Silica particles and process for producing the same

Abstract: Silica particles having: an average particle size of from 5 to 100 µm, a BET specific surface area of not more than 20 m²/g, and a pore volume of not more than 0.1 ml/g, each of said silica particles having on the surface thereof a plurality of protuberances with a smooth configuration, the diameter at half the protuberance height of each protuberance being from 0.2 to 5.0 µm and the height of each protuberance being 0.2 to 4.0 µm.

Description: The present invention relates to silica particles having protuberances on their surfaces, which particles are suitable for incorporation in a resin or rubber, and a process for producing the silica particles. The silica particles according to the present invention are useful as a filler for semiconductor sealant resin compositions, polyesters, engineering plastics and silicone rubber. Various inorganic fillers, especially silica, are popularly used to improve the properties of high polymeric materials. For instance, in IC sealants, a silica filler in a ratio of about 70 wt% is blended with a matrix resin such as an epoxy resin, polyphenylene sulfide or polyimide to adjust the coefficient of thermal expansion. With the recent tendency towards higher integration of semiconductors and oversizing of chips, a need is developing for a greater purity of the sealant, lower stress and improvement of crack resistance. However, with the present state of art, these requirements are not yet fulfilled sufficiently. Conventional silica filler is obtained by the following methods: (1) melt pulverization of natural quartz, (2) calcination and pulverization of silica gel prepared by using sodium silicate, (3) decomposition of silicon tetrachloride by oxyhydrogen flames, and (4) sol-gel of alkoxysilane. These methods, however, have the problems set forth below. Method (1) has a problem in stable supply of natural quartz of good quality. It is also impossible with this method to reduce the content of radioactive elements such as uranium and thorium, which could cause erroneous operation (soft errors) of IC's. Silica produced by method (2) is unusable as a silica sealant for highly integrated semiconductor devices because of the probability of contamination with metal components such as sodium and aluminium, or ionic impurities from the sodium silicate used as a starting material or a neutralizing agent. Method (3) has problems of high production cost and difficulty in controlling particle size and shape. It is also impossible with this method to avoid inclusion of chlorine ions as an impurity. Method (4), although capable of producing high-purity silica by the purifying-treatment of the raw material, has a complicated production process, so that the silica produced is costly and its use consequently limited. As regards the shape of silica filler, there has been mostly used square silica produced by molten silica pulverization. A composition containing square silica, however, has poor fluidity and its use tends to cause "hard errors" such as deformation of wiring or package cracking due to stress caused by the sharp ends of the particles, so that recently spherical silica has come to be used, usually to improve the fluidity and dispersion of stress. However spherical silica still has problems that it is relatively costly and that adhesion to resin is deteriorated, resulting in reduced strength of the molded package, since the silica particle surface is smoothened as a result of melting or sintering during the heat treatment in the production process. As prior art regarding silica particles having specific shapes, JP-A-88/182212 discloses perfectly circular silica particles having a jagged surface, and US-A-4,010,242 discloses a method of producing fine particles using colloidal particles of 5 to 500 µm size as a starting material. The silica particles proposed hitherto have various problems in preparation and practical application, and accordingly the development of new silica particles free from the problems such as concentration of stress, low fluidity and unsatisfactory adhesion to resin, which are observed in the use of conventional square or spherical silica as a filler, has been required. As a result of the present inventors' extensive and intensified studies for solving the said problems, silica particles with a specific surface configuration have been found to be excellently suited for use as a filler. The present invention provides silica particles having: an average particle size of from 5 to 100 µm, a BET specific surface area of not more than 20 m²/g, and a pore volume of not more than 0.1 ml/g, each of said silica particles having on the surface thereof a plurality of protuberances with a smooth configuration, the diameter at half the protuberance height of each protuberance being from 0.2 to 5.0 µm and the height of each protuberance being 0.2 to 4.0 µm. The present invention also provides a process for producing silica particles as defined above, said process comprising: (A) reacting hydrosilicofluoric acid, ammoniumsilicofluoride or a mixture thereof with ammonia in an aqueous medium to form a silica slurry, (B) separating silica from said slurry by means of a solid/liquid separation, and (C) calcining, after drying if desired, the silica at a temperature of not less than 500°C. The present invention also provides a composition comprising (i) silica particles as defined above, and (ii) a macromolecular material. The present invention also provides the use of silica particles as defined above as a filler. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron micrograph (× 200 magnification) showing the structure of silica particles A obtained in Example 1. Fig. 2 is a scanning electron micrograph (× 1000 magnification) showing the structure of silica particles A obtained in Example 1. Fig. 3 is a scanning electron micrograph (× 200 magnification) showing the structure of silica particles B obtained in Example 2. Fig. 4 is a scanning electron micrograph (× 1000 magnification) showing the structure of silica particles B obtained in Example 2. Fig. 5 is a scanning electron micrograph (× 200 magnification) showing the structure of silica particles C obtained in Example 3. Fig. 6 is a scanning electron micrograph (× 1000 magnification) showing the structure of silica particles C obtained in Example 3. The average particle size of the silica particles according to the present invention is from 5 to 100 µm, preferably 5 to 50 µm. When the average particle size is less than 5 µm, a composition containing the particles has deteriorated fluidity and moldability, and when the average particle size exceeds 100 µm, it becomes impossible to fill silica to a high density in a composite and the mechanical strength of the composite is reduced. Although the average particle size is from 5 to 100 µm, it is also undesirable, for the same reason, that fine silica particles of less than 5 µm in diameter or coarse silica particles exceeding 100 µm in diameter be contained in a high percentage. The specific surface area, as measured by the BET method, of the silica particles according to the present invention is not more than 20 m²/g, preferably not more than 10 m²/g. When the BET specific surface area is more than 20 m²/g, adverse effects arise due to the large content of fine particles, and also the mechanical strength of the silica particles themselves is reduced. When the silica particles of the present invention are used as a filler for an IC sealant, the BET specific surface area of the said particles is preferably less than 10 m²/g, more preferably less than 5 m²/g. The pore volume of the silica particles of the present invention is not more than 0.1 ml/g, preferably not more than 0.05 ml/g. When it exceeds 0.1 ml/g, the mechanical strength of the particles themselves is reduced, and also air tends to be trapped in the pores, thereby causing air-release, or formation of voids in the course of kneading with a resin or in practical use of the composite. This unfavorably influences the quality of the composite or the products. The protuberances in the surfaces of the silica particles according to the present invention have a smooth configuration, in other words a generally roundish configuration. The term "smooth configuration" used herein is to be understood to mean that there exists no sharp or spicular part on the particle surface. The height of such a protuberance is 0.2 to 4.0 µm, preferably 0.2 to 3.0 µm, wherein the height is measured from the bottom of the recess between the adjoining protuberances. The diameter of such a protuberance is 0.2 to 5.0 µm, preferably 0.2 to 3.0 µm at the height level which is half of the height of the protuberance (at half the protuberance height). It is also preferable that the height of the protuberance is 1.0 to 0.6-fold of the diameter. The average number of protuberances per one silica particle is ordinarily not less than 100, preferably not less than 500, more preferably not less than 1000. The height of the protuberances is preferably not more than 30%, more preferably not more than 10%, based on the average particle size of the particles. The protuberances on the silica particle surface according to the present invention contribute to the improvement of adhesion between the silica particles and a matrix resin, resulting in enhanced mechanical strength of the resin composite. When the diameter at half the protuberance height is less than 0.2 µm, the adhesion improving effect of the protuberances does not become conspicuous, and when the diameter exceeds 5 µm, the number of the protuberances which are able to exist is reduced and also the contact area with the matrix resin is reduced, so that the adhesion improving effect does not become conspicuous in comparison with conventional spherical silica. It is also to be noted that appropriate roundness of the protuberances on the particle surface is able to disperse stress as opposed to the conventional pulverized square silica particles in which stress is concentrated at the end portions. The silica particles of the present invention having the protuberances of a specific configuration on the surface thereof and also possessing the above properties can typically be obtained by reacting hydrosilicofluoric acid and/or an ammonium salt thereof with ammonia in an aqueous medium, separating a silica and calcining the thus separated silica. By the use of these starting materials, it is possible to produce silica particles which have not only said specific configuration and properties but also high purity as these particles are substantially free of metallic impurities. The production process of the silica particles according to the present invention comprises: (A) reacting hydrosilicofluoric acid and/or an ammonium salt thereof with ammonia in an aqueous medium to form a silica slurry; (B) separating silica from the slurry by means of a solid/liquid separation; and (C) optionally drying the separated silica, and calcining the resultant silica. As hydrosilicofluoric acid used as a starting material in the step (A), there can be used commercially available reagents or the by-product formed in the wet preparation process of phosphoric acid. It can be also produced by aqueous liquid absorption of a gas containing silicon tetrafluoride. This hydrosilicofluoric acid is used in the form an aqueous solution with a concentration usually of about 5 to 40%. The ammonium salt of hydrosilicofluoric acid, namely ammonium silicofluoride, can be easily obtained by adding gaseous or aqueous ammonia to hydrosilicofluoric acid. It is also obtainable by ammonium fluoride liquid absorption of a gas containing silicon tetrafluoride. In the present invention, hydrosilicofluoric acid and ammonium silicofluoride can be used either singly or in the form of a mixture. Ammonia may be used either in a gaseous state or in the form of an aqueous solution. The purity of the starting reactants can be properly selected according to the use of the produced silica. For obtaining silica particles with high purity, hydrosilicofluoric acid is purified either directly by distillation or through aqueous liquid absorption of a silicon tetrachloride-containing gas by acid decomposition, while ammonium silicofluoride is purified by recrystallization or other suitable methods. If necessary, both ammonia of a high purity and an aqueous medium which contains little metal impurity may be used. As an aqueous medium, water and an inert aqueous organic solvent which reacts with neither the raw material nor the reaction product may be used. Water is preferable for handling. The reaction of hydrosilicofluoric acid and/or an ammonium salt thereof with ammonia proceeds as follows: H₂SiF₆ + 2NH₃ → (NH₄)₂SiF₆ (NH₄)₂SiF₆ + 4NH₃ + 2H₂O → SiO₂ + 6NH₄F The molar ratio of ammonia to hydrosilicofluoric acid is 6:1 stoichiometrically, but the ratio used is usually range of 3:1 to 10:1, preferably 4:1 to 8:1. When the molar ratio is low, the reaction rate is lowered correspondingly and the pH of the final reaction slurry is on the acid side or around neutrality. When the molar ratio is high, the reaction rate is raised and the pH of the final reaction slurry is on the basic side. The pH of the reaction system is an important factor for controlling the shape of silica particles or their properties. The molar ratio of ammonia to ammonium silicofluoride is 4:1 stoichiometrically, but the ratio used is usually 1:1 to 8:1, preferably 2:1 to 6:1. The reaction may be carried out either batch-wise or continuously. As for the way of addition of the starting materials, the following methods are usable: (1) ammonia is added into an aqueous medium containing hydrosilicofluoric acid and/or an ammonium salt thereof; (2) contrary to method (1), hydrosilicofluoric and and/or an ammonium salt thereof is (are) added into an aqueous medium containing ammonia; (3) hydrosilicofluoric acid and/or an ammonium salt thereof and ammonia are added simultaneously into the aqueous medium; or (4) the above methods are used in combination. When method (1) is used, silica is produced in a pH region on the acid side in the early phase of reaction, and although the result is variable according to the other reaction conditions, there are generally obtained silica particles which have small (height and diameter) protuberances on the surface thereof, relatively compact and fine. According to method (2), silica is produced in a high pH region and there is a tendency toward production of coarse silica particles with relatively large-sized protuberances on the particle surface. When using method (3), the silica particles can be grown under a fixed pH condition by controlling the starting material feed rate to the reaction system. In the production of silica particles according to the present invention, method (3), is preferred. Especially, continuous supply of the two starting component materials in the presence of seed silica causes the growth of the silica particles and there can be easily obtained silica particles having the said protuberances on the surface. The seed silica may be produced according to method (1). The reaction of hydrosilicofluoric acid and/or an ammonium salt thereof with ammonia in an aqueous medium is usually started at a temperature of 0 to 100°C, typically at around room temperature, and the reaction is conducted or accompanied by a rise of temperature of about 10 to 50°C by the heat of reaction. In some cases, the reaction can be conducted at a high temperature above 80°C. The above reaction is ordinarily carried out under normal pressure or therearound, but it may be conducted under pressure at a temperature above 100°C or under reduced pressure at a temperature below 80°C. The rise of reaction temperature has a tendency to enlarge the particle size of the produced silica particles or the protuberance diameter. The reaction is ordinarily carried out at pH 4 to 11, preferably 5 to 10. The reaction time cannot be specified as it is variable depending on the reaction style, starting material addition method and other reaction conditions. Usually it is from one minute to 10 hours, preferably from 10 minutes to 5 hours. After the reaction, the reaction mixture may be subjected to aging. The silica concentration in the reaction system is usually 0.5 to 18 wt%, preferably 1 to 10 wt%, more preferably 2 to 7 wt%. A too low silica concentration results in poor productivity of the objective silica particles, while a too high silica concentration makes it difficult to control the reaction. In carrying out the above reaction according to the present invention, the reaction system may for example contain, beside the starting materials, an additive or additives such as various salts (for example ammonium fluoride, ammonium chloride or ammonium sulfate), polyvinyl alcohol, a binder such as cellulose or a surfactant. Thus, in the step (A) of the process according to the present invention, a silica slurry is obtained by carrying out the above-described reaction by properly selecting the said reaction conditions such as the kind and molar ratio of the starting materials, reaction style, adding method, pH, temperature, silica concentration and additive(s), and the slurry thus obtained is subjected to the next step (B). Since the silica slurry formed by the above reaction coexists with by-produced ammonium fluoride solution, in step (B) the reaction product is subjected to a solid/liquid separation such as filtration under reduced pressure, filtration under pressure or centrifugation to form silica cakes. Since the obtained silica cakes contain a small quantity of ammonium fluoride due to adhesion of the mother liquor, the cakes are washed with water or an organic solvent to remove the ammonium fluoride. It is also possible to remove the coexisting ammonia by carrying out a suitable treatment such as an acid washing or a hot water extraction. The water and acid used for washing or the said treatment need to be substantially free of impurities (especially metals). In step (C), the said wet silica is calcined, after drying if necessary, to obtain the silica particles of the present invention. The drying is usually effected by hot-air drying, vacuum drying, spray drying, flash drying or fluidized drying at a temperature of 50 to 200°C. The calcination is performed at a high temperature of not less than 500°C, preferably above 900°C, but use of an excessively high temperature is undesirable for maintaining the specified shape and properties of the silica particles obtained. Usually the calcining temperature is below the melting point of silica, preferably below 1,500°C. The silica particles obtained according to the present invention can be worked into a high-purity product with high added-value such as a filler for resin, rubber and other materials, and the metallic impurity in the composite can be reduced to a level below 1,000 ppm, preferably below 100 ppm, more preferably below 10 ppm, expressed as the total content of metal oxides. In using the silica particles of the present invention as a material for electrical parts, it is preferable that the particles are substantially free of alkaline metals such as sodium and potassium. Also, the silica particles produced according to the present invention can meet the requirement of low α-ray emission in use as an IC sealant since according to the production process of the present invention, there can be formed the silica particles with a content of radioactive elements such as uranium and thorium below 10 ppb, preferably below 1 ppb, more preferably below 0.5 ppb, by purification treatments at the raw material stage. The silica particles of the present invention are expected to have a wide scope of practical use, but they are particularly useful as a filler for improving the properties of macromolecular materials such as resins and rubbers by making use of the said specific shape and properties of the particles. Especially, the silica particles are useful as a reinforcing agent or an adjuster of the coefficient of thermal expansion of the macromolecular material. The amount of the silica particles used depends on the kinds of the macromolecular materials and purposes of the use, and it is not specified, but the amount of the silica particles is ordinarily 1 to 95%, preferably 5 to 90%, by weight based on the total amount of the macromolecular material and the silica particles. As the resin for the matrix of the composite of the present invention, there can for example be used thermoplastic resins such as polyvinyl chloride, polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, poly(meth)acrylic esters, polycarbonate, polyester, polyamide, polysulfone, polyphenylene sulfide and liquid crystal polymers, and thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, polyimide and unsaturated polyester resin. As the rubber, natural rubber, synthetic rubber and silicone rubber may be exemplified. The composite can be obtained by molding a composition comprising the silica particles and the macromolecular material by a conventional method. The composition may be obtained by mixing the silica particles and a powder of the macromolecular material or by kneading the silica particles and the macromolecular material and pulverizing. The composition has excellent fluidity and moldability. The composite or the composition composed of the silica particles of the present invention and the resin or the rubber may contain an additive such as a coupling agent and a release agent, in an ordinarily usable amount. A surface treatment, for example, a treatment with a coupling agent such as a silicone compound or titanium compound, and a surface graft polymerization treatment, may be conducted on the surface of the silica particles to further improve the adhesion and compatibility between matrix resin and silica particles, and prevent intrusion (absorption) of moisture from the outside of the system to enhance the performance of the silica particles. Especially, a composite comprising the silica particles and an epoxy resin is useful as an IC sealant. As described above, since the silica particles of the present invention have high purity, and the specific surface configuration, such silica particles according to the present invention are free from the concentration of stress, and have a sufficient adhesion to the resin. Furthermore the silica particles are useful as a raw material for the composite which has excellent properties such as bending strength. [Examples] The present invention is described in further detail in the following Examples. The properties of silica particles were evaluated according to the following: (1) Average particle size Measured by a laser diffraction particle size distribution analyzer. (2) Specific surface area Measured according to the BET method using nitrogen. (3) Pore volume Measured according to a nitrogen-adsorption method. (4) Height and diameter of a protuberance Measured on a electron micrograph. (5) The content of metal impurities From a sample, a silica component was removed as a volatile component by hydrofluoric acid treatment. The residue was dissolved in a dilute acid and the content of metal impurities was determined according to ICP (Inductivity Coupled Plasma) emission spectroscopic analysis. (6) Ignition loss After a sample which was previously dried at 105°C was heated at 950°C for 1 hour, the loss in weight was measured. Example 1 Into a 20-liter reactor provided with a stirrer (stirring reactor), 3 kg of 25% ammonia water was supplied. Then, 11 kg of 20% hydrosilicofluoric acid solution and 4.5 kg of 25% ammonia water were added thereto simultaneously at room temperature at the flow rates of 0.37 kg/hr and 0.15 kg/hr, respectively, by using constant delivery pumps. The resultantly formed silica slurry was centrifuged. The ammonium fluoride solution was removed as mother liquor and the silica cakes were washed with 100 liters of water and 5 liters of methanol. The washed silica cakes were subjected to 12-hour hot-air drying at 105°C and then calcined in an electric muffle furnace at 1,200°C for 2 hours to obtain 0.9 kg of calcined silica particles A. These silica particles, as observed from their scanning electron micrographs (see Figs.1 and 2), had a plurality of roundish protuberances forming ruggedness over the whole particle surface. Protuberances were observed, which had heights of 0.3 to 2.0 µm and diameters at half the protuberance heights of 0.3 to 2.0 µm. The average particle size was 25.8 µm. The particles also had a BET specific surface area of 2.5 m²/g and a pore volume of 0.01 ml/g. The content of metallic impurities calculated in terms of contents of oxides was as follows (unit: ppm): A blend of the silica particles A and the following materials was kneaded by heated rolls, then cooled and pulverized to obtain an epoxy resin composition. Blend formulation In addition, the same composition as above was prepared except that square silica particles (average particle size: 25 µm) produced by a crushing method were used instead of the silica particle A. The composition containing the silica particles A had excellent fluidity, compared with the composition containing square silica particles (average particle size: 25 µm) produced by the crushing method. Example 2 Into a 10-liter stirring reactor, 3.6 kg of purified 20% hydrosilicofluoric acid solution was supplied, followed by addition of 2.65 kg of 25% ammonia water over a period of 30 minutes. The reaction temperature rose from 20°C to 57°C and fine silica particles were produced. The resultantly formed silica slurry was homogenized by stirring. 1.25 kg of this silica slurry was collected and transferred into an another 10-liter reactor. Into this seed silica slurry were added simultaneously 3.6 kg of purified 20% hydrosilicofluoric acid solution and 2.45 kg of 25% ammonia water over a period of one hour. The temperature of the reaction solution rose from 21°C to 38°C. There was obtained 7.1 kg of primary reaction silica slurry. Into the other 10-liter reactor, 1.25 kg of this primary reaction silica slurry was transferred, and hydrosilicofluoric acid solution and ammonia water were added thereto simultaneously under the same conditions as in the case of the primary reaction to obtain 7.2 kg of secondary reaction silica slurry. This secondary reaction silica slurry was subjected to a solid/liquid separating operation using a vacuum filter to remove the ammonium fluoride solution (mother liquor) containing excess ammonia, and the silica cakes were washed with a large amount of pure water and then hot-air dried at 120°C. The dried silica cakes were then calcined at 1,250°C for 3 hours to obtain 0.33 kg of silica particles B of the present invention. The impurity content (ppm) expressed as contents of metal oxides was as follows: The contents (ppb) of the radioactive elements were as follows: U <1.0 Th <1.0 These silica particles B as observed from their scanning electron micrographs (see Figs. 3 and 4) had a plurality of roundish protuberances over the whole particle surface. Protuberances were observed, which had heights of 0.5 to 3.0 µm and diameters at half the protuberance heights of 0.5 to 3.0 µm. The average particle size was 26.0 µm. These particles also had a BET specific surface area of 0.6 m²/g and a pore volume of 0.003 ml/g. In the same way as Example 1, compositions were prepared except that the silica particles B and spherical silica particles having an average particle size of 25 µm were respectively used. Each of the compositions was cast into a heated mold to obtain a hardened body (composite). The bending strength of each of the composites was measured. The bending strength of the composite containing the silica particles B was larger by 30% than that of the composite containing the spherical silica particles having an average particle size of 25 µm. Example 3 Into a 20-liter stirring reactor, 7.5 kg of 25% ammonia water was supplied, and then 11 kg of purified 20% hydrosilicofluoric acid solution was added thereto over a period of 60 minutes to form a silica slurry. This silica slurry was filtered under reduced pressure, and the formed silica cakes were washed with 150 liters of water and one liter of methanol and then hot-air dried at 105°C to obtain dry silica particles C'. These dry silica particles C' were calcined in an electric furnace at 1,200°C for 2 hours to obtain 0.9 kg of silica particles C of the present invention. These silica particles C, as observed from their scanning electron micrographs (see Figs. 5 and 6), had a plurality of roundish protuberances forming a continuum of concavities and convexities over the whole particle surface. Protuberances were observed, which had heights of 0.2 to 1.0 µm and diameters at half the protuberance heights of 0.2 to 1.0 µm. The properties of said silica particles C and C' are shown below. The impurity content (ppm) expressed as the contents of metal oxides was as shown below: In the same way as Example 2, compositions and composites were prepared except that the silica particles C and the silica particles C' were respectively used. In the case that silica particles C were used, fluidity, bending strength and packing property were excellent. But, in the case that silica particles C' were used, there occurred air-release and break of the particles during kneading with the resin and the fluidity was inferior.

Claims: Silica particles having: an average particle size of from 5 to 100 µm, a BET specific surface area of not more than 20 m²/g, and a pore volume of not more than 0.1 ml/g, each of said silica particles having on the surface thereof a plurality of protuberances with a smooth configuration, the diameter at half the protuberance height of each protuberance being from 0.2 to 5.0 µm and the height of each protuberance being 0.2 to 4.0 µm. Silica particles according to claim 1, wherein the content of metal impurities, expressed as the content of metal oxides, is not more than 1,000 ppm. Silica particles according to claim 1, wherein an average number of said protuberances per one silica particle is not less than 100. A process for producing silica particles as defined in any one of the preceding claims, said process comprising: (A) reacting hydrosilicofluoric acid, ammonium silicofluoride or a mixture thereof with ammonia in an aqueous medium to form a silica slurry, (B) separating silica from said slurry by means of a solid/liquid separation, and (C) calcining, after drying if desired, the silica at a temperature of not less than 500°C. A process according to claim 4, wherein in step (A) the hydrosilicofluoric acid, ammonium silicofluoride or a mixture thereof and ammonia are added simultaneously into an aqueous medium. A process according to claim 5, wherein said aqueous medium contains a seed silica. A composition comprising: (i) silica particles as defined in any one of claims 1 to 3, and (ii) a macromolecular material. A process for producing a composite which comprises molding a composition as defined in claim 7. Use of silica particles as defined in any one of claims 1 to 3 as a filler.

Inventors: KUBO MASAO, MOCHIYAMA TOKUMI, TAKAKO YASUSHI, TSUGENO MAKOTO, YURI YOSHITO, KUBO, MASAO, MOCHIYAMA, TOKUMI, TAKAKO, YASUSHI, TSUGENO, MAKOTO, YURI, YOSHITO
Applicants: NISSAN CHEMICAL IND LTD, NISSAN CHEMICAL INDUSTRIES, LIMITED
Application year: 1990
Main classification: C01B33
IPC codes: C01B33, C09C1, C08K3