WO2001042139A1 - Production de carbonate de calcium de forme cubique - Google Patents

Production de carbonate de calcium de forme cubique Download PDF

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Publication number
WO2001042139A1
WO2001042139A1 PCT/JP2000/008564 JP0008564W WO0142139A1 WO 2001042139 A1 WO2001042139 A1 WO 2001042139A1 JP 0008564 W JP0008564 W JP 0008564W WO 0142139 A1 WO0142139 A1 WO 0142139A1
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Prior art keywords
calcium carbonate
suspension
calcium
particle size
concentration
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PCT/JP2000/008564
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English (en)
Japanese (ja)
Inventor
Kazunori Ohide
Norio Matsuura
Hisakazu Hojo
Seiya Shimizu
Noritsugu Ebisuya
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Maruo Calcium Company Limited
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Application filed by Maruo Calcium Company Limited filed Critical Maruo Calcium Company Limited
Priority to JP2001543446A priority Critical patent/JP4658431B2/ja
Priority to AU16511/01A priority patent/AU1651101A/en
Publication of WO2001042139A1 publication Critical patent/WO2001042139A1/fr

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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
    • C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
    • 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
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow

Definitions

  • the present invention relates to a method for producing cubic calcium carbonate having almost no secondary agglomeration, excellent dispersibility, uniformity, high-temperature stability, and long-term stability of individual particles, and reduced impurities contained therein.
  • the particle shape is cubic, the particle size can be arbitrarily selected over a wide range, the individual particle sizes are uniform, the dispersibility is good, the chemical stability is high, and the ammonium ions are alkali metal ions.
  • Calcium carbonate has many advantages, such as the abundant production of limestone as a raw material in Japan, and it is inexpensive, has high whiteness, is harmless, and can be obtained in various particle sizes. It is used in a variety of fields as additives for paints, paints, extenders for inks, pigments for paper rubbing, pigments for paper coating, pharmaceuticals, cosmetics, foods, agriculture, etc.
  • calcium carbonate is produced by mechanically pulverizing limestone, classifying the pulverized material to adjust it to various grades, and reacting with quick lime obtained by calcining limestone at a high temperature and water to react with lime milk.
  • the lime milk is made to pass through the carbon dioxide gas generated during limestone firing to synthesize calcium carbonate.
  • the lime soda process reacts lime milk with sodium carbonate.
  • the lime soda is added to calcium chloride.
  • Precipitated carbonated calcium carbonate synthetic carbonic acid calcium
  • synthetic carbonic acid calcium prepared by a chemical method such as a soda process (Pum) is roughly divided into two types.
  • Precipitated calcium carbonate is generally produced using a carbon dioxide compounding process from an economic point of view.
  • Synthetic calcium carbonate produced using the carbon dioxide compounding process has relatively uniform primary particle shapes, but usually the primary particles aggregate or aggregate to form secondary particles (aggregate particles of primary particles). It has properties that make it easy to do. Therefore, it is impossible to produce precipitated calcium carbonate completely free of secondary particles without performing post-processing such as wet pulverization by conventional techniques, and it cannot be used particularly in advanced industrial applications.
  • the da process is a method in which a soluble calcium salt such as calcium chloride is reacted with a soluble carbonate such as sodium carbonate.
  • Japanese Patent Publication No. 3-21888 discloses an acrylic resin.
  • inorganic particles such as barium sulfate, calcium carbonate, silicon dioxide, talc, titanium dioxide, and aluminum hydroxide.
  • light diffusing property is imparted to a lighting cover or the like by utilizing the difference in refractive index between the resin base material and the inorganic particles, and at the same time, the light transmitting property is designed by designing the average particle diameter and the filling amount of the inorganic particles. It is intended to control
  • inorganic particles having a uniform particle shape, good dispersibility, and a sharp particle size distribution are required.
  • inorganic particles capable of freely selecting the average particle size while maintaining the particle size distribution and particle shape are desired. ing.
  • Japanese Patent Application Laid-Open No. 7-1966316 discloses that The formation of calcium carbonate in a sodab mouth process with a strictly defined reaction method results in almost no secondary agglomeration, excellent dispersibility and uniformity of individual particles, high-temperature stability, and stability over time.
  • a method for producing cubic calcium carbonate in which an arbitrary average particle size can be selected within a range has been proposed. With such a technique, when calcium carbonate is used as a light diffusing material, it has become possible to obtain an optimum light transmissivity by selecting a high light diffusing property and a particle size and a filling amount.
  • Calcium carbonate has also been used in advanced industrial applications such as anti-blocking agents for films and fibers through various studies and improvements.
  • film applications are described as follows: for capacitors, for magnetic recording media such as audio tape and video tape, for photography, and packaging. And polyester films used for HP and the like.
  • the purpose of using calcium carbonate in these applications is to form irregularities on the film surface by adding calcium carbonate to polyester, as shown in, for example, Japanese Patent Application Laid-Open No. 9-111101, This is to give the film or processed product slipperiness ⁇ ⁇ ⁇ ⁇ abrasion resistance.
  • the irregularities on the film surface must be within a specific range and must be minimized, and the particles that form the irregularities must have a high degree of dispersibility, uniformity, Optional sharpness of particle size distribution and particle size
  • High physical properties such as stability at high temperature against heat applied during polyester resin synthesis and long-term stability are considered indispensable.
  • capacitor films with a film thickness of 2.5 ⁇ or less are used. It came to be.
  • the particles added for the purpose of imparting smoothness to the film are the above-mentioned individual particles with high dispersibility, uniformity of the particles and sharpness of the particle size distribution.
  • physical properties such as arbitrary setting of particle size, high-temperature stability against heat applied during polyester resin synthesis, and long-term stability over time are required.
  • ammonium ions, alkali metal ions, etc. decrease the electrical characteristics and charging ability of the final product capacitor. Ammonium ions, alkali metal ions, and chloride ions contained as impurities have become problematic.
  • the particles described in the above-mentioned Japanese Patent Application Laid-Open No. 7-196316 are sufficient even if they are added to a film having a thickness of 2.5 m or less.
  • removal of ammonium ions, alkali metal ions, chloride ions, etc., which are by-produced during particle generation, cannot be said to be complete.
  • the ion has the disadvantage that the insulating property and the charging ability are reduced.
  • each particle has a high degree of dispersibility, and excellent properties such as uniformity of particles, sharpness of particle size distribution and arbitrary setting of particle size, high-temperature stability, and long-term stability over time.
  • ammonium ions, alkali metal ions, halo, etc. which hinder the final products such as lighting covers, light diffusion plates for transmissive displays, lighting signboards, film for condensers, etc.
  • the present invention is useful for advanced industrial applications, has good dispersibility, does not contain unnecessary fine or coarse particles, has a very uniform particle size, and has a sharp particle size distribution.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, after including a specific amount of a reaction buffer and performing a carbonation reaction under specific conditions, washing, diluting and leaving Removal of calcium ions, alkali metal ions, and halide ions in calcium carbonate obtained by standing, etc. to improve dispersibility and particle uniformity, sharp particle size distribution, and possible particle size range
  • the particle size is wide and the particle size can be set arbitrarily.
  • the present invention includes a method for producing cubic calcium carbonate, comprising the following steps.
  • the carbonate ion concentration and the calcium ion concentration are each 0.1 to 3.0 mol / s, and the concentration ratio of calcium ions to carbonate ions is 0.5 to 2.0.
  • the obtained calcium carbonate suspension is subjected to at least one removal method selected from the following (a) to (: f) to remove at least one of ammonium ion, alkali metal ion, and halide ion. Remove the seeds,
  • the electric conductivity of the aqueous suspension is not more than 500 S / cm when the concentration of carbonic acid is 3 wt%.
  • (V) Cubic calcium carbonate obtained by drying contains less than 1, OOOppm of halide ions.
  • the total amount of ammonium ions and alkali metal ions contained in the cubic calcium carbonate obtained by drying is 5, OOOppm or less, and halide ion is 500 ppm or less.
  • the total of the ammonium ion and the aluminum metal ion contained in the cubic calcium carbonate obtained by drying is 2,000 ppm or less, and the halide ion is 200 ⁇ or less.
  • Figure 1 is a schematic diagram showing the equipment used to evaluate the wear characteristics of the film.
  • Examples of the carbonate used in the present invention include sodium, potassium, ammonium and the like. These can be used alone or in combination of two or more, but it is preferable to use sodium carbonate alone from the viewpoint of economy.
  • Carbonate solution is prepared by dissolving the above carbonate in water As long as it is available as a carbonate solution and it is economically advantageous, the present invention may be used even if the carbonate solution is used by adjusting its concentration by operations such as concentration and dilution.
  • concentration of the carbonate solution varies depending on the desired particle diameter / set temperature, reaction buffer amount, ratio with calcium salt, reaction time, etc., but usually 0.1 to 3.0 m01 ZL is appropriate.
  • the concentration of the carbonate solution is less than 0.1 mo1 / L, not only is it economically disadvantageous, but also the carbonated calcium carbonate of the present invention having the following characteristics cannot be obtained, which is preferable. Absent. If the concentration of the carbonate solution exceeds 3.Omo 1 / L, calcium carbonate having the following characteristics cannot be obtained, which is not preferable.
  • Examples of the calcium salt used in the present invention include water-soluble calcium salts such as calcium chloride, calcium nitrate, calcium nitrite, calcium bromide and calcium iodide. These can be used alone or in combination of two or more, but calcium chloride is preferably used alone from the viewpoint of economy.
  • the calcium ion solution is prepared by dissolving the above calcium salt in water, but it is available as a calcium salt solution, and if it is economically advantageous, adjust the concentration by concentrating and diluting the calcium salt solution.
  • the present invention can be used without any problem.
  • the concentration of the calcium salt solution varies depending on the particle size to be obtained, the set temperature, the amount of the reaction buffer, the ratio to the carbonate, the reaction time, and the like, but usually 0.1 to 3.0 mo 1 ZL is appropriate. It is an index representing the uniformity of the particle size of each primary particle of the calcium carbonate obtained by the present invention. When the relative standard deviation S described below is set to 0.4 or less, 0.3 to 2.5mo 1 ZL is preferable, and when the relative standard deviation S is set to 0.3 or less, 0.5 to 2.0 mo 1 ZL is preferred.
  • the concentration of the calcium salt solution is less than 0.1 mol 1 ZL, it is not only economically disadvantageous but also unfavorable because the carbonated calcium carbonate of the present invention having the following characteristics cannot be obtained.
  • the concentration of the calcium salt solution exceeds 3.times.mo1 / L, calcium carbonate having the following characteristics is not obtained, which is not preferable.
  • the concentration ratio of the calcium ion in the calcium salt solution to the carbonate in the carbonate solution is 0.5 to 2.0, preferably 0.75 to 1.33, and more preferably 0.8. 9 to 1.13. If the concentration ratio exceeds 2.0 or is less than 0.5, carbonate ions or calcium ions that do not contribute to the reaction are not preferable because they adversely affect the reaction.
  • the reaction buffer solution used in the present invention is mixed with a carbonate solution or a calcium salt solution or both, but from the viewpoint of reducing the complexity of the concentration adjustment and increasing the accuracy of the concentration adjustment in the reaction, a carbonic acid solution is used. It is preferable to mix only the salt solution or only the calcium salt solution.
  • the reaction buffer may be an electrolyte, and examples thereof include alkali metal or ammonium hydroxides, nitrates, sulfates, and chlorides. These may be used alone or in combination of two or more. From the viewpoint of economy, sodium, potassium hydroxide and sulfate are preferred. In addition, since most of the above-mentioned electrolytes react with calcium ions to generate calcium salts, in the present invention, it is preferable to mix only the carbonate solution.
  • the amount of the reaction buffer is such that the solution concentration after the addition is in the range of 0.001 to 2.Omo1 / L, preferably 0.05 to 1.5 mol / L, and 1. Omo 1 ZL is more preferred. Also, the carbonate concentration in the carbonate solution It is desirable not to exceed the calcium salt concentration in the calcium salt solution.
  • the amount of the reaction buffer is less than 0.001 m0.1 / L, unstable amorphous calcium carbonate or paterite-type calcium carbonate is present in a large amount, which is the object of the present invention. Calcium carbonate cannot be obtained.
  • the amount of the reaction buffer exceeds 2.0 OmolZL, not only the carbonation reaction becomes difficult to occur, but also the characteristic carbonic acid calcium which is the object of the present invention cannot be obtained. Further, if the concentration of the carbonate in the carbonate solution or the concentration of potassium salt in the calcium salt solution is exceeded, the reaction is adversely affected, and the calcium carbonate, which is the object of the present invention, cannot be obtained.
  • the carbonate solution and the calcium salt solution to which the reaction buffer has been added, prepared by the above method, are mixed under stirring to carry out a carbonation reaction.
  • the carbonate solution may be added dropwise to the calcium salt solution, or the calcium salt solution may be added dropwise to the carbonate solution. The latter method is preferred.
  • the temperature in the carbonation reaction system is preferably maintained at 5 to 40 ° C, more preferably 15 to 20 ° C, from the viewpoint of homogenizing the primary particles. If the temperature in the carbonation reaction system is lower than 5 ° C., the obtained particles are likely to become unstable amorphous calcium carbonate, and the calcium carbonate intended in the present invention cannot be obtained. Further, when the temperature in the carbonation reaction system exceeds 40 ° C., it becomes aragonite-type calcium carbonate, and crystal grows in a needle-like manner from the primary crystal particles of calcium carbonate in all directions, so that calcium carbonate, which is the object of the present invention, is obtained. I can't get it.
  • the temperature of each of the carbonate solution and the calcium salt solution to which the reaction buffer is added is not particularly limited, but the temperature difference between the solutions is 2 (preferably TC or less, and 10 ° C or less. More preferred.
  • the dripping mixing time begins when one salt solution is dropped and mixed with the other salt solution. From 70 to 1200 seconds.
  • the relative standard deviation described below which is an index representing the uniformity of each primary particle of the calcium carbonate obtained by the present invention, is set to 0.4 or less, it is preferably 180 to 900 seconds, and the relative standard deviation Is set to 0.3 or less, 240 to 600 seconds is more preferable.
  • the mixing time is less than 70 seconds, a large amount of vaterite-type spherical calcium carbonate is mixed, which is not preferable.
  • the mixing time exceeds 1200 seconds a sharp edge is formed. It is unfavorable because it becomes calcium carbonate of cubic calcite crystal with a standard deviation exceeding 0.5.
  • the aqueous suspension containing calcium carbonate prepared by the above method is subjected to at least one removal method selected from the following (a) to (f) to remove the ammonium carbonate containing calcium carbonate particles. Remove at least one of the impurities selected from ions, alkali metal ions, and halide ions.
  • At least one method selected from the following (a1) to (: f1) is more preferable.
  • the temperature is preferably adjusted to 55 to 100, more preferably 70 to 100 ° C, and preferably 8 to 100 ° C. Washing is performed after standing or stirring for at least 16 hours, more preferably at least 16 hours.
  • the upper limit of the standing or stirring time is preferably 100 hours or less for the same reason as described above.
  • the suspension obtained in (a) or a diluent thereof is adjusted to preferably 55 to 100 ° C, more preferably 70 to 100 ° C, and more preferably for 8 hours or more. More preferably, it is washed after being left or stirred for 16 hours or more. Also, the upper limit of the standing or stirring time is preferably 100 hours or less for the same reason as described above.
  • the mole number of calcium is preferably 0.5 times or more, more preferably 1 time, with respect to the mole number of calcium carbonate in the suspension at the time of standing or stirring. More preferably, a water-soluble calcium salt solution having twice or more moles is added.
  • water-soluble calcium salt examples include calcium chloride, calcium acetate, calcium nitrate, calcium nitrite, calcium bromide, calcium iodide, and the like. These may be used alone or in combination of two or more. Calcium chloride and calcium acetate are preferably used from the viewpoint of economy.
  • the number of moles of calcium in the water-soluble calcium salt solution is less than 0.5 times the number of moles of calcium carbonate in the suspension, the effect is higher than when no water-soluble calcium salt solution is added. If there is no big difference, and if it exceeds 20 times, it is not preferable in terms of economy.
  • (F 1) in the above methods (a) ⁇ (d), left or at the time of stirring, dissolved in equilibrium constant K (or Ka) is a solution of 1 X 10_ 4 ⁇ 1 X 10- 7 , or water, the One or more of solids and gases exhibiting an equilibrium constant are selected and added to a calcium carbonate suspension or a diluent thereof, and the pH of the suspension or diluent is preferably 5 or more, more preferably 2 or more. More preferably, it is reduced by 2.5 or more.
  • As the above acid it is preferable to blow carbon dioxide gas into the liquid for economic reasons.
  • the water-soluble salt and the water-soluble acid which react with calcium to form an insoluble or hardly soluble salt used in the present invention include: fatty acids or salts thereof, resin acids or salts thereof, phosphoric acid, phosphate esters, phosphates, and 6 Monoethylenically unsaturated polycarboxylic acids or salts thereof or (co) polymers thereof can be exemplified.
  • alkali metal salts of phosphoric acid, ammonium salts, and alkali metal salts of monoethylenically unsaturated monocarboxylic acids and ammonium salts are preferred. It is preferable to use an alkali metal salt or an ammonium salt of condensed phosphoric acid such as hexametaphosphoric acid and tripolyphosphoric acid.
  • the water-soluble salt or water-soluble acid should be added after the step in which the carbonate solution is added to the calcium salt solution, or the calcium salt solution is added dropwise to the carbonate solution to carry out the carbonation reaction. Although it is good, it is preferable to add it after performing the above operations (a) to (f).
  • the washing of the calcium carbonate suspension may be carried out according to a conventional method.
  • the operations such as concentration and dilution may be repeated using a centrifuge, a dehydrator, or the like, or may be performed using a rotary filter, a filter press, or the like. Is also good.
  • the reason why the content of ammonium ion, alkali metal ion or halide ion in the calcium carbonate obtained by drying the suspension can be reduced by the method of the present invention is not clear, but it is estimated as follows. .
  • Ammonia ions, alkali metals, which are free in the suspension liquid Ions and halide ions can be removed by washing, but those that are chemically or physically adsorbed on the particle surface or present inside the particle cannot be removed simply by washing .
  • the above method is adjusted so as to satisfy the following conditions (I) to (V), and preferably adjusted so as to satisfy the following conditions (Ia) to (IIIa).
  • the electrical conductivity of the water suspension is 500 uS / cm or less when the calcium carbonate concentration is 3% by weight.
  • (V) Cubic calcium carbonate obtained by drying contains less than 1, OOOppm of halide ions.
  • the total amount of ammonium ions and alkali metal ions in the aqueous suspension is preferably 200 ppm or less, more preferably 100 ppm or less.
  • ammonium ion and alkali metal ion of a 3% by weight calcium carbonate suspension were measured using an ion concentration meter "Ionme-Ichiichi IM-40S" manufactured by Toa Denpa Kogyo Co., Ltd. 115B), potassium ion (K-135), and ammonium ion (AE-235).
  • the halide ion concentration in the aqueous suspension is preferably 50 ppm or less, more preferably 20 ppm or less.
  • the measurement of the halide ion of a 3% by weight calcium carbonate suspension was carried out by using an ion concentration meter “Ionmeter IM-4OS” manufactured by Toa Denpa Kogyo Co., Ltd. using chlorine ion (CI-125B) and iodine.
  • the ion (1-125) and fluoride ion (F-125) electrodes are used.
  • the electric conductivity of the aqueous suspension when the concentration of calcium carbonate is 3% by weight is preferably 300 S / cm or less, more preferably 100 S / cm or less.
  • the measurement of the electric conductivity of the 3% by weight calcium carbonate suspension is performed using an electric conductivity meter “model SC-82” manufactured by Yokogawa Electric Corporation.
  • Calcium carbonate obtained by the above method has a number of characteristics as described below. -
  • the essential shape is cubic, but the corners and edges of the vertices are rounded, and there are very few sharp knife-shaped edges of cubic carbonic acid rubbish prepared by conventional methods. .
  • the resulting cubic calcium carbonate has extremely low contents of ammonium ion, alkali metal ion and halide ion.
  • DS 2 Diameter (m) of a sphere obtained by volume conversion from the average (im) of one side length of cubic calcium carbonate particles examined by a scanning electron microscope
  • DP1 Particle size (zm) at a cumulative weight of 10% calculated from the large particle size in the particle size distribution measured using a scattering type laser analysis type particle size distribution analyzer (Microcrac-FRA manufactured by Northrop).
  • DP 2 Particle size (m) at 25% cumulative weight calculated from the large particle size in the particle size distribution measured using a scattering type laser analysis type particle size distribution analyzer (Microcrac-FRA manufactured by Northrop).
  • DP 5 Scattering laser—In the particle size distribution measured using an analytical particle size distribution analyzer (Microtrac-FRA manufactured by Northrop Co., Ltd.), the particle size (/ im )
  • the calcium carbonate obtained by the present invention has an average
  • the particle size can be freely selected by adjusting the above conditions over a wide range, specifically, for example, between 0.1 and 20 m.
  • the average particle diameter is 0.1 to 10 in terms of slipperiness, abrasion resistance, light diffusing property, light transmitting property and the like. m is preferable, and 0.1 to 5 ⁇ m is more preferable. If the average particle diameter is less than 0.1 m, the sliding property, abrasion resistance, light diffusion and light transmittance are poor, and if it exceeds 20 m, the abrasion resistance and light transmittance tend to be poor.
  • the calcium carbonate obtained by the present invention has excellent dispersibility and uniformity
  • the dispersibility and uniformity of calcium carbonate are indicated by the relative standard deviation of the particle size.However, the calcium carbonate obtained by the present invention has its relative standard deviation adjusted by adjusting the above conditions. Can be freely selected
  • the relative standard deviation is preferably 0.5 or less from the viewpoint of slipperiness, abrasion resistance, light diffusing property, light transmitting property and the like. , 0.3 or less, more preferably 0.2 or less. If the relative standard deviation exceeds 0.5, the slipperiness and light transmittance tend to be poor.
  • the calcium carbonate obtained by the present invention can reduce the total amount of ammonium ion and aluminum metal contained in the dry powder to 10, OOOppm or less.
  • the total amount of the contained ammonium ions and metal ions is preferably 10, from the viewpoint of yellowing and reddish coloring of transmitted light. OOOppm or less is preferred, 5, OOOppm or less is more preferred, 3, OOOppm or less is more preferred, and l. OOOppm or less is most preferred.
  • the total amount of ammonium ions and metal ions exceeds 10,000 OOp pm, the transmitted light of the obtained lighting cover becomes yellowish / reddish.
  • the measurement of the ammonium ion contained in the dry powder of calcium carbonate is carried out using the phenol blue absorption spectrophotometry in accordance with JI SK 0102-4.2.1.
  • the measurement of alkali metal ions is performed by flame atomic absorption spectroscopy in accordance with JI SK 0102—47.2 (Natrium), 48.2 (Liuium) and the like.
  • the calcium carbonate obtained by the present invention can reduce the total amount of halide ions contained in the dry powder to 1, OOOppm or less.
  • the total amount of halide ions contained is preferably 1, OOO ppm or less, more preferably 500 ppm or less, from the viewpoint of coloring transmitted light. , 300 ppm or less, most preferably 100 ppm or less.
  • the halide ion exceeds lOOOOppm, the transmitted light of the lighting cover is undesirably colored yellowish to reddish.
  • calcium carbonate prepared by the method of the present invention has almost no secondary agglomeration, good dispersibility, uniform individual particles, excellent high-temperature stability, excellent stability over time, ammonium ion, It is a cubic calcium carbonate having a low content of alkali metal ions and halide ions.
  • the calcium carbonate prepared by the method of the present invention may be used in order to further enhance its dispersibility and stability, or depending on the intended use, organic acids such as fatty acids, resin acids, acrylic acid, methacrylic acid, oxalic acid, citric acid, etc.
  • organic acids such as fatty acids, resin acids, acrylic acid, methacrylic acid, oxalic acid, citric acid, etc.
  • organic acids such as fatty acids, resin acids, acrylic acid, methacrylic acid, oxalic acid, citric acid, etc.
  • Organic acids tartaric acid, phosphoric acid, condensed phosphoric acid
  • the surface treatment amount is generally used in an amount of 5% by weight or less based on calcium carbonate.
  • the calcium carbonate prepared by the method of the present invention is dehydrated and concentrated, then dried and pulverized, and is used as a powder in various applications, as well as an aqueous suspension or a suspension of another solvent depending on the application.
  • Calcium carbonate prepared by the method of the present invention may contain other particles used as a light-diffusing material, such as kaolin, talc, black carbon, molybdenum sulfide, gypsum, aluminum oxide, aluminum hydroxide, and sulfuric acid. It can be used in combination with barium, lithium fluoride, calcium fluoride, zeolite, calcium phosphate, silicon dioxide, titanium dioxide, heat-resistant polymers, and the like.
  • calcium carbonate prepared by the method of the present invention includes oxazole-based and coumarin-based fluorescent whitening agents used as colorants for lighting covers and the like, bluing agents such as ultramarine blue, various stabilizers, antioxidants, Even if various additives such as a processing aid and an antistatic agent are added together, the light diffusion property and light transmittance of the calcium carbonate of the present invention are not impaired.
  • the calcium carbonate obtained by the present invention can be used not only for the light diffusing material described so far but also as an additive for other synthetic resins for advanced industrial applications because of its characteristics.
  • synthetic resins include polyolefins such as polyethylene and polypropylene, polystyrene, polyvinyl acetate, and polyacrylic acid.
  • thermosetting resin examples include a phenol resin, an epoxy resin, an unsaturated polyester resin, an alkyd resin, a urea resin, a melamine resin, a urethane resin, and a silicon resin.
  • R 1 magnification of the calcium ion amount of the calcium salt solution added to the number of moles of calcium carbonate in the suspension.
  • Q 2 The ratio of the amount of the liquid after washing and dilution to the amount of the suspension immediately after the reaction when left standing while heating.
  • R 2 Magnification of the amount of potassium salt of the calcium salt solution to be added to the number of moles of calcium carbonate in the suspension when left standing.
  • N 1 Ammonium contained in calcium carbonate dry powder Total amount [ppm]
  • N 2 The amount of chloride ions contained in the dry powder of calcium carbonate.
  • the obtained calcium carbonate suspension was left under stirring for 1 hour, and sodium hexame phosphate equivalent to 0.4% by weight based on the calcium carbonate in the suspension was added to the suspension. Then, the mixture was stirred for 20 minutes. Thereafter, the suspension was repeatedly concentrated and diluted using a centrifugal dehydrator, and the total of the ammonium ion concentration and the alkali metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm, and the electric conductivity was 5%. Was washed to 20 SZ cm.
  • the calcium carbonate suspension was dried, and the amount of ammonium 'Natrium' potassium in the dry powder was determined. The total amount was 9400 ppm, and the amount of chloride ion was 900 ppm. Was.
  • As a result of observing the obtained calcium carbonate with an electron microscope it was found to be a cubic calcium carbonate having a layered aggregate, rounded apexes and edges, and having irregularities on the particle surface. Further, as a result of observation by X-ray diffraction, it was confirmed that the crystal form of the obtained calcium carbonate was almost calcite.
  • Table 1 shows the production conditions of this example, and Table 2 shows the physical properties of the obtained calcium carbonate. Examples 2 and 3
  • a calcium carbonate suspension was prepared under the same conditions as in Example 1 except that the standing time under stirring was changed to 11 hour.
  • the carbonated calcium suspension was dried in the same manner as in Example 1, and the total amount of the ammonium powder and sodium hydroxide in the dry powder was N 1 pm, and the amount of chloride ion was N 2 pm.
  • the obtained calcium carbonate was observed with an electron microscope. As a result, it was found to be a cubic calcium carbonate having a layered aggregate with rounded apexes and edges, and having irregularities or pores on the particle surface.
  • Table 1 shows the production conditions of this example, and Table 2 shows the physical properties of the obtained calcium carbonate.
  • the calcium carbonate suspension prepared under the reaction conditions of Example 1 was allowed to stand for 1 hour with stirring, then the temperature of the suspension was adjusted to 45 ° C, and the suspension was left for 1 hour with stirring. Next, sodium hexaphosphate was added to the suspension in an amount equivalent to 0.4% by weight based on the calcium carbonate in the suspension, and the mixture was stirred for 20 minutes.
  • the suspension was repeatedly concentrated and diluted by a centrifugal dehydrator, and the total of the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm, and the electric conductivity was 2%. Washed until 0 // SZ cm.
  • the calcium carbonate suspension was dried, and the amount of ammonium, sodium and potassium in the dried powder was determined. The total amount was 780 ppm and the amount of chloride ions was 76 O ppm.
  • the obtained calcium carbonate With an electron microscope, it was found to be a cubic calcium carbonate having a layered aggregate, rounded vertices and edges, and having irregularities or pores on the particle surface. Was. Further, as a result of observation by X-ray diffraction, it was confirmed that the crystal form of the obtained calcium carbonate was almost calcite.
  • Table 1 shows the production conditions of this example, and Table 2 shows the physical properties of the obtained calcium carbonate. Examples 5 to 9
  • Example 4 After leaving for 1 hour under stirring, adjust the temperature of the suspension to T1, and change to leave it for 02 hours under stirring, under the same conditions as in Example 4, except for the calcium carbonate suspension. A liquid was made.
  • the suspension of calcium carbonate was dried in the same manner as in Example 1, and the total amount of ammonium 'sodium' potassium in the dry powder was N lppm and the amount of chloride ion was N2ppm.
  • -As a result of observing the obtained calcium carbonate with an electron microscope, it was found to be a cubic calcium carbonate having a layered aggregate, rounded apexes and edges, and having irregularities or pores on the particle surface. .
  • Table 1 shows the production conditions of this example
  • Table 2 shows the physical properties of the obtained calcium carbonate.
  • Example i After the calcium carbonate suspension prepared under the reaction conditions of Example i was left under stirring for 16 hours, the suspension was repeatedly concentrated and diluted with a centrifugal dehydrator to obtain a suspension having a calcium carbonate concentration of 3% by weight. The suspension was washed until the total of the ammonium ion concentration and the metal ion concentration of the aluminum hydroxide became 5 ppm and the electric conductivity became 20 Scm. The suspension after washing was diluted with water to a volume 4 times that of the original reaction solution, the temperature of the suspension was adjusted to 85 ° C, and the suspension was left under stirring for 16 hours.
  • sodium hexamethaphosphate was added to the suspension in an amount equivalent to 0.4% by weight based on the calcium carbonate in the suspension, and the mixture was stirred for 20 minutes.
  • the suspension was repeatedly concentrated and diluted by a centrifugal dehydrator, and the total of the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm, and the electric conductivity was 20%. Washed to S / cm.
  • the carbonated calcium suspension was dried, and the amount of ammonium sodium-potassium in the dry powder was determined. The total amount was 350 ppm, and the chlorine amount was 8 ppm. .
  • Observation of the obtained calcium carbonate with an electron microscope revealed that the shape consisted of a layered aggregate and was rounded at the top and edges. Cubic carbon dioxide with irregularities and pores on the particle surface
  • the calcium carbonate suspension prepared under the reaction conditions of Example 1 was repeatedly concentrated and diluted with a centrifugal dehydrator, and the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight were repeated.
  • the sample was washed until the total was 5 ppm and the electrical conductivity was 20 ⁇ SZ cm.
  • the suspension after washing was diluted with water to an equal volume of the original reaction solution, and left for 1 hour with stirring. Further, sodium hexametaphosphate equivalent to 0.4% by weight based on the calcium carbonate in the suspension was added to the suspension, and the mixture was stirred for 20 minutes.
  • the calcium carbonate suspension prepared under the reaction conditions of Example 1 was repeatedly concentrated and diluted with a centrifugal dehydrator to obtain a suspension having a calcium carbonate concentration of 3% by weight.
  • the concentration of ammonium ions and the concentration of metal ions were measured, and the samples were washed until the total was 5 pm and the electric conductivity was 20 SZcm.
  • the suspension after washing was diluted with water to a volume 4 times that of the original reaction solution, and left under stirring for 16 hours.
  • the suspension was again concentrated and diluted by a centrifugal dehydrator, and the ammonium ion concentration and the alkali metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight were measured.
  • Washing was performed until the electric conductivity reached 2 l / S / cm.
  • the washed suspension was diluted with water to a volume 4 times that of the original reaction solution, and left under stirring for 01 hour. Further, the suspension after washing was diluted with water to a volume four times that of the original reaction solution, adjusted to 85 ° C., and left under stirring for 16 hours.
  • the suspension was concentrated and diluted three times with a centrifugal dehydrator, and the ammonium ion concentration and alkali metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight were measured. Washing was performed until the electric conductivity reached 20 ⁇ SZcm at pm.
  • sodium hexahexaphosphate was added to the suspension in an amount equivalent to 0.4% by weight based on the calcium carbonate in the suspension, and the mixture was stirred for 20 minutes.
  • the suspension was concentrated and diluted with a centrifugal dehydrator four times, and the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight were measured. Washing was performed until the electric conductivity reached 20 S / cm.
  • the calcium carbonate suspension was dried, and the amounts of ammonium, sodium, and potassium in the dry powder were determined. The total was 180 ppm and the amount of chloride ions was 4 ppm.
  • Example 2 To the calcium carbonate suspension prepared under the reaction conditions of Example 1, a calcium chloride solution corresponding to 0.5 times the number of moles of calcium ion relative to the number of moles of calcium carbonate in the suspension was added, The mixture was allowed to stand for 16 hours under stirring, and then 0.4% by weight of sodium hexametaphosphate based on calcium carbonate in the suspension was added to the suspension and stirred for 20 minutes. The suspension was repeatedly concentrated and diluted with a centrifugal dehydrator. The total of the ammonium and aluminum metal concentrations of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm, and the electrical conductivity was 2 ppm. Washed to 0 SZ cm.
  • the carbonated calcium suspension was dried, and the amount of ammonium, sodium and potassium in the dried powder was determined.
  • the total amount was 250 ppm.
  • the chlorine content was determined to be 220 ppm.
  • As a result of observing the obtained calcium carbonate with an electron microscope it was found to be a cubic calcium carbonate having a layered aggregate and rounded apexes and edge portions.
  • Table 1 shows the production conditions of this example, and Table 2 shows the physical properties of the obtained calcium carbonate.
  • Example 2 To the calcium carbonate suspension prepared under the reaction conditions of Example 1, a calcium chloride solution corresponding to calcium ions in an amount R times the number of moles of calcium carbonate in the suspension was added, and stirred. For 0.1 hour, and then an amount of 0.4% by weight, based on the calcium carbonate in the suspension, of sodium hexamephosphate was added to the suspension and stirred for 20 minutes. The suspension was repeatedly concentrated and diluted by a centrifugal dehydrator. The total of the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm, and the electric conductivity was 20%. Washed to / SZ cm.
  • the carbonated calsi The aluminum suspension was dried, and the amount of ammonium, sodium, and potassium in the dried powder was determined. The total amount was N 1 ppm. When the amount of chlorine ions was determined, it was N 2 ppm. Observation of the obtained calcium carbonate with an electron microscope revealed that the shape was a cubic calcium carbonate composed of a layered aggregate and having rounded vertices and edges. Further, as a result of observation by X-ray diffraction, it was confirmed that the crystal form of the obtained calcium carbonate was almost calcite. Table 1 shows the production conditions of this example, and Table 2 shows the physical properties of the obtained calcium carbonate.
  • the calcium carbonate suspension prepared under the reaction conditions of Example 1 was repeatedly concentrated and diluted with a centrifugal dehydrator to reduce the ammonium ion concentration and alkaline metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight. It was washed until the total was 5 ppm and the electrical conductivity was 20 S / cm. The suspension after washing is diluted with water to an equivalent volume of the original reaction solution, and acetic acid corresponding to 0.5 times the number of moles of calcium ions with respect to the number of moles of calcium carbonate in the suspension. The calcium solution was added and left under stirring for 16 hours.
  • the suspension was again concentrated and diluted by a centrifugal dehydrator, and the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight were measured. Washing was performed until the electric conductivity reached 20 pm / SZcm. Dilute the suspension after washing with water to make the same volume as the original reaction solution, adjust to 85 ° C, and use 0.5 times the number of moles of calcium carbonate in the suspension. A calcium acetate solution corresponding to the calcium ions was added and left under stirring for 16 hours.
  • the calcium carbonate suspension prepared under the reaction conditions of Example 1 was repeatedly concentrated and diluted with a centrifugal dehydrator, and the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight were repeated.
  • the sample was washed until the total was 5 ppm and the electric conductivity was 20 SZ cm. Dilute the suspension after washing with water to the same volume as the original reaction solution.Calcium acetate solution corresponding to 1 times the number of moles of calcium ions relative to the number of moles of calcium carbonate in the suspension was added and left under stirring for 01 hour.
  • the suspension was again concentrated and diluted by a centrifugal dehydrator, and the concentration of ammonium carbonate and the concentration of metal ion in a suspension having a calcium carbonate concentration of 3% by weight were measured. Washing was performed until the conductivity reached 20 SZcm at ppm. Dilute the suspension after washing with water to make the same volume as the original reaction solution, adjust to T 1 ° C, and R 2 times the number of moles of calcium carbonate in the suspension. A calcium acetate solution corresponding to the calcium ion was added, and the mixture was left under stirring for 02 hours.
  • Carbon dioxide gas was blown into the calcium carbonate suspension prepared under the reaction conditions of Example 1 until the pH of the suspension dropped to 3.0, and the suspension was left under stirring for 1 hour. After standing, the suspension was repeatedly concentrated and diluted by a centrifugal dehydrator, and the concentration of ammonium carbonate and the concentration of metal ions in the suspension having a calcium carbonate concentration of 3% by weight were measured.
  • the concentration of ammonium carbonate and the concentration of metal ions in the suspension having a calcium carbonate concentration of 3% by weight were measured.
  • the calcium carbonate suspension was dried, and the amount of ammonium, sodium, and potassium in the dried powder was determined. The total amount was 320 ppm, and the amount of chloride ions was 300 ppm. Observation of the obtained calcium carbonate with an electron microscope revealed that the shape was a rounded cubic calcium carbonate composed of a layered aggregate at the vertices and edges. Further, as a result of observation by X-ray diffraction, it was confirmed that the crystal form of the obtained calcium carbonate was almost calcite. Table 1 shows the production conditions of this example, and Table 2 shows the physical properties of the obtained calcium carbonate.
  • N1 Ammonia 'alkali amount (ppm) 5800 180 2500 2400 2200 800 780 760 3200
  • N2 halide ion amount (ppm) 550 4 220 210 200 20 18 16 300
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10
  • the suspension was repeatedly concentrated and diluted by a centrifugal dehydrator to obtain a total of 400 ppm of the ammonium ion concentration and the aluminum ion concentration of the suspension having a calcium carbonate concentration of 3% by weight. Washing was performed until the total halide ion content reached 200 ppm and the electrical conductivity reached 600 SZ cm.
  • the calcium carbonate suspension was dried, and the amount of ammonium, sodium and potassium in the dried powder was determined, and the total amount was 5800 ppm. Further, the amount of chloride ions was 600,000 ppm.
  • the shape was a rounded cubic carbonic acid luminum having layered aggregates at the vertices and edges.
  • Table 3 shows the production conditions of this comparative example, and Table 4 shows the physical properties of the obtained carbonated calcium carbonate.
  • the suspension was repeatedly concentrated and diluted by a centrifugal dehydrator, and the total of the ammonium ion concentration and the metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm. Washing was performed until the conductivity reached 20 // SZ cm.
  • the calcium carbonate suspension was dried, and the amount of ammonium and sodium potassium in the dried powder was determined. The total amount was 360,000 ppm and the amount of chloride ion was 290 ppm. Was.
  • the resulting carbonic acid As a result of observing the calcium with an electron microscope, it was found to be a rounded cubic calcium carbonate composed of layered aggregates at the vertices and edges.
  • the calcium carbonate suspension obtained by adding sodium hexaphosphate and obtained in Comparative Example 1 and washed was further concentrated and diluted by a centrifugal dehydrator to repeat the ammonium carbonate suspension having a calcium carbonate concentration of 3% by weight. Washing was performed until the sum of the metal ion concentration and the alkali metal ion concentration became 1 ppm and the gas conductivity reached 5 S / cm.
  • the calcium carbonate suspension was dried, and the amount of ammonium, sodium, and potassium in the dry powder was determined. The total amount was 1,800 ppm. Further, the amount of chloride ions was 190,000 ppm. Observation of the obtained calcium carbonate with an electron microscope revealed that the shape was rounded cubic calcium carbonate composed of a layered aggregate at the vertices and edges. Further, as a result of observation by X-ray diffraction, it was confirmed that the crystal form of the obtained calcium carbonate was almost calcite. Table 3 shows the production conditions of this comparative example, and Table 4 shows the physical properties of the obtained calcium carbonate.
  • Example 1 The calcium carbonate suspension prepared under the reaction conditions of Example 1 was allowed to stand for 45 minutes under stirring, and then suspended with 0.4% by weight of sodium hexametaphosphate equivalent to calcium carbonate in the suspension. Added to the suspension and stirred for 20 minutes
  • the calcium carbonate suspension prepared under the reaction conditions of Example 1 was adjusted to 85 and allowed to stand under stirring for 1 hour. Then, an amount equivalent to 0.4% by weight based on the calcium carbonate in the suspension was obtained. Sodium hexaphosphate was added to the suspension and stirred for 20 minutes. After that, the suspension was repeatedly concentrated and diluted by a centrifugal dehydrator, and the total of the ammonium ion concentration and the alkali metal ion concentration of the suspension having a calcium carbonate concentration of 3% by weight was 5 ppm. Was washed to 20 S / cm. The calcium carbonate suspension was dried, and the amount of ammonium “sodium” potassium in the dry powder was determined. The total amount was 1150 ppm.
  • the amount of chloride ions was 130 ppm.
  • the obtained calcium carbonate As a result of observing the obtained calcium carbonate with an electron microscope, it was found to be a cubic calcium carbonate having a rounded shape composed of a layered aggregate at the vertices and edges, and having irregularities or pores on the particle surface. Further, as a result of observation by X-ray diffraction, it was confirmed that the crystal form of the obtained calcium carbonate was almost calcite.
  • Table 3 shows the production conditions of this comparative example, and Table 4 shows the physical properties of the obtained calcium carbonate. Comparative Examples 6, 7
  • Comparative Example 6 a calcium carbonate reagent special grade (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared. As Comparative Example 7, heavy calcium carbonate “R heavy coal” (manufactured by Maruo Calcium) was prepared.
  • R1 Calcium salt addition rate ⁇ 1 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Other ⁇ 1 ⁇ Finish after washing ⁇ 1 ⁇ Washing before heating and standing ⁇ 1 ⁇ 1 No ⁇ ⁇
  • N1 Ammonia 'alkali content (ppm) 58000 36000 18000 12000 11500 ⁇ 5 250
  • N2 halide ion amount (ppm) 6000 2900 1900 1100 1300 ⁇ 1 21
  • the molten resin was extruded from a T-die at a resin temperature of 265 ° C using (Tanabe Plastics Machinery Co., Ltd.), and passed through three polishing rolls to obtain a sheet having a width of 23 cm and a thickness of 2 mm.
  • the obtained sheet was observed with a transmission microscope and judged according to the following criteria. A: No aggregated particles or coarse particles are observed.
  • the obtained sheet was visually determined and evaluated according to the following criteria.
  • ⁇ Irregularities are visible on a part of the surface.
  • T t Total light transmittance
  • the following transmitted light intensity was measured using an automatic goniophotometer GR-1R (manufactured by Murakami Color Research Laboratory). / Is light diffusing. .
  • the yellowness of reflected light and transmitted light was determined using SM-2 manufactured by Suga Test Instruments. The higher the number, the more yellow.
  • ⁇ More preferable than the conventional light diffusion sheet.
  • ⁇ equivalent to a conventional light diffusion sheet.
  • X Not suitable as a light diffusion sheet.
  • the suspensions of calcium carbonate obtained in Examples 1, 3, 10, 15 and 18 and Comparative Examples 1 to 5 were added with a surface treatment agent (acrylic) equivalent to 5% by weight based on calcium carbonate.
  • a surface treatment agent (acrylic) equivalent to 5% by weight based on calcium carbonate.
  • the surface treatment of a copolymer of acid and butyl methacrylate in which the weight ratio of each is 70:30, in which 20% of the total carboxyl groups in the acrylic acid portion are in the form of an ammonium salt) is carried out with stirring.
  • ethylene glycol slurry was added, and further, the water was removed by flushing using an evaporator to prepare ethylene glycol slurry of calcium carbonate.
  • the solid concentration of calcium carbonate in ethylene glycol was 20.0 weight.
  • the film was stretched in the transverse direction at a temperature of 90 ° C. and then heat-treated at 200 to obtain a biaxially oriented film having a thickness of 10 / m.
  • the quality of the film thus obtained was evaluated by the following method. Tables 7 and 8 show the results.
  • the polyester composition was observed with a transmission microscope and judged according to the following criteria.
  • Fig. 1 is the take-out reel
  • 2 is the tension controller
  • 1 1 is a free roller
  • 4 is a tension detector (entrance)
  • 7 is a stainless steel net SUS304 fixed pin (outer diameter 5 mm)
  • 10 is a tension detector
  • a slit of film with a width of 1.27 cm (1Z2 inch) was placed on a stainless steel fixing pin 7 (surface roughness 0.58) at an angle of 150 ° using the above device. Contact and reciprocate about 15 cm at a speed of 2 m / min. In this case, the entry side tension T] is 70 g.
  • ⁇ Scratches account for half of the film surface.
  • the sharpness of the film running surface is evaluated using a five-stage mini super calendar.
  • the force renderer is a five-stage force renderer consisting of a nip roll and a steel roll.
  • the processing temperature is 80 ° C
  • the linear pressure on the film is 200 kg cm
  • the film speed is 7 OmZ.
  • the dirt adhering to the top roller of the force renderer is used to evaluate the scalability of the film based on the following criteria.
  • the measurement was performed using an AC withstand voltage tester in accordance with JIS-C2318. That is, using a 10 kV DC withstanding voltage tester, the voltage was increased at a rate of 100 / ⁇ 6 in an atmosphere of 23 ° C and 50% RH, and the film was broken and the The voltage at the time of shutdown was measured.
  • the obtained aluminum-deposited polyester film was slit into a 4.5 mm wide tape having a left or right margin of 1 mm. Further, one roll of each of the left margin and right margin vapor deposition films was wound in the width direction such that the vapor deposition portion protruded by 0.5 mm to obtain a roll.
  • the wound body was pressed for 5 minutes at a temperature 1 4 0 ° C ⁇ pressure 4 9. 0 3 5 1 0 5 P a (5 0 K g ⁇ cm 2), Metariko on both end surfaces of the wound body after pressing After melting the lead into a lead wire, impregnating it with a liquid epoxy resin, then heating and melting the powdered epoxy resin to provide a 0.5 mm thick outer casing with a capacitance of 0.1 ⁇ F A film capacitor was obtained.
  • the capacitance [C] of the obtained film capacitor was measured using a Yokogawa Hewlett Packard LCR meter 4284 A under an atmosphere of 23 ° C and 50% RH.
  • the obtained film capacitor was applied with a DC voltage of 100 V between the electrodes of the capacitor at 23 ° C using a high resistance meter 4329 A made by Yokogawa Hyurette Packard Co., Ltd.
  • the resistance value R was measured. Note that the resistance value R showed the maximum value immediately after the voltage was applied, and then decreased.
  • the resulting film was comprehensively evaluated according to the following criteria.
  • A Optimum as a film capacitor.
  • ⁇ More preferable than the conventional film capacitor, ⁇ : Equivalent to the conventional film capacitor, X: Unsuitable as the film capacitor.
  • Example 18 Particle dispersibility in polyester composition ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ specific resistance when melted polyester composition ( ⁇ [ ⁇ 'cm]) 1 X 10 one 7 7x 10- 7 4x10- 8 7x 10- 7 3.5X 1 ( ⁇ 8 wear properties of film evaluation I ⁇ O O O ⁇ ⁇ Evaluation of film wear characteristics ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Number of coarse protrusions on the film surface Class 5 Class 5 Class 5 Class 5 Dielectric breakdown voltage of film [V'jUm] 730 650 530 530 680 700 Insulation resistance characteristics of film '[CX R [ ⁇ -F ]] 2.8 X 10- 4 3.1 X 10- 4 4.0 X 10- 4 3.1 10- 4 3.5 X 10- 4 overall evaluation O ⁇ _ ⁇ ⁇ ⁇ ⁇ _ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • the dispersibility is good, the unnecessary fine particles and the coarse particles are not contained, the particle size is extremely uniform, and the particle size distribution can be obtained in a sharp particle size range.
  • Cubic calcium carbonate with a wide range of sizes, arbitrarily set particle size, high-temperature stability, extremely long-term stability, and a low content of ammonium ions, alkali metal ions, and halide ions.
  • it can be suitably used in applications where the presence of ammonium ions, alkali metal ions, and chloride ions interferes, and its usefulness is extremely large.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne un procédé de fabrication de carbonate de calcium en cubes. A partir d'une solution carbonatée et d'une solution de calcium, dont l'une au moins renferme un agent tampon, le procédé consiste à : ajouter goutte par goutte la solution carbonée dans la solution de calcium, ou ajouter goutte à goutte la solution de calcium à la solution carbonée, tout en brassant, de manière à déclencher une réaction donnant du carbonate de calcium; laisser reposer ou agiter la suspension de carbonate de calcium ou la solution diluée de carbonate de calcium ainsi obtenues pendant une heure ou plus, avec chauffage éventuel ou traitement analogue, de manière à extraire les ions ammonium, alcali ou halide; ajouter un sel ou un acide hydrosoluble capable de réagir avec le calcium et de former un sel non soluble ou difficile à dissoudre dans l'eau en une fois après formation du carbonate de calcium. Ce procédé permet d'obtenir du carbonate de calcium sous forme cubique pratiquement exempt d'agglomérats secondaires, qui est remarquable en termes de dispersibilité des différentes particules, d'homgénéité, de stabilité à haute température et de stabilité à long terme, et qui se caractérise en outre par une faible teneur en impuretés.
PCT/JP2000/008564 1999-12-06 2000-12-04 Production de carbonate de calcium de forme cubique WO2001042139A1 (fr)

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JP2001543446A JP4658431B2 (ja) 1999-12-06 2000-12-04 立方体状炭酸カルシウムの製造方法
AU16511/01A AU1651101A (en) 1999-12-06 2000-12-04 Method for producing calcium carbonate in cubic form

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JP11/345819 1999-12-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006027915A (ja) * 2004-07-12 2006-02-02 Maruo Calcium Co Ltd 多面体炭酸カルシウムの製造方法
JP2009518280A (ja) * 2005-12-12 2009-05-07 ソルヴェイ（ソシエテ アノニム） 沈降炭酸カルシウムの粒子、該粒子を製造するための方法及び該粒子の充填剤としての使用
JP2013512298A (ja) * 2009-11-27 2013-04-11 ビーエーエスエフ ソシエタス・ヨーロピア ポリマー含有被覆の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102450679B1 (ko) * 2022-03-30 2022-10-06 한국지질자원연구원 첨가제 없이 칼슘 용액과 탄산 용액의 혼합 조건 조절을 통한 탄산칼슘의 크기 및 형태 조절방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100264A (en) * 1976-12-23 1978-07-11 Westinghouse Electric Corp. Process for the preparation of calcium carbonate for use in fluorescent lamp phosphors
JPH07196316A (ja) * 1993-12-29 1995-08-01 Maruo Calcium Co Ltd 立方体状炭酸カルシウムの製造方法
JPH10130020A (ja) * 1996-10-25 1998-05-19 Maruo Calcium Co Ltd 粒子径が制御された立方体炭酸カルシウムの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100264A (en) * 1976-12-23 1978-07-11 Westinghouse Electric Corp. Process for the preparation of calcium carbonate for use in fluorescent lamp phosphors
JPH07196316A (ja) * 1993-12-29 1995-08-01 Maruo Calcium Co Ltd 立方体状炭酸カルシウムの製造方法
JPH10130020A (ja) * 1996-10-25 1998-05-19 Maruo Calcium Co Ltd 粒子径が制御された立方体炭酸カルシウムの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006027915A (ja) * 2004-07-12 2006-02-02 Maruo Calcium Co Ltd 多面体炭酸カルシウムの製造方法
JP4711648B2 (ja) * 2004-07-12 2011-06-29 丸尾カルシウム株式会社 多面体炭酸カルシウムの製造方法
JP2009518280A (ja) * 2005-12-12 2009-05-07 ソルヴェイ（ソシエテ アノニム） 沈降炭酸カルシウムの粒子、該粒子を製造するための方法及び該粒子の充填剤としての使用
JP2013512298A (ja) * 2009-11-27 2013-04-11 ビーエーエスエフ ソシエタス・ヨーロピア ポリマー含有被覆の製造方法

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