CA1084911A - Preparation of alpha-, beta-, and gamma-copper phthalocyanine pigments - Google Patents
Preparation of alpha-, beta-, and gamma-copper phthalocyanine pigmentsInfo
- Publication number
- CA1084911A CA1084911A CA259,457A CA259457A CA1084911A CA 1084911 A CA1084911 A CA 1084911A CA 259457 A CA259457 A CA 259457A CA 1084911 A CA1084911 A CA 1084911A
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- Prior art keywords
- copper
- grams
- weight
- copper phthalocyanine
- pigment
- Prior art date
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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
- C09B67/0033—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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- Organic Chemistry (AREA)
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Abstract
PREPARATION OF ALPHA-, BETA, AND GAMMA-COPPER PHTHALOCYANINE
PIGMENTS
Abstract of the Disclosure A process for the production of alpha-, beta-, and gamma-copper phthalocyanine pigments by reacting an aromatic or aromatic heterocyclic ortho-dinitrile compound 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 a alkaline substance in a hydrophilic aliphatic organic solvent containing one or more hydroxy groups and adding a copper phthalocyanine in conventional pigmentary form from the beginning of the reaction as a catalyst or crystal form controller or both.
PIGMENTS
Abstract of the Disclosure A process for the production of alpha-, beta-, and gamma-copper phthalocyanine pigments by reacting an aromatic or aromatic heterocyclic ortho-dinitrile compound 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 a alkaline substance in a hydrophilic aliphatic organic solvent containing one or more hydroxy groups and adding a copper phthalocyanine in conventional pigmentary form from the beginning of the reaction as a catalyst or crystal form controller or both.
Description
- 10849~
The preseIlt invention relates to tIIe direct proparation of pi~lcIltary phthalocyan~nes.
It is Icnown 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 additior. of metal phthalocyanine derivatives durin~
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 100C.
Japanese Patent Publication 83726/l974 describcs 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 temperaturc of not more than l00C in a hydrophilic organic æolvent in the presence of an alkaline substance and milled copper phthalocyanine of average particle diamcter not more than 10 m~ the individual particles of which have a surface ïn the solvent-unstable form while the centre contains a nucleus of solvent-stable form.
_z ' ~ :
~49~3 We have found, surprisingly, that by adding a copper phthalocyanine in conventional pigmentary form from the beginning of the reaction at a tem-perature below 100 C in a process for the preparation of alpha-, beta- or gamma-phthalocyanine it acts as a catalyst or crystal form controller or both and much better yield is obtained. High quality pigments are obtained with-out the need for acid-pasting or mechanical pulverisation.
According to the present invention there is provided in a process for-!the production of alpha-, beta- or gamma-copper phthalocyanine pigments which comprises reacting an ortho-phthalodinitrilo or substituted ortho-phthalodinitrile compound of the general formula ~ CN
Xn ~ CN
in which X i8 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 a hydroxide, oxide, peroxide, alkoxide or carbon- .
: ate of an alkali metal or of an alkaline earth metal in a hydrophilic ali-phatic organic solvent containing one or more hydroxy groups, the improvement whereby high quality pigments are obtained without need for acid-pasting or mechanical pulverization which comprises adding as crystal form controller from the beginning of the reaction:
(i) in the case where an alpha-copper phthalocyanine pigment i9 required:
~; - 3 -~, .
~. , ; .
1~349~1 (a) 0.5% to 40% by weight, based on the weight of pigment synthe-sized, of an alpha-phase copper phthalocyanine pigment or (b) 0.5% to 10% by weight, based on the weight of pigment synthe-si~ed, of a copper phthalocyanine derivative selected from the group consist-ing of chlorinated copper phthalocyanine, copper phthalocyanine sulfonic acid, 1,2,4-trichloro-3-phenoxy copper phthalocyanine or CuPc \(S03H)2 (ii) in the case where a beta-copper phthalocyanine pigment is required, 40% to 150% by weight, based on the weight of pigment synthesized, of a beta-phase copper phthalocyanine pigment, or (iii) in the case where a gamma-copper phthalocyanine pigment is required, 0.5% to 40% by weight, based on the weight of pigment synthesized, of a gamma-phase copper phthalocyanine pigment.
Examples of substituted phthalodinitriles include, halogenated di-nitrile compounds such as mono-, di-, tri- or tetra-chloro-phthalodinitrile and mono-, di-, tri- or tetra-bromo-phthalodinitrile, sulphonic acid-substituted phthalodinitrile compounds; carboxylic acid-substituted phthalodi-nitrile compounds such as carboxylic acid phthalodinitrile: nitro-substituted phthalodinitrile compounds; amino-substituted phthalodinitrile compounds;
alkyl-substituted phthalodinitrile compounds such as methyl phthalodinitrile and ethyl phthalodinitrile; alkoxy phthalodinitrile compounds such as methoxy phthalodinitrile, and ethoxy phthalodinitrile. The dinitrile compounds may be u~ed in admixhbre.
,-~
- iO84913 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.
- 4a --' ' ~
491~
Examples of alkaline materials which may be used in the present invention are sodium oxide, sodium peroxide, sodium carbonate, potas6ium oxide, potassium peroxide, potassium hydroxide, potassium methoxlde, potassium carbonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium peroxide, calcium hydroxide, barium oxide, barium hyd_oxide 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 s othly.
The alkaline materials are sultably used ln an amount of up to
The preseIlt invention relates to tIIe direct proparation of pi~lcIltary phthalocyan~nes.
It is Icnown 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 additior. of metal phthalocyanine derivatives durin~
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 100C.
Japanese Patent Publication 83726/l974 describcs 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 temperaturc of not more than l00C in a hydrophilic organic æolvent in the presence of an alkaline substance and milled copper phthalocyanine of average particle diamcter not more than 10 m~ the individual particles of which have a surface ïn the solvent-unstable form while the centre contains a nucleus of solvent-stable form.
_z ' ~ :
~49~3 We have found, surprisingly, that by adding a copper phthalocyanine in conventional pigmentary form from the beginning of the reaction at a tem-perature below 100 C in a process for the preparation of alpha-, beta- or gamma-phthalocyanine it acts as a catalyst or crystal form controller or both and much better yield is obtained. High quality pigments are obtained with-out the need for acid-pasting or mechanical pulverisation.
According to the present invention there is provided in a process for-!the production of alpha-, beta- or gamma-copper phthalocyanine pigments which comprises reacting an ortho-phthalodinitrilo or substituted ortho-phthalodinitrile compound of the general formula ~ CN
Xn ~ CN
in which X i8 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 a hydroxide, oxide, peroxide, alkoxide or carbon- .
: ate of an alkali metal or of an alkaline earth metal in a hydrophilic ali-phatic organic solvent containing one or more hydroxy groups, the improvement whereby high quality pigments are obtained without need for acid-pasting or mechanical pulverization which comprises adding as crystal form controller from the beginning of the reaction:
(i) in the case where an alpha-copper phthalocyanine pigment i9 required:
~; - 3 -~, .
~. , ; .
1~349~1 (a) 0.5% to 40% by weight, based on the weight of pigment synthe-sized, of an alpha-phase copper phthalocyanine pigment or (b) 0.5% to 10% by weight, based on the weight of pigment synthe-si~ed, of a copper phthalocyanine derivative selected from the group consist-ing of chlorinated copper phthalocyanine, copper phthalocyanine sulfonic acid, 1,2,4-trichloro-3-phenoxy copper phthalocyanine or CuPc \(S03H)2 (ii) in the case where a beta-copper phthalocyanine pigment is required, 40% to 150% by weight, based on the weight of pigment synthesized, of a beta-phase copper phthalocyanine pigment, or (iii) in the case where a gamma-copper phthalocyanine pigment is required, 0.5% to 40% by weight, based on the weight of pigment synthesized, of a gamma-phase copper phthalocyanine pigment.
Examples of substituted phthalodinitriles include, halogenated di-nitrile compounds such as mono-, di-, tri- or tetra-chloro-phthalodinitrile and mono-, di-, tri- or tetra-bromo-phthalodinitrile, sulphonic acid-substituted phthalodinitrile compounds; carboxylic acid-substituted phthalodi-nitrile compounds such as carboxylic acid phthalodinitrile: nitro-substituted phthalodinitrile compounds; amino-substituted phthalodinitrile compounds;
alkyl-substituted phthalodinitrile compounds such as methyl phthalodinitrile and ethyl phthalodinitrile; alkoxy phthalodinitrile compounds such as methoxy phthalodinitrile, and ethoxy phthalodinitrile. The dinitrile compounds may be u~ed in admixhbre.
,-~
- iO84913 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.
- 4a --' ' ~
491~
Examples of alkaline materials which may be used in the present invention are sodium oxide, sodium peroxide, sodium carbonate, potas6ium oxide, potassium peroxide, potassium hydroxide, potassium methoxlde, potassium carbonate, magnesium oxide, magnesium hydroxide, calcium oxide, calcium peroxide, calcium hydroxide, barium oxide, barium hyd_oxide 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 s othly.
The alkaline materials are sultably used ln an amount of up to
2 les per le of dinitrile, but the amount of alkaline sub-stance 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 ls monovalent it is preferred to use from 0.25 to 0.5 les of NaOH per le of the dinitrile compound and when the copper is divalent it is preferred to use from 0.5 to 0.75 moles of NaO~ per le of the dlnltrlle compound.
~ ydrophlllc aliphatlc solvents contalning a hydroxyl group whlch may be used ln the process of the lnvention lnclude, for ex-ample, monohydrlc or polyhydrlc hydrophilic alcohols such as propanol, isopropanol, n-butanol, isobutanol, secondary butanol, t-butanol and ethylene glycol, preferably methanol and ethanol;
hydrophillc Cellosolves ("Cellosolve"
-- S --,, : . . .
' . ' '" ' ' .
.
~084~
is a negistered Trade ~lark) such as methyl ~ellosolve~ ethyl Cellosolvc and diethylene ~lycol cthyl 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 i5 times the amount Or dinitrile compound.
The copper phthalocyanine which is used in the reaction as a catalyst and/or crystal form controller may be alpha-, beta-, or gamma depending on the type of pigment B required. The amount of copper phthalocyanine used may vary from o.59b to ~ by weight based on the weight of pigment synthesi~ed depending on whether an alpha-, beta-, or gamma-pigrnent iB r¢quired, In the preparation of an alpha-, or garnrna-pnthalocyanine, the amount of alpha- or gamma-phthalocyanine added may be from 0. ~o,b to 40% by weight and prererably from 0.5% to 20~o by weight for alpha-pl~3ents and from 20% to 40% by weight for gamma-pi~n~ents based on the 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 40% and preferably at least 51% by weight based on the weight of pigment synthcsi~ed and especially from 100~,b to 150%. By using such amounts a 100~/o beta pign3ent can be prepared directly in a one-step prccess. If the ~uantity Or beta copper phthalocyanine added during synthesis is less than 40% by weight, gamma/beta mi.~tures are obtained instead of a 100~ beta piglnent. The gall~na/beta mi~tures are .
~ ' :
.' ' ~ . ' ' ....................... .
- ~0849~
con~erte~ to a 100r/o beta-pigment by a subsequent acid-treatment or treatment with a suitable aroma1ic organic solvent suc~ a~
toluen~ xylc,n~J or Aiethylanil.inc.
A further embodi1nent of the inven-~ion is to use one Ol more organic or inor~ranic ammoniwn salts in addition to the alkaline substance Examples of suitable inorganic and or~an.ic ammonium salts are ammonium chloride, ammoni sulphate, ammonium persulphate, ammonium orthophosphate, ammonium metaphosphate, ammonium pyrophosphate, ammonium carbonate, ammonium bicarbonate, ammonium formate, an~onium acetate, and ammonium oxalate. The ammonium salts are suitably used in an amount of from 0.1 to 10~ by wei~]lt, preferably from 0.5 to 60~o by weight, based on the dinitrile compound.
It has al60 been found advantageous to use a reducing agent such as sodium hydrosulphite and/or a nitrogen containing ba~e such a~ pyridine.
If de~ired there may aiso be added a metal phthalocyanine other than copper phthalocyanine or a metal phthalocyanine derivative which ~uppres~es crystal ~rowth and al~o in the ca~e of the alpha P$8ment8, to achieve ~tability. Ex~mples of phthalocyanine derivatives are:-~ 7 -' : ' :
9~$
(i) Chlorinated copper phthalocyanines e.g. mono, di and trichloro copper phthalocyanine.
(ii) Copper phthalocyanine sulphonic acids e.g.
CuPc (S03H) (where n = 1 to 4) (iii) CuPc--(SO 2NH-CH2CH20H)2 (S03H)2 and (iv) 1,2.4-trichloro-3-phenoxy copper phthalocyanine.
lhe amount of phthalocy~nine derivative added may be from 1% to 20% by weight, preferably 1% to 1~/o by wei~ht baæed on the weight of pigment synthesized. The metal phthalocyanine derivative may be added at any time during or after ~ynthe~i8 or may be prepared in s~tu at the ~ame time a~ the copper phthalo¢y ~ ne pigment.
~ he condensation rea¢tlon of the present invention i8 carrled out at a temperature below 100C and the a¢ ~ l temperature may vary according to the solvent used, ~owever, particularly, a temperature of about 7OC gives good results After completion of the re~ction, a pigment having a clean shade and a high colour strength may be obtained even by immediate filtration, water washing ~nd 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 coppcr phthalocyanine pi~nents thus prepared . . . ~ . .
- - . . - : . ,- -. .
10~911 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, for example dimethylglyoxime, which can form a com-plex with the copper salt used in the reaction is added to the reaction mix-ture in any of the previous described embodiments of the invention, a phthalo-cyanine pigment can be produced in a higher yield. It is preferred that the amount of the compound which can form a complex with the copper salt is from 0.2% to 5% by weight, ba~ed on the weight of the dinitrile compound.
It has also been found, in accordance with another embodiment of the invention, that, when using a hydrophilic organic solvent, if a s~
amount of an acid is added, followed by stirring, immediately after completion of the reaction without isolation of the pigment, a pigment with improved texture is obtained.
Acids which may be used include inorganic acids such as hydro-chloric acid, sulphuric acid, phosphoric acid; and organic acids such as acetic acid, propionic acid and oxalic acid.
When the acid is added to a stabilized alpha-pigment or a beta-piBment, the amount of the acid used will vary somewhat depending on the na-ture of the hydrophilic organic solvent but it will usually be used in anamount of from 0.5% to 75% by weight, preferably from 3% to 50% by weight based on the hydrophilic organic solvent. This amount corresponds to about 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.
_ g _ B
~ . . . . .
.
. . .
10~491~
~ en the acid i~ added to a ~uspension of an unstabilised alp~a-pigment the amount of strong mineral acid used, e.g. 9~o sulphuric acid or concentrated phosphoric acid, preferably does not exceed 30% by weight based on the wei~ht of solvent and the amount of or~anic acid does not exçeed 4~/o by weight based on the weight of 601vent.
The acid is ~uitably added dropwise, and after completion of the acid reaction the mixture may ~e filtered? washed and dried to obtain a pig~.ent. If nece~sary the reaction mixture can be further treated with a dilute alkaline aqueous 601ution 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 stirrin~ 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 Mixcr Model L2R capable of speeds of 6000 revolutions per minute. The actual speed used varies depending upon the nature and size of the experiment.
m e following Examples 1 to 34 further illustrate the in~ention.
.
-. . . .
.' ' ' '. .,~ . ' . '- .' :
1~49~
Example 1 ~ o 100 grams methanol were added 0.9 grams dimethyl-glyoxime. When a solution had been obtained 6.2 grams cuprous chloride were added and the mixture was ~tirred until complete Qolution was obtained (a dark brown complex formation). Then there was added: -32 grams phthalonitrile
~ ydrophlllc aliphatlc solvents contalning a hydroxyl group whlch may be used ln the process of the lnvention lnclude, for ex-ample, monohydrlc or polyhydrlc hydrophilic alcohols such as propanol, isopropanol, n-butanol, isobutanol, secondary butanol, t-butanol and ethylene glycol, preferably methanol and ethanol;
hydrophillc Cellosolves ("Cellosolve"
-- S --,, : . . .
' . ' '" ' ' .
.
~084~
is a negistered Trade ~lark) such as methyl ~ellosolve~ ethyl Cellosolvc and diethylene ~lycol cthyl 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 i5 times the amount Or dinitrile compound.
The copper phthalocyanine which is used in the reaction as a catalyst and/or crystal form controller may be alpha-, beta-, or gamma depending on the type of pigment B required. The amount of copper phthalocyanine used may vary from o.59b to ~ by weight based on the weight of pigment synthesi~ed depending on whether an alpha-, beta-, or gamma-pigrnent iB r¢quired, In the preparation of an alpha-, or garnrna-pnthalocyanine, the amount of alpha- or gamma-phthalocyanine added may be from 0. ~o,b to 40% by weight and prererably from 0.5% to 20~o by weight for alpha-pl~3ents and from 20% to 40% by weight for gamma-pi~n~ents based on the 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 40% and preferably at least 51% by weight based on the weight of pigment synthcsi~ed and especially from 100~,b to 150%. By using such amounts a 100~/o beta pign3ent can be prepared directly in a one-step prccess. If the ~uantity Or beta copper phthalocyanine added during synthesis is less than 40% by weight, gamma/beta mi.~tures are obtained instead of a 100~ beta piglnent. The gall~na/beta mi~tures are .
~ ' :
.' ' ~ . ' ' ....................... .
- ~0849~
con~erte~ to a 100r/o beta-pigment by a subsequent acid-treatment or treatment with a suitable aroma1ic organic solvent suc~ a~
toluen~ xylc,n~J or Aiethylanil.inc.
A further embodi1nent of the inven-~ion is to use one Ol more organic or inor~ranic ammoniwn salts in addition to the alkaline substance Examples of suitable inorganic and or~an.ic ammonium salts are ammonium chloride, ammoni sulphate, ammonium persulphate, ammonium orthophosphate, ammonium metaphosphate, ammonium pyrophosphate, ammonium carbonate, ammonium bicarbonate, ammonium formate, an~onium acetate, and ammonium oxalate. The ammonium salts are suitably used in an amount of from 0.1 to 10~ by wei~]lt, preferably from 0.5 to 60~o by weight, based on the dinitrile compound.
It has al60 been found advantageous to use a reducing agent such as sodium hydrosulphite and/or a nitrogen containing ba~e such a~ pyridine.
If de~ired there may aiso be added a metal phthalocyanine other than copper phthalocyanine or a metal phthalocyanine derivative which ~uppres~es crystal ~rowth and al~o in the ca~e of the alpha P$8ment8, to achieve ~tability. Ex~mples of phthalocyanine derivatives are:-~ 7 -' : ' :
9~$
(i) Chlorinated copper phthalocyanines e.g. mono, di and trichloro copper phthalocyanine.
(ii) Copper phthalocyanine sulphonic acids e.g.
CuPc (S03H) (where n = 1 to 4) (iii) CuPc--(SO 2NH-CH2CH20H)2 (S03H)2 and (iv) 1,2.4-trichloro-3-phenoxy copper phthalocyanine.
lhe amount of phthalocy~nine derivative added may be from 1% to 20% by weight, preferably 1% to 1~/o by wei~ht baæed on the weight of pigment synthesized. The metal phthalocyanine derivative may be added at any time during or after ~ynthe~i8 or may be prepared in s~tu at the ~ame time a~ the copper phthalo¢y ~ ne pigment.
~ he condensation rea¢tlon of the present invention i8 carrled out at a temperature below 100C and the a¢ ~ l temperature may vary according to the solvent used, ~owever, particularly, a temperature of about 7OC gives good results After completion of the re~ction, a pigment having a clean shade and a high colour strength may be obtained even by immediate filtration, water washing ~nd 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 coppcr phthalocyanine pi~nents thus prepared . . . ~ . .
- - . . - : . ,- -. .
10~911 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, for example dimethylglyoxime, which can form a com-plex with the copper salt used in the reaction is added to the reaction mix-ture in any of the previous described embodiments of the invention, a phthalo-cyanine pigment can be produced in a higher yield. It is preferred that the amount of the compound which can form a complex with the copper salt is from 0.2% to 5% by weight, ba~ed on the weight of the dinitrile compound.
It has also been found, in accordance with another embodiment of the invention, that, when using a hydrophilic organic solvent, if a s~
amount of an acid is added, followed by stirring, immediately after completion of the reaction without isolation of the pigment, a pigment with improved texture is obtained.
Acids which may be used include inorganic acids such as hydro-chloric acid, sulphuric acid, phosphoric acid; and organic acids such as acetic acid, propionic acid and oxalic acid.
When the acid is added to a stabilized alpha-pigment or a beta-piBment, the amount of the acid used will vary somewhat depending on the na-ture of the hydrophilic organic solvent but it will usually be used in anamount of from 0.5% to 75% by weight, preferably from 3% to 50% by weight based on the hydrophilic organic solvent. This amount corresponds to about 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.
_ g _ B
~ . . . . .
.
. . .
10~491~
~ en the acid i~ added to a ~uspension of an unstabilised alp~a-pigment the amount of strong mineral acid used, e.g. 9~o sulphuric acid or concentrated phosphoric acid, preferably does not exceed 30% by weight based on the wei~ht of solvent and the amount of or~anic acid does not exçeed 4~/o by weight based on the weight of 601vent.
The acid is ~uitably added dropwise, and after completion of the acid reaction the mixture may ~e filtered? washed and dried to obtain a pig~.ent. If nece~sary the reaction mixture can be further treated with a dilute alkaline aqueous 601ution 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 stirrin~ 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 Mixcr Model L2R capable of speeds of 6000 revolutions per minute. The actual speed used varies depending upon the nature and size of the experiment.
m e following Examples 1 to 34 further illustrate the in~ention.
.
-. . . .
.' ' ' '. .,~ . ' . '- .' :
1~49~
Example 1 ~ o 100 grams methanol were added 0.9 grams dimethyl-glyoxime. When a solution had been obtained 6.2 grams cuprous chloride were added and the mixture was ~tirred until complete Qolution 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-trichlaro-3-phenoxy-copper phthalocyanine - The mixture ~ras 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 Or methanol were added dropwise while adding the sodium hydroxide. Ihe mixture was stirred for a further 30 minuteQ ~t room temperature after the last addition of eodium hydroxide and pyridine.
~ he mixture was then refluxed for 8 hours, allowed to cool to room temperature and then 60 grams of 9~/~ ~ulphuric acid were added dropwise and Qtirred for 1 hour at room temperature. Ihe mixture wa~ then neutralised to pH 7 to 8 with aqueous sodium hydroxide followed by stirring for ~ hour at room temperature and then ~0 millilitres of diethylaniline were added. The mixture wae refiuxed for 1~ hours when the produot was 10~/o beta-phthalocyanine.
50yo hydrochloric acid was then added at room temperature until the pH was 1 to 2 and the mixture stirred for ~ hour. The product ~, . .
.
10~491~
wa~ finally filtered, washed with methanol and then with hot dilute hydrochlori¢ acid, then hot dilute sodium hydroxide and dried at 50 to 60C. ~he yield wag~ 36 grams.
Exam~le 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 9~/o sulphuric acid wa6 added dropwise and the mixture stirred for 1 hour at room t_mperature and then refluxed for half an hour. ~he mixture was finally filtered~-washed with methanol, hot dilute hydrochioric acid and hot dilute sodium hydroxide before drying at 50-60C.
m e yield was 36~.of pigmentary alpha copper phthalocyanine.
Exam~le 3 .
0.9 grams dimethylglyoxime were added to 350 millilitres of methanol and when a solution had been obtained, 6.2 grams of ouprou6 chloride were added and the mixture stirred till the dark brown complex formation is complete. ~here 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 49~
l~le mixt~re wa~ ~tirred for 1 hour at room temperature ~nd ~hen 4 grams of so~ium metal wa~ addea slowly o~er 40 minu~es together with 1 gram of pyridine dissolved in 10 mLillilitres methanol dropwise. ~ne mixture was stirrea for ~ hour at room temperature after the last addition of sodiu~n and pyridine.
Ihe mixture was refluxed for 8 hours and finally filtered, wa~hed with methanol and then with hot dilute sodium hydroxide.
After washing with wat~r and then stirring for 1 hour at 90-95C
in dilute aqueous h~drochloric acid, the product was filtered, wa6hed neutral and dried at 50-60 C, ~he yield was 77g of pig~lent~,ry ~copper phthalocyanine.
Comparative Example A `
To 100 grams CE30~ add:
32 gram~ phthalonitrile (95~ pure)
~ he mixture was then refluxed for 8 hours, allowed to cool to room temperature and then 60 grams of 9~/~ ~ulphuric acid were added dropwise and Qtirred for 1 hour at room temperature. Ihe mixture wa~ then neutralised to pH 7 to 8 with aqueous sodium hydroxide followed by stirring for ~ hour at room temperature and then ~0 millilitres of diethylaniline were added. The mixture wae refiuxed for 1~ hours when the produot was 10~/o beta-phthalocyanine.
50yo hydrochloric acid was then added at room temperature until the pH was 1 to 2 and the mixture stirred for ~ hour. The product ~, . .
.
10~491~
wa~ finally filtered, washed with methanol and then with hot dilute hydrochlori¢ acid, then hot dilute sodium hydroxide and dried at 50 to 60C. ~he yield wag~ 36 grams.
Exam~le 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 9~/o sulphuric acid wa6 added dropwise and the mixture stirred for 1 hour at room t_mperature and then refluxed for half an hour. ~he mixture was finally filtered~-washed with methanol, hot dilute hydrochioric acid and hot dilute sodium hydroxide before drying at 50-60C.
m e yield was 36~.of pigmentary alpha copper phthalocyanine.
Exam~le 3 .
0.9 grams dimethylglyoxime were added to 350 millilitres of methanol and when a solution had been obtained, 6.2 grams of ouprou6 chloride were added and the mixture stirred till the dark brown complex formation is complete. ~here 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 49~
l~le mixt~re wa~ ~tirred for 1 hour at room temperature ~nd ~hen 4 grams of so~ium metal wa~ addea slowly o~er 40 minu~es together with 1 gram of pyridine dissolved in 10 mLillilitres methanol dropwise. ~ne mixture was stirrea for ~ hour at room temperature after the last addition of sodiu~n and pyridine.
Ihe mixture was refluxed for 8 hours and finally filtered, wa~hed with methanol and then with hot dilute sodium hydroxide.
After washing with wat~r and then stirring for 1 hour at 90-95C
in dilute aqueous h~drochloric acid, the product was filtered, wa6hed neutral and dried at 50-60 C, ~he yield was 77g of pig~lent~,ry ~copper phthalocyanine.
Comparative Example A `
To 100 grams CE30~ add:
32 gram~ phthalonitrile (95~ pure)
4.5 gra~s NaO~
2 Brams Na2C03 ~ tir at room temperature to obtain a solution or fine dlspersion. Then add:
1 gram ammonium chloride 2 gram~ ammonium phosphate 8.4 gram~ cupric chloride Stir 1 hour, at room temperature and th~ reflux 10 hour~.
~ilter, wa6h with methanol, hot dil., ~Cl and hot dil., ~7aC~.
Wash neutral and d~y at 50-60C. The yield wa~ 19.4 gram~.
10~
Comparative E~m~ B
~o 100 gT~ms CH30H ada:
32 grams phthalonitrile (95% pure) 6.2 grams cuprous chloride 3.0 gram~ ammonium chloride Stir 1 hour, at room temperature and the aad:
2 Brams Na2C03 ~ tir at room temperature to obtain a solution or fine dlspersion. Then add:
1 gram ammonium chloride 2 gram~ ammonium phosphate 8.4 gram~ cupric chloride Stir 1 hour, at room temperature and th~ reflux 10 hour~.
~ilter, wa6h with methanol, hot dil., ~Cl and hot dil., ~7aC~.
Wash neutral and d~y at 50-60C. The yield wa~ 19.4 gram~.
10~
Comparative E~m~ B
~o 100 gT~ms CH30H ada:
32 grams phthalonitrile (95% pure) 6.2 grams cuprous chloride 3.0 gram~ ammonium chloride Stir 1 hour, at room temperature and the aad:
5 grams l~aO~ 810wly and ~tir for 10 mins.
~hen add:
O,9 grams dimethyl glyoxima Stir ~ hour at room temperatvre and then reflux ~ hours.
Filter, wash with methanol, hot d lute ~Cl and hot dilute l~aO~.
Wa6h neutral and dry at 50-60C. The yield was 22 gr2ms.
~:xamPle_4 ~o 100 grams C~30~ add:
32 grams phthalonitrile (9~o pure)
~hen add:
O,9 grams dimethyl glyoxima Stir ~ hour at room temperatvre and then reflux ~ hours.
Filter, wash with methanol, hot d lute ~Cl and hot dilute l~aO~.
Wa6h neutral and dry at 50-60C. The yield was 22 gr2ms.
~:xamPle_4 ~o 100 grams C~30~ add:
32 grams phthalonitrile (9~o pure)
6.2 grams ouprou~ chloriae 3.0 grams ~mmonium chloride 1 gram unsubstituted pigmentary-copper phtnalocyaIline Stir 1 hour at room temperature and then add:
5 grams ~a0H slowly and stir for 10 minutes.
men add-O.9 grams dimethylglyoxime Stir ~ hour at room temperature and then reflux for 8 hours.
Filter, wash with methanol, hot dilute ~Cl and hot dilute Na0~.
Wash neutral and d~y at 50-~0C. ~h9 yield was 32 grams.
.. . . .
.
' ' " . " ' . ' . , . - "
1084~
Example 5 ~o 140 gram~ ~3~I add:
0.9 ~rams dimethylglyoxime When a solution has been obtained add:
6.2 grams c~prous chloride Stir till the dark bro~m complex formation is complete and then add:
32 ~rams phthalonitrile (9~/o pure) 3.0 gr~ms a~monium chloride 1 Bram pigmentary beta-oopper phthalocyanine.
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal (slowly) 1 gram pyridin,e dissolved in 10 millilitres CH30~
m e pyridine i~ added dropwise whilst adding the sodium metal. Stir ~ hour at room temperature after the last addition ..
Or sodium and pyridine. ~inally reflux 8 hour~. ~he pigment lsolated and purified in the manner of ~x~ple4.
lhe yield was 31.5 eram~ of pigmentary gamma-copper phthalooyanine together with a traoe of beta-oopper phthalocyanine whioh is equivalent to the pigmentary beta-oopper phthalooyanine added during synthe~is.
' ExamPle 6 ~ o 140 grams C~30H add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
- IS --` -, , - - , -1~491~
6.2 grams cuprol~ ~hloride Stir till the dark bro~rr. complex fo~atior is complete and then add: ~
32 gramG phthalonitrile (95% pure) 3.0 grar.3 ammonium chloride 12.4 grams pi~entary gamma-copper phthaiocyanine Stir 1 hour at room temperature and then add:
2.9 gram~ sodium metal (slowlJ-) 1 ~ram p~ridine dissolved in 10 millil~tres C~30E
~ he pyridins is added dropwise ~hilst adding the sodium metal. Stir ~ hour at room temperature after the la~t addition of sodium and pyridine. ~inally re~lux a hours. The pigment i~ isolated and purified in the manr.er of Example 4. The yield ~ras 43.4 grams of pig~ent~ry ga~a-coppar phthalocyanine.
Exam~le 7 ~ o 100 ~rem~ CH30a add:
32 ~rams ~h~haloni~rile (95% pure) 6.2 grams cuprou~ chloride 3.0 gram~ ammonium chloride 1 gram of a copper phthalocyanine derivative hav~ng the following formula:
~ (S02~H.C~2C~20~)2 copper phthalocyanine ' (S~3~1)2 . . .'.' ' ~ ' ,' . ~: :
1~84~1~
Stir 1 hour at rocm temperature ~Id then add:
5 grams NaOH, slowly 1 eram pyridine dissolved in 10 mi]lilitr~ C~3~E
The pyridine is added dropuise whilst adding the ~aOH.
Stir ~ hour at room te~perature after the last additio~ of l~aOH ~nd pyridine.
Then add:
0.9 grams dimethylglyoxime Stir 15 minute~ at room temperature and fin~lly refiux ~ hours. The pigment i9 isolated by riltration and then washed uith C~30~. The press-cake is re-slurried in 1-~/o aqueous ~Cl and stirred at 90-95C for 1 hour. The pig~ent i9 then filtered and uashed neutral. Thi~ process i8 repeated using 1-~/~ aqueou3 NaO~. After washing neutral, the pl~ment is dried at 50-60C. ~he yield wa~ 30 6rams of pigmentary alpha-copper phthalocyanine.
~xam~le ~ -~o 100 OE ~ms CH30H add:
~9 OE ams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown co~plex formation is complete and then add:
.', ., . ~ .
1~4~1~
~2 grams phthalonitrile (95% pure) 3.0 grams ammonium chloride 1 gram / (S02N~CH~CH20H)2 copper phthalocJ-anine ( S 03~I ) 2 Stir 1 hour at room temperature and then add:
2,9 grams sodium metal, slowly 1 gram pyridine di~sol~ed in 10 millilitres CH30H.
~ he pyridine is added dropwise whil~t adding the sodium metal. Stir ~ 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 (9~/o) ~2S04, dropwise Stir 1 hour at room temperature and then reflux 1 hour.
~llter, wash with methanol and then wa~h neutral with water.
Ihe press-cake is re-slurried in 1-~/o aqueous NaO~.and stirred at 90-95C for 1 hour. Finally filter, ~;ash neutral and dry at 50-60 C. The yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Exam~le 9 ~o 100 gr~ms CH30H add:
- 0.9 grams dimethylglyoxime When a solution has been obtained add:
-: -. . .
:, , 9~
6.2 gram~ cuprous chloride Stir till the dark brown complex formation i9 complete - and then add:
32 gram6 phthalonitrile (9~/o pure) 3.0 gram8 ammonium chloride 1 gram / (S02N~CH2CH20~)2 copper phthalocyanine (S03H)2 Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly 1 gram pyridine di~olved in 10 millilitres CH30H
~ he pyridine ie added aropwise whilst adding the ~odium metal. Stir ~ hour at room temperature after the laet addition of eodium and pyridine. Finally reflux 8 hours. Allow to oool to room temperature and then add:
30 grams concentrated (9~/o) H2S04, dropwi~e ; Stir 1 hour at room temperature and then reflux 1 hour.
qhe product is isolated and after-treated (purified) in the mnnner of Example ~. Ihe yield wa~ 31 grams of pigmentary alpha-copper phthalocyanine.
xample 10 ~ o 100 grams CH30H add:
0.9 grams dimethylglyoxime 1~4911 When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown complex fo~mation is oomplete and t,hen add:
32 grams phthalonitrile (9~/o pure) 3.0 gram~ ammonium chloride 1 gram copper phthalocyanine dyestuff of the formula:
(So2.N~.C~2cH20~)2 - ~ (S03H)2 ætir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly 1 gram pyridine di~sol~ed in 10 millilitres CE30E
qhe pyridine is added dropwi6e whilst adding the sodium metal, Stir ~ hour at room temperature after the last addition Or ~odium and pyrid~ne. ~inally reflux 8 hour~. , Allow to cool to room temperature and then aad:
60 grams concentrated (98%) H2Sq4, dropwise - ~tir 1 hour at room temperature and then reflux ~ hoùr.
Ihe pigment iB i~olated and purified in the manner of Example S.
The yield wa~ 31 gram~ of pigmentary alpha-copper phthalocyanine.
. . , . ' , 10~491~
Exa~ole 11 To 100 grams CX30~ add:
32 grams phthalonitrile-(95~ pure) 6.2 gram~ cuprous chloride 3.0 gram~ ammonium chloride 1 gram 1,2,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hour at room temperature, then add:
5 BTam9 NaOH, slowly 1 gram pyridine dissolved in 10 millilitre~ CH30H
~he pyridine is added dropwise whilst adding the NaC~.
Stir ~ hour after the last addition of NaCH and pyridine, then add:
0.9 gram~ dimethylglyoxime Stir 15 minute~ at room temperature and then reflux 8 hGurs.
The product i~ isolated and purified in the manner of Example 7 Ihe yield was 31 g~am~ of pigmentary alpha-copper phthalocyanine~
Examole 12 ~o 100 grams CH3CH add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown complex formation $~ complete ~nd then add:
32 grams phthalonitrile (95% pure) 3.0 ~rams ammonium chloride 1 gram 1,2,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hour at room temperature and then add:
.. ' ~
. ' ~08491~
2.9 grams sodium metal, 810wly 1 gram pyridine' dissolved in 10 millilitres CH30~
~ he pyridine is added dropwise, whilst adding the æodium metal. Stir ~ hour at room temperature after the last addition of ~odium and pyridine. ~inally reflux 8 hours. ~llow to cool to room temperature and then add:
12 grams concentrated (9~/o) H2S04, dropwise Stir 1 hour at room temperature and then reflux 1 hour.
The pigment is isolated and purified in the manner of Example 8 .
~he yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Example 13 ~ o 100 grams C~30~ add:
0.9 grams dimethylglyoxime When a solution has been obtained, add:
6.2 gram~ ouprous chloride Stlr t~ll the dark brown complex formation is complete ana then aaa:
32 grams phthalonitrile (95% pure) 3.0 gsams ammonium chloride 1 gram 1,?,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly 1 gram pyridine dissol~ed in 10 millilitres CH30H
The pyridine is added dropwi~e, whilst adding the sodium metal. Stir -~ hour at room temperature, after the last addition .
49~
of sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
30 grams concentrated (9~o) ~2S04, dropwise Stir 1 hour at room temperature and then reflux 1 hour.
~he pigment is isol~ted and purified in the manner of Example 8 .
~he yield was 31 grams of pigmentary alpha-copper phthalocyanine.
ExamPle 14 - -~ o 100 grams CH30H add:
0.9 ~rams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark browm 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 ~odium metal, slowly 1 gram pyridine dissolved i~ 10 millilitres C~30H
The pyridine is added dropwise, whilst adding the ~odium metal. Stir ~ hour at room temperature after the last addition of sodium and pyridine. ~inally reflux 8 hours.
Allow to cool to room temperature and then add:
60 grams concentrated (985~) ~2S04,dropwiee Stir 1 hour at room temperature and then reflux ~ hour.
- 23 ~
1~849~
The pi~ment i9 isolated and after-treated (purified) in the manner of Example 8. The yield was 31 ~rams of pigmentary alpha-copper phthalocyanine.
Examl~le 15 ~o 100 grams CH30~ add:
- ~9 OE an8 dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprou~ chloride Stir till the dark bro~m complex formation i8 complete and then add:
32 grams phthalonitrile (95% pure) 3.0 grams ammonium chloride 1 gram unsub~tituted pigmentary alpha-copper phthalocyanine Stir 1 hour at room temperature and then add:
2.9 OE ams sodium metal, slowly 1 gram pyridlne dis801ved in 10 millilitres CH30H
The pyriaine i~ added dropwise whil~t adding the sodium metal~ Stir ~ hour at room temperature after the last additio;~
Or sodium ~nd pyridine. Finally ~eflux ~ hours.The pi~n~n~.i.s isolated and purified in the manner of ~xample 7~ ~he yield was 32 grams of pigmentary alpha-copper phthalocyanine.
' .
1~84913 Example 16 To 120 grams CH30H add:
0.9 grams dlmethylglyoxime 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 sodlum metal, slowly 1 gram pyrldine dissolved ln 10 millilitres CH30H
The pyridine is added dropwise whilst adding the sodium metal.
Stir L/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 plgment i~ l~olated and purlfled ln the manner of Example 8.
The ylela was 31 grams plgmentary alpha-copper phthalocyanine.
Example 17 To 100 grams CH30H add:
32 grams phthalonltrile (95% pure) 6.2 grams cuprous chloride 3.0 grams ammonium chloride 1 gram pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
10~49~
5 gram~ NaOH slowly 1 gram pyridine dis601vea in 10 millilitres CH30 ~he pyridine is added~dropwise whilst adding the NaO~
Stir ~ hour at room temperature after the last addition of NaO~ and pyridine. Then add:
0.9 grams dimethylB yoxime Stir 15 minutes at room temperature and then reflux 7-8 hours.
Allow to cool to room temperature and then add:
60 grams concentrated (9~/~) X2S04, drop~;lise tir 1 hour at room temperature and then reflux till 10~o beta is obtained. Ihis normally takes -~ hour to 1 hour. The pigment is isolated in the manner of Example 8. The yield was 32 grams of beta-co~per phthalocyanine.
ExamPle 1~s To 100 grams C~30~ add:
0.9 gram~ dimethylglyoximè
When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown oomplex formation is complete and then add:
32 grams phthalonitrile (9~/o pure) 3.0 grams ammonium chloride 6 grams pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add.
2.9 grams sodium metal, slowly 1 ~ram pyridine dissolved in 10 millil~tres C~30~.
. ~
1~8491~ .
The pyridine i~ added dropwise whilst adding the sodium metal. Stir ~ hour at room temperature, after the last addition of 60diuM and pyridine. Finally reflux 8 hour~. Allow to ¢ool to room temperature and then add:
24 grams 9~/o H2S04, dropwise Stir 1 hour at room temperature and then neutralise with NaOH till pH = 7 to 8. Add extra metharDl if required.
Finally reflux, till 100% beta i8 obtained. The pi~e~t i~
isolated and purified in the manner of Exa~ple 7. r~e yield was 37 Kram3 of pigmentary beta-copper phthalocyanine.
Exa~ple 1~
- To 280 grams CE30E add:
0.9 gram~ dimethylglyoxim~
When a solution has been obtained, add:
6.2 OE am8 ouprous chloride Stlr till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (9~o pure) 3.0 grams ammonium chloride 45 gram~ pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
4 grams sodium metal, 810wly 1 gram pyridine dissolved in 10 millilitres C~30~
The pyridine is added dropwise whilst adding the ~odium metal.
Stir ~ hour at room temperature after the last addition of sodium - 27 ~
i , - .
~49~
and pyridine. ~in~lly reflux 8 hour~. The pig~ent is isolated and after-treated (purified) ir. the manner of Example 7. ~he y~eld wa~ 76 gramg of pig~lentary beta-copper phthalocyanine.
Exam~le 2~ .
To 280 gram~ C~30H add:
O . 9 gramB dimethylglyoxime When a solution has been obtained, add:
6.2 grams cuprous chloxide 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 phthalocyanine Stir 1 hour at room temperature and then add:
4 gram~ Eod~um metal, slowly 1 gram pyridine dissolved in 10 millilitres CH~0~
qhe pyridine iB addea dropwise, whilst adding the ~odium metal. Stir ~ hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to - oool to room temperature and then add:
- 60 gram~ concentrated (9~/o) ~2S04, dropwiss ; Stir 2 hour~ at room temperature and then isolate and ; purify in the manner of Example 8. ~he yield was 76 gTams of pigmentary beta-copper phthalocyanine.
. .
~ - 28 -. . .
. ', . .- . ., , . .
~849~
ExamPle 21 ~o 240 gra~s CH30~ add:
-9 OE ams dimethylglyoxime When a solution has been obtained add:
6.2 gra~s cuprous chloride Stir till the dark brown complex formation i8 complete and then add:
32 grams phthalonitrile (9~% pure) 3.0 grams ammonium chloride ~0 grgms pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly 1 gram pyridine diEsolved in 10 millilitres CH30H
~ he pyridine i~ added dropwise ~Jhilst adding the sodium metal. Stir ~ hour at room temperature after the last addition Or sodium and pyridine. ~inally reflux 8 hours. Allow to oool to room temperature and then add:
60 grams ¢oncentrated (9~o) H2S04, dropwise Stir 2 hours at room temperature. The pigment i~ isolated and purified in the manner of Example 8. The yield was 61 grams Or pigmentary beta-copper phthalocyanine.
Example 22 ~ o 200 gram~ C~30H add:
O.9 gr~ms dimethylglyoxime When a solution has been obtainea add:
'' ': : . . .
1~491~
6.2 gram~ cuprous chloride Stir till the dark brown complex formation is com~lete and then add:
32 grams phthalonitrile (95% pure) 3.0 gr&ms ammonium chloride 18 gram~ pi&mentary beta-copper phthalocyanine Stir ~ hour at room temperature and then add:
4 erams sodium metal, slowly 1 gram pyridine dissolved in 10 millilitres CH30H
~ he pyrldine is added dropwise, whilst adding the sodium metal. Stir ~ 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%) H2S04, dropwise Stir 2 hours at room temperature. The pi g ent is isolated and after-treated (purified) in the manner of Example 8.
The yield wa~ 49 gram~ of pigmentary beta-co~er phthalocyanine.
ExamPle 23 ~ o 160 Brams C~30~ add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
6.2 grams ¢uprous chloride Stir till the dark brown complex formation is complete and tben add;
32 grams phthalonitrile (95% pure) . . .
. - - , ', : ' ' ~ .
.' . ' '' ' '~ ' 49~L
3.0 grams a~nonium chloride 12 grams pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
3-5 Bram8 ~odium metal, slowly 1 gram pyridine dissolved in 10 millilitres CH30~
T~le pyridine is added dropwise whilst adding the Eodium metal. Stir -~ hour at room temperature, after the last addition o~ sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then ada:
60 ~rams concentrated (9~/o) H2S04, dropwi~e Stir 2 hour~ at room temperature. The pigment i8 isolated and purified in the manner of Example 8. Ihe yield was 43 grams Or pigmentary beta-copper phthalocyanine.
~xample 24 To 1400 millilitres CH30~ add:
3.6 gram~ dimethylglyoxime When a ~olution has been obtained add:
24.8 grams cuprous chloride Stir till the dark brown oomplex formation iY complete and then add: .
128 gr2ms phthalonitrile ~95% pure) 12.0 grams ammonium chloride 180 gr~Jms pigmentary beta-copper phtha'ocyanine 4 grams 1,2,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hffur at room temperature and then add:
16 grams sodiu~ metal, slowly ,. : - : ..
:, . . :: .
: . : ' ~ '. ' : ' . .
: . : : . ' :: ' : ~ . : ' ~491~
4 millilitres pyridine dissolved in 40 millilitres CH30H
The pyridine is added dropwise whilst adding the ~odium metal. Stir ~ hour at room temperature after the last addition of sodium and pyridine, ~inally reflux 8 hours. ~he product is lsolated and after-treated in the manner of Example 7. m e yield was 308 grams pigmentary beta-copper phthalocyanine.
Exam~le 25 ~ o 280 gram~ CH30H add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown complex formation i~ complete and then add:
32 grams phthalonitrile (9~% pure) 3 Bram~ ammonium chloride 45 grams pigmentary beta-copper phthalocyanine 1 gram , ~ (S02~ H2CH2.01I)2 copper phthalocyanine (S03H)2 stir 1 hour at room temperature and then add:
4 grams sodium metal, ~lowly 1 millilitre pyridine dis~olved in 10 millilitres C~30H
~he pyridine is added dropwise, whilst addi~g the ~odiu~
; ~ 32 -491$
.
metal. Stir ~ hcur at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to oool to room temperature and then add:
60 grams concentrated (9~o) H2S04, dropwise Stir 1 hour at room ternperature and then reflux ~ hour.
The product is isolated and purified in the manrer of Ex3mple 8.
~he yield was 77 grams of pig~entary beta-copper phthalocyænine.
Exam~le 26 ~o 1050 millilitres C~30~ add:
2.7 grams dimethylglyoxime When a solution has been obtained add:
18.6 gr~ms cuprous chloride St~r till the dark browm complex formation i8 complete and then add:
96 erams phth~lonitrile (95% pure) 9 Bram~ ammonium chloride 3 grams 1,2,4-trichloro-3-phenoxy-copper phthalocyanine 135 grams pigmentary be ~ copper phthalocyanine Stir 1 hour at room temperature and then add:
12 grams sodium metal, slowly 3 gram~ pyridine dissolved in 30 millilitres C~30 ~he pyridine is added dropwise, whilst adding the sodium metal. Stir ~ 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:
1~849~
180 grams concentrated (98~) H2S04, dropwise Stir 1 hour at room temperature and then reflux L/2 hour.
The product is isolated and after-treated in the manner of Example 8.
The yield was 228 grams pigmentary beta-copper phthalocyanine.
Example 27 To a 500 millilitre flask add:-lS0 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 CH30H.
After the addition of sodium methoxide add 1.5 grams pigmentary mono-chloro-copper phthalocyanine. Finally raise the temperfiture to reflux and reflux 8 hours. After refluxing for 8 hours, filter, wash with methanol and then water. The pig-ment is purified in the manner of Example 7. The yield was 18 grams of pigmentary alpha copper phthalocyanine.
-:
.
10~49~
Example 28 ~ y fol] OWillg a similar procedure to that described in Example 27 ~ut using 4 grams ammoniunl acetate in place of the ammonium chloride there used, 20 grams of,pigmentary alpha copper phthalocyanille were obtained.
Example 29 To a 500 millilitre flask add:-100 millilitres methanol j2.7 grams phtha~odinitrile ( 98/o) 0.9 grams dimethylglyoxime 3.0 grams ammonium chlo,ride 2.0 grams triethanolamine ' 8.8 grams cupric chloride Then add dropwise over 30 minutes:-80 millilitre~ of a 25% solution of sodium methoxide ln CH30H
After the addition of sodium methoxide add 1. 5 grams pigmentary mono-chloro-copper phthalocyaninc. Finally raise the temperature to reflux and reflux 8 hours. After reflux, filter, wa.sh with methanol and then water. The pigment is purified in the manner of Example 7 to give 28 grams of pign1entary alpha copper phthalocyaninc, . .
'' .
~ 35 -.. . ~ . - ~
, .
9'~
Exam~le ~0 To a 1 litrc flask add:-150 millilitres methanol -' 34.3 grams phthalodinitrile ( 98C~b) 0.9 grams dimethylglyoxime 6.4 grams cuprous chloride 3.0 grams ammoniwn chloride 1.0 grams 1,2,3,4 tetrachloro copper phthalocyanine.
1.0 ~rams potassiwn 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 i8 purified in the manner of Examplè 7 to give 26.5 grams of pigmentary alpha copper phthalocyanine.
~xan-p le 31 To a litre flask add:-150 millilitres methanol 32.7 grams phthalodinitrile ( 98%) O. 9 grams dimetllylglyo~;ime 3.0 grams ammonium chloride 6.4 grams cuprous chloride 1.0 gram , 1,Z,3,4-tetra~chloro-copper phthalocyanine.
Add:-.
10~49~$
5.5. grams ~aOH whilst the reaction rnixture is high spced stirred using a Silvcrson Higll Speed stirrer. High Rpeed stir for 10 minutes-after the last addition of NaOH.
The reactiorl 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 pigmcntary alpha copper phthalocyanine.
Example ~2 By following a similar procedure to that described in Example 31 but adding 6.o 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.
,xample ~3 ~ y ~ollowing a similar procedure to that described in Example 31 but usin~ 6.o gran.s ammonium sulphate in place of the ammonium chloride therc used, 26.5 grams of pigmentary alpha copper phthalocyanine were obtained.
Example 34 By following a similar procedure to that described in Example 31 but adding 1.0 gram sodiwn dithionite after the addition of ammonium chloride and prior to the addition of cuprous chloride, 28 grams of pigmentary alpha copper phthalocyanine were ~btained.
,: ~ ' ' ' ,- , .
. ~ '.
5 grams ~a0H slowly and stir for 10 minutes.
men add-O.9 grams dimethylglyoxime Stir ~ hour at room temperature and then reflux for 8 hours.
Filter, wash with methanol, hot dilute ~Cl and hot dilute Na0~.
Wash neutral and d~y at 50-~0C. ~h9 yield was 32 grams.
.. . . .
.
' ' " . " ' . ' . , . - "
1084~
Example 5 ~o 140 gram~ ~3~I add:
0.9 ~rams dimethylglyoxime When a solution has been obtained add:
6.2 grams c~prous chloride Stir till the dark bro~m complex formation is complete and then add:
32 ~rams phthalonitrile (9~/o pure) 3.0 gr~ms a~monium chloride 1 Bram pigmentary beta-oopper phthalocyanine.
Stir 1 hour at room temperature and then add:
2.9 grams sodium metal (slowly) 1 gram pyridin,e dissolved in 10 millilitres CH30~
m e pyridine i~ added dropwise whilst adding the sodium metal. Stir ~ hour at room temperature after the last addition ..
Or sodium and pyridine. ~inally reflux 8 hour~. ~he pigment lsolated and purified in the manner of ~x~ple4.
lhe yield was 31.5 eram~ of pigmentary gamma-copper phthalooyanine together with a traoe of beta-oopper phthalocyanine whioh is equivalent to the pigmentary beta-oopper phthalooyanine added during synthe~is.
' ExamPle 6 ~ o 140 grams C~30H add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
- IS --` -, , - - , -1~491~
6.2 grams cuprol~ ~hloride Stir till the dark bro~rr. complex fo~atior is complete and then add: ~
32 gramG phthalonitrile (95% pure) 3.0 grar.3 ammonium chloride 12.4 grams pi~entary gamma-copper phthaiocyanine Stir 1 hour at room temperature and then add:
2.9 gram~ sodium metal (slowlJ-) 1 ~ram p~ridine dissolved in 10 millil~tres C~30E
~ he pyridins is added dropwise ~hilst adding the sodium metal. Stir ~ hour at room temperature after the la~t addition of sodium and pyridine. ~inally re~lux a hours. The pigment i~ isolated and purified in the manr.er of Example 4. The yield ~ras 43.4 grams of pig~ent~ry ga~a-coppar phthalocyanine.
Exam~le 7 ~ o 100 ~rem~ CH30a add:
32 ~rams ~h~haloni~rile (95% pure) 6.2 grams cuprou~ chloride 3.0 gram~ ammonium chloride 1 gram of a copper phthalocyanine derivative hav~ng the following formula:
~ (S02~H.C~2C~20~)2 copper phthalocyanine ' (S~3~1)2 . . .'.' ' ~ ' ,' . ~: :
1~84~1~
Stir 1 hour at rocm temperature ~Id then add:
5 grams NaOH, slowly 1 eram pyridine dissolved in 10 mi]lilitr~ C~3~E
The pyridine is added dropuise whilst adding the ~aOH.
Stir ~ hour at room te~perature after the last additio~ of l~aOH ~nd pyridine.
Then add:
0.9 grams dimethylglyoxime Stir 15 minute~ at room temperature and fin~lly refiux ~ hours. The pigment i9 isolated by riltration and then washed uith C~30~. The press-cake is re-slurried in 1-~/o aqueous ~Cl and stirred at 90-95C for 1 hour. The pig~ent i9 then filtered and uashed neutral. Thi~ process i8 repeated using 1-~/~ aqueou3 NaO~. After washing neutral, the pl~ment is dried at 50-60C. ~he yield wa~ 30 6rams of pigmentary alpha-copper phthalocyanine.
~xam~le ~ -~o 100 OE ~ms CH30H add:
~9 OE ams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown co~plex formation is complete and then add:
.', ., . ~ .
1~4~1~
~2 grams phthalonitrile (95% pure) 3.0 grams ammonium chloride 1 gram / (S02N~CH~CH20H)2 copper phthalocJ-anine ( S 03~I ) 2 Stir 1 hour at room temperature and then add:
2,9 grams sodium metal, slowly 1 gram pyridine di~sol~ed in 10 millilitres CH30H.
~ he pyridine is added dropwise whil~t adding the sodium metal. Stir ~ 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 (9~/o) ~2S04, dropwise Stir 1 hour at room temperature and then reflux 1 hour.
~llter, wash with methanol and then wa~h neutral with water.
Ihe press-cake is re-slurried in 1-~/o aqueous NaO~.and stirred at 90-95C for 1 hour. Finally filter, ~;ash neutral and dry at 50-60 C. The yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Exam~le 9 ~o 100 gr~ms CH30H add:
- 0.9 grams dimethylglyoxime When a solution has been obtained add:
-: -. . .
:, , 9~
6.2 gram~ cuprous chloride Stir till the dark brown complex formation i9 complete - and then add:
32 gram6 phthalonitrile (9~/o pure) 3.0 gram8 ammonium chloride 1 gram / (S02N~CH2CH20~)2 copper phthalocyanine (S03H)2 Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly 1 gram pyridine di~olved in 10 millilitres CH30H
~ he pyridine ie added aropwise whilst adding the ~odium metal. Stir ~ hour at room temperature after the laet addition of eodium and pyridine. Finally reflux 8 hours. Allow to oool to room temperature and then add:
30 grams concentrated (9~/o) H2S04, dropwi~e ; Stir 1 hour at room temperature and then reflux 1 hour.
qhe product is isolated and after-treated (purified) in the mnnner of Example ~. Ihe yield wa~ 31 grams of pigmentary alpha-copper phthalocyanine.
xample 10 ~ o 100 grams CH30H add:
0.9 grams dimethylglyoxime 1~4911 When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown complex fo~mation is oomplete and t,hen add:
32 grams phthalonitrile (9~/o pure) 3.0 gram~ ammonium chloride 1 gram copper phthalocyanine dyestuff of the formula:
(So2.N~.C~2cH20~)2 - ~ (S03H)2 ætir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly 1 gram pyridine di~sol~ed in 10 millilitres CE30E
qhe pyridine is added dropwi6e whilst adding the sodium metal, Stir ~ hour at room temperature after the last addition Or ~odium and pyrid~ne. ~inally reflux 8 hour~. , Allow to cool to room temperature and then aad:
60 grams concentrated (98%) H2Sq4, dropwise - ~tir 1 hour at room temperature and then reflux ~ hoùr.
Ihe pigment iB i~olated and purified in the manner of Example S.
The yield wa~ 31 gram~ of pigmentary alpha-copper phthalocyanine.
. . , . ' , 10~491~
Exa~ole 11 To 100 grams CX30~ add:
32 grams phthalonitrile-(95~ pure) 6.2 gram~ cuprous chloride 3.0 gram~ ammonium chloride 1 gram 1,2,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hour at room temperature, then add:
5 BTam9 NaOH, slowly 1 gram pyridine dissolved in 10 millilitre~ CH30H
~he pyridine is added dropwise whilst adding the NaC~.
Stir ~ hour after the last addition of NaCH and pyridine, then add:
0.9 gram~ dimethylglyoxime Stir 15 minute~ at room temperature and then reflux 8 hGurs.
The product i~ isolated and purified in the manner of Example 7 Ihe yield was 31 g~am~ of pigmentary alpha-copper phthalocyanine~
Examole 12 ~o 100 grams CH3CH add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown complex formation $~ complete ~nd then add:
32 grams phthalonitrile (95% pure) 3.0 ~rams ammonium chloride 1 gram 1,2,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hour at room temperature and then add:
.. ' ~
. ' ~08491~
2.9 grams sodium metal, 810wly 1 gram pyridine' dissolved in 10 millilitres CH30~
~ he pyridine is added dropwise, whilst adding the æodium metal. Stir ~ hour at room temperature after the last addition of ~odium and pyridine. ~inally reflux 8 hours. ~llow to cool to room temperature and then add:
12 grams concentrated (9~/o) H2S04, dropwise Stir 1 hour at room temperature and then reflux 1 hour.
The pigment is isolated and purified in the manner of Example 8 .
~he yield was 31 grams of pigmentary alpha-copper phthalocyanine.
Example 13 ~ o 100 grams C~30~ add:
0.9 grams dimethylglyoxime When a solution has been obtained, add:
6.2 gram~ ouprous chloride Stlr t~ll the dark brown complex formation is complete ana then aaa:
32 grams phthalonitrile (95% pure) 3.0 gsams ammonium chloride 1 gram 1,?,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hour at room temperature and then add:
2.9 grams sodium metal, slowly 1 gram pyridine dissol~ed in 10 millilitres CH30H
The pyridine is added dropwi~e, whilst adding the sodium metal. Stir -~ hour at room temperature, after the last addition .
49~
of sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then add:
30 grams concentrated (9~o) ~2S04, dropwise Stir 1 hour at room temperature and then reflux 1 hour.
~he pigment is isol~ted and purified in the manner of Example 8 .
~he yield was 31 grams of pigmentary alpha-copper phthalocyanine.
ExamPle 14 - -~ o 100 grams CH30H add:
0.9 ~rams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark browm 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 ~odium metal, slowly 1 gram pyridine dissolved i~ 10 millilitres C~30H
The pyridine is added dropwise, whilst adding the ~odium metal. Stir ~ hour at room temperature after the last addition of sodium and pyridine. ~inally reflux 8 hours.
Allow to cool to room temperature and then add:
60 grams concentrated (985~) ~2S04,dropwiee Stir 1 hour at room temperature and then reflux ~ hour.
- 23 ~
1~849~
The pi~ment i9 isolated and after-treated (purified) in the manner of Example 8. The yield was 31 ~rams of pigmentary alpha-copper phthalocyanine.
Examl~le 15 ~o 100 grams CH30~ add:
- ~9 OE an8 dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprou~ chloride Stir till the dark bro~m complex formation i8 complete and then add:
32 grams phthalonitrile (95% pure) 3.0 grams ammonium chloride 1 gram unsub~tituted pigmentary alpha-copper phthalocyanine Stir 1 hour at room temperature and then add:
2.9 OE ams sodium metal, slowly 1 gram pyridlne dis801ved in 10 millilitres CH30H
The pyriaine i~ added dropwise whil~t adding the sodium metal~ Stir ~ hour at room temperature after the last additio;~
Or sodium ~nd pyridine. Finally ~eflux ~ hours.The pi~n~n~.i.s isolated and purified in the manner of ~xample 7~ ~he yield was 32 grams of pigmentary alpha-copper phthalocyanine.
' .
1~84913 Example 16 To 120 grams CH30H add:
0.9 grams dlmethylglyoxime 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 sodlum metal, slowly 1 gram pyrldine dissolved ln 10 millilitres CH30H
The pyridine is added dropwise whilst adding the sodium metal.
Stir L/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 plgment i~ l~olated and purlfled ln the manner of Example 8.
The ylela was 31 grams plgmentary alpha-copper phthalocyanine.
Example 17 To 100 grams CH30H add:
32 grams phthalonltrile (95% pure) 6.2 grams cuprous chloride 3.0 grams ammonium chloride 1 gram pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
10~49~
5 gram~ NaOH slowly 1 gram pyridine dis601vea in 10 millilitres CH30 ~he pyridine is added~dropwise whilst adding the NaO~
Stir ~ hour at room temperature after the last addition of NaO~ and pyridine. Then add:
0.9 grams dimethylB yoxime Stir 15 minutes at room temperature and then reflux 7-8 hours.
Allow to cool to room temperature and then add:
60 grams concentrated (9~/~) X2S04, drop~;lise tir 1 hour at room temperature and then reflux till 10~o beta is obtained. Ihis normally takes -~ hour to 1 hour. The pigment is isolated in the manner of Example 8. The yield was 32 grams of beta-co~per phthalocyanine.
ExamPle 1~s To 100 grams C~30~ add:
0.9 gram~ dimethylglyoximè
When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown oomplex formation is complete and then add:
32 grams phthalonitrile (9~/o pure) 3.0 grams ammonium chloride 6 grams pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add.
2.9 grams sodium metal, slowly 1 ~ram pyridine dissolved in 10 millil~tres C~30~.
. ~
1~8491~ .
The pyridine i~ added dropwise whilst adding the sodium metal. Stir ~ hour at room temperature, after the last addition of 60diuM and pyridine. Finally reflux 8 hour~. Allow to ¢ool to room temperature and then add:
24 grams 9~/o H2S04, dropwise Stir 1 hour at room temperature and then neutralise with NaOH till pH = 7 to 8. Add extra metharDl if required.
Finally reflux, till 100% beta i8 obtained. The pi~e~t i~
isolated and purified in the manner of Exa~ple 7. r~e yield was 37 Kram3 of pigmentary beta-copper phthalocyanine.
Exa~ple 1~
- To 280 grams CE30E add:
0.9 gram~ dimethylglyoxim~
When a solution has been obtained, add:
6.2 OE am8 ouprous chloride Stlr till the dark brown complex formation is complete and then add:
32 grams phthalonitrile (9~o pure) 3.0 grams ammonium chloride 45 gram~ pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
4 grams sodium metal, 810wly 1 gram pyridine dissolved in 10 millilitres C~30~
The pyridine is added dropwise whilst adding the ~odium metal.
Stir ~ hour at room temperature after the last addition of sodium - 27 ~
i , - .
~49~
and pyridine. ~in~lly reflux 8 hour~. The pig~ent is isolated and after-treated (purified) ir. the manner of Example 7. ~he y~eld wa~ 76 gramg of pig~lentary beta-copper phthalocyanine.
Exam~le 2~ .
To 280 gram~ C~30H add:
O . 9 gramB dimethylglyoxime When a solution has been obtained, add:
6.2 grams cuprous chloxide 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 phthalocyanine Stir 1 hour at room temperature and then add:
4 gram~ Eod~um metal, slowly 1 gram pyridine dissolved in 10 millilitres CH~0~
qhe pyridine iB addea dropwise, whilst adding the ~odium metal. Stir ~ hour at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to - oool to room temperature and then add:
- 60 gram~ concentrated (9~/o) ~2S04, dropwiss ; Stir 2 hour~ at room temperature and then isolate and ; purify in the manner of Example 8. ~he yield was 76 gTams of pigmentary beta-copper phthalocyanine.
. .
~ - 28 -. . .
. ', . .- . ., , . .
~849~
ExamPle 21 ~o 240 gra~s CH30~ add:
-9 OE ams dimethylglyoxime When a solution has been obtained add:
6.2 gra~s cuprous chloride Stir till the dark brown complex formation i8 complete and then add:
32 grams phthalonitrile (9~% pure) 3.0 grams ammonium chloride ~0 grgms pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
4 grams sodium metal, slowly 1 gram pyridine diEsolved in 10 millilitres CH30H
~ he pyridine i~ added dropwise ~Jhilst adding the sodium metal. Stir ~ hour at room temperature after the last addition Or sodium and pyridine. ~inally reflux 8 hours. Allow to oool to room temperature and then add:
60 grams ¢oncentrated (9~o) H2S04, dropwise Stir 2 hours at room temperature. The pigment i~ isolated and purified in the manner of Example 8. The yield was 61 grams Or pigmentary beta-copper phthalocyanine.
Example 22 ~ o 200 gram~ C~30H add:
O.9 gr~ms dimethylglyoxime When a solution has been obtainea add:
'' ': : . . .
1~491~
6.2 gram~ cuprous chloride Stir till the dark brown complex formation is com~lete and then add:
32 grams phthalonitrile (95% pure) 3.0 gr&ms ammonium chloride 18 gram~ pi&mentary beta-copper phthalocyanine Stir ~ hour at room temperature and then add:
4 erams sodium metal, slowly 1 gram pyridine dissolved in 10 millilitres CH30H
~ he pyrldine is added dropwise, whilst adding the sodium metal. Stir ~ 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%) H2S04, dropwise Stir 2 hours at room temperature. The pi g ent is isolated and after-treated (purified) in the manner of Example 8.
The yield wa~ 49 gram~ of pigmentary beta-co~er phthalocyanine.
ExamPle 23 ~ o 160 Brams C~30~ add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
6.2 grams ¢uprous chloride Stir till the dark brown complex formation is complete and tben add;
32 grams phthalonitrile (95% pure) . . .
. - - , ', : ' ' ~ .
.' . ' '' ' '~ ' 49~L
3.0 grams a~nonium chloride 12 grams pigmentary beta-copper phthalocyanine Stir 1 hour at room temperature and then add:
3-5 Bram8 ~odium metal, slowly 1 gram pyridine dissolved in 10 millilitres CH30~
T~le pyridine is added dropwise whilst adding the Eodium metal. Stir -~ hour at room temperature, after the last addition o~ sodium and pyridine. Finally reflux 8 hours. Allow to cool to room temperature and then ada:
60 ~rams concentrated (9~/o) H2S04, dropwi~e Stir 2 hour~ at room temperature. The pigment i8 isolated and purified in the manner of Example 8. Ihe yield was 43 grams Or pigmentary beta-copper phthalocyanine.
~xample 24 To 1400 millilitres CH30~ add:
3.6 gram~ dimethylglyoxime When a ~olution has been obtained add:
24.8 grams cuprous chloride Stir till the dark brown oomplex formation iY complete and then add: .
128 gr2ms phthalonitrile ~95% pure) 12.0 grams ammonium chloride 180 gr~Jms pigmentary beta-copper phtha'ocyanine 4 grams 1,2,4-trichloro-3-phenoxy-copper phthalocyanine Stir 1 hffur at room temperature and then add:
16 grams sodiu~ metal, slowly ,. : - : ..
:, . . :: .
: . : ' ~ '. ' : ' . .
: . : : . ' :: ' : ~ . : ' ~491~
4 millilitres pyridine dissolved in 40 millilitres CH30H
The pyridine is added dropwise whilst adding the ~odium metal. Stir ~ hour at room temperature after the last addition of sodium and pyridine, ~inally reflux 8 hours. ~he product is lsolated and after-treated in the manner of Example 7. m e yield was 308 grams pigmentary beta-copper phthalocyanine.
Exam~le 25 ~ o 280 gram~ CH30H add:
0.9 grams dimethylglyoxime When a solution has been obtained add:
6.2 grams cuprous chloride Stir till the dark brown complex formation i~ complete and then add:
32 grams phthalonitrile (9~% pure) 3 Bram~ ammonium chloride 45 grams pigmentary beta-copper phthalocyanine 1 gram , ~ (S02~ H2CH2.01I)2 copper phthalocyanine (S03H)2 stir 1 hour at room temperature and then add:
4 grams sodium metal, ~lowly 1 millilitre pyridine dis~olved in 10 millilitres C~30H
~he pyridine is added dropwise, whilst addi~g the ~odiu~
; ~ 32 -491$
.
metal. Stir ~ hcur at room temperature after the last addition of sodium and pyridine. Finally reflux 8 hours. Allow to oool to room temperature and then add:
60 grams concentrated (9~o) H2S04, dropwise Stir 1 hour at room ternperature and then reflux ~ hour.
The product is isolated and purified in the manrer of Ex3mple 8.
~he yield was 77 grams of pig~entary beta-copper phthalocyænine.
Exam~le 26 ~o 1050 millilitres C~30~ add:
2.7 grams dimethylglyoxime When a solution has been obtained add:
18.6 gr~ms cuprous chloride St~r till the dark browm complex formation i8 complete and then add:
96 erams phth~lonitrile (95% pure) 9 Bram~ ammonium chloride 3 grams 1,2,4-trichloro-3-phenoxy-copper phthalocyanine 135 grams pigmentary be ~ copper phthalocyanine Stir 1 hour at room temperature and then add:
12 grams sodium metal, slowly 3 gram~ pyridine dissolved in 30 millilitres C~30 ~he pyridine is added dropwise, whilst adding the sodium metal. Stir ~ 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:
1~849~
180 grams concentrated (98~) H2S04, dropwise Stir 1 hour at room temperature and then reflux L/2 hour.
The product is isolated and after-treated in the manner of Example 8.
The yield was 228 grams pigmentary beta-copper phthalocyanine.
Example 27 To a 500 millilitre flask add:-lS0 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 CH30H.
After the addition of sodium methoxide add 1.5 grams pigmentary mono-chloro-copper phthalocyanine. Finally raise the temperfiture to reflux and reflux 8 hours. After refluxing for 8 hours, filter, wash with methanol and then water. The pig-ment is purified in the manner of Example 7. The yield was 18 grams of pigmentary alpha copper phthalocyanine.
-:
.
10~49~
Example 28 ~ y fol] OWillg a similar procedure to that described in Example 27 ~ut using 4 grams ammoniunl acetate in place of the ammonium chloride there used, 20 grams of,pigmentary alpha copper phthalocyanille were obtained.
Example 29 To a 500 millilitre flask add:-100 millilitres methanol j2.7 grams phtha~odinitrile ( 98/o) 0.9 grams dimethylglyoxime 3.0 grams ammonium chlo,ride 2.0 grams triethanolamine ' 8.8 grams cupric chloride Then add dropwise over 30 minutes:-80 millilitre~ of a 25% solution of sodium methoxide ln CH30H
After the addition of sodium methoxide add 1. 5 grams pigmentary mono-chloro-copper phthalocyaninc. Finally raise the temperature to reflux and reflux 8 hours. After reflux, filter, wa.sh with methanol and then water. The pigment is purified in the manner of Example 7 to give 28 grams of pign1entary alpha copper phthalocyaninc, . .
'' .
~ 35 -.. . ~ . - ~
, .
9'~
Exam~le ~0 To a 1 litrc flask add:-150 millilitres methanol -' 34.3 grams phthalodinitrile ( 98C~b) 0.9 grams dimethylglyoxime 6.4 grams cuprous chloride 3.0 grams ammoniwn chloride 1.0 grams 1,2,3,4 tetrachloro copper phthalocyanine.
1.0 ~rams potassiwn 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 i8 purified in the manner of Examplè 7 to give 26.5 grams of pigmentary alpha copper phthalocyanine.
~xan-p le 31 To a litre flask add:-150 millilitres methanol 32.7 grams phthalodinitrile ( 98%) O. 9 grams dimetllylglyo~;ime 3.0 grams ammonium chloride 6.4 grams cuprous chloride 1.0 gram , 1,Z,3,4-tetra~chloro-copper phthalocyanine.
Add:-.
10~49~$
5.5. grams ~aOH whilst the reaction rnixture is high spced stirred using a Silvcrson Higll Speed stirrer. High Rpeed stir for 10 minutes-after the last addition of NaOH.
The reactiorl 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 pigmcntary alpha copper phthalocyanine.
Example ~2 By following a similar procedure to that described in Example 31 but adding 6.o 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.
,xample ~3 ~ y ~ollowing a similar procedure to that described in Example 31 but usin~ 6.o gran.s ammonium sulphate in place of the ammonium chloride therc used, 26.5 grams of pigmentary alpha copper phthalocyanine were obtained.
Example 34 By following a similar procedure to that described in Example 31 but adding 1.0 gram sodiwn dithionite after the addition of ammonium chloride and prior to the addition of cuprous chloride, 28 grams of pigmentary alpha copper phthalocyanine were ~btained.
,: ~ ' ' ' ,- , .
. ~ '.
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for the production of alpha-, beta- or gamma-copper phthalocyanine pigments which comprises reacting an ortho-phthalodinitrilo or substituted ortho-phthalodinitrile compound of the general formula in which 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 a hydroxide, oxide, peroxide, alkoxide or car-bonate of an alkali metal or of an alkaline earth metal in a hydrophilic ali-phatic organic solvent containing one or more hydroxy groups, the improvement whereby high quality pigments are obtained without need for acid-pasting or mechanical pulverization which comprises adding as crystal form controller from the beginning of the reaction:
(i) in the case where an alpha-copper phthalocyanine pigment is required:
(a) 0.5% to 40% by weight, based on the weight of pigment synthe-sized, of an alpha-phase copper phthalocyanine pigment or (b) 0.5% to 10% by weight, based on the weight of pigment synthe-sized, of a copper phthalocyanine derivative selected from the group consist-ing of chlorinated copper phthalocyanine, copper phthalocyanine sulfonic acid, 1,2,4-trichloro-3-phenoxy copper phthalocyanine or (ii) in the case where a beta-copper phthalocyanine pigment is required, 40% to 150% by weight, based on the weight of pigment synthesized, of a beta-phase copper phthalocyanine pigment, or (iii) in the case where a gamma-copper phthalocyanine pigment is required, 0.5% to 40% by weight, based on the weight of pigment synthesized, of of a gamma-phase copper phthalocyanine pigment.
(i) in the case where an alpha-copper phthalocyanine pigment is required:
(a) 0.5% to 40% by weight, based on the weight of pigment synthe-sized, of an alpha-phase copper phthalocyanine pigment or (b) 0.5% to 10% by weight, based on the weight of pigment synthe-sized, of a copper phthalocyanine derivative selected from the group consist-ing of chlorinated copper phthalocyanine, copper phthalocyanine sulfonic acid, 1,2,4-trichloro-3-phenoxy copper phthalocyanine or (ii) in the case where a beta-copper phthalocyanine pigment is required, 40% to 150% by weight, based on the weight of pigment synthesized, of a beta-phase copper phthalocyanine pigment, or (iii) in the case where a gamma-copper phthalocyanine pigment is required, 0.5% to 40% by weight, based on the weight of pigment synthesized, of of a gamma-phase copper phthalocyanine pigment.
2. A process as claimed in Claim 1 in which the orthodinitrile is phthalodinitrile.
3. A process as claimed in Claim 1 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 Claim 1 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 Claim 1 in which the alkaline material is sodium metal, sodium methoxide or sodium hydroxide.
6. A process as claimed in Claim 1 in which the alkaline material is used in an amount of up to 2 moles per mole of dinitrile.
7. A process as claimed in Claim 1 in which the hydrophilic aliphatic solvent containing a hydroxyl group is methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary butanol, t-butanol, ethylene giycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether.
8. A process as claimed in Claim 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 Claim 1 in which the alpha copper phthalo-cyanine is added in an amount of from 0.5% to 20% by weight based on the weight of pigment synthesized.
10. A process as claimed in Claim 1 in which the gamma copper phthalo-cyanine is added in an amount from 20% to 40% by weight based on the weight of pigment synthesized.
11. A process as claimed in Claim 1 in which the beta copper phthalo-cyanine is added in an amount from 100% to 150% by weight based on the weight of pigment synthesized.
12. A process as claimed in Claim 1 in which there is used in addition an organic or inorganic ammonium salt.
13. A process as claimed in Claim 12 in which the ammonium salt is am-monium chloride, ammonium sulphate, ammonium persulphate, ammonium ortho-phosphate, ammonium metaphosphate, ammonium pyrophosphate, ammonium carbonate, ammonium bicarbonate, ammonium formate, ammonium acetate, or ammonium oxalate.
14. A process as claimed in Claim 12 in which the amount of ammonium salt used is from 0.5% to 6% by weight, based on the weight of dinitrile compound.
15. A process as claimed in Claim 1 in which there is used in addition sodium hydrosulphite and/or pyridine.
16. A process as claimed in Claim 1 in which there is added in addition a metal phthalocyanine other than copper phthalocyanine.
17. A process as claimed in Claim 1 in which there is added from 1% to 10% by weight, based on the weight of pigment synthesized, of a metal phthalo-cyanine derivative which is a chlorinated copper phthalocyanine, a copper phthalocyanine sulphonic acid, 1, 2, 4-trichloro-3-phenoxy copper phthalo-cyanine or
18. A process as claimed in Claim 1 in which a compound which can form a complex with the copper salt used in the reaction is added to the reaction mixture.
19. A process as claimed in Claim 18 in which the compound which can form a complex with the copper salt used in the reaction is dimethylglyoxime.
20. A process as claimed in Claim 18 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.
21. A process as claimed in Claim 1 in which a small amount of acid is added, followed by stirring, immediately after completion of the reaction without isolation of the pigment.
22. A process as claimed in Claim 21 in which the acid used is hydro-chloric acid, sulphuric acid, acetic acid, propionic acid or oxalic acid.
23. A process as claimed in Claim 21 in which the amount of acid used is from 3% to 50% by weight based on the weight of the hydrophilic organic solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3470775A GB1558663A (en) | 1975-08-21 | 1975-08-21 | Preparation of pigmentary phtalocyanine |
| GB34707/75 | 1975-08-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084911A true CA1084911A (en) | 1980-09-02 |
Family
ID=10368974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA259,457A Expired CA1084911A (en) | 1975-08-21 | 1976-08-19 | Preparation of alpha-, beta-, and gamma-copper phthalocyanine pigments |
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) |
Families Citing this family (6)
| 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 |
| GB8515600D0 (en) * | 1985-06-20 | 1985-07-24 | Ciba Geigy Ag | Pigmentary copper phthalocyanine |
| 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 DE DE19762637202 patent/DE2637202A1/en not_active Withdrawn
- 1976-08-18 CH CH1051476A patent/CH626114A5/en not_active IP Right Cessation
- 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
Also Published As
| Publication number | Publication date |
|---|---|
| GB1558663A (en) | 1980-01-09 |
| FR2321527A1 (en) | 1977-03-18 |
| CH626114A5 (en) | 1981-10-30 |
| JPS5226529A (en) | 1977-02-28 |
| FR2321527B1 (en) | 1979-06-29 |
| DE2637202A1 (en) | 1977-03-03 |
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