WO2006082927A1 - Procede de production de poudre de silicate lamellaire - Google Patents

Procede de production de poudre de silicate lamellaire Download PDF

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Publication number
WO2006082927A1
WO2006082927A1 PCT/JP2006/301873 JP2006301873W WO2006082927A1 WO 2006082927 A1 WO2006082927 A1 WO 2006082927A1 JP 2006301873 W JP2006301873 W JP 2006301873W WO 2006082927 A1 WO2006082927 A1 WO 2006082927A1
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Prior art keywords
positively charged
organic compound
charged organic
flaky
layered silicate
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PCT/JP2006/301873
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English (en)
Japanese (ja)
Inventor
Kenji Tamura
Hirohisa Yamada
Shingo Yokoyama
Hikaru Uno
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National Institute For Materials Science
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Priority to JP2007501647A priority Critical patent/JP4747343B2/ja
Publication of WO2006082927A1 publication Critical patent/WO2006082927A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type

Definitions

  • a composite composed of a non-swellable layered silicate having a K ion between layers and a primary particle diameter of more than 2 m and a positively charged organic compound is heated at a temperature of 400 ° C or higher.
  • the present invention relates to a method for producing a flaky silicate powder by cleaving a laminate by burning a positively charged organic compound.
  • flaky inorganic powders such as mica have a particle thickness of 1 m or less, they are affected by the so-called “volume effect” and “surface effect”. It was used as an additive.
  • a flaky inorganic powder is coated on a surface with a transparent or translucent metal oxide layer (for example, acid titanium oxide iron oxide) having a high refractive index on the surface.
  • Pigments are marketed as pearlescent pigments that give off a pearly luster and are used in many areas of the industry, such as automotive paints, decorative coatings, plastic coloring, paints, printing inks, especially paper as a support, plastics Alternatively, it is used in various fields such as interference pigments for the production of anti-counterfeiting security applications (Patent Document 1) based on other base materials.
  • Patent Document 1 interference pigments for the production of anti-counterfeiting security applications
  • the thickness of the flaky inorganic substrate itself was controlled and prepared by changing the material type and synthesis conditions of the substrate or using a mechanical method such as grinding.
  • a mechanical method such as grinding.
  • synthetic mica it can be obtained by a melt synthesis method or a solid phase synthesis method using other silicate compounds as starting materials. Control is difficult.
  • layered titaure use the swelling property between layers It is known to obtain a flaky fine powder by firing a dried sample having organic molecules inserted therein or by firing a gelled product in which an organic thickener is added to an inorganic sol! / Patent Document 4 , Five).
  • Smectite which has a crystal structure similar to mica, is known as a substance that can be easily exfoliated because of its swelling property, but it is a polycrystal of the smallest inorganic fine particles in the soil and has a primary particle size of 2.0 m. It is defined as follows (see: “Clay Nord Book” 2nd edition, edited by the Japan Clay Society, paragraphs 1-6), and the stacking is very irregular. In X-ray diffraction, a broad two-dimensional reflection (hk band) is seen except for the bottom reflection, and it is considered a two-dimensional crystal without a three-dimensional structure by regular stacking. Due to these characteristics, smectite cannot provide satisfactory characteristics for the above applications.
  • the synthetic fluorine my strength which is swellable with water and the like as with smectite, is larger than smectite in terms of a single sheet area with a higher crystallinity of the layer surfaces in the a and b axis directions, but is a regular lamination.
  • non-swellable layered silicates such as mica minerals, mica clay minerals, and vermiculite.
  • non-swellable mica clay minerals and mica minerals are generally said to have no ion exchange properties (for example, Non-patent document 1), it was difficult to obtain an intercalation compound in which an organic molecule was inserted between layers.
  • Non-Patent Document 1 H.van Olphen.Chap. 5 Clay Mineralogy, III. ILLITE (NONEXPANDI ND 2: 1 LAYER CLAYS), In "Anlntroduction to Clay Colloid Chemistry: for clay tec hnologists, geologists, andsoil scientists" 2nd ed, New York: Wiley, (1977) 68-69.
  • Patent Document 1 Special Table 2004-532284
  • Patent Document 2 Japanese Patent Laid-Open No. 08-176459
  • Patent Document 3 Japanese Patent Laid-Open No. 10-279828
  • Patent Document 4 Japanese Patent Laid-Open No. 09-0222712
  • Patent Document 5 Japanese Patent Laid-Open No. 11-079712
  • the present invention provides a thin film by cleaving a regular stack of non-swellable silicates having a large primary particle size. It aims at providing the method of manufacturing flake silicate powder industrially.
  • the present inventor has heated the composite of non-swelled layered silicate and positively charged organic compound under an average particle size of more than 2 m under specific conditions. By processing, it was found that the organic matter was burned, the non-swellable layered silicate was cleaved, and the exfoliated powder could be recovered, and the present invention was made based on this finding.
  • the present invention provides a method for producing a flaky silicate powder by forming an organic-inorganic composite of a non-swelled layered silicate and a positively charged organic compound, and then heating at a temperature of 400 ° C or higher. It is. That is, the present invention has been solved by adopting the configurations shown in the following [1] to [7].
  • a composite composed of a non-swellable layered silicate having a K ion between layers and a primary particle size of more than 2 m and a positively charged organic compound is heated at a temperature of 400 ° C or higher to be positively charged.
  • M is a cation other than K between the layers, Li, Na, Rb, Cs, NH
  • X and Y are metals that enter the octahedron formed in the 2: 1 type sheet X is at least one of Mg, Fe, Mn, Cu, Ni, Zn, and Li, and Y is at least one of Al, Fe, ⁇ , Ti, and Cr.
  • the positively charged organic compound is a primary to tertiary amine salt, quaternary ammonium salt, or amino acid salt having 6 or more carbon atoms.
  • Process for producing flaky silicate powder is a primary to tertiary amine salt, quaternary ammonium salt, or amino acid salt having 6 or more carbon atoms.
  • the concentration of the positively charged organic compound solution is 0.01 N or more, and the solid-liquid ratio of the non-swellable layered silicate Z positively charged organic compound solution is 0.1 (mass ratio) or less 0.001 or more
  • the non-expandable layered silicate powder is added to a solution of a positively charged organic compound and heat-treated at a temperature in the range of 40 to 200 ° C., so that K ions between the layers of the layered silicate crystal are reduced.
  • 0.6 ⁇ a ⁇ l. 0, 0 ⁇ b ⁇ 0. 1, 0 ⁇ c ⁇ 3, 0 ⁇ d ⁇ 2, 2 ⁇ c + d ⁇ 3, 0 ⁇ e ⁇ 4, 0 ⁇ f ⁇ 2 M is a cation other than K between the layers, Li, Na, Rb, Cs, NH,
  • At least one of Be, Mg, Ca, Sr, Ba, Mn, Fe, Ni, Cu, Zn, Al, X and Y are metals that enter the octahedron formed in the 2: 1 type sheet.
  • X is at least one of Mg, Fe, Mn, Cu, Ni, Zn, and Li
  • Y is at least one of Al, Fe, ⁇ , Ti, and Cr.
  • the sheet (2: 1 type sheet) here refers to two tetrahedral layers in which silicon or aluminum enters the center of anions such as oxygen as cations, and octagons centered on divalent or trivalent cations. This means a single unit layer structure that is composed of one face layer and its thickness is about lnm.
  • Layered silicate has a three-dimensional crystal structure made up of stacked sheets.
  • the K ions between the layers are substituted between the layers so as to balance the negative charge of the silicate sheet, and the amount is the coefficient a in the above chemical formula, the number of charges per half unit cell (charge density). ).
  • charge density the number of charges per half unit cell
  • the range of 0.6 ⁇ a ⁇ l. 0 is applied. If the charge density is less than 0.6, it becomes a smectite region. The core diameter tends to be small, and if it exceeds 1.0, the attractive force between the laminated sheets becomes too strong, making it difficult to replace the layers with organic substances.
  • the layered silicate defined by the above composition formula in the range of 0.6 ⁇ a ⁇ l.0 is specifically mica (my force) such as muscovite, phlogopite, biotite, brittle mica,
  • mica my force
  • Illustrative examples include mica clay minerals such as illite, sericite, sea green stone (Groconite), and celadonite, and vermiculites such as dioctahedral vermiculite and 3-octahedral vermiculite.
  • the primary particles having an average particle diameter of ⁇ ⁇ m to 500 ⁇ m are applied, and the range of 2 ⁇ m to 200 ⁇ m is further applied. Is preferred.
  • the primary particle size of the non-swellable layered silicate is large, and the positively charged organic compound burns after the heat treatment, whereby the lamination is cleaved, and a thinned sheet having a large layer surface can be obtained. If the average particle size is less than 2 m, the layer area becomes small and the properties as a flaky inorganic substrate may be impaired. If the average particle size exceeds 500 m, the positively charged organic compound may be inter-forced between the layers. It becomes difficult.
  • a sedimentation type particle size measurement method in a solvent such as water, a light scattering method, a method of directly observing the particles with a microscope, etc., and the like can be applied. Since the layered silicate is a plate-like crystal, the a- and b-axis directions of the crystal are directly observed with a transmission electron microscope and a scanning electron microscope rather than the sedimentation-type particle size measurement method and light scattering method, which are obtained by spherical conversion. A method for obtaining the ratio of the major axis to the minor axis from the projected two-dimensional image is preferable, and this method is also used in the present invention.
  • the organic-inorganic composite of the present invention comprises a non-swellable layered silicate and a positively charged organic compound, and the positively charged organic compound reacts with the layered silicate by intermolecular forces such as electrostatic interaction and hydrogen bonding. It is compounded. That is, a form in which organic molecules are adsorbed on the end of the non-swellable layered silicate layer by an interaction such as a hydrogen bond is also included.
  • a particularly preferred form is an intercalation compound in which a positively charged organic compound is inter-forced between non-swellable silicate layers.
  • the type of the positively charged organic compound used in the present invention is not particularly limited, but preferred examples include primary amines, secondary amines, tertiary amines having 6 or more carbon atoms, and salts thereof. Quaternary ammonium salts, amine compounds, amino acid derivatives, nitrogen-containing heterocyclic compounds Or phospho-um salt.
  • the upper limit of the carbon number is not particularly limited, but it may be about 100 or less.
  • the amount of the positively charged organic compound in the organic-inorganic composite of the present invention preferably contains 0.4 to 5 equivalents with respect to the interlayer Kion amount of the layered silicate. 3 equivalents are most preferred That's right.
  • the positively charged organic compound content here refers to the positively charged organic compound that is physically adsorbed on the surface of the organic / inorganic composite, rather than only the positively charged organic compound that is ion-exchanged with the K ions between the layers. This is the total amount of organic substances, including compounds, that can be estimated for thermogravimetry.
  • the exfoliation may not proceed sufficiently, and if it exceeds 5 equivalent, excess positively charged organic It takes a long time to burn the compound, which may increase the cost.
  • the thickness of the exfoliated sheet obtained by heat-treating the organic-inorganic composite can be controlled by the content of the positively charged organic compound, the combustion conditions, and the like. For example, by reducing the amount of processing of positively charged organic compounds and leaving a K ion-containing layer (untreated layered silicate) in the organic-inorganic composite, a flake sheet with a thickness of tens of layers after combustion is prepared. can do.
  • the concentration of the positively charged organic compound solution is 0.
  • the solid-liquid ratio of the non-swellable layered silicate Z positively charged organic compound solution is 0.1 N or more, and is characterized by being 0.1 (mass ratio) or less.
  • concentration is less than 01N, a sufficient ion exchange reaction cannot be induced, and even if it is treated for a long time, it is only necessary to exchange potassium ions between some layers. It cannot be used as a preparation.
  • concentration of the positively charged organic compound solution can be up to the limit concentration obtained as a solution.
  • Non-swellable layered silicate Z If the solid-liquid ratio of the positively charged organic compound solution is lower than 0.001, it is not desirable in terms of cost.
  • the layered silicate powder is added to a concentrated solution of the positively charged organic compound and subjected to heat treatment.
  • the K ion between the layers of the layered silicate crystal is replaced with a positively charged organic compound and organically modified.
  • the treatment temperature at this time is preferably in the range of 40 to 200 ° C. If the temperature is lower than 40 ° C, the positively charged organic compound cannot be uniformly intercalated between the layers. If the temperature is higher than 200 ° C, decomposition of organic substances and polymerization may occur.
  • an organic-inorganic composite can be produced by a two-stage ion exchange method in which an organic-inorganic composite is formed with the specific positively-charged organic compound and then replaced with a different positive-charged organic compound.
  • the flaky silicate particles in the present invention are recovered as a fine powder by heat-treating the organic-inorganic composite.
  • the temperature at which the positively charged organic compound is burned off by heating is 400 ° C or higher, usually 400 to 1200, preferably 600 to 1000. Do in C. 400. If it is less than C, there is a risk that the carbonized residue of the positively charged organic compound will increase, and that thinning will not be sufficiently achieved.
  • the organic compound is periodically inserted between the layers of the layered silicate, and the organic compound between the layers is burned out by the combustion of the positively charged organic compound, so that the flaky silicate fine powder of uniform particle size Can be easily obtained.
  • an organic thickener can be used as an additive agent in the concentrated solution in order to relieve secondary aggregation during combustion.
  • the organic thickener include stearic acid, stearylamine, gelatin, hydroxyethyl cellulose, and polyvinyl alcohol. These are concentrated solutions of positively charged organic compounds including non-swellable layered silicates. By adding in, the effect which suppresses aggregation of particle
  • nonionic organic thickeners such as alkyl cellulose compounds and high molecular polysaccharides are suitable so as not to impair their electrostatic interaction.
  • This organic thickener is present between the non-swellable layered silicate particles and acts to prevent secondary aggregation of the particles.
  • Cation exchange capacity (CEC) measurement method applied to swellable clay minerals Column penetration method (Reference: “Clay Handbook” 2nd edition, Japan Clay Society, pp. 576-577, Gihodo edition) Adsorption method (Japan Bentonite Industry Association Standard Test Method, JBAS-107-9 The method 1) cannot be applied. Therefore, a method for estimating by chemical composition analysis is applied. Specifically, plasma spectroscopy (ICP) analysis, X-ray fluorescence analysis (XRF), X-ray microanalyzer (EPMA), etc. are used.
  • ICP plasma spectroscopy
  • XRF X-ray fluorescence analysis
  • EPMA X-ray microanalyzer
  • DA was able to interact between layers (Fig. 2c).
  • the amount of ODA estimated by thermogravimetry (TG) was about 32% by mass, corresponding to 0.6 equivalent of the total amount of potassium ions between layers.
  • This ODA-Z20 was heat-treated at 700 ° C for 6 hours, and then a sample was collected and subjected to XRD measurement. As a result, a weak and broad 001 reflection was observed, and the bottom distance of sericite was reduced to about 1. Onm (Fig. 6). As a result of observing the morphology of this sample, a thinned sheet was confirmed, and its thickness was approximately 10-30 nm (Fig. 7).
  • Example 2 All tests were performed in the same manner as in Example 2 except that the heat treatment conditions in Example 2 were changed to 1000 ° C for 3 hours. As a result of XRD measurement of the sample after combustion, 001 reflection was not observed (Fig. 8). In the SEM image of this sample, a sheet that was thinned to a thickness of several to several tens of nanometers and flexed flexibly was confirmed (Fig. 9).
  • a mixture of a non-swellable layered silicate added with a positively charged organic compound is heated to burn the positively charged organic compound, whereby a silicic acid having a flaky form is obtained.
  • the salt powder can be provided. The thickness can be controlled, and application to cosmetics and paints is expected.
  • FIG. 6 X-ray diffraction (Fe—Ka line) pattern of the flaky powder sample prepared in Example 2.
  • FIG. 8 shows an X-ray diffraction (Fe—Ka line) pattern of the flaky powder sample prepared in Example 3.

Abstract

L’invention concerne un procédé de production à l’échelle industrielle d’une poudre de silicate lamellaire en clivant des couches régulièrement superposées d’un silicate non gonflant qui ont un diamètre de particules primaires élevé. Un composite d’un phyllosilicate non gonflant ayant des ions potassium entre les feuilles de celui-ci et un diamètre de particules moyen supérieur à 2 µm avec un composé organique chargé positivement est chauffé pour brûler la substance organique et cliver le phyllosilicate non gonflant, et une poudre lamellaire est recueillie. Le contrôle de l’épaisseur est possible et la poudre est destinée à être appliquée sur des produits cosmétiques ou des matériaux de revêtement. Le phyllosilicate non gonflant est représenté par la formule générale suivante. [(KaM0.1-b)(XcYd)(Si4-eAle)O10(OHfF2-f)] Dans la formule, 0,6≤a≤1,0 ; 0≤b≤0,1 ; 0≤c≤3 ; 0≤d≤2 ; 2≤c+d≤3 ; 0≤e<4 ; 0≤f≤2 ; M est un cation, autre que le potassium, présent entre les feuilles ; et X et Y sont chacun un métal incorporé dans l’octaèdre formé dans une feuille de type 2:1.
PCT/JP2006/301873 2005-02-03 2006-02-03 Procede de production de poudre de silicate lamellaire WO2006082927A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011165642A (ja) * 2010-01-13 2011-08-25 Toyota Motor Corp リチウムイオン二次電池
JP2016141793A (ja) * 2015-02-05 2016-08-08 Dic株式会社 ポリオレフィン樹脂組成物、及びガスバリア材

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000264823A (ja) * 1999-03-17 2000-09-26 Noevir Co Ltd 耐紫外線組成物及び容器
JP2001200179A (ja) * 2000-01-21 2001-07-24 Noevir Co Ltd 表面被覆処理粉体及びその製造方法、並びにそれを含有する皮膚外用剤
JP2003095639A (ja) * 2001-09-27 2003-04-03 Topy Ind Ltd 撥水性層状ケイ酸塩粉体、その製法及び該粉体を含有する化粧料
JP2004307311A (ja) * 2003-02-19 2004-11-04 National Institute Of Advanced Industrial & Technology 板状ケイ酸カルシウムとその製造方法、並びに板状ケイ酸カルシウムから得た板状シリカ多孔体とその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000264823A (ja) * 1999-03-17 2000-09-26 Noevir Co Ltd 耐紫外線組成物及び容器
JP2001200179A (ja) * 2000-01-21 2001-07-24 Noevir Co Ltd 表面被覆処理粉体及びその製造方法、並びにそれを含有する皮膚外用剤
JP2003095639A (ja) * 2001-09-27 2003-04-03 Topy Ind Ltd 撥水性層状ケイ酸塩粉体、その製法及び該粉体を含有する化粧料
JP2004307311A (ja) * 2003-02-19 2004-11-04 National Institute Of Advanced Industrial & Technology 板状ケイ酸カルシウムとその製造方法、並びに板状ケイ酸カルシウムから得た板状シリカ多孔体とその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011165642A (ja) * 2010-01-13 2011-08-25 Toyota Motor Corp リチウムイオン二次電池
JP2016141793A (ja) * 2015-02-05 2016-08-08 Dic株式会社 ポリオレフィン樹脂組成物、及びガスバリア材

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JP4747343B2 (ja) 2011-08-17

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