JPS6212821B2 - - Google Patents
Info
- Publication number
- JPS6212821B2 JPS6212821B2 JP8270379A JP8270379A JPS6212821B2 JP S6212821 B2 JPS6212821 B2 JP S6212821B2 JP 8270379 A JP8270379 A JP 8270379A JP 8270379 A JP8270379 A JP 8270379A JP S6212821 B2 JPS6212821 B2 JP S6212821B2
- Authority
- JP
- Japan
- Prior art keywords
- copper phthalocyanine
- sulfur
- chloride
- highly chlorinated
- solvent
- 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.)
- Expired
Links
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 101
- 239000002904 solvent Substances 0.000 claims description 50
- 238000005660 chlorination reaction Methods 0.000 claims description 44
- 239000007795 chemical reaction product Substances 0.000 claims description 32
- 239000000460 chlorine Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 32
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 30
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
- NNTJKSMVNWGFTB-UHFFFAOYSA-N disulfuryl chloride Chemical compound ClS(=O)(=O)OS(Cl)(=O)=O NNTJKSMVNWGFTB-UHFFFAOYSA-N 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 9
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 description 46
- 235000017168 chlorine Nutrition 0.000 description 20
- 239000000049 pigment Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000001056 green pigment Substances 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- -1 aluminum chloride-salt Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GUYIZQZWDFCUTA-UHFFFAOYSA-N (pentadecachlorophthalocyaninato(2-))-copper Chemical compound [Cu+2].N1=C([N-]2)C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3C2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC2=C(C(Cl)=C(C(Cl)=C3)Cl)C3=C1[N-]2 GUYIZQZWDFCUTA-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- DSPXASHHKFVPCL-UHFFFAOYSA-N 1-isocyanocyclohexene Chemical compound [C-]#[N+]C1=CCCCC1 DSPXASHHKFVPCL-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
【発明の詳細な説明】
本発明は、銅フタロシアニンの塩素化により高
塩素化銅フタロシアニンを製造する方法であり、
とくに該塩素化をクロルスルホン酸等の硫黄の酸
素酸の酸塩化物中で工業的に有利に実施する方法
に関する。
本来、銅フタロシアニンは青色の顔料である
が、これを塩素化し、銅フタロシアニン分子のベ
ンゼン核の16個の水素原子のうち、12個以上を塩
素原子と置換することにより緑色を帯び、通常は
13個以上が実用的な置換数とされ、とくに14個以
上を置換すれば黄色を帯びた鮮明な緑色顔料とな
る。
この高塩素化銅フタロシアニン顔料を一般に銅
フタロシアニングリーンまたはフタロシアニング
リーンと呼ぶが、これはきわめて耐光性耐溶剤性
にすぐれた顔料である。
従来、銅フタロシアニンの塩素化による高塩素
化銅フタロシアニンの工業的製造法として、最も
広く行なわれている方法は、無水塩化アルミニウ
ムおよび食塩の混融物に銅フタロシアニンを溶解
して150〜200℃で塩素ガスと接触せしめて塩素化
したのち、該反応混合物を大量の氷水中に投入し
て、塩素化生成物を分離する方法である。この方
法は、
(1) 無水塩化アルミニウムを銅フタロシアニンの
５〜８重量倍用い、反応後水中に投入するた
め、無水塩化アルミニウムおよび食塩の回収は
コスト高となつて工業的に不可能であり、また
廃水中に含まれる塩化アルミニウムの処理費用
も多大となり、
(2) 150〜200の高い反応温度で塩素化反応が行な
われるために、種々の副生成物が生成しやすく
収率低下の原因となる。
などの欠点があるが、帯黄緑色の鮮明な顔料が比
較的容易に得られるため最も広く工業的に用いら
れている。
一方、クロルスルホン酸に銅フタロシアニンを
溶解せしめて、触媒の存在下塩素ガスを通じて、
高塩素化銅フタロシアニンを製造する方法（米国
特許2662085号明細書1953年）も知られている。
この方法は、
(1) 反応温度がせいぜい115℃であり、そのため
塩化アルミニウム−食塩法に比較して工程操作
は容易であり、材質の腐蝕度も低く
(2) クロルスルホン酸は塩化アルミニウムより安
価である。
などの利点もあるが、工業的に余り用いられてい
ない。それは
(1) 塩化アルミニウム−食塩法にくらべて収率が
かなり低く
(2) 生成した顔料の色調がさえず、青味を帯び鮮
明な帯黄緑色とならない、等の理由のためであ
る。
また、塩化ピロスルフリルを溶媒として、塩化
チオニルを用いて塩素化する方法（特公昭37−
15790号公報）も提案されているが、この方法は
大量の塩化チオニルを用いるので実用的ではな
い。
本発明の目的は、上述のクロルスルホン酸等の
硫黄の酸素酸の酸塩化物中で銅フタロシアニンを
塩素化する方法の欠点を除くことにある。
すなわち、銅フタロシアニンを硫黄の酸素酸の
酸塩化物中で塩素化する安価な方法において、塩
素化物の収率を上げることおよび鮮明な帯黄緑色
を有する高度に塩素化された銅フタロシアニン顔
料を高収率で工業的に有利に製造する方法を提供
することにある。
この方法として本発明者らはすでに、特願昭52
−148081号明細書において、「硫黄の酸素酸の酸
塩化物溶媒としてクロルスルホン酸又は塩化ピロ
スルフリル溶媒を用い触媒として硫黄および／又
は硫黄の塩化物を加え、その他の塩素化触媒を添
加又は添加せずに、塩素を用いて銅フタロシアニ
ンを塩素化する高塩素化銅フタロシアニンの製造
法において、クロルスルホン酸に対しては硫黄と
して７重量％以上200重量％以下、塩化ピロスル
フリル対しては硫黄として１重量％以上200重量
％以下、それぞれの硫黄及び／又は硫黄の塩化物
を加え、１〜20Kg／cm2Ｇの加圧下で塩素化するこ
とを特徴とする高塩素化銅フタロシアニンの製造
法、ならびに、上記の硫黄の酸素酸の酸塩化物と
して、クロルスルホン酸又は塩化ピロスルフリル
を用いるこの二つの方法により、銅フタロシアニ
ンを塩素化し、得られた塩素化反応生成物を蒸留
して得た留出物をそのまゝ用い、これに銅フタロ
シアニンを添加して再び塩素化し、さらに得られ
た塩素化反応生成物を蒸留して得た留出物を用
い、これに銅フタロシアニンを添加して塩素化す
る操作を繰り返してもよいことを特徴とする高塩
素化銅フタロシアニンの製造法」を明らかにして
詳細に説明した。
上記の製造法では、得られた塩素化反応生成物
から溶媒を分離する方法として蒸留法を用いてい
る。この方法の長所は蒸留により溶媒のほとんど
が回収される点にある。この場合、溶媒の回収率
を大きくするためには、生成した高塩素化銅フタ
ロシアニンが変質しない範囲で減圧蒸留における
加熱温度をできるだけ高く、真空度を高めなけれ
ばならない。しかも反応生成物から溶媒が蒸発し
てゆくにつれて、残存溶媒量が減少し、高塩素化
銅フタロシアニンの濃度が大きくなるので反応液
の粘度が著増するという欠点がある。
この様な粘度の著増する反応生成物から溶媒成
分を、スムーズに最大限蒸発により回収するため
には反応液を強制的に撹拌することが必要であ
る。即ち、内部撹拌型蒸発器を用いるのが一般的
である。この様な装置は通常は鉄およびステンレ
ス鋼で作られる。これ以外の材質では、強度が小
さく工業装置としては経済的に不利である。
溶媒のクロルスルホン酸は、塩素化条件下で１
部ピロスルフリルクロライド（S3O8Cl2、
S4O11Cl2）となり高沸点物化すると考えられ、こ
れらを蒸発させるためには、加熱ジヤケツト温度
を130℃以上、減圧度は50Torr以下にする必要が
ある。クロルスルホン酸を始め、これらの化合物
を含む溶媒成分は金属に対する腐蝕性は大きく、
耐蝕性のある金属材料は相当の高級材料となる。
これらの材質上の欠点を解消するべく鋭意研究を
すゝめた結果、上記製造法における銅フタロシア
ニンの塩素化反応において添加する塩化硫黄ある
いは／および硫黄のクロルスルホン酸あるいはピ
ロスルフリルクロライドに対する添加割合を増加
させるにしたがつて生成した高塩素化銅フタロシ
アニンの溶解度が急激に減少し、ついにはほとん
ど結晶として晶出し、これを適当な固液分離方法
例えば過だけで高塩素化銅フタロシアニンを容
易に分離することができることがわかつた。
例えば、クロルスルホン酸を溶媒として用いた
場合を例にとり、塩化硫黄（S2Cl2）を添加し銅フ
タロシアニンを塩素化した場合に、塩化硫黄の添
加量に対する生成した高塩素化銅フタロシアニン
（塩素置換数約15ケ）の溶解度の変化を示したの
が第１図である。図中、縦軸は高塩素化銅フタロ
シアニンの溶解度（ｇ／100ｇ・溶媒）及び横軸
は塩化硫黄の添加量、（但し、硫黄換算の対クロ
ルスルホン酸重量％）であり、測定温度は室温で
ある。この図より塩化硫黄の量が約14％から高塩
素化銅フタロシアニンの溶解度が減少し始め、約
19％以上になると溶解度は最低になり、生成高塩
素化銅フタロシアニンが殆んど大部分晶出するこ
とが明らかとなる。
このように晶出した高塩素化銅フタロシアニン
の分離は常温で行なうことが出来る。この塩素化
反応生成物のステンレス鋼に対する腐蝕度は温度
の影響が著しく、75℃以下ではほとんど腐蝕をう
けないが、100℃以上では耐蝕性がなくなる。し
たがつて過機等の固液分離機の材質は汎用ステ
ンレスなど何でも使用することが出来るが溶媒を
蒸留により回収する場合には塩素化反応液を100
℃以上に加熱しなければならないために、汎用ス
テンレスはすべて使用することは出来ないからハ
ステロイ等の特殊高級材料を用いざるを得ない。
したがつて、溶媒の回収率は蒸留法の場合の方が
すぐれているが、材質の選定がむつかしく、低温
で晶出した高塩素化銅フタロシアニンを固液分離
する例えば、過法を採用した方が材質上全く問
題がないので工業的に有利といえる。
上記過等により分離した高塩素化銅フタロシ
アニンを含むケーキは水または希硫酸で洗いだ
し、酸洗過、アルカリ洗過、水洗、乾燥する
という通常の後処理方法を実施することにより、
高塩素化銅フタロシアニンを高収率で得る。得ら
れた粗製物は常法の顔料化を行なうことにより鮮
明性のすぐれた帯黄緑色の顔料を得ることがで
き、分離液は反応溶媒として再使用することがで
きることを見出し、本発明に到達した。
すなわち、本発明は、前述の溶媒の蒸留法の材
質上の問題点を解消して工業的にきわめて有利に
鮮明かつ着色力のよりすぐれた帯黄緑色を有する
高塩素化銅フタロシアニンの製造法を提供せんと
するもので、その要旨とするところは、硫黄の酸
素酸の酸塩化物溶媒としてクロルスルホン酸ある
いは塩化ピロスルフリルを用い、触媒として硫黄
および／又は硫黄の塩化物を加えその他の塩素化
触媒を添加又は添加せずに、塩素を用いて銅フタ
ロシアニンを塩素化して高塩素化銅フタロシアニ
ン顔料を製造するに当り、クロルスルホン酸に対
しては硫黄として14重量％以上200重量％以下、
塩化ピロスルフリルに対しては、硫黄として８重
量％以上200重量％以下、それぞれに相当する量
の硫黄および又は硫黄の塩化物を加え、１〜20
Kg／cm2Ｇの加圧下で塩素化し、得られた塩素化反
応生成物から晶出した結晶を分離して得た分離液
をそのまま用い、これに銅フタロシアニンを添加
して再び塩素化し、さらに得られた塩素化反応生
成物から晶出した高塩素化銅フタロシアニンを分
離し、得られた分離液を用い、これに銅フタロシ
アニンを添加して塩素化する操作をくり返しても
よいことを特徴とする高塩素化銅フタロシアニン
の製造法に存する。
本発明の方法において、硫黄の酸素酸の酸塩化
物溶媒としては、一般にはクロルスルホン酸又は
塩化ピロスルフリルが用いられ、塩化スルフリ
ル、塩化チオニルを用いる場合はこれと併用する
ことが好ましい。
上記の溶媒の使用量は基本的には、原料の銅フ
タロシアニンを溶解又は懸濁し、塩素ガスと接触
が充分行われる範囲がよいが、通常工業的に一般
に用いられる撹拌機で反応溶液を撹拌することが
できる量が好ましく、原料銅フタロシアニンの約
３重量倍から約50重量倍、工業的には４〜８重量
倍が好ましい。
本発明の方法における塩素化反応はまず触媒と
して硫黄もしくは硫黄の塩化物（以下Ａ触媒とい
う。）を加えて行なわれる。該反応はその他の塩
素化触媒（以下Ｂ触媒という。）の添加または不
添加のいづれでも実施し得るが、通常はヨウ素等
のＢ触媒を併用する方が好ましく、Ｂ触媒を溶媒
に対し0.01〜10重量％添加することによつて鮮明
な帯黄緑色の顔料が高収率で得られる。
前記Ａ触媒と併用するＢ触媒としては、ヨウ
素、一塩化ヨウ素、三塩化ヨウ素等のヨウ素の塩
化物、無水塩化アルミニウム、無水塩化第２鉄、
３塩化アンチモン、塩化第２銅等の金属化合物が
挙げられる。
上記のＡ触媒は、硫黄もしくは硫黄の塩化物単
独でもよいが、もちろん併用してもよい。
その添加量としてはクロルスルホン酸溶媒に対
しては硫黄として換算して14重量％以上、好まし
くは16重量％以上、さらに好ましくは18重量％以
上、塩化ピロスルフリルに対しては８重量％以
上、好ましくは10重量％以上、さらに好ましくは
12重量％以上のそれぞれに相当する量でなければ
ならない。
上記硫黄あるいは／および塩化硫黄のクロルス
ルホン酸又は塩化ピロスルフリルに対する下限添
加量以上（硫黄として）においては、Ｂ触媒およ
び銅フタロシアニンの共存下、20〜120℃、１〜
20Kg／cm2Ｇで塩素ガスを接触せしめた時、銅フタ
ロシアニンがそのベンゼン核の水素原子が13ケ以
上塩素化された高塩素化銅フタロシアニンである
とき、その反応溶媒（塩素化反応生成物の高塩素
化銅フタロシアニン以外の総量）に対する溶解度
は著しく減少し、１ｇ／100ｇ反応溶媒以下とな
る。
一方、Ａ触媒の含有量は上記両溶媒のいづれに
対してもあまり多くなるとやゝ塩素化しにくくな
るため、高塩素化銅フタロシアニン１分子中の塩
素置換数は13ケ以上が緑色顔料の実用的置換数と
されることからすれば１触媒の好ましい上限は上
記の溶媒に対し硫黄として200重量％以下、好ま
しくは100重量％以下であるといえよう。
なお、本発明の塩素化反応において、溶媒とし
てクロルスルホン酸を用いた場合は主としてクロ
ルスルホン酸がＡ触媒および塩素と次式の様に反
応して塩化ピロスルフリルを主成分とする混合物
を生成し、しかるのち銅フタロシアニンの塩素化
反応が進行するものと推定される。
8SO2（OH）Cl＋2S＋6Cl2→4S2O5Cl2
＋2SO2Cl2＋8HCl
8SO2（OH）Cl＋S2Cl2＋5Cl2→4S2O5Cl2
＋2SO2Cl2＋8HCl
I2＋Cl2→2ICl又はICl3
S2Cl2＋Cl2→2SCl2
すなわち、前記したように、クロルスルホン酸
溶媒を出発して本発明を実施した場合溶媒に対し
て硫黄として約６〜７重量％に相当する量は塩化
ピロスルフリルの生成に消費され、いずれの場合
も、実質的には塩化ピロスルフリルを中心とする
混合溶媒中で行なわれているのと同じ方法である
と考えられる。
塩化ピロスルフリルは公知の方法により調製す
ることができる。
一般的には、クロルスルホン酸に硫黄をクロル
スルホン酸の６〜７重量％又はそれに相当する塩
化硫黄を加え、その混合物に塩素を供給すること
により調製するが、その他、例えば無水硫酸と四
塩化炭素から調製することもできる。けだし、ク
ロルスルホン酸及び塩化ピロスルフリルいずれの
溶媒の場合でも実質的に同様の結果は得られるの
はもちろんである。
本発明方法の塩素化反応において、反応圧力は
高収率で帯黄緑色の鮮明な顔料を得るためには顕
著な効果を示し、１〜20Kg／cm2Ｇ好ましくは２〜
８Kg／cm2Ｇ、さらに好ましくは３〜７Kg／cm2Ｇが
よい。１〜２Kg／cm2Ｇでは粗製高塩素化銅フタロ
シアニンの収率は96％（対理論）以上で鮮明な顔
料が得られるが、やゝ青味がつよい。
２Kg／cm2Ｇ、とくに３Kg／cm2Ｇ以上では帯黄緑
色の鮮明な粗製高塩素化銅フタロシアニンを高収
率で得ることができる。塩素は液状又はガス状で
加えることも出来るが、一般的にはガス状で加え
る。即ち、20Kg／cm2Ｇ以上は工業的に不利であ
り、一般的には10Kg／cm2Ｇ以下、通常は常温で塩
素の液化が起らない８Kg／cm2Ｇ以下、とくに７
Kg／cm2Ｇ以下が好ましい。
また、反応温度は初期は低く、例えば常温から
の反応の進行にしたがい、100〜120℃まで昇温す
る。最高反応温度においては反応圧力をできるだ
け昇圧するのが有利である。120℃以上になると
得られた顔料の色調は帯黄緑色で充分に鮮明であ
るが収率は著しく減少する。
本発明の方法において、塩素化反応を実施する
には通常硫黄の酸素酸の酸塩化物溶媒としてクロ
ルスルホン酸又は塩化ピロスルフリルを用い、Ａ
触媒および場合によりヨウ素等のＢ触媒ならびに
銅フタロシアニンの所定量を加え、所定の加圧下
で塩素と接触せしめて、一般に常温から徐々に
100〜115℃まで昇温する。
通常はさらにその温度に約1hr〜4hr保持したの
ち、塩素化反応を終了する。
本発明の方法において、上記のようにして得た
反応生成物には高塩素化銅フタロシアニンが晶出
しているが、通常は冷却して結晶を適当な分離方
法例えば過法、遠心分離法（デカンター等）、
自然沈降法などにより溶媒の大部分もしくは１部
分を分離液として回収することができる。
該分離液中には若干の高塩素化銅フタロシアニ
ンが含まれているが、分離液の量の１％以下であ
り、又回収した分離液には溶媒成分はもちろんＡ
触媒やＢ触媒も含まれているので、この分離液を
新たにＡ触媒やＢ触媒を加えることなくそのまゝ
用い、これに所定量の原料銅フタロシアニンを加
え前記の本発明方法の圧力および温度条件で塩素
を用いて、これに銅フタロシアニンを添加して塩
素化する操作をくり返すことも可能であり、かゝ
る方法により同様にすぐれた高塩素化銅フタロシ
アニンを高収率で得ることが出来る。また、上記
の分離液として回収した溶媒に、塩素化反応時お
よび過等の分離操作における溶媒の損失分およ
びケーキに随伴する溶媒の損失分に相当する溶媒
量および触媒量を補充して再び本発明の方法の溶
媒または触媒として再使用できることは云うまで
もない。
本発明の方法において、行なう過等の分離操
作における反応生成物の温度は、反応生成物中に
は蒸気圧の大きいSO2Cl2、SOCl2、SCl2等の化合
物が含まれているので、これらの低沸分の損失量
が少ない室温近辺で行なうのがよい。
分離方法としては、一般には過法が用いられ
過機はどんな型式でも使用し得るが、減圧過
型式よりも加圧密閉型式の方が好ましい。
本発明の方法において行なう過等の分離操作
は、前記のとおり、常温近辺で行なうため、過
機等の固液分離機の材質について特別の対策が不
必要であるので、汎用金属材料の腐蝕が大きく材
質選定がむずかしい溶媒を蒸留により回収する場
合に較べて工業的に有利である。
溶媒を回収した後の高塩素化銅フタロシアニン
を含むケーキは通常40〜70％の溶媒成分が含まれ
ているが、そのまゝ水または希硫酸に投入し、酸
洗過、アルカリ洗過、乾燥という精製を行な
つてもよいが、前述のケーキの含液分として含ま
れている溶媒分を、次回塩素化反応で分離液とし
て回収された溶媒に、不足分として追加するべき
クロルスルホン酸と塩化硫黄の混合物でケーキ洗
浄を行ない、ケーキ中の液体成分（可溶高塩素化
銅フタロシアニンを含む）をクロルスルホン酸と
塩化硫黄の新規溶媒に置換したのち、このケーキ
を直接水あるいは稀硫酸に投入し、酸洗過、ア
ルカリ洗過、乾燥する。ケーキ洗浄したときの
液は前述の反応生成物の分離液と合して反応溶
媒として再使用することができる。
得られた粗製高塩素化銅フタロシアニンをソル
トグラインデイング法により顔料化を行なつた。
この顔料は、直接水投入法で得られた粗製品を同
様に顔料化した場合にくらべて鮮明性において明
らかにすぐれていた。
本発明は、反応生成物から高塩素化銅フタロシ
アニン結晶を分離例えば過し、その分離液を反
応溶媒として用いて銅フタロシアニンの塩素化反
応を実施するとき、クロルスルホン酸、ピロスル
フリルクロライド、Ａ触媒およびヨウ素ならびに
塩素の使用量を大巾に節減し、さらに得られた顔
料の品位がすぐれているという工業的にきわめて
顕著な効果を奏することができる。
次に、本発明をさらに詳細に説明するが、本発
明は以下の実施例に制限されるものではない。
実施例 １
銅フタロシアニンの塩素化
クロルスルホン酸380部、硫黄80部（21％対ク
ロルスルホン酸）およびヨウ素3.7部をまず反応
器に入れ、これに粗製銅フタロシアニン75部（純
度92％）を加え、撹拌溶解せしめた。
次に該溶液に塩素ガスを常温から徐々に100℃
まで昇温しながら供給した。このとき反応器の圧
力は約20分で３Kg／cm2Ｇとなり、以後この圧力を
保持する様に供給塩素量に適合せしめて反応器出
口の調節弁の開度を調整した。該溶液の色が緑黒
色から次第に赤味を帯び深紅色になるまで、５時
間にわたつて360部の塩素を供給した。
その結果、塩素化反応生成物644部が得られ
た。反応生成物は50℃以下に冷却したのち、300
部の氷水中に撹拌しながら投入する。
つぎにこれを撹拌しながら90℃に加熱し、１時
間撹拌後ろ過し、次いでこのケーキを２％苛性ソ
ーダ水溶液3000部に投入し、90℃１時間撹拌後ろ
過、水洗、乾燥して、鮮明な帯黄緑色の粗製塩素
化銅フタロシアニン132部を得た。該生成物のフ
タロシアニン分子の置換塩素数は、14.5ケであ
り、純度は96％、収率は98％（対理論）であつ
た。
実施例 ２
実施例１と同様にして得られた塩素化反応生成
物644部を２つに分け、そのうち300部を内径80mm
のヌツチエでサラン製布を用いて減圧過を行
なつたところ、過ケーキ165部（含液率62％）
と液110部、過時における溶媒ロスは25部で
あつた。この過ケーキを２％硫酸水溶液600部
中に入れ、90℃で１時間撹拌後過水洗した。次
にこの過ケーキを２％カセイソーダ水溶液中で
同様に処理したのち乾燥した。
得られた粗製高塩素化銅フタロシアニンは62部
であつた。
もう一方の反応生成物300部を２％硫酸600部中
に投入し、以下上記の過ケーキの場合と同様に
酸洗過、アルカリ洗過、乾燥して、粗製高塩
素化銅フタロシアニン63部を得た（比較例１）。
この双方の粗製高塩素化銅フタロシアニンをソ
ルトグラインデイング法（米国特許2982666号明
細書参照）により顔料化すると、それらの顔料の
うち直接水投入法（比較例１）による場合よりも
反応生成物を過して得た過ケーキの場合の方
が鮮明度がすぐれていた第１表にこれらの顔料の
鮮明性の測定値を示す。ただし、鮮明性は
National Bureau of StandardによりHunterの
Lab方式で測定し、色素絶対値で表した。以下実
施例２、３、５、７及び比較例１〜３についても
同様に測定した。
実施例 ３
実施例１と同様にして得られた塩素化反応生成
物300部を内径80mmのヌツチエ型加圧過器で窒
素ガス加圧下（６Kg／cm2Ｇ）過を行なつたとこ
ろ、過ケーキ150部（含液率59％）と液130
部、過時における溶媒ロスは20部であつた。
これを実施例２の減圧過の場合と比較すると
加圧過の場合の方が、過ケーキ含液率で３％
少なく、過時のロス量で２％少なかつた。
この過ケーキを実施例２と同様に精製を行な
つたところ、粗製塩素化銅フタロシアニン62部を
えた。
これを実施例２と同様にソルトグラインデイン
グ法により顔料化を行なつたところ、その鮮明度
（第１表参照）は実施例２の減圧過の場合と変
らなかつた。
実施例 ４
実施例１と同様に実施した塩素化反応生成物を
過することによりえられた液480部に粗製銅
フタロシアニン（純度92％）75部を加え撹拌して
溶解せしめたのち、実施例１の様に常温から徐々
に100℃に昇温しながら塩素を供給し、反応圧は
3.0Kg／cm2Ｇを保つ様に反応器出口弁の開度を調
節する。液の色は茶黒色から次第に赤味を帯びて
くる。深紅色になるまで４時間にわたつて塩素を
供給する。塩素の総供給量は160部であつた。
反応生成物は実施例２のごとく析出した高塩素
化銅フタロシアニンを過により分離したのち、
酸洗過、アルカリ洗過、水洗、乾燥して鮮明
な帯黄緑色の粗製高塩素化銅フタロシアニン136
部を得た。該生成物のフタロシアニン分子の塩素
置換数は15.1ケ、純度96％、収率は98％（対理
論）であつた。さらに、上記の液として回収さ
れた溶媒をそのまゝ用い、上記と同様な割合で粗
製銅フタロシアニンを添加し、上記と同様に塩素
化して後、析出した高塩素化銅フタロシアニンを
過により分離したのち処理して粗製高塩素化銅
フタロシアニンを得るという操作を順次４回繰返
したところ、いずれも上記と同様に良好な結果を
得た。
なお実施例２の液として回収された溶媒に、
損失分のクロルスルホン酸、硫黄およびヨウ素を
追加したほかは本実施例と同様に実施して同様な
結果を得た。
実施例 ５
実施例４と全く同様に塩素化反応を実施し、こ
の反応生成物を２分して一方は実施例２のごとく
過法により、他方は直接水投入法（比較例２）
により粗製高塩素化銅フタロシアニンを得た。
この双方の粗製高塩素化銅フタロシアニンを実
施例２のごとくソルトグラインデイング法により
顔料化すると、それらの顔料のうち直接水投入法
による場合よりも、過法の場合の方が鮮明度が
すぐれていた（第１表参照）。
実施例 ６
(1) 精製塩化ピロスルフリルの調製
無水硫酸780部に四塩化炭素1200部を添加
し、これを常温から80℃まで3.5時間で昇温す
ると、ほゞガス発生が終了した。これ以後さら
に１時間この80℃に保持した。この生成分1620
部を常圧下蒸留し、精製塩化ピロスルフリル
（bp 147〜152℃）933部を得た。
(2) 銅フタロシアニンの塩素化
上記(1)で得た精製塩化ピロスルフリル380部
に硫黄57部（15％対塩化ピロスルフリル）およ
びヨウ素3.7部をまず反応器に入れ、これに粗
製銅フタロシアニン75部（純度92％）を加え、
実施例１と同様に実施した。
その結果、塩素化反応生成物590部が得られ
た。
この反応生成物は実施例１と同様に処理して
帯黄緑色の鮮明な高塩素化銅フタロシアニン
135部を得た。
該生成物のフタロシアニン分子の置換塩素数
は15.0ケ純度は96％、収率は99％（対理論）で
あつた。
実施例 ７
実施例６と同様にして得られた塩素化反応生成
物640部を２つに分け、そのうち290部を実施例１
と同様に過を行なつたところ、過ケーキ154
部（含液率60％）と液116部、過時における
溶媒ロスは20部であつた。
この過ケーキを実施例２と同様に後処理て粗
製高塩素化銅フタロシアニン62部を得た。
もう一方の反応生成物290部を実施例２のよう
に直接水投入法（比較例３）により後処理して粗
製高塩素化銅フタロシアニン63部を得た。
この双方の粗製高塩素化銅フタロシアニンを実
施例２のごとくソルトグラインデイング法により
顔料化するとそれらの顔料のうち、直接水投入法
による場合よりも反応生成物を過して得た過
ケーキの方が鮮明度がすぐれていた（第１表参
照）。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for producing highly chlorinated copper phthalocyanine by chlorinating copper phthalocyanine,
In particular, it relates to an industrially advantageous method for carrying out the chlorination in an acid chloride of a sulfur oxygen acid such as chlorosulfonic acid. Copper phthalocyanine is originally a blue pigment, but by chlorinating it and replacing 12 or more of the 16 hydrogen atoms in the benzene nucleus of the copper phthalocyanine molecule with chlorine atoms, it takes on a green color and usually
A practical number of substitutions is 13 or more, and especially if 14 or more are substituted, a clear green pigment with a yellow tinge will be produced. This highly chlorinated copper phthalocyanine pigment is generally called copper phthalocyanine green or phthalocyanine green, and is a pigment with extremely excellent light resistance and solvent resistance. Conventionally, the most widely used industrial method for producing highly chlorinated copper phthalocyanine by chlorinating copper phthalocyanine is dissolving copper phthalocyanine in a mixture of anhydrous aluminum chloride and common salt at 150 to 200°C. In this method, the reaction mixture is chlorinated by contacting with chlorine gas, and then the reaction mixture is placed in a large amount of ice water to separate the chlorinated product. In this method, (1) anhydrous aluminum chloride is used 5 to 8 times the weight of copper phthalocyanine and is poured into water after the reaction, so recovery of anhydrous aluminum chloride and common salt is expensive and industrially impossible; In addition, the cost of processing aluminum chloride contained in wastewater is considerable; (2) Since the chlorination reaction is carried out at a high reaction temperature of 150 to 200 °C, various by-products are likely to be produced, which causes a decrease in yield. Become. However, it is the most widely used industrially because it is relatively easy to obtain a clear yellowish-green pigment. On the other hand, copper phthalocyanine was dissolved in chlorosulfonic acid, and chlorine gas was passed through it in the presence of a catalyst.
A method for producing highly chlorinated copper phthalocyanine (US Pat. No. 2,662,085, 1953) is also known.
This method has the following advantages: (1) The reaction temperature is at most 115°C, so the process operation is easier and the material is less corrosive than the aluminum chloride-salt method. (2) Chlorosulfonic acid is cheaper than aluminum chloride. It is. Although it has some advantages, it is not widely used industrially. This is because (1) the yield is much lower than that of the aluminum chloride-salt method, and (2) the color tone of the pigment produced is dull and does not have a bluish, clear yellowish-green color. In addition, a method of chlorination using thionyl chloride in pyrosulfuryl chloride as a solvent (Japanese Patent Publication No. 37-197-
15790) has also been proposed, but this method uses a large amount of thionyl chloride and is therefore not practical. The object of the present invention is to eliminate the disadvantages of the above-mentioned process for chlorinating copper phthalocyanines in acid chlorides of sulfur oxyacids such as chlorosulfonic acid. Namely, in an inexpensive process of chlorinating copper phthalocyanine in acid chlorides of sulfur oxyacids, it is possible to increase the yield of chloride and to prepare highly chlorinated copper phthalocyanine pigments with a bright yellowish-green color. It is an object of the present invention to provide an industrially advantageous manufacturing method with high yield. As for this method, the present inventors have already proposed a patent application filed in 1973.
- In Specification No. 148081, ``Chlorsulfonic acid or pyrosulfuryl chloride solvent is used as an acid chloride solvent of sulfur oxygen acid, sulfur and/or sulfur chloride is added as a catalyst, and other chlorination catalysts are added or added. In the production method of highly chlorinated copper phthalocyanine, in which copper phthalocyanine is chlorinated using chlorine, chlorsulfonic acid contains 7% by weight or more and 200% by weight or less as sulfur, and pyrosulfuryl chloride contains 7% by weight or more and 200% by weight as sulfur. A method for producing highly chlorinated copper phthalocyanine, which comprises adding 1% by weight or more and 200% by weight or less of each of sulfur and/or chloride of sulfur, and chlorinating under a pressure of 1 to 20 Kg/cm 2 G. In addition, copper phthalocyanine is chlorinated by these two methods using chlorosulfonic acid or pyrosulfuryl chloride as the acid chloride of the sulfur oxygen acid, and the resulting chlorination reaction product is distilled. Using the raw material as it is, adding copper phthalocyanine to it and chlorinating it again, using the distillate obtained by distilling the obtained chlorination reaction product, adding copper phthalocyanine to it and chlorinating it again. A method for producing highly chlorinated copper phthalocyanine, which is characterized in that the step of chlorinating copper phthalocyanine may be repeated, was clarified and explained in detail. In the above production method, a distillation method is used to separate the solvent from the obtained chlorination reaction product. The advantage of this method is that most of the solvent is recovered by distillation. In this case, in order to increase the recovery rate of the solvent, the heating temperature in vacuum distillation must be as high as possible and the degree of vacuum must be increased within a range that does not alter the quality of the highly chlorinated copper phthalocyanine produced. Moreover, as the solvent evaporates from the reaction product, the amount of remaining solvent decreases and the concentration of highly chlorinated copper phthalocyanine increases, resulting in a significant increase in the viscosity of the reaction solution. In order to smoothly recover the solvent component from the reaction product whose viscosity increases by evaporation to the maximum extent possible, it is necessary to forcibly stir the reaction solution. That is, it is common to use an internally stirred evaporator. Such devices are usually made of iron and stainless steel. Other materials have low strength and are economically disadvantageous for industrial equipment. The solvent chlorosulfonic acid is 1 under chlorinated conditions.
Pyrosulfuryl chloride (S 3 O 8 Cl 2 ,
S 4 O 11 Cl 2 ), which is thought to become a high-boiling point product, and in order to evaporate these, the heating jacket temperature needs to be 130° C. or higher and the degree of vacuum needs to be 50 Torr or lower. Solvent components containing these compounds, including chlorosulfonic acid, are highly corrosive to metals.
Corrosion-resistant metal materials are quite high-grade materials.
As a result of intensive research to eliminate these material defects, we increased the ratio of sulfur chloride and/or sulfur added to chlorosulfonic acid or pyrosulfuryl chloride in the chlorination reaction of copper phthalocyanine in the above production method. As the temperature increases, the solubility of the highly chlorinated copper phthalocyanine that is produced decreases rapidly, and finally, most of it crystallizes out, and the highly chlorinated copper phthalocyanine can be easily separated using an appropriate solid-liquid separation method, such as filtration. I found out that it is possible. For example, if chlorosulfonic acid is used as a solvent and copper phthalocyanine is chlorinated by adding sulfur chloride (S 2 Cl 2 ), the amount of highly chlorinated copper phthalocyanine (chlorine Figure 1 shows the change in solubility for approximately 15 substitutions. In the figure, the vertical axis is the solubility of highly chlorinated copper phthalocyanine (g/100g/solvent), and the horizontal axis is the amount of sulfur chloride added (weight% of chlorosulfonic acid in terms of sulfur), and the measurement temperature is room temperature. It is. This figure shows that the solubility of highly chlorinated copper phthalocyanine starts to decrease when the amount of sulfur chloride is about 14%, and the solubility of highly chlorinated copper phthalocyanine starts to decrease.
When it exceeds 19%, the solubility becomes the lowest, and it becomes clear that most of the produced highly chlorinated copper phthalocyanine crystallizes. The highly chlorinated copper phthalocyanine thus crystallized can be separated at room temperature. The degree of corrosion of this chlorination reaction product to stainless steel is significantly affected by temperature; at temperatures below 75°C there is almost no corrosion, but above 100°C corrosion resistance is lost. Therefore, any material such as general-purpose stainless steel can be used for the solid-liquid separator such as a filter, but when recovering the solvent by distillation, the chlorination reaction liquid must be
Because it has to be heated above ℃, it is not possible to use all general-purpose stainless steel, so special high-grade materials such as Hastelloy must be used.
Therefore, although the recovery rate of the solvent is better in the case of distillation, it is difficult to select the material, and it is difficult to use a method that uses a filtration method, for example, to separate solid-liquid highly chlorinated copper phthalocyanine that crystallizes at low temperatures. However, since there are no problems with the material, it can be said to be industrially advantageous. The cake containing highly chlorinated copper phthalocyanine separated by the above filtration is washed with water or dilute sulfuric acid, and the usual post-treatment method of acid washing, alkali washing, water washing, and drying is carried out.
Highly chlorinated copper phthalocyanine is obtained in high yield. The inventors discovered that a yellowish-green pigment with excellent clarity can be obtained by converting the obtained crude product into a pigment using a conventional method, and that the separated liquid can be reused as a reaction solvent, leading to the present invention. did. That is, the present invention solves the material problems of the above-mentioned solvent distillation method and provides an extremely advantageous industrial method for producing highly chlorinated copper phthalocyanine having a yellowish green color with excellent coloring power. The gist of the proposed solution is to use chlorosulfonic acid or pyrosulfuryl chloride as a sulfur oxygen acid chloride solvent, add sulfur and/or sulfur chloride as a catalyst, and perform other chlorination reactions. When producing a highly chlorinated copper phthalocyanine pigment by chlorinating copper phthalocyanine with chlorine, with or without adding a catalyst, 14% by weight or more and 200% by weight or less as sulfur with respect to chlorosulfonic acid,
For pyrosulfuryl chloride, add sulfur and or sulfur chloride in amounts equivalent to 8% by weight or more and 200% by weight or less as sulfur, and add 1 to 20% by weight of sulfur.
Chlorination was carried out under a pressure of Kg/cm 2 G, the crystals crystallized from the obtained chlorination reaction product were separated, the separated liquid obtained was used as it was, copper phthalocyanine was added thereto, chlorination was carried out again, and further The method is characterized in that the highly chlorinated copper phthalocyanine crystallized from the obtained chlorination reaction product may be separated, the obtained separated liquid may be used, and the operation of adding copper phthalocyanine thereto and chlorinating the same may be repeated. The invention consists in a method for producing highly chlorinated copper phthalocyanine. In the method of the present invention, chlorosulfonic acid or pyrosulfuryl chloride is generally used as the acid chloride solvent for the sulfur oxygen acid, and when sulfuryl chloride or thionyl chloride is used, it is preferable to use them together. Basically, the amount of the above solvent to be used should be within a range that dissolves or suspends the raw copper phthalocyanine and makes sufficient contact with the chlorine gas, but the reaction solution should be stirred using a stirrer commonly used in industry. The amount is preferably about 3 times to about 50 times the weight of the raw copper phthalocyanine, and industrially preferably 4 to 8 times the weight of the raw material copper phthalocyanine. The chlorination reaction in the method of the present invention is first carried out by adding sulfur or sulfur chloride (hereinafter referred to as catalyst A) as a catalyst. The reaction can be carried out with or without the addition of another chlorination catalyst (hereinafter referred to as B catalyst), but it is usually preferable to use a B catalyst such as iodine in combination, and the B catalyst is added to the solvent in a ratio of 0.01 to By adding 10% by weight, a bright yellowish-green pigment can be obtained in high yield. Catalyst B used in combination with catalyst A includes iodine, iodine chlorides such as iodine monochloride and iodine trichloride, anhydrous aluminum chloride, anhydrous ferric chloride,
Examples include metal compounds such as antimony trichloride and cupric chloride. The above catalyst A may be sulfur or sulfur chloride alone, but of course may be used in combination. The amount added is 14% by weight or more, preferably 16% by weight or more, more preferably 18% by weight or more, calculated as sulfur, for the chlorosulfonic acid solvent, and 8% by weight or more for the pyrosulfuryl chloride. Preferably 10% by weight or more, more preferably
The amount must be equivalent to 12% or more by weight. When the amount of sulfur or/and sulfur chloride added to chlorosulfonic acid or pyrosulfuryl chloride is above the lower limit (as sulfur), in the coexistence of catalyst B and copper phthalocyanine, at 20 to 120°C, 1 to
When the copper phthalocyanine is a highly chlorinated copper phthalocyanine in which 13 or more hydrogen atoms in the benzene nucleus are chlorinated when contacted with chlorine gas at 20 kg/cm 2 G, the reaction solvent (the chlorinated reaction product) The solubility in the total amount other than the highly chlorinated copper phthalocyanine decreases significantly to 1 g/100 g of reaction solvent or less. On the other hand, if the content of catalyst A is too large for either of the above solvents, chlorination becomes difficult, so the number of chlorine substitutions in one molecule of highly chlorinated copper phthalocyanine should be 13 or more for practical use in green pigments. Considering the number of substitutions, it can be said that the preferable upper limit for one catalyst is 200% by weight or less, preferably 100% by weight or less, as sulfur based on the above solvent. In addition, in the chlorination reaction of the present invention, when chlorosulfonic acid is used as a solvent, chlorosulfonic acid mainly reacts with catalyst A and chlorine as shown in the following formula to produce a mixture containing pyrosulfuryl chloride as the main component. It is presumed that the chlorination reaction of copper phthalocyanine then proceeds. 8SO 2 (OH)Cl+2S+6Cl 2 →4S 2 O 5 Cl 2 +2SO 2 Cl 2 +8HCl 8SO 2 (OH)Cl+S 2 Cl 2 +5Cl 2 →4S 2 O 5 Cl 2 +2SO 2 Cl 2 +8HCl I 2 +Cl 2 →2ICl or ICl 3 S 2 Cl 2 +Cl 2 →2SCl 2 That is, as mentioned above, when carrying out the present invention starting from a chlorosulfonic acid solvent, an amount equivalent to about 6 to 7% by weight of sulfur based on the solvent is pyrochloride. It is believed that the process is essentially the same as that carried out in a mixed solvent mainly consisting of pyrosulfuryl chloride. Pyrosulfuryl chloride can be prepared by known methods. Generally, it is prepared by adding sulfur to chlorosulfonic acid in an amount of 6 to 7% by weight of chlorosulfonic acid or equivalent sulfur chloride, and supplying chlorine to the mixture, but other methods such as sulfuric anhydride and tetrachloride It can also be prepared from carbon. Of course, substantially the same results can be obtained with any of the solvents, chlorosulfonic acid and pyrosulfuryl chloride. In the chlorination reaction of the method of the present invention, the reaction pressure is 1 to 20 Kg/cm 2 G, preferably 2 to
8 Kg/cm 2 G, more preferably 3 to 7 Kg/cm 2 G. At 1 to 2 Kg/cm 2 G, the yield of crude highly chlorinated copper phthalocyanine is 96% or more (relative to theory) and a clear pigment can be obtained, but the pigment has a rather strong bluish tinge. At 2 Kg/cm 2 G, especially above 3 Kg/cm 2 G, a clear yellowish green crude highly chlorinated copper phthalocyanine can be obtained in high yield. Although chlorine can be added in liquid or gaseous form, it is generally added in gaseous form. That is, 20 Kg/cm 2 G or more is industrially disadvantageous, and generally 10 Kg/cm 2 G or less, usually 8 Kg/cm 2 G or less where chlorine does not liquefy at room temperature, especially 7
Kg/cm 2 G or less is preferable. Further, the reaction temperature is initially low, and is raised from room temperature to 100 to 120°C as the reaction progresses, for example. At the highest reaction temperature it is advantageous to increase the reaction pressure as much as possible. When the temperature exceeds 120°C, the color tone of the pigment obtained is yellowish green and sufficiently clear, but the yield decreases significantly. In the process of the present invention, the chlorination reaction is usually carried out using chlorosulfonic acid or pyrosulfuryl chloride as the acid chloride solvent for the sulfuric acid;
A catalyst, optionally a B catalyst such as iodine, and a specified amount of copper phthalocyanine are added, and the mixture is brought into contact with chlorine under a specified pressure, generally gradually starting from room temperature.
Raise the temperature to 100-115℃. Usually, the temperature is maintained for about 1 to 4 hours, and then the chlorination reaction is completed. In the method of the present invention, highly chlorinated copper phthalocyanine is crystallized in the reaction product obtained as described above, but it is usually cooled and the crystals are separated by an appropriate method such as filtration, centrifugation (decantation), etc. etc),
Most or a portion of the solvent can be recovered as a separated liquid by natural sedimentation or the like. The separated liquid contains a small amount of highly chlorinated copper phthalocyanine, but it is less than 1% of the amount of the separated liquid, and the recovered separated liquid contains not only the solvent component but also A
Since the catalyst and B catalyst are also included, this separated liquid is used as it is without adding new catalyst A or B, and a predetermined amount of raw material copper phthalocyanine is added to it to adjust the pressure and temperature of the method of the present invention described above. It is also possible to repeat the chlorination operation by adding copper phthalocyanine to it using chlorine under certain conditions, and by such a method, similarly excellent highly chlorinated copper phthalocyanine can be obtained at a high yield. I can do it. In addition, the solvent recovered as the above-mentioned separated liquid was replenished with an amount of solvent and catalyst corresponding to the loss of solvent during the chlorination reaction and excessive separation operation, and the loss of solvent accompanying the cake, and the main process was carried out again. It goes without saying that it can be reused as a solvent or catalyst in the process of the invention. In the method of the present invention, the temperature of the reaction product in the separation operation to be carried out is as follows, since the reaction product contains compounds with high vapor pressure such as SO 2 Cl 2 , SOCl 2 , SCl 2 , etc. It is preferable to carry out the reaction at around room temperature, where the amount of loss of these low-boiling components is small. As a separation method, a filtration method is generally used, and any type of filtration machine can be used, but a pressurized sealing type is preferable to a vacuum filtration type. As mentioned above, the separation operation in the method of the present invention, such as filtration, is carried out at around room temperature, so there is no need to take any special measures regarding the material of the solid-liquid separator, such as filtration, so that corrosion of general-purpose metal materials is avoided. This is industrially advantageous compared to recovering solvents by distillation, which is difficult to select. After recovering the solvent, the cake containing highly chlorinated copper phthalocyanine, which usually contains 40 to 70% solvent, is directly poured into water or dilute sulfuric acid, followed by acid washing, alkali washing, and drying. However, the solvent contained as the liquid content of the cake described above may be added to the solvent recovered as a separated liquid in the next chlorination reaction with chlorosulfonic acid, which should be added as the missing amount. After washing the cake with a mixture of sulfur chloride and replacing the liquid components in the cake (including soluble highly chlorinated copper phthalocyanine) with a new solvent of chlorosulfonic acid and sulfur chloride, the cake is directly washed with water or dilute sulfuric acid. Pour in, pickle wash, alkaline wash, and dry. The solution obtained when washing the cake can be combined with the above-mentioned separated solution of the reaction product and reused as a reaction solvent. The obtained crude highly chlorinated copper phthalocyanine was converted into a pigment by a salt grinding method.
This pigment was clearly superior in sharpness compared to the case where the crude product obtained by the direct water injection method was similarly made into a pigment. In the present invention, highly chlorinated copper phthalocyanine crystals are separated from a reaction product, for example, by filtration, and the separated liquid is used as a reaction solvent to conduct a chlorination reaction of copper phthalocyanine. Furthermore, the amount of iodine and chlorine used can be greatly reduced, and the quality of the pigment obtained is excellent, which is an extremely remarkable effect industrially. Next, the present invention will be explained in more detail, but the present invention is not limited to the following examples. Example 1 Chlorination of copper phthalocyanine 380 parts of chlorosulfonic acid, 80 parts of sulfur (21% to chlorosulfonic acid) and 3.7 parts of iodine were first placed in a reactor, to which 75 parts of crude copper phthalocyanine (92% purity) was added. , stirred and dissolved. Next, add chlorine gas to the solution gradually from room temperature to 100°C.
It was supplied while raising the temperature to . At this time, the pressure in the reactor reached 3 Kg/cm 2 G in about 20 minutes, and the opening degree of the control valve at the outlet of the reactor was adjusted to match the amount of chlorine supplied so as to maintain this pressure thereafter. 360 parts of chlorine were fed over a period of 5 hours until the color of the solution changed from green-black to gradually reddish-crimson. As a result, 644 parts of chlorination reaction product were obtained. After cooling the reaction product to below 50℃,
Pour into ice water while stirring. Next, this was heated to 90°C with stirring, stirred for 1 hour, and filtered. Next, this cake was poured into 3000 parts of a 2% aqueous sodium hydroxide solution, stirred at 90°C for 1 hour, filtered, washed with water, and dried to give a crisp 132 parts of yellowish-green crude chlorinated copper phthalocyanine was obtained. The number of substituted chlorines in the phthalocyanine molecule of the product was 14.5, the purity was 96%, and the yield was 98% (based on theory). Example 2 644 parts of the chlorination reaction product obtained in the same manner as in Example 1 was divided into two parts, and 300 parts of them were divided into two parts with an inner diameter of 80 mm.
When vacuum filtration was carried out using Saran cloth in Nutsutie, 165 parts of filtrate cake (liquid content 62%) was obtained.
and 110 parts of liquid, and the solvent loss over time was 25 parts. This filter cake was placed in 600 parts of a 2% aqueous sulfuric acid solution, stirred at 90°C for 1 hour, and then washed with water. Next, this overcake was treated in the same manner in a 2% caustic soda aqueous solution and then dried. The amount of crude highly chlorinated copper phthalocyanine obtained was 62 parts. 300 parts of the other reaction product were added to 600 parts of 2% sulfuric acid, followed by acid washing, alkali washing, and drying in the same manner as in the case of the overcake above to obtain 63 parts of crude highly chlorinated copper phthalocyanine. (Comparative Example 1). When these two types of crude highly chlorinated copper phthalocyanine are converted into pigments by the salt grinding method (see US Pat. No. 2,982,666), reaction products are produced more than when using the direct water injection method (Comparative Example 1). Table 1 shows the measured values of the sharpness of these pigments. However, the sharpness
Hunter by National Bureau of Standard
It was measured using the Lab method and expressed as an absolute dye value. The following measurements were made in the same manner for Examples 2, 3, 5, and 7 and Comparative Examples 1 to 3. Example 3 300 parts of the chlorinated reaction product obtained in the same manner as in Example 1 was filtered under nitrogen gas pressure (6 kg/cm 2 G) in a Nutstier type pressurizer with an inner diameter of 80 mm. 150 parts of cake (liquid content 59%) and 130 parts of liquid
part, and the solvent loss over time was 20 parts. Comparing this with the case of vacuum filtration in Example 2, the case of pressurization filtration has a liquid content of 3% per cake.
The amount of loss over time was reduced by 2%. When this percake was purified in the same manner as in Example 2, 62 parts of crude chlorinated copper phthalocyanine was obtained. When this was converted into a pigment by the salt grinding method in the same manner as in Example 2, the sharpness (see Table 1) was the same as in Example 2, which was obtained by applying reduced pressure. Example 4 75 parts of crude copper phthalocyanine (purity 92%) was added to 480 parts of a liquid obtained by filtering the chlorination reaction product carried out in the same manner as in Example 1, and the mixture was stirred and dissolved. As in step 1, chlorine is supplied while gradually increasing the temperature from room temperature to 100℃, and the reaction pressure is
Adjust the opening of the reactor outlet valve to maintain 3.0Kg/cm 2 G. The color of the liquid changes from brownish-black to gradually reddish. Feed chlorine for 4 hours until deep red color. The total amount of chlorine fed was 160 parts. The reaction product was obtained by separating the precipitated highly chlorinated copper phthalocyanine by filtration as in Example 2.
Crude highly chlorinated copper phthalocyanine 136 with a clear yellowish green color after acid washing, alkali washing, water washing and drying.
I got the department. The number of chlorine substitutions in the phthalocyanine molecules of the product was 15.1, the purity was 96%, and the yield was 98% (based on theory). Furthermore, using the solvent recovered as the above liquid as is, crude copper phthalocyanine was added in the same proportion as above, and after chlorination in the same manner as above, the precipitated highly chlorinated copper phthalocyanine was separated by filtration. The subsequent treatment to obtain crude highly chlorinated copper phthalocyanine was repeated four times in sequence, and good results were obtained in all cases, similar to the above. In addition, in the solvent recovered as the liquid in Example 2,
The same results as in this example were obtained except that chlorosulfonic acid, sulfur, and iodine were added to compensate for losses. Example 5 A chlorination reaction was carried out in exactly the same manner as in Example 4, and the reaction product was divided into two parts, one by the filtration method as in Example 2 and the other by the direct water injection method (Comparative Example 2).
A crude highly chlorinated copper phthalocyanine was obtained. When these two types of crude highly chlorinated copper phthalocyanine were converted into pigments by the salt grinding method as in Example 2, the sharpness of the pigments obtained by the salt grinding method was better than that obtained by the direct water injection method. (See Table 1). Example 6 (1) Preparation of purified pyrosulfuryl chloride 1200 parts of carbon tetrachloride was added to 780 parts of anhydrous sulfuric acid, and when the temperature was raised from room temperature to 80°C over 3.5 hours, gas generation almost stopped. Thereafter, the temperature was maintained at 80°C for an additional hour. This generation amount is 1620
A portion was distilled under normal pressure to obtain 933 parts of purified pyrosulfuryl chloride (bp 147-152°C). (2) Chlorination of copper phthalocyanine First, 380 parts of purified pyrosulfuryl chloride obtained in (1) above, 57 parts of sulfur (15% to pyrosulfuryl chloride) and 3.7 parts of iodine were placed in a reactor, and 75 parts of crude copper phthalocyanine was added to the reactor. (purity 92%),
It was carried out in the same manner as in Example 1. As a result, 590 parts of chlorination reaction product was obtained. This reaction product was treated in the same manner as in Example 1 to produce a yellowish-green, highly chlorinated copper phthalocyanine.
Obtained 135 copies. The number of substituted chlorines in the phthalocyanine molecule of the product was 15.0, the purity was 96%, and the yield was 99% (based on theory). Example 7 640 parts of the chlorination reaction product obtained in the same manner as in Example 6 was divided into two parts, of which 290 parts were divided into Example 1.
When I did the same thing, I got 154 overcakes.
(liquid content: 60%) and 116 parts of liquid, and the solvent loss over time was 20 parts. This filter cake was post-treated in the same manner as in Example 2 to obtain 62 parts of crude highly chlorinated copper phthalocyanine. 290 parts of the other reaction product was post-treated by the direct water injection method (Comparative Example 3) as in Example 2 to obtain 63 parts of crude highly chlorinated copper phthalocyanine. When these two types of crude highly chlorinated copper phthalocyanine are converted into pigments by the salt grinding method as in Example 2, the overcake obtained by filtering the reaction product is superior to that obtained by the direct water injection method. The clarity was excellent (see Table 1). 【table】
第１図は、クロルスルホン酸を溶媒とし、塩化
硫黄の添加量を変えて銅フタロシアニンを塩素化
した場合に塩化硫黄の添加量に対する生成した高
塩素化銅フタロシアニン（塩素置換数約15ケ）の
溶解度を表す。
Figure 1 shows the ratio of highly chlorinated copper phthalocyanine (approximately 15 chlorine substitutions) to the amount of sulfur chloride added when copper phthalocyanine was chlorinated using chlorosulfonic acid as a solvent and varying the amount of sulfur chloride added. Represents solubility.
Claims (1)
スルホン酸を使用し塩素を用いて、銅フタロシア
ニンを塩素化する高塩素化銅フタロシアニンの製
造法において、クロルスルホン酸に対して硫黄と
して14重量％以上200重量％以下の硫黄および／
または硫黄の塩化物を触媒として加え、その他の
塩素化触媒を添加または添加せずに、１〜20Kg／
cm2Ｇの加圧下で塩素化し、得られた塩素化反応生
成物から晶出した高塩素化銅フタロシアニンを分
離し、得られた分離液をそのまま用いこれに銅フ
タロシアニンを添加して再び塩素化し、さらに得
られた塩素化反応生成物から晶出した高塩素化銅
フタロシアニンを分離し、得られた分離液を用
い、これに銅フタロシアニンを添加して塩素化す
る操作をくり返してもよいことを特徴とする高塩
素化銅フタロシアニンの製造法。 ２ 硫黄の酸素酸の酸塩化物溶媒として塩化ピロ
スルフリルを使用し塩素を用いて、銅フタロシア
ニンを塩素化する高塩素化銅フタロシアニンの製
造法において、塩化ピロスルフリルに対して硫黄
として８重量％以上200重量％以下の硫黄およ
び／または硫黄の塩化物を触媒として加え、その
他の塩素化触媒を添加または添加せずに、１〜20
Kg／cm2Ｇの加圧下で塩素化し、得られた塩素化反
応生成物から晶出した高塩素化銅フタロシアニン
を分離し、得られた分離液をそのまま用いこれに
銅フタロシアニンを添加して再び塩素化し、さら
に得られた塩素化反応生成物から晶出した高塩素
化銅フタロシアニンを分離し、得られた分離液を
用い、これに銅フタロシアニンを添加して塩素化
する操作を繰り返してもよいことを特徴とする高
塩素化銅フタロシアニンの製造法。[Claims] 1. In a method for producing highly chlorinated copper phthalocyanine in which copper phthalocyanine is chlorinated using chlorosulfonic acid and chlorine as an acid chloride solvent for a sulfur oxygen acid, 14% to 200% by weight of sulfur and/or
Or add sulfur chloride as a catalyst, with or without adding other chlorination catalyst, 1-20Kg/
The highly chlorinated copper phthalocyanine crystallized from the resulting chlorination reaction product was chlorinated under a pressure of cm 2 G, and the resulting separated liquid was used as it was and copper phthalocyanine was added thereto for chlorination again. Furthermore, it was found that it is possible to separate the highly chlorinated copper phthalocyanine crystallized from the obtained chlorination reaction product, use the obtained separated liquid, and repeat the operation of adding copper phthalocyanine to it and chlorinating it. Characteristic method for producing highly chlorinated copper phthalocyanine. 2. A method for producing highly chlorinated copper phthalocyanine in which copper phthalocyanine is chlorinated using pyrosulfuryl chloride as a sulfur oxygen acid chloride solvent and 8% by weight or more of sulfur based on pyrosulfuryl chloride. 1 to 20% by weight of sulfur and/or sulfur chloride as a catalyst, with or without the addition of other chlorination catalysts.
Chlorination was carried out under a pressure of Kg/cm 2 G, and the highly chlorinated copper phthalocyanine crystallized from the obtained chlorination reaction product was separated. The operation of chlorinating, separating highly chlorinated copper phthalocyanine crystallized from the obtained chlorination reaction product, using the obtained separated liquid, adding copper phthalocyanine to it, and chlorinating it may be repeated. A method for producing highly chlorinated copper phthalocyanine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8270379A JPS568457A (en) | 1979-07-02 | 1979-07-02 | Production of highly chlorinated copper phthalocyanine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8270379A JPS568457A (en) | 1979-07-02 | 1979-07-02 | Production of highly chlorinated copper phthalocyanine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS568457A JPS568457A (en) | 1981-01-28 |
| JPS6212821B2 true JPS6212821B2 (en) | 1987-03-20 |
Family
ID=13781752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8270379A Granted JPS568457A (en) | 1979-07-02 | 1979-07-02 | Production of highly chlorinated copper phthalocyanine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS568457A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4649689B2 (en) | 1999-07-09 | 2011-03-16 | ダイキン工業株式会社 | Process for producing polyfluoroalkyl esters and process for producing fluorine-containing acrylic copolymer using the ester |
-
1979
- 1979-07-02 JP JP8270379A patent/JPS568457A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS568457A (en) | 1981-01-28 |
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