JPH02175604A - Production of copper phosphite compound - Google Patents
Production of copper phosphite compoundInfo
- Publication number
- JPH02175604A JPH02175604A JP33205888A JP33205888A JPH02175604A JP H02175604 A JPH02175604 A JP H02175604A JP 33205888 A JP33205888 A JP 33205888A JP 33205888 A JP33205888 A JP 33205888A JP H02175604 A JPH02175604 A JP H02175604A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- compound
- phosphorous acid
- reaction
- phosphite compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 copper phosphite compound Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005751 Copper oxide Substances 0.000 claims abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 7
- 238000010303 mechanochemical reaction Methods 0.000 claims abstract description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 5
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 3
- KZEXYOGRFYDXLQ-UHFFFAOYSA-K C([O-])([O-])=O.[OH-].[Cu+3] Chemical compound C([O-])([O-])=O.[OH-].[Cu+3] KZEXYOGRFYDXLQ-UHFFFAOYSA-K 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 abstract description 14
- 150000001880 copper compounds Chemical class 0.000 abstract description 14
- 238000004898 kneading Methods 0.000 abstract description 14
- 239000010949 copper Substances 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 5
- WOLVYCFDDSCRDJ-UHFFFAOYSA-L copper;oxido hydrogen carbonate Chemical compound [Cu+2].OOC([O-])=O.OOC([O-])=O WOLVYCFDDSCRDJ-UHFFFAOYSA-L 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- NHQSYENHCTXNIG-UHFFFAOYSA-N [Cu+3].[O-]P([O-])[O-] Chemical compound [Cu+3].[O-]P([O-])[O-] NHQSYENHCTXNIG-UHFFFAOYSA-N 0.000 description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PVLIWNWMRNQALM-UHFFFAOYSA-L O.O.S(=O)([O-])[O-].[Cu+2] Chemical group O.O.S(=O)([O-])[O-].[Cu+2] PVLIWNWMRNQALM-UHFFFAOYSA-L 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- FMWMEQINULDRBI-UHFFFAOYSA-L copper;sulfite Chemical compound [Cu+2].[O-]S([O-])=O FMWMEQINULDRBI-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/163—Phosphorous acid; Salts thereof
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は亜リン酸銅化合物の製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for producing a copper phosphite compound.
［従来の技術］
亜リン酸銅は防かび・防菌剤、導電性剤、ポリマー安定
剤等とじで塗料やプラスチックに配合される有用な化合
物である。そして、亜リン酸銅は、Ｃ）通常、亜リン酸
水溶液にヒドロキシ炭酸銅を溶解し、この溶液を真空濃
縮することにより製造されている。[Prior Art] Copper phosphite is a useful compound that is incorporated into paints and plastics as a fungicide, antibacterial agent, conductive agent, polymer stabilizer, etc. Copper phosphite is C) usually produced by dissolving copper hydroxy carbonate in an aqueous solution of phosphorous acid and concentrating this solution in vacuum.
に） また、晶析法による亜リン酸水溶液に銅化合物を
溶解し析出する結晶を脱水・乾燥する方法、あるいは、
（ハ） 反応を十分に完結させるために加熱した亜リン
酸液に銅化合物を溶解させる方法、に） 水可溶性銅化
合物の水溶液に水可溶性面リン酸塩を加えて難溶性の亜
リン酸銅結晶を析出させ、結晶を脱水、乾燥するイオン
交換反応による方法、
も行なわれる。(2) In addition, a method of dissolving a copper compound in an aqueous phosphorous acid solution using a crystallization method and dehydrating and drying the precipitated crystals, or (3) dissolving a copper compound in a heated phosphorous acid solution to sufficiently complete the reaction. (2) A method using an ion exchange reaction in which sparingly soluble copper phosphite crystals are precipitated by adding a water-soluble surface phosphate to an aqueous solution of a water-soluble copper compound, and the crystals are dehydrated and dried. .
［発明が解決しようとする課題］
しかしながら、前記した従来の（イ）の製造法は真空濃
縮工程が工業化に際して多大な設備費用を必要とし、大
量生産的でない。このため塗料用やプラスチック用の配
合剤としては高価となり適用し難い問題があった。[Problems to be Solved by the Invention] However, in the conventional production method (a) described above, the vacuum concentration step requires a large amount of equipment cost upon industrialization, and is not suitable for mass production. For this reason, it is expensive and difficult to apply as a compounding agent for paints or plastics.
前記■の！ＩＩ造法は、未反応銅化合物及び遊離亜リン
酸が付着混入し、乾燥時に酸化銅、亜酸化銅、リン酸銅
が生成して黒色に変化して、不純物の多い亜リン酸銅化
合物となる問題があった。The above ■! In the II manufacturing method, unreacted copper compounds and free phosphorous acid are attached and mixed, and copper oxide, cuprous oxide, and copper phosphate are produced during drying and turn black, resulting in copper phosphite compounds containing many impurities. There was a problem.
そして、前記（ハ）の製造法は、反応時点で反応液が茶
褐色に変化して亜酸化銅が生成され、亜すン酸銅の生成
が困難となる問題がある。The production method (c) has a problem in that the reaction solution turns brown at the time of reaction and cuprous oxide is produced, making it difficult to produce copperous sulfite.
また、に）の製造法は複製する水可溶性の塩類が混入し
、水洗等の精製が必要となり、製造工程を複雑とするの
みならず重金属を含む排水処理費用を増大させる問題が
ある。In addition, the production method (2) involves the contamination of replicating water-soluble salts and requires purification such as washing with water, which not only complicates the production process but also increases the cost of treating wastewater containing heavy metals.
そこで本発明の目的は、前記した従来製造法の問題点を
解決せんとしたものであって、複雑な工程をなくし、安
価に製造でき、かつ黒色変化させず純度の高い安定した
亜リン酸銅化合物の製造法を提供することにある。Therefore, an object of the present invention is to solve the problems of the conventional manufacturing method described above, and to eliminate complicated steps, to produce copper phosphite at low cost, and to produce stable copper phosphite with high purity without changing its black color. The object of the present invention is to provide a method for producing a compound.
また、本発明の他の目的は小規模生産及び工業生産にお
いても実施し易い亜リン酸銅化合物の製造法を提供する
ことにある。Another object of the present invention is to provide a method for producing a copper phosphite compound that is easy to implement in both small-scale and industrial production.
［ｉｉ！ｉ！題を解決するための手段］前記目的を達成
するための本発明の手段は、ヒドロオキシ炭酸銅、炭酸
銅、水酸化銅及び酸化銅の群中より選んだ少なくとも一
種と、亜リン酸とをＣｕ／Ｐ＝ １．０の化学量論比と
なるように配合し、これを機械的手段により練和し、メ
カノケミカル的反応によって化学反応を終了せしめ、微
細な亜リン酸銅化合物の結晶性粉末を得る亜リン酸銅化
合物の製造法である。[ii! i! [Means for Solving the Problem] The means of the present invention for achieving the above object is to combine at least one selected from the group of hydroxy copper carbonate, copper carbonate, copper hydroxide and copper oxide and phosphorous acid with Cu. /P = 1.0 stoichiometric ratio, kneaded by mechanical means, and completed the chemical reaction by mechanochemical reaction, resulting in fine crystalline powder of copper phosphite compound. This is a method for producing a copper phosphite compound.
本発明において使用される銅化合物はヒドロオキシ炭酸
銅、炭酸銅、水酸化銅及び酸化銅であり、この囲者の群
中から選んだ少なくとも一種の化合物が採用される。前
記銅化合物は亜リン酸と乾式あるいは湿式の練和により
亜リン酸銅化合物（Ｃｕ ｌ−（Ｐ Ｏｎ ｌ−１２帆
ただしｎ＝Ｑ又は２）の平均粒子径が約１０μｍ以下の
微細な結晶性粉末を得ることができる。なお、銅化合物
として硫酸塩、硝酸塩及び有機酸塩を使用しないのは、
亜リン酸銅化合物の結晶生成後に０８１１節、水洗等の
複雑な工程をなしく、製造工程を簡易的にするとともに
不純物の混入を少なくするためである。The copper compounds used in the present invention are hydroxycopper carbonate, copper carbonate, copper hydroxide, and copper oxide, and at least one compound selected from this group is employed. The copper compound is mixed with phosphorous acid in a dry or wet process to form fine crystals of copper phosphite compound (Cu l-(P On l-12, where n=Q or 2) having an average particle size of about 10 μm or less. In addition, sulfate, nitrate, and organic acid salts are not used as copper compounds.
This is to simplify the manufacturing process and reduce contamination of impurities by eliminating complicated steps such as washing with water after crystallization of the copper phosphite compound.
本発明を実施する機械的手段の練和は、振動ミル、ボー
ルミル、ライカイ機等の摩砕能力のある練和機を直接あ
るいは間接的に使用し得る。練和は乾式あるいは湿式の
いずれも行ない１（）る１゜本発明は銅化合物と亜リン
酸をＣＵ／Ｐ＝ １．０の化学量論比（モル比）とな
るよう配合し、直接あるいは間接的に摩砕能力のある練
和機を使用することで、ｐＨ調節、水洗等の複雑な工程
を必要とすることなく、純度の高い安定した微細な亜リ
ン酸銅化合物の結晶性粉末をたとえば９０％以上の高収
率で製造することが可能である。For the kneading of mechanical means for carrying out the present invention, a kneading machine having a grinding capacity such as a vibrating mill, a ball mill, or a grinding machine can be used directly or indirectly. Kneading can be carried out either dry or wet.1()1゜In the present invention, the copper compound and phosphorous acid are blended at a stoichiometric ratio (molar ratio) of CU/P=1.0, and kneaded directly or By using a kneading machine with indirect grinding ability, we can produce stable and fine crystalline powder of copper phosphite compound with high purity without the need for complicated processes such as pH adjustment and water washing. For example, it is possible to produce with a high yield of 90% or more.
［作 用１
亜リン酸と銅化合物は機械的手段の練和によって反応さ
せる。練和は化学反応の終了するまで行なわれる。摩砕
を伴う練和によりメカノケミカル的反応が高ｖＡ度下で
進行づるため、結晶生長が抑制され、微細４１結晶が生
成するとともに、温和な条イ′４下であるため銅化合物
による亜リン酸の酸化あるいは亜リン酸による銅化合物
の還元が発生ぜず、不純物の少ない微細な亜リン酸銅化
合物の結晶性わ）末となる。[Action 1: Phosphorous acid and copper compound are reacted by kneading by mechanical means. Mixing is continued until the chemical reaction is completed. As mechanochemical reactions proceed under high vA degrees due to kneading accompanied by grinding, crystal growth is suppressed and fine 41 crystals are produced. Oxidation of the acid or reduction of the copper compound by phosphorous acid does not occur, resulting in a fine crystalline powder of the copper phosphite compound with few impurities.
「実施例（ 次に本発明の詳細な説明する。"Example( Next, the present invention will be explained in detail.
実施例１
ヒドロオキシ炭酸銅（ＣｕＣＯ−Ｃｕ（０１１）２−
８２０ ） ４７８．３ｇヲ水１６００ｄに分散させ
スラリー状とした後に、４０％亜リン酸水溶液、８２０
ｑを撹拌さぜながら１時間が【プて添加し反応させた（
反応時のＣＵ／Ｐの化学量論比は１．０）。反応終了後
、６時間撹拌を続【ノ反応液を安定にさせた、。Example 1 Hydroxycopper carbonate (CuCO-Cu(011)2-
820) After dispersing 478.3 g in 1600 d of water to form a slurry, add 40% phosphorous acid aqueous solution, 820
q was added and reacted for 1 hour with stirring.
The stoichiometric ratio of CU/P during the reaction was 1.0). After the reaction was completed, stirring was continued for 6 hours to stabilize the reaction solution.
安定化後の反応液はｐＨ２，００であった。この反応液
１５００ｇを２ｇのアルミナ製ボールミルに移し、３時
間の湿式練和を行なった。一方、残りの反応液は、その
まま３時間撹拌を続（′、Ｉた１、アルミナ製ボールミ
ルによる３時間練和後のスラリー液はｒ）１１６．２０
であった。残りの撹拌を続（）た反応液はｐＨ２，０で
変らなかった。これらのスラリーはそれぞれ常法により
濾過し、フィルターケーキは６゜°Ｃで２４時間乾燥し
て粉末とした。The pH of the reaction solution after stabilization was 2.00. 1500 g of this reaction solution was transferred to a 2 g alumina ball mill and wet kneaded for 3 hours. On the other hand, the remaining reaction solution was continued to be stirred for 3 hours.
Met. The remaining stirring of the reaction solution remained at pH 2.0. Each of these slurries was filtered by a conventional method, and the filter cake was dried at 6°C for 24 hours to form a powder.
なお、前記した従来例（へ）のＶ進法（反応時のＣＬｌ
／Ｐの化学量論比１．０）にで得ｌ〔亜すン酸銅を実施
例１の比較量粉末とした。比較量粉末は粉末粒子が大き
く黒色を呈するものであった。In addition, the V-adic system (CLl at the time of reaction) of the conventional example (to) described above
A comparative amount of copper sulfite was used as powder in Example 1. The comparative amount of powder had large powder particles and a black color.
実施例２
水酸化銅（Ｃｕ （○Ｈ）２）粉末４０６．５ＳＦ （
９６％含量）と亜リン酸結晶（ＨＰＯ３）３２８ｑを２
」のアルミナ製の振動ミルに入れ、室温２０℃において
３時間乾式にて練和したく反応時のＣｕ ／ ｌ”の化
学量論比は１０）。練和後振動ミルより取出し６０℃で
２４時間乾燥して粉末とした。Example 2 Copper hydroxide (Cu (○H)2) powder 406.5SF (
96% content) and phosphorous acid crystals (HPO3) 328q.
The stoichiometric ratio of Cu/l'' at the time of the reaction was 10).The stoichiometric ratio of Cu/l'' at the time of reaction was 10). It was dried for several hours to form a powder.
実施例３
酸化銅（Ｃｕｂ）粉末４７７．３！？と８０％亜リン酸
液６１５！７を混練機の混練部に入れて混練し、混練に
より反応させた反応物を得た（反応時のＣｕ／Ｐの化学
量論比は１．０）。この反応物５０（ｌを容量２ρのア
ルミナ製ボールミルに入れ、水４００成を加えて室温２
０ ’Ｃで５時間の湿式練和をした。練和後のスラリー
はｐＨ６，７０であった。このスラリーは常法により濾
過し、フィルターケーキは６０℃で２４時間乾燥して粉
末とし１＝ ０前記実施例１，２．３で得られた各粉末
はＸ線回折による結晶の同定、化学分析、粒度分布測定
を行なった。測定の結果、ｘｍ回折では各実施例にお（
プる粉末は亜すン酸銅２水化物（Ｃｕ ｌ−Ｉ Ｐ ０
３・２Ｈ２０）であることが認められた。ただし、実施
例１の比較として反応液を脱水して得られた粉末（比較
量粉末）には亜酸化銅（Ｃｕ２０）の結晶が認められた
。Example 3 Copper oxide (Cub) powder 477.3! ? and 80% phosphorous acid solution 615!7 were put into the kneading section of a kneader and kneaded, and a reactant was obtained by kneading (the stoichiometric ratio of Cu/P at the time of reaction was 1.0). Put 50 (l) of this reaction product into an alumina ball mill with a capacity of 2ρ, add 400 m of water, and
Wet kneading was carried out for 5 hours at 0'C. The slurry after kneading had a pH of 6.70. This slurry was filtered by a conventional method, and the filter cake was dried at 60°C for 24 hours to form a powder.1 = 0 Each powder obtained in Examples 1 and 2.3 was subjected to crystal identification by X-ray diffraction and chemical analysis. , particle size distribution measurements were performed. As a result of the measurement, xm diffraction showed (
The powder is copper sulfite dihydrate (Cu l-I P 0
3.2H20). However, as a comparison with Example 1, cuprous oxide (Cu20) crystals were observed in the powder obtained by dehydrating the reaction solution (comparative amount powder).
そして、化学分析では実施例１，２．３における粉末は
亜すン酸銅２水化物の計算値のＣＵ二３５．４０ｗｔ％
、Ｐ ： １７．２５ｗｔ％に非常に近似していた。た
だし、実施例１の比較量粉末はＣｕ ３７．６１ｗｔ％
、ｐ ： １６．６６ｗｔ％と銅含量が高く、リン含量
が低い値であった。According to chemical analysis, the powder in Examples 1 and 2.3 was 35.40 wt% of the calculated value of copper sulfite dihydrate.
, P: 17.25 wt%. However, the comparative amount powder of Example 1 contained Cu 37.61wt%
, p: 16.66 wt%, which was a high copper content and a low phosphorus content.
粒度分布測定による平均粒径は実施例の１．２゜３の粉
末は５．０μｍ以下であった。The average particle diameter of the 1.2°3 powder of Example as determined by particle size distribution measurement was 5.0 μm or less.
実施例１．２．３で得た各粉末の特性は数表に示す通り
である。The characteristics of each powder obtained in Example 1.2.3 are as shown in the numerical table.
上表より前記実施例１，２．３の各粉末は、酸化銅、亜
酸化銅、リン酸銅及び酸性亜すン酸銅（Ｃｕ （ｌ−Ｉ
ＰＯ３） ２ ）等の塩類を含まない微軸な結晶で
あることがわかる。From the table above, each of the powders of Examples 1 and 2.3 contains copper oxide, cuprous oxide, copper phosphate, and acidic copper sulfite (Cu (l-I
It can be seen that it is a microaxial crystal that does not contain salts such as PO3) 2).
［発明の効果］
しかして本発明は前記銅化合物と亜リン酸とをＣｕ／Ｐ
＝ １．０の化学量論比となるように配合し、これを
機械的手段の練和により化学反応させて亜リン酸銅化合
物の結晶性粉末を得るようにしたので、従来の一殻内亜
リン酸銅化合物製造にお（プる複雑な工程を省略できて
、製造工程を簡単になし得て、さらに重金属を含む排水
処理を軽減させることで安価に製造できるとともに、不
純物の混入の少ない安定した微細な結晶性粉末を得るこ
とができる。[Effects of the invention] However, the present invention combines the copper compound and phosphorous acid into Cu/P
= 1.0 and chemically reacted by kneading with mechanical means to obtain a crystalline powder of copper phosphite compound. In the production of copper phosphite compounds, it is possible to simplify the manufacturing process by omitting the complicated steps involved in the production of copper phosphite compounds. Furthermore, by reducing the need for wastewater treatment containing heavy metals, production can be made at low cost, and there is less contamination of impurities. A stable, fine, crystalline powder can be obtained.
また、本発明は真空濃縮等の設備を要せず、簡単な工程
にて製造できるので、小規模及び大規模の生産において
も実施し易い。Further, the present invention does not require equipment such as vacuum concentration, and can be manufactured through simple steps, so it is easy to implement in both small-scale and large-scale production.
本発明より得た亜リン酸銅化合物の粉末は不純物が少な
く微細な結晶性の粉末であるので、防カビ防菌性剤、導
電性剤及びポリマー安定剤として塗料プラスデックの配
合剤等として使用するに適するものである。The copper phosphite compound powder obtained from the present invention is a fine crystalline powder with few impurities, so it can be used as a compounding agent for paint plus deck as an antifungal agent, conductive agent, and polymer stabilizer. It is suitable for
出願人 太平化学産業株式会社Applicant: Taihei Kagaku Sangyo Co., Ltd.
Claims (1)
銅の群中より選んだ少なくとも一種と、亜リン酸とをＣ
ｕ／Ｐ＝１．０の化学量論比となるように配合し、これ
を機械的手段により練和し、メカノケミカル的反応によ
って化学反応を終了せしめ、微細な亜リン酸銅化合物の
結晶性粉末を得ることを特徴とする亜リン酸銅化合物の
製造法。(1) At least one selected from the group of hydroxy copper carbonate, copper carbonate, copper hydroxide and copper oxide and phosphorous acid
The mixture is blended so that the stoichiometric ratio of u/P=1.0 is obtained, the mixture is kneaded by mechanical means, and the chemical reaction is terminated by a mechanochemical reaction, resulting in fine crystallinity of the copper phosphite compound. A method for producing a copper phosphite compound, characterized by obtaining a powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33205888A JPH02175604A (en) | 1988-12-28 | 1988-12-28 | Production of copper phosphite compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33205888A JPH02175604A (en) | 1988-12-28 | 1988-12-28 | Production of copper phosphite compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02175604A true JPH02175604A (en) | 1990-07-06 |
Family
ID=18250671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33205888A Pending JPH02175604A (en) | 1988-12-28 | 1988-12-28 | Production of copper phosphite compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02175604A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013083248A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Mixtures of aluminium hydrogenphosphites with aluminium salts, process for the production thereof and the use thereof |
| WO2013083250A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Aluminium hydrogen phosphites, a process for preparing them and their use |
| WO2013083249A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
| CN104114486A (en) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | Mixtures of aluminium phosphite with sparingly soluble aluminium salts and foreign ions, process for the production thereof and the use thereof |
| US9481831B2 (en) | 2011-12-05 | 2016-11-01 | Clariant International Ltd. | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
| US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
-
1988
- 1988-12-28 JP JP33205888A patent/JPH02175604A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013083248A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Mixtures of aluminium hydrogenphosphites with aluminium salts, process for the production thereof and the use thereof |
| WO2013083250A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Aluminium hydrogen phosphites, a process for preparing them and their use |
| WO2013083249A1 (en) * | 2011-12-05 | 2013-06-13 | Clariant International Ltd | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
| CN104114486A (en) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | Mixtures of aluminium phosphite with sparingly soluble aluminium salts and foreign ions, process for the production thereof and the use thereof |
| CN104114484A (en) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
| CN104114485A (en) * | 2011-12-05 | 2014-10-22 | 科莱恩金融(Bvi)有限公司 | Mixtures of aluminium hydrogenphosphites with aluminium salts, process for the production thereof and the use thereof |
| JP2015505798A (en) * | 2011-12-05 | 2015-02-26 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Aluminum hydrogen phosphite, process for its production and use thereof |
| US9481831B2 (en) | 2011-12-05 | 2016-11-01 | Clariant International Ltd. | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
| US9505904B2 (en) | 2011-12-05 | 2016-11-29 | Clariant International Ltd. | Mixtures of aluminum hydrogenphosphites with aluminum salts, process for the production thereof and the use thereof |
| US10202549B2 (en) | 2011-12-05 | 2019-02-12 | Clariant International Ltd. | Mixtures of aluminum phosphite with sparingly soluble aluminum salts and foreign ions, process for the production thereof and the use thereof |
| US10421909B2 (en) | 2011-12-05 | 2019-09-24 | Clariant International Ltd. | Mixed alkali-aluminum phosphites, method for producing same, and the use thereof |
| US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
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