WO2017043585A1 - リン酸カルシウム微粒子と繊維との複合体、および、その製造方法 - Google Patents
リン酸カルシウム微粒子と繊維との複合体、および、その製造方法 Download PDFInfo
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- WO2017043585A1 WO2017043585A1 PCT/JP2016/076476 JP2016076476W WO2017043585A1 WO 2017043585 A1 WO2017043585 A1 WO 2017043585A1 JP 2016076476 W JP2016076476 W JP 2016076476W WO 2017043585 A1 WO2017043585 A1 WO 2017043585A1
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- composite
- fibers
- calcium carbonate
- calcium phosphate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Definitions
- the present invention relates to a composite of calcium phosphate fine particles and fibers and a method for producing the same.
- the present invention relates to a composite in which calcium phosphate fine particles having an average primary particle diameter of 5 ⁇ m or less are attached to the fiber surface and a method for producing the same.
- calcium carbonate is produced by physically pulverizing and classifying natural limestone and weathered shells as raw materials, and "synthetic calcium carbonate" produced by chemically reacting limestone as a raw material ( Light calcium carbonate).
- synthetic calcium carbonate As a synthetic method of synthetic calcium carbonate, a carbon dioxide gas method, a lime / soda method, and a soda method are known. Although the lime / soda method and the soda method are partially used for special purposes, they are industrially used. The synthesis of calcium carbonate is generally performed by the carbon dioxide method.
- the synthesis of calcium carbonate by the carbon dioxide method is carried out by reacting quick lime and carbon dioxide, and generally, a dehydration step of adding water to quick lime CaO to obtain slaked lime Ca (OH) 2 , and carbon dioxide CO 2 into the slaked lime. And carbonation step of obtaining calcium carbonate CaCO 3 by blowing 2 .
- carbonation step of obtaining calcium carbonate CaCO 3 by blowing 2 Today, various techniques for controlling the particle shape and particle diameter of the product calcium carbonate by controlling the reaction conditions of the calcium carbonate synthesis process, particularly the carbonation process, have been proposed.
- Patent Document 1 describes a composite in which crystalline calcium carbonate is mechanically bonded onto a fiber.
- 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.
- 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 taken in by depositing calcium carbonate in a step of forming a fiber web (wet paper).
- calcium phosphate is known as an inorganic salt of calcium.
- Calcium phosphate is a salt made of calcium ion and phosphate ion or diphosphate ion, and about 70% of bone is made of hydroxyapatite, which is a kind of calcium phosphate.
- Calcium phosphate is also used in the manufacture of fertilizers and foods such as cheese as food additives.
- calcium phosphate is widely used as a toothpaste and supplement to promote remineralization of teeth. Since this calcium phosphate has a high adsorption function, it can be used as a functional base material such as a filter if it can be combined with fibers.
- Patent Document 6 discloses that a cellulose fiber is preliminarily esterified under a high temperature condition of 100 ° C. or higher, and is then added to a solution containing calcium ions for about 10 days. A technique of immersing in a solution containing acid ions or the like for about 10 days is disclosed.
- Titanium is widely used as a substance having photocatalytic activity.
- problems such as poor yield when trying to add it internally to paper, and pulp fibers being decomposed by the catalytic ability of titanium when exposed to light for a long time.
- Patent Document 7 discloses that calcium carbonate and titanium previously aggregated with a polymer are used as a filler.
- Patent Document 8 discloses a method of adding titanium when synthesizing calcium carbonate to synthesize a composite of calcium carbonate and titanium.
- An object of the present invention is to provide a composite of calcium phosphate fine particles and fibers and an efficient production technique thereof. Furthermore, it is providing the composite which made the composite carry
- calcium phosphate is widely used for various applications, but it is expected that unique properties are produced by complexing it with fibers.
- inorganic particles such as calcium phosphate
- the present inventor has found that a complex of calcium phosphate and fiber can be obtained by reacting phosphoric acid and a calcium source in the presence of the fiber.
- a complex of calcium phosphate and fiber can be obtained efficiently, and have completed the present invention.
- a composite of calcium carbonate and fiber having a particularly small primary particle diameter can be efficiently produced by synthesizing calcium carbonate in the presence of cavitation bubbles.
- a calcium phosphate / fiber composite In the composite obtained by the present invention, the shape of the calcium phosphate fine particles adhering to the fiber is extremely uniform, and it is possible to impart unique characteristics to the fiber. Furthermore, since it adheres to the fiber, it can be dehydrated and dried to make it easy to handle.
- the present invention includes, but is not limited to, the following inventions.
- the method according to (7) comprising the step of: (9) The method according to (8), wherein calcium carbonate is synthesized in a solution containing fibers in the presence of cavitation bubbles.
- a calcium phosphate / fiber composite having an average primary particle diameter of 5 ⁇ m or less can be efficiently produced.
- the particle diameter of inorganic fine particles fixed on the fibers can be reduced.
- titanium such as titanium dioxide can be fixed to the composite by allowing titanium to be present when calcium carbonate and phosphoric acid are reacted.
- the present invention it is possible to obtain a calcium phosphate / fiber composite having a high yield on a product (article) and a high adsorption and deodorizing effect. Moreover, when the composite obtained by the present invention is made into a sheet, a high ash content sheet can be easily obtained.
- a complex firmly supported on the fiber could be obtained by combining calcium ions adsorbed on the fiber surface and penetrating into the fiber with carbon dioxide gas.
- An excellent quality calcium phosphate / fiber composite can be obtained by manufacturing a calcium phosphate / fiber composite from such a calcium carbonate / fiber composite.
- FIG. 1 is a schematic view showing a reaction apparatus used in an example of the present invention.
- FIG. 2 is an electron micrograph of the calcium carbonate / fiber composite (sample A) obtained in Experiment 1 (magnification: 2000 times).
- FIG. 3 is an electron micrograph of the calcium phosphate / fiber composite (sample 1) synthesized in Experiment 2 (magnification: left 3000 times, right 50000 times).
- FIG. 4 is an electron micrograph of the calcium phosphate / fiber composite (sample 2) synthesized in Experiment 2 (magnification: left 10,000 times, right 50000 times).
- FIG. 2 is an electron micrograph of the calcium carbonate / fiber composite (sample A) obtained in Experiment 1 (magnification: 2000 times).
- FIG. 3 is an electron micrograph of the calcium phosphate / fiber composite (sample 1) synthesized in Experiment 2 (magnification: left 3000 times, right 50000 times).
- FIG. 4 is an electron micrograph of
- FIG. 5 is an electron micrograph of the calcium phosphate / fiber composite (sample 3) synthesized in Experiment 2 (magnification: left 10,000 times, right 50000 times).
- FIG. 6 is an electron micrograph of the calcium phosphate / fiber composite (sample 4) synthesized in Experiment 2 (magnification: left 10,000 times, right 50000 times).
- FIG. 7 is an analysis result of sheet # 1 of Experiment 3 (with a retention agent) (magnification 3000 times, right: electron micrograph, left: element mapping image).
- FIG. 8 shows the analysis result of sheet # 2-1 (with a retention agent) of Experiment 3 (magnification 3000 times, right: electron micrograph, left: element mapping image).
- FIG. 9 shows the analysis result of sheet # 2-2 (no retention agent) in Experiment 3 (magnification 3000 times, right: electron micrograph, left: element mapping image).
- FIG. 10 shows the analysis result of sheet # 3 of Experiment 3 (with a retention agent) (magnification 3000 times, right: electron micrograph, left: element mapping image).
- FIG. 11 is an analysis result of sheet # 4-1 (with a retention agent) of Experiment 3 (magnification 3000 times, right: electron micrograph, left: element mapping image).
- FIG. 12 shows the analysis results of sheet # 4-2 (no retention agent) in Experiment 3 (magnification 3000 times, right: electron micrograph, left: element mapping image).
- the present invention relates to a calcium phosphate / fiber composite having an average primary particle diameter of 5 ⁇ m or less and a method for producing the same.
- the calcium phosphate / fiber composite of the present invention can be obtained, for example, by reacting the calcium carbonate / fiber composite with phosphoric acid.
- a composite of calcium phosphate and fiber can be synthesized by reacting the fiber, phosphoric acid, and calcium source.
- the complex which is a reaction product is obtained as a suspension, so that it can be stored in a storage tank or concentrated, dehydrated, pulverized, classified, aged, dispersed, etc. as necessary. Processing can be performed. These can be performed by known processes, and may be appropriately determined in consideration of the application and energy efficiency.
- the concentration / dehydration treatment is performed using a centrifugal dehydrator, a sedimentation concentrator, or the like.
- the centrifugal dehydrator include a decanter and a screw decanter.
- the type is not particularly limited and a general one can be used.
- 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.
- a vacuum drum dehydrator such as an Oliver filter.
- 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 into a filler or pigment in a suspension state without being completely dehydrated, but can also be dried to form a powder.
- a drying for example, an airflow dryer, a band dryer, a spray dryer etc. can be used conveniently.
- the present invention relates to a composite of calcium phosphate and fiber, but in a preferred embodiment, 15% or more of the fiber surface is coated with calcium phosphate.
- the composite of the present invention has a fiber coverage (area ratio) of 25% or more by calcium phosphate, more preferably 40% or more, but according to the present invention, the coverage is 60% or more and 80%. It is also possible to produce more than% composite.
- Calcium phosphate obtained by the present invention has a feature that the particle diameter is smaller than that obtained by a general method using calcium carbonate and phosphoric acid as raw materials.
- the particle diameter of calcium phosphate obtained by a normal method is basically 10 ⁇ m or more, and the particle diameter of calcium phosphate according to Comparative Example 2 described in JP-A-2016-69243 is about 8 ⁇ m.
- the reason why the particle size is smaller than that of the normal method is that the particle size of calcium carbonate used as a raw material is small, and the reaction is performed in the presence of fibers, so that a large share is considered.
- One of the effects of obtaining calcium phosphate with a small particle size is that the specific surface area of the product is increased.
- the specific surface area is increased, the adsorbing ability is also improved, so that it is preferable when used for adsorbents and deodorants.
- the smaller the particle size the easier the calcium phosphate is fixed by the fiber.
- calcium phosphate and fiber are complexed according to the present invention, calcium phosphate is easy to yield in the product compared to the case where calcium phosphate is simply mixed with the fiber, and a product in which the calcium phosphate is uniformly dispersed without aggregation can be obtained. .
- the complex obtained by the present invention can be modified by a known method.
- the surface can be hydrophobized to improve miscibility with a resin or the like.
- the calcium phosphate / fiber composite of the present invention may contain titanium. Titanium such as titanium dioxide is known to have various activities such as photocatalytic activity, and composite particles having various activities can be obtained by fixing such titanium to the composite.
- a heterogeneous material such as titanium can be incorporated into the composite by the presence of titanium when phosphoric acid and calcium carbonate are reacted.
- a molded article body
- a high ash content sheet can be easily obtained.
- the paper machine (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. It is done.
- 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.
- starch, various polymers, pigments, and mixtures thereof may be applied to the formed sheet by impregnation or coating.
- paper strength enhancer When forming into a sheet, a wet and / or dry paper strength agent (paper strength enhancer) can be added. Thereby, the intensity
- 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.
- 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.
- a polymer or an inorganic substance can be added to promote the fixing of the filler to the fiber or improve the yield of the filler or fiber.
- 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
- a polymer obtained by copolymerizing an anionic group such as a carboxyl group or a sulf
- Onritchi of zwitterionic polymer and a mixture of cationic polymer and an anionic or zwitterionic polymers may be used.
- a retention agent a cationic, anionic, or amphoteric polyacrylamide-based material can be used.
- 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 using one or more inorganic fine particles such as polysilicic acid or polysilicate microgel and modified aluminum thereof, or organic fine particles having a particle size of 100 ⁇ m or less, which is called a micropolymer obtained by crosslinking polymerization of acrylamide. Also good.
- 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.
- a copolymer of quaternary ammonium salt of acrylate ester and acrylamide, or acrylamide And a quaternized ammonium salt after copolymerization of acrylate and acrylate 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.
- 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.
- 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 it can be shaped like a ceramic by adding a mineral such as silica or alumina and firing.
- 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 it can be shaped like a ceramic by adding a mineral such as silica or alumina and
- the average primary particle diameter of the calcium phosphate constituting the composite according to the present invention is 5 ⁇ m or less, but the average primary particle diameter may be 1 ⁇ m or less or 200 nm or less.
- Calcium carbonate / fiber composite As described above, the calcium phosphate / fiber composite of the present invention can be produced, for example, by reacting calcium carbonate / fiber composite with phosphoric acid.
- the calcium carbonate / fiber composite can be efficiently produced by synthesizing calcium carbonate in a solution containing fibers.
- a composite of calcium carbonate and fiber having a small average particle diameter can be efficiently produced by synthesizing calcium carbonate in the presence of cavitation bubbles.
- the average primary particle size of the calcium carbonate fine particles constituting the composite is less than 5 ⁇ m, but the average primary particle size is 1 ⁇ m or less or 500 nm or less, and the average primary particle size is 200 nm or less or 100 nm or less.
- the average primary particle diameter of the calcium carbonate fine particles can be 10 nm or more.
- calcium carbonate may take the form of secondary particles in which fine primary particles are aggregated, and secondary particles can be generated according to the application by an aging process, and aggregates can be formed by pulverization. You can also make it 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
- 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, filter materials, flame retardant materials, sanitary products (disposable diapers, sanitary napkins, incontinence pads, breast milk pads, etc.), etc.
- Building materials asphalt, asbestos, cement, board, concrete, brick, tile, plywood
- adsorbents impurity removal, deodorization, dehumidification, etc.
- filter materials e.g., kaolin, kaolin, etc.
- sanitary products e.g., diapers, sanitary napkins, incontinence pads, breast milk pads
- 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.
- particles generally called inorganic fillers and organic fillers and various fibers can be used in combination.
- 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.
- 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.
- 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.
- 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 kraft method, sulfite method, soda method, polysulfide method, etc .; 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).
- non-wood-derived pulp examples 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.
- 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 and shape of calcium phosphate constituting the composite of the present invention can be confirmed by observation with an electron microscope. Furthermore, fine particles having various sizes and shapes can be complexed with fibers by adjusting the conditions for synthesizing calcium carbonate and calcium phosphate.
- Cavitation bubbles In the method for producing a composite according to the present invention, in one embodiment, calcium carbonate and / or calcium phosphate can be synthesized in the presence of cavitation bubbles.
- 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.
- the reaction may be performed under conditions where cavitation bubbles are present in the reaction vessel, or the reaction may be performed under conditions that do not cause cavitation bubbles.
- the reaction vessel is preferably a pressure vessel that can maintain a sealed state, but there is no problem even if an open reaction vessel is used.
- 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 can be generated in the reaction vessel by a known method.
- 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).
- cavitation bubbles since the generation and control of cavitation bubbles are easy, it is preferable to generate cavitation bubbles by jetting a fluid at a high pressure.
- a fluid jet 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.
- controlled cavitation bubbles are present when synthesizing calcium carbonate and / or calcium phosphate, and are clearly different from cavitation bubbles that cause uncontrollable harm that naturally occurs in fluid machinery.
- cavitation can be generated by using a reaction solution such as a raw material as a jet liquid as it is, or cavitation bubbles can be generated by jetting 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.
- 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 fluid in which solid particles or gas are dispersed or mixed in the liquid or liquid, and refers to a liquid jet containing slurry or bubbles of pulp or inorganic particles.
- the gas referred to here may include bubbles due to cavitation.
- the cavitation number (Cavitation Number) ⁇ is defined as the following formula 1 (Yoji Kato's new edition of cavitation, basics and recent advances, 1999).
- the cavitation number ⁇ 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.
- the pressure difference between p1, p2, and pv is large and p1 >> p2 >> pv. Therefore, the cavitation number ⁇ 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 ⁇ 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 ⁇ 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.
- the pressure of the injection liquid 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.
- 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.
- the pressure in the container is preferably 0.005 MPa to 0.9 MPa in static pressure.
- the ratio between the pressure in the container and the pressure of the jet liquid is preferably in the range of 0.001 to 0.5.
- 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.
- the jet velocity is less than 1 m / sec, the effect is weak because the pressure drop is low and cavitation hardly occurs.
- 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.
- the cavitation generation place in the present invention may be generated in a reaction vessel for synthesizing calcium carbonate and / or calcium phosphate. 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.
- the solid content concentration of the aqueous suspension of slaked lime that is 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.
- 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.
- 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.
- the flow velocity of the jetting liquid is increased, and accordingly, the pressure is lowered and more powerful cavitation can be generated.
- 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.
- 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.
- 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.
- the energy required to generate cavitation can be reduced by adding a surfactant.
- a surfactant 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.
- a method for synthesizing calcium carbonate can be performed by a known method.
- calcium carbonate can be synthesized by a carbon dioxide method, a soluble salt reaction method, a lime / soda method, a soda method, or the like.
- calcium carbonate is synthesized by a carbon dioxide method.
- lime is used as a calcium source
- water is added to quick lime CaO to obtain slaked lime Ca (OH) 2
- 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 .
- 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.
- slaked lime may be directly used as a calcium source.
- carbonation may be carried out by introducing carbon dioxide into the reaction system.
- 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.
- carbonation reactor 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.
- slaked lime suspension limestone
- 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.
- 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.
- 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.
- jet cavitation sufficient stirring can be performed without a mechanical stirrer such as a blade.
- 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.
- 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 still more 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 a preferred embodiment of 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) with a high solid content concentration is used. .
- 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.
- concentration of CaO can be 0.1 wt% or more, preferably 1 wt% or more, and the temperature can be 20 to 100 ° C., preferably 30 to 100 ° C. .
- 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 2 hours or less.
- the slaker may be batch or continuous.
- 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.
- water is used for the preparation of the suspension.
- 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.
- the reaction liquid in the carbonation reaction tank can be circulated and used as a liquid containing calcium hydroxide.
- the reaction efficiency is increased and it is easy to obtain the desired calcium carbonate.
- a gas containing carbon dioxide (carbon dioxide gas) is blown into the reaction vessel and mixed with the reaction solution.
- carbon dioxide gas can be supplied to the reaction solution without a gas supply device such as a fan or a blower.
- a gas supply device such as a fan or a blower.
- carbonation can be efficiently performed because carbon dioxide is refined by the cavitation bubbles.
- the carbon dioxide concentration of the gas containing carbon dioxide is not particularly limited, but a higher carbon dioxide concentration is preferable.
- the amount of carbon dioxide introduced into the reaction vessel is not limited and can be selected as appropriate. For example, it is preferable to use carbon dioxide at a flow rate of 100 to 10,000 L / 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 gas.
- a gas containing an inert gas such as air or nitrogen can be used as a gas containing carbon dioxide.
- 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.
- a carbonation reaction can also be performed using carbon dioxide generated from the lime baking step.
- auxiliary agents can be added.
- chelating agents can be added to the carbonation reaction, specifically, polyhydroxycarboxylic acids such as citric acid, malic acid and tartaric acid, dicarboxylic acids such as oxalic acid, sugar acids such as gluconic acid, Aminopolycarboxylic acids such as acetic acid and ethylenediaminetetraacetic 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, acetoacetic acid Examples thereof include ketones such as methyl and allyl acetoacetate, saccharides such as sucrose, and polyols such as sorbitol.
- 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
- a dispersing agent can also be used as needed.
- 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 carbonation reaction.
- Such additives can be added in an amount of preferably 0.001 to 20%, more preferably 0.1 to 10% with respect to slaked lime.
- Fibers constituting the composite are not particularly limited.
- natural fibers such as cellulose, synthetic fibers that are artificially synthesized from raw materials such as petroleum, and regenerated fibers such as rayon and lyocell (semi-synthetic fibers)
- inorganic fibers can be used without limitation.
- 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 materials include red pine, black pine, todomatsu, spruce, beech pine, larch, fir, tsuga, cedar, hinoki, larch, syrup, spruce, hiba, douglas fir, hemlock, white fur, spruce, balsam fur, cedar, pine, Coniferous trees such as Merck pine, Radiata pine, and mixed materials thereof, beech, hippopotamus, alder tree, oak, tab, shii, birch, broadleaf tree, poplar, tamo, dry willow, eucalyptus, mangrove, lawan, acacia, etc. Examples are materials.
- Wood pulp can be classified by pulping method, for example, chemical pulp digested by kraft method, sulfite method, soda method, polysulfide method, etc .; 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).
- non-wood-derived pulp examples include cotton, hemp, sisal hemp, manila hemp, flax, straw, bamboo, bagasse, kenaf, sugar cane, corn, rice straw, cocoon, honey and others.
- 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 calcium carbonate fixation can be expected.
- Synthetic fibers include polyester, polyamide, polyolefin, acrylic fiber, semi-spun fibers include rayon and acetate, and inorganic fibers include glass fiber, carbon fiber, various metal fibers, and the like.
- these cellulose raw materials are further processed to give powdery cellulose, chemically modified cellulose such as oxidized cellulose, and cellulose nanofiber: CNF (microfibrillated cellulose: MFC, TEMPO oxidized CNF, phosphate esterified CNF, carboxymethylated). CNF, machine pulverized CNF, etc.) can also be used.
- CNF microfibrillated cellulose: MFC, TEMPO oxidized CNF, phosphate esterified CNF, carboxymethylated
- CNF machine pulverized CNF, etc.
- the powdered cellulose used in the present invention for example, a fixed particle size in the form of a rod shaft produced by a method of purifying and drying an undegraded residue obtained after acid hydrolysis of a selected pulp, pulverizing and sieving.
- a crystalline cellulose powder having a distribution may be used, or commercially available products such as KC Flock (manufactured by Nippon Paper Industries), Theolas (manufactured by Asahi Kasei Chemicals), and Avicel (manufactured by FMC) may be used.
- the degree of polymerization of cellulose in the powdered cellulose is preferably about 100 to 1500
- the degree of crystallinity of the powdered cellulose by X-ray diffraction is preferably 70 to 90%
- the volume average particle size by a laser diffraction type particle size distribution analyzer Is preferably 1 ⁇ m or more and 100 ⁇ m 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.
- a method of defibrating the cellulose raw material is used.
- 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 nanofibers can be confirmed by observation with an electron microscope or the like, 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.
- an arbitrary compound may be further added and reacted with the cellulose nanofiber to modify the hydroxyl group. it can.
- 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.
- 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.
- sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate and sodium polyphosphate which are sodium salts of phosphoric acid are mentioned.
- potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate which are potassium salts of phosphoric acid are mentioned.
- ammonium dihydrogen phosphate diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate which are ammonium salts of phosphoric acid are included.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- these functional groups can be removed after defibrating and / or pulverization to return to the original hydroxyl group.
- 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.
- the fibers constituting the composite of the present invention are pulp fibers.
- 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.
- a substance that is not directly involved in the carbonation reaction but is taken into the product calcium carbonate to form composite particles can be used.
- fibers such as pulp fibers are used, but these substances are further incorporated by synthesizing calcium carbonate in a solution containing inorganic particles, organic particles, polymers and the like. Composite particles can be produced.
- the conditions for the carbonation reaction are not particularly limited, and can be appropriately set according to the application.
- the temperature of the carbonation reaction can be 0 to 90 ° C., and preferably 10 to 70 ° C.
- the reaction temperature can control the temperature of the reaction solution with a temperature control device. If the temperature is low, the reaction efficiency decreases and the cost increases. On the other hand, if the temperature exceeds 90 ° C., coarse calcium carbonate particles tend to increase. .
- the carbonation reaction can be a batch reaction or a continuous reaction. In general, it is preferable to perform a batch reaction step because of the convenience of discharging the residue after the carbonation 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.
- the carbonation reaction can be controlled by monitoring the pH of the reaction suspension and reaches, for example, below pH 9, preferably below pH 8, more preferably around pH 7, depending on the pH profile of the reaction solution. Carbonation reaction can be carried out until
- the carbonation reaction can be controlled by monitoring the conductivity of the reaction solution. It is preferable to carry out the carbonation reaction until the conductivity decreases to 1 mS / cm or less.
- the carbonation reaction can be controlled by the reaction time, and specifically, it can be controlled by adjusting the time during which the reactant stays in the reaction tank.
- reaction can also be controlled by stirring the reaction liquid of a carbonation reaction tank, or making carbonation reaction multistage reaction.
- the reaction temperature of the system As the phosphorylation reaction conditions in the present invention, the reaction temperature of the system, the addition time of phosphoric acid, the addition rate of phosphoric acid, the agitation conditions, the agitation time after mixing (aging), the concentration of the reaction system, etc. are changed.
- the reaction temperature is preferably 20 to 80 ° C, more preferably 30 to 60 ° C.
- phosphoric acid As the charging time of phosphoric acid, it is generally preferable to add phosphoric acid to a water slurry of calcium carbonate, but in this case, a method of charging over 10 to 60 minutes or more is preferable instead of adding phosphoric acid all at once. .
- the particles When charged at once, the particles tend to agglomerate and the pores become distorted. For example, it can be added at a rate of 0.01 to 5000 g / min, depending on the scale of the reaction and the concentration of the raw material used.
- the addition rate of phosphoric acid is preferably 10 to 100%, more preferably 20 to 60%, based on the solid content of calcium carbonate.
- stirring conditions it is desirable to stir with a strong stirring force of a certain level or more. If the stirring force is weak, there is a tendency that a uniform pore state cannot be formed in the entire particle. For example, stirring can be performed at 100 to 5000 rpm.
- the concentration of calcium carbonate suspension is preferably 10% by mass or less, and more preferably 5% by mass in consideration of the production efficiency of calcium carbonate.
- the concentration of phosphoric acid and / or water-soluble phosphate is preferably 40 to 60% by mass.
- Water-soluble phosphates used include sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, triammonium phosphate, dihydrogen phosphate Examples include ammonium and ammonium dihydrogen phosphate.
- the calcium phosphate obtained by the present invention is characterized in that the particle size is smaller than that obtained by a general method using calcium carbonate and phosphoric acid as raw materials, and the primary particle size is 5 ⁇ m or less, preferably 2.5 ⁇ m or less, and may be 1 ⁇ m or less.
- Experiment 1 Synthesis of a composite of calcium carbonate fine particles and pulp fiber Including calcium hydroxide (slaked lime: Ca (OH) 2 , 1250 g) and hardwood bleached kraft pulp (LBKP, Canadian standard freeness CSF: 460 mL, 1250 g) 100 L of an aqueous suspension was prepared. This aqueous suspension was put into a 500-liter cavitation apparatus, carbon dioxide gas was blown into the reaction vessel, and a composite of calcium carbonate fine particles and fibers was synthesized by the carbon dioxide gas method.
- calcium hydroxide slaked lime: Ca (OH) 2 , 1250 g
- LKP hardwood bleached kraft pulp
- 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
- the reaction was stopped when the pH of the reaction solution reached about 7 (before the reaction). PH is about 12.8).
- 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.
- Example A When the obtained product (sample A) was observed with an electron microscope, it was confirmed that a composite in which calcium carbonate having a primary particle size of 60 to 90 nm covered the pulp fiber surface was formed (FIG. 2). . In the composite, it was observed that calcium carbonate was self-fixed on the pulp fiber. As a result of measuring ash, it was 56%. Here, the ash content of the composite was calculated 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 P8251: 2003).
- Sample 1 (FIG. 3): Phosphoric acid (manufactured by Tosoh Corporation, concentration 10%, 57 g) was added to sample A (595 mL, concentration 4.2%) And stirred to obtain a composite of calcium phosphate and pulp. Specifically, sample A was stirred at 850 rpm with a three-one motor in a water bath at 40 ° C., and phosphoric acid was added thereto at a rate of 0.5 g / min with a peristaltic pump. Aging was carried out with stirring for 30 minutes.
- Sample 2 (FIG. 3): Phosphoric acid (manufactured by Tosoh Corporation, concentration 10%, 57 g) was added to sample A (595 mL, concentration 4.2%) And stirred to obtain a composite of calcium phosphate and pulp. Specifically, sample A was stirred at 850 rpm with a three-one motor in a water bath at 40 ° C., and phosphoric acid was added thereto at a rate
- Sample A (595 mL, concentration 4.2%) was mixed with titanium dioxide (manufactured by Sakai Chemical Industry Co., Ltd., SSP-25, 1.4 g) and phosphoric acid (manufactured by Tosoh Corporation, concentration 10). %, 57 g) was added and stirred to obtain a composite of calcium phosphate and pulp incorporating titanium. The reaction was performed in the same manner as Sample 1 except that titanium dioxide was added to Sample A in advance.
- Sample 3 (FIG. 5): A complex was synthesized in the same manner as (1) except that the concentration of phosphoric acid was 60% and the addition amount of phosphoric acid was 9.5 g.
- Sample 4 (FIG. 6): A complex was synthesized in the same manner as in (2) above except that the concentration of phosphoric acid was 60% and the addition amount of phosphoric acid was 9.5 g.
- Experiment 3 Manufacture and evaluation of composite sheet ⁇ Manufacture of composite sheet>
- the composites prepared in Experiment 1 and Experiment 2 (Sample A, Samples 1 to 4) were formed into sheets (basis weight: about 60 g / m 2 ) by the following procedure.
- a retention agent 100 ppm of a cationic retention agent (ND300, manufactured by Hymo) and 100 ppm of an anionic retention agent (FA230, manufactured by Hymo) are added, and the suspension is stirred at 500 rpm. Was prepared. Based on JIS P 8222, a composite sheet having a basis weight of about 60 g / m 2 was produced from the obtained suspension. When no retention agent was added, composite sheets having a basis weight of about 60 g / m 2 were produced using the composite slurry (sheets # 2-2 and # 4-2).
- Table 2 shows the results of evaluating the physical properties of the obtained sheet measured by the following method. Compared with the fine particle light calcium carbonate composite sheet (# 5) before conversion to phosphoric acid, the calcium phosphate composite sheet had improved opacity. In addition, the calcium phosphate composite sheet was bulky and high in bending stiffness. -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 Specific scattering coefficient: Calculated by the formula defined in TAPPI T425 (ISO 9416).
Abstract
Description
(1) 平均一次粒子径が5μm以下のリン酸カルシウム粒子と繊維との複合体。
(2) リン酸カルシウム粒子の平均一次粒子径が1μm以下である、(1)に記載の複合体。
(3) 前記繊維がパルプ繊維である、(1)または(2)に記載の複合体。
(4) 前記リン酸カルシウム粒子と前記繊維との重量比が5:95~95:5である、(1)~(3)のいずれかに記載の複合体。
(5) さらにチタンが定着している、(1)~(4)のいずれかに記載の複合体。
(6) (1)~(5)のいずれかに記載の複合体を含んでなるシート。
(7) 繊維を含む溶液においてカルシウム源とリン酸源を反応させることによって、平均一次粒子径が5μm以下のリン酸カルシウム粒子と繊維との複合体を製造する方法。
(8) 繊維を含む溶液において炭酸カルシウムを合成して、平均一次粒子径が5μm未満の炭酸カルシウム粒子と繊維との複合体を得る工程;この複合体とリン酸を反応させてリン酸カルシウムと繊維との複合体を得る工程;を含む、(7)に記載の方法。
(9) キャビテーション気泡の存在下で、繊維を含む溶液において炭酸カルシウムを合成する、(8)に記載の方法。
(10) 炭酸カルシウム粒子の平均一次粒子径が1μm以下である、(8)または(9)に記載の方法。
(11) キャビテーション気泡の存在下で、消石灰の水性懸濁液と二酸化炭素を含む気体とを反応させて炭酸カルシウムを合成する、(8)~(10)のいずれかに記載の方法。
(12) 反応容器内に液体を噴射することによってキャビテーション気泡を発生させる、(8)~(11)のいずれかに記載の方法。
(13) 前記繊維が、パルプ繊維を含む、(8)~(12)のいずれかに記載の方法。
(14) 消石灰の水性懸濁液を反応容器内に噴射することによってキャビテーション気泡を発生させる、(8)~(13)のいずれかに記載の方法。
(15) 消石灰の水性懸濁液として、前記反応容器から循環させた反応液を用いる、(8)~(14)のいずれかに記載の方法。
(16) チタンの存在下でリン酸を反応させて、チタンが定着したリン酸カルシウム・繊維複合体を得る工程を含む、(8)~(15)のいずれかに記載の方法。
(17) (1)~(5)のいずれかに記載の複合体を含んでなる製品。
(18) 前記製品がシートの形態である、(17)に記載の製品。
本発明は、平均一次粒子径が5μm以下であるリン酸カルシウムと繊維の複合体およびその製造方法に関する。本発明のリン酸カルシウム・繊維複合体は、1つの態様において、例えば、炭酸カルシウム・繊維複合体をリン酸と反応させることによって得ることができる。また別の態様において、繊維、リン酸、カルシウム源を反応させることによって、リン酸カルシウムと繊維の複合体を合成することもできる。
上述したように、本発明のリン酸カルシウム・繊維複合体は、例えば、炭酸カルシウム・繊維複合体とリン酸を反応させることによって製造することができる。
本発明に係る複合体の製法においては、1つの態様において、キャビテーション気泡の存在下で炭酸カルシウムおよび/またはリン酸カルシウムを合成することができる。本発明においてキャビテーションとは、流体の流れの中で圧力差により短時間に泡の発生と消滅が起きる物理現象であり、空洞現象とも言われる。キャビテーションによって生じる気泡(キャビテーション気泡)は、流体の中で圧力がごく短時間だけ飽和蒸気圧より低くなったとき、液体中に存在する100ミクロン以下のごく微小な「気泡核」を核として生じる。
本発明の一つの態様において、繊維を含む溶液中で炭酸カルシウムを合成する場合、炭酸カルシウムの合成方法は、公知の方法によることができる。例えば、炭酸ガス法、可溶性塩反応法、石灰・ソーダ法、ソーダ法などによって炭酸カルシウムを合成することができ、好ましい態様において、炭酸ガス法によって炭酸カルシウムを合成する。
本発明においては、リン酸カルシウムと繊維とを複合体化する。複合体を構成する繊維は特に制限されないが、例えば、セルロースなどの天然繊維はもちろん、石油などの原料から人工的に合成される合成繊維、さらには、レーヨンやリヨセルなどの再生繊維(半合成繊維)、さらには無機繊維などを制限なく使用することができる。天然繊維としては上記の他にウールや絹糸やコラーゲン繊維等の蛋白系繊維、キチン・キトサン繊維やアルギン酸繊維等の複合糖鎖系繊維等が挙げられる。セルロース系の原料としては、パルプ繊維(木材パルプや非木材パルプ)、バクテリアセルロース、ホヤなどの動物由来セルロース、藻類などが例示され、木材パルプは、木材原料をパルプ化して製造すればよい。木材原料としては、アカマツ、クロマツ、トドマツ、エゾマツ、ベニマツ、カラマツ、モミ、ツガ、スギ、ヒノキ、カラマツ、シラベ、トウヒ、ヒバ、ダグラスファー、ヘムロック、ホワイトファー、スプルース、バルサムファー、シーダ、パイン、メルクシマツ、ラジアータパイン等の針葉樹、及びこれらの混合材、ブナ、カバ、ハンノキ、ナラ、タブ、シイ、シラカバ、ハコヤナギ、ポプラ、タモ、ドロヤナギ、ユーカリ、マングローブ、ラワン、アカシア等の広葉樹及びこれらの混合材が例示される。
本発明において炭酸化反応の条件は、特に制限されず、用途に応じて適宜設定することができる。例えば、炭酸化反応の温度は0~90℃とすることができ、10~70℃とすることが好ましい。反応温度は、反応液の温度を温度調節装置によって制御することができ、温度が低いと反応効率が低下しコストが高くなる一方、90℃を超えると粗大な炭酸カルシウム粒子が多くなる傾向がある。
水酸化カルシウム(消石灰:Ca(OH)2、1250g)と広葉樹晒クラフトパルプ(LBKP、カナダ標準濾水度CSF:460mL、1250g)を含む水性懸濁液100Lを準備した。この水性懸濁液を、500L容のキャビテーション装置に入れ、反応容器中に炭酸ガスを吹き込んで炭酸ガス法によって炭酸カルシウム微粒子と繊維との複合体を合成した。反応温度は約25℃、炭酸ガスは市販の液化ガスを供給源とし、炭酸ガスの吹き込み量は12L/minであり、反応液のpHが約7になった段階で反応を停止した(反応前のpHは約12.8)。
(1)サンプル1(図3):サンプルA(595mL、濃度4.2%)にリン酸(東ソー社製、濃度10%、57g)を添加して攪拌し、リン酸カルシウムとパルプの複合体を得た。具体的には、サンプルAを40℃のウォーターバス中でスリーワンモータにて850rpmで撹拌し、そこにリン酸をペリスターポンプで0.5g/分の速度で添加して、滴下終了後、さらに30分間撹拌を続けて熟成を行った。
(2)サンプル2(図4):サンプルA(595mL、濃度4.2%)に、二酸化チタン(堺化学工業社製、SSP-25、1.4g)およびリン酸(東ソー社製、濃度10%、57g)を添加して攪拌し、チタンが組み込まれたリン酸カルシウムとパルプの複合体を得た。サンプルAに二酸化チタンをあらかじめ添加しておいた以外は、サンプル1と同様にして反応を行った。
(3)サンプル3(図5):リン酸の濃度を60%、リン酸の添加量9.5gとした以外は、上記(1)と同様に複合体を合成した。
(4)サンプル4(図6):リン酸の濃度を60%、リン酸の添加量9.5gとした以外は、上記(2)と同様に複合体を合成した。
<複合体シートの製造>
実験1および実験2で製造した複合体(サンプルA、サンプル1~4)を、以下の手順によりシート化した(坪量:約60g/m2)。
得られたシートをSEM-EDSで分析した結果を図7~12に示す。SEM-EDS測定を行った結果、チタンを添加したサンプルは、シート上にチタンが分布して定着していることが明らかとなった(元素マッピング画像の青色部分がチタンである)。
・坪量:JIS P 8124:1998
・厚さ:JIS P 8118:1998
・密度:厚さ、坪量の測定値より算出
・灰分:JIS P 8251:2003
・白色度:JIS P 8212:1998
・不透明度:JIS P 8149:2000
・比散乱係数:TAPPI T425(ISO 9416)に規定される式により算出した。
・透気抵抗度:JIS P 8117:2009
・平滑度:JIS P 8155:2010
・L&W曲げこわさ:ISO 2493に準じて、L&W Bending Tester(Lorentzen&Wettre社製)で、曲げ角度が15度の曲げこわさを測定した。
・裂断長:JIS P 8113:2006
・BET比表面積:マイクロメリティックス・ジェミニ2360(島津製作所製)を用いて窒素吸着法により算出した。
Claims (18)
- 平均一次粒子径が5μm以下のリン酸カルシウム粒子と繊維との複合体。
- リン酸カルシウム粒子の平均一次粒子径が1μm以下である、請求項1に記載の複合体。
- 前記繊維がパルプ繊維である、請求項1または2に記載の複合体。
- 前記リン酸カルシウム粒子と前記繊維との重量比が5:95~95:5である、請求項1~3のいずれかに記載の複合体。
- さらにチタンが定着している、請求項1~4のいずれかに記載の複合体。
- 請求項1~5のいずれかに記載の複合体を含んでなるシート。
- 繊維を含む溶液においてカルシウム源とリン酸源を反応させることによって、平均一次粒子径が5μm以下のリン酸カルシウム粒子と繊維との複合体を製造する方法。
- 繊維を含む溶液において炭酸カルシウムを合成して、平均一次粒子径が5μm未満の炭酸カルシウム粒子と繊維との複合体を得る工程、
この複合体とリン酸を反応させてリン酸カルシウムと繊維との複合体を得る工程、
を含む、請求項7に記載の方法。 - キャビテーション気泡の存在下で、繊維を含む溶液において炭酸カルシウムを合成する、請求項8に記載の方法。
- 炭酸カルシウム粒子の平均一次粒子径が1μm以下である、請求項8または9に記載の方法。
- キャビテーション気泡の存在下で、消石灰の水性懸濁液と二酸化炭素を含む気体とを反応させて炭酸カルシウムを合成する、請求項8~10のいずれかに記載の方法。
- 反応容器内に液体を噴射することによってキャビテーション気泡を発生させる、請求項8~11のいずれかに記載の方法。
- 前記繊維が、パルプ繊維を含む、請求項8~12のいずれかに記載の方法。
- 消石灰の水性懸濁液を反応容器内に噴射することによってキャビテーション気泡を発生させる、請求項8~13のいずれかに記載の方法。
- 消石灰の水性懸濁液として、前記反応容器から循環させた反応液を用いる、請求項8~14のいずれかに記載の方法。
- チタンの存在下でリン酸を反応させて、チタンが定着したリン酸カルシウム・繊維複合体を得る工程を含む、請求項8~15のいずれかに記載の方法。
- 請求項1~5のいずれかに記載の複合体を含んでなる製品。
- 前記製品がシートの形態である、請求項17に記載の製品。
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CN201680051554.1A CN108026700A (zh) | 2015-09-08 | 2016-09-08 | 磷酸钙微粒与纤维的复合体及其制造方法 |
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WO2021054312A1 (ja) | 2019-09-20 | 2021-03-25 | 日本製紙株式会社 | 繊維と無機粒子との複合繊維を含有する顆粒 |
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CN110678605A (zh) * | 2017-03-31 | 2020-01-10 | 日本制纸株式会社 | 无机粒子复合纤维片材的制造方法 |
US11268241B2 (en) | 2017-03-31 | 2022-03-08 | Nippon Paper Industries Co., Ltd | Method for manufacturing inorganic particle composite fiber sheet |
CN110678605B (zh) * | 2017-03-31 | 2022-07-08 | 日本制纸株式会社 | 无机粒子复合纤维片材的制造方法 |
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CN111511979A (zh) * | 2017-10-31 | 2020-08-07 | 日本制纸株式会社 | 氧化钛复合纤维及其制造方法 |
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JP2019131929A (ja) * | 2018-02-01 | 2019-08-08 | 第一工業製薬株式会社 | セルロース繊維複合体及びその製造方法 |
JP2019183322A (ja) * | 2018-04-10 | 2019-10-24 | 株式会社バイオアパタイト | 微小繊維 |
JP7177460B2 (ja) | 2018-04-10 | 2022-11-24 | 株式会社バイオアパタイト | 微小繊維 |
WO2021054312A1 (ja) | 2019-09-20 | 2021-03-25 | 日本製紙株式会社 | 繊維と無機粒子との複合繊維を含有する顆粒 |
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EP3348709A4 (en) | 2019-03-27 |
CN108026700A (zh) | 2018-05-11 |
US10737940B2 (en) | 2020-08-11 |
JPWO2017043585A1 (ja) | 2018-06-28 |
EP3348709A1 (en) | 2018-07-18 |
US20180346333A1 (en) | 2018-12-06 |
CA2997940A1 (en) | 2017-03-16 |
JP6833699B2 (ja) | 2021-02-24 |
EP3348709B1 (en) | 2023-07-05 |
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