WO2017043580A1 - 炭酸マグネ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
炭酸マグネ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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- WO2017043580A1 WO2017043580A1 PCT/JP2016/076467 JP2016076467W WO2017043580A1 WO 2017043580 A1 WO2017043580 A1 WO 2017043580A1 JP 2016076467 W JP2016076467 W JP 2016076467W WO 2017043580 A1 WO2017043580 A1 WO 2017043580A1
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- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/008—Processes for carrying out reactions under cavitation conditions
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols
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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
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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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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- 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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
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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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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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
- C01P2004/30—Particle morphology extending in three dimensions
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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
- C01P2004/50—Agglomerated particles
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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
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
Definitions
- the present invention relates to a composite of magnesium carbonate fine particles and fibers and a method for producing the same.
- the present invention relates to a composite in which magnesium carbonate fine particles adhere to the fiber surface and a method for producing the same.
- magnesium carbonate is produced by physically pulverizing and classifying natural magnesite (rhizobite) or by adding sodium carbonate or potassium carbonate to a magnesium salt aqueous solution and precipitating (basic magnesium carbonate).
- MgCO 3 .Mg (OH) 2 The composition of basic magnesium carbonate varies depending on the production method, and it is often a ratio of 3-5 MgCO 3 and 3-7 H 2 O to Mg (OH) 2 .
- Magnesium carbonate is a white powder that is slightly soluble in water, and is widely used as an antacid, an abrasive, and an anti-slip material for various sports equipment.
- magnesium bicarbonate is obtained from magnesium hydroxide and carbon dioxide, and magnesium carbonate is converted into normal magnesium carbonate, and then the basic magnesium carbonate is obtained by increasing the temperature and pH. It has been known.
- 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.
- An object of the present invention is to provide a composite of magnesium carbonate fine particles and fibers and an efficient manufacturing technique thereof.
- the present inventor found that the magnesium carbonate fine particles form a stable composite with the fibers by synthesizing the magnesium carbonate fine particles in the presence of the fibers, thereby completing the present invention. It came.
- a composite of magnesium carbonate and fibers having a small primary particle diameter can be efficiently produced by synthesizing magnesium carbonate in the presence of cavitation bubbles.
- the composite of magnesium carbonate fine particles and fibers obtained by the present invention has the same shape of the magnesium carbonate fine particles attached to the fibers, and can impart unique characteristics to the fibers. 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.
- a composite of magnesium carbonate fine particles and fibers can be efficiently produced by synthesizing magnesium carbonate in the presence of fibers. Moreover, when the composite of the obtained magnesium carbonate microparticles
- a composite of magnesium carbonate fine particles and fibers can be synthesized in a short time by synthesizing magnesium carbonate in the presence of cavitation bubbles in a solution containing fibers. Details of this reason are not clear, and the present invention is not limited to the following assumptions, but is considered as follows. That is, the efficiency of dissolution and fine dispersion of carbon dioxide gas is improved by the occurrence of cavitation under pressurized conditions, and the reaction is activated by fine bubbles generated by cavitation. As a result, magnesium carbonate fine particles are efficiently produced, Furthermore, the composite of the present invention has unique characteristics.
- the fiber functions as a carrier for magnesium carbonate, so that magnesium carbonate fine particles are deposited on the fiber surface, resulting in a composite with unique characteristics. Presumed to have been.
- a composite strongly supported on the fiber could be obtained by binding the magnesium ion adsorbed on the fiber surface and penetrating into the fiber and carbon dioxide gas.
- 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 a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-1 (magnification: left 3000 times, right 10,000 times).
- FIG. 3 is an electron micrograph of a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-2 (magnification: left 3000 times, right 10,000 times).
- FIG. 4 is an electron micrograph of a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-3 (magnification: left 3000 times, right 10,000 times).
- 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 a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-1 (magnification: left 3000 times, right 10,000 times).
- FIG. 5 is an electron micrograph of the composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-4 (magnification: left 3000 times, right 10,000 times).
- FIG. 6 is an electron micrograph of a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-5 (magnification: left 3000 times, right 10000 times).
- FIG. 7 is an electron micrograph of a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-6 (magnification: left 3000 times, right 10,000 times).
- FIG. 8 is an electron micrograph of a composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-7 (magnification: left 500 times, right 3000 times).
- FIG. 9 is an electron micrograph of the composite of magnesium carbonate fine particles and fibers (LBKP) synthesized in Experiment 1-8 (magnification: left 3000 times, right 10000 times).
- FIG. 10 is an electron micrograph of Sample 1 manufactured in Experiment 2 (magnification: 500 times, left: with a retention agent, right: without a retention agent).
- FIG. 11 is an electron micrograph of Sample 2 produced in Experiment 2 (magnification: 500 times, left: with retention agent, right: without retention agent).
- FIG. 12 is an electron micrograph of Sample 3 produced in Experiment 2 (magnification: 500 times, left: with retention agent, right: without retention agent).
- FIG. 13 is an electron micrograph of the magnesium carbonate particles synthesized in Experiment 3-1 (magnification: 10,000 times).
- FIG. 14 is an electron micrograph of the magnesium carbonate particles synthesized in Experiment 3-2 (magnification: 10000 times).
- FIG. 15 is an electron micrograph of the magnesium carbonate particles synthesized in Experiment 3-3 (magnification: 10000 times).
- FIG. 16 is an appearance photograph of the sheet after the fire resistance test of Experiment 4.
- a composite of magnesium carbonate fine particles and fibers is produced by synthesizing magnesium carbonate in the presence of cavitation bubbles in a solution containing fibers.
- Magnesium carbonate According to the present invention, a composite of magnesium carbonate and fiber can be efficiently produced.
- the average particle diameter of the magnesium carbonate fine particles constituting the composite according to the present invention is less than 50 ⁇ m, but magnesium carbonate having an average particle diameter of 30 ⁇ m or less can also be used.
- the average primary particle diameter of the magnesium carbonate fine particles can be about 10 nm to 3 ⁇ m.
- the magnesium carbonate obtained in the present invention may take the form of secondary particles in which fine primary particles are aggregated, and can generate secondary particles according to the application.
- magnesium carbonate can be synthesized from, for example, a raw material selected from the group consisting of magnesium oxide, magnesite, dolomite, huntite, magnesium carbonate, magnesium hydroxide, brucite, and mixtures thereof.
- the magnesium carbonate of the present invention is synthesized from magnesium hydroxide.
- 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) , Dehumidifier, etc.), anti-wrinkle agent, clay, abrasive, modifier, repair material, heat insulating material, heat resistant material, heat radiating material, moisture proof material, water repellent material, water resistant material, light shielding material, sealant, shield material, insect repellent , Adhesives, inks, cosmetics, medical materials, paste materials, anti-discoloring agents, food additives, tablet excipients, dispersants, shape retention agents, water retention agents, filter aids, essential oil materials
- 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.
- a composite of magnesium carbonate fine particles and fibers can be obtained, so that a large amount of magnesium carbonate can be fixed to the fibers.
- magnesium carbonate having a small primary particle diameter is simply blended in the fiber, it is possible to obtain a sheet in which magnesium carbonate is not only easily retained but also uniformly dispersed without agglomeration.
- the magnesium carbonate can be generated not only on the outer surface of the fiber and the inner side of the lumen, but also on the inner side of the microfibril, and this state can be confirmed by observation with an electron microscope.
- 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), 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, calcium sulfate, Zeolite, inorganic filler that regenerates and uses the ash content obtained from the deinking process, and 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 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, 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).
- 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.
- 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 mechanically pulverized 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 size and shape of the magnesium carbonate constituting the composite of the present invention can be confirmed by observation with an electron microscope. Furthermore, by adjusting the conditions for synthesizing magnesium carbonate, magnesium carbonate fine particles having various sizes and shapes can be combined with fibers.
- the method for producing a composite according to the present invention essentially synthesizes magnesium carbonate in a solution containing fibers.
- the fibers can be dispersed in the reaction solution. Further, the fiber can be dispersed in the step of obtaining magnesium carbonate from magnesium hydroxide.
- the reaction solution is alkaline, the fibers can be swollen by being immersed in the reaction solution, and a composite of magnesium carbonate and fibers can be obtained efficiently.
- the carbonation reaction can be started immediately after the fibers are dispersed, or the carbonation reaction can be started after the fiber is further swollen by stirring for 15 minutes or more.
- magnesium carbonate may be synthesized by injecting an aqueous suspension containing magnesium hydroxide into a reaction vessel.
- an aqueous suspension containing magnesium hydroxide into a reaction vessel.
- 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, but there is no problem even if an open reaction vessel is used.
- the pressure vessel in the present invention can apply a 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 In the method for producing a composite according to the present invention, it is preferable to synthesize magnesium carbonate 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 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.
- 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 magnesium carbonate, which is 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 pressure of the spray liquid 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.
- 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 magnesium carbonate. 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 magnesium hydroxide as 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 preferably has a solid content 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 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 lower limit of the reaction temperature may be 20 ° C, and the upper limit may be 80 ° C.
- 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.
- magnesium carbonate fine particles are synthesized in a solution containing fibers.
- the method for synthesizing magnesium carbonate can be based on a known method.
- magnesium bicarbonate can be synthesized from magnesium hydroxide and carbon dioxide
- basic magnesium carbonate can be synthesized from magnesium bicarbonate via normal magnesium carbonate.
- Magnesium carbonate can obtain magnesium bicarbonate, normal magnesium carbonate, basic magnesium carbonate, and the like by a synthesis method, but the magnesium carbonate according to the composite of the present invention is particularly preferably basic magnesium carbonate.
- magnesium bicarbonate is relatively low in stability, and normal magnesium carbonate, which is a columnar (needle-like) crystal, may be difficult to fix to the fiber.
- normal magnesium carbonate which is a columnar (needle-like) crystal
- the present invention relates to a composite of magnesium carbonate and fiber, but in a preferred embodiment, 15% or more of the fiber surface is coated with magnesium carbonate.
- the composite of the present invention has a fiber coverage (area ratio) of 25% or more by magnesium carbonate, more preferably 40% or more, but according to the present invention, the coverage is 60% or more. It is also possible to produce more than 80% of the composite.
- the magnesium carbonate and the fiber are complexed according to the present invention
- the magnesium carbonate is not only easily mixed with the fiber compared with the case where the magnesium carbonate is mixed with the fiber, but also a product in which the magnesium carbonate is uniformly dispersed without agglomeration.
- the yield of the composite of magnesium carbonate and fiber to the product can be set to 60% or more, such as 70% or more and 90%. % Or more.
- cavitation bubbles exist when synthesizing magnesium carbonate.
- cavitation bubbles need not be present in all of the synthesis routes of magnesium carbonate, and cavitation bubbles may be present in at least one stage.
- magnesium oxide MgO is used as a magnesium source, and carbon dioxide gas CO 2 is blown into magnesium hydroxide Mg (OH) 2 obtained from magnesium oxide to produce magnesium bicarbonate Mg (HCO 3 2 ) and basic magnesium carbonate is obtained from magnesium bicarbonate through normal magnesium carbonate MgCO 3 .3H 2 O.
- the magnesium carbonate is synthesized, the basic magnesium carbonate can be synthesized on the fiber by allowing the fiber to be present.
- cavitation bubbles may be present when synthesizing magnesium carbonate.
- cavitation bubbles may be present in any synthesis step of magnesium carbonate.
- cavitation bubbles can be present in the step of synthesizing magnesium bicarbonate from magnesium hydroxide.
- cavitation bubbles can be present in the step of synthesizing basic magnesium carbonate from magnesium bicarbonate or normal magnesium carbonate.
- basic magnesium carbonate can be present when synthesized and then aged.
- a gas blowing type apparatus and a mechanical stirring type apparatus are known as reaction vessels for producing magnesium carbonate.
- carbon dioxide gas is blown into the reaction vessel containing magnesium hydroxide to react, but it is difficult to control the size of the bubbles uniformly and finely by simply blowing carbon dioxide gas.
- a mechanical stirring type apparatus a stirrer is provided inside the apparatus, and carbon dioxide gas is introduced near the stirrer, whereby the carbon dioxide gas is made into fine bubbles and the reaction efficiency with carbon dioxide gas is improved.
- jet cavitation sufficient stirring can be performed without a mechanical stirrer such as a blade.
- a conventionally known reaction vessel can be used, and of course, the above-described gas blowing type or mechanical stirring type device can be used without any problem, and a nozzle or the like is used for these vessels.
- the jet cavitation may be combined.
- the solid content concentration of the aqueous magnesium hydroxide suspension is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, still more preferably 1 to About 20% by weight. 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 magnesium 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 concentration is used.
- the aqueous suspension containing magnesium hydroxide a commonly used one can be used.
- it can be prepared by mixing magnesium hydroxide with water or by adding magnesium oxide to water.
- the conditions for preparing a magnesium hydroxide slurry from magnesium oxide are not particularly limited.
- the MgO concentration is 0.1 wt% or more, preferably 1 wt% or more, and the temperature is 20 to 100 ° C., preferably 30
- the treatment is preferably carried out at -100 ° C. for 5 minutes to 5 hours (preferably within 2 hours).
- the apparatus may be a batch type or a continuous type.
- the preparation of the magnesium hydroxide slurry and the carbonation reaction may be performed using separate apparatuses or in a single reaction tank.
- 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 magnesium carbonate slurry obtained in the reaction step of the present invention can be preferably used.
- the reaction liquid can be circulated and used as a liquid containing magnesium hydroxide.
- the reaction efficiency is increased and it becomes easy to obtain the desired magnesium carbonate.
- a gas containing carbon dioxide (carbon dioxide gas) is blown into the reaction vessel and mixed with the reaction solution.
- carbon dioxide can be supplied to the reaction solution without a gas supply device such as a fan or blower, and the carbonation can be efficiently performed because carbon dioxide is refined by cavitation bubbles. Can do.
- 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 appropriately selected. For example, it is preferable to use carbon dioxide at a flow rate of 100 to 10,000 L / hour per 1 kg of magnesium hydroxide.
- 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 an additive can be added in an amount of preferably 0.001 to 20%, more preferably 0.1 to 10% with respect to magnesium hydroxide.
- the magnesium carbonate fine particles and the fiber are combined.
- the 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 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.
- 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).
- 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 fixing of magnesium carbonate 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 magnesium carbonate to form composite particles can be used.
- fibers such as pulp fibers are used.
- these substances are further incorporated by synthesizing magnesium 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 reaction temperature for obtaining magnesium bicarbonate or basic magnesium carbonate from magnesium hydroxide can be 0 to 90 ° C, and preferably 10 to 70 ° C.
- the lower limit of the reaction temperature may be 20 ° C, and the upper limit may be 80 ° C.
- the reaction temperature can control the temperature of the reaction solution with a temperature adjusting device. If the temperature is low, the reaction efficiency may be reduced or the reaction may not be converted into basic magnesium carbonate. On the other hand, when it exceeds 90 ° C., the cost for heating may be increased or the workability may be deteriorated, and coarse 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 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.
- the carbonation reaction can be controlled by monitoring the pH of the reaction suspension, and is, for example, less than pH 9, preferably less than 8.5, more preferably pH 8.3, depending on the pH profile of the reaction solution.
- the carbonation reaction can be carried out until it reaches below about pH 8.0 or even below pH 8.0.
- the carbonation reaction can be controlled by monitoring the conductivity of the reaction solution. It is preferable to perform the carbonation reaction until the conductivity increases to 4 mS / cm or more (400 mS / m or more).
- the reaction solution can be aged after the carbonation reaction is completed. Specifically, after confirming the end of the carbonation reaction by a change in pH or conductivity as described above, the blowing of carbon dioxide gas can be stopped, and then an aging time can be provided at any temperature or stirring method. .
- the aging temperature can be, for example, 20 to 90 ° C., preferably 40 to 90 ° C., and more preferably 60 to 90 ° C.
- the aging time can be, for example, 1 minute or longer, preferably 15 minutes or longer, and more preferably 30 minutes or longer. Further, this ripening reaction can be carried out as it is in the reaction vessel at the time of the carbonation reaction, or can be carried out after being transferred to another reaction vessel.
- 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 complex which is a reaction product 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.
- 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 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 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.
- a molded product (the body).
- a product with a high ash content can be easily obtained.
- 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 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 ⁇ m or less, called so-called micropolymers 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
- Experiment 1 Synthesis of a composite of magnesium carbonate fine particles and fibers ⁇ Experiment 1-1 (FIG. 2)> An aqueous suspension containing 140 g of magnesium hydroxide (Wako Pure Chemical Industries) and 140 g of hardwood bleached kraft pulp (LBKP, CSF: 370 ml, average fiber length: 0.75 mm) was prepared. 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.
- LLKP hardwood bleached kraft pulp
- 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.
- the pH of the reaction solution reached about 8 (pH 7.8)
- the introduction of CO 2 was stopped (the pH before the reaction was about 9.5), and then, for 30 minutes, the generation of cavitation and the slurry in the apparatus Circulation was continued to obtain Sample 1-1.
- 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 was injected at high pressure through a nozzle (nozzle diameter: 1.5 mm) to generate cavitation bubbles.
- the jet velocity was about 70 m / s, and the inlet pressure (upstream pressure) was The outlet pressure (downstream pressure) was 7 MPa and 0.3 MPa.
- Example 1-7 (FIG. 8)> A composite of magnesium carbonate and fiber was synthesized in the same manner as in Experiment 1-1 except that aging was not performed after the introduction of carbon dioxide gas was stopped (Sample 1-7).
- Example 1-9 (Surface Modification)> Sodium oleate (0.15 g) dissolved in 90 ° C. warm water (10 mL) is added to the slurry of sample 1-1 (concentration 2.5%, 100 mL), and stirred for 5 minutes with a lab mixer to remove the particle surface. Hydrophobized (Sample 1-9).
- Electron micrographs of the obtained composite are shown in FIGS.
- a large number of magnesium carbonate particles were deposited on the fiber surface.
- Most of the primary particles of magnesium carbonate were scaly and had a primary particle diameter (major axis diameter) of about 0.1 to 3 ⁇ m.
- amorphous magnesium carbonate coats the entire fiber surface.
- spherical 2 There were few secondary agglomerates.
- the ash content of these composites was measured, it was 29.6% by weight of the composites, which almost coincided with the theoretical value of 28.3% by weight calculated from the raw material (pulp / magnesium hydroxide) charge ratio. .
- 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).
- Experiment 2 Manufacture and Evaluation of Composite Sheet
- the composites (Sample 1-1 to Sample 1-6) manufactured in Experiment 1 were formed into sheets (Samples 1 to 6) by the following procedure.
- a sheet having a basis weight of about 60 g / m 2 was manufactured using LBKP (CSF: 370 ml) used in Experiment 1.
- the physical properties of the obtained sheet are shown in the table.
- a high ash sheet having an ash content of 50% or more could be easily prepared.
- the ash content was very high, and even though no chemicals such as a retention agent were added, the yield was high (Sample 1, Ash content: 92 %).
- Experiment 3 Synthesis of Magnesium Carbonate Particles ⁇ Experiment 3-1 (FIG. 13)> Magnesium carbonate particles were synthesized in the same manner as in Experiment 1-1 except that no fiber was added.
- ⁇ Evaluation of magnesium carbonate particles> 13 to 15 show electron micrographs of the obtained magnesium carbonate (magnification: 10,000 times).
- most of the primary particles were scaly, and the primary particle diameter (major axis diameter) was about 0.1 to 2.5 ⁇ m.
- the primary particle size was aggregated to form secondary particles, but the particles of Experiment 3-1 were found to be less aggregated than the others.
- the average particle diameter of the secondary particles was measured using a laser diffraction particle size distribution analyzer (Malvern Co., Ltd., Mastersizer 3000). The result was 6.5 ⁇ m in Experiment 3-1 and 30.4 ⁇ m in Experiment 3-2. In 3-3, it was 29.6 ⁇ m.
- # 3 A sheet was produced in the same manner as # 1 except that the slurry prepared by adding magnesium carbonate of Experiment 3-1 to the composite slurry of Experiment 1-1 was used as the raw material (ash content: about 87%).
- # 4 A sheet was produced in the same manner as # 2, except that only LBKP was used as a raw material.
- # 5 A sheet was produced in the same manner as # 2, except that light calcium carbonate fine particles (light cal 1, average particle size: about 100 nm, cubic particles) were used instead of magnesium carbonate as a filler.
- # 6 A sheet was produced in the same manner as # 2, except that light calcium carbonate fine particles (light cal 2, average particle size: about 3.5 ⁇ m, soecarnohedral type) were used instead of magnesium carbonate as a filler.
- Sheets # 1 to 3 containing magnesium carbonate have whiteness, opacity, and air permeability compared to sheets (# 4) made only from LBKP and sheets with light calcium carbonate (# 5 and # 6). Resistance and bending stiffness were high and density was low. In particular, the composite sheet # 1 was bulky, and its bending stiffness and tear length were higher than those of # 2 containing magnesium carbonate. In addition, the ash yield of # 1 using the composite as a raw material was extremely high, whereas # 2 containing magnesium carbonate was very low at about 17%.
- the end of the sheet was blown with a burner for about 2 seconds to evaluate the fire resistance of the sheet. While the sheet (# 4) produced only from LBKP burned out immediately, the sheet containing magnesium carbonate burned somewhat, but the fire did not spread and self-extinguishing properties were recognized. In addition, the sheet (# 5) produced from the composite of calcium carbonate and fiber burned out more easily than the sheet (# 4) produced from LBKP alone (FIG. 16).
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Abstract
Description
(1) 繊維を含む溶液において炭酸マグネシウムを合成することを含む、炭酸マグネシウム粒子と繊維との複合体の製造方法。
(2) 炭酸マグネシウム粒子の平均粒子径が50μm以下である、(1)に記載の製造方法。
(3) 水酸化マグネシウムから炭酸マグネシウムを合成する、(1)または(2)に記載の製造方法。
(4) 水酸化マグネシウムを含む水性懸濁液を反応容器内に噴射することによって炭酸マグネシウムを合成することを含む、(1)~(3)のいずれかに記載の製造方法。
(5) キャビテーション気泡の存在下で炭酸マグネシウムを合成する、(1)~(4)のいずれかに記載の製造方法。
(6) キャビテーション気泡の存在下で、前記原料の水性懸濁液と二酸化炭素を含む気体とを反応させる、(1)~(5)のいずれかに記載の製造方法。
(7) 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、(1)~(6)のいずれかに記載の製造方法。
(8) 前記繊維がパルプ繊維である、(1)~(7)のいずれかに記載の製造方法。
(9) 水酸化マグネシウムを含む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、(1)~(8)のいずれかに記載の製造方法。
(10) 前記水性懸濁液として、前記反応容器から循環させた反応液を用いる、(1)~(9)のいずれかに記載の製造方法。
(11) 炭酸マグネシウムの一次粒子径が10nm~3μmである、(1)~(10)のいずれかに記載の製造方法。
(12) 炭酸マグネシウムと繊維の重量比が5:95~95:5である、(1)~(11)のいずれかに記載の製造方法。
(13) 前記反応容器が圧力容器である、(1)~(12)のいずれかに記載の製造方法。
(14) 水酸化マグネシウムとパルプを予め混合した水性懸濁液を使用する、(1)~(13)のいずれかに記載の方法。
(15) 前記複合体を疎水化する工程をさらに含む、(1)~(14)のいずれかに記載の方法。
(16) 平均粒子径が50μm以下の炭酸マグネシウム粒子と繊維との複合体。
(17) 前記繊維がパルプ繊維である、(16)に記載の複合体。
(18) 前記炭酸マグネシウム粒子と前記繊維との重量比が5:95~95:5である、(16)または(17)に記載の複合体。
(19) (1)~(15)のいずれかの方法によって合成された、(16)~(18)のいずれかに記載の複合体。
(20) 炭酸マグネシウムが、塩基性炭酸マグネシウムである、請求項16~19のいずれかに記載の複合体。
(21) (16)~(20)のいずれかに記載の複合体を含んでなる製品。
(22) 前記製品がシートの形態である、(21)に記載の製品。
さらに、本発明の複合体はユニークな特性を備えているが、これは、繊維が炭酸マグネシウムの担体として機能するため繊維表面に炭酸マグネシウム微粒子が析出し、ユニークな特性を備えた複合体となったものと推測される。また、繊維表面に吸着および内部に浸透したマグネシウムイオンと炭酸ガスが結びつくことで、強固に繊維に担持された複合体を得ることができたものと考えられる。
本発明によれば炭酸マグネシウムと繊維との複合体を効率的に製造することができる。本発明に係る複合体を構成する炭酸マグネシウム微粒子の平均粒径は50μm未満であるが、平均粒径が30μm以下の炭酸マグネシウムとすることもできる。また、好ましい態様において、炭酸マグネシウム微粒子の平均一次粒子径は10nm~3μm程度とすることも可能である。
本発明に係る複合体の製法においては、キャビテーション気泡の存在下で炭酸マグネシウムを合成することが好ましい。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。
本発明においては、繊維を含む溶液中で炭酸マグネシウム微粒子を合成するが、炭酸マグネ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、水酸化マグネシウムと炭酸ガスから重炭酸マグネシウムを合成し、重炭酸マグネシウムから正炭酸マグネシウムを経て塩基性炭酸マグネシウムを合成することができる。炭酸マグネシウムは合成方法によって重炭酸マグネシウム、正炭酸マグネシウム、塩基性炭酸マグネシウムなどを得ることができるが、本発明の複合体に係る炭酸マグネシウムは、塩基性炭酸マグネシムにすることが特に好ましい。なぜならば、重炭酸マグネシウムは安定性が比較的低く、柱状(針状)結晶である正炭酸マグネシウムは繊維へ定着しにくい場合があるためである。一方、繊維の存在下で塩基性炭酸マグネシウムにまで化学反応させることで、繊維表面をうろこ状などに被覆した炭酸マグネシウムと繊維の複合体を得ることができる。
本発明においては、炭酸マグネシウム微粒子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、水酸化マグネシウムから重炭酸マグネシウムや塩基性炭酸マグネシウムを得る反応の温度は0~90℃とすることができ、10~70℃とすることが好ましい。反応温度の下限は20℃としてもよく、上限は80℃としてもよい。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たり、塩基性炭酸マグネシウムにまで変換されない場合がある。一方、90℃を超えると加温のためのコストがかかる場合や作業性が低下する場合があり、粗大な粒子が多くなる傾向がある。
本発明に係る複合体を用いて、適宜、成形物(体)を製造することも可能である。例えば、本発明によって得られた複合体を含有させると、高灰分の製品を容易に得ることができる。特に、本発明によって得られた複合体をシート化すると、高灰分のシートを容易に得ることができる。シート製造に用いる抄紙機(抄造機)としては、例えば長網抄紙機、丸網抄紙機、ギャップフォーマ、ハイブリッドフォーマ、多層抄紙機、これらの機器の抄紙方式を組合せた公知の抄造機などが挙げられる。抄紙機におけるプレス線圧、後段でカレンダー処理を行う場合のカレンダー線圧は、いずれも操業性や複合体シートの性能に支障を来さない範囲内で定めることができる。また、形成されたシートに対して含浸や塗布により澱粉や各種ポリマー、顔料およびそれらの混合物を付与しても良い。
<実験1-1(図2)>
水酸化マグネシウム140g(和光純薬)と広葉樹晒クラフトパルプ140g(LBKP、CSF:370ml、平均繊維長:0.75mm)を含む水性懸濁液を準備した。この水性懸濁液14Lを、45L容のキャビテーション装置に入れ、反応溶液を循環させながら、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マグネ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36℃、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4L/minとした。反応液のpHが約8(pH7.8)になった段階でCO2の導入を停止し(反応前のpHは約9.5)、その後30分間、キャビテーションの発生と装置内でのスラリーの循環を続け、サンプル1-1を得た。
実験1-1で炭酸ガスの吹き込みを停止した後、すぐに70℃の温浴中に移し、キャビテーションをかけずに反応溶液を撹拌機で30分間撹拌した他は、実験1-1と同様にして、炭酸マグネシウムと繊維の複合体を合成した(サンプル1-2)。
反応容器に3Lのステンレス製容器を用い、パルプの仕込み量を20g、炭酸ガスの吹き込み量を0.57L/minとし、炭酸化反応を35℃のウォーターバス中でスリーワンモーターを用いて撹拌(800rpm)しながら行った以外は、実験1-2と同様に実験した(サンプル1-3)。
入口圧力を1.8MPaとした以外は、実験1-1と同様にして炭酸マグネシウムと繊維の複合体を合成した(サンプル1-4)。
入口圧力を1.8MPaとした以外は、実験1-2と同様にして炭酸マグネシウムを合成した(サンプル1-5)。
炭酸ガスの吹き込みを停止した後、30分間キャビテーションをかけ続ける代わりに反応溶液中に水酸化ナトリウム(0.4mol品を150mL)を添加した以外は、実験1-4と同様に実験した(サンプル1-6)。
炭酸ガスの導入を停止後、熟成を行わなかった以外は、実験1-1と同様にして炭酸マグネシウムと繊維の複合体を合成した(サンプル1-7)。
開始温度を50℃とした以外は、実験1-4と同様にして炭酸マグネシウムと繊維の複合体を合成した(サンプル1-8)。
サンプル1-1のスラリー(濃度2.5%、100mL)に、90℃の温水(10mL)で溶解したオレイン酸ナトリウム(0.15g)を添加し、ラボミキサーで5分間撹拌して粒子表面を疎水化した(サンプル1-9)。
得られた複合体の電子顕微鏡写真を図2~9に示す。図から明らかなように、いずれの場合にも、繊維表面に多数の炭酸マグネシウム粒子が析出していた。炭酸マグネウムの一次粒子の多くは鱗片状であり、一次粒子径(長軸径)が0.1~3μm程度であった。中でも実験例1-1は、それらの鱗片状の結晶に加えて、不定形な炭酸マグネシウムが繊維表面全体を被覆しており、実験例1-2や実験例1-3と比べて球状の2次凝集物は少なかった。実験1-4、1-6および1-7においては、幅1~2μm、長さ10~30μm程度の柱状結晶が析出しており、これらは正炭酸マグネシウムの結晶であると考えられた。この結果から、反応開始時の温度を高め(45℃以上)に設定したり、反応終了後に50℃以上の高温で熟成させたりすることで、より効率良く塩基性炭酸マグネシムが生成し、繊維との複合化も進行すると考えられた。なお、球状の2次凝集物は塩基性炭酸マグネシウム、柱状の結晶は正炭酸マグネシウムと考えられた。
実験1で製造した複合体(サンプル1-1~サンプル1-6)を以下の手順によりシート化した(サンプル1~6)。
・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
<実験3-1(図13)> 繊維を添加しなかった以外は、実験1-1と同様にして炭酸マグネシウム粒子を合成した。
図13~15に、得られた炭酸マグネシウムの電子顕微鏡写真を示す(倍率:10000倍)。いずれの場合も、一次粒子の多くは鱗片状であり、一次粒子径(長軸径)は0.1~2.5μm程度であった。いずれの場合も1次粒子径が凝集して2次粒子を形成していたが、実験3-1の粒子は、他と比べてその凝集が弱いように認められた。レーザー回折式粒度分布測定器(マルバーン社製、マスターサイザー3000)を用いて2次粒子の平均粒子径を測定したところ、実験3-1では6.5μm、実験3-2では30.4μm、実験3-3では29.6μmであった。
実験1-1の複合体(サンプル1-1)、実験3-1の炭酸マグネシウム、LBKP(CSF:460ml)を用い、下記の手順によって坪量が約60g/m2のシートを製造した。なお、歩留剤は全てのシートについて添加した。
・#1:実験2のシート1と同様にして複合体シートを製造した。
・#2:LBKP(CSF=460ml)に実験3-1の炭酸マグネシウムを添加して調製したスラリーを原料に用いた他は、#1と同様にしてシートを製造した(灰分:約58%)。
・#3:実験1-1の複合体のスラリーに実験3-1の炭酸マグネシウムを添加して調製したスラリーを原料に用いた他は、#1と同様にしてシートを製造した(灰分:約87%)。
・#4:LBKPのみを原料として用いた他は#2と同様にしてシートを製造した。
・#5:填料として炭酸マグネシウムの代わりに軽質炭酸カルシウム微粒子(軽カル1、平均粒径:約100nm、立方体粒子)を用いた他は#2と同様にしてシートを製造した。
・#6:填料として炭酸マグネシウムの代わりに軽質炭酸カルシウム微粒子(軽カル2、平均粒径:約3.5μm、スカルノヘドラル型)を用いた他は#2と同様にしてシートを製造した。
Claims (22)
- 繊維を含む溶液において炭酸マグネシウムを合成することを含む、炭酸マグネシウム粒子と繊維との複合体の製造方法。
- 炭酸マグネシウム粒子の平均粒子径が50μm以下である、請求項1に記載の製造方法。
- 水酸化マグネシウムから炭酸マグネシウムを合成する、請求項1または2に記載の製造方法。
- 水酸化マグネシウムを含む水性懸濁液を反応容器内に噴射することによって炭酸マグネシウムを合成することを含む、請求項1~3のいずれかに記載の製造方法。
- キャビテーション気泡の存在下で炭酸マグネシウムを合成する、請求項1~4のいずれかに記載の製造方法。
- キャビテーション気泡の存在下で、前記原料の水性懸濁液と二酸化炭素を含む気体とを反応させる、請求項1~5のいずれかに記載の製造方法。
- 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1~6のいずれかに記載の製造方法。
- 前記繊維がパルプ繊維である、請求項1~7のいずれかに記載の製造方法。
- 水酸化マグネシウムを含む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1~8のいずれかに記載の製造方法。
- 前記水性懸濁液として、前記反応容器から循環させた反応液を用いる、請求項1~9のいずれかに記載の製造方法。
- 炭酸マグネシウムの一次粒子径が10nm~3μmである、請求項1~10のいずれかに記載の製造方法。
- 炭酸マグネシウムと繊維の重量比が5:95~95:5である、請求項1~11のいずれかに記載の製造方法。
- 前記反応容器が圧力容器である、請求項1~12のいずれかに記載の製造方法。
- 水酸化マグネシウムとパルプを予め混合した水性懸濁液を使用する、請求項1~13のいずれかに記載の方法。
- 前記複合体を疎水化する工程をさらに含む、請求項1~14のいずれかに記載の方法。
- 平均粒子径が50μm以下の炭酸マグネシウム粒子と繊維との複合体。
- 前記繊維がパルプ繊維である、請求項16に記載の複合体。
- 前記炭酸マグネ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16または17に記載の複合体。
- 請求項1~15のいずれかの方法によって合成された、請求項16~18のいずれかに記載の複合体。
- 炭酸マグネシウムが、塩基性炭酸マグネシウムである、請求項16~19のいずれかに記載の複合体。
- 請求項16~20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21に記載の製品。
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Application Number | Priority Date | Filing Date | Title |
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US15/757,731 US11053133B2 (en) | 2015-09-08 | 2016-09-08 | Complexes of magnesium carbonate microparticles and fibers as well as processes for preparing them |
JP2017539218A JP6661644B2 (ja) | 2015-09-08 | 2016-09-08 | 炭酸マグネシウム微粒子と繊維との複合体、および、その製造方法 |
EP16844441.2A EP3348519B1 (en) | 2015-09-08 | 2016-09-08 | Complex of fibers and magnesium carbonate microparticles, and production method therefor |
CN201680049654.0A CN107922207A (zh) | 2015-09-08 | 2016-09-08 | 碳酸镁微粒与纤维的复合体及其制造方法 |
CA2997687A CA2997687A1 (en) | 2015-09-08 | 2016-09-08 | Complexes of magnesium carbonate microparticles and fibers as well as processes for preparing them |
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JP2018145553A (ja) * | 2017-03-03 | 2018-09-20 | 日本製紙株式会社 | 炭酸マグネシウムと繊維の複合繊維の溶解抑制 |
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JP2019137948A (ja) * | 2018-02-13 | 2019-08-22 | 日本製紙株式会社 | 難燃複合繊維およびその製造方法 |
JPWO2019159943A1 (ja) * | 2018-02-13 | 2021-02-04 | 日本製紙株式会社 | 難燃化した複合繊維およびその製造方法 |
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WO2017043580A1 (ja) | 2015-09-08 | 2017-03-16 | 日本製紙株式会社 | 炭酸マグネシウム微粒子と繊維との複合体、および、その製造方法 |
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WO2018097324A1 (ja) * | 2016-11-28 | 2018-05-31 | 日本製紙株式会社 | 繊維と無機粒子の複合体の製造方法、および、繊維と無機粒子の複合体を含有する積層体 |
JP2018145553A (ja) * | 2017-03-03 | 2018-09-20 | 日本製紙株式会社 | 炭酸マグネシウムと繊維の複合繊維の溶解抑制 |
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JP7199409B2 (ja) | 2018-02-13 | 2023-01-05 | 日本製紙株式会社 | 難燃化した複合繊維およびその製造方法 |
JPWO2019159943A1 (ja) * | 2018-02-13 | 2021-02-04 | 日本製紙株式会社 | 難燃化した複合繊維およびその製造方法 |
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US11053133B2 (en) | 2021-07-06 |
CN107922207A (zh) | 2018-04-17 |
EP3348519B1 (en) | 2022-03-16 |
EP3348519A4 (en) | 2019-04-17 |
JPWO2017043580A1 (ja) | 2018-06-28 |
CA2997687A1 (en) | 2017-03-16 |
US20190047872A1 (en) | 2019-02-14 |
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JP6661644B2 (ja) | 2020-03-11 |
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