GB1558663A - Preparation of pigmentary phtalocyanine - Google Patents
Preparation of pigmentary phtalocyanine Download PDFInfo
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- GB1558663A GB1558663A GB3470775A GB3470775A GB1558663A GB 1558663 A GB1558663 A GB 1558663A GB 3470775 A GB3470775 A GB 3470775A GB 3470775 A GB3470775 A GB 3470775A GB 1558663 A GB1558663 A GB 1558663A
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- copper phthalocyanine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
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Abstract
Alpha-, beta- or gamma-Copper tetrazaporphin pigments are prepared by reacting an aromatic or aromatic heterocyclic orthodinitrile compound with copper or a copper donor at a temperature below 100 DEG C in the presence of an alkaline substance in a hydrophilic aliphatic organic solvent containing one or more hydroxyl groups, a copper tetrazaporphin pigment being added at the start of the reaction as a catalyst or/and to control the crystal shape. Pigments of excellent quality are obtained in high yield.
Description
(54) PREPARATION OF PIGMENTARY PHTHALOCYANINE
(71) We, CIBA-GEIGY AG., a Swiss
Body Corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method bv which it is to be performed, to be particularly described in and by the following statement: The present invention relates to the direct preparation of pigmentary phthalocyanines.
It is known that copper phthalocyanines can be prepared in which a metal phthalocyanine in conventional pigmentary form is added to the reaction mixture during synthesis, a) as a catalyst for increasing the rate of
phthalocyanine formation and to obtain
increased yields and b) as a seed to obtain a particular crystal
form of the copper phthalocyanine.
The addition of metal phthalocyanine derivatives during synthesis as crystal growth inhibitors is also known.
However the processes described in patent literature in which a metal phthalocyanine in conventional pigmentary form is added during synthesis take place above 100"C.
Japanese Patent Publication 83726/1974 describes the preparation of solvent stable copper phthalocyanine pigments, characterized as the reaction of a phthalodinitrile or indolenine compound with copper or a compound thereof at a temperature of not more than 100"C in a hydrophilic organic solvent in the presence of an alkaline substance and milled copper phthalocyanine of average particle diameter not more than 10 m, the individual particles of which have a surface in the solvent-unstable form while the centre contains a nucleus of solvent-stable form.
We have found, surprisingly, that by adding a copper phthalocyanine in conventional pigmentary form or certain copper phthalocyanine derivatives from the beginning of the reaction at a temperature below 100"C in a process for the preparation of alpha-, beta- or gamma phthalocyanine they act as catalysts or crystal form controllers or both and much better yield is obtained. High quality pigments are obtained without the need for acid-pasting or mechanical pulverisation. By "conventional pigmentery form" as used herein we mean a copper phthalocyanine which can be used as a pigment in its own right.
According to the present invention there is provided a process for the production of alpha-, beta-, and gamma-copper phthalocyanine pigments which comprises reacting an ortho-dinitrile compound of the general formula
in which A forms an aryl or aromatic heterocyclic radical, X is a hydrogen or halogen atom or a nitro, amino, sulphonic acid, carboxylic acid, alkyl or alkoxy group and n is an integer from 1 to 4; and copper or a copper compound capable of providing the central metal atom of a phthalocyanine pigment at a temperature below 100"C in the presence of an alkaline substance which is an alkali metal, a hydroxide, oxide, peroxide, alkoxide or carbonate of an alkali metal or of an alkaline earth metal in a hydrophilic aliphatic organic solvent containing one or more hydroxy groups and adding a catalyst or crystal form controller or both from the beginning of the reaction a) for alpha-, beta- or gamma pigments from
0.5 to 200% by weight of a copper
phthalocyanine in conventional pigmentary
form based on the theoretical weight of
pigment synthesized, or b) for alpha-pigments, from 0.5 to 10% by
weight of a copper phthalocyanine deriva
tive with a limited degree of substitution
as hereinafter defined based on the
theoretical weight of pigment synthesized.
Examples of the dinitriles are: aromatic dinitrile compounds such as phthalodinitrile, halogenated dinitrile compounds such as mono-, di-, tri- or tetra-chloro-phthalodinitrile and mono-, di-, tri- or tetra-bromophthalodinitrile, sulphonic acid-substituted phthalodinitrile compounds; carboxylic acid-substituted phthalodintrile compounds such as carboxylic acid phthalodintrile: nitro-substituted phthalodinitrile compounds; amino-substituted phthalodinitrile compounds; alkyl-substituted phthalodinitrile compounds such as methyl phthalodintrile and ethyl phthalodinitrile; alkoxy or aryloxy phthalodinitrile compounds such as methoxy phthalodinitrile, phenoxy phthalodinitrile and ethoxy phthalodinitrile; and heterocyclic dinitrile compounds such as 2,3-dicyano pyridine. The dinitrile compounds may be used in admixture.
Copper compounds that may be used in the present invention include, for example, cuprous oxide, cupric oxide, cuprous bromide, cupric bromide, copper sulphate, copper hydroxide and preferably cuprous chloride, cupric chloride and copper acetate. If copper is used it may be used as copper powder.
The copper or copper compound is preferably used in an amount of one or more moles per four moles of the dinitrile compound.
Examples of alkaline materials which may be used in the present invention are sodium oxide, sodium peroxide, sodium carbonate, potassium oxide, potassium peroxide, potassium hydroxide, potassium methoxide, potassium carbonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium peroxide, calcium hydroxide, barium oxide, barium hydroxide and preferably sodium metal, sodium methoxide and sodium hydroxide.
The alkaline material serves to maintain the reaction system in the alkaline state and to allow the reaction to proceed smoothly.
The alkaline materials are suitably used in an amount of up to 2 moles per mole of dinitrile, but the amount of alkaline substance may vary depending upon the copper salt used and the valency of the metal of the alkaline substance. For example, when sodium hydroxide is used, if the copper is monovalent it is preferred to use from 0.25 to 0.5 moles of NaOH per mole of the dinitrile compound and when the copper is divalent it is preferred to use from 0.5 to 0.75 moles of NaOH per mole of the dinitrile compound.
Hydrophilic aliphatic solvents containing a hydroxyl group which may be used in the process of the invention include, for example, monohydric or polyhydric hydrophilic alcohols such as propanol, isopropanol, n-butanol, isobutanol, secondary butanol, t-butanol and ethylene glycol, preferably methanol and ethanol; hydrophilic Cellosolves ("Cellosolve" is a Registered Trade Mark) such as methyl Cellosolve, ethyl Cellosolve and diethylene glycol ethyl ether. These solvents can be used alone or in admixture.
The solvents may be used in any desired amount provided that the reaction proceeds smoothly. Usually, the solvent will be used in amounts of from 2.0 to 15 times the amount of dinitrile compound.
When the catalyst and/or crystal form controller added from the beginning of the reaction is a copper phthalocyanine in conventional pigment, it may be alpha-, beta-, or gamma depending on the type of pigment required. The amount of copper phthalocyanine used may vary from 0.5 % to 200% by weight based on the theoretical weight of pigment synthesized depending on whether an alpha-, beta-, or gamma pigment is required. In the preparation of an alpha-, or gamma-phthXlo- cyanine, the amount of alpha- or gammaphthalocyanine added may be from 0.5 % to 40% by weight and preferably from 0.5% to 20% /) by weight for alpha-pigments and from 20% to 40% by weight for gamma-pigments based on the theoretical weight of pigment synthesized.However, in the preparation of beta-copper phthalocyanine the amount of beta copper phthalocyanine added as a crystal form controller/catalyst may be at least 400,0, and preferably at least 51% by weight based on the theoretical weight of pigment synthesized and especially from 100% to 150%.
By using such amounts a 100% beta pigment can be prepared directly in a one-step process. If the quantity of beta copper phthalocyanine added during synthesis is less than 40% by weight, gamma/beta mixtures are obtained instead of a 100% beta pigment.
The gamma/beta mixtures are converted to a 100% beta-pigment by a subsequent acidtreatment or treatment with a suitable aromatic organic solvent such as toluene, xylene or diethylaniline.
Then the catalyst and/or crystal form controller added from the beginning of the reaction in the preparation of alpha pigments is a copper phthalocyanine derivative with a limited degree of substitution, the degree of substitution of the copper phthalocyanine derivative is such that the substituents do not interfere substantially with the mechanism of the reaction and not more than 4 hydrogen atoms are replaced by other groups such as chloride, hydroxy or phenoxy.
The amount of copper phthalocyanine derivative is preferably from 1% to 7% by weight, based on the weight of alpha pigment synthesized. The copper phthalocyanine derivative may also act as a stabiliser for the alpha pigmentary form and also as a crystal growth inhibitor.
Examples of chlorinated copper phthalocyanines are mono-, di-, tri- and tetra-chloro copper phthalocyanine and examples of copper phthalocyanine sulphonic acids are those having the formula Cu Pc (SOsH),l (where n=l to 4).
A further embodiment of the invention is to use one or more organic or inorganic ammonium salts in addition to the alkaline substance. Examples of suitable inorganic and organic ammonium salts are ammonium chloride, ammonium sulphate; ammonium per sulphate, ammonium orthophosphate, ammonium metaphosphate, ammonium pyrophosphate, ammonium carbonate, ammonium bicarbonate, ammonium formate, ammonium acetate, and ammonium oxalate. The ammonium salts are suitably used in an amount of from 0.1 to l0 t, by weight, preferably from 0.5 to 6' > ' by weight, based on the dinitrile compound.
It has also been found advantageous to use a reducing agent such as sodium hydrosulphite and/or a nitrogen containing base such as pyridine.
When the catalyst and/or crystal form controller added from the beginning of the reaction is a copper phthalocyanine in the conventional pigmentary form, if desired there may also be added a metal phthalocyanine other than copper phthalocyanine or a metal phthalocyanine derivative which suppresses crystal growth and also in the case of the alpha pigments, achieves stability. Examples of metal phthalocyanine derivatives that may be used are those which may be added from the beginning of the reaction for the preparation of alpha pigments, as illustrated above.
The amount of phthalocyanine derivative added when used as a crystal growth inhibitor and added in addition to a catalyst and/or crystal form controller in conventional pigmentary form may be from 1% to 20% by weight, preferably leo/, to 10 % by weight based on the theoretical weight of pigment synthesized. The metal phthalocyanine derivative may be added at any time during or after synthesis or may be prepared in situ at the same time as the copper phthalocyanine pigments
The condensation reaction of the present invention is carried out at a temperature below 100"C and the actual temperature may vary according to the solvent used. However, particularly, a temperature of about 70"C gives good results.
After completion of the reaction, a pigment having a clean shade and a high colour strength may be obtained even by immediate filtration, water washing and drying of the reaction product. The pigment may be further treated with a dilute aqueous acid and/or a dilute aqueous alkali prior to the filtration and drying, if necessary.
The copper phthalocyanine pigments thus prepared exhibit high colour strength and clean hue and the pigments do not require a particle size reduction step as is the case with pigments synthesized by conventional methods.
If a compound such as dimethylglyoxime which can form a complex with the copper salt used in the reaction is added to the reaction mixture in any of the previous described embodiments of the invention, a phthalocyanine pigment can be produced in a higher yield.
It has also been found, in accordance-with another embodiment of the invention, that, when using a hydrophilic organic solvent, if up to 75, by weight of an acid based on the weight of hydrophilic organic solvent is added, followed by stirring, immediately after completion of the reaction without isolation if the pigment, a pigment with improved texture is obtained.
Acids which may be used include inorganic acids such as hydrochloric acid, sulphuric acid, phosphoric acid; and organic acids such as acetic acid, propionic acid and oxalic acid.
When the acid is added to a stabilised alphapigment or a beta-pigment, the amount of the acid will vary somewhat depending on the nature of the hydrophilic organic solvent but it will preferably be used in an amount of from 0.5 to 75'. bv weight especially from 3 to 50 Ó by weight based on the hydrophilic organic solvent. This amount corresponds to 0.015 to 2 times the amount of pigment formed and the process is commercially advantageous in that such a small amount of the acid is sufficient.
When the acid is added to a suspension of an unstabilised alpha-pigment the amount of strong mineral acid used, e.g. 98% sulphuric acid or concentrated phosphoric acid, preferably does not exceed 30% by weight based on the weight of solvent and the amount of organic acid does not exceed 40% by weight based on the weight of solvent.
The acid is suitably added dropwise, and after completion of the acid reaction the mixture may be filtered, washed and dried to obtain a pigment. If necessary the reaction mixture can be further treated with a dilute alkaline aqueous solution after filtration. The acid can be sufficiently removed from the pigment by filtration and water-washing.
In another embodiment of the present invention, high-speed stirring may be employed at the beginning of the reaction and the duration may conveniently be up to 30 minutes.
An example of a high-speed stirrer is a Silverson Mixer Model L2R capable of speeds of 6000 revolutions per minute. The actual speed used varies depending upon The nature and size of the experiment.
The following Examples 1 to 34 further illustrate the invention.
Example 1
To 100 grams methanol were added 0.9 grams dimethylglyoxime. When a solution had been obtained 6.2 grams cuprous chloride were added and the mixture was stirred until complete solution was obtained (a dark brown complex formation). Then there was added:
32 grams phthalonitrile
3.0 grams ammonium chloride
3.0 grams beta copper phthalocyanine
1.0 gram 1,2,4 - trichloro - 3 - phenoxy
copper phthalocyanine
The mixture was stirred for 1 hour at room temperature, and then 5 grams of sodium hydroxide were added slowly and 1 gram of pyridine dissolved in 10 millilitres of methanol were added dropwise while adding the sodium hydroxide. The mixture was stirred for a further 30 minutes at room temperature after the last addition of sodium hydroxide and pyridine.
The mixture was then reflexed for 8 hours, allowed to cool to room temperature and then 60 grams of 98 .. sulphuric acid were added dropwise and stirred for 1 hour at room temperature. The mixture was then neutralised to pH 7 to 8 with aqueous sodium hydroxide followed by stirring for 1/2 hour at room temperature and then 30 millilitres of diethylaniline were added. The mixture was refiuxed for 1-1/2 hours when the product was 100% beta-phthalocyanine.
50-;' hydrochloric acid was then added at room temperature until the pH was 1 to 2 and the mixture stirred for 1/2 hour. The product was finally filtered, washed with methanol and then with hot dilute hydrochloric acid, then hot dilute sodium hydroxide and dried at 50 to 60or. The yield was 36 grams.
Example 2
A similar procedure to that described in
Example 1 was followed except that an alpha phthalocyanine was used instead of beta phthalocyanine as the seed and after the 8 hour reflux and allowing to cool to room temperature 60 grams of 98% sulphuric acid was added dropwise and the mixture stirred for 1 hour at room temperature and then refluxed for half an hour. The mixture was finally filtered, washed with methanol, hot dilute hydrochloric acid and hot dilute sodium hydroxide before drying at 50--60"C. The yield was 36 g. of pigmentary alpha copper phthalocyanine.
Example 3
0.9 grams dimethylglyoxime were added to 350 millilitres of methanol and when a solution had been obtained, 6.2 grams of cuprous chloride were added and the mixture stirred till the dark brown complex formation is complete. There was then added:
32 grams phthalonitrile
3.0 grams ammonium chloride
45 grams beta copper phthalocyanine
1 gram 1,2,4 - trichloro - 3 - phenoxy- copper phthalocyanine.
The mixture was stirred for 1 hour at room temperature and then 4 grams of sodium metal was added slowly over 40 minutes together with 1 gram of pyridine dissolved in 10 millilitres methanol dropwise. The mixture was stirred for 1/2 hour at room temperature after the last addition of sodium and pyridine.
The mixture was refluxed for 8 hours and finally filtered, washed with methanol and then with hot dilute sodium hydroxide. After washing with water and then stirring for 1 hour at 9095 ~ C in dilute aqueous hydrochloric acid, the product was filtered washed neutral and dried at 50--60"C. The yield was 77 g. of pigmentary copper phthalocyanine.
Comparative Example A
To 100 grams CM ,OOH add:
32 grams phthalonitrile (95 ' . pure)
4.5 grams NaOH
2 grams Na,CO, Stir at room temperature to obtain a solution or fine dispersion. Then add:
1 gram ammonium chloride
2 grams ammonium phosphate
8.4 grams cupric chloride
Stir 1 hour, at room temperature and then reflux 10 hours. Filter, wash with methanol, hot dil., HCI and hot dil., NaOH. Wash neutral and dry at 50--60"C. The yield was 19.4 grams.
Comparative Example B
To 100 grams CHsOH add:
32 grams phthalonitrile (95 % pure)
6.2 grams cuprous chloride
3.0 grams ammonium chloride
Stir 1 hour, at room temperature and then add:
5 grams NaOH slowly and stir for 10
mins.
Then add:
0.9 grams dimethylglyoxime
Stir 1/2 hour at room temperature and then reflux 8 hours. Filter, wash with methanol, hot dilute HC1 and hot dilute NaOH. Wash neutral and dry at 50--60"C. The yield was 22 grams.
Example 4
To 100 grams CH,OH add:
32 grams phthalonitrile (95 0c, pure
6.2 grams cuprous chloride
3.0 grams ammonium chloride
1 gram unsubstituted pigmentary copper
phthalocyanine
Still 1 hour at room temperature and then add:
5 grams NaOH slowly and stir for 10
minutes.
Then add:
0.9 grams dimethylglyoxime
Stir 1/2 hour at room temperature and then reflux for 8 hours. Filter, wash with methanol, hot dilute HCI and hot dilute NaOH. Wash neutral and dry at 50-60 C. The yield was 32 grams.
Example 5
To 140 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95r;00 pure)
3.0 grams ammonium chloride
1 gram pigmentary beta-copper phthalo
cyanine.
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal (slowly)
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. The pigment is isolated and purified in the manner of Example 4.
The yield was 31.5 grams of pigmentary gamma-copper phthalocyanine together with a trace of beta-copper phthalocyanine which is equivalent to the pigmentary beta-copper phthalocyanine added during synthesis.
Example 6
To 140 grams CH3OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 ) pure)
3.0 grams ammonium chloride
12.4 grams pigmentary gamma-copper
phthalocyanine
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal (slowly)
1 gram pyridine dissolved in 10 millilitres CHaOH The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. The pigment is isolated and purified in the manner of Example 4. The yield was 43.4 grams of pigmentary gamma-copper phthalocyanine.
Example 7
To 100 grams CH,OH add:
32 grams phthalonitrile (95% pure)
6.2 grams cuprous chloride
3.0 grams ammonium chloride
1 gram of a copper phthalocyanine deriva
tive having the following formula:
(SO2 NH. CH2CH2OH)2 copper phthalocyanine tSO3H)2 Stir 1 hour at room temperature and then add:
5 grams NaOH, slowly
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise whilst adding the NaOH. Stir 1/2 hour at room temperature after the last addition of NaOH and pyridine.
Then add:
0.9 grams dimethylglyoxime
Stir 15 minutes at room temperature and finally reflux 8 hours. The pigment is isolated by filtration and then washed with CH3OH.
The press-cake is re-slurried in 1-2 % aqueous HCI and stirred at 9e95"C for 1 hour.
The pigment is then filtered and washed neutral. This process is repeated using 12% aqueous NaOH. After washing neutral, the pigment is dried at 50--60"C. The yield was 30 grams of pigmentary alpha-copper phthalocyanine.
Example 8
To 100 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95% pure)
3.0 grams ammonium chloride
1 gram
(SO NH. CH2CH2OH)2 copper phthalocyanine (SO3H)2 Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CH,OH.
lhe pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature, after the last addition of sodium and pyridine. Finally reflux 8 hours.
Allow to cool to room temperature and then add:
12 grams concentrated (98%) H2SO4, drop
wise
Stir 1 hour at room temperature and then reflux 1 hour. Filter, wash with methanol and then wash neutral with water. The press-cake is re-slurried in 12% aqueous NaOH and stirred at 90-95 0C for 1 hour. Finally filter, wash neutral and dry at 50--60"C. The yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Example 9
To 100 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 ;,. pure)
3.0 grams ammonium chloride
1 gram
(SO, NH. CH2CH2OH)2 copper phthalocyanine 'SO3H)e Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours.Allow to cool to room temperature and then add:
30 grams concentrated (98%) H2SO4, drop
wise
Stir 1 hour at room temperature and then reflux 1 hour. The product is isolated and after-treated (purified) in the manner of Example 8. The yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Example 10
To 100 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 ' pure)
3.0 grams ammonium chloride
1 gram copper phthalocyanine dyestuff of
the formula:
(SO, NH. CH2CH,OH), copper phthalocyanine (SO,H), Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours.Allow to cool to room temperature and then add: 60 grams concentrated (985C) ) H2SO4, drop- wise
Stir 1 hour at room temperature and then reflux 1/2 hour. The pigment is isolated and purified in the manner of Example 8. The yield was 31 grams of pigmentary alphacopper phthalocyanine.
Example 11
To 100 grams Cff?,OH add:
32 grams phthalonitrile (95% pure)
6.2 grams cuprous chloride
3.0 grams ammonium chloride
1 gram 1,2,4 - trichloro - 3 - phenoxy
copper phthalocyanine
Stir 1 hour at room temperature, then add:
5 grams NaOH, slowly
1 gram pyridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise whilst adding the NaOH. Stir 1/2 hour after the last addi- tion of NaOH and pyridine, then add:
0.9 grams dimethylglyoxime
Stir 15 minutes at room temperature and then reflux 8 hours. The product is isolated and purified in the manner of Example 7. The yield was 31 grams of pigmentary alphacopper phthalocyanine.
Example 12
To 100 grams CH.OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add: 32 grams phthalonitrile (95 pure) 3.0 grams ammonium chloride
1 gram 1,2,4 - trichloro - 3 - phenoxy
copper phthalocyanine
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CM SOH The pyridine is added dropwise, whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours.Allow to cool to room temperatrue and then add:
12 grams concentrated (98 1) H2SO4) drop
wise
Stir 1 hour at room temperature and then reflux 1 hour. The pigment is isolated and purified in the manner of Example 8. The yield was 31 grams of pigmentary alphacopper phthalocyanine.
Example 13
0.9 grams dimethylglyoxime
0.9 gram dimethylglyoxime
When a solution has been obtained, add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95% pure)
3.0 grams ammonium chloride
1 gram 1,2,4 - trichloro - 3 - phenoxy- copper phthalocyanine
Stir 1 hour at room temperature and then
add:
2.9 grams sodium metal, slowly
1 gram pvridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise, whilst adding
the sodium metal. Stir 1/2 hour at room temperature, after the last addition of sodium
and pyridine. Finally reflux 8 hours. Allow
to cool to room temperature and then add:
30 grams concentrated (98%) H2SO4, drop
wise
Stir 1 hour at room temperature and then reflux 1 hour.The pigment is isolated and purified in the manner of Example 8. The
yield was 31 grams of pigmentary alphacopper phthalocyanine.
Example 14
To 100 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is
complete and then add:
32 grams phthalonitrile (95 ojO pure)
3.0 grams ammonium chloride
1 gram 1,2,4 - trichloro - 3 - phenoxy- copper phthalocyanine
Stir 1 hour at room temperature and then
add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CHOH The pyridine is added dropwise, whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours.
Allow to cool to room temperature and then add:
60 grams concentrated (9S'.) H-SO1, drop
wise
Stir 1 hour at room temperature and then reflux 1/2 hour. The pigment is isolated and after-treated (purified) in the manner of Example 8. The yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Example 15
To 100 grams CH3OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 CO pure)
3.0 grams ammonium chloride
1 gram unsubstituted pigmentary alpha
copper phthalocyanine
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours, The pigment is isolated and purified in the manner of Example 7. The yield was 32 grams of pigmentary alpha-copper phthalocyanine.
Example 16
To 120 grams CH3OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 % pure) 3.G grams ammonium chloride
1 gram 1,2,4 - trichloro - 3 - phenoxy- copper phthalocyanine
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
100 grams acetic acid, dropwise
Stir 1 hour at room temperature and then reflux 2 hours.The pigment is isolated and purified in the manner of Example 8. The yield was 31 grams pigmentary alpha-copper phthalocyanine.
Example 17
To 100 grams CH.OH add:
32 grams phthalonitrile (950/;, pure)
6.2 grams cuprous chloride
3.0 grams ammonium chloride
1 gram pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
5 grams NaOH slowly
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise whilst adding the NaOH. Stir 1/2 hour at room temperature after the last addition of NaOH and pyridine.
Then add:
0.9 grams dimethylglyoxime
Stir 15 minutes at room temperature and then reflux 7-8 hours. Allow to cool to room temperature and then add:
60 grams concentrated (98%) H2SO4, drop
wise
Stir 1 hour at room temperature and then reflux till 100% beta is obtained. This normally takes 1/2 hour to 1 hour. The pigment is isolated in the manner of Example 8. The yield was 32 grams of beta-copper phthalocanine.
Example 18
To 100 grams CH3OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 % pure)
3.0 grams ammonium chloride
6 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature, after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
24 grams 98% H.SO4, dropwise
Stir 1 hour at room temperature and then neutralise with NaOH till pH=7 to 8.Add extra methanol if required. Finally reflux, till 100% beta is obtained. The pigment is isolated and purified in the manner of Example 7.
The yield was 37 grams of pigmentary betacopper phthalocyanine.
Example 19
To 280 grams CH:.OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained, add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile f950,i, pure)
3.0 grams ammonium chloride
45 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. The pigment is isolated and after-treated (purified) in the manner of Example 7. The yield was 76 grams of pigmentary beta-copper phthalocanine.
Example 20
To 280 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained, add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95 % pure)
3.0 grams ammonium chloride
45 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise, whilst adding
the sodium metal. Stir 1/2 hour at room
temperature after the last addition of sodium
and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
60 grams concentrated (98%) H2SO4, drop
wise
Stir 2 hours at room temperature and then isolate and purify in the manner of Example 8. The yield was 76 grams of pigmentary beta-copper phthalocyanine.
Example 21
To 240 grams CH3OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95S0 pure)
3.0 grams ammonium chloride
30 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres
CH,OH
The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last additioa of sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
60 grams concentrated (98:1) H2SO4, drop
wise
Stir 2 hours at room temperature. The pigment is isolated and purified in the manner of Example 8.The yield was 61 grams of pigmentary beta-copper phthalocyanine.
Example 22
To 200 grams CH,OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95% pure)
3.0 grams ammonium chloride
18 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly
1 gram pyridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise, whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
60 grams concentrated (98%) H2SO4, drop
wise
Stir 2 hours at room temperature.The pigment is isolated and after-treated (purified) in the manner of Example 8. The yield was 49 grams of pigmentary beta-copper phthalocyanine.
Example 23
To 160 grams CH:OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95çXo pure)
3.0 grams ammonium chloride
12 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
3.5 grams sodium metal, slowly
1 gram pvridine dissolved in 10 millilitres CH3OH The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature, after the last addition of sodium and pvridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
60 grams concentrated (98%) H SOr, drop
wise
Stir 2 hours at room temperature.The pigment is isolated and purified in the manner of Example 8. The yield was 43 grams of pigmentary beta-copper phthalocyanine.
Example 24
To 1400 millilitres CH. OH add:
3.6 grams dimethylglyoxime
When a solution has been obtained add:
24.8 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
128 grams phthalonitrile (95 Ó pure)
12.0 grams ammonium chloride
180 grams pigmentary beta-copper phthalo
cyanine
4 grams 1,2,4 - trichloro - 3 - phenoxy
copper phthalocyanine
Stir 1 hour at room temperature and then add:
16 grams sodium metal, slowly
4 millilitres pyridine dissolved in 40 milli
litres CH3OH The pyridine is added dropwise whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. The product is isolated and after-treated in the manner of Example 7.The yield was 308 grams pigmentary beta-copper phthalocyanine.
Example 25
To 280 grams CH3OH add:
0.9 grams dimethylglyoxime
When a solution has been obtained add:
6.2 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (95u,b pure)
3 grams ammonium chloride
45 grams pigmentary beta-copper phthalo
cyanine
1 gram
(SO2 NH. CWCH2OH) copper phthalocyanine (SO3H)2 stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly
1 millilitre pyridine dissolved in 10 milli
litres CH,OH
The pvridine is added dropwise, whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours.Allow to cool to room temperature and then add:
60 grams concentrated (98 5) H.2SO4, drop
wise
Stir 1 hour at room temperature and then reflux 1/2 hour. The product is isolated and purified in the manner of Example 8. The yield was 77 grams of pigmentary beta-copper phthalocyanine.
Example 26
To 1050 millilitres CH3OH add:
2.7 grams dimethylglyoxime
When a solution has been obtained add:
18.6 grams cuprous chloride
Stir till the dark brown complex formation is complete and then add:
96 grams phthalonitrile (95 % pure)
9 grams ammonium chloride
3 grams 1,2,4 - trichloro - 3 - phenoxy
copper phthalocyanine
135 grams pigmentary beta-copper phthalo
cyanine
Stir 1 hour at room temperature and then add:
12 grams sodium metal, slowly
3 grams pyridine dissolved in 30 millilitres cH,OH The pyridine is added dropwise, whilst adding the sodium metal. Stir 1/2 hour at room temperature after the last addition of sodium and pyridine. Finally - reflux 8 hours.Allow to cool to room temperature and then add:
180 grams concentrated (98%) ISO,, dropwise
Stir 1 hour at room temperature and then reflux 1/2 hour. The product is isolated and after-treated in the manner of Example 8.
The yield was 228 grams pigmentary betacopper phthalocyanine.
Example 27
To a 500 millilitre flask add:
150 millilitres ethylene glycol
32.7 grams phthalodinitrile (98%)
0.9 grams dimethylglyoxime
3.0 grams ammonium chloride
8.8 grams cupric chloride
Then add dropwise over 30 minutes:
80 millilitres of a 25% solution of sodium
methoxide in CHsOH After the addition of sodium methoxide add 1.5 grams pigmentary mono-chloro-copper phthalocyanine. Finally raise the temperature to reflux and reflux 8 hours. After refluxing for 8 hours, filter, wash with methanol and then water. The pigment is purified in the manner of Example 7. The yield was 18 grams of pigmentary alpha copper phthalocyanine.
Example 28
By following a similar procedure to that described in Example 27 but using 4 grams ammonium acetate in place of the ammonium chloride there used, 20 grams of pigmentary alpha copper phthalocyanine were obtained.
Example 29
To a 500 millilitre flask add:
100 millilitres methanol
32.7 grams phthalodiniuile (98%)
0.9 grams dimethylglyoxime
3.0 grams ammonium chloride
2.0 grams triethanolamine 8.8 grams cupric chloride
Then add dropwise over 30 minutes:
80 millilitres of a 25 % solution of sodium
methoxide in CH,OH
After the addition of sodium methoxide add 1.5 grams pigmentary mono-chloro-copper phthalocyanine. Finally raise the temperature to reflux and reflux 8 hours. After reflux, filter, wash with methanol and then water. The pigment is purified in the manner of Example 7 to give 28 grams of pigmentary alpha copper phthalocyanine.
Example 30
To a 1 litre flask add:
150 millilitres methanol
34.3 grams phthalodinitrile (98 ,S,) 0.9 grams dimethylglyoxime
6.4 grams cuprous chloride
3.0 grams ammonium chloride
10 grams 1,2,3,4 tetrachloro copper phthalo
cyanine.
1.0 grams potassium hydroxide pellets are added whilst the suspension is high speed stirred using a Silverson High Speed stirrer.
High speed stir for 10 minutes after the last addition of potassium hydroxide. The reaction mixture is then refluxed under moderate agitation for 8 hours. After reflux, filter, wash with methanol and then water. The pigment is purified in the manner of Example 7 to give 26.5 grams of pigmentary alpha copper phthalocyanine.
Example 31
To a litre flask add:
150 millilitres methanol
32.7 grams phthalodinitrile (98%)
0.9 grams dimethylglyoxime
3.0 grams ammonium chloride
6.4 grams cuprous chloride
1.0 gram 1,2,3,4 - tetra - chloro - copper
phthalocyanine.
Add: 5.5 grams NaOH whilst the reaction mixture is high speed stirred using a Silverson
High Speed stirrer. High speed stir for 10 minutes after the last addition of NaOH. The reaction mixture is then refluxed under moderate agitation for 8 hours.
After reflux, filter, wash with methanol and then water. The pigment is purified in the manner of Example 7 to give 30.5 grams pigmentary alpha copper phthalocyanine.
Example 32
By following a similar procedure to that described in Example 31 but adding 6.0 grams urea after the addition of ammonium chloride and prior to the addition of cuprous chloride 26 grams of pigmentary alpha copper phthalocyanine were obtained.
Example 33
By following a similar procedure to that described in Example 31 but using 6.0 grams ammonium sulphate in place of the ammonium chloride there used, 26.5 grams nf pigmentary alpha copper phthalocyanine were obtained.
Example 34
By following a similar procedure to that described in Example 31 but adding 1.0 gram sodium dithionite after the addition of ammonium chloride and prior to the addition of cuprous chloride, 28 grams of pigmentary alpha copper phthalocyanine were obtained.
WHAT WE CLAIM IS:- 1. A process for the production of alpha-, beta-, and gamma-copper phthalocyanine pigments which comprises reacting an orthodinitrile compound of the general formula
in which A forms an aryl or aromatic heterocyclic radical, X is a hydrogen or halogen atom or a nitro, amino, sulphonic acid, carboxylic acid, alkyl or alkoxy group and n is an integer from 1 to 4; and copper or a copper compound capable of providing the central metal atom of a phthalocyanine pigment at a temperature below 100"C in the presence of an alkaline substance which is an alkali metal, a hydroxide, oxide, peroxide, alkoxide or carbonate of an alkali metal or of an alkaline earth metal in a hydrophilic aliphatic organic solvent containing one or more hydroxy groups and adding as catalyst or crystal form controller or both from the beginning of the reaction:: a) for alpha-, beta-, gamma pigments from
0.5 to 200% by weight of a copper
phthalocyanine in conventional pigmentary
form based on the theoretical weight of b) for alpha - pigments, from 0.5 to 10 O(, bv
pigment synthesized or
weight of a copper phthalocyanine deriva
tive with a limited degree of substitution
as hereinbefore defined based on the
theoretical weight of pigment svnthesized 2. A process as claimed in Claim 1 in which the orthodinitrile is phthalodinitrile.
3. A process as claimed in Claim 1 or
Claim 2 in which the copper compound capable of providing the central metal atom of the phthalocyanine pigment is cuprous chloride, cupric chloride or copper acetate.
4. A process as claimed in any of Claims 1 to 3 in which the copper or copper compound is used in an amount of one or more moles per four moles of the dinitrile compound.
5. A process as claimed in any of Claims 1 to 4 in which the alkaline material is sodium metal, sodium methoxide or sodium hydroxide.
6. A process as claimed in any of Claims 1 to 5 in which the alkaline material is used in ..it amount of up to 2 moles per mole of dinitrile.
7. A process as claimed in any of the preceding claims in which the hydrophlic aliphatic solvent containing a hydroxyl group is methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tbutanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether.
8. A process as claimed in any of Claims 1 to 7 in which the amount of hydrophilic aliphatic solvent is used in an amount of from 2.0 to 15 times the amount of dinitrile compound.
9. A process as claimed in any of the preceding claims in which the catalyst or crystal form controller added from the beginning of the reaction is an alpha-, beta-, or gamma copper phthalocyanine in conventional pigmentary form.
10. A process as claimed in Claim 9 in which the alpha copper phthalocyanine is added in an amount of from 0.5% to 40% by weight based on the theoretical weight of pigment synthesized.
11. A process as claimed in Claim 9 in which the gamma copper phthalocyanine is added in an amount from 0.5% to 40% by weight based on the theoretical weight of pigment synthesized.
12. A process as claimed in Claim 9 in which the beta copper phthalocyanine is added in an amount from 40% to 150% by weight based on the theoretical weight of pigment synthesized.
13. A process as claimed in any of Claims 1 to 8 for the preparation of an alpha-pigment in which the copper phthalocyanine derivative with a limited degree of substitution is added in an amount from 1 % to 7% by weight based on the theoretical weight of alpha pigment synthesized.
14. A process as claimed in any of Claims 1 to 8 and 13 in which the copper phthalocyanine derivative with a limited degree of substitution is a chlorinated copper phthalocyanine, a copper phthalocyanine sulphonic acid, 1,2,4 - trichloro - 3 - phenoxy copper phthalocyanine or
15. A process as claimed in claim 14 in which the chlorinated copper phthalocyanine
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (35)
1. A process for the production of alpha-, beta-, and gamma-copper phthalocyanine pigments which comprises reacting an orthodinitrile compound of the general formula
in which A forms an aryl or aromatic heterocyclic radical, X is a hydrogen or halogen atom or a nitro, amino, sulphonic acid, carboxylic acid, alkyl or alkoxy group and n is an integer from 1 to 4; and copper or a copper compound capable of providing the central metal atom of a phthalocyanine pigment at a temperature below 100"C in the presence of an alkaline substance which is an alkali metal, a hydroxide, oxide, peroxide, alkoxide or carbonate of an alkali metal or of an alkaline earth metal in a hydrophilic aliphatic organic solvent containing one or more hydroxy groups and adding as catalyst or crystal form controller or both from the beginning of the reaction:: a) for alpha-, beta-, gamma pigments from
0.5 to 200% by weight of a copper
phthalocyanine in conventional pigmentary
form based on the theoretical weight of b) for alpha - pigments, from 0.5 to 10 O(, bv
pigment synthesized or
weight of a copper phthalocyanine deriva
tive with a limited degree of substitution
as hereinbefore defined based on the
theoretical weight of pigment svnthesized
2. A process as claimed in Claim 1 in which the orthodinitrile is phthalodinitrile.
3. A process as claimed in Claim 1 or
Claim 2 in which the copper compound capable of providing the central metal atom of the phthalocyanine pigment is cuprous chloride, cupric chloride or copper acetate.
4. A process as claimed in any of Claims 1 to 3 in which the copper or copper compound is used in an amount of one or more moles per four moles of the dinitrile compound.
5. A process as claimed in any of Claims 1 to 4 in which the alkaline material is sodium metal, sodium methoxide or sodium hydroxide.
6. A process as claimed in any of Claims 1 to 5 in which the alkaline material is used in ..it amount of up to 2 moles per mole of dinitrile.
7. A process as claimed in any of the preceding claims in which the hydrophlic aliphatic solvent containing a hydroxyl group is methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tbutanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether.
8. A process as claimed in any of Claims 1 to 7 in which the amount of hydrophilic aliphatic solvent is used in an amount of from 2.0 to 15 times the amount of dinitrile compound.
9. A process as claimed in any of the preceding claims in which the catalyst or crystal form controller added from the beginning of the reaction is an alpha-, beta-, or gamma copper phthalocyanine in conventional pigmentary form.
10. A process as claimed in Claim 9 in which the alpha copper phthalocyanine is added in an amount of from 0.5% to 40% by weight based on the theoretical weight of pigment synthesized.
11. A process as claimed in Claim 9 in which the gamma copper phthalocyanine is added in an amount from 0.5% to 40% by weight based on the theoretical weight of pigment synthesized.
12. A process as claimed in Claim 9 in which the beta copper phthalocyanine is added in an amount from 40% to 150% by weight based on the theoretical weight of pigment synthesized.
13. A process as claimed in any of Claims 1 to 8 for the preparation of an alpha-pigment in which the copper phthalocyanine derivative with a limited degree of substitution is added in an amount from 1 % to 7% by weight based on the theoretical weight of alpha pigment synthesized.
14. A process as claimed in any of Claims 1 to 8 and 13 in which the copper phthalocyanine derivative with a limited degree of substitution is a chlorinated copper phthalocyanine, a copper phthalocyanine sulphonic acid, 1,2,4 - trichloro - 3 - phenoxy copper phthalocyanine or
15. A process as claimed in claim 14 in which the chlorinated copper phthalocyanine
is mono-, di-, tri- or tetra-chloro copper phthalocyanine.
16. A process as claimed in Claim 14 in which the copper phthalocyanine sulphuric acid has the formula CuPc(SO3H) where n is 1 to 4.
17. A process as claimed in any of the preceding claims in which there is used in addition an organic or inorganic ammonium salt.
18. A process as claimed in claim 17 in which the ammonium salt is ammonium chloride, ammonium sulphate, ammonium persulphate, ammonium orthophosphate, ammonium metaphosphate, ammonium pyrophosphate, ammonium carbonate, ammonium bicarbonate, ammonium formate, ammonium acetate, or ammonium oxalate.
19. A process as claimed in Claim 17 or
Claim 18 in which the amount of ammonium salt used is from 0.5% to 6% by weight, based on the weight of dinitrile compound.
20. A process as claimed in any of the preceding claims in which there is used in addition sodium hydrosulphite and/or pyridine.
21. A process as claimed in any of Claims 1 to 12 or 17 to 20 in which the catalyst and/or crystal form controller added from the beginning of the reaction is a copper phthalocyanine in conventional pigmentary form, there is added in addition a metal phthalocyanine other than copper phthalocyanine.
22. A process as claimed in any of Claims 1 to 12 or 17 to 20 in which the catalyst and/or crystal form controller added from the beginning of the reaction is a copper phthalocyanine in conventional pigmentary form, there is added in addition a metal phthalocyanine derivative.
23. A process as claimed in Claim 22 in which the metal phthalocyanine derivative is a chlorinated copper phthalocyanine, a copper phthalocyanine sulphuric acid, 1,2,4 - trichloro - 3 - phenoxy copper phthalocyanine or
24. A process as claimed in claim 23 in which the chlorinated copper phthalocyanine is mono-, di- tri- or tetra-chloro copper phthalocyanine.
25. A process as claimed in Claim 23 in which the copper phthalocyanine sulphonic acid has the formula CuPc(SO,H), where n is 1 to 4.
26. A process as claimed in any of Claims 22 to 25 in which the metal phthalocyanine derivative is added in an amount from ltjó to 20% by weight based on the theoretical weight of pigment synthesized.
27. A process as claimed in any of the preceding claims in which a compound which can form a complex with the copper salt used in the reaction is added to the reaction mixture.
28. A process as claimed in Claim 27 in which the compound which can form a complex with the copper salt used in the reaction is dimethylglyoxine.
29. A process as claimed in Claim 27 or
Claim 28 in which the amount of compound which can form a complex with the copper salt used in the reaction is from 0.2 to 5.0% by weight, based on the weight of the dinitrile compound.
30. A process as claimed in any of Claims 27 to 29 in which the reaction is carried out at a temperature from 60"C to 65"C.
31. A process as claimed in any of the preceding claims in which up to 75 ss0 by weight of acid is added, followed by stirring, immediately after completion of the reaction without isolation of the pigment.
32. A process as claimed in claim 31 in which the acid used is hydrochloric acid, sulphuric acid, phosphoric acid, acetic acid, propionic acid or oxalic acid.
33. A process as claimed in Claim 31 or
Claim 32 in which the amount of acid used is from 3% to 50 , by weight based on the weight of the hydrophilic organic solvent.
34. A process as claimed in Claim 1 sub stantially as described in any of Examples 1 to 34.
35. An alpha-, beta-, or gamma-copper phthalocyanine pigment whenever prepared by a process as claimed in any of the preceding claims.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3470775A GB1558663A (en) | 1975-08-21 | 1975-08-21 | Preparation of pigmentary phtalocyanine |
| CH1051476A CH626114A5 (en) | 1975-08-21 | 1976-08-18 | Process for preparing tetrazaporphin pigments |
| DE19762637202 DE2637202A1 (en) | 1975-08-21 | 1976-08-18 | METHOD FOR MANUFACTURING PHTHALOCYANINE PIGMENTS |
| CA259,457A CA1084911A (en) | 1975-08-21 | 1976-08-19 | Preparation of alpha-, beta-, and gamma-copper phthalocyanine pigments |
| FR7625309A FR2321527A1 (en) | 1975-08-21 | 1976-08-20 | PROCESS FOR THE PREPARATION OF COPPER PHTHALOCYAN PIGMENTS OF VARIETIES A, B E G |
| JP10012776A JPS5226529A (en) | 1975-08-21 | 1976-08-21 | Process for manufacture of alphaa* betaa* gammaacopper phthalocyanine pigments |
| US05/872,300 US4152171A (en) | 1975-08-21 | 1978-01-25 | Preparation of α- β- and γ-copper phthalocyanine pigments |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3470775A GB1558663A (en) | 1975-08-21 | 1975-08-21 | Preparation of pigmentary phtalocyanine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1558663A true GB1558663A (en) | 1980-01-09 |
Family
ID=10368974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3470775A Expired GB1558663A (en) | 1975-08-21 | 1975-08-21 | Preparation of pigmentary phtalocyanine |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5226529A (en) |
| CA (1) | CA1084911A (en) |
| CH (1) | CH626114A5 (en) |
| DE (1) | DE2637202A1 (en) |
| FR (1) | FR2321527A1 (en) |
| GB (1) | GB1558663A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4694078A (en) * | 1985-06-20 | 1987-09-15 | Ciba-Geigy Corporation | Production of pigmentary copper phthalocyanine |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3001002A1 (en) * | 1980-01-12 | 1981-07-16 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING METAL PHTHALOCYANINES |
| US4785091A (en) * | 1986-10-31 | 1988-11-15 | Sumitomo Chemical Company, Limited | Process for producing copper phthalocyanine pigment |
| GB9202291D0 (en) * | 1992-02-04 | 1992-03-18 | Ici Plc | Pigment composition |
| US5384342A (en) * | 1993-08-30 | 1995-01-24 | Dsm Desotech, Inc. | Vinyl ether urethane silanes |
| DE19652241A1 (en) * | 1996-12-16 | 1998-06-18 | Basf Ag | Process for the production of metal-free phthalocyanine under control of the modification formed |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR6909988D0 (en) * | 1968-08-26 | 1973-01-23 | Xerox Corp | PROCESS OF PREPARATION OF FATOCYANINE T IN FORMAL METAL FREE |
| US3897450A (en) * | 1970-02-10 | 1975-07-29 | Dainichiseika Color Chem | Metal phthalocyanine type pigment |
| JPS501122A (en) * | 1973-05-04 | 1975-01-08 | ||
| JPS5044225A (en) * | 1973-08-24 | 1975-04-21 |
-
1975
- 1975-08-21 GB GB3470775A patent/GB1558663A/en not_active Expired
-
1976
- 1976-08-18 CH CH1051476A patent/CH626114A5/en not_active IP Right Cessation
- 1976-08-18 DE DE19762637202 patent/DE2637202A1/en not_active Withdrawn
- 1976-08-19 CA CA259,457A patent/CA1084911A/en not_active Expired
- 1976-08-20 FR FR7625309A patent/FR2321527A1/en active Granted
- 1976-08-21 JP JP10012776A patent/JPS5226529A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4694078A (en) * | 1985-06-20 | 1987-09-15 | Ciba-Geigy Corporation | Production of pigmentary copper phthalocyanine |
| US4801638A (en) * | 1985-06-20 | 1989-01-31 | Ciba-Geigy Corporation | Production of pigmentary copper phthalocyanine |
| US4801634A (en) * | 1985-06-20 | 1989-01-31 | Ciba-Geigy Corporation | Production of pigmentary copper phthalocyanine |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1084911A (en) | 1980-09-02 |
| FR2321527A1 (en) | 1977-03-18 |
| FR2321527B1 (en) | 1979-06-29 |
| DE2637202A1 (en) | 1977-03-03 |
| JPS5226529A (en) | 1977-02-28 |
| CH626114A5 (en) | 1981-10-30 |
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