JPH0715068B2 - Method for producing oxytitanium phthalocyanine - Google Patents
Method for producing oxytitanium phthalocyanineInfo
- Publication number
- JPH0715068B2 JPH0715068B2 JP31993689A JP31993689A JPH0715068B2 JP H0715068 B2 JPH0715068 B2 JP H0715068B2 JP 31993689 A JP31993689 A JP 31993689A JP 31993689 A JP31993689 A JP 31993689A JP H0715068 B2 JPH0715068 B2 JP H0715068B2
- Authority
- JP
- Japan
- Prior art keywords
- oxytitanium phthalocyanine
- methanol
- ray diffraction
- type
- sulfuric acid
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4
- C09B67/0019—Influencing the physical properties by treatment with an acid, H2SO4 of phthalocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0026—Crystal modifications; Special X-ray patterns of phthalocyanine pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は低結晶性オキシチタニウムフタロシアニンの製
造法に関する。さらに詳しくは特願平１−189199記載の
CuKα特性Ｘ線回折におけるブラッグ角２θの7.2±0.2
°、14.2±0.2°、24.0±0.2°および27.2±0.2°に強
いピークを有する低結晶性Ｍ型オキシチタニウムフタロ
シアニンの製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing low crystalline oxytitanium phthalocyanine. For more details, see Japanese Patent Application No. 1-189199
CuKα Characteristic X-ray diffraction Bragg angle 2θ 7.2 ± 0.2
The present invention relates to a method for producing low crystalline M-type oxytitanium phthalocyanine having strong peaks at °, 14.2 ± 0.2 °, 24.0 ± 0.2 ° and 27.2 ± 0.2 °.
従来、フタロシアニン系顔料は塗料、インキ、樹脂の着
色などの用途の他、触媒や電子写真感光体、太陽電池、
センサーなどに用いられる電子材料として注目され、盛
んに用いられるようになった。Conventionally, phthalocyanine-based pigments are used for coatings, inks, resin coloring, etc., as well as catalysts, electrophotographic photoreceptors, solar cells,
It has attracted attention as an electronic material used for sensors and has become popular.
オキシチタニウムフタロシアニンは、製造条件の微妙な
違いによって種々の結晶形が得られる。例えば、特開昭
59−49544号公報（USP4,444,861）、特開昭59−166959
号公報、特開昭61−239248号公報（USP4,728,592）、特
開昭62−67094号公報（USP4,664,997）、特開昭63−366
号公報、特開昭63−116158号公報、特開昭63−198067号
公報および特開昭64−17066号公報に示されているよう
に結晶形の異なるオキシチタニウムフタロシアニンが、
種々の条件により製造できる。Oxytitanium phthalocyanine can be obtained in various crystal forms depending on subtle differences in production conditions. For example,
59-49544 (USP 4,444,861), JP-A-59-166959
JP-A-61-239248 (USP4,728,592), JP-A-62-67094 (USP4,664,997), JP-A-63-366
JP-A-63-116158, JP-A-63-198067 and JP-A-64-17066, oxytitanium phthalocyanine having a different crystal form,
It can be manufactured under various conditions.
低結晶性Ｍ型オキシチタニウムフタロシアニンは、特願
平１−189199記載の製造法により実験室的に容易に、安
定して製造されるが、Ｍ型を得るために必要である非晶
質なオキシチタニウムフタロシアニンを製造する際に行
なう乾式粉砕は、強力な粉砕力を必要としており、大量
生産の際の装置の摩耗や、金属粉等の混入が起る。また
非晶質なオキシチタニウムフタロシアニンを製造する他
の方法として挙げられるアシツドペーシテイング法は、
生成する結晶が非常に細かく、濾過が遅いなど取り扱い
が難しかった。The low crystalline M-type oxytitanium phthalocyanine can be easily and stably produced in a laboratory by the production method described in Japanese Patent Application No. 1-189199, but it is an amorphous oxy-type compound necessary for obtaining the M-type. The dry crushing performed when manufacturing titanium phthalocyanine requires a strong crushing force, which causes wear of the device during mass production and mixing of metal powder and the like. In addition, the acid spacing method, which is another method for producing amorphous oxytitanium phthalocyanine, is
The crystals formed were very fine and the filtration was slow, making handling difficult.
従って、本発明は、工業化に適した、大量生産のできる
低結晶性Ｍ型オキシチタニウムフタロシアニンの製造方
法を提供することを目的とする。Therefore, it is an object of the present invention to provide a method for producing low-crystalline M-type oxytitanium phthalocyanine suitable for industrialization and capable of mass production.
本発明者らはＭ型オキシチタニウムフタロシアニンを工
業化に適した方法で製造するべく鋭意検討を重ねた結
果、濃硫酸に溶解させたのち、メタノールと水の混合溶
液中で再沈させることによりＭ型オキシチタニウムフタ
ロシアニンが得られることを見出し、本発明に至った。The present inventors have conducted extensive studies to produce M-type oxytitanium phthalocyanine by a method suitable for industrialization. As a result, the M-type oxytitanium phthalocyanine was dissolved in concentrated sulfuric acid and then reprecipitated in a mixed solution of methanol and water to give M-type. The inventors have found that oxytitanium phthalocyanine can be obtained, and completed the present invention.
すなわち、本発明は、オキシチタニウムフタロシアニン
を硫酸に溶解させたのち、メタノールと水の混合溶液中
で再沈させることを特徴とするCuKα特性Ｘ線回折にお
けるブラッグ角２θの7.2±0.2°、14.2±0.2°、24.0
±0.2°および27.2±0.2°に強いピークを有する低結晶
性オキシチタニウムフタロシアニンの製造方法である。That is, the present invention is characterized in that oxytitanium phthalocyanine is dissolved in sulfuric acid and then reprecipitated in a mixed solution of methanol and water, and the Bragg angle 2θ of CuKα characteristic X-ray diffraction is 7.2 ± 0.2 ° and 14.2 ±. 0.2 °, 24.0
It is a method for producing low crystalline oxytitanium phthalocyanine having strong peaks at ± 0.2 ° and 27.2 ± 0.2 °.
ここでオキシチタニウムフタロシアニンの構造は で表わされる。Where the structure of oxytitanium phthalocyanine is It is represented by.
ただし、X1，X2，X3，X4はClまたはBrを表わし、n,m,l,
kは０〜４の整数である。However, X 1 , X 2 , X 3 , and X 4 represent Cl or Br, and n, m, l,
k is an integer of 0-4.
Ｍ型オキシチタニウムフタロシアニンを製造するための
原料として用いるオキシチタニウムフタロシアニンは、
濃硫酸に溶解してから使用するため、いかなる結晶であ
っても、種々の多形の混合物であってもよい。用いる濃
硫酸の量はオキシチタニウムフタロシアニン１重量部に
対して10〜60重量部好ましくは25〜40重量部である。再
沈時に必要なメタノールと水の混合溶液の混合比は10％
〜90％、好ましくは40〜80％（メタノール重量％）であ
る。Oxytitanium phthalocyanine used as a raw material for producing M-type oxytitanium phthalocyanine is
Since it is used after being dissolved in concentrated sulfuric acid, any crystals may be used as well as a mixture of various polymorphs. The amount of concentrated sulfuric acid used is 10 to 60 parts by weight, preferably 25 to 40 parts by weight, based on 1 part by weight of oxytitanium phthalocyanine. Mixing ratio of methanol and water required for reprecipitation is 10%
˜90%, preferably 40 to 80% (methanol weight%).
〔実施例１〕 特開昭61−239248号公報（USP4,728,592）に開示されて
いる製造例に従って得られたＢ型のオキシチタニウムフ
タロシアニン1.0kgを、５℃以下に保った濃硫酸30.0kg
中に撹拌しながらゆつくりと加え、溶解させた。次に15
0kgのメタノールと150kgの氷水を混合、−10℃まで冷却
して、先のオキシチタニウムフタロシアニンの硫酸溶液
をこのメタノール−氷水溶液が−５℃以下になるように
冷却しながら４時間かけて滴下した。得られた青色結晶
を濾別、十分にメタノール及び水で洗浄して乾燥した。
このオキシチタニウムフタロシアニンはＸ線回折におけ
るブラッグ角２θの7.2°、14.0°、24.2°および27.2
°に強いピークを有しており、11.6°のところが肩にな
っていたがＭ型オキシチタニウムフタロシアニンであっ
た。Ｘ線回折図を第１図に示す。[Example 1] 1.0 kg of B-type oxytitanium phthalocyanine obtained according to the production example disclosed in JP-A-61-239248 (USP 4,728,592) and 30.0 kg of concentrated sulfuric acid kept at 5 ° C or lower
While stirring, the mixture was gently added and dissolved. Then 15
0 kg of methanol and 150 kg of ice water were mixed, cooled to -10 ° C, and the sulfuric acid solution of oxytitanium phthalocyanine was added dropwise over 4 hours while the methanol-ice aqueous solution was cooled to -5 ° C or lower. . The blue crystals obtained were filtered off, washed thoroughly with methanol and water and dried.
This oxytitanium phthalocyanine has a Bragg angle 2θ of 7.2 °, 14.0 °, 24.2 ° and 27.2 in X-ray diffraction.
It had a strong peak at 0 ° and had shoulders at 11.6 °, but it was M-type oxytitanium phthalocyanine. The X-ray diffraction pattern is shown in FIG.
〔実施例２〕 特開昭62−67094号公報（USP4,664,997）に開示されて
いる製造例に従って得られたＡ型のオキシチタニウムフ
タロシアニン1.0kgを、５℃以下に保った濃硫酸30.0kg
中に撹拌しながらゆつくりと加え、溶解させた。次に、
240kgのメタノールと60kgの氷水を混合、−10℃まで冷
却して、先のオキシチタニウムフタロシアニンの硫酸溶
液をこのメタノール−氷水溶液が−５℃以下になるよう
に冷却しながら６時間かけて滴下した。得られた青色結
晶を濾別、十分にメタノールおよび水で洗浄して乾燥し
た。このオキシチタニウムフタロシアニンは、Ｘ線回折
におけるブラッグ角２θの7.2°、14.0°、24.2°およ
び27.2°に強いピークを有しており、Ｍ型オキシチタニ
ウムフタロシアニンであった。Ｘ線回折図を第２図に示
す。[Example 2] 1.0 kg of A-type oxytitanium phthalocyanine obtained according to the production example disclosed in JP-A-62-67094 (USP 4,664,997) and concentrated sulfuric acid 30.0 kg kept at 5 ° C or lower
While stirring, the mixture was gently added and dissolved. next,
240 kg of methanol and 60 kg of ice water were mixed, cooled to -10 ° C, and the sulfuric acid solution of oxytitanium phthalocyanine was added dropwise over 6 hours while the methanol-ice aqueous solution was cooled to -5 ° C or lower. . The blue crystals obtained were filtered off, washed thoroughly with methanol and water and dried. This oxytitanium phthalocyanine was a M-type oxytitanium phthalocyanine because it had strong peaks at Bragg angles 2θ of 7.2 °, 14.0 °, 24.2 ° and 27.2 ° in X-ray diffraction. The X-ray diffraction pattern is shown in FIG.
比較例１ 実施例１で用いたＢ型オキシチタニウムフタロシアニン
2.0kgを濃硫酸60kg中に５℃以下でゆつくりと投入、溶
解させ、800kgの水中に25℃で１時間かけて滴下した。
得られた顔料を濾別、十分に水洗したのち乾燥した。得
られたオキシチタニウムフタロシアニンのＸ線回折図を
第３図に示す。Comparative Example 1 B-type oxytitanium phthalocyanine used in Example 1
2.0 kg was slowly added to 60 kg of concentrated sulfuric acid at 5 ° C. or lower, dissolved, and added dropwise to 800 kg of water at 25 ° C. over 1 hour.
The obtained pigment was filtered, washed thoroughly with water, and then dried. The X-ray diffraction pattern of the obtained oxytitanium phthalocyanine is shown in FIG.
比較例２ 実施例２で用いたＡ型オキシチタニウムフタロシアニン
20kgを濃硫酸60kg中に５℃以下でゆつくりと投入、溶解
させ、600kgのメタノール中に５℃で６時間かけて滴下
した。得られた顔料を濾別、十分に水洗浄、メタノール
洗浄を繰り返したのち乾燥した。Comparative Example 2 A-type oxytitanium phthalocyanine used in Example 2
20 kg was slowly added to 60 kg of concentrated sulfuric acid at 5 ° C. or lower, dissolved, and added dropwise to 600 kg of methanol at 5 ° C. over 6 hours. The obtained pigment was separated by filtration, washed sufficiently with water and washed with methanol, and then dried.
得られたオキシチタニウムフタロシアニンのＸ線回折図
を第４図に示す。The X-ray diffraction pattern of the obtained oxytitanium phthalocyanine is shown in FIG.
第１図、第２図は、それぞれ実施例1,2で得られた低結
晶性Ｍ型オキシチタニウムフタロシアニンのＸ線回折
図、 第３図、第４図はそれぞれ比較例1,2で得られたオキシ
チタニウムフタロシアニンのＸ線回折図、 第５図は実施例、比較例で使用したＢ型オキシチタニウ
ムフタロシアニンのＸ線回折図、 第６図は実施例、比較例で使用したＡ型オキシチタニウ
ムフタロシアニンのＸ線回折図である。1 and 2 are X-ray diffraction patterns of the low crystalline M-type oxytitanium phthalocyanine obtained in Examples 1 and 2, and FIGS. 3 and 4 are obtained in Comparative Examples 1 and 2, respectively. X-ray diffraction diagram of oxytitanium phthalocyanine, FIG. 5 is an X-ray diffraction diagram of B-type oxytitanium phthalocyanine used in Examples and Comparative Examples, and FIG. 6 is A-type oxytitanium phthalocyanine used in Examples and Comparative Examples. 2 is an X-ray diffraction diagram of FIG.
Claims (1)
溶解させたのち、メタノールと水の混合溶液中で再沈さ
せることを特徴とするCuKα特性Ｘ線回折におけるブラ
ッグ角２θの7.2±0.2°、14.2±0.2°、24.0±0.2°お
よび27.2±0.2°に強いピークを有する低結晶性オキシ
チタニウムフタロシアニンの製造方法。Claims: 1. Oxytitanium phthalocyanine is dissolved in sulfuric acid and then reprecipitated in a mixed solution of methanol and water. The Bragg angle 2θ in CuKα characteristic X-ray diffraction is 7.2 ± 0.2 ° and 14.2 ± 0.2. A process for producing low crystalline oxytitanium phthalocyanine having strong peaks at °, 24.0 ± 0.2 ° and 27.2 ± 0.2 °.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31993689A JPH0715068B2 (en) | 1989-12-08 | 1989-12-08 | Method for producing oxytitanium phthalocyanine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31993689A JPH0715068B2 (en) | 1989-12-08 | 1989-12-08 | Method for producing oxytitanium phthalocyanine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03181570A JPH03181570A (en) | 1991-08-07 |
| JPH0715068B2 true JPH0715068B2 (en) | 1995-02-22 |
Family
ID=18115896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31993689A Expired - Fee Related JPH0715068B2 (en) | 1989-12-08 | 1989-12-08 | Method for producing oxytitanium phthalocyanine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0715068B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH078961B2 (en) * | 1990-03-20 | 1995-02-01 | 富士ゼロックス株式会社 | Titanyl phthalocyanine crystal form conversion method |
| JPH04189873A (en) * | 1990-11-22 | 1992-07-08 | Fuji Xerox Co Ltd | Oxytitanium phthalocyanine hydrate crystal and electronic photograph photosensitizer using the same |
| JPH04198367A (en) * | 1990-11-28 | 1992-07-17 | Fuji Xerox Co Ltd | Titanylphthalocyanin crystal and electrophotographic photoreceptor using the same |
| JP2814872B2 (en) * | 1993-03-25 | 1998-10-27 | 富士ゼロックス株式会社 | Hydroxygallium phthalocyanine crystal, method for producing the same, and electrophotographic photoreceptor using the same |
-
1989
- 1989-12-08 JP JP31993689A patent/JPH0715068B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03181570A (en) | 1991-08-07 |
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