WO2013141164A1 - Method for producing zinc cyanamide - Google Patents
Method for producing zinc cyanamide Download PDFInfo
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- WO2013141164A1 WO2013141164A1 PCT/JP2013/057476 JP2013057476W WO2013141164A1 WO 2013141164 A1 WO2013141164 A1 WO 2013141164A1 JP 2013057476 W JP2013057476 W JP 2013057476W WO 2013141164 A1 WO2013141164 A1 WO 2013141164A1
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- cyanamide
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- cyanurate
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Definitions
- the present invention relates to a method for producing cyanamide zinc and a method for producing an antirust pigment composition using the same.
- anti-rust pigments that surpass the anti-rust performance of chromium compounds and lead compounds, such as red lead, basic lead chromate, zinc chromate, basic zinc potassium chromate, cyanamide lead, calcium lead acid, basic lead sulfate Therefore, these chromium compound and lead compound rust preventive pigments are still used. For this reason, there is an urgent need for anti-corrosive pigments that are free of lead and chromium and have excellent anti-rust performance.
- phosphates such as aluminum phosphate, zinc phosphate, zinc phosphite, calcium phosphate, molybdate such as zinc molybdate, aluminum molybdate, calcium molybdate, cyanamide zinc
- molybdate such as zinc molybdate, aluminum molybdate, calcium molybdate
- cyanamide zinc there are cyanamide-based compounds such as cyanamide zinc calcium, among which cyanamide zinc (chemical formula: ZnCN 2 ) is cited as a promising candidate.
- cyanamide zinc As a method for producing cyanamide zinc by a wet coprecipitation method, a method of reacting zinc inorganic acid salt or organic acid salt or zinc oxide and cyanamide solution while maintaining alkalinity, washing, filtering, drying and pulverizing is disclosed.
- lime nitrogen composed of calcium cyanamide is used as the cyanamide solution.
- a zinc sulfate aqueous solution and a sodium cyanamide aqueous solution mixed at 1: 1 (molar ratio) and coprecipitated were fired in argon gas at a temperature of 570 ° C. or higher for 70 hours or longer to obtain a cyanamide zinc single crystal.
- Non-Patent Document 1 it is necessary to remove the by-product sodium sulfate by water washing before firing.
- soluble salts composed of alkali metal ions or calcium ions and anions such as nitric acid, sulfuric acid and hydrochloric acid appear as by-products.
- washing is required, which causes a large amount of waste water, which has the disadvantage of increasing the production cost.
- it is generally impossible to completely remove these soluble salts. Since these soluble salts are generally corrosion accelerators, there is a risk that the antirust performance of the anticorrosive pigment composition using cyanamide zinc may be reduced even in the presence of a small amount.
- a firing method is disclosed as another method for producing cyanamide zinc. Although it is disclosed that zinc carbonate is obtained by treating zinc carbonate in ammonia gas at 400 ° C. and 8-10 atm for 3 hours, only 50% of zinc carbonate is converted to cyanamide zinc (Patent Document) 2).
- a pigment such as cyanamide zinc is produced by heating a mixture of zinc oxide and excess urea or dicyanamide at 135 to 200 ° C. in a nitrogen atmosphere or under reduced pressure, followed by baking at 600 to 800 ° C. for 2 hours.
- the cyanamide zinc produced has a disadvantage that it has a low specific surface area and porosity due to high-temperature firing, and has a relatively dense structure, so that the reactivity is low and does not exhibit a high degree of corrosion inhibition activity. (Refer to Patent Document 3).
- a rust preventive paint using cyanamide zinc as a rust preventive pigment is that a cyanamide zinc pigment is contained in an oil-based or synthetic resin vehicle as a rust preventive paint to be applied to an iron material to prevent its corrosion.
- An anti-corrosion paint is disclosed (see Patent Document 1).
- a rust preventive paint on the back of the mirror a copper plating film is attached on the silver film formed on one side of the mirror to prevent corrosion, but silver corrosion cannot be prevented only by the copper plating film.
- an organic rust preventive paint is applied on the copper plating layer, and cyanamide zinc is cited as a rust preventive pigment blended in the organic rust preventive paint (see Patent Document 4).
- the object of the present invention is to solve the above-mentioned problems of the prior art. That is, the present invention provides a method for producing cyanamide zinc having high rust prevention performance that does not contain soluble by-products and lead, chromium and other harmful substances that interfere with rust prevention performance, and is obtained by the present invention. The present invention provides a method for producing a rust preventive pigment composition using cyanamide zinc.
- the present inventors have found a method for producing cyanamide zinc that is substantially free of soluble by-products and lead and chromium harmful substances and has high rust prevention performance.
- cyanamide is characterized in that zinc cyanurate or basic zinc cyanurate is fired at 460 ° C. or higher and 900 ° C. or lower in an atmosphere of nitrogen gas or a rare gas of Group 18 element.
- the second aspect of the present invention is a method for producing cyanamide zinc according to the first aspect, characterized in that a nitrogen-containing organic compound is mixed in advance with zinc cyanurate or basic zinc cyanurate,
- a nitrogen-containing organic compound is mixed in advance with zinc cyanurate or basic zinc cyanurate
- the zinc atom in the mixture
- It is a method for producing cyanamide zinc in which the molar ratio of nitrogen atoms (N / Zn) is 3 or more
- the fourth aspect of the present invention is a method for producing cyanamide zinc according to the second aspect or the third aspect, wherein the nitrogen-containing organic compound is cyanuric acid or urea.
- the manufacturing method of the antirust pigment composition characterized by mix
- Oil-based binder or synthetic resin binder (b) From the group consisting of water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate
- At least one selected diluent (c) is cyanamide zinc obtained by the method according to any one of the first to fourth aspects.
- the cyanamide zinc obtained by the present invention is substantially free of unnecessary soluble by-products and has a very high content of cyanamide zinc. Can be used.
- the cyanamide zinc obtained is white gray, when used in a rust preventive pigment composition, there is almost no influence on other color pigments, and rust preventive pigment compositions of various colors can be prepared.
- Example 7 is an XRD diffraction pattern of Example 7.
- the zinc cyanurate used as a raw material in the present invention is a slurry obtained by adding zinc oxide and cyanuric acid into pure water so that the molar ratio of zinc oxide / cyanuric acid is 1.5, and is 60 ° C. or less. And can be produced by wet dispersion using a dispersion medium or strong dispersion using a disper.
- the obtained slurry containing zinc cyanurate can be filtered with a filter press or the like, dried at less than 100 ° C., and then dry pulverized to obtain zinc cyanurate powder.
- the basic zinc cyanurate used as a raw material in the present invention is a compound represented by the chemical formula: Zn 5 (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O, and International Publication No. 2011/162354. It can be produced by the method described in the pamphlet. For example, a slurry obtained by adding zinc oxide and cyanuric acid into pure water so that the molar ratio of zinc oxide / cyanuric acid is 2.5 is obtained using a dispersion medium in a temperature range of 5 to 55 ° C. It can be produced by wet dispersion or strong dispersion with a disper.
- the basic zinc cyanurate produced in this way is obtained as a slurry, filtered with a filter press, etc., then the wet cake is dried at 200 ° C. or lower, and dry pulverized to thereby obtain basic zinc cyanurate. Powder.
- zinc oxide and cyanuric acid were introduced into a Laedige mixer apparatus (heating and stirring apparatus: manufactured by Chuo Kiko Co., Ltd.) so that the molar ratio of zinc oxide / cyanuric acid was 2.5, and 50 to 100 ° C.
- the basic cyanuric acid zinc is obtained as a powder by adding 20 to 40% by mass of water to the raw material powder (zinc oxide + cyanuric acid) while heating and stirring with heating.
- Calcination for producing cyanamide zinc in the present invention is performed in an atmosphere of nitrogen gas or a rare gas of Group 18 element.
- rare gases of Group 18 elements include helium, neon, and argon. From the viewpoint of cost, nitrogen gas is more preferable.
- the baking apparatus used in the present invention is a batch type electric furnace, a rotary kiln or the like, but must be an apparatus capable of controlling the atmosphere.
- Calcination temperature is preferably 460 ° C. or higher, more preferably 480 ° C. or higher.
- the firing temperature is 900 ° C. or lower.
- the formation of cyanamide zinc is insufficient, which is not preferable.
- a calcination temperature exceeds 900 degreeC, since cyanamide zinc thermally decomposes, it is unpreferable.
- Cyanamide zinc becomes zinc oxide when exposed to temperatures higher than 200 ° C. in an oxidizing atmosphere such as oxygen and air. Therefore, the firing atmosphere of the present invention must be performed in an atmosphere of nitrogen gas or a rare gas of a Group 18 element, and an oxidizing gas such as oxygen or air must be reduced as much as possible.
- the oxidizing gas such as oxygen or air in the atmosphere of nitrogen gas or a rare gas of Group 18 element is preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less.
- zinc cyanurate or basic zinc cyanurate is preliminarily added. It is preferable to mix a nitrogen-containing organic compound.
- the nitrogen-containing organic compound used include cyanuric acid and urea. Cyanuric acid is more preferable as a nitrogen-containing organic compound to be used because it is thermally decomposed at about 360 ° C. without passing through a molten state in the heating process and contributes to the formation of cyanamide zinc.
- the cyanamide zinc content is very high.
- a high baked product is obtained. This is because cyanuric acid is thermally decomposed at about 360 ° C. in an atmosphere of nitrogen gas or a rare gas of Group 18 element, whereas basic zinc cyanurate is thermally decomposed at 300 to 320 ° C., which is substantially the same temperature. It is estimated that the reaction of both compounds is likely to occur.
- the molar ratio (N / Zn) of nitrogen atoms to zinc atoms contained in the mixture is preferably 3 or more, and the molar ratio (N / Zn) is more preferably 3 or more and 6 or less.
- the molar ratio (N / Zn) is less than 3, a cyanamide zinc single phase cannot be obtained.
- the molar ratio (N / Zn) is larger than 6, only nitrogen-containing organic compounds that do not contribute to the firing reaction increase in the system, which is not efficient.
- the zinc cyanurate or basic zinc cyanurate and the nitrogen-containing organic compound are mixed in a container having a heating and stirring function such as a V-shaped mixer or a Laedige mixer apparatus.
- the cyanamide zinc obtained by the present invention is high-purity cyanamide zinc and is a light grayish white powder.
- the cyanamide zinc obtained has a specific surface area of 0.5 to 30 m 2 / g.
- the surface charge of the water system is negative in the range of pH 4 to pH 10. For this reason, when preparing an aqueous
- cyanamide zinc of the present invention zinc cyanurate or basic zinc cyanurate is used as a starting material, and a compound containing another metal element is not used in the process, and the firing temperature is used in the process.
- a compound having an inorganic acid radical that is not decomposed even in the temperature range of, for example, chloride, sulfate, phosphate and the like is not used. Therefore, the cyanamide zinc obtained does not substantially contain soluble by-products that hinder rust prevention performance, and is, for example, 500 ppm or less, or 50 ppm or less.
- the zinc cyanurate used as a raw material or basic cyanuric acid zinc or a nitrogen-containing organic compound does not contain lead and chromium substantially, the cyanamide zinc obtained does not contain lead and chromium similarly.
- the manufacturing method of the antirust pigment composition of this invention mix
- Oil-based binder or synthetic resin binder (b) Organic such as water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate
- Cyanamide zinc obtained by the method according to any one of the first to fourth aspects of the present invention.
- the rust preventive pigment composition obtained by the present invention comprises: It can be prepared by combining color pigments, anti-sagging agents, anti-skinning agents, drying accelerators, dispersants, anti-settling agents and the like.
- oil-based binder as component (a) examples include boil oil, linseed oil, soybean oil, safflower oil, castor oil, and the like.
- synthetic resin binder examples include phthalic acid resin, acrylic resin, amino resin, epoxy resin, silicon resin, polyurethane resin, fluororesin, and vinyl chloride resin.
- the mixing ratio of the components (a), (b) and (c) is arbitrary, but for example, the component (a) is 30 to 80 parts by mass, ( By blending component (b) in an amount of 5 to 20 parts by mass and component (c) in an amount of 2 to 50 parts by mass, a rust preventive pigment composition having excellent rust preventive performance can be produced.
- the rust preventive pigment composition obtained by the present invention is a viscous slurry.
- the rust preventive pigment composition obtained by the present invention is a pollution-free rust preventive pigment composition that exhibits a rust preventive effect equivalent to or higher than that of a rust preventive pigment composition containing harmful substances such as red lead and cyanamide lead. Since this rust preventive pigment composition does not contain harmful substances such as lead and chromium, it can be applied as a pollution-free rust preventive pigment composition in a rust preventive paint used for station buildings, road guard rails and the like that are easily contacted by humans.
- cyanamide zinc obtained by the present invention is white gray, it is possible to obtain a rust preventive pigment composition colored in an arbitrary color by mixing with a coloring pigment.
- the rust preventive pigment composition obtained by the present invention can be applied using a generally known coating method such as brush, roll, spray gun or the like.
- the rust preventive pigment composition obtained by the present invention is a rust preventive pigment composition for short-term durability use, unlike a long-term durable heavy anticorrosion rust preventive composition such as zinc rich paint. For this reason, it is suitable for applications such as the above-mentioned station buildings and road guard rails where dirt is conspicuous and can be repainted in a 5- to 10-year cycle.
- the analyzes in the synthesis examples, examples, and comparative examples were performed using the following apparatus and conditions.
- Slurry solid content measurement About 2 g of the sample was put in a porcelain crucible, precisely weighed, and the solid content (% by mass) was calculated from the mass after drying at 110 ° C.
- Powder X-ray diffraction analysis A powder X-ray diffraction apparatus RINT Ultimate type (manufactured by Rigaku Corporation) was used.
- the diffraction intensity of a diffraction peak at .8 ° (hereinafter referred to as peak B) was measured.
- Elemental analysis fully automatic elemental analyzer CHNS / O analyzer 2400 (manufactured by Perkin Elmer) Flame spectroscopic analysis: SpectraAA (Varian) ICP emission spectral analysis: Plasma Spectrometer SPS7800 (manufactured by Seiko Instruments Inc.) Ion chromatographic analysis: Ion chromatography IC25 (manufactured by DIONEX)
- the molar ratio of zinc oxide / cyanuric acid was 2.50, and the cyanuric acid concentration relative to water was 2.9% by mass.
- the temperature of the slurry became 50 ° C., and this temperature was maintained.
- This slurry was strongly dispersed for 9 hours while maintaining the rotational speed of the disperse blades at 800 rpm.
- 397 kg of a white slurry having a pH of 7.6, an electrical conductivity of 28 ⁇ S / cm, a viscosity of 1070 mPa ⁇ s, and a solid content of 8.5% by mass when dried at 110 ° C. was obtained.
- powder X-ray diffraction analysis was performed on the 110 ° C.
- the disk of the system zeta was rotated at a peripheral speed of 7.1 m / sec, and the slurry in the circulation tank was circulated for 7 hours at a supply speed of 22.1 kg / min to be dispersed. During this time, the circulating slurry temperature was maintained at 34 ° C. As a result, 170 kg of white slurry having a pH of 6.5, an electric conductivity of 446 ⁇ S / cm, a viscosity of 17 mPa ⁇ s, and a solid content concentration of 3.8% by mass was obtained.
- the carbon content was 17.2% by mass and the nitrogen content was 20.0% by mass.
- This dry powder had a composition of 3.0 moles of nitrogen atoms per mole of zinc atoms. Thereby, it was calculated as a mixed powder of 79 parts by mass of zinc cyanurate and 21 parts by mass of cyanuric acid.
- this acicular particle was zinc cyanurate of Zn 3 (C 3 N 3 O 3 ) 2 and had a composition of 2.0 moles of nitrogen atoms per mole of zinc atoms.
- the specific surface area of the 70 ° C. dry powder was 8 m 2 / g.
- flour was white and the moisture content was 2.2 mass%.
- powder X-ray diffraction analysis was performed. As a result, a diffraction peak of basic zinc cyanurate Zn 5 (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O was observed. It was.
- fine particles having a major axis of 200 to 500 nm and a minor axis of 40 to 80 nm were confirmed.
- the specific surface area after drying at 110 ° C. was 13 m 2 / g.
- Example 1 30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 10 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Then, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 460 ° C. For 6 hours.
- nitrogen gas oxygen concentration of 1 ppm or less
- Example 2 30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 10 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration 1 ppm or less) was flowed into the replacement furnace for 1 hour at a flow rate of 2 liters / minute, and then purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute and the nitrogen gas atmosphere was 490 ° C. Baked for 6 hours.
- nitrogen gas oxygen concentration 1 ppm or less
- the metal impurities in the fired powder were sodium 14 ppm, potassium 2 ppm, calcium 3 ppm, magnesium 1 ppm, lead 5 ppm, and chromium 0 ppm.
- chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
- Example 3 30 g of the dried block of zinc cyanurate obtained in Synthesis Example 3 was pulverized for 6 minutes with a home mixer. 15 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 490 ° C. For 6 hours.
- nitrogen gas oxygen concentration of 1 ppm or less
- Example 4 30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 15. Mixture obtained by mixing 10.0 g of the pulverized powder and 4.0 g of cyanuric acid, and adding cyanuric acid so that the nitrogen atom is 2.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 0 g was put into a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.).
- nitrogen gas oxygen concentration of 1 ppm or less
- nitrogen gas oxygen concentration of 1 ppm or less
- the nitrogen gas flow rate was changed to 0.5 liters / minute
- the nitrogen gas atmosphere was 490 ° C.
- 7.6 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis.
- the intensity of peak A was 3915 counts
- the intensity of peak B was 877counts.
- the cyanamide zinc content of this baked powder was calculated to be 62 mass%.
- Example 5 30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 20. A mixture obtained by mixing 12.7 g of this pulverized powder and 7.3 g of cyanuric acid, and adding cyanuric acid so that the nitrogen atom is 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 0 g was put into a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.).
- nitrogen gas oxygen concentration of 1 ppm or less
- nitrogen gas oxygen concentration of 1 ppm or less
- the nitrogen gas flow rate was changed to 0.5 liters / minute, under a nitrogen gas atmosphere 480.
- 9.8 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 3542counts.
- the cyanamide zinc content of this baked powder was calculated with 97 mass%.
- the calcined powder had a specific surface area of 25.6 m 2 / g.
- the obtained calcined powder was subjected to the same operation as in Example 2 to collect a supernatant, and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis.
- metal impurities in the fired powder were sodium 11 ppm, potassium 3 ppm, calcium 5 ppm, magnesium 1 ppm, lead 5 ppm, and chromium 0 ppm.
- chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
- Example 6 The same operation as in Example 5 was performed except that the firing temperature in a nitrogen gas atmosphere was 490 ° C. and the holding time was 11 hours. After cooling, 9.2 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4173 counts. Further, when CHN elemental analysis was performed, it was found that the nitrogen content was 26.3% by mass and carbon 11.5% by mass. Moreover, the specific surface area of this baked powder was 20.0 m 2 / g.
- Example 7 2.0 kg of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a Henschel mixer for 10 minutes. This pulverized powder (2.0 kg) and cyanuric acid (1.55 kg) were mixed, and the mixture in which cyanuric acid was added so that the nitrogen atom was 3.6 mol with respect to 1 mol of zinc atom was again mixed with a Henschel mixer for 20 minutes. Crushed. 400 g of this pulverized powder was placed in an alumina crucible, covered with an alumina lid, and then loaded into a gas displacement furnace (manufactured by Denken Co., Ltd.).
- nitrogen gas oxygen concentration of 1 ppm or less
- nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 6 ° C. for 6 hours.
- 173 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4548 counts.
- the cyanamide zinc content of this baked powder was calculated with 100 mass%.
- the specific surface area of the fired powder was 8.2 m 2 / g.
- the obtained calcined powder was subjected to the same operation as in Example 2 to collect a supernatant, and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis.
- the metal impurities in the fired powder were sodium 7 ppm, potassium 2 ppm, calcium 4 ppm, magnesium 1 ppm, lead 1 ppm, and chromium 0 ppm.
- chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
- 1 g of the obtained calcined powder and 80 ml of pure water were put into a 100 ml beaker and the surface charge was measured with a laser zeta electrometer ELS-6000 (manufactured by Otsuka Electronics Co., Ltd.). The surface charge was minus in the range of pH 3-10. Met.
- the pH adjustment for measuring the surface charge was performed with 1% dilute hydrochloric acid on the neutral to acidic side, and with 1% sodium hydroxide aqueous solution on the neutral to alkaline side.
- Example 8 The same firing operation as in Example 7 was performed except that the firing temperature in a nitrogen gas atmosphere was 560 ° C. and the holding time was 5 hours. After cooling, 172 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 5423counts. Moreover, since it was 26.8 mass% of nitrogen and 11.5 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 4.6 m 2 / g.
- Example 9 The same baking operation as in Example 7 was performed except that the baking temperature in a nitrogen gas atmosphere was 600 ° C. and the holding time was 5 hours. After cooling, 170 g of the obtained off-white calcined powder was taken out and identified with a powder X-ray diffractometer. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 6965 counts. Moreover, since it was 27.1 mass% of nitrogen and 11.3 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 3.9 m 2 / g.
- Example 10 The same firing operation as in Example 5 was performed except that the firing temperature in a nitrogen gas atmosphere was 700 ° C. and the holding time was 4 hours. After cooling, 9.1 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 7593 counts. Moreover, since it was 27.2 mass% of nitrogen and 11.3 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the calcined powder was 1.8 m 2 / g.
- Example 11 The same baking operation as in Example 5 was performed except that the baking temperature was 900 ° C. and the holding time was 2 hours in a nitrogen gas atmosphere. After cooling, 6.9 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 9364 counts. Moreover, since it was 27.1 mass% of nitrogen and 11.4 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the calcined powder was 0.6 m 2 / g.
- Example 12 30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 12.5 g of this pulverized powder and 7.5 g of cyanuric acid are mixed, and a mixture obtained by adding cyanuric acid so that the nitrogen atom is 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate is porcelain. After putting in a crucible and covering with a porcelain lid, it was loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.).
- Example 13 50 g of the dry powder of basic cyanuric acid obtained in Synthesis Example 4 was pulverized for 6 minutes with a household mixer. 38.5 g of cyanuric acid measured so that the nitrogen atom is 3.6 mol per 1 mol of zinc atom of the basic zinc cyanurate and the zinc atom of the basic cyanurate was sealed in a polyethylene bag. The bag was shaken to mix both powders uniformly. 27 g of this mixed powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken).
- a gas replacement furnace manufactured by Denken
- nitrogen gas oxygen concentration of 1 ppm or less
- nitrogen gas flow rate was changed to 0.5 liters / minute
- 11.5 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 5633counts.
- the cyanamide zinc content of this baked powder was calculated with 100 mass%.
- the calcined powder had a specific surface area of 4.0 m 2 / g.
- Example 14 30 g of 70 ° C. dry powder of the white slurry obtained in Synthesis Example 2 was pulverized for 6 minutes with a household mixer. 30 g of this pulverized powder is a mixed powder of 24 g of zinc cyanurate and 6 g of cyanuric acid. 15 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, and then purged with nitrogen. Baked at 6 ° C. for 6 hours.
- nitrogen gas oxygen concentration of 1 ppm or less
- metal impurities in the fired powder were sodium 23 ppm, potassium 4 ppm, calcium 5 ppm, magnesium 1 ppm, lead 3 ppm, and chromium 0 ppm.
- chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
- Example 15 30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 4.2 g of this pulverized powder and 6.5 g of urea were mixed, and urea was added so that the nitrogen atom was 7.2 mol with respect to 1 mol of zinc atom of basic zinc cyanurate. 10.0 g of the mixture was placed in a porcelain crucible, covered with a porcelain lid, and then charged into a gas replacement furnace (manufactured by Denken Co., Ltd.).
- nitrogen gas oxygen concentration of 1 ppm or less
- nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 5 ° C. for 5 hours.
- 2.2 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis.
- the intensity of peak A was 1959 counts, and the intensity of peak B was 110 counts.
- Example 2 The same operation as in Example 2 was performed, and the supernatant was collected and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis.
- metal impurities in the fired powder were sodium 10 ppm, potassium 3 ppm, calcium 4 ppm, magnesium 1 ppm, lead 2 ppm, and chromium 0 ppm.
- chlorine ion, sulfate ion, and nitrate ion were all 1 ppm or less.
- Example 1 The same baking operation as Example 1 was performed except having changed the baking temperature in nitrogen gas atmosphere into 450 degreeC. After cooling, 14.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as low as 775counts. No diffraction peak of cyanamide zinc was detected.
- Example 2 The same baking operation as Example 3 was performed except having changed the baking temperature in nitrogen gas atmosphere into 450 degreeC. After cooling, 14.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as low as 821counts. No diffraction peak of cyanamide zinc was detected.
- Example 3 The same baking operation as Example 4 was performed except having changed the calcination temperature in nitrogen gas atmosphere to 430 degreeC. After cooling, 11.1 g of the obtained light pinkish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as small as 266counts. No diffraction peak of cyanamide zinc was detected.
- Example 4 The same baking operation as Example 5 was performed except having changed the baking temperature in nitrogen gas atmosphere into 1000 degreeC. After cooling, the inside of the crucible was confirmed, but there was no residue. The cyanamide zinc was destroyed by thermal decomposition.
- Example 5 The same baking operation as Example 3 was performed except having changed the baking temperature in nitrogen gas atmosphere into 1000 degreeC. After cooling, the inside of the crucible was confirmed, but there was no residue. The cyanamide zinc was destroyed by thermal decomposition.
- Example 6 The same baking operation as in Example 5 was performed except that an air atmosphere was used instead of the nitrogen gas atmosphere. After cooling, 7.4 g of the obtained flesh-colored calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the zinc oxide diffraction peak was detected, and the cyanamide zinc peak was not detected. The intensity of peak B corresponding to zinc oxide was 3847 counts.
- the obtained fired powder had an appearance in which skin color and metal color were mixed.
- Example 8 The same baking operation as in Example 2 was performed except that 6.0 g of a commercially available zinc oxide powder (two types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was used as the zinc source. After cooling, 6.0 g of the obtained white calcined powder was taken out and identified with a powder X-ray diffractometer. As a result, only peak B corresponding to zinc oxide was detected, and no diffraction peak corresponding to cyanamide zinc was detected.
- a commercially available zinc oxide powder two types of zinc oxide manufactured by Sakai Chemical Co., Ltd.
- a lead-based anticorrosive pigment, red lead (manufactured by NI Chemtech Co., Ltd.) instead of cyanamide zinc
- a commercially available cyanamide lead (trade name: cyanami (manufactured by Kikuchi Color Co., Ltd.)) specific surface area 3.0 m 2 / g )
- cyanamide zinc calcium-based inorganic pigment (trade name: LF Bowsei ZK-S2 (manufactured by Kikuchi Color Co., Ltd.)) specific surface area 11.1 m 2 / g
- cyanamide zinc content 50 mass%
- zinc oxide 40 wt% Each test piece was prepared using 10% by mass of calcium carbonate.
- test pieces each were placed in a combined cycle tester (manufactured by Suga Test Instruments Co., Ltd.), sprayed with 5% by weight saline at 30 ° C. for 5 minutes, and then 1.
- the wet test was conducted for 5 hours, followed by hot air drying at 50 ° C. for 2 hours, and then hot air drying at 30 ° C. for 2 hours was defined as one cycle (required time 6 hours).
- the test piece was taken out, washed with tap water, and dried at 25 ° C. The test piece was visually observed for the presence or absence of swelling, peeling and rust of the coating film.
- paints for evaluating rust prevention using the cyanamide obtained in the present invention are lead rust pigments (Evaluation Example 4), commercially available cyanamide lead (evaluation example 4). Rust generation was less than that of the anticorrosive paint using Evaluation Example 5), and the antirust performance was excellent. Furthermore, it was found that the occurrence of rust was clearly less than that of the cyanamide zinc calcium based inorganic pigment (Evaluation Example 6), and the rust prevention performance was very excellent.
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Abstract
A method for producing zinc cyanamide, said method comprising calcining zinc cyanurate or basic zinc cyanurate in an atmosphere of nitrogen gas or noble gas of a Group 18 element at 460-900oC inclusive. A method for producing zinc cyanamide, said method comprising calcining zinc cyanurate or basic zinc cyanurate that has been preliminarily mixed with a nitrogen-containing organic compound.
Description
本発明は、シアナミド亜鉛の製造方法及びそれを用いた防錆顔料組成物の製造方法に関する。
The present invention relates to a method for producing cyanamide zinc and a method for producing an antirust pigment composition using the same.
鋼構造物用塗料や鏡の裏塗料などに使用される防錆顔料において、鉛・クロムフリーが必要になっている。その背景には、2006年に欧州連合で施行された環境規制であるRoHS指令(電子・電気機器における特定有害物質の使用規制)及びWEEE指令(廃電気電子機器指令:製品の回収、リサイクル率に関連する)により鉛、水銀、カドミウム、六価クロム、ポリ臭化ビフェニル、ポリ臭化ジフェニルエーテルの有害物質6品目が指定値を超えて含まれた電子・電気機器は販売することができなくなったことにある。このうち六価クロム、鉛の場合は1000ppm以下という制限が設けられている。
Lead- and chrome-free materials are required for anti-corrosive pigments used in steel structure paints and mirror back paints. In the background, the RoHS Directive (regulation on the use of specified hazardous substances in electronic and electrical equipment) and the WEEE Directive (Waste Electrical and Electronic Equipment Directive: Product recovery and recycling rate), which are environmental regulations enforced in the European Union in 2006 (Related)) Electronic and electrical equipment containing 6 hazardous substances exceeding the specified value such as lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyl, and polybrominated diphenyl ether can no longer be sold. It is in. Among these, in the case of hexavalent chromium and lead, there is a limit of 1000 ppm or less.
経済産業省が「企業が行うべき製品に含有する環境負荷物質の情報開示対象物質としてRoHS指令で規制される6品目が妥当」と表明していることから、同指令対応は日本でも必須となり、また対象製品も現在の電気電子群から他の製品群にも拡大していく方向である。また、日本において1999年に「特定化学物質の環境への排出量の把握等及び管理の改善の促進に関する法律」(PRTR法、化管法、化学物質排出把握管理促進法)が法制化され、政令指定対象物質354物質が指定されている。クロム化合物と鉛化合物は指定物質になっている。
The Ministry of Economy, Trade and Industry has stated that “6 items regulated by the RoHS directive are appropriate as substances subject to disclosure of environmentally hazardous substances contained in products that companies should carry out”. The target products are also expanding from the current electrical and electronic group to other product groups. In 1999, the “Law Concerning the Determination of the Release of Specific Chemical Substances into the Environment and the Promotion of Improvement of Management” (PRTR Law, PRTR Law, Chemical Substance Emission Management Promotion Law) was legislated in 1999. 354 substances designated by government ordinance are designated. Chromium compounds and lead compounds are designated substances.
しかし、鉛丹、塩基性クロム酸鉛、クロム酸亜鉛、塩基性クロム酸亜鉛カリウム、シアナミド鉛、鉛酸カルシウム、塩基性硫酸鉛などのクロム化合物及び鉛化合物の防錆性能を凌駕する防錆顔料がほとんどないため、これらクロム化合物及び鉛化合物の防錆顔料が未だに使用されている。このため鉛・クロムフリーで防錆性能が優れた防錆顔料が早急に強く求められている。
However, anti-rust pigments that surpass the anti-rust performance of chromium compounds and lead compounds, such as red lead, basic lead chromate, zinc chromate, basic zinc potassium chromate, cyanamide lead, calcium lead acid, basic lead sulfate Therefore, these chromium compound and lead compound rust preventive pigments are still used. For this reason, there is an urgent need for anti-corrosive pigments that are free of lead and chromium and have excellent anti-rust performance.
鉛・クロムフリーの防錆顔料として、リン酸アルミニウム、リン酸亜鉛、亜リン酸亜鉛、リン酸カルシウムなどのリン酸塩、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウムなどのモリブデン酸塩、シアナミド亜鉛、シアナミド亜鉛カルシウムなどのシアナミド系化合物などがあるが、その中の有力候補としてシアナミド亜鉛(化学式:ZnCN2)が挙げられている。
As lead / chromium-free rust preventive pigments, phosphates such as aluminum phosphate, zinc phosphate, zinc phosphite, calcium phosphate, molybdate such as zinc molybdate, aluminum molybdate, calcium molybdate, cyanamide zinc, There are cyanamide-based compounds such as cyanamide zinc calcium, among which cyanamide zinc (chemical formula: ZnCN 2 ) is cited as a promising candidate.
シアナミド亜鉛の湿式共沈法による製造方法としては、亜鉛の無機酸塩若しくは有機酸塩又は酸化亜鉛とシアナミド液とをアルカリ性に保持しながら反応させ、水洗、濾過、乾燥、粉砕する方法が開示されている(特許文献1参照。)。ここでシアナミド液とは、カルシウムシアナミドからなる石灰窒素が使われている。また、硫酸亜鉛水溶液とナトリウムシアナミド水溶液を1:1(モル比)で混合して共沈させたものをアルゴンガス中で570℃以上の温度で70時間以上焼成してシアナミド亜鉛の単結晶が得られているが、焼成の前に副生する硫酸ナトリウムを水洗で除去する必要がある(非特許文献1参照。)。しかし、これら湿式共沈法は、副生成物としてアルカリ金属イオン又はカルシウムイオンと硝酸、硫酸、塩酸などの陰イオンからなる可溶性塩が出現する。これら副生成物を除くためには洗浄が必要であり、これにより大量の排水が生じるため、製造コストが高くなるという欠点を有する。更にこれらの可溶性塩を完全に除去することは一般的に不可能である。これら可溶性塩は、一般的に腐食促進剤であるため、微量の存在でもシアナミド亜鉛を用いた防錆顔料組成物の防錆性能を低下させる恐れがある。
As a method for producing cyanamide zinc by a wet coprecipitation method, a method of reacting zinc inorganic acid salt or organic acid salt or zinc oxide and cyanamide solution while maintaining alkalinity, washing, filtering, drying and pulverizing is disclosed. (See Patent Document 1). Here, lime nitrogen composed of calcium cyanamide is used as the cyanamide solution. Also, a zinc sulfate aqueous solution and a sodium cyanamide aqueous solution mixed at 1: 1 (molar ratio) and coprecipitated were fired in argon gas at a temperature of 570 ° C. or higher for 70 hours or longer to obtain a cyanamide zinc single crystal. However, it is necessary to remove the by-product sodium sulfate by water washing before firing (see Non-Patent Document 1). However, in these wet coprecipitation methods, soluble salts composed of alkali metal ions or calcium ions and anions such as nitric acid, sulfuric acid and hydrochloric acid appear as by-products. In order to remove these by-products, washing is required, which causes a large amount of waste water, which has the disadvantage of increasing the production cost. Furthermore, it is generally impossible to completely remove these soluble salts. Since these soluble salts are generally corrosion accelerators, there is a risk that the antirust performance of the anticorrosive pigment composition using cyanamide zinc may be reduced even in the presence of a small amount.
シアナミド亜鉛の別の製造方法として、焼成法が開示されている。炭酸亜鉛を400℃、8~10気圧のアンモニアガス中で3時間処理することによりシアナミド亜鉛が得られることが開示されているが、炭酸亜鉛の50%しかシアナミド亜鉛に転換されていない(特許文献2参照。)。
A firing method is disclosed as another method for producing cyanamide zinc. Although it is disclosed that zinc carbonate is obtained by treating zinc carbonate in ammonia gas at 400 ° C. and 8-10 atm for 3 hours, only 50% of zinc carbonate is converted to cyanamide zinc (Patent Document) 2).
また、窒素雰囲気下又は減圧下で、酸化亜鉛と過剰の尿素又はジシアナミドとの混合物を135~200℃で加熱処理し、その後600~800℃で2時間焼成することによりシアナミド亜鉛などの顔料が製造されている。しかし、製造されるシアナミド亜鉛は、高温焼成をするため比表面積及び多孔度が低く、比較的密な組織を有するため、反応性が低下しており、高度の腐食防止活性を示さない欠点を有することが記載されている(特許文献3参照。)。
In addition, a pigment such as cyanamide zinc is produced by heating a mixture of zinc oxide and excess urea or dicyanamide at 135 to 200 ° C. in a nitrogen atmosphere or under reduced pressure, followed by baking at 600 to 800 ° C. for 2 hours. Has been. However, the cyanamide zinc produced has a disadvantage that it has a low specific surface area and porosity due to high-temperature firing, and has a relatively dense structure, so that the reactivity is low and does not exhibit a high degree of corrosion inhibition activity. (Refer to Patent Document 3).
また、シアナミド亜鉛を防錆顔料に用いた防錆塗料の用途例は、鉄材に塗布してその腐食を防ぐための防錆塗料として、油性又は合成樹脂系のビヒクルにシアナミド亜鉛顔料が含有された防錆塗料が開示されている(特許文献1参照。)。
In addition, an example of the use of a rust preventive paint using cyanamide zinc as a rust preventive pigment is that a cyanamide zinc pigment is contained in an oil-based or synthetic resin vehicle as a rust preventive paint to be applied to an iron material to prevent its corrosion. An anti-corrosion paint is disclosed (see Patent Document 1).
また、鏡の裏面の防錆塗料として、鏡の片面に形成された銀膜上に腐食を防止するために銅メッキ膜が付けられるが、銅メッキ膜だけでは銀の腐食を防止することができない。そこで銅メッキ層の上に有機防錆塗料が塗装されるが、その有機防錆塗料に配合される防錆顔料としてシアナミド亜鉛が挙げられている(特許文献4参照。)。
Also, as a rust preventive paint on the back of the mirror, a copper plating film is attached on the silver film formed on one side of the mirror to prevent corrosion, but silver corrosion cannot be prevented only by the copper plating film. . Thus, an organic rust preventive paint is applied on the copper plating layer, and cyanamide zinc is cited as a rust preventive pigment blended in the organic rust preventive paint (see Patent Document 4).
本発明の課題は、上述の従来技術の問題点を解決することにある。即ち本発明は、防錆性能の妨げとなる可溶性副生物及び鉛、クロムなどの有害物質を含まない防錆性能の高いシアナミド亜鉛の製造方法を提供するものであり、そして、本発明により得られるシアナミド亜鉛を用いた防錆顔料組成物の製造方法を提供するものである。
The object of the present invention is to solve the above-mentioned problems of the prior art. That is, the present invention provides a method for producing cyanamide zinc having high rust prevention performance that does not contain soluble by-products and lead, chromium and other harmful substances that interfere with rust prevention performance, and is obtained by the present invention. The present invention provides a method for producing a rust preventive pigment composition using cyanamide zinc.
上記課題を解決するために本発明者らは鋭意検討した結果、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛を窒素ガス又は第18族元素の希ガスの雰囲気において、一定の温度範囲で焼成することにより、可溶性副生物及び鉛、クロムの有害物質をほぼ含まず、防錆性能の高いシアナミド亜鉛を製造する方法を見出した。
As a result of intensive studies by the present inventors to solve the above-mentioned problems, by firing zinc cyanurate or basic zinc cyanurate in a nitrogen gas or a rare gas of a Group 18 element in a certain temperature range. The present inventors have found a method for producing cyanamide zinc that is substantially free of soluble by-products and lead and chromium harmful substances and has high rust prevention performance.
即ち、本発明の第1観点としては、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛を窒素ガス又は第18族元素の希ガスの雰囲気において、460℃以上900℃以下で焼成することを特徴とするシアナミド亜鉛の製造方法であり、
本発明の第2観点としては、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛にあらかじめ窒素含有有機化合物を混合することを特徴とする第1観点に記載のシアナミド亜鉛の製造方法であり、
本発明の第3観点としては、第2観点に記載のシアナミド亜鉛の製造方法において、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛と窒素有機含有化合物とを混合する際に、該混合物中の亜鉛原子に対する窒素原子のモル比(N/Zn)を3以上とするシアナミド亜鉛の製造方法であり、
本発明の第4観点としては、前記窒素含有有機化合物がシアヌル酸又は尿素である第2観点又は第3観点に記載のシアナミド亜鉛の製造方法であり、
本発明の第5観点としては、下記(a)、(b)及び(c)の成分を配合することを特徴とする防錆顔料組成物の製造方法:
(a)油性バインダー又は合成樹脂バインダー
(b)水、テレピン油、ミネラルスピリット、トルエン、キシレン、メチルイソブチルケトン、セルソルブアセテート、エタノール、ブタノール、イソプロピルアルコール、シクロヘキサン、酢酸エチル、酢酸ブチルからなる群から選ばれる少なくとも一種以上の希釈剤
(c)第1観点~第4観点のいずれか一つに記載の方法により得られるシアナミド亜鉛
である。 That is, as a first aspect of the present invention, cyanamide is characterized in that zinc cyanurate or basic zinc cyanurate is fired at 460 ° C. or higher and 900 ° C. or lower in an atmosphere of nitrogen gas or a rare gas of Group 18 element. A method for producing zinc,
The second aspect of the present invention is a method for producing cyanamide zinc according to the first aspect, characterized in that a nitrogen-containing organic compound is mixed in advance with zinc cyanurate or basic zinc cyanurate,
As a third aspect of the present invention, in the method for producing cyanamide zinc described in the second aspect, when the cyanuric acid zinc or basic cyanuric acid zinc and the nitrogen organic-containing compound are mixed, the zinc atom in the mixture It is a method for producing cyanamide zinc in which the molar ratio of nitrogen atoms (N / Zn) is 3 or more,
The fourth aspect of the present invention is a method for producing cyanamide zinc according to the second aspect or the third aspect, wherein the nitrogen-containing organic compound is cyanuric acid or urea.
As a 5th viewpoint of this invention, the manufacturing method of the antirust pigment composition characterized by mix | blending the component of following (a), (b) and (c):
(A) Oil-based binder or synthetic resin binder (b) From the group consisting of water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate At least one selected diluent (c) is cyanamide zinc obtained by the method according to any one of the first to fourth aspects.
本発明の第2観点としては、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛にあらかじめ窒素含有有機化合物を混合することを特徴とする第1観点に記載のシアナミド亜鉛の製造方法であり、
本発明の第3観点としては、第2観点に記載のシアナミド亜鉛の製造方法において、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛と窒素有機含有化合物とを混合する際に、該混合物中の亜鉛原子に対する窒素原子のモル比(N/Zn)を3以上とするシアナミド亜鉛の製造方法であり、
本発明の第4観点としては、前記窒素含有有機化合物がシアヌル酸又は尿素である第2観点又は第3観点に記載のシアナミド亜鉛の製造方法であり、
本発明の第5観点としては、下記(a)、(b)及び(c)の成分を配合することを特徴とする防錆顔料組成物の製造方法:
(a)油性バインダー又は合成樹脂バインダー
(b)水、テレピン油、ミネラルスピリット、トルエン、キシレン、メチルイソブチルケトン、セルソルブアセテート、エタノール、ブタノール、イソプロピルアルコール、シクロヘキサン、酢酸エチル、酢酸ブチルからなる群から選ばれる少なくとも一種以上の希釈剤
(c)第1観点~第4観点のいずれか一つに記載の方法により得られるシアナミド亜鉛
である。 That is, as a first aspect of the present invention, cyanamide is characterized in that zinc cyanurate or basic zinc cyanurate is fired at 460 ° C. or higher and 900 ° C. or lower in an atmosphere of nitrogen gas or a rare gas of Group 18 element. A method for producing zinc,
The second aspect of the present invention is a method for producing cyanamide zinc according to the first aspect, characterized in that a nitrogen-containing organic compound is mixed in advance with zinc cyanurate or basic zinc cyanurate,
As a third aspect of the present invention, in the method for producing cyanamide zinc described in the second aspect, when the cyanuric acid zinc or basic cyanuric acid zinc and the nitrogen organic-containing compound are mixed, the zinc atom in the mixture It is a method for producing cyanamide zinc in which the molar ratio of nitrogen atoms (N / Zn) is 3 or more,
The fourth aspect of the present invention is a method for producing cyanamide zinc according to the second aspect or the third aspect, wherein the nitrogen-containing organic compound is cyanuric acid or urea.
As a 5th viewpoint of this invention, the manufacturing method of the antirust pigment composition characterized by mix | blending the component of following (a), (b) and (c):
(A) Oil-based binder or synthetic resin binder (b) From the group consisting of water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate At least one selected diluent (c) is cyanamide zinc obtained by the method according to any one of the first to fourth aspects.
本発明により得られるシアナミド亜鉛は、不要な可溶性副生物を実質的に含まず、シアナミド亜鉛の含有率が非常に高いため、防錆性能が優れた鉛・クロムフリーの無公害の防錆顔料として用いることができる。
The cyanamide zinc obtained by the present invention is substantially free of unnecessary soluble by-products and has a very high content of cyanamide zinc. Can be used.
また、得られるシアナミド亜鉛は白灰色であるため、防錆顔料組成物に用いた場合、他の着色顔料への影響はほとんどなく、様々な色調の防錆顔料組成物を調製することができる。
Further, since the cyanamide zinc obtained is white gray, when used in a rust preventive pigment composition, there is almost no influence on other color pigments, and rust preventive pigment compositions of various colors can be prepared.
本発明において原料として用いられるシアヌル酸亜鉛は、酸化亜鉛とシアヌル酸とを酸化亜鉛/シアヌル酸のモル比が1.5になるように純水中に投入して得たスラリーを、60℃以下で分散メディアを用いて湿式分散又はディスパーによる強分散することにより製造することができる。そして、得られるシアヌル酸亜鉛を含有するスラリーは、フィルタープレスなどで濾過し、100℃未満で乾燥後、乾式粉砕することによりシアヌル酸亜鉛の粉末とすることができる。
The zinc cyanurate used as a raw material in the present invention is a slurry obtained by adding zinc oxide and cyanuric acid into pure water so that the molar ratio of zinc oxide / cyanuric acid is 1.5, and is 60 ° C. or less. And can be produced by wet dispersion using a dispersion medium or strong dispersion using a disper. The obtained slurry containing zinc cyanurate can be filtered with a filter press or the like, dried at less than 100 ° C., and then dry pulverized to obtain zinc cyanurate powder.
本発明において原料として用いられる塩基性シアヌル酸亜鉛は、化学式:Zn5(C3N3O3)2(OH)3・3H2Oで表される化合物であり、国際公開第2011/162354号パンフレットに記載された方法により製造することができる。例えば、酸化亜鉛とシアヌル酸とを酸化亜鉛/シアヌル酸のモル比が2.5になるように純水中に投入して得たスラリーを、5~55℃の温度範囲で分散メディアを用いて湿式分散を行う又はディスパーによる強分散を行うことにより製造することができる。このようにして製造される塩基性シアヌル酸亜鉛はスラリー状物として得られ、フィルタープレスなどで濾別した後、そのウェットケーキを200℃以下で乾燥し、乾式粉砕することにより塩基性シアヌル酸亜鉛の粉末とすることができる。また、酸化亜鉛とシアヌル酸とを酸化亜鉛/シアヌル酸のモル比が2.5になるようにレーディゲミキサー装置(加熱撹拌装置:中央機工(株)製)に投入し、50~100℃に加熱しながら、原料粉(酸化亜鉛+シアヌル酸)に対して20~40質量%の水を添加して加熱撹拌することにより塩基性シアヌル酸亜鉛が粉末として得られる。
The basic zinc cyanurate used as a raw material in the present invention is a compound represented by the chemical formula: Zn 5 (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O, and International Publication No. 2011/162354. It can be produced by the method described in the pamphlet. For example, a slurry obtained by adding zinc oxide and cyanuric acid into pure water so that the molar ratio of zinc oxide / cyanuric acid is 2.5 is obtained using a dispersion medium in a temperature range of 5 to 55 ° C. It can be produced by wet dispersion or strong dispersion with a disper. The basic zinc cyanurate produced in this way is obtained as a slurry, filtered with a filter press, etc., then the wet cake is dried at 200 ° C. or lower, and dry pulverized to thereby obtain basic zinc cyanurate. Powder. In addition, zinc oxide and cyanuric acid were introduced into a Laedige mixer apparatus (heating and stirring apparatus: manufactured by Chuo Kiko Co., Ltd.) so that the molar ratio of zinc oxide / cyanuric acid was 2.5, and 50 to 100 ° C. The basic cyanuric acid zinc is obtained as a powder by adding 20 to 40% by mass of water to the raw material powder (zinc oxide + cyanuric acid) while heating and stirring with heating.
本発明においてシアナミド亜鉛を製造するための焼成は、窒素ガス又は第18族元素の希ガスの雰囲気において行われる。第18族元素の希ガスとしては、ヘリウム、ネオン、アルゴンなどが挙げられる。コストの点からは、窒素ガスがより好ましい。
Calcination for producing cyanamide zinc in the present invention is performed in an atmosphere of nitrogen gas or a rare gas of Group 18 element. Examples of rare gases of Group 18 elements include helium, neon, and argon. From the viewpoint of cost, nitrogen gas is more preferable.
本発明において用いられる焼成装置は、バッチ式電気炉、ロータリーキルンなどであるが、雰囲気制御が可能な装置でなければならない。
The baking apparatus used in the present invention is a batch type electric furnace, a rotary kiln or the like, but must be an apparatus capable of controlling the atmosphere.
焼成温度は460℃以上が好ましく、より好ましくは480℃以上である。また焼成温度は900℃以下である。焼成温度が460℃より低い場合、シアナミド亜鉛の生成が不充分となるため好ましくない。また焼成温度が900℃を超える場合、シアナミド亜鉛が熱分解するので好ましくない。
Calcination temperature is preferably 460 ° C. or higher, more preferably 480 ° C. or higher. The firing temperature is 900 ° C. or lower. When the firing temperature is lower than 460 ° C., the formation of cyanamide zinc is insufficient, which is not preferable. Moreover, when a calcination temperature exceeds 900 degreeC, since cyanamide zinc thermally decomposes, it is unpreferable.
シアナミド亜鉛は、酸素、空気などの酸化性雰囲気で200℃より高い温度に晒されると酸化亜鉛になる。そのため本発明の焼成雰囲気は、窒素ガス又は第18族元素の希ガスの雰囲気で行い、酸素、空気などの酸化性ガスを極力減らさなければならない。窒素ガス又は第18族元素の希ガスの雰囲気中の酸素、空気などの酸化性ガスは100ppm以下にすることが好ましく、50ppm以下がより好ましく、10ppm以下が最も好ましい。
Cyanamide zinc becomes zinc oxide when exposed to temperatures higher than 200 ° C. in an oxidizing atmosphere such as oxygen and air. Therefore, the firing atmosphere of the present invention must be performed in an atmosphere of nitrogen gas or a rare gas of a Group 18 element, and an oxidizing gas such as oxygen or air must be reduced as much as possible. The oxidizing gas such as oxygen or air in the atmosphere of nitrogen gas or a rare gas of Group 18 element is preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less.
また、水素などを含む還元性ガス雰囲気でシアヌル酸亜鉛又は塩基性シアヌル酸亜鉛を焼成すると、酸化亜鉛と金属亜鉛が生成し、シアナミド亜鉛は得られない。
In addition, when zinc cyanurate or basic zinc cyanurate is fired in a reducing gas atmosphere containing hydrogen or the like, zinc oxide and metal zinc are generated, and cyanamide zinc cannot be obtained.
本発明では、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛を窒素ガス又は第18族元素の希ガスの雰囲気において460℃以上900℃以下で焼成する際に、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛にあらかじめ窒素含有有機化合物を混合することが好ましい。用いられる窒素含有有機化合物としては、シアヌル酸又は尿素が挙げられる。シアヌル酸は、加熱過程において溶融状態を経ずに約360℃で熱分解し、シアナミド亜鉛の生成に寄与するため、用いる窒素含有有機化合物としてより好ましい。
In the present invention, when zinc cyanurate or basic zinc cyanurate is baked at 460 ° C. or higher and 900 ° C. or lower in an atmosphere of nitrogen gas or a rare gas of Group 18 element, zinc cyanurate or basic zinc cyanurate is preliminarily added. It is preferable to mix a nitrogen-containing organic compound. Examples of the nitrogen-containing organic compound used include cyanuric acid and urea. Cyanuric acid is more preferable as a nitrogen-containing organic compound to be used because it is thermally decomposed at about 360 ° C. without passing through a molten state in the heating process and contributes to the formation of cyanamide zinc.
本発明において、塩基性シアヌル酸亜鉛にあらかじめシアヌル酸を混合して窒素ガス又は第18族元素の希ガスの雰囲気において460℃以上900℃以下で焼成することにより、シアナミド亜鉛の含有率が非常に高い焼成生成物が得られる。これは、窒素ガス又は第18族元素の希ガスの雰囲気においてシアヌル酸が約360℃で熱分解するのに対して、塩基性シアヌル酸亜鉛がほぼ同じ温度の300~320℃で熱分解するために両化合物の反応が起こりやすいためと推定される。
In the present invention, by mixing cyanuric acid with basic zinc cyanurate in advance and firing in an atmosphere of nitrogen gas or a rare gas of Group 18 element at 460 ° C. or higher and 900 ° C. or lower, the cyanamide zinc content is very high. A high baked product is obtained. This is because cyanuric acid is thermally decomposed at about 360 ° C. in an atmosphere of nitrogen gas or a rare gas of Group 18 element, whereas basic zinc cyanurate is thermally decomposed at 300 to 320 ° C., which is substantially the same temperature. It is estimated that the reaction of both compounds is likely to occur.
シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛にあらかじめ窒素含有有機化合物を混合する場合、その混合物に含まれる亜鉛原子に対する窒素原子のモル比(N/Zn)を3以上とすることが好ましく、該モル比(N/Zn)は3以上6以下がより好ましい。モル比(N/Zn)が3より小さい場合は、シアナミド亜鉛の単一相が得られない。また、モル比(N/Zn)が6より大きい場合には、焼成反応に寄与しない窒素含有有機化合物が系内に増えるだけであり、効率的ではない。
When a nitrogen-containing organic compound is mixed in advance with zinc cyanurate or basic zinc cyanurate, the molar ratio (N / Zn) of nitrogen atoms to zinc atoms contained in the mixture is preferably 3 or more, and the molar ratio (N / Zn) is more preferably 3 or more and 6 or less. When the molar ratio (N / Zn) is less than 3, a cyanamide zinc single phase cannot be obtained. On the other hand, when the molar ratio (N / Zn) is larger than 6, only nitrogen-containing organic compounds that do not contribute to the firing reaction increase in the system, which is not efficient.
シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛と窒素含有有機化合物との混合は、V字型混合機、レーディゲミキサー装置などの加熱及び攪拌機能付きの容器で混合することが好ましい。
It is preferable that the zinc cyanurate or basic zinc cyanurate and the nitrogen-containing organic compound are mixed in a container having a heating and stirring function such as a V-shaped mixer or a Laedige mixer apparatus.
本発明により得られるシアナミド亜鉛は、高純度のシアナミド亜鉛であり、薄い灰白色の粉末である。得られるシアナミド亜鉛は、比表面積は0.5~30m2/gである。
The cyanamide zinc obtained by the present invention is high-purity cyanamide zinc and is a light grayish white powder. The cyanamide zinc obtained has a specific surface area of 0.5 to 30 m 2 / g.
また、その表面電荷は、水系ではpH4からpH10の範囲で負電荷を有する。このため水系防錆塗料を調製する際に合成樹脂やエマルジョンなどとの相溶性が良好であり、安定な水系防錆塗料を得ることができる。
Also, the surface charge of the water system is negative in the range of pH 4 to pH 10. For this reason, when preparing an aqueous | water-based anticorrosion coating material, compatibility with a synthetic resin, an emulsion, etc. is favorable, and a stable aqueous | water-based anticorrosion coating material can be obtained.
本発明のシアナミド亜鉛の製造方法は、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛が出発原料として使用され、そして、その工程において他の金属元素を含む化合物は使用されず、また、その工程において焼成温度の温度域でも分解されない無機の酸根を有する化合物、例えば塩化物、硫酸塩、リン酸塩等は使用されない。そのため、得られるシアナミド亜鉛は防錆性能の妨げとなる可溶性副生物を実質的に含まず、例えば500ppm以下、若しくは50ppm以下である。また、原料として使用されるシアヌル酸亜鉛又は塩基性シアヌル酸亜鉛若しくは窒素含有有機化合物は、実質的に鉛、クロムを含有しないため、得られるシアナミド亜鉛も同様に鉛、クロムを含まないのである。
In the method for producing cyanamide zinc of the present invention, zinc cyanurate or basic zinc cyanurate is used as a starting material, and a compound containing another metal element is not used in the process, and the firing temperature is used in the process. A compound having an inorganic acid radical that is not decomposed even in the temperature range of, for example, chloride, sulfate, phosphate and the like is not used. Therefore, the cyanamide zinc obtained does not substantially contain soluble by-products that hinder rust prevention performance, and is, for example, 500 ppm or less, or 50 ppm or less. Moreover, since the zinc cyanurate used as a raw material or basic cyanuric acid zinc or a nitrogen-containing organic compound does not contain lead and chromium substantially, the cyanamide zinc obtained does not contain lead and chromium similarly.
本発明の防錆顔料組成物の製造方法は、下記(a)、(b)及び(c)の成分を配合することを特徴とする。
(a)油性系バインダー又は合成樹脂バインダー
(b)水、テレピン油、ミネラルスピリット、トルエン、キシレン、メチルイソブチルケトン、セルソルブアセテート、エタノール、ブタノール、イソプロピルアルコール、シクロヘキサン、酢酸エチル、酢酸ブチルなどの有機溶剤から選ばれる一種以上の有機溶剤
(c)本発明の第1観点~第4観点のいずれか一つに記載の方法により得られるシアナミド亜鉛
また、本発明により得られる防錆顔料組成物は、着色顔料、ダレ止め剤、皮張り防止剤、乾燥促進剤、分散剤、沈降防止剤などを組合せて調製することができる。 The manufacturing method of the antirust pigment composition of this invention mix | blends the component of following (a), (b) and (c), It is characterized by the above-mentioned.
(A) Oil-based binder or synthetic resin binder (b) Organic such as water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate One or more organic solvents selected from solvents (c) Cyanamide zinc obtained by the method according to any one of the first to fourth aspects of the present invention. Further, the rust preventive pigment composition obtained by the present invention comprises: It can be prepared by combining color pigments, anti-sagging agents, anti-skinning agents, drying accelerators, dispersants, anti-settling agents and the like.
(a)油性系バインダー又は合成樹脂バインダー
(b)水、テレピン油、ミネラルスピリット、トルエン、キシレン、メチルイソブチルケトン、セルソルブアセテート、エタノール、ブタノール、イソプロピルアルコール、シクロヘキサン、酢酸エチル、酢酸ブチルなどの有機溶剤から選ばれる一種以上の有機溶剤
(c)本発明の第1観点~第4観点のいずれか一つに記載の方法により得られるシアナミド亜鉛
また、本発明により得られる防錆顔料組成物は、着色顔料、ダレ止め剤、皮張り防止剤、乾燥促進剤、分散剤、沈降防止剤などを組合せて調製することができる。 The manufacturing method of the antirust pigment composition of this invention mix | blends the component of following (a), (b) and (c), It is characterized by the above-mentioned.
(A) Oil-based binder or synthetic resin binder (b) Organic such as water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate One or more organic solvents selected from solvents (c) Cyanamide zinc obtained by the method according to any one of the first to fourth aspects of the present invention. Further, the rust preventive pigment composition obtained by the present invention comprises: It can be prepared by combining color pigments, anti-sagging agents, anti-skinning agents, drying accelerators, dispersants, anti-settling agents and the like.
(a)成分である油性系バインダーとしては、ボイル油、アマニ油、大豆油、サフラワー油、ヒマシ油などが挙げられる。また、合成樹脂バインダーとしては、フタル酸樹脂、アクリル樹脂、アミノ樹脂、エポキシ樹脂、シリコン樹脂、ポリウレタン樹脂、フッ素樹脂、塩化ビニル樹脂などが挙げられる。
Examples of the oil-based binder as component (a) include boil oil, linseed oil, soybean oil, safflower oil, castor oil, and the like. Examples of the synthetic resin binder include phthalic acid resin, acrylic resin, amino resin, epoxy resin, silicon resin, polyurethane resin, fluororesin, and vinyl chloride resin.
本発明の防錆顔料組成物の製造方法においては、前記(a)、(b)及び(c)の成分の配合割合は任意であるが、例えば(a)成分を30~80質量部、(b)成分を5~20質量部、(c)成分を2~50質量部で配合することにより、防錆性能に優れた防錆顔料組成物を製造することができる。
In the method for producing a rust preventive pigment composition of the present invention, the mixing ratio of the components (a), (b) and (c) is arbitrary, but for example, the component (a) is 30 to 80 parts by mass, ( By blending component (b) in an amount of 5 to 20 parts by mass and component (c) in an amount of 2 to 50 parts by mass, a rust preventive pigment composition having excellent rust preventive performance can be produced.
本発明により得られる防錆顔料組成物は、粘性のあるスラリーである。
The rust preventive pigment composition obtained by the present invention is a viscous slurry.
本発明により得られる防錆顔料組成物は、鉛丹、シアナミド鉛などの有害物質を含有する防錆顔料組成物と同等以上の防錆効果を発揮する無公害の防錆顔料組成物である。この防錆顔料組成物は、鉛、クロムの有害物質を含まないので、人が接触しやすい駅舎、道路のガードレールなどに用いる防錆塗料において無公害防錆顔料組成物として適用できる。
The rust preventive pigment composition obtained by the present invention is a pollution-free rust preventive pigment composition that exhibits a rust preventive effect equivalent to or higher than that of a rust preventive pigment composition containing harmful substances such as red lead and cyanamide lead. Since this rust preventive pigment composition does not contain harmful substances such as lead and chromium, it can be applied as a pollution-free rust preventive pigment composition in a rust preventive paint used for station buildings, road guard rails and the like that are easily contacted by humans.
また、本発明により得られるシアナミド亜鉛は白灰色のため、着色顔料と混ぜて任意の色に着色した防錆顔料組成物を得ることができる。
Moreover, since cyanamide zinc obtained by the present invention is white gray, it is possible to obtain a rust preventive pigment composition colored in an arbitrary color by mixing with a coloring pigment.
本発明により得られる防錆顔料組成物は、ハケ、ロール、スプレーガンなど一般に知られる塗工方法を用いて塗布することができる。
The rust preventive pigment composition obtained by the present invention can be applied using a generally known coating method such as brush, roll, spray gun or the like.
また、本発明により得られる防錆顔料組成物は、ジンクリッチペイントなどの長期耐久性の重防食防錆組成物とは異なり、短期耐久性用途の防錆顔料組成物である。このため、前述の駅舎や道路のガードレールなど、汚れが目立って5~10年サイクルで塗り替えられる用途に適している。
Also, the rust preventive pigment composition obtained by the present invention is a rust preventive pigment composition for short-term durability use, unlike a long-term durable heavy anticorrosion rust preventive composition such as zinc rich paint. For this reason, it is suitable for applications such as the above-mentioned station buildings and road guard rails where dirt is conspicuous and can be repainted in a 5- to 10-year cycle.
以下、合成例、実施例、比較例及び参考例に基づいてさらに詳述するが、本発明はこの実施例により何ら限定されるものではない。
Hereinafter, the present invention will be described in more detail based on synthesis examples, examples, comparative examples, and reference examples, but the present invention is not limited to the examples.
(測定装置)
合成例、実施例及び比較例における分析には、以下の装置、条件で行なった。
透過型電子顕微鏡観察:JEM-1010型(日本電子(株)製)
レーザー回折法粒子径測定:SALD-7000型((株)島津製作所製)、試料1gを純水中に分散させて測定した。
比表面積測定:窒素吸着法表面積測定装置Monosorb(Quantachrome社製)
スラリー固形分測定:試料を磁器製ルツボに約2g入れて精秤後、110℃で乾燥後の質量より固形分(質量%)を算出した。
粉末X線回折分析:粉末X線回折装置RINT Ultima型((株)リガク製)を用いた。
シアナミド亜鉛(化学式:ZnCN2)の(211)面に相当する2θ=28.0°の回折ピーク(以後、ピークAと記載する。)、及び酸化亜鉛の(100)面に相当する2θ=31.8°の回折ピーク(以後、ピークBと記載する。)の回折強度を測定した。
元素分析:全自動元素分析装置CHNS/Oアナライザー2400(パーキン・エルマー社製)
炎光分光分析:SpectraAA (VARIAN社製)
ICP発光分光分析:Plasma Spectrometer SPS7800(セイコーインスツル(株)製)
イオンクロマトグラフ分析:イオンクロマトグラフィーIC25 (DIONEX社製) (measuring device)
The analyzes in the synthesis examples, examples, and comparative examples were performed using the following apparatus and conditions.
Transmission electron microscope observation: JEM-1010 type (manufactured by JEOL Ltd.)
Laser diffraction particle size measurement: SALD-7000 type (manufactured by Shimadzu Corporation), 1 g of sample was dispersed in pure water and measured.
Specific surface area measurement: Nitrogen adsorption surface area measuring device Monosorb (manufactured by Quantachrome)
Slurry solid content measurement: About 2 g of the sample was put in a porcelain crucible, precisely weighed, and the solid content (% by mass) was calculated from the mass after drying at 110 ° C.
Powder X-ray diffraction analysis: A powder X-ray diffraction apparatus RINT Ultimate type (manufactured by Rigaku Corporation) was used.
A diffraction peak at 2θ = 28.0 ° corresponding to the (211) plane of cyanamide zinc (chemical formula: ZnCN 2 ) (hereinafter referred to as peak A), and 2θ = 31 corresponding to the (100) plane of zinc oxide. The diffraction intensity of a diffraction peak at .8 ° (hereinafter referred to as peak B) was measured.
Elemental analysis: fully automatic elemental analyzer CHNS / O analyzer 2400 (manufactured by Perkin Elmer)
Flame spectroscopic analysis: SpectraAA (Varian)
ICP emission spectral analysis: Plasma Spectrometer SPS7800 (manufactured by Seiko Instruments Inc.)
Ion chromatographic analysis: Ion chromatography IC25 (manufactured by DIONEX)
合成例、実施例及び比較例における分析には、以下の装置、条件で行なった。
透過型電子顕微鏡観察:JEM-1010型(日本電子(株)製)
レーザー回折法粒子径測定:SALD-7000型((株)島津製作所製)、試料1gを純水中に分散させて測定した。
比表面積測定:窒素吸着法表面積測定装置Monosorb(Quantachrome社製)
スラリー固形分測定:試料を磁器製ルツボに約2g入れて精秤後、110℃で乾燥後の質量より固形分(質量%)を算出した。
粉末X線回折分析:粉末X線回折装置RINT Ultima型((株)リガク製)を用いた。
シアナミド亜鉛(化学式:ZnCN2)の(211)面に相当する2θ=28.0°の回折ピーク(以後、ピークAと記載する。)、及び酸化亜鉛の(100)面に相当する2θ=31.8°の回折ピーク(以後、ピークBと記載する。)の回折強度を測定した。
元素分析:全自動元素分析装置CHNS/Oアナライザー2400(パーキン・エルマー社製)
炎光分光分析:SpectraAA (VARIAN社製)
ICP発光分光分析:Plasma Spectrometer SPS7800(セイコーインスツル(株)製)
イオンクロマトグラフ分析:イオンクロマトグラフィーIC25 (DIONEX社製) (measuring device)
The analyzes in the synthesis examples, examples, and comparative examples were performed using the following apparatus and conditions.
Transmission electron microscope observation: JEM-1010 type (manufactured by JEOL Ltd.)
Laser diffraction particle size measurement: SALD-7000 type (manufactured by Shimadzu Corporation), 1 g of sample was dispersed in pure water and measured.
Specific surface area measurement: Nitrogen adsorption surface area measuring device Monosorb (manufactured by Quantachrome)
Slurry solid content measurement: About 2 g of the sample was put in a porcelain crucible, precisely weighed, and the solid content (% by mass) was calculated from the mass after drying at 110 ° C.
Powder X-ray diffraction analysis: A powder X-ray diffraction apparatus RINT Ultimate type (manufactured by Rigaku Corporation) was used.
A diffraction peak at 2θ = 28.0 ° corresponding to the (211) plane of cyanamide zinc (chemical formula: ZnCN 2 ) (hereinafter referred to as peak A), and 2θ = 31 corresponding to the (100) plane of zinc oxide. The diffraction intensity of a diffraction peak at .8 ° (hereinafter referred to as peak B) was measured.
Elemental analysis: fully automatic elemental analyzer CHNS / O analyzer 2400 (manufactured by Perkin Elmer)
Flame spectroscopic analysis: SpectraAA (Varian)
ICP emission spectral analysis: Plasma Spectrometer SPS7800 (manufactured by Seiko Instruments Inc.)
Ion chromatographic analysis: Ion chromatography IC25 (manufactured by DIONEX)
(合成例1)
容積700Lのジャケット付きステンレス製容器に純水368kgを仕込み、直径300mmのディスパー羽根を取り付けた攪拌機(アシザワファインテック(株)製、商品名:ハイパー)でディスパー羽根を500rpmで回転させながら酸化亜鉛粉末(堺化学(株)製2種酸化亜鉛)19.7kgを投入した。この酸化亜鉛スラリーを加熱して40℃に到達したところでディスパー羽根の回転数を800rpmに上げて強分散しながら、シアヌル酸粉末(日産化学工業(株)製)12.5kgを3分割して30分おきに投入した。酸化亜鉛/シアヌル酸のモル比は2.50、水に対するシアヌル酸濃度は2.9質量%であった。シアヌル酸粉末を投入後、スラリーの温度は50℃になり、この温度を保持した。このスラリーをディスパー羽根の回転数を800rpmのままで9時間強分散した。これにより、pH7.6、電導度28μS/cm、粘度1070mPa・s、110℃乾燥時の固形分が8.5質量%の白色スラリーが397kg得られた。得られた白色スラリーの110℃乾燥粉について粉末X線回折分析を行ったところ、国際公開第2011/162354号パンフレット(出願人:日産化学工業(株))に記載の塩基性シアヌル酸亜鉛Zn5(C3N3O3)2(OH)3・3H2Oの回折ピークが観察された。得られた白色スラリーに含まれる微粒子は、透過型電子顕微鏡観察では長軸が200~1000nm、短軸が40~60nmであり、110℃乾燥後の比表面積は34m2/gであった。得られたスラリー50kgをフィルタープレスでウェットケーキにした後、110℃で乾燥して、塩基性シアヌル酸亜鉛の乾燥ブロック4.25kgを得た。 (Synthesis Example 1)
Zinc oxide powder while rotating the disper blade at 500 rpm with a stirrer (manufactured by Ashizawa Finetech Co., Ltd., trade name: Hyper) charged with 368 kg of pure water in a 700 L jacketed stainless steel container and equipped with a 300 mm diameter disper blade (19.7 kg of 2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. When this zinc oxide slurry was heated to 40 ° C., the dispersion speed of the disperse blade was increased to 800 rpm and strongly dispersed, while 12.5 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was divided into three parts to 30 Thrown every minute. The molar ratio of zinc oxide / cyanuric acid was 2.50, and the cyanuric acid concentration relative to water was 2.9% by mass. After adding the cyanuric acid powder, the temperature of the slurry became 50 ° C., and this temperature was maintained. This slurry was strongly dispersed for 9 hours while maintaining the rotational speed of the disperse blades at 800 rpm. As a result, 397 kg of a white slurry having a pH of 7.6, an electrical conductivity of 28 μS / cm, a viscosity of 1070 mPa · s, and a solid content of 8.5% by mass when dried at 110 ° C. was obtained. When powder X-ray diffraction analysis was performed on the 110 ° C. dry powder of the obtained white slurry, basic zinc cyanurate Zn 5 described in International Publication No. 2011/162354 pamphlet (Applicant: Nissan Chemical Industries, Ltd.) A diffraction peak of (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O was observed. The fine particles contained in the obtained white slurry had a major axis of 200 to 1000 nm and a minor axis of 40 to 60 nm as observed with a transmission electron microscope, and a specific surface area after drying at 110 ° C. was 34 m 2 / g. 50 kg of the obtained slurry was made into a wet cake with a filter press, and then dried at 110 ° C. to obtain 4.25 kg of a basic zinc cyanurate drying block.
容積700Lのジャケット付きステンレス製容器に純水368kgを仕込み、直径300mmのディスパー羽根を取り付けた攪拌機(アシザワファインテック(株)製、商品名:ハイパー)でディスパー羽根を500rpmで回転させながら酸化亜鉛粉末(堺化学(株)製2種酸化亜鉛)19.7kgを投入した。この酸化亜鉛スラリーを加熱して40℃に到達したところでディスパー羽根の回転数を800rpmに上げて強分散しながら、シアヌル酸粉末(日産化学工業(株)製)12.5kgを3分割して30分おきに投入した。酸化亜鉛/シアヌル酸のモル比は2.50、水に対するシアヌル酸濃度は2.9質量%であった。シアヌル酸粉末を投入後、スラリーの温度は50℃になり、この温度を保持した。このスラリーをディスパー羽根の回転数を800rpmのままで9時間強分散した。これにより、pH7.6、電導度28μS/cm、粘度1070mPa・s、110℃乾燥時の固形分が8.5質量%の白色スラリーが397kg得られた。得られた白色スラリーの110℃乾燥粉について粉末X線回折分析を行ったところ、国際公開第2011/162354号パンフレット(出願人:日産化学工業(株))に記載の塩基性シアヌル酸亜鉛Zn5(C3N3O3)2(OH)3・3H2Oの回折ピークが観察された。得られた白色スラリーに含まれる微粒子は、透過型電子顕微鏡観察では長軸が200~1000nm、短軸が40~60nmであり、110℃乾燥後の比表面積は34m2/gであった。得られたスラリー50kgをフィルタープレスでウェットケーキにした後、110℃で乾燥して、塩基性シアヌル酸亜鉛の乾燥ブロック4.25kgを得た。 (Synthesis Example 1)
Zinc oxide powder while rotating the disper blade at 500 rpm with a stirrer (manufactured by Ashizawa Finetech Co., Ltd., trade name: Hyper) charged with 368 kg of pure water in a 700 L jacketed stainless steel container and equipped with a 300 mm diameter disper blade (19.7 kg of 2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was added. When this zinc oxide slurry was heated to 40 ° C., the dispersion speed of the disperse blade was increased to 800 rpm and strongly dispersed, while 12.5 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) was divided into three parts to 30 Thrown every minute. The molar ratio of zinc oxide / cyanuric acid was 2.50, and the cyanuric acid concentration relative to water was 2.9% by mass. After adding the cyanuric acid powder, the temperature of the slurry became 50 ° C., and this temperature was maintained. This slurry was strongly dispersed for 9 hours while maintaining the rotational speed of the disperse blades at 800 rpm. As a result, 397 kg of a white slurry having a pH of 7.6, an electrical conductivity of 28 μS / cm, a viscosity of 1070 mPa · s, and a solid content of 8.5% by mass when dried at 110 ° C. was obtained. When powder X-ray diffraction analysis was performed on the 110 ° C. dry powder of the obtained white slurry, basic zinc cyanurate Zn 5 described in International Publication No. 2011/162354 pamphlet (Applicant: Nissan Chemical Industries, Ltd.) A diffraction peak of (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O was observed. The fine particles contained in the obtained white slurry had a major axis of 200 to 1000 nm and a minor axis of 40 to 60 nm as observed with a transmission electron microscope, and a specific surface area after drying at 110 ° C. was 34 m 2 / g. 50 kg of the obtained slurry was made into a wet cake with a filter press, and then dried at 110 ° C. to obtain 4.25 kg of a basic zinc cyanurate drying block.
(合成例2)
純水22kgと酸化亜鉛粉末(堺化学(株)製2種酸化亜鉛)2.5kgとを容積200Lの混合用タンクに投入し、ディスパーで混合して、酸化亜鉛換算濃度が10.3質量%のスラリー24.3kgを調製した。次に有効容積10.66Lで内壁がウレタン樹脂の横型ビーズミル(アシザワファインテック(株)製、商品名:システムゼータLMZ25)にφ1mmの安定化ジルコニア製粉砕ビーズ66kgを仕込んだ。水温13℃のシャケット水を用いた容積300Lの循環タンクに純水121kgを仕込んだ後、システムゼータLMZ25のディスクを周速7.1m/秒で回転させながら供給速度22.1kg/分で純水をシステムゼータに供給して、純水を循環させた。循環開始後にシアヌル酸粉末(日産化学工業(株)製)4.0kgを循環タンクに投入した。シアヌル酸の循環スラリーの温度を34℃に保持しながら、先に調製した酸化亜鉛換算濃度10.3質量%の酸化亜鉛スラリー24.6kgを5分割して10分かけてシアヌル酸の循環スラリーに添加した。酸化亜鉛スラリーの添加後もシステムゼータのディスクを周速7.1m/秒で回転させ、供給速度22.1kg/分で循環タンク中のスラリーを7時間循環し、分散した。また、この間も循環スラリー温度は34℃を保持した。これにより、pH6.5、電導度446μS/cm、粘度17mPa・s、固形分濃度3.8質量%の白色スラリーが170kg得られた。得られた白色スラリーの透過型電子顕微鏡観察では、長軸が200~2000nm、短軸が25~400nmの針状粒子が確認された。得られた白色スラリーから1500gを分取し、ステンレス製容器に移した後、70℃で乾燥して乾燥粉57gを得た。この乾燥粉の粉末X線回折分析を行ったところ、シアヌル酸亜鉛に相当する回折ピークとシアヌル酸に相当する回折ピークが検出された。シアヌル酸に相当する回折ピークは小さいピークであった。得られた乾燥粉を1000℃で灼熱して得られた酸化亜鉛を定量して亜鉛含有量を求めたところ、31質量%であった。更に炭素及び窒素含有量をCHN元素分析で定量した結果、炭素分は17.2質量%、窒素分は20.0質量%であった。この乾燥粉は亜鉛原子1モルに対して窒素原子3.0モルの組成であった。これにより、シアヌル酸亜鉛79質量部、シアヌル酸21質量部の混合粉と計算された。 (Synthesis Example 2)
22 kg of pure water and 2.5 kg of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) are put into a 200 L mixing tank and mixed with a disper to give a zinc oxide equivalent concentration of 10.3 mass%. 24.3 kg of a slurry was prepared. Next, 66 kg of stabilized zirconia crushed beads of φ1 mm were charged into a horizontal bead mill (Ashizawa Finetech Co., Ltd., trade name: System Zeta LMZ25) having an effective volume of 10.66 L and an inner wall of urethane resin. After charging 121 kg of pure water into a 300 L capacity circulation tank using water at a temperature of 13 ° C., pure water at a supply speed of 22.1 kg / min while rotating the disk of the system zeta LMZ25 at a peripheral speed of 7.1 m / sec. Was supplied to the system zeta to circulate pure water. After the start of circulation, 4.0 kg of cyanuric acid powder (Nissan Chemical Co., Ltd.) was charged into the circulation tank. While maintaining the temperature of the cyanuric acid circulating slurry at 34 ° C., 24.6 kg of the previously prepared zinc oxide slurry of 10.3% by mass in terms of zinc oxide was divided into 5 parts to form a cyanuric acid circulating slurry over 10 minutes. Added. After the addition of the zinc oxide slurry, the disk of the system zeta was rotated at a peripheral speed of 7.1 m / sec, and the slurry in the circulation tank was circulated for 7 hours at a supply speed of 22.1 kg / min to be dispersed. During this time, the circulating slurry temperature was maintained at 34 ° C. As a result, 170 kg of white slurry having a pH of 6.5, an electric conductivity of 446 μS / cm, a viscosity of 17 mPa · s, and a solid content concentration of 3.8% by mass was obtained. Observation of the obtained white slurry with a transmission electron microscope confirmed acicular particles having a major axis of 200 to 2000 nm and a minor axis of 25 to 400 nm. 1500 g was collected from the obtained white slurry, transferred to a stainless steel container, and dried at 70 ° C. to obtain 57 g of dry powder. When powder X-ray diffraction analysis of this dry powder was performed, a diffraction peak corresponding to zinc cyanurate and a diffraction peak corresponding to cyanuric acid were detected. The diffraction peak corresponding to cyanuric acid was a small peak. It was 31 mass% when zinc content obtained by quantifying the zinc oxide obtained by heating the obtained dry powder at 1000 degreeC was determined. Furthermore, as a result of quantifying the carbon and nitrogen contents by CHN elemental analysis, the carbon content was 17.2% by mass and the nitrogen content was 20.0% by mass. This dry powder had a composition of 3.0 moles of nitrogen atoms per mole of zinc atoms. Thereby, it was calculated as a mixed powder of 79 parts by mass of zinc cyanurate and 21 parts by mass of cyanuric acid.
純水22kgと酸化亜鉛粉末(堺化学(株)製2種酸化亜鉛)2.5kgとを容積200Lの混合用タンクに投入し、ディスパーで混合して、酸化亜鉛換算濃度が10.3質量%のスラリー24.3kgを調製した。次に有効容積10.66Lで内壁がウレタン樹脂の横型ビーズミル(アシザワファインテック(株)製、商品名:システムゼータLMZ25)にφ1mmの安定化ジルコニア製粉砕ビーズ66kgを仕込んだ。水温13℃のシャケット水を用いた容積300Lの循環タンクに純水121kgを仕込んだ後、システムゼータLMZ25のディスクを周速7.1m/秒で回転させながら供給速度22.1kg/分で純水をシステムゼータに供給して、純水を循環させた。循環開始後にシアヌル酸粉末(日産化学工業(株)製)4.0kgを循環タンクに投入した。シアヌル酸の循環スラリーの温度を34℃に保持しながら、先に調製した酸化亜鉛換算濃度10.3質量%の酸化亜鉛スラリー24.6kgを5分割して10分かけてシアヌル酸の循環スラリーに添加した。酸化亜鉛スラリーの添加後もシステムゼータのディスクを周速7.1m/秒で回転させ、供給速度22.1kg/分で循環タンク中のスラリーを7時間循環し、分散した。また、この間も循環スラリー温度は34℃を保持した。これにより、pH6.5、電導度446μS/cm、粘度17mPa・s、固形分濃度3.8質量%の白色スラリーが170kg得られた。得られた白色スラリーの透過型電子顕微鏡観察では、長軸が200~2000nm、短軸が25~400nmの針状粒子が確認された。得られた白色スラリーから1500gを分取し、ステンレス製容器に移した後、70℃で乾燥して乾燥粉57gを得た。この乾燥粉の粉末X線回折分析を行ったところ、シアヌル酸亜鉛に相当する回折ピークとシアヌル酸に相当する回折ピークが検出された。シアヌル酸に相当する回折ピークは小さいピークであった。得られた乾燥粉を1000℃で灼熱して得られた酸化亜鉛を定量して亜鉛含有量を求めたところ、31質量%であった。更に炭素及び窒素含有量をCHN元素分析で定量した結果、炭素分は17.2質量%、窒素分は20.0質量%であった。この乾燥粉は亜鉛原子1モルに対して窒素原子3.0モルの組成であった。これにより、シアヌル酸亜鉛79質量部、シアヌル酸21質量部の混合粉と計算された。 (Synthesis Example 2)
22 kg of pure water and 2.5 kg of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) are put into a 200 L mixing tank and mixed with a disper to give a zinc oxide equivalent concentration of 10.3 mass%. 24.3 kg of a slurry was prepared. Next, 66 kg of stabilized zirconia crushed beads of φ1 mm were charged into a horizontal bead mill (Ashizawa Finetech Co., Ltd., trade name: System Zeta LMZ25) having an effective volume of 10.66 L and an inner wall of urethane resin. After charging 121 kg of pure water into a 300 L capacity circulation tank using water at a temperature of 13 ° C., pure water at a supply speed of 22.1 kg / min while rotating the disk of the system zeta LMZ25 at a peripheral speed of 7.1 m / sec. Was supplied to the system zeta to circulate pure water. After the start of circulation, 4.0 kg of cyanuric acid powder (Nissan Chemical Co., Ltd.) was charged into the circulation tank. While maintaining the temperature of the cyanuric acid circulating slurry at 34 ° C., 24.6 kg of the previously prepared zinc oxide slurry of 10.3% by mass in terms of zinc oxide was divided into 5 parts to form a cyanuric acid circulating slurry over 10 minutes. Added. After the addition of the zinc oxide slurry, the disk of the system zeta was rotated at a peripheral speed of 7.1 m / sec, and the slurry in the circulation tank was circulated for 7 hours at a supply speed of 22.1 kg / min to be dispersed. During this time, the circulating slurry temperature was maintained at 34 ° C. As a result, 170 kg of white slurry having a pH of 6.5, an electric conductivity of 446 μS / cm, a viscosity of 17 mPa · s, and a solid content concentration of 3.8% by mass was obtained. Observation of the obtained white slurry with a transmission electron microscope confirmed acicular particles having a major axis of 200 to 2000 nm and a minor axis of 25 to 400 nm. 1500 g was collected from the obtained white slurry, transferred to a stainless steel container, and dried at 70 ° C. to obtain 57 g of dry powder. When powder X-ray diffraction analysis of this dry powder was performed, a diffraction peak corresponding to zinc cyanurate and a diffraction peak corresponding to cyanuric acid were detected. The diffraction peak corresponding to cyanuric acid was a small peak. It was 31 mass% when zinc content obtained by quantifying the zinc oxide obtained by heating the obtained dry powder at 1000 degreeC was determined. Furthermore, as a result of quantifying the carbon and nitrogen contents by CHN elemental analysis, the carbon content was 17.2% by mass and the nitrogen content was 20.0% by mass. This dry powder had a composition of 3.0 moles of nitrogen atoms per mole of zinc atoms. Thereby, it was calculated as a mixed powder of 79 parts by mass of zinc cyanurate and 21 parts by mass of cyanuric acid.
(合成例3)
合成例2で得られた白色スラリー(シアヌル酸亜鉛とシアヌル酸と水との混合スラリー:pH6.5、電導度446μS/cm、粘度17mPa・s、固形分濃度3.8質量%)170kgのうち1500gを分取し、ヌッチェを用いて濾過してウェットケーキとした後、該ウェットケーキを純水で洗浄してシアヌル酸を除去した。洗浄されたウェットケーキをステンレス製容器に移し、70℃で乾燥して白色乾燥粉を45g得た。得られた白色乾燥粉を空気中1000℃で灼熱して得られた酸化亜鉛を定量して亜鉛含有量を求めたところ、44質量%であった。更に炭素及び窒素含有量をCHN元素分析で定量した結果、炭素分は16.1質量%、窒素分は18.7質量%であった。これらの結果から、この針状粒子は、Zn3(C3N3O3)2のシアヌル酸亜鉛であり、亜鉛原子1モルに対して窒素原子を2.0モルの組成であった。また70℃乾燥粉の比表面積は8m2/gであった。 (Synthesis Example 3)
Of 170 kg of the white slurry obtained in Synthesis Example 2 (mixed slurry of zinc cyanurate, cyanuric acid and water: pH 6.5, conductivity 446 μS / cm, viscosity 17 mPa · s, solid content concentration 3.8 mass%) 1500 g was collected and filtered using a Nutsche to obtain a wet cake, and then the wet cake was washed with pure water to remove cyanuric acid. The washed wet cake was transferred to a stainless steel container and dried at 70 ° C. to obtain 45 g of white dry powder. It was 44 mass% when zinc content obtained by quantifying the zinc oxide obtained by heating the obtained white dry powder at 1000 degreeC in the air was determined. Furthermore, as a result of quantifying the carbon and nitrogen contents by CHN elemental analysis, the carbon content was 16.1% by mass and the nitrogen content was 18.7% by mass. From these results, this acicular particle was zinc cyanurate of Zn 3 (C 3 N 3 O 3 ) 2 and had a composition of 2.0 moles of nitrogen atoms per mole of zinc atoms. The specific surface area of the 70 ° C. dry powder was 8 m 2 / g.
合成例2で得られた白色スラリー(シアヌル酸亜鉛とシアヌル酸と水との混合スラリー:pH6.5、電導度446μS/cm、粘度17mPa・s、固形分濃度3.8質量%)170kgのうち1500gを分取し、ヌッチェを用いて濾過してウェットケーキとした後、該ウェットケーキを純水で洗浄してシアヌル酸を除去した。洗浄されたウェットケーキをステンレス製容器に移し、70℃で乾燥して白色乾燥粉を45g得た。得られた白色乾燥粉を空気中1000℃で灼熱して得られた酸化亜鉛を定量して亜鉛含有量を求めたところ、44質量%であった。更に炭素及び窒素含有量をCHN元素分析で定量した結果、炭素分は16.1質量%、窒素分は18.7質量%であった。これらの結果から、この針状粒子は、Zn3(C3N3O3)2のシアヌル酸亜鉛であり、亜鉛原子1モルに対して窒素原子を2.0モルの組成であった。また70℃乾燥粉の比表面積は8m2/gであった。 (Synthesis Example 3)
Of 170 kg of the white slurry obtained in Synthesis Example 2 (mixed slurry of zinc cyanurate, cyanuric acid and water: pH 6.5, conductivity 446 μS / cm, viscosity 17 mPa · s, solid content concentration 3.8 mass%) 1500 g was collected and filtered using a Nutsche to obtain a wet cake, and then the wet cake was washed with pure water to remove cyanuric acid. The washed wet cake was transferred to a stainless steel container and dried at 70 ° C. to obtain 45 g of white dry powder. It was 44 mass% when zinc content obtained by quantifying the zinc oxide obtained by heating the obtained white dry powder at 1000 degreeC in the air was determined. Furthermore, as a result of quantifying the carbon and nitrogen contents by CHN elemental analysis, the carbon content was 16.1% by mass and the nitrogen content was 18.7% by mass. From these results, this acicular particle was zinc cyanurate of Zn 3 (C 3 N 3 O 3 ) 2 and had a composition of 2.0 moles of nitrogen atoms per mole of zinc atoms. The specific surface area of the 70 ° C. dry powder was 8 m 2 / g.
(合成例4)
原料粉として、酸化亜鉛粉末(堺化学(株)製2種酸化亜鉛)5.3kg及びシアヌル酸粉末(日産化学工業(株)製)3.36kgをレーディゲミキサー装置M-20(中央機工(株)製)に仕込んだ後、ミキサーの主軸を230rpmで回転させながら3分間プレミックスした。続いてレーディゲミキサー装置のジャケット水を110℃のスチームに切り替えて原料粉の温度を100℃に昇温させた後、装置内に純水2.3kgを1時間かけて噴霧した。更に原料粉を100℃で30分保持した後、装置内にある粉を排出した。排出された粉は白色であり、水分量は2.2質量%であった。排出粉を110℃で乾燥した後、粉末X線回折分析を行ったところ、塩基性シアヌル酸亜鉛Zn5(C3N3O3)2(OH)3・3H2Oの回折ピークが観察された。排出粉を透過型電子顕微鏡で観察したところ、長軸が200~500nm、短軸が40~80nmの微粒子が確認された。また、110℃乾燥後の比表面積は13m2/gであった。 (Synthesis Example 4)
As raw material powder, 5.3 kg of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) and 3.36 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) were used. And then premixed for 3 minutes while rotating the main spindle of the mixer at 230 rpm. Subsequently, after the jacket water of the Ladige mixer apparatus was switched to steam at 110 ° C. to raise the temperature of the raw material powder to 100 ° C., 2.3 kg of pure water was sprayed into the apparatus over 1 hour. Furthermore, after holding | maintaining raw material powder for 30 minutes at 100 degreeC, the powder in an apparatus was discharged | emitted. The discharged | emitted powder | flour was white and the moisture content was 2.2 mass%. After the discharged powder was dried at 110 ° C., powder X-ray diffraction analysis was performed. As a result, a diffraction peak of basic zinc cyanurate Zn 5 (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O was observed. It was. When the discharged powder was observed with a transmission electron microscope, fine particles having a major axis of 200 to 500 nm and a minor axis of 40 to 80 nm were confirmed. The specific surface area after drying at 110 ° C. was 13 m 2 / g.
原料粉として、酸化亜鉛粉末(堺化学(株)製2種酸化亜鉛)5.3kg及びシアヌル酸粉末(日産化学工業(株)製)3.36kgをレーディゲミキサー装置M-20(中央機工(株)製)に仕込んだ後、ミキサーの主軸を230rpmで回転させながら3分間プレミックスした。続いてレーディゲミキサー装置のジャケット水を110℃のスチームに切り替えて原料粉の温度を100℃に昇温させた後、装置内に純水2.3kgを1時間かけて噴霧した。更に原料粉を100℃で30分保持した後、装置内にある粉を排出した。排出された粉は白色であり、水分量は2.2質量%であった。排出粉を110℃で乾燥した後、粉末X線回折分析を行ったところ、塩基性シアヌル酸亜鉛Zn5(C3N3O3)2(OH)3・3H2Oの回折ピークが観察された。排出粉を透過型電子顕微鏡で観察したところ、長軸が200~500nm、短軸が40~80nmの微粒子が確認された。また、110℃乾燥後の比表面積は13m2/gであった。 (Synthesis Example 4)
As raw material powder, 5.3 kg of zinc oxide powder (2 types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) and 3.36 kg of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) were used. And then premixed for 3 minutes while rotating the main spindle of the mixer at 230 rpm. Subsequently, after the jacket water of the Ladige mixer apparatus was switched to steam at 110 ° C. to raise the temperature of the raw material powder to 100 ° C., 2.3 kg of pure water was sprayed into the apparatus over 1 hour. Furthermore, after holding | maintaining raw material powder for 30 minutes at 100 degreeC, the powder in an apparatus was discharged | emitted. The discharged | emitted powder | flour was white and the moisture content was 2.2 mass%. After the discharged powder was dried at 110 ° C., powder X-ray diffraction analysis was performed. As a result, a diffraction peak of basic zinc cyanurate Zn 5 (C 3 N 3 O 3 ) 2 (OH) 3 .3H 2 O was observed. It was. When the discharged powder was observed with a transmission electron microscope, fine particles having a major axis of 200 to 500 nm and a minor axis of 40 to 80 nm were confirmed. The specific surface area after drying at 110 ° C. was 13 m 2 / g.
(実施例1)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉10gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下460℃で6時間焼成した。冷却後、得られた薄黄土色の焼成粉7.0gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛、酸化亜鉛及び微小な帰属不明の回折ピークが検出された。シアヌル酸亜鉛に帰属されるピークAの強度は1090counts、酸化亜鉛に帰属されるピークBの強度は861countsであった。 Example 1
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 10 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Then, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 460 ° C. For 6 hours. After cooling, 7.0 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, cyanamide zinc, zinc oxide, and a fine diffraction peak with unknown attribution were detected. The intensity of peak A attributed to zinc cyanurate was 1090 counts, and the intensity of peak B attributed to zinc oxide was 861 counts.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉10gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下460℃で6時間焼成した。冷却後、得られた薄黄土色の焼成粉7.0gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛、酸化亜鉛及び微小な帰属不明の回折ピークが検出された。シアヌル酸亜鉛に帰属されるピークAの強度は1090counts、酸化亜鉛に帰属されるピークBの強度は861countsであった。 Example 1
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 10 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Then, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 460 ° C. For 6 hours. After cooling, 7.0 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, cyanamide zinc, zinc oxide, and a fine diffraction peak with unknown attribution were detected. The intensity of peak A attributed to zinc cyanurate was 1090 counts, and the intensity of peak B attributed to zinc oxide was 861 counts.
(実施例2)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉10gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた薄ピンク色の焼成粉6.5gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛と酸化亜鉛の混合物であり、ピークAの強度は1322counts、ピークBの強度は997countsであった。またCHN元素分析を行ったところ窒素8.2質量%、炭素3.5質量%であったため、この焼成粉のシアナミド亜鉛の含有率は31質量%と計算された。焼成粉1.0gを精秤し、ポリ瓶中で純水79.0gと混合後、超音波分散機で30分間分散した。これを2週間静置後、遠心分離機で固液分離し、上澄液について炎光分光分析(ナトリウム、カリウムの定量分析)、ICP発光分光分析(カルシウム、マグネシウム、鉛、クロムの定量分析)及びイオンクロマトグラフ分析(塩素イオン、硫酸イオン、硝酸イオンの定量分析)を行なった。この結果、焼成粉中の金属不純物は、ナトリウム14ppm、カリウム2ppm、カルシウム3ppm、マグネシウム1ppm、鉛5ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 2)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 10 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration 1 ppm or less) was flowed into the replacement furnace for 1 hour at a flow rate of 2 liters / minute, and then purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute and the nitrogen gas atmosphere was 490 ° C. Baked for 6 hours. After cooling, 6.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, it was a mixture of cyanamide zinc and zinc oxide. The intensity of peak A was 1322counts, and the intensity of peak B was 997 counts. Moreover, since it was 8.2 mass% of nitrogen and 3.5 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 31 mass%. 1.0 g of the calcined powder was precisely weighed, mixed with 79.0 g of pure water in a plastic bottle, and then dispersed with an ultrasonic disperser for 30 minutes. After standing for 2 weeks, this was solid-liquid separated with a centrifuge, and the supernatant liquid was analyzed by flame spectroscopy (quantitative analysis of sodium and potassium) and ICP emission spectroscopy (quantitative analysis of calcium, magnesium, lead and chromium). And ion chromatographic analysis (quantitative analysis of chloride ion, sulfate ion and nitrate ion). As a result, the metal impurities in the fired powder were sodium 14 ppm, potassium 2 ppm, calcium 3 ppm, magnesium 1 ppm, lead 5 ppm, and chromium 0 ppm. In addition, chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉10gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた薄ピンク色の焼成粉6.5gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛と酸化亜鉛の混合物であり、ピークAの強度は1322counts、ピークBの強度は997countsであった。またCHN元素分析を行ったところ窒素8.2質量%、炭素3.5質量%であったため、この焼成粉のシアナミド亜鉛の含有率は31質量%と計算された。焼成粉1.0gを精秤し、ポリ瓶中で純水79.0gと混合後、超音波分散機で30分間分散した。これを2週間静置後、遠心分離機で固液分離し、上澄液について炎光分光分析(ナトリウム、カリウムの定量分析)、ICP発光分光分析(カルシウム、マグネシウム、鉛、クロムの定量分析)及びイオンクロマトグラフ分析(塩素イオン、硫酸イオン、硝酸イオンの定量分析)を行なった。この結果、焼成粉中の金属不純物は、ナトリウム14ppm、カリウム2ppm、カルシウム3ppm、マグネシウム1ppm、鉛5ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 2)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 10 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration 1 ppm or less) was flowed into the replacement furnace for 1 hour at a flow rate of 2 liters / minute, and then purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute and the nitrogen gas atmosphere was 490 ° C. Baked for 6 hours. After cooling, 6.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, it was a mixture of cyanamide zinc and zinc oxide. The intensity of peak A was 1322counts, and the intensity of peak B was 997 counts. Moreover, since it was 8.2 mass% of nitrogen and 3.5 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 31 mass%. 1.0 g of the calcined powder was precisely weighed, mixed with 79.0 g of pure water in a plastic bottle, and then dispersed with an ultrasonic disperser for 30 minutes. After standing for 2 weeks, this was solid-liquid separated with a centrifuge, and the supernatant liquid was analyzed by flame spectroscopy (quantitative analysis of sodium and potassium) and ICP emission spectroscopy (quantitative analysis of calcium, magnesium, lead and chromium). And ion chromatographic analysis (quantitative analysis of chloride ion, sulfate ion and nitrate ion). As a result, the metal impurities in the fired powder were sodium 14 ppm, potassium 2 ppm, calcium 3 ppm, magnesium 1 ppm, lead 5 ppm, and chromium 0 ppm. In addition, chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
(実施例3)
合成例3で得られたシアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉15gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた薄黄土色の焼成粉9.4gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛と酸化亜鉛の混合物で、ピークAの強度は5919counts、ピークBの強度は337countsであった。またCHN元素分析したところ窒素21.0質量%、炭素9.0質量%であったため、この焼成粉のシアナミド亜鉛の含有率は79質量%と計算された。 (Example 3)
30 g of the dried block of zinc cyanurate obtained in Synthesis Example 3 was pulverized for 6 minutes with a home mixer. 15 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 490 ° C. For 6 hours. After cooling, 9.4 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, it was a mixture of cyanamide zinc and zinc oxide, the intensity of peak A was 5919counts, and the intensity of peak B was 337counts. Met. Moreover, since it was 21.0 mass% of nitrogen and 9.0 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 79 mass%.
合成例3で得られたシアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉15gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた薄黄土色の焼成粉9.4gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛と酸化亜鉛の混合物で、ピークAの強度は5919counts、ピークBの強度は337countsであった。またCHN元素分析したところ窒素21.0質量%、炭素9.0質量%であったため、この焼成粉のシアナミド亜鉛の含有率は79質量%と計算された。 (Example 3)
30 g of the dried block of zinc cyanurate obtained in Synthesis Example 3 was pulverized for 6 minutes with a home mixer. 15 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 490 ° C. For 6 hours. After cooling, 9.4 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, it was a mixture of cyanamide zinc and zinc oxide, the intensity of peak A was 5919counts, and the intensity of peak B was 337counts. Met. Moreover, since it was 21.0 mass% of nitrogen and 9.0 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 79 mass%.
(実施例4)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉10.0gとシアヌル酸4.0gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が2.0モルとなるようにシアヌル酸を添加した混合物14.0gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた薄黄土色の焼成粉7.6gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛と酸化亜鉛の混合物であり、ピークAの強度は3915counts、ピークBの強度は877countsであった。またCHN元素分析を行ったところ窒素17.0質量%、炭素7.1質量%であったため、この焼成粉のシアナミド亜鉛の含有率は62質量%と計算された。 (Example 4)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 15. Mixture obtained by mixing 10.0 g of the pulverized powder and 4.0 g of cyanuric acid, and adding cyanuric acid so that the nitrogen atom is 2.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 0 g was put into a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 490 ° C. For 6 hours. After cooling, 7.6 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, it was a mixture of cyanamide zinc and zinc oxide. The intensity of peak A was 3915 counts, and the intensity of peak B was 877counts. Moreover, since it was 17.0 mass% of nitrogen and 7.1 mass% of carbon when the CHN elemental analysis was conducted, the cyanamide zinc content of this baked powder was calculated to be 62 mass%.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉10.0gとシアヌル酸4.0gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が2.0モルとなるようにシアヌル酸を添加した混合物14.0gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた薄黄土色の焼成粉7.6gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛と酸化亜鉛の混合物であり、ピークAの強度は3915counts、ピークBの強度は877countsであった。またCHN元素分析を行ったところ窒素17.0質量%、炭素7.1質量%であったため、この焼成粉のシアナミド亜鉛の含有率は62質量%と計算された。 (Example 4)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 15. Mixture obtained by mixing 10.0 g of the pulverized powder and 4.0 g of cyanuric acid, and adding cyanuric acid so that the nitrogen atom is 2.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 0 g was put into a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, and the nitrogen gas atmosphere was 490 ° C. For 6 hours. After cooling, 7.6 g of the obtained light ocher baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, it was a mixture of cyanamide zinc and zinc oxide. The intensity of peak A was 3915 counts, and the intensity of peak B was 877counts. Moreover, since it was 17.0 mass% of nitrogen and 7.1 mass% of carbon when the CHN elemental analysis was conducted, the cyanamide zinc content of this baked powder was calculated to be 62 mass%.
(実施例5)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉12.7gとシアヌル酸7.3gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が3.0モルとなるようにシアヌル酸を添加した混合物20.0gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下480℃で6時間焼成した。冷却後、得られた灰白色の焼成粉9.8gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は3542countsであった。またCHN元素分析を行ったところ窒素25.7質量%、炭素11.1質量%であったため、この焼成粉のシアナミド亜鉛の含有率は97質量%と計算された。またこの焼成粉の比表面積は25.6m2/gであった。得られた焼成粉について実施例2と同じ操作を行って上澄液を採取し、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム11ppm、カリウム3ppm、カルシウム5ppm、マグネシウム1ppm、鉛5ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 5)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 20. A mixture obtained by mixing 12.7 g of this pulverized powder and 7.3 g of cyanuric acid, and adding cyanuric acid so that the nitrogen atom is 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 0 g was put into a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed to the gas replacement furnace at a flow rate of 2 liters / minute for 1 hour to perform nitrogen purge, and then the nitrogen gas flow rate was changed to 0.5 liters / minute, under a nitrogen gas atmosphere 480. Baked at 6 ° C. for 6 hours. After cooling, 9.8 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 3542counts. Moreover, since it was 25.7 mass% of nitrogen and 11.1 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 97 mass%. The calcined powder had a specific surface area of 25.6 m 2 / g. The obtained calcined powder was subjected to the same operation as in Example 2 to collect a supernatant, and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis. As a result, metal impurities in the fired powder were sodium 11 ppm, potassium 3 ppm,calcium 5 ppm, magnesium 1 ppm, lead 5 ppm, and chromium 0 ppm. In addition, chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉12.7gとシアヌル酸7.3gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が3.0モルとなるようにシアヌル酸を添加した混合物20.0gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下480℃で6時間焼成した。冷却後、得られた灰白色の焼成粉9.8gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は3542countsであった。またCHN元素分析を行ったところ窒素25.7質量%、炭素11.1質量%であったため、この焼成粉のシアナミド亜鉛の含有率は97質量%と計算された。またこの焼成粉の比表面積は25.6m2/gであった。得られた焼成粉について実施例2と同じ操作を行って上澄液を採取し、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム11ppm、カリウム3ppm、カルシウム5ppm、マグネシウム1ppm、鉛5ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 5)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 20. A mixture obtained by mixing 12.7 g of this pulverized powder and 7.3 g of cyanuric acid, and adding cyanuric acid so that the nitrogen atom is 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 0 g was put into a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed to the gas replacement furnace at a flow rate of 2 liters / minute for 1 hour to perform nitrogen purge, and then the nitrogen gas flow rate was changed to 0.5 liters / minute, under a nitrogen gas atmosphere 480. Baked at 6 ° C. for 6 hours. After cooling, 9.8 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 3542counts. Moreover, since it was 25.7 mass% of nitrogen and 11.1 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 97 mass%. The calcined powder had a specific surface area of 25.6 m 2 / g. The obtained calcined powder was subjected to the same operation as in Example 2 to collect a supernatant, and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis. As a result, metal impurities in the fired powder were sodium 11 ppm, potassium 3 ppm,
(実施例6)
窒素ガス雰囲気下での焼成温度を490℃とし、保持時間を11時間とした以外は実施例5と同じ操作を行った。冷却後、得られた灰白色の焼成粉9.2gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は4173countsであった。またCHN元素分析を行ったところ窒素26.3質量%、炭素11.5質量%であったため、この焼成粉のシアナミド亜鉛の含有率は99質量%と計算された。また、この焼成粉の比表面積は20.0m2/gであった。 (Example 6)
The same operation as in Example 5 was performed except that the firing temperature in a nitrogen gas atmosphere was 490 ° C. and the holding time was 11 hours. After cooling, 9.2 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4173 counts. Further, when CHN elemental analysis was performed, it was found that the nitrogen content was 26.3% by mass and carbon 11.5% by mass. Moreover, the specific surface area of this baked powder was 20.0 m 2 / g.
窒素ガス雰囲気下での焼成温度を490℃とし、保持時間を11時間とした以外は実施例5と同じ操作を行った。冷却後、得られた灰白色の焼成粉9.2gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は4173countsであった。またCHN元素分析を行ったところ窒素26.3質量%、炭素11.5質量%であったため、この焼成粉のシアナミド亜鉛の含有率は99質量%と計算された。また、この焼成粉の比表面積は20.0m2/gであった。 (Example 6)
The same operation as in Example 5 was performed except that the firing temperature in a nitrogen gas atmosphere was 490 ° C. and the holding time was 11 hours. After cooling, 9.2 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4173 counts. Further, when CHN elemental analysis was performed, it was found that the nitrogen content was 26.3% by mass and carbon 11.5% by mass. Moreover, the specific surface area of this baked powder was 20.0 m 2 / g.
(実施例7)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック2.0kgをヘンシェルミキサーで10分間粉砕した。この粉砕粉2.0kgとシアヌル酸1.55kgとを混合し、亜鉛原子1モルに対して窒素原子を3.6モルとなるようにシアヌル酸を添加した混合物を再度へンシェルミキサーで20分間粉砕した。この粉砕粉400gをアルミナ製ルツボに入れ、アルミナ製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下500℃で6時間焼成した。冷却後、得られた灰白色の焼成粉173gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は4548countsであった。またCHN元素分析を行ったところ窒素26.6質量%、炭素11.8質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は8.2m2/gであった。
得られた焼成粉について実施例2と同じ操作をして上澄液を採取し、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム7ppm、カリウム2ppm、カルシウム4ppm、マグネシウム1ppm、鉛1ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。得られた焼成粉1gと純水80mlを100mlのビーカーに入れ、レーザーゼータ電位計ELS-6000(大塚電子(株)製)で表面電荷を測定したところ、pH3~10の範囲で表面電荷はマイナスであった。表面電荷を測定する際のpH調整は、中性から酸性側では1%の希塩酸で、中性からアルカリ性側は1%水酸化ナトリウム水溶液で行った。 (Example 7)
2.0 kg of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a Henschel mixer for 10 minutes. This pulverized powder (2.0 kg) and cyanuric acid (1.55 kg) were mixed, and the mixture in which cyanuric acid was added so that the nitrogen atom was 3.6 mol with respect to 1 mol of zinc atom was again mixed with a Henschel mixer for 20 minutes. Crushed. 400 g of this pulverized powder was placed in an alumina crucible, covered with an alumina lid, and then loaded into a gas displacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute and purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 6 ° C. for 6 hours. After cooling, 173 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4548 counts. Moreover, since it was 26.6 mass% of nitrogen and 11.8 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 8.2 m 2 / g.
The obtained calcined powder was subjected to the same operation as in Example 2 to collect a supernatant, and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis. As a result, the metal impurities in the fired powder were sodium 7 ppm, potassium 2 ppm, calcium 4 ppm, magnesium 1 ppm, lead 1 ppm, and chromium 0 ppm. In addition, chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less. 1 g of the obtained calcined powder and 80 ml of pure water were put into a 100 ml beaker and the surface charge was measured with a laser zeta electrometer ELS-6000 (manufactured by Otsuka Electronics Co., Ltd.). The surface charge was minus in the range of pH 3-10. Met. The pH adjustment for measuring the surface charge was performed with 1% dilute hydrochloric acid on the neutral to acidic side, and with 1% sodium hydroxide aqueous solution on the neutral to alkaline side.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック2.0kgをヘンシェルミキサーで10分間粉砕した。この粉砕粉2.0kgとシアヌル酸1.55kgとを混合し、亜鉛原子1モルに対して窒素原子を3.6モルとなるようにシアヌル酸を添加した混合物を再度へンシェルミキサーで20分間粉砕した。この粉砕粉400gをアルミナ製ルツボに入れ、アルミナ製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下500℃で6時間焼成した。冷却後、得られた灰白色の焼成粉173gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は4548countsであった。またCHN元素分析を行ったところ窒素26.6質量%、炭素11.8質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は8.2m2/gであった。
得られた焼成粉について実施例2と同じ操作をして上澄液を採取し、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム7ppm、カリウム2ppm、カルシウム4ppm、マグネシウム1ppm、鉛1ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。得られた焼成粉1gと純水80mlを100mlのビーカーに入れ、レーザーゼータ電位計ELS-6000(大塚電子(株)製)で表面電荷を測定したところ、pH3~10の範囲で表面電荷はマイナスであった。表面電荷を測定する際のpH調整は、中性から酸性側では1%の希塩酸で、中性からアルカリ性側は1%水酸化ナトリウム水溶液で行った。 (Example 7)
2.0 kg of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a Henschel mixer for 10 minutes. This pulverized powder (2.0 kg) and cyanuric acid (1.55 kg) were mixed, and the mixture in which cyanuric acid was added so that the nitrogen atom was 3.6 mol with respect to 1 mol of zinc atom was again mixed with a Henschel mixer for 20 minutes. Crushed. 400 g of this pulverized powder was placed in an alumina crucible, covered with an alumina lid, and then loaded into a gas displacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute and purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 6 ° C. for 6 hours. After cooling, 173 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4548 counts. Moreover, since it was 26.6 mass% of nitrogen and 11.8 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 8.2 m 2 / g.
The obtained calcined powder was subjected to the same operation as in Example 2 to collect a supernatant, and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis. As a result, the metal impurities in the fired powder were sodium 7 ppm, potassium 2 ppm, calcium 4 ppm, magnesium 1 ppm, lead 1 ppm, and chromium 0 ppm. In addition, chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less. 1 g of the obtained calcined powder and 80 ml of pure water were put into a 100 ml beaker and the surface charge was measured with a laser zeta electrometer ELS-6000 (manufactured by Otsuka Electronics Co., Ltd.). The surface charge was minus in the range of pH 3-10. Met. The pH adjustment for measuring the surface charge was performed with 1% dilute hydrochloric acid on the neutral to acidic side, and with 1% sodium hydroxide aqueous solution on the neutral to alkaline side.
(実施例8)
窒素ガス雰囲気下での焼成温度を560℃とし、保持時間を5時間とした以外は実施例7と同じ焼成操作を行った。冷却後、得られた灰白色の焼成粉172gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は5423countsであった。またCHN元素分析を行ったところ窒素26.8質量%、炭素11.5質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は4.6m2/gであった。 (Example 8)
The same firing operation as in Example 7 was performed except that the firing temperature in a nitrogen gas atmosphere was 560 ° C. and the holding time was 5 hours. After cooling, 172 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 5423counts. Moreover, since it was 26.8 mass% of nitrogen and 11.5 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 4.6 m 2 / g.
窒素ガス雰囲気下での焼成温度を560℃とし、保持時間を5時間とした以外は実施例7と同じ焼成操作を行った。冷却後、得られた灰白色の焼成粉172gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は5423countsであった。またCHN元素分析を行ったところ窒素26.8質量%、炭素11.5質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は4.6m2/gであった。 (Example 8)
The same firing operation as in Example 7 was performed except that the firing temperature in a nitrogen gas atmosphere was 560 ° C. and the holding time was 5 hours. After cooling, 172 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 5423counts. Moreover, since it was 26.8 mass% of nitrogen and 11.5 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 4.6 m 2 / g.
(実施例9)
窒素ガス雰囲気下での焼成温度を600℃とし、保持時間を5時間とした以外は実施例7と同じ焼成操作を行った。冷却後、得られた灰白色の焼成粉170gを取出し、粉末X線回折装置で同定したところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は6965countsであった。またCHN元素分析を行ったところ窒素27.1質量%、炭素11.3質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は3.9m2/gであった。 Example 9
The same baking operation as in Example 7 was performed except that the baking temperature in a nitrogen gas atmosphere was 600 ° C. and the holding time was 5 hours. After cooling, 170 g of the obtained off-white calcined powder was taken out and identified with a powder X-ray diffractometer. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 6965 counts. Moreover, since it was 27.1 mass% of nitrogen and 11.3 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 3.9 m 2 / g.
窒素ガス雰囲気下での焼成温度を600℃とし、保持時間を5時間とした以外は実施例7と同じ焼成操作を行った。冷却後、得られた灰白色の焼成粉170gを取出し、粉末X線回折装置で同定したところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は6965countsであった。またCHN元素分析を行ったところ窒素27.1質量%、炭素11.3質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は3.9m2/gであった。 Example 9
The same baking operation as in Example 7 was performed except that the baking temperature in a nitrogen gas atmosphere was 600 ° C. and the holding time was 5 hours. After cooling, 170 g of the obtained off-white calcined powder was taken out and identified with a powder X-ray diffractometer. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 6965 counts. Moreover, since it was 27.1 mass% of nitrogen and 11.3 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the fired powder was 3.9 m 2 / g.
(実施例10)
窒素ガス雰囲気下での焼成温度を700℃とし、保持時間を4時間とした以外は実施例5と同じ焼成操作をした。冷却後、得られた灰白色の焼成粉9.1gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は7593countsであった。またCHN元素分析を行ったところ窒素27.2質量%、炭素11.3質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は1.8m2/gであった。 (Example 10)
The same firing operation as in Example 5 was performed except that the firing temperature in a nitrogen gas atmosphere was 700 ° C. and the holding time was 4 hours. After cooling, 9.1 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 7593 counts. Moreover, since it was 27.2 mass% of nitrogen and 11.3 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the calcined powder was 1.8 m 2 / g.
窒素ガス雰囲気下での焼成温度を700℃とし、保持時間を4時間とした以外は実施例5と同じ焼成操作をした。冷却後、得られた灰白色の焼成粉9.1gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は7593countsであった。またCHN元素分析を行ったところ窒素27.2質量%、炭素11.3質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。また、この焼成粉の比表面積は1.8m2/gであった。 (Example 10)
The same firing operation as in Example 5 was performed except that the firing temperature in a nitrogen gas atmosphere was 700 ° C. and the holding time was 4 hours. After cooling, 9.1 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 7593 counts. Moreover, since it was 27.2 mass% of nitrogen and 11.3 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the calcined powder was 1.8 m 2 / g.
(実施例11)
窒素ガス雰囲気下で焼成温度を900℃とし、保持時間を2時間とした以外は実施例5と同じ焼成操作をした。冷却後、得られた灰白色の焼成粉6.9gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は9364countsであった。またCHN元素分析を行ったところ窒素27.1質量%、炭素11.4質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。またこの焼成粉の比表面積は0.6m2/gであった。 (Example 11)
The same baking operation as in Example 5 was performed except that the baking temperature was 900 ° C. and the holding time was 2 hours in a nitrogen gas atmosphere. After cooling, 6.9 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 9364 counts. Moreover, since it was 27.1 mass% of nitrogen and 11.4 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the calcined powder was 0.6 m 2 / g.
窒素ガス雰囲気下で焼成温度を900℃とし、保持時間を2時間とした以外は実施例5と同じ焼成操作をした。冷却後、得られた灰白色の焼成粉6.9gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は9364countsであった。またCHN元素分析を行ったところ窒素27.1質量%、炭素11.4質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。またこの焼成粉の比表面積は0.6m2/gであった。 (Example 11)
The same baking operation as in Example 5 was performed except that the baking temperature was 900 ° C. and the holding time was 2 hours in a nitrogen gas atmosphere. After cooling, 6.9 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 9364 counts. Moreover, since it was 27.1 mass% of nitrogen and 11.4 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The specific surface area of the calcined powder was 0.6 m 2 / g.
(実施例12)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉12.5gとシアヌル酸7.5gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が3.0モルになるようにシアヌル酸を添加した混合物を磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉にヘリウムガス(酸素濃度10ppm以下)を流量2リットル/分で1時間流してパージした後、ヘリウムガス流量を0.5リットル/分に変更して、ヘリウムガス雰囲気下490℃で6時間焼成した。冷却後、得られた灰白色の焼成粉9.4gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は4500countsであった。またCHN元素分析を行ったところ窒素27.0質量%、炭素11.1質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。 Example 12
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 12.5 g of this pulverized powder and 7.5 g of cyanuric acid are mixed, and a mixture obtained by adding cyanuric acid so that the nitrogen atom is 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate is porcelain. After putting in a crucible and covering with a porcelain lid, it was loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.). After purging with helium gas (oxygen concentration of 10 ppm or less) at a flow rate of 2 liters / minute for 1 hour in the gas replacement furnace, the helium gas flow rate was changed to 0.5 liters / minute and 490 ° C. in a helium gas atmosphere. For 6 hours. After cooling, 9.4 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4500 counts. Moreover, since it was 27.0 mass% of nitrogen and 11.1 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉12.5gとシアヌル酸7.5gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が3.0モルになるようにシアヌル酸を添加した混合物を磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉にヘリウムガス(酸素濃度10ppm以下)を流量2リットル/分で1時間流してパージした後、ヘリウムガス流量を0.5リットル/分に変更して、ヘリウムガス雰囲気下490℃で6時間焼成した。冷却後、得られた灰白色の焼成粉9.4gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は4500countsであった。またCHN元素分析を行ったところ窒素27.0質量%、炭素11.1質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。 Example 12
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 12.5 g of this pulverized powder and 7.5 g of cyanuric acid are mixed, and a mixture obtained by adding cyanuric acid so that the nitrogen atom is 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate is porcelain. After putting in a crucible and covering with a porcelain lid, it was loaded into a gas replacement furnace (manufactured by Denken Co., Ltd.). After purging with helium gas (oxygen concentration of 10 ppm or less) at a flow rate of 2 liters / minute for 1 hour in the gas replacement furnace, the helium gas flow rate was changed to 0.5 liters / minute and 490 ° C. in a helium gas atmosphere. For 6 hours. After cooling, 9.4 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 4500 counts. Moreover, since it was 27.0 mass% of nitrogen and 11.1 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%.
(実施例13)
合成例4で得られた塩基性シアヌル酸亜鉛の乾燥粉50gを家庭用ミキサーで6分間粉砕した。この塩基性シアヌル酸亜鉛の粉砕粉と該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が3.6モルとなるように計量したシアヌル酸38.5gをポリエチレン製の袋に密封し、袋ごと振って両方の粉を均一に混ぜた。この混合粉27gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下560℃で5時間焼成した。冷却後、得られた灰白色の焼成粉11.5gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は5633countsであった。またCHN元素分析を行ったところ窒素27.1質量%、炭素11.8質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。またこの焼成粉の比表面積は4.0m2/gであった。 (Example 13)
50 g of the dry powder of basic cyanuric acid obtained in Synthesis Example 4 was pulverized for 6 minutes with a household mixer. 38.5 g of cyanuric acid measured so that the nitrogen atom is 3.6 mol per 1 mol of zinc atom of the basic zinc cyanurate and the zinc atom of the basic cyanurate was sealed in a polyethylene bag. The bag was shaken to mix both powders uniformly. 27 g of this mixed powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute and purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 5 ° C. for 5 hours. After cooling, 11.5 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 5633counts. Moreover, since it was 27.1 mass% of nitrogen and 11.8 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The calcined powder had a specific surface area of 4.0 m 2 / g.
合成例4で得られた塩基性シアヌル酸亜鉛の乾燥粉50gを家庭用ミキサーで6分間粉砕した。この塩基性シアヌル酸亜鉛の粉砕粉と該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が3.6モルとなるように計量したシアヌル酸38.5gをポリエチレン製の袋に密封し、袋ごと振って両方の粉を均一に混ぜた。この混合粉27gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下560℃で5時間焼成した。冷却後、得られた灰白色の焼成粉11.5gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は5633countsであった。またCHN元素分析を行ったところ窒素27.1質量%、炭素11.8質量%であったため、この焼成粉のシアナミド亜鉛の含有率は100質量%と計算された。またこの焼成粉の比表面積は4.0m2/gであった。 (Example 13)
50 g of the dry powder of basic cyanuric acid obtained in Synthesis Example 4 was pulverized for 6 minutes with a household mixer. 38.5 g of cyanuric acid measured so that the nitrogen atom is 3.6 mol per 1 mol of zinc atom of the basic zinc cyanurate and the zinc atom of the basic cyanurate was sealed in a polyethylene bag. The bag was shaken to mix both powders uniformly. 27 g of this mixed powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute and purged with nitrogen, then the nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 5 ° C. for 5 hours. After cooling, 11.5 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 5633counts. Moreover, since it was 27.1 mass% of nitrogen and 11.8 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 100 mass%. The calcined powder had a specific surface area of 4.0 m 2 / g.
(実施例14)
合成例2で得られた白色スラリーの70℃乾燥粉30gを家庭用ミキサーで6分間粉砕した。この粉砕粉30gは、シアヌル酸亜鉛24gとシアヌル酸6gの混合粉である。この粉砕粉15gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた灰白色の焼成粉7.9gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は6800countsであった。またCHN元素分析を行ったところ窒素26.5質量%、炭素11.7質量%であったため、この焼成粉のシアナミド亜鉛の含有率は97質量%と計算された。また、この焼成粉の比表面積は6.2m2/gであった。焼成粉中の金属不純物の定量分析は、実施例2と同じ操作を行って、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム23ppm、カリウム4ppm、カルシウム5ppm、マグネシウム1ppm、鉛3ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 14)
30 g of 70 ° C. dry powder of the white slurry obtained in Synthesis Example 2 was pulverized for 6 minutes with a household mixer. 30 g of this pulverized powder is a mixed powder of 24 g of zinc cyanurate and 6 g of cyanuric acid. 15 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, and then purged with nitrogen. Baked at 6 ° C. for 6 hours. After cooling, 7.9 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 6800 counts. Moreover, since it was 26.5 mass% of nitrogen and 11.7 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 97 mass%. The specific surface area of the fired powder was 6.2 m 2 / g. The quantitative analysis of the metal impurities in the baked powder was performed in the same manner as in Example 2, and flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis were performed. As a result, metal impurities in the fired powder were sodium 23 ppm, potassium 4 ppm,calcium 5 ppm, magnesium 1 ppm, lead 3 ppm, and chromium 0 ppm. In addition, chlorine ions, sulfate ions, and nitrate ions in the fired powder were all 1 ppm or less.
合成例2で得られた白色スラリーの70℃乾燥粉30gを家庭用ミキサーで6分間粉砕した。この粉砕粉30gは、シアヌル酸亜鉛24gとシアヌル酸6gの混合粉である。この粉砕粉15gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた灰白色の焼成粉7.9gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛の回折ピークのみ検出され、ピークAの強度は6800countsであった。またCHN元素分析を行ったところ窒素26.5質量%、炭素11.7質量%であったため、この焼成粉のシアナミド亜鉛の含有率は97質量%と計算された。また、この焼成粉の比表面積は6.2m2/gであった。焼成粉中の金属不純物の定量分析は、実施例2と同じ操作を行って、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム23ppm、カリウム4ppm、カルシウム5ppm、マグネシウム1ppm、鉛3ppm、クロム0ppmであった。また、焼成粉中の塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 14)
30 g of 70 ° C. dry powder of the white slurry obtained in Synthesis Example 2 was pulverized for 6 minutes with a household mixer. 30 g of this pulverized powder is a mixed powder of 24 g of zinc cyanurate and 6 g of cyanuric acid. 15 g of this pulverized powder was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (manufactured by Denken). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute, and then purged with nitrogen. Baked at 6 ° C. for 6 hours. After cooling, 7.9 g of the obtained off-white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the diffraction peak of cyanamide zinc was detected, and the intensity of peak A was 6800 counts. Moreover, since it was 26.5 mass% of nitrogen and 11.7 mass% of carbon when the CHN elemental analysis was carried out, the cyanamide zinc content of this baked powder was calculated with 97 mass%. The specific surface area of the fired powder was 6.2 m 2 / g. The quantitative analysis of the metal impurities in the baked powder was performed in the same manner as in Example 2, and flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis were performed. As a result, metal impurities in the fired powder were sodium 23 ppm, potassium 4 ppm,
(実施例15)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉4.2gと尿素6.5gとを混合し、塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が7.2モルとなるように尿素を添加した。該混合物10.0gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下600℃で5時間焼成した。冷却後、得られた灰白色の焼成粉2.2gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛、酸化亜鉛の回折ピーク及び帰属不明の微小なピークが検出された。ピークAの強度は1959counts、ピークBの強度は110countsであった。実施例2と同じ操作をして上澄液を採取し、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム10ppm、カリウム3ppm、カルシウム4ppm、マグネシウム1ppm、鉛2ppm、クロム0ppmであった。また、塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 15)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 4.2 g of this pulverized powder and 6.5 g of urea were mixed, and urea was added so that the nitrogen atom was 7.2 mol with respect to 1 mol of zinc atom of basic zinc cyanurate. 10.0 g of the mixture was placed in a porcelain crucible, covered with a porcelain lid, and then charged into a gas replacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute and purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 5 ° C. for 5 hours. After cooling, 2.2 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, diffraction peaks of cyanamide zinc and zinc oxide and a minute peak with unknown attribution were detected. The intensity of peak A was 1959 counts, and the intensity of peak B was 110 counts. The same operation as in Example 2 was performed, and the supernatant was collected and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis. As a result, metal impurities in the fired powder weresodium 10 ppm, potassium 3 ppm, calcium 4 ppm, magnesium 1 ppm, lead 2 ppm, and chromium 0 ppm. Moreover, chlorine ion, sulfate ion, and nitrate ion were all 1 ppm or less.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉4.2gと尿素6.5gとを混合し、塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子が7.2モルとなるように尿素を添加した。該混合物10.0gを磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン製)に装填した。その後、ガス置換炉に窒素ガス(酸素濃度1ppm以下)を流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して、窒素ガス雰囲気下600℃で5時間焼成した。冷却後、得られた灰白色の焼成粉2.2gを取出し、粉末X線回折分析を行ったところ、シアナミド亜鉛、酸化亜鉛の回折ピーク及び帰属不明の微小なピークが検出された。ピークAの強度は1959counts、ピークBの強度は110countsであった。実施例2と同じ操作をして上澄液を採取し、炎光分光分析、ICP発光分光分析及びイオンクロマトグラフ分析を行なった。この結果、焼成粉中の金属不純物は、ナトリウム10ppm、カリウム3ppm、カルシウム4ppm、マグネシウム1ppm、鉛2ppm、クロム0ppmであった。また、塩素イオン、硫酸イオン、硝酸イオンは、いずれも1ppm以下であった。 (Example 15)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 4.2 g of this pulverized powder and 6.5 g of urea were mixed, and urea was added so that the nitrogen atom was 7.2 mol with respect to 1 mol of zinc atom of basic zinc cyanurate. 10.0 g of the mixture was placed in a porcelain crucible, covered with a porcelain lid, and then charged into a gas replacement furnace (manufactured by Denken Co., Ltd.). Thereafter, nitrogen gas (oxygen concentration of 1 ppm or less) was flowed into the gas replacement furnace for 1 hour at a flow rate of 2 liters / minute and purged with nitrogen. Then, the nitrogen gas flow rate was changed to 0.5 liters / minute, Baked at 5 ° C. for 5 hours. After cooling, 2.2 g of the obtained grayish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, diffraction peaks of cyanamide zinc and zinc oxide and a minute peak with unknown attribution were detected. The intensity of peak A was 1959 counts, and the intensity of peak B was 110 counts. The same operation as in Example 2 was performed, and the supernatant was collected and subjected to flame spectroscopic analysis, ICP emission spectroscopic analysis, and ion chromatographic analysis. As a result, metal impurities in the fired powder were
(比較例1)
窒素ガス雰囲気下での焼成温度を450℃に変更した以外は実施例1と同じ焼成操作を行った。冷却後、得られた薄ピンク色の焼成粉14.5gを取出し、粉末X線回折分析を行ったところ、酸化亜鉛に相当するピークB及び帰属不明のピークが検出された。ピークBの回折強度は775countsと小さかった。シアナミド亜鉛の回折ピークは全く検出されなかった。 (Comparative Example 1)
The same baking operation as Example 1 was performed except having changed the baking temperature in nitrogen gas atmosphere into 450 degreeC. After cooling, 14.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as low as 775counts. No diffraction peak of cyanamide zinc was detected.
窒素ガス雰囲気下での焼成温度を450℃に変更した以外は実施例1と同じ焼成操作を行った。冷却後、得られた薄ピンク色の焼成粉14.5gを取出し、粉末X線回折分析を行ったところ、酸化亜鉛に相当するピークB及び帰属不明のピークが検出された。ピークBの回折強度は775countsと小さかった。シアナミド亜鉛の回折ピークは全く検出されなかった。 (Comparative Example 1)
The same baking operation as Example 1 was performed except having changed the baking temperature in nitrogen gas atmosphere into 450 degreeC. After cooling, 14.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as low as 775counts. No diffraction peak of cyanamide zinc was detected.
(比較例2)
窒素ガス雰囲気下での焼成温度を450℃に変更した以外は実施例3と同じ焼成操作を行った。冷却後、得られた薄ピンク色の焼成粉14.5gを取出し、粉末X線回折分析を行ったところ、酸化亜鉛に相当するピークB及び帰属不明のピークが検出された。ピークBの回折強度は821countsと小さかった。シアナミド亜鉛の回折ピークは全く検出されなかった。 (Comparative Example 2)
The same baking operation as Example 3 was performed except having changed the baking temperature in nitrogen gas atmosphere into 450 degreeC. After cooling, 14.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as low as 821counts. No diffraction peak of cyanamide zinc was detected.
窒素ガス雰囲気下での焼成温度を450℃に変更した以外は実施例3と同じ焼成操作を行った。冷却後、得られた薄ピンク色の焼成粉14.5gを取出し、粉末X線回折分析を行ったところ、酸化亜鉛に相当するピークB及び帰属不明のピークが検出された。ピークBの回折強度は821countsと小さかった。シアナミド亜鉛の回折ピークは全く検出されなかった。 (Comparative Example 2)
The same baking operation as Example 3 was performed except having changed the baking temperature in nitrogen gas atmosphere into 450 degreeC. After cooling, 14.5 g of the obtained light pink baked powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as low as 821counts. No diffraction peak of cyanamide zinc was detected.
(比較例3)
窒素ガス雰囲気下での焼成温度を430℃に変更した以外は実施例4と同じ焼成操作を行った。冷却後、得られた薄ピンクを帯びた白色の焼成粉11.1gを取出し、粉末X線回折分析を行ったところ、酸化亜鉛に相当するピークB及び帰属不明のピークが検出された。ピークBの回折強度は266countsと小さかった。シアナミド亜鉛の回折ピークは全く検出されなかった。 (Comparative Example 3)
The same baking operation as Example 4 was performed except having changed the calcination temperature in nitrogen gas atmosphere to 430 degreeC. After cooling, 11.1 g of the obtained light pinkish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as small as 266counts. No diffraction peak of cyanamide zinc was detected.
窒素ガス雰囲気下での焼成温度を430℃に変更した以外は実施例4と同じ焼成操作を行った。冷却後、得られた薄ピンクを帯びた白色の焼成粉11.1gを取出し、粉末X線回折分析を行ったところ、酸化亜鉛に相当するピークB及び帰属不明のピークが検出された。ピークBの回折強度は266countsと小さかった。シアナミド亜鉛の回折ピークは全く検出されなかった。 (Comparative Example 3)
The same baking operation as Example 4 was performed except having changed the calcination temperature in nitrogen gas atmosphere to 430 degreeC. After cooling, 11.1 g of the obtained light pinkish white calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a peak B corresponding to zinc oxide and an unidentified peak were detected. The diffraction intensity of peak B was as small as 266counts. No diffraction peak of cyanamide zinc was detected.
(比較例4)
窒素ガス雰囲気下での焼成温度を1000℃に変更した以外は実施例5と同じ焼成操作を行った。冷却後、ルツボの中を確認したが残留物が全くなかった。シアナミド亜鉛は熱分解して消滅していた。 (Comparative Example 4)
The same baking operation as Example 5 was performed except having changed the baking temperature in nitrogen gas atmosphere into 1000 degreeC. After cooling, the inside of the crucible was confirmed, but there was no residue. The cyanamide zinc was destroyed by thermal decomposition.
窒素ガス雰囲気下での焼成温度を1000℃に変更した以外は実施例5と同じ焼成操作を行った。冷却後、ルツボの中を確認したが残留物が全くなかった。シアナミド亜鉛は熱分解して消滅していた。 (Comparative Example 4)
The same baking operation as Example 5 was performed except having changed the baking temperature in nitrogen gas atmosphere into 1000 degreeC. After cooling, the inside of the crucible was confirmed, but there was no residue. The cyanamide zinc was destroyed by thermal decomposition.
(比較例5)
窒素ガス雰囲気下での焼成温度を1000℃に変更した以外は実施例3と同じ焼成操作を行った。冷却後、ルツボの中を確認したが残留物が全くなかった。シアナミド亜鉛は熱分解して消滅していた。 (Comparative Example 5)
The same baking operation as Example 3 was performed except having changed the baking temperature in nitrogen gas atmosphere into 1000 degreeC. After cooling, the inside of the crucible was confirmed, but there was no residue. The cyanamide zinc was destroyed by thermal decomposition.
窒素ガス雰囲気下での焼成温度を1000℃に変更した以外は実施例3と同じ焼成操作を行った。冷却後、ルツボの中を確認したが残留物が全くなかった。シアナミド亜鉛は熱分解して消滅していた。 (Comparative Example 5)
The same baking operation as Example 3 was performed except having changed the baking temperature in nitrogen gas atmosphere into 1000 degreeC. After cooling, the inside of the crucible was confirmed, but there was no residue. The cyanamide zinc was destroyed by thermal decomposition.
(比較例6)
窒素ガス雰囲気の代わりに空気雰囲気とした以外は実施例5と同じ焼成操作をした。冷却後、得られた肌色の焼成粉7.4gを取り出し、粉末X線回折分析を行ったところ、酸化亜鉛の回折ピークだけが検出され、シアナミド亜鉛のピークは検出されなかった。また、酸化亜鉛に相当するピークBの強度は3847countsであった。 (Comparative Example 6)
The same baking operation as in Example 5 was performed except that an air atmosphere was used instead of the nitrogen gas atmosphere. After cooling, 7.4 g of the obtained flesh-colored calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the zinc oxide diffraction peak was detected, and the cyanamide zinc peak was not detected. The intensity of peak B corresponding to zinc oxide was 3847 counts.
窒素ガス雰囲気の代わりに空気雰囲気とした以外は実施例5と同じ焼成操作をした。冷却後、得られた肌色の焼成粉7.4gを取り出し、粉末X線回折分析を行ったところ、酸化亜鉛の回折ピークだけが検出され、シアナミド亜鉛のピークは検出されなかった。また、酸化亜鉛に相当するピークBの強度は3847countsであった。 (Comparative Example 6)
The same baking operation as in Example 5 was performed except that an air atmosphere was used instead of the nitrogen gas atmosphere. After cooling, 7.4 g of the obtained flesh-colored calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, only the zinc oxide diffraction peak was detected, and the cyanamide zinc peak was not detected. The intensity of peak B corresponding to zinc oxide was 3847 counts.
(比較例7)
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉12.5gとシアヌル酸7.5gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子を3.0モルとなるようにシアヌル酸を添加した。該混合物20.0gを両端が直径1cm、長さ20cm、中心部を直径5cm、長さが10cmになるように太くした石英ガラス製焼成菅に入れ、水素ガス20ml/分と窒素ガス180ml/分の混合ガスの気流中、600℃で5時間焼成した。冷却後、得られた焼成粉を取出し、粉末X線回折分析を行ったところ、酸化亜鉛と金属亜鉛の回折ピークが検出され、シアナミド亜鉛のピークは検出されなかった。また酸化亜鉛に相当するピークBの強度は2934countsであった。得られた焼成粉は、肌色と金属色の混ざった外観であった。 (Comparative Example 7)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 12.5 g of this pulverized powder and 7.5 g of cyanuric acid were mixed, and cyanuric acid was added so that the nitrogen atom would be 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 20.0 g of the mixture was placed in a quartz glass baking jar thickened so that both ends had a diameter of 1 cm, a length of 20 cm, a center portion of a diameter of 5 cm, and a length of 10 cm,hydrogen gas 20 ml / min and nitrogen gas 180 ml / min. Was fired at 600 ° C. for 5 hours in a mixed gas stream. After cooling, the obtained calcined powder was taken out and subjected to powder X-ray diffraction analysis. As a result, a diffraction peak of zinc oxide and metal zinc was detected, and a peak of cyanamide zinc was not detected. The intensity of peak B corresponding to zinc oxide was 2934counts. The obtained fired powder had an appearance in which skin color and metal color were mixed.
合成例1で得られた塩基性シアヌル酸亜鉛の乾燥ブロック30gを家庭用ミキサーで6分間粉砕した。この粉砕粉12.5gとシアヌル酸7.5gとを混合し、該塩基性シアヌル酸亜鉛の亜鉛原子1モルに対して窒素原子を3.0モルとなるようにシアヌル酸を添加した。該混合物20.0gを両端が直径1cm、長さ20cm、中心部を直径5cm、長さが10cmになるように太くした石英ガラス製焼成菅に入れ、水素ガス20ml/分と窒素ガス180ml/分の混合ガスの気流中、600℃で5時間焼成した。冷却後、得られた焼成粉を取出し、粉末X線回折分析を行ったところ、酸化亜鉛と金属亜鉛の回折ピークが検出され、シアナミド亜鉛のピークは検出されなかった。また酸化亜鉛に相当するピークBの強度は2934countsであった。得られた焼成粉は、肌色と金属色の混ざった外観であった。 (Comparative Example 7)
30 g of the basic zinc cyanurate block obtained in Synthesis Example 1 was pulverized with a household mixer for 6 minutes. 12.5 g of this pulverized powder and 7.5 g of cyanuric acid were mixed, and cyanuric acid was added so that the nitrogen atom would be 3.0 mol with respect to 1 mol of zinc atom of the basic zinc cyanurate. 20.0 g of the mixture was placed in a quartz glass baking jar thickened so that both ends had a diameter of 1 cm, a length of 20 cm, a center portion of a diameter of 5 cm, and a length of 10 cm,
(比較例8)
亜鉛源として市販の酸化亜鉛粉末(堺化学(株)製二種酸化亜鉛)6.0gを用いた以外は実施例2と同じ焼成操作を行った。冷却後、得られた白色焼成粉6.0gを取出し、粉末X線回折装置で同定したところ、酸化亜鉛に相当するピークBのみ検出され、シアナミド亜鉛に相当する回折ピークは検出されなかった。 (Comparative Example 8)
The same baking operation as in Example 2 was performed except that 6.0 g of a commercially available zinc oxide powder (two types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was used as the zinc source. After cooling, 6.0 g of the obtained white calcined powder was taken out and identified with a powder X-ray diffractometer. As a result, only peak B corresponding to zinc oxide was detected, and no diffraction peak corresponding to cyanamide zinc was detected.
亜鉛源として市販の酸化亜鉛粉末(堺化学(株)製二種酸化亜鉛)6.0gを用いた以外は実施例2と同じ焼成操作を行った。冷却後、得られた白色焼成粉6.0gを取出し、粉末X線回折装置で同定したところ、酸化亜鉛に相当するピークBのみ検出され、シアナミド亜鉛に相当する回折ピークは検出されなかった。 (Comparative Example 8)
The same baking operation as in Example 2 was performed except that 6.0 g of a commercially available zinc oxide powder (two types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) was used as the zinc source. After cooling, 6.0 g of the obtained white calcined powder was taken out and identified with a powder X-ray diffractometer. As a result, only peak B corresponding to zinc oxide was detected, and no diffraction peak corresponding to cyanamide zinc was detected.
(比較例9)
市販の酸化亜鉛粉末(堺化学(株)製二種酸化亜鉛)6.0gとシアヌル酸11.4gを混合し、酸化亜鉛の亜鉛原子1モルに対して窒素原子を3.6モルになるようにシアヌル酸を添加した。該混合物を磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン)に装填した後、ガス置換炉に酸素濃度1ppm以下の窒素ガスを流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた肌色の焼成粉6.8gを取出し、粉末X線回折装置で同定したところ、シアナミド亜鉛と酸化亜鉛の混合物であり、ピークAの強度は240counts、ピークBの強度は3966countsであった。またCHN元素分析したところ窒素分は1.4質量%、炭素分は0.6質量%であったため、この焼成粉のシアナミド亜鉛の含有率は5質量%と計算された。
実施例1~15、比較例1~9を表1にまとめた。 (Comparative Example 9)
6.0 g of commercially available zinc oxide powder (two types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) and 11.4 g of cyanuric acid are mixed so that the nitrogen atom becomes 3.6 mol with respect to 1 mol of zinc atom of zinc oxide. Was added with cyanuric acid. The mixture was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (Denken Co., Ltd.). Then, nitrogen gas having an oxygen concentration of 1 ppm or less was flowed into the gas replacement furnace at a flow rate of 2 liters / minute. After purging with nitrogen for a period of time, the nitrogen gas flow rate was changed to 0.5 liter / min, and firing was performed at 490 ° C. for 6 hours in a nitrogen gas atmosphere. After cooling, 6.8 g of the obtained flesh-colored calcined powder was taken out and identified with a powder X-ray diffractometer. It was a mixture of cyanamide zinc and zinc oxide. The intensity of peak A was 240 counts, and the intensity of peak B was 3966 counts. there were. Further, when CHN elemental analysis was performed, the nitrogen content was 1.4% by mass and the carbon content was 0.6% by mass. Therefore, the cyanamide zinc content of the calcined powder was calculated to be 5% by mass.
Examples 1 to 15 and Comparative Examples 1 to 9 are summarized in Table 1.
市販の酸化亜鉛粉末(堺化学(株)製二種酸化亜鉛)6.0gとシアヌル酸11.4gを混合し、酸化亜鉛の亜鉛原子1モルに対して窒素原子を3.6モルになるようにシアヌル酸を添加した。該混合物を磁器製ルツボに入れ、磁器製蓋を被せた後、ガス置換炉((株)デンケン)に装填した後、ガス置換炉に酸素濃度1ppm以下の窒素ガスを流量2リットル/分で1時間流して窒素パージした後、窒素ガス流量を0.5リットル/分に変更して窒素ガス雰囲気下490℃で6時間焼成した。冷却後、得られた肌色の焼成粉6.8gを取出し、粉末X線回折装置で同定したところ、シアナミド亜鉛と酸化亜鉛の混合物であり、ピークAの強度は240counts、ピークBの強度は3966countsであった。またCHN元素分析したところ窒素分は1.4質量%、炭素分は0.6質量%であったため、この焼成粉のシアナミド亜鉛の含有率は5質量%と計算された。
実施例1~15、比較例1~9を表1にまとめた。 (Comparative Example 9)
6.0 g of commercially available zinc oxide powder (two types of zinc oxide manufactured by Sakai Chemical Co., Ltd.) and 11.4 g of cyanuric acid are mixed so that the nitrogen atom becomes 3.6 mol with respect to 1 mol of zinc atom of zinc oxide. Was added with cyanuric acid. The mixture was placed in a porcelain crucible, covered with a porcelain lid, and then loaded into a gas replacement furnace (Denken Co., Ltd.). Then, nitrogen gas having an oxygen concentration of 1 ppm or less was flowed into the gas replacement furnace at a flow rate of 2 liters / minute. After purging with nitrogen for a period of time, the nitrogen gas flow rate was changed to 0.5 liter / min, and firing was performed at 490 ° C. for 6 hours in a nitrogen gas atmosphere. After cooling, 6.8 g of the obtained flesh-colored calcined powder was taken out and identified with a powder X-ray diffractometer. It was a mixture of cyanamide zinc and zinc oxide. The intensity of peak A was 240 counts, and the intensity of peak B was 3966 counts. there were. Further, when CHN elemental analysis was performed, the nitrogen content was 1.4% by mass and the carbon content was 0.6% by mass. Therefore, the cyanamide zinc content of the calcined powder was calculated to be 5% by mass.
Examples 1 to 15 and Comparative Examples 1 to 9 are summarized in Table 1.
(防錆評価)
JISK5625に準拠し、フタル酸樹脂ワニス(乾性油脂肪変性フタル酸樹脂50部をキシレン50部で溶かしたもの)4.0gと実施例7、実施例8又は実施例9で得られたシアナミド亜鉛を含有する焼成粉4.0gを100mlのビーカーに入れ、ガラス棒で十分に攪拌して分散し、それぞれ塗料を調製した。耐水研磨紙によって調製した鋼板SPCC-SS(150mm×70mm×0.8mm)に調製した塗料1.0gをはけ塗りした後、40℃で乾燥させた。更に2時間乾燥後、同じ塗料1.0gを最初の塗膜の上にはけ塗りした後、40℃で乾燥させた。塗膜が形成された鋼板を各塗料につき3枚づつ作製した。該鋼板の塗膜面をナイフでクロス傷を付けた後、裏面を保護シールで覆い、試験片を作製した。比較として、シアナミド亜鉛の代わりに鉛系防錆顔料の鉛丹(NIケミテック(株)製)、市販のシアナミド鉛(商品名:シアナミ(キクチカラー(株)製)比表面積3.0m2/g)、市販のシアナミド亜鉛カルシウム系無機顔料(商品名:LFボウセイZK-S2(キクチカラー(株)製)比表面積11.1m2/g、シアナミド亜鉛の含有率50質量%、酸化亜鉛40重量%、炭酸カルシウム10質量%)を用いて各々試験片を作製した。 (Rust prevention evaluation)
Based on JISK5625, 4.0 g of phthalic acid resin varnish (50 parts of dry oil / fat-modified phthalic acid resin dissolved in 50 parts of xylene) and cyanamide zinc obtained in Example 7, Example 8 or Example 9 were used. 4.0 g of the calcined powder contained was put into a 100 ml beaker and dispersed with sufficient stirring with a glass rod to prepare paints. After coating 1.0 g of the prepared paint on a steel plate SPCC-SS (150 mm × 70 mm × 0.8 mm) prepared with water-resistant abrasive paper, it was dried at 40 ° C. After further drying for 2 hours, 1.0 g of the same paint was brushed on the first coating film and then dried at 40 ° C. Three steel plates on which a coating film was formed were prepared for each paint. After the coating surface of the steel plate was cross-scratched with a knife, the back surface was covered with a protective seal to prepare a test piece. For comparison, a lead-based anticorrosive pigment, red lead (manufactured by NI Chemtech Co., Ltd.) instead of cyanamide zinc, a commercially available cyanamide lead (trade name: cyanami (manufactured by Kikuchi Color Co., Ltd.)) specific surface area 3.0 m 2 / g ), Commercially available cyanamide zinc calcium-based inorganic pigment (trade name: LF Bowsei ZK-S2 (manufactured by Kikuchi Color Co., Ltd.)) specific surface area 11.1 m 2 / g,cyanamide zinc content 50 mass%, zinc oxide 40 wt% , Each test piece was prepared using 10% by mass of calcium carbonate.
JISK5625に準拠し、フタル酸樹脂ワニス(乾性油脂肪変性フタル酸樹脂50部をキシレン50部で溶かしたもの)4.0gと実施例7、実施例8又は実施例9で得られたシアナミド亜鉛を含有する焼成粉4.0gを100mlのビーカーに入れ、ガラス棒で十分に攪拌して分散し、それぞれ塗料を調製した。耐水研磨紙によって調製した鋼板SPCC-SS(150mm×70mm×0.8mm)に調製した塗料1.0gをはけ塗りした後、40℃で乾燥させた。更に2時間乾燥後、同じ塗料1.0gを最初の塗膜の上にはけ塗りした後、40℃で乾燥させた。塗膜が形成された鋼板を各塗料につき3枚づつ作製した。該鋼板の塗膜面をナイフでクロス傷を付けた後、裏面を保護シールで覆い、試験片を作製した。比較として、シアナミド亜鉛の代わりに鉛系防錆顔料の鉛丹(NIケミテック(株)製)、市販のシアナミド鉛(商品名:シアナミ(キクチカラー(株)製)比表面積3.0m2/g)、市販のシアナミド亜鉛カルシウム系無機顔料(商品名:LFボウセイZK-S2(キクチカラー(株)製)比表面積11.1m2/g、シアナミド亜鉛の含有率50質量%、酸化亜鉛40重量%、炭酸カルシウム10質量%)を用いて各々試験片を作製した。 (Rust prevention evaluation)
Based on JISK5625, 4.0 g of phthalic acid resin varnish (50 parts of dry oil / fat-modified phthalic acid resin dissolved in 50 parts of xylene) and cyanamide zinc obtained in Example 7, Example 8 or Example 9 were used. 4.0 g of the calcined powder contained was put into a 100 ml beaker and dispersed with sufficient stirring with a glass rod to prepare paints. After coating 1.0 g of the prepared paint on a steel plate SPCC-SS (150 mm × 70 mm × 0.8 mm) prepared with water-resistant abrasive paper, it was dried at 40 ° C. After further drying for 2 hours, 1.0 g of the same paint was brushed on the first coating film and then dried at 40 ° C. Three steel plates on which a coating film was formed were prepared for each paint. After the coating surface of the steel plate was cross-scratched with a knife, the back surface was covered with a protective seal to prepare a test piece. For comparison, a lead-based anticorrosive pigment, red lead (manufactured by NI Chemtech Co., Ltd.) instead of cyanamide zinc, a commercially available cyanamide lead (trade name: cyanami (manufactured by Kikuchi Color Co., Ltd.)) specific surface area 3.0 m 2 / g ), Commercially available cyanamide zinc calcium-based inorganic pigment (trade name: LF Bowsei ZK-S2 (manufactured by Kikuchi Color Co., Ltd.)) specific surface area 11.1 m 2 / g,
各々3枚の試験片を複合サイクル試験機(スガ試験機(株)製)内に設置し、30℃で5質量%の食塩水を5分間塩水噴霧した後、30℃湿度95%で1.5時間湿潤試験をし、続いて50℃で2時間熱風乾燥した後、30℃で2時間温風乾燥する操作を1サイクル(所要時間6時間)とした。このサイクルを12回行なった後、試験片を取出し、水道水で洗浄した後、25℃で乾燥した。試験片を目視によって、塗膜の膨れ、はがれ及び錆の有無を観察した。
Three test pieces each were placed in a combined cycle tester (manufactured by Suga Test Instruments Co., Ltd.), sprayed with 5% by weight saline at 30 ° C. for 5 minutes, and then 1. The wet test was conducted for 5 hours, followed by hot air drying at 50 ° C. for 2 hours, and then hot air drying at 30 ° C. for 2 hours was defined as one cycle (required time 6 hours). After performing this cycle 12 times, the test piece was taken out, washed with tap water, and dried at 25 ° C. The test piece was visually observed for the presence or absence of swelling, peeling and rust of the coating film.
表2の通り、本発明で得られたシアナミドを用いた防錆性評価用塗料(評価例1~3)は、鉛系防錆顔料である鉛丹(評価例4)、市販のシアナミド鉛(評価例5)を用いた防錆塗料よりも錆の発生が少なく、防錆性能が優れていた。更に、シアナミド亜鉛カルシウム系無機顔料(評価例6)と比較して錆の発生が明らかに少なく、防錆性能が非常に優れていることが判明した。
As shown in Table 2, paints for evaluating rust prevention using the cyanamide obtained in the present invention (Evaluation Examples 1 to 3) are lead rust pigments (Evaluation Example 4), commercially available cyanamide lead (evaluation example 4). Rust generation was less than that of the anticorrosive paint using Evaluation Example 5), and the antirust performance was excellent. Furthermore, it was found that the occurrence of rust was clearly less than that of the cyanamide zinc calcium based inorganic pigment (Evaluation Example 6), and the rust prevention performance was very excellent.
本発明によれば、防錆性能の高いシアナミド亜鉛を製造することができ、得られたシアナミド亜鉛により防錆性能の優れた鉛・クロムフリーの無公害防錆塗料を製造することができる。
According to the present invention, it is possible to produce cyanamide zinc having high rust prevention performance, and it is possible to produce a lead / chromium-free pollution-free rust-proof paint having excellent rust prevention performance from the obtained cyanamide zinc.
Claims (5)
- シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛を窒素ガス又は第18族元素の希ガスの雰囲気において、460℃以上900℃以下で焼成することを特徴とするシアナミド亜鉛の製造方法。 A method for producing cyanamide zinc, characterized in that zinc cyanurate or basic zinc cyanurate is baked at 460 ° C. or higher and 900 ° C. or lower in an atmosphere of nitrogen gas or a rare gas of Group 18 element.
- シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛にあらかじめ窒素含有有機化合物を混合することを特徴とする請求項1に記載のシアナミド亜鉛の製造方法。 The method for producing cyanamide zinc according to claim 1, wherein a nitrogen-containing organic compound is mixed in advance with zinc cyanurate or basic zinc cyanurate.
- 請求項2に記載のシアナミド亜鉛の製造方法において、シアヌル酸亜鉛又は塩基性シアヌル酸亜鉛と窒素含有有機化合物とを混合する際に、該混合物中の亜鉛原子に対する窒素原子のモル比(N/Zn)を3以上とするシアナミド亜鉛の製造方法。 In the method for producing cyanamide zinc according to claim 2, when mixing zinc cyanurate or basic zinc cyanurate and a nitrogen-containing organic compound, the molar ratio of nitrogen atom to zinc atom in the mixture (N / Zn) ) Is a method for producing cyanamide zinc having 3 or more.
- 前記窒素含有有機化合物がシアヌル酸又は尿素である請求項2又は3に記載のシアナミド亜鉛の製造方法。 The method for producing cyanamide zinc according to claim 2 or 3, wherein the nitrogen-containing organic compound is cyanuric acid or urea.
- 下記(a)、(b)及び(c)の成分を配合することを特徴とする防錆顔料組成物の製造方法。
(a)油性バインダー又は合成樹脂バインダー
(b)水、テレピン油、ミネラルスピリット、トルエン、キシレン、メチルイソブチルケトン、セルソルブアセテート、エタノール、ブタノール、イソプロピルアルコール、シクロヘキサン、酢酸エチル、酢酸ブチルからなる群から選ばれる少なくとも一種以上の希釈剤
(c)請求項1~4のいずれか一項に記載の方法により得られるシアナミド亜鉛 The manufacturing method of the antirust pigment composition characterized by mix | blending the component of following (a), (b) and (c).
(A) Oil-based binder or synthetic resin binder (b) From the group consisting of water, turpentine oil, mineral spirit, toluene, xylene, methyl isobutyl ketone, cellosolve acetate, ethanol, butanol, isopropyl alcohol, cyclohexane, ethyl acetate, butyl acetate At least one or more selected diluent (c) cyanamide zinc obtained by the method according to any one of claims 1 to 4.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110194468A (en) * | 2019-06-10 | 2019-09-03 | 陕西科技大学 | A kind of In2.24(NCN)3Raw powder's production technology |
CN111994921A (en) * | 2020-08-04 | 2020-11-27 | 宁夏锦华化工有限公司 | Monocyanamide decoloring method |
CN116285692A (en) * | 2019-09-20 | 2023-06-23 | 日产化学株式会社 | Coating composition, method for producing same, and coating film |
Families Citing this family (2)
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CN110228817A (en) * | 2019-06-10 | 2019-09-13 | 陕西师范大学 | A method of preparing a nanometer cyanogen ammonification indium powder |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62288113A (en) * | 1986-06-03 | 1987-12-15 | Kyowa Gas Chem Ind Co Ltd | Production of aqueous solution of calcium dicyanamide |
JPH0841375A (en) * | 1994-08-02 | 1996-02-13 | Nippon Chem Ind Co Ltd | White rustproof pigment and its production |
JPH0841374A (en) * | 1994-08-02 | 1996-02-13 | Nippon Chem Ind Co Ltd | White rustproof pigment and its production |
JPH0841376A (en) * | 1994-08-02 | 1996-02-13 | Nippon Chem Ind Co Ltd | White rustproof pigment and its production |
JPH11256063A (en) * | 1998-03-06 | 1999-09-21 | Toho Ganryo Kogyo Kk | Rustproof pigment and production thereof |
JP2006206873A (en) * | 2004-12-28 | 2006-08-10 | Kansai Paint Co Ltd | Coating composition |
-
2012
- 2012-03-23 JP JP2012067598A patent/JP2015110486A/en active Pending
-
2013
- 2013-03-15 WO PCT/JP2013/057476 patent/WO2013141164A1/en active Application Filing
- 2013-03-21 TW TW102110047A patent/TW201406659A/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62288113A (en) * | 1986-06-03 | 1987-12-15 | Kyowa Gas Chem Ind Co Ltd | Production of aqueous solution of calcium dicyanamide |
JPH0841375A (en) * | 1994-08-02 | 1996-02-13 | Nippon Chem Ind Co Ltd | White rustproof pigment and its production |
JPH0841374A (en) * | 1994-08-02 | 1996-02-13 | Nippon Chem Ind Co Ltd | White rustproof pigment and its production |
JPH0841376A (en) * | 1994-08-02 | 1996-02-13 | Nippon Chem Ind Co Ltd | White rustproof pigment and its production |
JPH11256063A (en) * | 1998-03-06 | 1999-09-21 | Toho Ganryo Kogyo Kk | Rustproof pigment and production thereof |
JP2006206873A (en) * | 2004-12-28 | 2006-08-10 | Kansai Paint Co Ltd | Coating composition |
Cited By (4)
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CN110194468B (en) * | 2019-06-10 | 2022-06-14 | 陕西科技大学 | In2.24(NCN)3Method for preparing powder |
CN116285692A (en) * | 2019-09-20 | 2023-06-23 | 日产化学株式会社 | Coating composition, method for producing same, and coating film |
CN111994921A (en) * | 2020-08-04 | 2020-11-27 | 宁夏锦华化工有限公司 | Monocyanamide decoloring method |
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