less. It is preferable that it is 2 MPa or more and 15 MPa or less. When the upstream pressure is less than 0.01 MPa, it is difficult to produce a pressure difference with the downstream pressure, and the effect is small. On the other hand, when the pressure is higher than 30 MPa, a special pump and a pressure vessel are required, and energy consumption increases, which is disadvantageous in terms of cost. On the other hand, the pressure in the container (downstream pressure) is preferably 0.005 MPa to 0.9 MPa in static pressure.
Moreover, the ratio of the pressure in the container and the pressure of the jet liquid is preferably in the range of 0.001 to 0.5.

  In the present invention, the inorganic particles can also be synthesized by spraying the spray liquid under conditions that do not generate cavitation bubbles. Specifically, it is more preferable that the pressure of the spray liquid (upstream pressure) is 2 MPa or less, preferably 1 MPa or less, and the pressure of the spray liquid (downstream pressure) is released to 0.05 MPa or less.

  The jet velocity of the jet liquid is desirably in the range of 1 m / second to 200 m / second, and preferably in the range of 20 m / second to 100 m / second. When the jet velocity is less than 1 m / sec, the effect is weak because the pressure drop is low and cavitation hardly occurs. On the other hand, when it is higher than 200 m / sec, a high pressure is required and a special device is required, which is disadvantageous in terms of cost.

  What is necessary is just to generate the cavitation generation | occurrence | production place in this invention in the reaction container which synthesize | combines an inorganic particle. Moreover, although it is possible to process by one pass, it can also circulate as many times as necessary. Furthermore, it can be processed in parallel or in permutation using a plurality of generating means.

  The liquid injection for generating cavitation may be performed in a container open to the atmosphere, but is preferably performed in a pressure container in order to control cavitation.

  When cavitation is generated by liquid injection, the solid content concentration of the reaction solution is preferably 30% by weight or less, and more preferably 20% by weight or less. This is because the cavitation bubbles easily act on the reaction system uniformly at such a concentration. In addition, the aqueous suspension of slaked lime that is the reaction solution preferably has a solid concentration of 0.1% by weight or more from the viewpoint of reaction efficiency.

  In the present invention, for example, when a complex of calcium carbonate and cellulose fiber is synthesized, the pH of the reaction solution is basic at the start of the reaction but changes to neutral as the carbonation reaction proceeds. Therefore, the reaction can be controlled by monitoring the pH of the reaction solution.

  In the present invention, by increasing the jetting pressure of the liquid, the flow velocity of the jetting liquid is increased, and accordingly, the pressure is lowered, and stronger cavitation can be generated. Further, by pressurizing the pressure in the reaction vessel, the pressure in the region where the cavitation bubbles collapse is increased and the pressure difference between the bubbles and the surroundings increases, so that the bubbles collapse violently and the impact force can be increased. Furthermore, dissolution and dispersion of the introduced carbon dioxide gas can be promoted. The reaction temperature is preferably 0 ° C. or higher and 90 ° C. or lower, and particularly preferably 10 ° C. or higher and 60 ° C. or lower. In general, the impact force is considered to be the maximum at the midpoint between the melting point and the boiling point. Therefore, in the case of an aqueous solution, a temperature around 50 ° C. is suitable, but even below that temperature is affected by the vapor pressure. Therefore, a high effect can be obtained within the above range.

  In the present invention, the energy necessary for generating cavitation can be reduced by adding a surfactant. As the surfactant to be used, known or novel surfactants, for example, nonionic surfactants such as fatty acid salts, higher alkyl sulfates, alkylbenzene sulfonates, higher alcohols, alkylphenols, alkylene oxide adducts such as fatty acids, etc. , Anionic surfactants, cationic surfactants, amphoteric surfactants and the like. These may consist of a single component or a mixture of two or more components. The addition amount may be an amount necessary for reducing the surface tension of the jet liquid and / or the liquid to be jetted.

Synthesis of a composite of inorganic particles and cellulose fibers In one embodiment of the present invention, a fiber composite can be synthesized by synthesizing inorganic particles in a solution containing cellulose fibers. , Can be performed by a known method. In the case of synthesizing calcium carbonate, for example, calcium carbonate can be synthesized by a carbon dioxide method, a soluble salt reaction method, a lime / soda method, a soda method, etc. In a preferred embodiment, calcium carbonate can be synthesized by a carbon dioxide method. Synthesize.

In general, when calcium carbonate is produced by the carbon dioxide method, lime is used as a calcium source, water is added to quick lime CaO to obtain slaked lime Ca (OH) ₂ , and carbon dioxide CO ₂ is added to the slaked lime. Calcium carbonate is synthesized by the carbonation step of blowing calcium to obtain calcium carbonate CaCO ₃ . At this time, a slaked lime suspension prepared by adding water to quick lime may be passed through a screen to remove low-solubility lime particles contained in the suspension. Further, slaked lime may be directly used as a calcium source. In the present invention, when calcium carbonate is synthesized by the carbon dioxide method, the carbonation reaction may be performed in the presence of cavitation bubbles.

  Generally, a gas blowing type carbonator and a mechanical stirring type carbonator are known as reaction vessels (carbonation reactor: carbonator) for producing calcium carbonate by the carbon dioxide method. In a gas blowing type carbonator, carbon dioxide gas is blown into a carbonation reaction tank containing slaked lime suspension (lime milk) to react slaked lime with carbon dioxide gas. Is difficult to control uniformly and finely, and is limited in terms of reaction efficiency. On the other hand, in the mechanical agitator type carbonator, a stirrer is provided inside the carbonator, and carbon dioxide gas is introduced near the stirrer to make the carbon dioxide gas fine bubbles, improving the reaction efficiency between slaked lime and carbon dioxide gas. (“Cement, Gypsum, Lime Handbook”, Gihodo Publishing, 1995, 495 pages).

  However, when stirring with a stirrer provided inside the carbonation reaction tank, such as a mechanical stirring type carbonator, if the concentration of the reaction liquid is high or the carbonation reaction proceeds, the resistance of the reaction liquid is large and it is difficult to sufficiently stir Therefore, it is difficult to precisely control the carbonation reaction, and in order to perform sufficient stirring, a considerable load is applied to the stirrer, which may be disadvantageous in terms of energy. In addition, the gas inlet is located at the bottom of the carbonator, and the blades of the stirrer are installed near the bottom of the carbonator to improve the stirring. Lime screen residue with low solubility is always settled at the bottom due to fast sedimentation, which may block the gas blowing port or break the balance of the stirrer. Furthermore, in the conventional method, in addition to the carbonator, a stirrer and equipment for introducing carbon dioxide into the carbonator are necessary, and the equipment is also expensive. In the mechanical stirring type carbonator, the carbon dioxide gas supplied near the stirrer is refined by the stirrer to improve the reaction efficiency between slaked lime and carbon dioxide gas. However, when the concentration of the reaction liquid is high, the carbon dioxide gas is sufficient. In view of the carbonation reaction, it is sometimes difficult to accurately control the form of calcium carbonate produced. In the present invention, by synthesizing calcium carbonate in the presence of cavitation bubbles, it becomes possible to efficiently advance the carbonation reaction and produce uniform calcium carbonate fine particles. In particular, by using jet cavitation, sufficient stirring can be performed without a mechanical stirrer such as a blade. In the present invention, conventionally known reaction vessels can be used, and of course, the above-described gas blowing type carbonator and mechanical stirring type carbonator can be used without any problem. You may combine jet cavitation using.

  When synthesizing calcium carbonate by the carbon dioxide method, the solid content concentration of the aqueous suspension of slaked lime is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, and further preferably 1 to 20%. It is about wt%. If the solid content concentration is low, the reaction efficiency is low and the production cost is high. If the solid content concentration is too high, the fluidity is deteriorated and the reaction efficiency is lowered. In the present invention, since calcium carbonate is synthesized in the presence of cavitation bubbles, the reaction solution and carbon dioxide can be suitably mixed even when a suspension (slurry) having a high solid content is used.

  As an aqueous suspension containing slaked lime, those generally used for calcium carbonate synthesis can be used, for example, prepared by mixing slaked lime with water, or slaked (digested) quick lime (calcium oxide) with water. Can be prepared. There are no particular restrictions on the conditions for soaking, but for example, the concentration of CaO is 0.1% by weight or more, preferably 1% by weight or more, and the temperature is 20 to 100 ° C., preferably 30 to 100 ° C. . Moreover, the average residence time in the soaking reaction tank (slaker) is not particularly limited, but can be, for example, 5 minutes to 5 hours, and preferably within 2 hours. Of course, the slaker may be batch or continuous. In the present invention, the carbonation reaction tank (carbonator) and the decontamination reaction tank (slaker) may be separated, and one reaction tank may be used as the carbonation reaction tank and the decontamination reaction tank. Good.

  In the present invention, water is used for the preparation of the suspension. As this water, normal tap water, industrial water, ground water, well water, etc. can be used, ion-exchanged water, distilled water, Pure water, industrial waste water, and water obtained when separating and dehydrating the calcium carbonate slurry obtained in the carbonation step can be suitably used.

  Moreover, in this invention, the reaction liquid of a reaction tank can be circulated and used. By circulating the reaction solution in this manner and increasing the contact between the reaction solution and carbon dioxide, the reaction efficiency can be increased and desired inorganic particles can be easily obtained.

  In the present invention, a gas such as carbon dioxide (carbon dioxide gas) can be blown into the reaction vessel and mixed with the reaction solution. According to the present invention, carbon dioxide gas can be supplied to the reaction liquid without a gas supply device such as a fan or a blower, and the reaction can be efficiently performed because the carbon dioxide gas is refined by cavitation bubbles. .

  In the present invention, the carbon dioxide concentration of the gas containing carbon dioxide is not particularly limited, but a higher carbon dioxide concentration is preferable. Moreover, there is no restriction | limiting in the quantity of the carbon dioxide gas introduce | transduced into an injector, Although it can select suitably, For example, it is preferable to use the carbon dioxide gas of the flow rate of 100-10000L / hour per kg of slaked lime.

  The gas containing carbon dioxide of the present invention may be substantially pure carbon dioxide gas or a mixture with other gases. For example, in addition to carbon dioxide gas, a gas containing an inert gas such as air or nitrogen can be used as a gas containing carbon dioxide. Further, as the gas containing carbon dioxide, in addition to carbon dioxide gas (carbon dioxide gas), exhaust gas discharged from an incinerator of a paper mill, a coal boiler, a heavy oil boiler, or the like can be suitably used as the carbon dioxide-containing gas. In addition, a carbonation reaction can also be performed using carbon dioxide generated from the lime baking step.

  When producing the composite of the present invention, various known auxiliaries can be further added. For example, chelating agents can be added. Specifically, polyhydroxycarboxylic acids such as citric acid, malic acid and tartaric acid, dicarboxylic acids such as oxalic acid, sugar acids such as gluconic acid, iminodiacetic acid, ethylenediaminetetra Aminopolycarboxylic acids such as acetic acid and their alkali metal salts, alkali metal salts of polyphosphoric acid such as hexametaphosphoric acid and tripolyphosphoric acid, amino acids such as glutamic acid and aspartic acid and their alkali metal salts, acetylacetone, methyl acetoacetate, acetoacetic acid Examples include ketones such as allyl, saccharides such as sucrose, and polyols such as sorbitol. In addition, as surface treatment agents, saturated fatty acids such as palmitic acid and stearic acid, unsaturated fatty acids such as oleic acid and linoleic acid, resin acids such as alicyclic carboxylic acid and abietic acid, salts, esters and ethers thereof, alcohols Activators, sorbitan fatty acid esters, amide or amine surfactants, polyoxyalkylene alkyl ethers, polyoxyethylene nonyl phenyl ether, sodium alpha olefin sulfonate, long chain alkyl amino acids, amine oxides, alkyl amines, fourth A quaternary ammonium salt, aminocarboxylic acid, phosphonic acid, polyvalent carboxylic acid, condensed phosphoric acid and the like can be added. Moreover, a dispersing agent can also be used as needed. Examples of the dispersant include sodium polyacrylate, sucrose fatty acid ester, glycerin fatty acid ester, acrylic acid-maleic acid copolymer ammonium salt, methacrylic acid-naphthoxypolyethylene glycol acrylate copolymer, methacrylic acid-polyethylene glycol. Examples include monomethacrylate copolymer ammonium salts and polyethylene glycol monoacrylate. These can be used alone or in combination. The timing of addition may be before or after the synthesis reaction. Such an additive can be added in an amount of preferably 0.001 to 20%, more preferably 0.1 to 10% with respect to the inorganic particles.

  When synthesizing the complex in the present invention, the reaction conditions are not particularly limited, and can be appropriately set according to the application. For example, the temperature of the synthesis reaction can be 0 to 90 ° C, preferably 10 to 70 ° C. The reaction temperature can be controlled by a temperature controller, and if the temperature is low, the reaction efficiency decreases and the cost increases, whereas if it exceeds 90 ° C., coarse inorganic particles tend to increase.

  In the present invention, the reaction can be a batch reaction or a continuous reaction. In general, it is preferable to perform a batch reaction step for the convenience of discharging the residue after the reaction. The scale of the reaction is not particularly limited, but the reaction may be performed on a scale of 100 L or less, or may be performed on a scale of more than 100 L. The size of the reaction vessel can be, for example, about 10 L to 100 L, or about 100 L to 1000 L.

  Furthermore, the reaction can be controlled, for example, by monitoring the pH of the reaction solution. According to the pH profile of the reaction solution, for example, if it is a carbonation reaction of calcium carbonate, the reaction solution is less than pH 9, preferably less than pH 8, More preferably, the reaction can be performed until the pH reaches around 7.

  On the other hand, the reaction can be controlled by monitoring the conductivity of the reaction solution. If it is a carbonation reaction of calcium carbonate, for example, it is preferable to carry out the carbonation reaction until the conductivity is reduced to 1 mS / cm or less.

  Furthermore, the reaction can be controlled simply by the reaction time, and specifically, it can be controlled by adjusting the time during which the reactant stays in the reaction vessel. In addition, in this invention, reaction can also be controlled by stirring the reaction liquid of a reaction tank or making reaction multistage reaction.

  In the present invention, since the complex which is a reaction product is obtained as a suspension, it can be stored in a storage tank or subjected to processing such as concentration, dehydration, pulverization, classification, aging, and dispersion as necessary. Can do. These can be performed by known processes, and may be appropriately determined in consideration of the application and energy efficiency. For example, the concentration / dehydration treatment is performed using a centrifugal dehydrator, a sedimentation concentrator, or the like. Examples of the centrifugal dehydrator include a decanter and a screw decanter. When using a filter or a dehydrator, the type is not particularly limited and a general one can be used. For example, a pressure-type dehydrator such as a filter press, a drum filter, a belt press, a tube press, A calcium carbonate cake can be obtained by suitably using a vacuum drum dehydrator such as an Oliver filter. For grinding, ball mill, sand grinder mill, impact mill, high-pressure homogenizer, low-pressure homogenizer, dyno mill, ultrasonic mill, kanda grinder, attritor, stone mill, vibration mill, cutter mill, jet mill, breaker, beater Short shaft extruder, twin screw extruder, ultrasonic stirrer, household juicer mixer and the like. Examples of the classification method include a sieve such as a mesh, an outward type or inward type slit or round hole screen, a vibrating screen, a heavy foreign matter cleaner, a lightweight foreign matter cleaner, a reverse cleaner, a sieving tester, and the like. Examples of the dispersion method include a high-speed disperser and a low-speed kneader.

  The composite obtained by the present invention can be blended in a filler or pigment in a suspension state without being completely dehydrated, but can also be dried to form a powder. Although there is no restriction | limiting in particular also about the dryer in this case, For example, an airflow dryer, a band dryer, a spray dryer etc. can be used conveniently.

  The composite obtained by the present invention can be modified by a known method. For example, in an embodiment, the surface can be hydrophobized to improve miscibility with a resin or the like.

  The fiber composite of cellulose fibers and inorganic particles of the present invention is not simply a mixture of cellulose fibers and inorganic particles, but cellulose fibers and inorganic particles are bound to some extent by hydrogen bonding, etc. The inorganic particles are less likely to fall off. The binding strength between the cellulose fibers and the inorganic particles in the composite can be evaluated, for example, by a numerical value such as ash yield (%), that is, (sheet ash content / composite ash content before disaggregation) × 100. . Specifically, the composite is dispersed in water, adjusted to a solid content concentration of 0.2%, and disaggregated for 5 minutes with a standard disintegrator specified in JIS P 8220-1: 2012, and then in accordance with JIS P 8222: 1998. The ash yield when sheeted using a 150 mesh wire can be used for evaluation. In a preferred embodiment, the ash yield is 20% by mass or more, and in a more preferred embodiment, the ash yield is 50% by mass or more. is there.

  The cellulose fiber to be combined is not particularly limited as long as 15% or more of the fiber surface is coated with inorganic particles. For example, the weight ratio of cellulose fiber to inorganic particles is 5/95 to 95/95. 5 or 10/90 to 90/10, 20/80 to 80/20, 30/70 to 70/30, or 40/60 to 60/40.

  In the fiber composite according to the present invention, 15% or more of the fiber surface is coated with inorganic particles, and if the cellulose fiber surface is coated with such an area ratio, characteristics due to the inorganic particles are greatly generated. On the other hand, the characteristic resulting from the cellulose fiber surface becomes small.

Processed Paper In the present invention, the processed paper includes release paper, moisture-proof packaging, glass paper, or base paper for wallpaper. Among these, wallpaper base paper is preferable.

The processed paper of the present invention is obtained by papermaking a pulp slurry containing the fiber composite of cellulose fibers and inorganic particles. The processed paper obtained by the present invention can easily obtain a sheet having a high ash content and a high yield of inorganic particles. At that time, the processed paper of the present invention may be a single-layer sheet or a multilayer sheet. In the case of a multilayer sheet, only one layer may be placed in any layer of the multilayer papermaking, or a single sheet may be bonded and combined with the same sheet or another sheet after papermaking. The obtained sheets can be bonded to form a multilayer sheet.

The processed paper of the present invention may contain a chemical additive such as a filler, a sizing agent, a paper strength enhancer, and a yield improver, and a paste in addition to the fiber composite of cellulose fibers and inorganic particles. Further, the base paper for wallpaper of the present invention may contain other functional substances such as antibacterial agents and flame retardants.

  The base paper for wallpaper of the present invention can be blended with non-cellulosic fibers such as glass fibers and / or synthetic fibers. In that case, the blending ratio of non-cellulosic fibers is preferably 20% by weight or less, more preferably. Is 15% by weight or less. As the blending ratio of non-cellulosic fibers increases, it becomes impossible to solve the problem of operability at the time of papermaking when a large amount of non-cellulosic fibers, which is the object of the present invention, is used. According to the experience of the present inventors, the problem of operability is small if it is up to about 15% by weight. For example, even a base paper for wallpaper in which synthetic fibers are blended up to about 15% by weight, the blending of the remainder with a fiber composite makes it possible to obtain higher dimensional stability without impairing operability.

  Examples of such non-cellulosic fibers include polyolefin resin fibers such as polyethylene and polypropylene, polyester resin fibers such as polyethylene terephthalate, polyamide resin fibers such as nylon, acrylic resin fibers such as polyacrylonitrile, and polyurethane resins. Thermoplastic synthetic fibers such as fibers and halogen-containing resin fibers such as polyvinyl chloride can be used. Further, a synthetic fiber obtained by copolymerizing the thermoplastic synthetic resin, or a composite fiber containing two or more different thermoplastic synthetic resins having a core-sheath structure, a sea-island structure, or the like in one fiber is also used. be able to. These synthetic fibers may be used alone or as a mixture of a plurality of types.

  The sizing agent can be internally and / or externally added to the base paper for wallpaper of the present invention in the same manner as ordinary paper. In the case of acidic papermaking, the sizing agent may be a rosin sizing agent, a rosin emulsion sizing agent, an alpha carboxymethyl saturated fatty acid, or the like. On the other hand, in the case of neutral papermaking, rosin sizing agents for neutral papermaking, alkyl ketene dimers, alkenyl succinic anhydrides, and cationic polymer sizing agents can be used. The addition amount of the sizing agent is not particularly limited, but it is preferably 10 seconds or more in terms of Steecht sizing. In addition, a surface sizing agent such as rosin or synthetic resin can also be used for external addition such as a size press.

  In the base paper for wallpaper of the present invention, it is preferable to apply at least a coating layer containing a water-soluble polymer and / or a water-dispersible polymer as a main component on the surface on which the decorative layer is provided in order to increase the surface strength. For example, in the case of vinyl wallpaper, a vinyl chloride paste is applied to the surface of the wallpaper base paper, and after the vinyl chloride paste is cured, it is subjected to a printing process so that the vinyl chloride layer becomes a decorative layer. At this time, when the surface strength of the base paper for wallpaper is low, the fiber on the paper surface becomes fluffed when the decorative layer is applied, and the fluffed part becomes a projection on the surface of the wallpaper after curing, causing printing failure.

  As the water-soluble polymer used in the present invention, various modified starches such as oxidized starch and enzyme-modified starch, polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, casein and the like can be used as appropriate. As the water dispersible polymer, styrene / butadiene copolymer latex, methyl methacrylate / butadiene copolymer latex, acrylic emulsion, vinyl acetate emulsion and the like can be used as appropriate. At this time, the water-soluble polymer and / or the water-dispersed polymer may be used alone, but may be used by mixing with various pigments such as clay, kaolin, calcium carbonate, titanium dioxide and silica.

The coating amount of the water-soluble polymer and / or water-dispersible polymer is preferably 0.2 to 10 g / m ² in terms of solid content. When the coating amount is less than 0.2 g / m ^2, fuzzing increases, and when it is 10 g / m ² or more, the surface of the base paper is completely covered with a polymer, so that an anchor effect is produced between the decorative layer and the base paper layer. descend.

Further, fixing agents, dry paper strength agents, wet paper strength agents, fillers, yield improvers, dyes, pigments, and the like can be used as internal additives as long as the quality is not affected. Furthermore, surface paper strength agents, dyes, pigments and the like can be used as external chemicals to be applied or impregnated with a size press or the like.

  The base paper for wallpaper of the present invention is produced by a known paper machine, but the paper making conditions are not particularly defined. As the paper machine, a long net paper machine, a twin wire paper machine, a circular net paper machine, or the like is used.

The basis weight of the base paper for wallpaper of the present invention is preferably 40 g / m ² or more and 300 g / m ² or less. If the basis weight is less than 40 g / m ² , the strength is low and paper breakage is likely to occur during processing. On the other hand, if the basis weight exceeds 300 g / m ² , it becomes too hard when processed into wallpaper, which makes construction difficult and problematic.

As for the base paper for wallpaper of this invention, it is desirable that the water elongation shown to following formula 1 is 2.5% or less.
(Formula 1)
Elongation in water (%) = {(length after immersion in water for 2 hours) − (length before immersion in water)} / (length before immersion in water) × 100
Specifically, the strip-shaped test piece of wallpaper backing paper was conditioned at 23 ° C. and 50% R / H atmosphere, and the length of the test piece in the horizontal direction of the papermaking, and the test piece in water for 1 hour. The water elongation determined using the length measured immediately after being immersed and taken out is 2.5% or less.

  Using the fiber composite according to the present invention, processed paper (wallpaper base paper) is produced. Examples of the paper machine used for sheet production include a long paper machine, a round paper machine, a gap former, a hybrid former, a multilayer paper machine, and a known paper machine that combines the paper making methods of these devices. Can be mentioned. The press linear pressure in the paper machine and the calendar linear pressure in the case where the calendar process is performed later can be determined within a range that does not hinder the operability and the performance of the composite sheet. In addition, starch, various polymers, pigments, and mixtures thereof may be applied to the formed sheet by impregnation or coating.

  When forming into a sheet, a wet and / or dry paper strength agent (paper strength enhancer) can be added. Thereby, the intensity | strength of a composite sheet can be improved. Examples of paper strength agents include urea formaldehyde resin, melamine formaldehyde resin, polyamide, polyamine, epichlorohydrin resin, vegetable gum, latex, polyethyleneimine, glyoxal, gum, mannogalactan polyethyleneimine, polyacrylamide resin, polyvinylamine. And a resin such as polyvinyl alcohol; a composite polymer or copolymer composed of two or more selected from the above resins; starch and processed starch; carboxymethylcellulose, guar gum, urea resin, and the like. The addition amount of the paper strength agent is not particularly limited.

Moreover, in order to promote the fixing of the filler to the fiber or to improve the yield of the filler or fiber, a high molecular weight polymer or an inorganic substance can be added. For example, polyethyleneimine and modified polyethyleneimines containing tertiary and / or quaternary ammonium groups, polyalkylenimines, dicyandiamide polymers, polyamines, polyamine / epichlorohydrin polymers, and dialkyldiallyl quaternary ammonium monomers, dialkyls as coagulants Cations such as aminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide and polymers of acrylamide and dialkylaminoalkyl methacrylamide, polymers of monoamines and epihalohydrin, polymers with polyvinylamine and vinylamine moieties, and mixtures thereof In addition to the functional polymer, a polymer obtained by copolymerizing an anionic group such as a carboxyl group or a sulfone group in the polymer molecule. Onritchi of zwitterionic polymer, and a mixture of cationic polymer and an anionic or zwitterionic polymers may be used. As a retention agent, a cationic, anionic, or amphoteric polyacrylamide-based material can be used. In addition to these, a retention system called a so-called dual polymer that uses at least one kind of cation or anionic polymer can also be applied, and at least one kind of anionic bentonite, colloidal silica, polysilicic acid, It is a multi-component yield system that uses inorganic fine particles such as polysilicic acid or polysilicate microgels and their modified aluminum products, or one or more organic fine particles having a particle size of 100 μm or less, called so-called micropolymers obtained by crosslinking polymerization of acrylamide. Also good. In particular, when the polyacrylamide material used alone or in combination has a weight average molecular weight of 2 million daltons or more by the intrinsic viscosity method, a good yield can be obtained, preferably 5 million daltons or more, more preferably Can obtain a very high yield in the case of the above-mentioned acrylamide-based material of 10 million daltons or more and less than 30 million daltons. The form of the polyacrylamide-based material may be an emulsion type or a solution type. The specific composition is not particularly limited as long as the substance contains an acrylamide monomer unit as a structural unit. For example, a copolymer of quaternary ammonium salt of acrylate ester and acrylamide, or acrylamide And a quaternized ammonium salt after copolymerization of acrylate and acrylate. The cationic charge density of the cationic polyacrylamide material is not particularly limited.
In addition, according to the purpose, inorganic particles such as drainage improver, internal sizing agent, pH adjuster, antifoaming agent, pitch control agent, slime control agent, bulking agent, calcium carbonate, kaolin, talc, silica (so-called Etc.). The amount of each additive used is not particularly limited.

  It is also possible to use a molding method other than sheeting, for example, a method of pouring raw materials into a mold and drawing it by suction dehydration and drying as called a pulp mold, or spreading and drying on the surface of a molded product such as resin or metal Thereafter, molded articles having various shapes can be obtained by a method of peeling from the substrate. Further, it can be molded into a plastic like by mixing a resin, or can be shaped like a ceramic by adding and firing minerals such as silica and alumina, and can be modeled by a 3D printer. In the blending / drying / molding described above, only one type of composite can be used, or two or more types of composites can be mixed and used. When two or more types of composites are used, those obtained by mixing them in advance can be used, or those obtained by blending, drying and molding each can be mixed later.

  Further, various organic substances such as polymers and various inorganic substances such as pigments may be added to the composite molded article later.

  Hereinafter, although the present invention will be described in more detail with specific experimental examples, the present invention is not limited to the following experimental examples. Unless otherwise specified in the present specification, concentrations and parts are based on weight, and numerical ranges are described as including the end points.

Experiment 1: Synthesis of composite (1) Composite of calcium carbonate particles and cellulose fiber Calcium hydroxide (slaked lime: Ca (OH) ₂ , 300 g) and hardwood bleached kraft pulp (LBKP, Canadian standard freeness CSF: 460 ml) And 30 L of an aqueous suspension containing an average fiber length: 0.8 mm, 300 g). This aqueous suspension is put into a 45 L sealed device, carbon dioxide gas is blown into the reaction vessel to generate cavitation, and a composite of calcium carbonate fine particles and fibers is synthesized by the carbon dioxide method to obtain sample 1. It was. The reaction temperature was about 25 ° C., carbon dioxide was supplied from a commercial liquefied gas, the amount of carbon dioxide blown was 12 L / min, and the reaction was stopped when the pH of the reaction solution reached about 7 (before the reaction). PH is about 12.8).

  In the synthesis of the complex, cavitation bubbles were generated in the reaction vessel by circulating the reaction solution and injecting it into the reaction vessel as shown in FIG. Specifically, the reaction solution is injected at high pressure through a nozzle (nozzle diameter: 1.5 mm) to generate cavitation bubbles, the jet velocity is about 70 m / s, the inlet pressure (upstream pressure) is 7 MPa, The outlet pressure (downstream pressure) was 0.3 MPa.

The composite fiber: inorganic particle weight ratio was 45:55. Here, the weight ratio was calculated based on the ash content of the composite obtained from the ratio between the weight of the remaining ash and the original solid content after the composite was heated at 525 ° C. for about 2 hours (JIS P 8251: 2003).
(2) A composite of magnesium carbonate particles and cellulose fiber An aqueous suspension containing 140 g of magnesium hydroxide (Wako Pure Chemical Industries) and 140 g of hardwood bleached kraft pulp (LBKP, CSF: 460 ml, average fiber length: 0.8 mm) Got ready. 14 L of this aqueous suspension was put into a 45 L volume cavitation apparatus, and carbon dioxide gas was blown into the reaction vessel while circulating the reaction solution, and a composite of magnesium carbonate fine particles and fibers was synthesized by the carbon dioxide gas method. The reaction temperature was about 36 ° C., the carbon dioxide gas was supplied from a commercially available liquefied gas, and the amount of carbon dioxide blown was 4 L / min. When the pH of the reaction solution reaches about 7.8, the introduction of CO ₂ is stopped (the pH before the reaction is about 9.5), and then cavitation is generated and the slurry is circulated in the apparatus for 30 minutes. Sample 2 was obtained.

  The weight ratio of fiber: inorganic particles of the composite was 45:55, which almost coincided with the theoretical value (47:53) calculated from the raw material (pulp / magnesium hydroxide) charge ratio.

(3) Composite of hydrotalcite and pulp fiber In order to synthesize Mg ₆ Al ₂ (OH) 16 CO ₃ .4H ₂ O as hydrotalcite (HT), Na ₂ CO ₃ ( A mixed aqueous solution of MgCl ₂ (Wako Pure Chemical) and AlCl ₃ (Wako Pure Chemical) was prepared as a mixed aqueous solution of Wako Pure Chemical) and NaOH (Wako Pure Chemical) and an acid solution (B solution).
・ Alkaline solution (A solution, Na ₂ CO ₃ concentration: 0.05M, NaOH concentration: 0.8M)
Acid solution (B solution, Mg-based, MgCl ₂ concentration: 0.3M, AlCl ₃ concentration: 0.1M)
Cellulose fibers were used as the fibers to be combined. Specifically, 8 hardwood bleached kraft pulp (LBKP, manufactured by Nippon Paper Industries) and 8 softwood bleached kraft pulp (NBKP, manufactured by Nippon Paper Industries)
: Pulp fibers containing a weight ratio of 2 and having a Canadian standard freeness adjusted to 390 ml using a single disk refiner (SDR) were used (average fiber length 0.8 mm).

Pulp fibers were added to the alkaline solution to prepare an aqueous suspension containing pulp fibers (pulp fiber concentration: 1.56%, pH: about 12.4). This aqueous suspension (pulp solid content 30 g) is put into a 10 L reaction vessel, and while stirring the aqueous suspension, an acid solution (Mg-based) is dropped to form a composite of hydrotalcite fine particles and fibers. Synthesized. Using an apparatus as shown in FIG.
The reaction temperature was 60 ° C., the dropping rate was 15 ml / min, and dropping was stopped when the pH of the reaction solution reached about 7. After completion of the dropping, the reaction solution was stirred for 30 minutes, and washed with 10 times the amount of water to remove the salt, thereby obtaining Sample 3.
The composite fiber: inorganic particle weight ratio was 50:50.
(4) 1% pulp slurry of composite of barium sulfate particles and cellulose fiber (LBKP / NBKP = 8/2, CSF = 390 mL, average fiber length: about 1.3 mm, 1300 g) and barium hydroxide octahydrate (Wako Pure Chemicals, 57 g) was mixed with a three-one motor (1000 rpm), and 2 g / min was added dropwise with an aluminum sulfate (sulfuric acid band, 77 g) peristaltic pump. After completion of the dropping, stirring was continued for 30 minutes to obtain Sample 4.

  The resulting composite slurry had a fiber: inorganic particle weight ratio of 27:73.

<Evaluation of fiber composite>
Each obtained composite sample was washed with ethanol and then observed with an electron microscope (FIGS. 3 to 6). As a result, in each sample, it was observed that the fiber surface was covered with an inorganic substance and self-fixed.

  FIG. 3 is an electron micrograph of Sample 1. It was confirmed that a composite in which calcium carbonate having a primary particle size of 30 to 90 nm covered the pulp fiber surface was generated. In the composite, FIG. 4 is an electron micrograph of Sample 2. It was confirmed that a large number of magnesium carbonate particles were deposited on the fiber surface. Most of the primary particles of magnesium carbonate were scaly, and the primary particle diameter (major axis diameter) was about 0.1 to 3 μm. FIG. 5 is an electron micrograph of Sample 3. The primary particle diameter of the hydrotalcite covering the fiber surface was about 40 to 60 nm. FIG. 6 is an electron micrograph of Sample 4. The barium sulfate fixed to the fiber was plate-like, and the primary particle size was 50 to 1000 nm. The average primary particle size of the inorganic particles in the composite was about 0.08 μm for sample 1, about 1.0 μm for sample 2, about 0.05 μm for sample 3, and 0.8 μm for sample 4.

  Moreover, about the obtained composite_body | complex, the coverage of the fiber surface was measured. The coverage is binarized in an image taken with an electron microscope so that the portion where the inorganic substance is present is (white) and the portion where the fiber is present is (black). The ratio (area ratio) of the portion where sigma exists was calculated and measured. Image processing software (Image J, National Institutes of Health) was used to measure the coverage.

The coverage was about 100% for sample 1, about 100% for sample 2, about 95% for sample 3, and about 100% for sample 4.
[Example 1]
100 ppm of cationic retention agent (ND300, manufactured by Hymo) and 100 ppm of anionic retention agent (FA230, manufactured by Hymo) are added to the composite slurry (about 0.5%) of Sample 1 and stirred at 500 rpm. To prepare a suspension. Based on JIS P 8222, a sheet having a basis weight of 140 to 160 g / m ² was produced from the obtained suspension according to JIS P 8222. The results of evaluating the sheet properties are shown in Tables 1 and 2.

Moreover, the result of having evaluated the powder omission of the obtained sheet | seat is shown in FIG.
<Evaluation method>
-Basis weight: JIS P 8124: 1998
・ Thickness: JIS P 8118: 1998
-Density: Calculated from measured values of thickness and basis weight-Ash content: JIS P 8251: 2003
Whiteness: JIS P 8212: 1998
・ Opacity: JIS P 8149: 2000
-Water elongation and shrinkage: The test piece was conditioned at 23 ° C and 50% R / H atmosphere, and the length of the test piece in the horizontal direction of the papermaking was measured. Thereafter, it was immersed in pure water for 2 hours and then taken out, and the length in the horizontal direction of the papermaking was immediately measured. Next, the test piece was air-dried in an atmosphere of 23 ° C. and 50% R / H, and the length in the papermaking lateral direction was measured. The water elongation and drying shrinkage ratio were calculated by the following formula.

Water elongation (%) = {(length after 1 hour immersion in water) − (length before water immersion)} / (length before water immersion) × 100
Shrinkage (%) = {(length before water immersion) − (length after water immersion / air drying)} / (length before water immersion) × 100

・ Powder falling: Each test piece is strip-shaped and arranged on a piece of Rash paper. Only the upper part is fixed and sandwiched in a clear file. After bending and stretching the clear file with a certain force, Powder fall was visually evaluated.
○: Almost no powder fall off ×: Powder fall off is seen, and the whole Rasha paper is slightly powdery

Deodorization evaluation: Based on the method of SEK mark textile product certification standard (JEC301, Fiber Evaluation Technology Council), deodorization characteristics (reduction rate,%) against ammonia under wet conditions were evaluated. A test piece (size: 100 cm 2) was conditioned at 20 ° C. and 65% RH for 24 hours or more, then about 1 ml of water was pipetted, and the ammonia concentration was measured by a detector tube method.
Decrease rate (%) = (1-concentration at the time of measurement / initial concentration) × 100

[Example 2]
A sheet was produced in the same manner as in Example 1 except that the composite slurry of Sample 2 was used. The results are shown in Tables 1 and 2.

[Example 3]
A sheet was produced in the same manner as in Example 1 except that the composite slurry of Sample 3 was used. The results are shown in Tables 1 and 2.

[Example 4]
A sheet was produced in the same manner as in Example 1 except that the composite slurry of Sample 4 was used. The results are shown in Tables 1 and 2.

[Comparative Example 1]
A sheet was produced in the same manner as in Example 1 except that pulp slurry (LBKP / NBKP = 80/20, CSF: 390 ml, average fiber length: 1.3 mm) was used instead of the fiber composite. The results are shown in Tables 1 and 2.

[Comparative Example 2]
Rosetta-type light calcium carbonate (manufactured by Specialty Minerals Inc., trade name: Albuquerque LO) and pulp slurry (LBKP / NBKP = 8/2, CSF: 390 ml, average fiber length: 1.3 mm) instead of the fiber composite A sheet was produced in the same manner as in Example 1 except that the one added so that the weight ratio was 50:50 was used. The results are shown in Tables 1 and 2.

  Moreover, the result of having evaluated the powder omission of the obtained sheet | seat is shown in FIG.

  As shown in Table 2, the sheet containing the fiber composite of cellulose fibers and inorganic particles of Examples 1 to 4 has whiteness, opacity, and dimensional stability as compared with the sheet of Comparative Example 1. It was good. Moreover, since the sheet | seat containing the fiber composite_body | complex of the cellulose fiber of Examples 1-4 and an inorganic particle has high ash compared with the sheet | seat of the comparative example 1, it is thought that a combustion calorie is low, and a flame retardance. It can be said that it has sex. Furthermore, the sheet containing the fiber composite of cellulose fibers and inorganic particles of Example 3 had a deodorizing effect as compared with the sheet of Comparative Example 1. Therefore, it is considered that various functions can be imparted (deodorant, antibacterial, radiation shielding, etc.) without processing by changing the type of inorganic particles.

  Moreover, as FIG.7, 8 shows, while the sheet | seat of Example 1 (sheet | seat containing the fiber composite of a magnesium carbonate particle and a cellulose fiber) has few powder falling, the sheet | seat of Comparative Example 2 (calcium carbonate particle) And the sheet containing cellulose fibers) had a lot of powder falling. Therefore, it can be seen that the inclusion of the fiber composite causes little powder falling even when the inorganic particles are highly blended, and is excellent in post-processing suitability.

Claims (9)

A processed paper containing a fiber composite of cellulose fibers and inorganic particles. The processed paper according to claim 1, wherein the processed paper is release paper, moisture-proof packaging, glass paper, or base paper for wallpaper. The processed paper of Claim 2 whose water elongation shown to following formula 1 is 2.5% or less.
(Formula 1)
Elongation in water (%) = {(length after immersion in water for 2 hours) − (length before immersion in water)} / (length before immersion in water) × 100 The processed paper according to any one of claims 1 to 3, wherein a fiber composite of the cellulose fibers and inorganic particles is coated with inorganic particles at 15% or more of the surface of the cellulose fibers.   The processed paper in any one of Claims 1-4 whose weight ratio of a cellulose fiber and an inorganic particle is 5 / 95-95 / 5.   The processed paper according to any one of claims 1 to 5, wherein at least a part of the inorganic particles are metal particles containing calcium, silicic acid, magnesium, barium or aluminum metal salt, or titanium, copper, or zinc.   The processed paper according to any one of claims 1 to 6, wherein the cellulose fibers are cellulose fibers derived from wood.   The processed paper in any one of Claims 1-7 whose said cellulose fiber is a pulp fiber derived from wood. A method for producing the processed paper according to any one of claims 1 to 8,
A step of synthesizing inorganic particles in a solution in the presence of fibers, a fiber composite of cellulose fibers and inorganic particles;
Producing a processed paper containing a fiber composite of the cellulose fibers and inorganic particles,
Including the above method.

Images