WO2005085168A1 - 有機酸アニオン含有アルミニウム塩水酸化物粒子、その製造方法およびその利用 - Google Patents
有機酸アニオン含有アルミニウム塩水酸化物粒子、その製造方法およびその利用 Download PDFInfo
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- WO2005085168A1 WO2005085168A1 PCT/JP2005/003831 JP2005003831W WO2005085168A1 WO 2005085168 A1 WO2005085168 A1 WO 2005085168A1 JP 2005003831 W JP2005003831 W JP 2005003831W WO 2005085168 A1 WO2005085168 A1 WO 2005085168A1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/06—Oxalic acid
- C07C55/07—Salts thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
- C07C59/08—Lactic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/255—Tartaric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
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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
Definitions
- the present invention relates to an organic acid anion-containing aluminum salt hydroxide particle, a method for producing a soybean and its use. That is, various fields, for example, construction, food, agriculture, semiconductor, electrophotography, medical, cosmetics, chemistry, resin, rice field
- the present invention relates to an aluminum oxide hydroxide-containing aluminum salt hydroxide particle which can be used in fibers, rubbers or other industrial fields, and a method for producing the same. More specifically, the present invention relates to a spherical, paired, rectangular parallelepiped, disk-shaped (go-stone) person hexagonal plate, rice grain or columnar resin having a small and uniform particle diameter, a resin, a rubber having little hygroscopicity.
- TECHNICAL FIELD The present invention relates to an organic acid anion-containing aluminum salt hydroxide particle excellent in the addition property to the like, a method for producing the same, and use thereof.
- a representative of the aluminite compounds is aluminite (amatite). Natural products occur as alunite in hot-deposited areas and acid-eroded areas formed by active volcanoes and hot springs. Synthetic aluminite is used industrially as an adsorbent, an additive to resins, a filler, and various carriers. The following synthesis methods are known.
- the document 1 Aluminum sulfate (A 1 2 (S 0 4 ) 3), sulfate potassium (K 2 S_ ⁇ 4), were mixed at a constant ratio sodium sulfate (N a 2 S_ ⁇ 4) under atmospheric pressure It describes a method of synthesizing alunite by keeping stirring at 100 ° C with a magnetic stirrer with a hot plate for 48 hours.
- Arunai bets generated in this way is a flaky aggregate having porosity, there is Sri Tsu preparative shaped pores of 1 5 to 3 0 A a width of about ice adsorptivity comparable to silica gel S_ ⁇ 2 It has been reported that it has high NO adsorption ability and also well adsorbs acid dyes.
- M represents a monovalent cation
- M ' represents A 1 or a combination of A 1 and F e ( ⁇ )
- a homogeneous composition comprising a layered compound having a chemical structure represented by the following formula and an aluminite-type or jarosite-type crystal structure, and amorphous silica or amorphous silica-alumina in an amount of 5 to 80% by weight based on the layered compound.
- an adsorbent composition having a BET specific surface area of at least 300 m 2 / g and a pore volume of at least 0.1 m 1 / g.
- the production method can be used to crystallize an aluminite-type and a jarosite-type layered compound depending on the starting material and the value of pH in the reaction, respectively.
- Reference 5 Japanese Unexamined Patent Publication No. 2000-7332 describes the formula
- the particle size at 25 % and 75 % of the volume-based cumulative particle size distribution curve by the Coulter method is D 25 and D 75 , respectively.
- Individual particles are independent spindle-shaped or spherical alkalis, specified by chemical composition, X-ray diffraction pattern different from Alnite, pH of 5% aqueous suspension, BET specific surface area and moisture absorption It describes aluminum-palladium hydroxide.
- the parameters such as the bulk density of the particles, the median diameter based on the volume, the sharpness of the particle size distribution, the aspect ratio, the refractive index, and the abrasion degree are optimized so that the compoundability in the resin is optimal.
- Salt hydroxides have been proposed. As for the production method, it is described that aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide are subjected to hydrothermal treatment.
- Document 6 Japanese Patent Application Laid-Open No. 6-122519
- Document 6 has a spherical shape, an average particle diameter of 3 to 30 ⁇ m, and a specific surface area BET value of 150 to 300 m 2 / ⁇ .
- a bulk density of 0.7-; L .. 1 g / m 1 formula
- the synthetic aluminite compound can be used as an additive to resins, rubbers, etc., as a filler, as an adsorbent for odorous components, or as a carrier for dyes and the like. .
- additives or fillers when adding additives or fillers to resins, rubbers, etc., they have low hygroscopicity, have acid resistance, improve the dispersibility of additives, and minimize the deterioration of mechanical properties such as tensile strength.
- transparency the smaller the particle size, the greater the total light transmittance and the smaller the HAZE
- the uniformity of particle shape and particle size closed (Sharpness of distribution) is often required.
- the filter when kneading with resin, the filter is less likely to be clogged, and in order to improve the processability when processing the kneaded material into fine fibers, it is required that the particle diameter be uniform. . In order to satisfy these requirements, it is required to reduce the particle size without lowering the dispersibility in the resin, and to secure the uniformity of the particle shape and the particle size. These requirements are mutually contradictory, and the particle size must be reduced for the purpose of improving mechanical properties and transparency. Then, secondary agglomeration is likely to occur, so that the dispersibility in resin, rubber and the like is reduced, and the mechanical properties and transparency are rather reduced.
- the composition described in Reference 2 has too high a hygroscopic property and cannot be used as an additive to resins, rubbers and the like.
- the above documents 3, 4 and 6 do not disclose the particle shape, particle size uniformity, or a method for securing these characteristics, and are not disclosed in terms of mechanical properties such as compoundability to resin, that is, dispersibility or tensile strength. It is unknown how maintainable it is.
- the literature 5 suggests a method of controlling the particle shape to either a spherical shape or a spindle shape by the pH control in the reaction, but this method is incomplete and is not suitable for the reaction.
- the water absorption in order to use it as an adsorbent or carrier, the water absorption must be as small as possible.
- the composition described in Reference 2 has too high a hygroscopic property, so that the gas adsorption ability is reduced in an environment having a high relative humidity.
- industrial adsorbents and carriers are often used in a strong acid environment, and are required to be acid-resistant. Therefore, it is necessary that the change in crystal structure related to adsorption and loading in a strong acid environment be as small as possible.
- a first object of the present invention is to provide organic acid anion-containing aluminum salt hydroxide particles having a uniform particle shape and a uniform particle diameter.
- a second object of the present invention is to present a novel shape which has not been known before.
- a third object of the present invention is to provide an excellent adsorption property for alkali substances and the like, without losing its function even in a strong acid environment, and having good dispersibility in resin and rubber and moldability, and high density. Contains an organic acid anion that has various excellent properties such that it does not lower the physical properties of the resin, rubber, etc. even when blended, and does not lower its fluidity when added to paints, etc. It is to provide aluminum salt hydroxide particles.
- a fourth object of the present invention is to provide a method for producing organic acid anion-containing aluminum salt hydroxide particles having a desired particle shape and a uniform particle diameter.
- a fifth object of the present invention is to provide an adsorbent, an ultraviolet absorber, and a resin composition using the organic acid-one-containing aluminum salt hydroxide particles. Means for solving the problem
- the present inventors have added a known aluminum hydroxide solution to a mixed solution of aluminum sulfate and sodium sulfate as a catalyst by adding an aqueous solution of sodium hydroxide and performing a heating reaction.
- a known aluminum hydroxide solution to a mixed solution of aluminum sulfate and sodium sulfate as a catalyst by adding an aqueous solution of sodium hydroxide and performing a heating reaction.
- oxalic acid C 2 H 2 0 4
- the present inventors added potassium hydroxide to a mixed solution of aluminum sulfate, potassium sulfate and oxalic acid to form a spherical organic acid having a smooth particle surface and extremely high particle diameter uniformity. It has been found that aluminum salt hydroxide particles containing -one can be synthesized.
- the present inventors have developed research based on many experiments based on the above findings, and as a result, have found that a mixed solution of a sulfate of a trivalent metal and a sulfate of a monovalent cation as a catalyst has An aqueous solution of aluminum hydroxide containing ions
- a mixed solution of a sulfate of a trivalent metal and a sulfate of a monovalent cation as a catalyst has An aqueous solution of aluminum hydroxide containing ions
- organic acid anion-containing aluminum salt hydroxide particles represented by the following formula (I) having diameter uniformity can be synthesized.
- organic acid anion-containing aluminum salt hydroxide particles having a desired particle size and particle shape according to the application. I found that I can do it. Specifically, it is possible to obtain not only a spherical particle but also a pair, a rectangular parallelepiped, a disk (go stone), a rice grain or a columnar organic acid-on-containing aluminum salt hydroxide particles.
- aluminum salt hydroxide particles containing an organic acid anion that is, composite particles of an organic acid and an aluminite compound are novel.
- novel organic acid-containing aluminum salt hydroxide particles are represented by the following formula (I).
- M is + N a, ⁇ +, which is one of cationic even without least selected from ⁇ 4 + and Eta 3 0 + group consisting.
- A is at least one kind of organic acid cation, preferably at least one kind selected from the group of carboxylic acids based on organic carboxylic acids or organic carboxylic acids, and more preferably 1 to 15 carbon atoms. At least one member selected from the group consisting of organic carboxylic acids or organic carboxylic acids having the following. A is more preferably an organic carboxylic acid or an organic carboxylic acid having 1 to 15 (particularly 2 to 10) carbon atoms and having 1 to 4 (preferably 1 or 2) carbonyl groups.
- At least one member selected from the group of anions based on the following, and particularly preferably at least one member selected from the group consisting of oxalate ion, citrate ion, malate ion and tartrate, glycerate ion, gallate ion and lactate ion. Is a seed. '
- Aeon inorganic acids least, but preferably, Ri least 1 Tanedea selected from inorganic acids Ayuon group taking tetrahedron structure, more preferably sulfate ion (so 4 2), phosphate ions (PO 4 3 _), nitrate ion (NOs 1 -) and Kei acid ion (S i 0 3 2 -, S i ⁇ 4 4 -, HS i 2 ⁇ 5 -, etc.) less selected from the group consisting of And at least one selected from sulfate ions, phosphate ions and potassium silicate. Most preferred is sulfate ion.
- a, b, n, m ⁇ x, y, and z are 0.7 ⁇ a ⁇ l.35, 2.7 ⁇ b ⁇ 3.3, 0 ⁇ m ⁇ 5, 4 ⁇ n ⁇ 7, 0 ⁇ x ⁇ 0.6, 1.7 ⁇ y ⁇ 2.4, 0.00.01 ⁇ z ⁇ 0.5, but the preferred range is 0.9 ⁇ a ⁇ l. 2, 2.8 ⁇ b ⁇ 3.2, 0 ⁇ m ⁇ 2, 5 ⁇ ⁇ ⁇ 6.5, 0 ⁇ ⁇ ⁇ 0.3, 1.8 ⁇ y ⁇ 2.2, 0.0 1 ⁇ ⁇ 0.4, the more preferred range is 0.9 ⁇ a ⁇ l.
- organic acid aunion-containing aluminum salt hydroxide particles represented by the following general formula (I).
- A represents at least one organic acid anion
- B represents at least one inorganic acid anion, wherein a, b, m, n, x, y and z are 0.7 ⁇ a ⁇ 1.35, 2.7 ⁇ b ⁇ 3, 3, 0 ⁇ m ⁇ 5, 4 ⁇ n ⁇ 7 s 0 ⁇ x ⁇ 0.6, 1. 7 ⁇ y ⁇ 2. 4. 0. 0 1 ⁇
- Organic acid aunion-containing aluminum salt hydroxide particles.
- the organic acid anion in the above formula (I) (A) is at least one selected from the group consisting of organic carboxylic acids having 1 to 15 carbon atoms and organic carboxylic acids.
- At least one metal salt hydrolyzate selected from the group consisting of Cu, Zn, Ni, Sn, Zr, Fe, and Ti is supported on the surface.
- the organic acid anion-containing aluminum salt hydroxide particles according to (1) are supported on the surface.
- the organic acid is at least one selected from organic carboxylic acids or organic oxycarboxylic acids or salts thereof.
- the group of inorganic acid salts is sulfate, nitrate, phosphate and silicate.
- a resin additive comprising the organic acid ion-containing aluminum salt hydroxide particles according to (1).
- An adsorbent composition comprising the organic acid anion-containing aluminum salt hydroxide particles according to (1).
- a dye carrier comprising the organic acid anion-containing aluminum salt hydroxide particles according to (1).
- FIG. 1 is a SEM photograph of the spherical particles according to Example 1A.
- FIG. 2 is an SEM photograph of the disk-shaped particles according to Example 1B.
- FIG. 3 is an SEM photograph of the paired particles according to Example 1... C.
- FIG. 4 is a SEM photograph of the spherical particles according to Example 1-D.
- FIG. 5 is a SEM photograph of the rectangular parallelepiped particles according to Example 11E.
- FIG. 6 is a SEM photograph of the hexagonal plate-like particles according to Example 11F.
- FIG. 7 is a SEM photograph of the granular rice grains according to Example 1-J.
- FIG. 8 is a SEM photograph of the columnar particles according to Example 1-O.
- FIG. 9 is a SEM photograph of the rectangular parallelepiped particles according to Example 1-P.
- FIG. 10 is a SEM photograph of the spherical particles according to Example 11W.
- FIG. 11 is a SEM photograph of the spherical particles according to Example 11N.
- Fig. 12 shows the organic acid anion-containing aluminum salt according to Example 11A. It is a particle size distribution figure of a hydroxide particle. The horizontal axis is the particle diameter, the left vertical axis is the frequency
- FIG. 13 is a particle size distribution diagram of the organic acid anion-containing aluminum salt hydroxide particles according to Example 11B.
- FIG. 14 is a particle size distribution diagram of the organic acid anion-containing aluminum salt hydroxide particles according to Example 11C.
- FIG. 15 is a particle size distribution diagram of the organic acid anion-containing aluminum salt hydroxide particles according to Example 11D.
- FIG. 16 is a particle size distribution diagram of the organic acid anion-containing aluminum salt hydroxide particles according to Example 11V.
- FIG. 17 is a graph showing the relationship between the solution temperature and the A 1 elution concentration from the immersed organic acid aion-containing aluminum salt hydroxide particles in the nitric acid solution according to Example 4-A.
- FIG. 18 is a graph showing the relationship between the solution temperature and the concentration of SO 4 eluted from immersed aluminum salt hydroxide particles containing organic acid anion in a nitric acid solution according to Example 41A.
- FIG. 19 is a graph showing the relationship between the solution temperature and the concentration of SO 4 eluted from the immersed organic acid anion-containing aluminum salt hydroxide particles in a sulfuric acid solution according to Example 4.
- FIG. 20 and FIG. 21 are IR spectra of the aluminum salt hydroxide particles containing an organic acid anion according to Example 9.
- the horizontal axis is the wave number (cm to x ), and the vertical axis is the reflectance (%).
- FIG. 22 is a UV-visible light reflection spectrum of an organic acid-one-containing aluminum salt hydroxide particle according to Example 10-A.
- the horizontal axis is the wavelength (nm), and the vertical axis is the reflectance (%).
- FIG. 23 is a UV-visible light reflection spectrum of the organic acid anion-containing aluminum salt hydroxide particles according to Example 10-B.
- FIG. 24 is a UV-visible light reflection spectrum of an organic acid-one-containing aluminum salt hydroxide particle according to Example 10-C.
- FIG. 25 is a light transmission spectrum of a low-density polyethylene film to which aluminum salt hydroxide particles containing organic acid a-one according to Example 13-A were added.
- FIG. 26 and FIG. 27 are differential thermal analysis diagrams of the aluminum salt hydroxide particles containing an organic acid-one according to Example 11. The horizontal axis is the wave number (cm- ⁇ ), and the vertical axis is the weight (%).
- FIG. 28 to FIG. 32 are X-ray diffraction diagrams of the organic acid aeon-containing aluminum salt hydroxide particles according to Example 14.
- organic acid anion-containing aluminum salt hydroxide particles of the present invention will be described in more detail.
- the particle size distribution maps according to the present invention (D 7 5 / D 2 5 Organic layer containing a new particle shape such as spherical, disk-shaped (go-stone), paired, rectangular parallelepiped, hexagonal, rice grain, or columnar with a uniform particle size.
- Luminium salt hydroxide particles were provided.
- the particles of these new shapes according to the present invention are characterized by good shape uniformity (points of uniform shape).
- the particles of the present invention have low cohesion and excellent dispersibility irrespective of their shape and despite their small particle size.
- FIGS. 1 to 11 are SEM images of representative particles obtained according to the example of the present invention. Is true. Spherical particles are shown in Figures 1, 4, 10, and 11, discotic particles are shown in Figure 2, paired particles are shown in Figure 3, and cuboid particles are shown in Figures 5 and 9. The hexagonal plate-like particles are shown in Figure 6; the rice granular particles are shown in Figure 7; and the columnar particles are shown in Figure 8. 'The SEM photographs in Figs. 1 to 11 are representative examples of the particles obtained in the examples.
- the shape of the particles of the present invention is observed based on SEM photographs magnified about 10,000 times to about 20,000 times.
- the particles of the present invention are characterized in that each of the photographs has a uniform and uniform particle size and a small agglomeration and a monodisperse shape. You. Another characteristic is that the particle size is relatively small.
- FIGS. 1, 4, 10, and 11 are almost spherical. Things.
- the spherical particles in FIG. 4 have a smooth surface force S, and the spherical particles in FIGS. 1, 10, and 11 have small irregularities or wrinkles on the surface.
- the disk-shaped particles are shown in Figure 2 and are almost symmetrical on the front and back, domed, and resemble goseki.
- the disk-shaped particles in Fig. 2 have a smooth surface.
- FIG. 3 shows a pair of particles.
- the feature of this particle is that two of the disk particles, whose bottom is a flat plate and whose opposite surface is dome-shaped, have a paired shape with the bottom as a symmetric surface, and the surrounding area where the two particles overlap. There is a space just before. In the overlapping center there is an aluminum salt hydroxide connecting the two disks. This pair of particles looks like a hamburger at first glance.
- FIG. 5 shows an example of a rectangular parallelepiped particle.
- the particle in FIG. 5 is a rectangular parallelepiped close to a regular hexahedron and has a smooth surface.
- FIG. 9 shows another example of the rectangular parallelepiped particles. The particles in FIG. 9 may be called octahedral particles.
- FIG. 6 shows hexagonal plate-like particles.
- the hexagonal plate-like particles are plate-like having a hexahedral surface formed by six sides. The six sides do not have to be the same length, and the contact of the two sides may have a rounded shape.
- the rice grain is shown in Figure 7.
- the rice grains have an elliptical projected shape and a substantially circular cross section in the longitudinal direction.
- the particles in Figure 7 have small wrinkles on the surface.
- An example of a columnar particle is shown in FIG.
- the columnar particles may have a shape in which the middle portion is bulged, such as a sake barrel (or a wine barrel), or a cylindrical particle having a substantially circular cross section.
- the particles in FIG. 8 have many irregularities on the surface.
- the particles of the present invention are characterized in that in each of the photographs, the particle shape is uniform, the size is uniform and the dispersibility is good. I have.
- the shape of each of the particles described above is classified and expressed in order to classify the respective particles, and there is no problem even if there is a slight deformation / mixing of other particles with a small percentage.
- the smoothness, the presence of minute irregularities or the presence of small wrinkles (wrinkles) on the surface of the particles are not particularly limited, and may or may not be present.
- S is closer to 1 as s is closer to a true sphere.
- a particle having a spherical shape may be a ball-like shape as shown in FIGS. 1, 4, 10, and 11, and the sphericity s of Wade 11 is 0. It is preferable that 9 5 ⁇ s ⁇ 1.
- the shape of the particles is disc-shaped (go stone shape) as shown in FIG. As shown, it has a spheroidal shape with the minor axis as the axis of rotation.
- the circularity c of Wade 11 is 0.95 ⁇ c ⁇ l
- a particle having a pair shape refers to a particle in which a pair of hemispherical particles (via a plane) overlap each other as shown in FIG.
- gaps exist on the periphery of the overlapping surface of the two hemispherical particles.
- the ratio t of the minor axis Z and the major axis of the paired particles is 0.1 and t ⁇ 0.5, and the ratio u of the minor axis is 0.05 ⁇ u ⁇ 0. Preferably it is 5.
- the shape of the particle is a rectangular parallelepiped when it is a shape similar to a hexahedron (including a regular hexahedron) or an octahedron as shown in FIGS. 5 and 9, and the sphericity s of the W ade 11 is It is preferred that 0.5 ⁇ s ⁇ 0.8.
- the shape of the particles being a hexagonal plate shape is a flat hexagonal prism-like shape as shown in FIG. 6, and a circular shape of Wade 11 with respect to the projected image of the particles viewed from the upper surface or the lower surface direction. It is preferable that the degree c is 0.95 c and 0.99, and the ratio b of the thickness Z (diagonal length of the regular hexagon) is 0.05 ⁇ b ⁇ 0.5.
- the shape of the particles is defined as rice grains when the particles have a spheroidal shape with the major axis as the axis of rotation as shown in FIG. 7 and the ratio a of the minor axis / major axis of the ellipse is 0.1 l ⁇ a ⁇ 0.5, and the sphericity s of the W ade 11 is preferably 0.4 ⁇ s ⁇ 0.75.
- the shape of the particles being cylindrical refers to a shape including a cylinder, in which the radius of the center of the cylinder in the height direction is 1.0 to 1.2 times the radius of the upper surface and the lower surface.
- the circularity c of Wade 11 with respect to the projected images of the upper and lower surfaces is 0.95 c and 0.99, and the height / 8 or the diameter of the lower surface) is preferably 1.5 ⁇ b ⁇ 3.
- Such a shape is shown in FIG.
- the organic acid aeon-containing aluminum salt hydroxide particles may be spherical, disk-shaped (goite-shaped), pair-shaped, rectangular parallelepiped, hexagonal plate-shaped, or rice-grain-shaped according to the use or purpose.
- various shapes such as a column shape can be provided, and the particle size can be controlled.
- the shape is spherical when added as an anti-blocking agent, rectangular parallelepiped, disk-shaped (goishi), spherical or hexagonal as a filler for semiconductor epoxy encapsulant, and adsorbent as a filler.
- organic acid anion-containing aluminum-palladium hydroxide particle having an optimal shape such as a pair, a column, a rice grain, or a disc (go stone).
- particle size it is possible to provide organic acid anion-containing aluminum salt hydroxide particles having an optimum particle size according to the application and the required packing ratio.
- the organic acid ion-containing aluminum salt hydroxide particles of the present invention have an average secondary particle diameter of 0.1 to 12 / m as measured by a laser diffraction method, and preferably 0.1 to 10 ⁇ m. m. Most preferably it is from 0.2 to 5111, especially from 0.2 to 2 im.
- the organic acid ion-containing aluminum salt hydroxide particles of the present invention have a low cohesiveness even with a fine particle diameter of 0.5 ⁇ m or less, particularly 2 ⁇ m or less, and the conventionally known aluminum Superior in dispersibility when filled into resin compared to salt hydroxide particles. Therefore, the particle size is formed to a particle size of 1 ⁇ 2 or less of the visible light wavelength (0.4 to 0.7 ⁇ ), and the refractive index is equivalent to that of the resin by optimizing the particle shape and composition. If it is set to, a resin composition having a small haze and a very good transparency can be provided.
- Organic acid-one-containing aluminum salt hydroxide provided by the present invention
- the compound particles have a relatively small particle size, they maintain a uniform particle size with almost no secondary aggregation.
- the horizontal axis represents the particle diameter
- the vertical axis represents the cumulative frequency.D25 is the particle size at which the cumulative frequency is 25 % from the largest particle size to the total number of particles.
- the particle diameter at a 7 5% and D 75 is often used to process I table the spread of particle size distribution by the value D 75 / D 25 ratio.
- D 75 ZD 25 is referred to as a particle size distribution ratio (D R ).
- the particle size distribution ratio (D R ) of the organic acid aion-containing aluminum hydroxide particles according to the present invention shows a value in the range of 1 to 1.8 regardless of the particle shape. Shows no particle size uniformity.
- the range of D R is in the preferred embodiment from 1.01 to 1.5, particularly preferably from 102 to 1.3. Most preferably D R of 1.0 3 to 1.2.
- the uniformity of the particle diameter can be indicated by the ratio of the number of particles having a particle diameter within a certain range centered on the average particle diameter or the median particle diameter to the total number of particles. This percentage, depending on the shape of the particle size distribution, the above D R (D 75 / D 25 ), is useful as a measure the half width and standard deviation, etc. to assess the uniformity of the particle diameter as a separate independent parameters .
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention have a particle size that is 0.85 times the average particle size determined by the laser diffraction method.
- the ratio of the number of particles included in the range of the particle diameter of 15 times is 40% or more, preferably 60% or more, particularly preferably 80% or more of the whole. This can be expressed by an equation: (Average particle diameter X 0.85) ⁇ 40 mm / The ratio of particles satisfying ⁇ W M m ⁇ (average particle diameter X 1.15). It is preferably at least 60%, particularly preferably at least 70%.
- the upper limit of this ratio is preferably as high as possible, but is generally 95%, preferably 97% in the present invention.
- the organic acid anion-containing aluminum hydroxide salt particles of the present invention have a specific surface area measured by the BET method of 0.1 to 300 m 2 / g, preferably 0.5 to 250 in 2 / g.
- a suitable range can be selected depending on the application.
- the specific surface area by the BET method is preferably 0.1 to 30 m 2 Zg. A more preferred range is 2 to 10 in 2 / g.
- the specific surface area by the BET method is preferably 0.5 to 300 m 2 / g. A more preferred range is 2 ⁇ 2 5 0 m 2 Z g .
- Such an aluminum salt hydroxide containing an organic acid aunion having uniform particle size has good dispersibility as an additive to a resin or rubber. Therefore, a conventionally known additive is added to a resin or rubber. Comparing the product with the aluminum salt hydroxide particles containing the organic acid-one of the present invention, the elongation of the latter in the tensile test was 5 to 10 times that of the former, indicating that the flexibility was higher. Can be granted.
- conventionally known fillers such as spherical silica are combined with two or more kinds of particles having an average particle diameter that satisfy the filling conditions determined by the equation of increase in the compounding of the semiconductor sealing resin or the like.
- D R the particle size distribution ratio
- the problem is that close packing cannot be achieved in practice because the percentage of particles that satisfy
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention have a uniform particle diameter, it is possible to achieve close packing as theoretically.
- the color of the resin into which the aluminum salt hydroxide particles containing an organic acid ion of the present invention are kneaded becomes milky white, and no yellowing or whitening of the resin is observed. Therefore, they are useful as additives for resins and rubbers, especially as fillers, antiblocking agents, and ultraviolet and infrared absorbers.
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention are insoluble in water, have excellent acid resistance, and can maintain their basic structure even in a strong acid environment. It is useful as a filter aid or as an additive for resin for food containers that dislikes elution of components.
- organic acid aunion-containing aluminum salt hydroxide particles of the present invention are useful when used alone as an adsorbent or a deodorant for malodorous gas, or when blended with fibers, resins and the like.
- organic acid ion-containing aluminum salt hydroxide particles of the present invention exhibit good dye adsorption properties, they are useful as dye carriers, coloring assistants, and external additives for electrophotographic color toners.
- the aluminum salt hydroxide particles containing an organic acid a-one according to the present invention include aluminum sulfate and a sulfate of M ′ in the formula (I); sulfates and organic acids and Z or organic acid salts of M, for example, in a mixed solution of oxalic acid (H 2 C 2 0 4) , thus generated thereby heating the reaction by the addition of hydroxide Al Chikarari aqueous solution containing the M Can be done. If necessary, the formed organic acid anion-containing aluminum salt hydroxide particles are filtered off, washed and dried to obtain a water-containing powder of the organic acid anion-containing aluminum salt hydroxide particles. Is obtained. ⁇
- the value (D R ) of the particle size distribution ratio indicating the particle size uniformity of the resulting organic acid anion-containing aluminum salt hydroxide particles increases.
- the shape of the generated particles is limited to a spherical shape or a shape similar thereto, and the object of the present invention is achieved because there is no freedom to form the particles into a shape according to the application. Can not.
- the particle size uniformity and the particle shape are ensured by the amount of the organic acid added, so that the pH is constantly monitored during the reaction to secure the particle size uniformity, as in a conventionally known method, and No need to control. Further, since particles having a uniform particle size and shape are already obtained at the end of the reaction, there is no need for pulverization or classification.
- the organic acid ion-containing aluminum salt hydroxide particles of the present invention have the following advantages in terms of (1) acid resistance, (2) fineness of the particles, and (3) versatility of the particle shape. And excellent-yes.
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention are excellent in dispersibility in resin and the like and high filling properties as compared with conventionally known alunite compound particles, and the resin composition to which this is added is Excellent in acid resistance and physical strength. Furthermore, the application is more versatile than conventionally known alunite compound particles having a small degree of freedom in shape.
- an organic acid anion-containing aluminum oxide formed from the combination of the cation M and the type of the organic acid is used under fixed reaction conditions.
- the particle size, particle shape, and chemical and physical properties of the salt hydroxide particles are uniquely determined.
- the reaction conditions are as follows: the molar ratio of the sulfate of M 'to alkali hydroxide in formula (I), the heating reaction temperature and the organic acid.
- the particle size, particle shape and chemical and physical properties of the resulting organic acid-containing aluminum salt hydroxide particles are uniquely determined.
- a mixture of a sulfate of 'aluminum sulfate and M' and an organic acid for example, a mixture of aluminum sulfate and titanium sulfate and a mixture of alkali hydroxide containing cation M are heated.
- the reaction can produce a solid solution of organic acid aion-containing aluminum salt hydroxide particles having a different composition from the above-mentioned solid solution.
- Such a metal-supported particle on the surface can also be obtained by a method in which various metal compounds are subsequently supported on a synthesized organic acid-containing aluminum salt hydroxide by a conventionally known method.
- aqueous solution of titanium sulfate is combined with an organic acid anion-containing aluminum salt solution.
- a base such as sodium hydroxide
- a heat-reaction between a sulfate of M ′ containing aluminum, a mixed solution of two or more kinds of organic acids different from each other, and a mixed solution of sulfate of cation M is carried out with an alkali hydroxide solution containing cation M
- an alkali hydroxide solution containing cation M By doing so, a solid solution of organic acid anion-containing aluminum salt hydroxide particles having a different composition from the above solid solution can be generated.
- nitrate, phosphate or silicate when synthesizing the organic acid anion-containing aluminum salt hydroxide particles, nitrate, phosphate or silicate may be used instead of the sulfate of M added as a catalyst.
- the present inventors have found that even when used repeatedly the reaction mother liquid containing a M 2 S 0 4 be produced in the reaction, with respect to the product organic acid Anion-containing aluminum salt hydroxide particles, does not adversely quite bad influence Was found. According to the method of the present invention, the reaction mother liquor can be used repeatedly, which is advantageous in that the production cost can be reduced.
- the organic acid ion-containing aluminum salt hydroxide particles of the present invention can be obtained at the end of the heating reaction step by setting the reaction conditions so that particles having a required shape and particle diameter are obtained according to various applications. Gives the desired particle size and particle shape. Therefore, there is no need for any subsequent pulverizing treatment, and the number of man-hours can be reduced, and the production cost can be reduced in this respect as well.
- Group 1 at least one cation inorganic salt and at least one sulfuric acid selected from the group consisting of Na +, K +, ⁇ ⁇ 4 + and ⁇ 30 +
- Group 2 When an alkali hydroxide solution selected from the second group is added to a mixed solution containing a salt or a nitrate to cause a heating reaction, the heating reaction is performed with an organic solvent.
- a method for producing organic acid cation-containing aluminum salt hydroxide particles which is carried out in the presence of an acid or an organic acid salt.
- the reaction temperature in the method of the present invention is higher than the boiling point and not higher than 300 ° C.
- the temperature is more preferably 90 to 250 ° C. If the reaction temperature is lower than 90 ° C, the reaction rate becomes extremely slow, and the production efficiency is poor. Conversely, if the reaction temperature exceeds 300 ° C., special equipment is required, which is not preferable.
- the reaction may be performed under sealed conditions using a autoclave or the like, or under open conditions. Preferred reaction temperatures are in the range from 100 ° C. to 200 ° C., especially from 120 ° C. to: L 70 ° C.
- the aluminum salt concentration in the reaction of the present invention is from 0.01 to 3.0 mol / L. More preferably 'is 0.01 to 2 mol ZL. If the aluminum salt concentration is less than 0.01 mol 1 ZL, the productivity will be poor, and if it exceeds 3 mol, aggregation between particles is likely to occur, and the uniformity of particle size and particle size Is difficult to control.
- the organic acid concentration in the reaction solution in the present invention is 1 to 2 or less of the aluminum salt concentration (mol). More preferably, it is 1 / 20-1Z2. If the value of (organic acid concentration) / (aluminum salt concentration) exceeds 1 Z2 or is less than 1 Z20, the shape, size and particle size of the particles become non-uniform.
- the organic acid is preferably an organic carboxylic acid or an organic carboxylic acid. They preferably have 1 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and particularly preferably have 1 to 4, preferably 1 to 2 carboxyl groups in the molecule. . These organic acids may be salts or isomers.
- the organic acid include at least one selected from the group consisting of oxalic acid, cunic acid, malic acid, tartaric acid, glyceric acid, gallic acid, and lactic acid, isomers thereof, and salts thereof.
- the molar ratio of the sulfate salt of M 'to the MOH hydroxide is 1: 3.8 to 4.7.
- the reaction formula at a molar ratio of 1: 4 is shown in the above formula, but if the value of the hydroxyl hydroxide is less than 4, the reaction may be insufficient.
- the value of alkali hydroxide exceeds 4.4, boehmite may be formed. Taking these points into account, the more preferable monole ratio is 1: 4 to 4.4.
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention are additives having excellent dispersibility even when used as they are, but they include higher fatty acids, cation-based surfactants, phosphates, coupling agents and polyvalents.
- Surface treatment with at least one type of surface treatment agent selected from the group consisting of alcohol and fatty acid esters can further improve dispersibility in resins, rubbers, and the like. The following are preferably used as the surface treatment agent.
- Higher fatty acids having 10 or more carbon atoms such as stearic acid, erlic acid, palmitic acid, lauric acid, and behenic acid; or alkali metal salts of the higher fatty acids; higher alcohols such as stearyl alcohol and oleinole alcohol; Estenolate sulfate; Polyethylene blended alcohol sulfate, amide-linked sulfate, ester-linked sulfate, ester-linked sulfonate, amide-linked sulfonate, ether-linked sulfonate, ether-linked alkylaryl sulfone Aron-based surfactants such as acid salts, ester-linked alkylaryl sulfonates, and amide-linked alkylaryl sulfonates; mono- or diesters such as orthotrinic acid and oleyl alcohol, stearyl alcohol, or both A mixture of Phosphoric acid esters such as the acid form or metal salts of acrylon
- the surface treatment of the organic acid anion-containing aluminum salt hydroxide particles with the surface treatment agent can be performed by a method known per se as a surface treatment method of the particles, and can be performed, for example, as follows.
- An aqueous solution of aluminum hydroxide is added to a mixed solution of a sulfate of a trivalent metal, a monovalent cation sulfate and / or a nitrate, and an organic acid, and the mixture is heated to cause a reaction.
- the surface treatment agent is removed after any of the heating reaction, filtration, washing or drying. It may be added. If kneading with rubber, resin, etc., a surface treatment agent may be added at that time.
- the surface treatment can be performed by a conventionally known method such as a wet method and a dry method.
- the amount of the surface treatment agent to be added is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the organic acid aion-containing aluminum hydroxide particles.
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention are subjected to surface modification with the following inorganic oxides, metals, ceramics, etc. to impart fluidity to these substances, Conductivity can be imparted to the aluminum-containing hydroxide particles; silica, alumina, antimony oxide, tin oxide, manganese dioxide, zirconium oxide, zinc oxide, titanium oxide, antimony-doped tin oxide, tin-doped indium oxide, ytterbium oxide And tungsten trioxide stainless.
- surface modification using the following inorganic oxides, metals, ceramics, etc. imparts fluidity to these substances, or imparts thermal conductivity to the aluminum salt hydroxide particles containing organic oxides. can do ;
- the aluminum salt hydroxide particles containing organic acid aeon, surface-modified with the above materials are kneaded with the resin according to the application, or are applied to different substrate materials such as various alloys, ceramics, or carbon by CVD, plasma CVD, PVD. It is also possible to provide a predetermined function by forming a film by such a method.
- organic acid anion-containing aluminum hydroxide hydroxide particles of the present invention By subjecting the organic acid anion-containing aluminum hydroxide hydroxide particles of the present invention to surface modification with an alkali metal silicate, mica, zeolite, imogolite or the like, various adsorbents such as a moisture adsorbent or a humidity control Agent, It can be used as a volatile organic substance (VOC) remover or a carrier for dyes.
- VOC volatile organic substance
- organic acid anion-containing aluminum salt hydroxide particles of the present invention which are surface-modified with an ultraviolet absorbent such as titanium oxide, can be used as a heat insulating agent for agricultural films, an ultraviolet Z infrared absorbing agent for cosmetics, and ultraviolet deterioration of rubber. Very useful as an inhibitor.
- the surface modification of the organic acid anion-containing aluminum hydroxide hydroxide particles by the inorganic oxide or the like is performed by adding a polyhydric alcohol to a mixture of the organic acid anion-containing aluminum salt hydroxide particles and, for example, a titanium oxide powder. Conventionally known methods such as polishing and baking can be used.
- the amount of the surface modifier to be added is 0.01 to 100 parts by weight, preferably 0.05 to 50 parts by weight, based on 100 parts by weight of the organic acid anion-containing aluminum salt hydroxide particles. .
- the organic acid anion-containing aluminum salt hydroxide particles of the present invention can be used after firing for 2 hours at a temperature in the range of 300 to 1,000 ° C. according to the intended use.
- organic acid anion-containing aluminum salt hydroxide particles of the present invention may be mixed with an organic polymer compound as described below as it is or after being subjected to the above-mentioned surface treatment, surface modification, firing, etc. Can be done. ;
- Resole-type and nopolak-type phenolic resins melamine resin, melamine-urea co-condensation resin, melamine-benzoguanamine co-condensation resin, melamine-phenol resin, bisphenol A-type epoxy resin, brominated epoxy resin, bisphenol F-type epoxy Resin, novolak epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, heterocyclic epoxy resin, urea resin, urea-formaldehyde-furfuryl alcohol resin, Saturated polyester resin, silicone resin, polyurethane, vinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride monovinyl acetate copolymer, vinylidene chloride copolymer, poly.ethylene, polyethyleneimine, polyethylene glycol Cornole, polyethylene terephthalate, poly (ethylene mono-trifluoroethylene), acrylic resin, polyethylene naphthalate, polybutylene terephthalate
- Polyamide MXD 6 T Polyamide MXD 6, Polyacetal, Polyester, Polypropylene, Modified Polyphenylene Ether, Polysulfone, Polyarylate, Polyether Imide, Polyether Sulfone, Polyamide Imide, Polyphenylene Sulfide, Liquid Crystal Resin such as polyester, alloys of plural kinds of resins selected from these; chloroprene rubber, styrene butadiene rubber, ptynole rubber, ethylene propylene rubber, -tril rubber, chlorosnoreon polyethylene rubber, urethane rubber, silicone rubber, fluorine Synthetic rubber such as rubber, polyisoprene rubber, butadiene rubber; synthetic fiber such as nylon, vinylon, acryl fiber, rayon; cellulose, alginic acid, starch, protein, collagen, natural wood (Natural organic polymers such as shellac, dammanole, amber, copanole, rosin, etc.); cellulosic resins (cellulose acetate
- the amount of the organic acid anion-containing aluminum and / or sodium salt hydroxide particles of the present invention to be added to the organic polymer compound is as follows.
- the amount is preferably 0.5 to 90 'parts by weight with respect to 100 parts by weight. If the amount is less than 0.5 part, the effect as an additive is insufficient, and if the amount exceeds 90 parts, the effect is not improved. Therefore, the amount is more preferably 1 to 80 parts by weight.
- the filler is preferably 0.5 to 0.5 parts by weight. If the amount is less than 0.5 part, the effect as a filler is insufficient, and if the amount exceeds 100 parts, the effect is not significantly improved.
- organic acid anion-containing aluminum salt hydroxide particles of the present invention have a small haze in the visible light region, their refractive index and dispersion can be adjusted by adding them to the following inorganic compounds.
- the addition to the inorganic compound can be performed by a method known per se, for example, by firing a mixture of the inorganic compound and the aluminum salt hydroxide particles containing an organic acid anion.
- the organic acid-an-containing aluminum salt hydroxide particles of the present invention include cement additives and curing accelerators; food additives, beer, soy sauce and other fermented food filter aids; pesticide additives and carriers; Additives for agricultural films; Additives for semiconductor encapsulants; Additives for heat-resistant ceramics; Toners for electronic photography and toner external additives; Cleaning agents; Two-component toner carriers; Pharmaceutical additives and various Carriers; Cosmetic additives, deodorants, antibacterial agents, antifungal agents, anti-algal agents and their carriers; dyes and pigment carriers and additives; catalysts; fiber deodorants, rubber, resin colorants , Anchor coating agent, heat conductive material carrier, magnetic material carrier, conductivity imparting material carrier, electromagnetic wave absorber carrier, anti-blocking agent and other additives; additives to glass, reuse of glass waste material Foaming agent for;.
- a first effect of the present invention is to provide a method for producing organic acid dione-containing aluminum salt hydroxide particles having a shape and a particle diameter most suitable for use at low cost, with good reproducibility, and with high yield.
- the second effect is that it is possible to provide organic acid anion-containing aluminum salt hydroxide particles which are fine particles, have a uniform particle shape and particle diameter, are highly dispersible, have low moisture absorption, and are acid-resistant.
- the third effect is that, even when added to resins, rubbers, etc., resins that have good dispersibility, can provide anti-blocking properties, acid resistance and other properties without lowering physical properties such as transparency and tensile strength, It can provide additives and fillers for rubber and the like.
- a fourth effect is that it is possible to provide particles, carriers and the like whose physical properties are not deteriorated even in an environment having a high relative humidity or a strong acid environment, in particular, the adsorbing / supporting ability is not reduced.
- Example 1_A shows the properties of the obtained aluminum-palladium hydroxide particles containing organic acid anion, and FIG. 14 shows the particle size distribution. The particle shape at this time was a pair as shown in SEM photograph Fig. 3.
- Example 11A Dissolve 0.1 mol of aluminum sulfate aqueous solution in 500 ml of water, add 0.1 mol of potassium nitrate and 0.125 mol of oxalic acid, and stir at room temperature for 30 minutes. Further, an aqueous solution of potassium hydroxide (20 Oml (0.4 mol)) was added, and a hydrothermal treatment was performed at 170 ° C for 10 hours. Other processing conditions were the same as in Example 11A. Table 11 shows the characteristics of the obtained aluminum salt hydroxide particles containing an organic acid anion, and FIG. 15 shows the particle size distribution. The particle shape at this time was spherical as shown in SEM photograph Fig. 4.
- Example 11A shows the properties of the obtained organic acid anion-containing aluminum salt hydroxide particles.
- the particle shape at this time was a rectangular parallelepiped as shown in SEM photograph FIG.
- Table 1-1 shows various characteristics of the spherical organic acid anion-containing aluminum salt hydroxide particles obtained in Example 11-I by changing citrate to DL_malic acid.
- Example 11 One L K 0. 99 A 1 3 ( S 0 4)!. 99 (C 6 H 5 0 7) o. 14 (OH) 5. 59 ⁇ synthesis of 0. 5 H 2 0
- Example 11 In Example I, spherical organic acid anion-containing aluminum salt hydroxide particles obtained by replacing sodium sulfate as a catalyst with sulfuric acid lime, oxalic acid with citric acid, and sodium hydroxide with potassium hydroxide. The characteristics of are shown in Table 11-11.
- Example 11 In Example I, spherical organic acid anion-containing aluminum salt hydroxide particles obtained by changing cunic acid to two kinds of organic acids, namely, oxalic acid 0.026 mo1 and tartaric acid 0.026 mo1. The characteristics of are shown in Table 11-1.
- Example 11 In Table I, various characteristics of the spherical organic acid anion-containing aluminum salt hydroxide particles obtained by using gallic acid [C 6 H 4 (OH) 3 C OOH] instead of cunic acid are shown. Shown in Figure 10. The particle shape at this time was spherical as shown in SEM photograph Fig. 11.
- Example 11 various properties of the organic acid aunion-containing aluminum salt hydroxide particles obtained by using DL-glyceric acid [HOCH 2 CH (OH) COOH] instead of cunic acid are shown in Table 1. One is shown in 1. The particle shape at this time was cylindrical as shown in SEM photograph Fig. 8.
- Example 1-I various properties of the aluminum salt hydroxide particles containing an organic acid cation obtained using L-lactic acid [CH 3 CH (OH) COOH] instead of cunic acid are shown in Table 1-11. Shown in The particle shape at this time was a round rectangular parallelepiped as shown in SEM photograph Fig. 9.
- Aqueous solution of aluminum sulfate 1.94 ml (0.2 mol), sodium sulfate 28.4 g (0.2 mo 1) and oxalic acid 6.3 g (0.05 mol 1) were mixed and ion-exchanged water. Dilute to 600 ml and dissolve the crystal with stirring. To this solution, 14.38 g (0.05 mol) of zinc sulfate was added and dissolved. Further, 23.5 ml (0.8 mol) of sodium hydroxide solution was added to the above mixture at room temperature for 6 minutes. After stirring at room temperature for 1 hour, hydrothermal treatment is performed at 170 ° C for 2 hours, and the reaction solution after the hydrothermal treatment is filtered, washed with water, and dried (at 150 ° C for 15 hours). Table 11 shows the properties of the aluminum salt hydroxide particles containing an organic acid cation.
- Example 11 Disc-shaped organic acid-one-containing aluminum salt hydroxide particles obtained by using 7.35 g (0.03 mol) of nickel sulfate instead of zinc sulfate in Example S. The characteristics are shown in Table 11-1.
- Example l-S iron sulfate in place of zinc sulfate 0. 0 2m o 1 (F e S 0 4 - 7 H 2 0: 5. 6 g) and zinc sulfate 0. 0 2 mo 1 (Z n S 0 4 ⁇ 7 H 2 0: 5. shows the various properties of the obtained disk-shaped organic acid Anion-containing aluminum salt hydroxide particles using 8 g) in Table 1 one 2.
- Table 1-2 shows the properties of anion-containing aluminum salt hydroxide particles.
- Fig. 16 shows the particle size distribution of these particles.
- Example 11 As a result of using titanium sulfate 0.08 mo 1 (30 g of a 30% solution) in place of zinc sulfate in one R, aluminum containing organic acid anion containing titanium and titanium hydrolyzate was used. Salt hydroxide particles were obtained. Table 2 shows properties of the obtained titanium hydrolyzate-supported composition. The particle shape at this time was a disk shape.
- Example 1 _R copper sulfate 0. 0 3 mo 1 in place of zinc sulfate (C u S 0 4 - 5 H 2 0: 7. 4 9 g) results using copper and copper hydrolyzate organic acid
- aluminum salt hydroxide particles containing iron-on were obtained.
- Table 2 shows properties of the obtained copper hydrolyzate-supported composition. At this time, the particle shape was a pair.
- the particle size of the organic acid anion-containing aluminum salt hydroxide particles synthesized in Examples 11A to 2-C was measured by a laser diffraction method.
- the results of particle size of 2 5% value and 7 5% value of the cumulative particle size distribution curve was a D 25 and D 75, respectively, to calculate the value D 7 5 ZD 25 ratio, this ratio is 1
- the values in the range of ⁇ 1.2 were shown.
- the ratio e (%) of the number of particles having a particle diameter m of 0.85A ⁇ W ⁇ 1.15A was read from each particle size distribution. Tables 11 and 12 show the results.
- Example 41A The organic acid aion-containing aluminum salt hydroxide particles synthesized in Example 11G were used. ⁇
- Comparative Example 2 Alnite-type compound particles synthesized in Comparative Example 1 were used.
- Aluminum in solution - the ⁇ beam level measurement in FIG. 1 7 shows an S 0 4 concentration measurement results in FIG 8.
- organic invention Sana - O emissions for-containing aluminum salt hydroxide particles it is understood that the amount of elution of Aruminiumu and S 0 4 is minimal. That is, the organic acid anion-containing aluminum salt hydroxide particles of the present invention hardly change under an acidic environment.
- organic acid ion-containing aluminum salt hydroxide particles of the present invention contain an organic acid, and thus have higher acid resistance than conventional alunite type compound particles.
- Example 41 The procedure was the same as in B.
- Example 41 The procedure was the same as in B.
- Table 3 shows the results of the above measurements performed on the sample synthesized in Example 1_G.
- Example 1 Table 3 shows the results of the above measurements performed on samples synthesized with 1H.
- Example 11 Table 3 shows the results of the above measurements performed on the sample synthesized in Example I.
- Example 11 Table 3 shows the results of the above measurements performed on the sample synthesized in Example 1J.
- Example 1 Table 3 shows the results of the above measurements performed on samples synthesized at 1K.
- Example 41 I Example 1 Table 3 shows the results of the above measurements performed on a sample synthesized in one liter.
- Example 11 Table 3 shows the results of the above measurements performed on the sample synthesized in Step P.
- Table 3 shows the results of the above measurements performed on the samples synthesized in Example 1-Q.
- the S 0 4 ion concentration in the case of changing the sulfuric acid concentration is shown in Figure 1 9.
- Increasing the concentration of sulfuric acid also increased the solubility of the sample, but the amount eluted was small and the particle shape did not change.
- the organic acid aunion-containing aluminum salt hydroxide particles of the present invention by containing an organic acid anion, exhibit much better acid resistance than conventional aluminite-type compounds, which have better acid resistance. Has been shown.
- the heat-treated solution was filtered, washed with water, and dried at 95 ° C for 15 hours to obtain aluminum oxide hydroxide particles containing a disc-shaped organic acid anion and having a BET specific surface area of 4 Oms / g. Was.
- Example 5 Similar to Example 5-A except that filtration, washing and drying were performed without autoclaving, aluminum oxide hydroxide particles containing an organic acid anion and having a BET specific surface area of 97 m 2 / g were obtained. Synthesized. Table 4 shows the results of the adsorption test.
- Example 11 Table 4 shows the results of an adsorption test performed on the sample synthesized at 1 G.
- Example 1 Table 4 shows the results of an adsorption test performed on the sample synthesized in 1H.
- Example 11 Table 4 shows the results of an adsorption test performed on the sample synthesized in Example I.
- Example 11 Table 4 shows the results of an adsorption test performed on the sample synthesized in Example 1J.
- Example 1 Table 4 shows the results of an adsorption test performed on samples synthesized at 1K.
- Example 1 Table 4 shows the results of an adsorption test performed on a sample synthesized in one liter.
- Example 1 Table 4 shows the results of an adsorption test performed on a sample synthesized at 1 M.
- Example 11 Table 4 shows the results of an adsorption test performed on the sample synthesized in Step P.
- Example 5 K ′
- Table 4 shows the results of an adsorption test performed on the sample synthesized in Q.
- Table 4 shows the results of adsorption tests on activated carbon.
- Table 4 below shows that the aluminum salt hydroxide particles containing an organic acid cation according to the present invention easily adsorb an alkaline substance such as ammonia.
- Example 6 The composition of the A ′ raw material is the same as the sample of Example 41-B. However, the conditions for the heat treatment differ as follows. The conditions for the autoclave treatment were 180 ° C. and 20 hours, and before the autoclave treatment, heat treatment was performed at 100 ° C. for 2 hours under open conditions.
- Example 41 A sample prepared in C was used.
- Example 4-D The sample prepared in Example 4-D was used.
- Example 1 A sample synthesized in H was used.
- Example 11 A sample synthesized in I was used.
- Example 11 A sample synthesized in step J was used.
- Example 1-K A sample synthesized in Example 1-K was used.
- Example 1 A sample synthesized in one liter was used.
- Example 11 A sample synthesized at 1 M was used.
- Example 1_P The sample synthesized in Example 1_P was used.
- Example 11 A sample synthesized in Q was used. Comparative Example 5-Activated carbon commonly used as an adsorbent was used.
- Example 6-A to Example 6-K show that the organic acid anion-containing aluminum salt hydroxide particles of the present invention adsorb acid dyes, direct dyes, basic dyes, reactive dyes and the like well. Is shown. Therefore, the organic acid-an-containing aluminum salt hydroxide particles of the present invention are useful as coloring aids, pigments and carriers for organic polymers such as resins.
- Example 7 For the whitening test, a piece of polypropylene containing aluminum salt hydroxide particles containing an organic acid aunion prepared in Example 7 was used. Further, as Comparative Example 7, the same polypropylene piece as Comparative Example 6 to which magnesium hydroxide generally used as an additive was added was used.
- FIG. 22 shows the absorption spectrum of the sample synthesized in 1H.
- FIG. 23 shows the absorption spectrum of the sample synthesized in Example 1-J.
- FIG. 24 shows the absorption spectrum of the sample synthesized in Example 2-A.
- the reflection spectrum was measured using a spectrophotometer with a sample piece obtained by molding the sample powder into a disk shape of 40 ⁇ 2 mm.
- organic acid anion-containing aluminum salt hydroxide particles of the present invention have an absorption band in the ultraviolet region of 200 to 38 O nm, and are useful as an ultraviolet absorber.
- Example 1 1 differential thermal analysis test 'Example 1 -B and Example N a AL 3 prepared in 1 one C (S 0 4) 2 ( OH) 6 results of differential thermal analysis for, FIG 6 And the result of Figure 27 was obtained. Both samples are thermally stable up to 400 ° C or higher.
- the organic acid-one-containing aluminum salt hydroxide particles of the present invention when the addition rate of the alkali hydroxide to be added and the concentration ratio of the sulfate are changed, the organic acid-one-containing aluminum is formed.
- Table 8 shows the results of measuring the particle size of the salt hydroxide particles by a laser diffraction method. Table 8 shows that the particle size of the organic acid anion-containing aluminum salt hydroxide particles depends on the concentration ratio between the hydroxide and the sulfate during the formation reaction.
- Table 9 shows the results of SEM observation of the particle shape of the organic acid anion-containing aluminum chloride hydroxide particles generated when the type of the organic acid to be added, the reaction conditions, and the reaction molar ratio were changed.
- Table 9 shows that the shape of the generated particles depends on the type and amount of organic acid added (Yes Molar ratio of mechanical acid to aluminum sulfate ': [organic acid] / [aluminum sulfate]) and reaction temperature.
- the molar ratio is 18 ⁇ [organic acid] / [aluminum sulfate]. ⁇ 1/4, and the reaction is performed by heating at 150-200 ° C for 2 hours.
- Example 1 After mixing the organic acid anion-containing aluminum salt hydroxide particles synthesized in _B at a mixing ratio of 0.1 part by weight per 100 parts by weight of low-density polyethylene (UF240), an extruder was used. The mixture was kneaded and melted at about 180 ° C to produce a pellet. Using this pellet, a 100 m thick film was produced at about 200 ° C. by the T-die method, and this was used as a test piece.
- UF240 low-density polyethylene
- the aluminite compound particles synthesized in Comparative Example 1 were mixed in the same manner as in Example 13-A at a mixing ratio of 0.1 part by weight per 100 parts by weight of low-density polyethylene (UF240). Using an extruder, the mixture was kneaded and melted at about 180 ° C. to produce a pellet. Using this pellet, a film having a thickness of 100 m at about 200 ° C. was produced by a T-die method and used as a test piece.
- UF240 low-density polyethylene
- Titanium oxide (ST-01: Ishihara Sangyo) was mixed in the same manner as in Example 13-A, except that the mixing ratio of 0.2 parts by weight per 100 parts by weight of low-density polyethylene (UF240) was Using an extruder, the mixture was kneaded and melted at about 180 ° C. to produce a pellet. Using this pellet, a film having a thickness of 100 m was produced at about 200 ° C. by a T-die method, and this was used as a test piece.
- UF240 low-density polyethylene
- a low-density polyethylene (UF240) without any blending was melted at approximately 180 ° C using an extruder to produce a pellet. Using this pellet, a 100 Am thick film was produced at approximately 200 ° C. by the T-die method and used as a test piece. (ii) Test method
- the transmittance and haze were measured using a haze meter (TC-H3DP: Nippon Denshoku).
- Table 11 shows the measurement results of the refractive index of the sample synthesized in Example 11-B.
- Example 14 41 B-Table 11 shows the results of measuring the refractive index of the sample synthesized in Example 11C.
- Example 11 Table 11 shows the measurement results of the refractive index of the sample synthesized in Example E.
- Example 14
- Example 11 shows the measurement results of the refractive index of the sample synthesized in Example 1F.
- Example 14_E ′ Example 11 Table 11 shows the results of measuring the refractive index of a sample synthesized in Example 1 with O.
- Table 11 shows the measurement results of the refractive index of the sample synthesized in Example 2-A.
- Table 11 shows the measurement results of the refractive index of the sample synthesized in Comparative Example 1.
- the organic acid-one-containing aluminum chloride hydroxide particles of the present invention have a refractive index of 1.49 to 1.55 depending on the kind of the organic acid contained therein, and are added to the resin to be added. It can be adjusted according to the requirements, and is particularly useful for resins requiring transparency.
- Example 11 Table 12-1 shows the results of component analysis of the sample synthesized in Example 1A.
- Example 11 Table 12-1 shows the results of component analysis of the sample synthesized in Step C. '
- Example 11 shows the results of component analysis of the sample synthesized in 1D.
- Example 11 Table 12-1 shows the results of component analysis of the sample synthesized in 1H.
- Example 11 Table 12-2 shows the results of component analysis of the sample synthesized in Example I.
- Example 11 Table 12-2 shows the results of component analysis of the sample synthesized in Example J.
- Example 15 Table 12-2 shows the results of component analysis of the sample synthesized in Example J.
- Example 1 shows the results of component analysis of the sample synthesized at 1K.
- Example 15—J ′ Example 1 Table 12-2 shows the results of component analysis of the sample synthesized in 1 L.
- Example 11 shows the results of component analysis of the sample synthesized in Q.
- Example 11 shows the results of component analysis of the sample synthesized in R.
- Apparatus NOVA 20000 high-speed specific surface area / pore distribution measurement device (Yuasa Ionitas)
- Dye adsorption test Method Put 2 g of the sample and 10 mg of the dye in 150 ml of pure water, stir well, and analyze the dye concentration at the beginning and after 15 hours.
- Adsorption rate (a-b) / a X 1 0 0 (%)
- 1 L is introduced into 50 ml of pure water, and the residual gas is measured by a pH calibration curve.
- Spectrophotometer 150-200 (Hitachi)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05720103.0A EP1731497B1 (en) | 2004-03-05 | 2005-03-01 | Particles of aluminum salt hydroxide containing organic acid anion and use thereof |
KR1020067017909A KR101157441B1 (ko) | 2004-03-05 | 2005-03-01 | 유기산 음이온 함유 알루미늄염 수산화물 입자, 그 제조방법 및 그 이용 |
CA2564630A CA2564630C (en) | 2004-03-05 | 2005-03-01 | Organic acid anion containing aluminum salt hydroxide particles, production method thereof, and use thereof |
CN2005800071434A CN1930107B (zh) | 2004-03-05 | 2005-03-01 | 含有机酸阴离子的铝盐氢氧化物粒子、其制造方法及其应用 |
US10/591,588 US7629480B2 (en) | 2004-03-05 | 2005-03-01 | Organic acid anion containing aluminum salt hydroxide particles, production method thereof, and use thereof |
JP2006510757A JP4931210B2 (ja) | 2004-03-05 | 2005-03-01 | 有機酸アニオン含有アルミニウム塩水酸化物粒子、その製造方法およびその利用 |
AU2005219753A AU2005219753B2 (en) | 2004-03-05 | 2005-03-01 | Particles of aluminum salt hydroxide containing organic acid anion, method for production thereof and use thereof |
IL177895A IL177895A0 (en) | 2004-03-05 | 2006-09-05 | Particles of aluminum salt hydroxide containing organic acid anion, method for production thereof and use thereof |
NO20064525A NO20064525L (no) | 2004-03-05 | 2006-10-05 | Partikler av aluminiumsalthydroksid inneholdende organisk syreanion, fremgangsmate for produksjon derav og anvendelse derav |
Applications Claiming Priority (2)
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JP2004062549 | 2004-03-05 | ||
JP2004-062549 | 2004-03-05 |
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WO2005085168A1 true WO2005085168A1 (ja) | 2005-09-15 |
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PCT/JP2005/003831 WO2005085168A1 (ja) | 2004-03-05 | 2005-03-01 | 有機酸アニオン含有アルミニウム塩水酸化物粒子、その製造方法およびその利用 |
Country Status (12)
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US (1) | US7629480B2 (ja) |
EP (1) | EP1731497B1 (ja) |
JP (1) | JP4931210B2 (ja) |
KR (1) | KR101157441B1 (ja) |
CN (1) | CN1930107B (ja) |
AU (1) | AU2005219753B2 (ja) |
CA (1) | CA2564630C (ja) |
IL (1) | IL177895A0 (ja) |
NO (1) | NO20064525L (ja) |
RU (1) | RU2360900C2 (ja) |
TW (1) | TWI365852B (ja) |
WO (1) | WO2005085168A1 (ja) |
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WO2010067881A1 (ja) | 2008-12-12 | 2010-06-17 | 協和化学工業株式会社 | 化粧料組成物 |
JP2010134097A (ja) * | 2008-12-03 | 2010-06-17 | Kyowa Chem Ind Co Ltd | 光拡散構造体 |
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- 2005-03-01 AU AU2005219753A patent/AU2005219753B2/en not_active Ceased
- 2005-03-01 WO PCT/JP2005/003831 patent/WO2005085168A1/ja active Application Filing
- 2005-03-01 EP EP05720103.0A patent/EP1731497B1/en not_active Not-in-force
- 2005-03-01 CN CN2005800071434A patent/CN1930107B/zh not_active Expired - Fee Related
- 2005-03-01 RU RU2006135118/04A patent/RU2360900C2/ru not_active IP Right Cessation
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- 2005-03-01 KR KR1020067017909A patent/KR101157441B1/ko not_active IP Right Cessation
- 2005-03-04 TW TW094106525A patent/TWI365852B/zh not_active IP Right Cessation
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2006
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Cited By (19)
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WO2007004713A1 (ja) * | 2005-06-30 | 2007-01-11 | Kyowa Chemical Industry Co., Ltd. | 銀含有アルミニウム硫酸塩水酸化物粒子よりなる抗菌剤およびその利用 |
JP2007039442A (ja) * | 2005-06-30 | 2007-02-15 | Kyowa Chem Ind Co Ltd | 銀及び有機酸アニオン含有アルミニウム硫酸塩水酸物粒子よりなる抗菌剤およびその利用 |
US8394392B2 (en) | 2005-06-30 | 2013-03-12 | Kyowa Chemical Industry Co., Ltd. | Antibacterial agent composed of silver-containing aluminum sulfate hydroxide particles and use thereof |
CN101212905B (zh) * | 2005-06-30 | 2013-01-09 | 协和化学工业株式会社 | 包含含有银的铝硫酸盐氢氧化物粒子的抗菌剂及其用途 |
AU2006266691B2 (en) * | 2005-06-30 | 2011-06-30 | Kyowa Chemical Industry Co., Ltd. | Antibacterial agent comprising silver-containing aluminum sulfate hydroxide particle and use thereof |
JP2007039444A (ja) * | 2005-07-01 | 2007-02-15 | Kyowa Chem Ind Co Ltd | 抗菌剤、その製造方法及びその利用 |
JP2007204293A (ja) * | 2006-01-31 | 2007-08-16 | Kyowa Chem Ind Co Ltd | 多孔質粒子およびその製造方法 |
JP2008120860A (ja) * | 2006-11-08 | 2008-05-29 | Fujifilm Corp | 顔料分散組成物、それを含有する着色感光性樹脂組成物及び感光性樹脂転写材料、並びにそれらを用いたカラーフィルタ及び液晶表示装置 |
JPWO2008082007A1 (ja) * | 2006-12-29 | 2010-04-30 | 協和化学工業株式会社 | 抗菌性粒子、その製造方法および抗菌性組成物 |
JP5158876B2 (ja) * | 2006-12-29 | 2013-03-06 | 協和化学工業株式会社 | 抗菌性粒子、その製造方法および抗菌性組成物 |
WO2008082007A1 (ja) * | 2006-12-29 | 2008-07-10 | Kyowa Chemical Industry Co., Ltd. | 抗菌性粒子、その製造方法および抗菌性組成物 |
JP2008254994A (ja) * | 2007-04-09 | 2008-10-23 | Ishihara Sangyo Kaisha Ltd | 酸化亜鉛及びその製造方法並びにそれを用いた化粧料 |
JP2011517309A (ja) * | 2007-09-25 | 2011-06-02 | ザ レジェンツ オブ ザ ユニヴァースティ オブ カリフォルニア | 食用に適した生体適合性金属有機構造体 |
JP2010047703A (ja) * | 2008-08-22 | 2010-03-04 | Kyowa Chem Ind Co Ltd | 難燃性樹脂組成物 |
JP2010134097A (ja) * | 2008-12-03 | 2010-06-17 | Kyowa Chem Ind Co Ltd | 光拡散構造体 |
WO2010067881A1 (ja) | 2008-12-12 | 2010-06-17 | 協和化学工業株式会社 | 化粧料組成物 |
JPWO2010067881A1 (ja) * | 2008-12-12 | 2012-05-24 | 協和化学工業株式会社 | 化粧料組成物 |
WO2011059105A1 (ja) * | 2009-11-10 | 2011-05-19 | 協和化学工業株式会社 | 遮熱剤組成物 |
JPWO2011059105A1 (ja) * | 2009-11-10 | 2013-04-04 | 協和化学工業株式会社 | 遮熱剤組成物 |
Also Published As
Publication number | Publication date |
---|---|
TW200540115A (en) | 2005-12-16 |
EP1731497A1 (en) | 2006-12-13 |
EP1731497B1 (en) | 2016-04-27 |
KR20060123611A (ko) | 2006-12-01 |
RU2360900C2 (ru) | 2009-07-10 |
NO20064525L (no) | 2006-10-05 |
US7629480B2 (en) | 2009-12-08 |
IL177895A0 (en) | 2006-12-31 |
US20070189986A1 (en) | 2007-08-16 |
CA2564630C (en) | 2013-09-03 |
JPWO2005085168A1 (ja) | 2008-01-17 |
RU2006135118A (ru) | 2008-04-10 |
EP1731497A4 (en) | 2008-03-05 |
CN1930107A (zh) | 2007-03-14 |
AU2005219753A1 (en) | 2005-09-15 |
TWI365852B (en) | 2012-06-11 |
CA2564630A1 (en) | 2005-09-15 |
JP4931210B2 (ja) | 2012-05-16 |
CN1930107B (zh) | 2011-07-27 |
KR101157441B1 (ko) | 2012-06-22 |
AU2005219753B2 (en) | 2010-06-03 |
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