CA1160402A - Process for the preparation of pigment alloys - Google Patents
Process for the preparation of pigment alloysInfo
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- CA1160402A CA1160402A CA000379969A CA379969A CA1160402A CA 1160402 A CA1160402 A CA 1160402A CA 000379969 A CA000379969 A CA 000379969A CA 379969 A CA379969 A CA 379969A CA 1160402 A CA1160402 A CA 1160402A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Developing Agents For Electrophotography (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
3-12916/+
Process for the preparation of pigment alloys Abstract Process for the preparation of pigment alloys, which comprises subjecting a mixture consisting of at least two pigments from different groups of the perylene, phthalocyanine, perinone, quinacridone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinoid, thioindigo, azo, methine or azomethine series, to thorough wet-grinding. Compared with conventional pig-ment mixtures, the pigment alloys obtained exhibit clearer colour shades, better application properties and more favourable physical properties.
Process for the preparation of pigment alloys Abstract Process for the preparation of pigment alloys, which comprises subjecting a mixture consisting of at least two pigments from different groups of the perylene, phthalocyanine, perinone, quinacridone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinoid, thioindigo, azo, methine or azomethine series, to thorough wet-grinding. Compared with conventional pig-ment mixtures, the pigment alloys obtained exhibit clearer colour shades, better application properties and more favourable physical properties.
Description
1 160~0~
-- 1 ~
3-12916/~
Process for the preparation of pigment alloys It is known that so-called super alloys, which are commercially available, are obtained by grinding together various metal, metal oxide or metal carbide powders in high-capacity ball mills (Scientific.~American 234/5, page 40 (1~76)) It is also known that, in the case o~ pigments which are very closely related in terms of colour and structure, mixed crystals can be produced by grinding or reprecipitation ~rom sulfuric acid (see U.S. Patent Specification 3,081,188 and German Offenlegungsschrift
-- 1 ~
3-12916/~
Process for the preparation of pigment alloys It is known that so-called super alloys, which are commercially available, are obtained by grinding together various metal, metal oxide or metal carbide powders in high-capacity ball mills (Scientific.~American 234/5, page 40 (1~76)) It is also known that, in the case o~ pigments which are very closely related in terms of colour and structure, mixed crystals can be produced by grinding or reprecipitation ~rom sulfuric acid (see U.S. Patent Specification 3,081,188 and German Offenlegungsschrift
2,842,468). :
Moreover, it is known that the mixing of pigments which are very di~ferent from one another in terms of colour and structure can lead to dull hues German Auslegeschrift 27110,999 describes a pro-cess for the preparation of Cu phthalocyanine pigments by mixing Cu phthalocyanine with one or more tinting pigments, a~ter which pigment mixtures are obtained byreprecipitation in sul~uric acid, by boiling or by the dry-grinding o~ Cu phthalocyanines with dioxazine compounds, isoindolinone compounds, indolizinedione compounds, azo compounds or thioindigo compounds, and these pigment mixtures are said to give more intense blue colorations with redder tints.
It has been shown that pigment mixtures prepared by the last-mentioned process bring certain advantages, but are unsatisfactory in respect of clarity, dispersibi-lity in plastîcs and t~.tiformity of the colorations.
;. ~
', .
-It has now been found that, by subjecting a mixture consisting of at least two pigments from different groups of the perylene, phthalocyanine, perinone, quinacridone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, thioindigo, methine or azomethine series or of the monoazo or disazo series of the 2,3-hydroxynaphthoic acid arylide, acetoacetic acid arylide, pyrazolone or benz-imidazolone group, to thorough wet-grinding in water until the pigments are alloyed with one another on the microscopic scale, pigment alloys are obtained which, in comparison with conventional pigment mixtures have clearer colour shades, better application properties and more favourable physical properties.
In the case of pigments of the phthalocyanine, methine or azomethine series, these can be both metal-free pigments and metal complexes.
The pigments to be used as starting materials must belong to two dif~erent pigment groups They must differ in essential structural characteristics and not only in the type o~ substituents or, in the case of metal complexes, in the type of metal. Thus, it is possible to start ~rom mixtures of one representative of the above-mentioned series with another representative of this series, for example a mixture o~ an isoindolinone with a perylene or azo pigment, or a mixture of a phthalocyanine with a dioxazine, azo, anthraquinone or perylene pigment, or a mixture o~ a quinacridone with an indigoid or with an azo, anthraquinone or dioxazine pigment. Particularly good results are achieved by grinding pigments of similar hardness, for example polycyclic pigments, such as dioxazines, perylenes, isoindolinones, quinacridones and phthalocyanines, with one another, or by grinding azo pigments with azomethine pigments.
l 1~0~02 The relative proportions of the pigments can vary within wide limits. 0.1 to 50 parts by weight of the pigment of one of the groups and 50-99.9 parts by weight of at least one pigment of the other group are preferably used per 100 parts by weight of a pigment mixture.
For the starting pigment mixture, the individual components can be in medium-to-fine crystalline form, but preferably in coarse- and medium-to-~ine crystalline form or only coarse crystalline form.
To intensi~y the grindlng action~ it can be advantageous to carry out the wet-grinding in the presence of organic grinding aids which are subsequently to be removed. Thus, for example, according to the process described in German Offenlegungsschrift 1,209,852, the aqueous wet-grinding can be carried out particularly effectively in the presence of a substantially water-insoluble organic compound which can subsequently be removed by sublimation or steam dlstillation or extraction, in particular solid hydrocarbons, such as naphthalene, or j a chlorohydrocarbon, such as hexachloroethane or p-di-¦ chlorobenzene, 0.5 - 1.5 parts o~ the grinding aid and 1 -].2 parts of water advantageously being used per 1 part of I dry pigment mixture.
Organic additives remaining in the product, such 1~0~2 as stearic acid, resinic acids, for example abietic acid and hydrogenated abietic acid, resinic acid esters, derivatives of a low-molecular or high-molecular addition resin or polymerisation resin, waxes or polyethylene gly-cols, can also be used as grinding aids, advantageously in amounts of 0.01 to 0.30 part, but preferably in small amounts, such as 0.01 to 0.15 part, of organic additive per 1 part of dry pigment mixture. In this process, such additives can additionally improve the application properties of the pigment alloy.
For carrying out the process, the pigment mixture, preferably suspended in the liquid together with the organic grinding aid and/or organic additives, is intro-duced into a wet-grinding device with a thorough action.
Any device which makes it possible to subject the pigments and, if appropriate, the carrier to intense mechanical forces, in a liquid medium, can be used as the apparatus. A relatively large number of apparatuses of this type are known. They are based, for example, on the principle of a large velocity gradient produced in a liquid medium, or a sudden change in direction, or, in particular, on the effect of collision or the mutual friction between grinding bodies, such as metal spheres, glass spheres or porcelain spheres, plastic granules or;
particles of sand, which are set in motion by the rotation of the vessel or, even more effectively, by vibrating devices or stirrer-like devices, for example as in the case of glass-bead mills.
The grinding temperature is not critical within technically reasonable limits, but, in the case where organic grinding aids are used, should be below their melting point. The grinding is advantageously carried out at temperatures between 5 and 80C, preferably at room temperature. Changes in the pH value, for example adjustment of pigment suspensions to an acid or alkaline pH, can also bring advantages in certain cases.
The wet-grinding is continued until the pigments are alloyed with one another on the microscopic scale This takes ~ hour to 24 hours, depending on the type of mill, the composition of the pigment mixture and, if appropriate, the grinding aid used. The time required to achieve the optimum properties of the pigment alloy for the special use envisaged can easily be determined by those skilled in the art. When starting from coarse crystalline pigments, the pigment crystals are greatly comminuted by the thorough grinding. Depending on its composition, the pigment alloy can be in a state similar to that of a substance which is amorphous to X-rays, Working-up is carried out in the customary manner by separating off the grinding bodies and isolating the pigment alloy by filtering the pigment suspension and dry-ing the pigment, When using organic grinding aids which are subsequently to be removed, these are advantage-ously removed after the grinding bodies have been separated off, for example by steam distillation of the pigment sus-pension or by sublimation during the drying of~the pigment press-cake.
The drying process is carried out in the conven-tional manner, for example in a vacuum cabinet or circulat-ing air cabinet, a paddle drier, a fluidised bed drier or freeze drier or also a spray drier. ~uring the drying of pigment press-cakes, irreversible agglomerations fre-quently occur and this results in poor dispersibility.
Surprisingly, in comparison with the separately ground, pure pigments, pigment alloys prepared according to the invention undergo in most cases substantially less irreversible agglomeration during drying, despite the particles being very fine.
The pigment alloys obtained according to the invention are sui-table for pigmenting high-molecular com-pounds, for example cellulose ethers and cellulose esters, such as ethylcellulose, acetylcellulose and nitrocellulose, polyamides and polyurethanes or polyesters, natural resins or synthetic resins, for example aminoplasts, especially l 160~02 -- 6 _ urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polyethylene, polypropylene and polystyrene, poly-vinyl chloride, polyacrylonitrile and polyacrylic acid esters, thermoplastic or thermosetting acrylic resins, rubber, casein, silicone and silicone resins, individually or in mixtures. The high-molecular compounds mentioned can be in the form of plastic masses or melts or in the i~orm of spinning solutions, lacquers or printing inks.
Depending on the intended use, it proves advantageous to use the pigment alloys as toners or in the form o~ pre-parations.
Because of the possibility of producing speciaI
physical properties, the pigment alloys prepared according to the invention can also be employed in other particular fields of application. Examples are the use of pigment alloy toners in the field of electrophotography, as absorption pigments in solar cells or as catalysts for diverse chemical reactions, for example redox reactions.
Pigment alloy toners with special properties, which can also be used, for example, as electrical semi-c~onductors, are advantageously obtained by the thorough grinding of pigment mixtures containing a) pigments with electron-donating properties and b) pigments with electron-accept-ing prope~ties, or of pigments with electron-donating or electron-accepting properties, together with organic addi-tives with electron-donating or electron-accepting proper-ties, respectively To produce special forms of pigment, the pigment alloy, suspended in water, and/or in organic solvents, can also be subjected to an after-treatment, preferably under the action of heat and/or, i~ appropriate, at a modified pressure.
In contrast to the conventional pigment mixtures, the pigment alloys obtained according to the invention are distinguished by more favourable physical properties and application properties, especially clearer and more uni-I ~160~02 ~orm hues, higher tinctorial strength and transparency andhigher gloss, and better dispersibility in plastics and lacquers. Because demixing cannot take place, in con-trast to the conventional mixtures, the hue is guaranteed to renain constant. Compared with individual pigments, the pigment alloys have a substantially smaller crystal growth in organic solvents and, in many cases, an improved fastness to light, weathering fastness and heat resistance.
In addition, itis tobe particularlyemphasised that theprocess accordingto theinvention isvery economical; novel pigments with particular desired colour shades can be prepared in a simple manner from commercial pigments.
In the following examples, parts and percentages are by weight, unless stated otherwise, and the tempera-tures are given in degrees centigrade, Example 1:
a) 28 parts of the orange-coloured pigment (I) of the formula ca3 ~
C!~ , N N ~ Cl Cl ~0 H~ , 7 parts of perylenetetracarboxylic dianhydride (II) and ~
35 parts of finely divided hexachloroethane are suspended in 630 parts~of water in a glass-bead mill with a capacity of 2,000 parts by volume, and thoroughly ground, for 24 hours, with 1,900 parts of glass spheres (diameter:
~.5-5.0 mm), at a stirring speed of 320 rpm, with external water-cooling The glass spheres are then separated of~ from the suspension and subsequently washed to some extent with water. In a stirred vessel, the hexa-chloroethane is removed by means o~ steam distillation.
The pigment suspension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70-80 and powdered. This gives 33 5 parts of a pigment alloy (A) which can very readily be dispersed in plasticised PVC and gives very intensely coloured, clear, uniform, orange-red milled sheets with excellent fastness properties~
b) The pigments I and II are ground separately, as described in la), for 24 hours, with hexachloroethane as the grinding aid, the glass spheres are separated off, the hexachloroethane is removed by steam distillation and the pigment suspensions are filtered. The press-cakes of the separately ground pigments I and II, in the same weight ratio as the powdered pigments above, are only mixed well, by stirring them in water again without further grinding, filtered off, washed and dried, afford-ing a pigment mixture (B) which, compared with the pigment alloy (A), has a substantially duller hue when incorporated into lacquers and plastics and has distinctly visible streaks of red perylene pigment when used to colour plasticised PVC milled sheets.
c) Investigation of the recrystallisation behaviour:
1 part of each of the two pigment samples A and B
is stirred separately in 30 parts of o-dichlorobenzene for 44 hours at 150 - 160. At certain intervals of time, samples are withdrawn and the increase in size of the crystals is observed under a light microscope. In the case of pigment mixture B, the perylenetetracarboxylic dianhydride shows a constantly progressing, strong crystal growth as a function of time, whereas in the case of pig-ment alloy A, a very small crystal gro~th could be observed, which ceased after 1 to 3 hours.
29,4 parts of C I, Pigment Yellow llO (iso-indolinone) and 5.6 parts of perylenetetracarboxylic acid diimide are ground together with 35 parts of finely divided hexachloroethane, according to the process des-cribed in Example la), and the mixture is worked up.
~his gives 33.8 parts of a brown pigment alloy which, when l 160402 . g used for colouring plas-ticised PVC milled shee-ts, gives brown, transparen-t, clear, uniform and intense colora-tions with excellent fastness proper-ties The dis-persibility of the pigment alloy is excellent. This is surprising because the perylenetetracarboxylic acid diimide pigment in the pure state is exceptionally poorly dispersible in plastics. The pigment alloy addition-ally exhibits equal dispersibility a~ lo~ as at high shear strength. Wen used for colouring lacquers, it exhibits very good fastness properties and high gloss.
Example 3: 30 8 parts of C I. Pigment Yellow I10 and 4 2 parts of perylenetetracarboxylic acid diimide, toge-ther with 3.9 parts of finely divided hydrogenated abietic acid (Staybelite Resin ~ from Hercules), are thoroughly ground, for 9 hours, in 670 parts bf water, in a glass~bead mill with a capacity of 2,000 parts by volume, with 1,900 parts of glass spheres (diameter: 4.5 - 5.0 mm), at a stirring speed of abou-t 320 rpm, with external oold water-cooling. The glass spheres are separated from~
the pigment suspension and washed withalittlewater. The pigment suspension is then filtered, the press-cake is washed with water and dried at 70 - 80 in a vacuum dry- -ing cabinet and the pigmen-t is powdered This gives 37.8 parts of a pigment alloy con-taining appro*imately 1~% of Staybelite resin, which can be used with excellent dispersibility for colouring plasticised PVC and gives brown, transparent, clear milledshee-ts ofuniform colour intensity and with very good fastness proper-ties.
The sheets exhibit equal dispersibility at low as at high shear strength.
Example 4: In a stirred vessel, 195 par-ts of C.I. Pig-ment Yellow 110 and 5 parts of 2,9-dichloroquinacridone~
together wi-th 22 2 parts of finely divided hydrogenated abietic acid, are stirred well, ~or one hour, in 900 parts of wa-ter. The pigment suspension is diluted wi~h water to a weight of 2,000 parts. In a KDL--type Dyno mill I ~60402 irom Willy A. Bachofen, Basel, provided with a steel grinding con-tainer wi-th a capaci-ty of 600 par-ts by volume, filled with 480 - 510 parts by volume of glass spheres having a diameter of 1 mm, the pigment suspension is thoroughly ground, for 90 minutes, at a stirring speed of
Moreover, it is known that the mixing of pigments which are very di~ferent from one another in terms of colour and structure can lead to dull hues German Auslegeschrift 27110,999 describes a pro-cess for the preparation of Cu phthalocyanine pigments by mixing Cu phthalocyanine with one or more tinting pigments, a~ter which pigment mixtures are obtained byreprecipitation in sul~uric acid, by boiling or by the dry-grinding o~ Cu phthalocyanines with dioxazine compounds, isoindolinone compounds, indolizinedione compounds, azo compounds or thioindigo compounds, and these pigment mixtures are said to give more intense blue colorations with redder tints.
It has been shown that pigment mixtures prepared by the last-mentioned process bring certain advantages, but are unsatisfactory in respect of clarity, dispersibi-lity in plastîcs and t~.tiformity of the colorations.
;. ~
', .
-It has now been found that, by subjecting a mixture consisting of at least two pigments from different groups of the perylene, phthalocyanine, perinone, quinacridone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, thioindigo, methine or azomethine series or of the monoazo or disazo series of the 2,3-hydroxynaphthoic acid arylide, acetoacetic acid arylide, pyrazolone or benz-imidazolone group, to thorough wet-grinding in water until the pigments are alloyed with one another on the microscopic scale, pigment alloys are obtained which, in comparison with conventional pigment mixtures have clearer colour shades, better application properties and more favourable physical properties.
In the case of pigments of the phthalocyanine, methine or azomethine series, these can be both metal-free pigments and metal complexes.
The pigments to be used as starting materials must belong to two dif~erent pigment groups They must differ in essential structural characteristics and not only in the type o~ substituents or, in the case of metal complexes, in the type of metal. Thus, it is possible to start ~rom mixtures of one representative of the above-mentioned series with another representative of this series, for example a mixture o~ an isoindolinone with a perylene or azo pigment, or a mixture of a phthalocyanine with a dioxazine, azo, anthraquinone or perylene pigment, or a mixture o~ a quinacridone with an indigoid or with an azo, anthraquinone or dioxazine pigment. Particularly good results are achieved by grinding pigments of similar hardness, for example polycyclic pigments, such as dioxazines, perylenes, isoindolinones, quinacridones and phthalocyanines, with one another, or by grinding azo pigments with azomethine pigments.
l 1~0~02 The relative proportions of the pigments can vary within wide limits. 0.1 to 50 parts by weight of the pigment of one of the groups and 50-99.9 parts by weight of at least one pigment of the other group are preferably used per 100 parts by weight of a pigment mixture.
For the starting pigment mixture, the individual components can be in medium-to-fine crystalline form, but preferably in coarse- and medium-to-~ine crystalline form or only coarse crystalline form.
To intensi~y the grindlng action~ it can be advantageous to carry out the wet-grinding in the presence of organic grinding aids which are subsequently to be removed. Thus, for example, according to the process described in German Offenlegungsschrift 1,209,852, the aqueous wet-grinding can be carried out particularly effectively in the presence of a substantially water-insoluble organic compound which can subsequently be removed by sublimation or steam dlstillation or extraction, in particular solid hydrocarbons, such as naphthalene, or j a chlorohydrocarbon, such as hexachloroethane or p-di-¦ chlorobenzene, 0.5 - 1.5 parts o~ the grinding aid and 1 -].2 parts of water advantageously being used per 1 part of I dry pigment mixture.
Organic additives remaining in the product, such 1~0~2 as stearic acid, resinic acids, for example abietic acid and hydrogenated abietic acid, resinic acid esters, derivatives of a low-molecular or high-molecular addition resin or polymerisation resin, waxes or polyethylene gly-cols, can also be used as grinding aids, advantageously in amounts of 0.01 to 0.30 part, but preferably in small amounts, such as 0.01 to 0.15 part, of organic additive per 1 part of dry pigment mixture. In this process, such additives can additionally improve the application properties of the pigment alloy.
For carrying out the process, the pigment mixture, preferably suspended in the liquid together with the organic grinding aid and/or organic additives, is intro-duced into a wet-grinding device with a thorough action.
Any device which makes it possible to subject the pigments and, if appropriate, the carrier to intense mechanical forces, in a liquid medium, can be used as the apparatus. A relatively large number of apparatuses of this type are known. They are based, for example, on the principle of a large velocity gradient produced in a liquid medium, or a sudden change in direction, or, in particular, on the effect of collision or the mutual friction between grinding bodies, such as metal spheres, glass spheres or porcelain spheres, plastic granules or;
particles of sand, which are set in motion by the rotation of the vessel or, even more effectively, by vibrating devices or stirrer-like devices, for example as in the case of glass-bead mills.
The grinding temperature is not critical within technically reasonable limits, but, in the case where organic grinding aids are used, should be below their melting point. The grinding is advantageously carried out at temperatures between 5 and 80C, preferably at room temperature. Changes in the pH value, for example adjustment of pigment suspensions to an acid or alkaline pH, can also bring advantages in certain cases.
The wet-grinding is continued until the pigments are alloyed with one another on the microscopic scale This takes ~ hour to 24 hours, depending on the type of mill, the composition of the pigment mixture and, if appropriate, the grinding aid used. The time required to achieve the optimum properties of the pigment alloy for the special use envisaged can easily be determined by those skilled in the art. When starting from coarse crystalline pigments, the pigment crystals are greatly comminuted by the thorough grinding. Depending on its composition, the pigment alloy can be in a state similar to that of a substance which is amorphous to X-rays, Working-up is carried out in the customary manner by separating off the grinding bodies and isolating the pigment alloy by filtering the pigment suspension and dry-ing the pigment, When using organic grinding aids which are subsequently to be removed, these are advantage-ously removed after the grinding bodies have been separated off, for example by steam distillation of the pigment sus-pension or by sublimation during the drying of~the pigment press-cake.
The drying process is carried out in the conven-tional manner, for example in a vacuum cabinet or circulat-ing air cabinet, a paddle drier, a fluidised bed drier or freeze drier or also a spray drier. ~uring the drying of pigment press-cakes, irreversible agglomerations fre-quently occur and this results in poor dispersibility.
Surprisingly, in comparison with the separately ground, pure pigments, pigment alloys prepared according to the invention undergo in most cases substantially less irreversible agglomeration during drying, despite the particles being very fine.
The pigment alloys obtained according to the invention are sui-table for pigmenting high-molecular com-pounds, for example cellulose ethers and cellulose esters, such as ethylcellulose, acetylcellulose and nitrocellulose, polyamides and polyurethanes or polyesters, natural resins or synthetic resins, for example aminoplasts, especially l 160~02 -- 6 _ urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polyethylene, polypropylene and polystyrene, poly-vinyl chloride, polyacrylonitrile and polyacrylic acid esters, thermoplastic or thermosetting acrylic resins, rubber, casein, silicone and silicone resins, individually or in mixtures. The high-molecular compounds mentioned can be in the form of plastic masses or melts or in the i~orm of spinning solutions, lacquers or printing inks.
Depending on the intended use, it proves advantageous to use the pigment alloys as toners or in the form o~ pre-parations.
Because of the possibility of producing speciaI
physical properties, the pigment alloys prepared according to the invention can also be employed in other particular fields of application. Examples are the use of pigment alloy toners in the field of electrophotography, as absorption pigments in solar cells or as catalysts for diverse chemical reactions, for example redox reactions.
Pigment alloy toners with special properties, which can also be used, for example, as electrical semi-c~onductors, are advantageously obtained by the thorough grinding of pigment mixtures containing a) pigments with electron-donating properties and b) pigments with electron-accept-ing prope~ties, or of pigments with electron-donating or electron-accepting properties, together with organic addi-tives with electron-donating or electron-accepting proper-ties, respectively To produce special forms of pigment, the pigment alloy, suspended in water, and/or in organic solvents, can also be subjected to an after-treatment, preferably under the action of heat and/or, i~ appropriate, at a modified pressure.
In contrast to the conventional pigment mixtures, the pigment alloys obtained according to the invention are distinguished by more favourable physical properties and application properties, especially clearer and more uni-I ~160~02 ~orm hues, higher tinctorial strength and transparency andhigher gloss, and better dispersibility in plastics and lacquers. Because demixing cannot take place, in con-trast to the conventional mixtures, the hue is guaranteed to renain constant. Compared with individual pigments, the pigment alloys have a substantially smaller crystal growth in organic solvents and, in many cases, an improved fastness to light, weathering fastness and heat resistance.
In addition, itis tobe particularlyemphasised that theprocess accordingto theinvention isvery economical; novel pigments with particular desired colour shades can be prepared in a simple manner from commercial pigments.
In the following examples, parts and percentages are by weight, unless stated otherwise, and the tempera-tures are given in degrees centigrade, Example 1:
a) 28 parts of the orange-coloured pigment (I) of the formula ca3 ~
C!~ , N N ~ Cl Cl ~0 H~ , 7 parts of perylenetetracarboxylic dianhydride (II) and ~
35 parts of finely divided hexachloroethane are suspended in 630 parts~of water in a glass-bead mill with a capacity of 2,000 parts by volume, and thoroughly ground, for 24 hours, with 1,900 parts of glass spheres (diameter:
~.5-5.0 mm), at a stirring speed of 320 rpm, with external water-cooling The glass spheres are then separated of~ from the suspension and subsequently washed to some extent with water. In a stirred vessel, the hexa-chloroethane is removed by means o~ steam distillation.
The pigment suspension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70-80 and powdered. This gives 33 5 parts of a pigment alloy (A) which can very readily be dispersed in plasticised PVC and gives very intensely coloured, clear, uniform, orange-red milled sheets with excellent fastness properties~
b) The pigments I and II are ground separately, as described in la), for 24 hours, with hexachloroethane as the grinding aid, the glass spheres are separated off, the hexachloroethane is removed by steam distillation and the pigment suspensions are filtered. The press-cakes of the separately ground pigments I and II, in the same weight ratio as the powdered pigments above, are only mixed well, by stirring them in water again without further grinding, filtered off, washed and dried, afford-ing a pigment mixture (B) which, compared with the pigment alloy (A), has a substantially duller hue when incorporated into lacquers and plastics and has distinctly visible streaks of red perylene pigment when used to colour plasticised PVC milled sheets.
c) Investigation of the recrystallisation behaviour:
1 part of each of the two pigment samples A and B
is stirred separately in 30 parts of o-dichlorobenzene for 44 hours at 150 - 160. At certain intervals of time, samples are withdrawn and the increase in size of the crystals is observed under a light microscope. In the case of pigment mixture B, the perylenetetracarboxylic dianhydride shows a constantly progressing, strong crystal growth as a function of time, whereas in the case of pig-ment alloy A, a very small crystal gro~th could be observed, which ceased after 1 to 3 hours.
29,4 parts of C I, Pigment Yellow llO (iso-indolinone) and 5.6 parts of perylenetetracarboxylic acid diimide are ground together with 35 parts of finely divided hexachloroethane, according to the process des-cribed in Example la), and the mixture is worked up.
~his gives 33.8 parts of a brown pigment alloy which, when l 160402 . g used for colouring plas-ticised PVC milled shee-ts, gives brown, transparen-t, clear, uniform and intense colora-tions with excellent fastness proper-ties The dis-persibility of the pigment alloy is excellent. This is surprising because the perylenetetracarboxylic acid diimide pigment in the pure state is exceptionally poorly dispersible in plastics. The pigment alloy addition-ally exhibits equal dispersibility a~ lo~ as at high shear strength. Wen used for colouring lacquers, it exhibits very good fastness properties and high gloss.
Example 3: 30 8 parts of C I. Pigment Yellow I10 and 4 2 parts of perylenetetracarboxylic acid diimide, toge-ther with 3.9 parts of finely divided hydrogenated abietic acid (Staybelite Resin ~ from Hercules), are thoroughly ground, for 9 hours, in 670 parts bf water, in a glass~bead mill with a capacity of 2,000 parts by volume, with 1,900 parts of glass spheres (diameter: 4.5 - 5.0 mm), at a stirring speed of abou-t 320 rpm, with external oold water-cooling. The glass spheres are separated from~
the pigment suspension and washed withalittlewater. The pigment suspension is then filtered, the press-cake is washed with water and dried at 70 - 80 in a vacuum dry- -ing cabinet and the pigmen-t is powdered This gives 37.8 parts of a pigment alloy con-taining appro*imately 1~% of Staybelite resin, which can be used with excellent dispersibility for colouring plasticised PVC and gives brown, transparent, clear milledshee-ts ofuniform colour intensity and with very good fastness proper-ties.
The sheets exhibit equal dispersibility at low as at high shear strength.
Example 4: In a stirred vessel, 195 par-ts of C.I. Pig-ment Yellow 110 and 5 parts of 2,9-dichloroquinacridone~
together wi-th 22 2 parts of finely divided hydrogenated abietic acid, are stirred well, ~or one hour, in 900 parts of wa-ter. The pigment suspension is diluted wi~h water to a weight of 2,000 parts. In a KDL--type Dyno mill I ~60402 irom Willy A. Bachofen, Basel, provided with a steel grinding con-tainer wi-th a capaci-ty of 600 par-ts by volume, filled with 480 - 510 parts by volume of glass spheres having a diameter of 1 mm, the pigment suspension is thoroughly ground, for 90 minutes, at a stirring speed of
3~000 rpm and a pumping speed of 30 rpm.
The pigment suspension is separated from the glass spheres, which are subsequently washed with 500 parts o~ water. The suspension is filtered, the press-cake is washed with 1,000 par-ts of water and dried in a vacuum drying cabinet at 70 - 80 and the pigment is powdered in an Osterizer mixer. This gives 210 parts of a pigment alloy containing about 10% of hydrogena-ted abietic acid, which, compared with the conventionally prepared, i,e. unground, mixture, gives substan-tially clearer, more uniform and more intense reddish yellow colorations when incorporated into plas-ticised PVC.
The pigment alloy exhibits an excellent dispersibility and equal dispersi~ility at low as at high shear strength.
When it is used for colouring lacquers, colorations wi-th high gloss and excellent fastness properties are obtained.
Example 5: The procedure described in Example 4 is repeated, excep-t that 2.5 parts of C.I. Pigment Red 177 (anthraquinone derivative) are used in place of -the 2,9~
dichloroquinacridone, affording a reddish yellow pigmen-t ;
alloy with equally good properties.
Example 6: The procedure described in Example 4 is ~
repeated, except that 2.5 parts of 1,4,9,10--tetrachloro-2,6-dimethoxy-triphendioxazine are used in place of the 2,9-dichloroquinacridone, affording a reddish yellow pig-ment alloy with equally good properties.
Example 7: The procedure described in Example 4 is repeated, excep-t tha-t 2 5 par-ts of 2,9-dimethylquin-acridone are used in place of the 2,9-dichloroquin-acridone, af~ording a reddish yellow pigmen-t alloy with equally good proper-ties.
Example 8: The procedure described in Example 4 is I 16~02 repea-ted, except that polys-tyrene granules having a dia-meter of 1 - 1.5 mm are used in place of glass spheres, affording a reddish yellow pigment alloy with equally good properties.
Example 9: In a glass-bead mill with a capacity of 500 parts by volume, 12 parts of C.I. Pigment Yellow 110, 3 parts of C.I. Pigmen-t Blue 15:3 (~-Cu phthalocyanine) and 1.7 parts of finely divi~ed hydrogenated abietic acid are s-tirred well, for 30 minutes, in 130 parts of water.
400 pa~rts of glass spheres having a diameter of 3.5 -
The pigment suspension is separated from the glass spheres, which are subsequently washed with 500 parts o~ water. The suspension is filtered, the press-cake is washed with 1,000 par-ts of water and dried in a vacuum drying cabinet at 70 - 80 and the pigment is powdered in an Osterizer mixer. This gives 210 parts of a pigment alloy containing about 10% of hydrogena-ted abietic acid, which, compared with the conventionally prepared, i,e. unground, mixture, gives substan-tially clearer, more uniform and more intense reddish yellow colorations when incorporated into plas-ticised PVC.
The pigment alloy exhibits an excellent dispersibility and equal dispersi~ility at low as at high shear strength.
When it is used for colouring lacquers, colorations wi-th high gloss and excellent fastness properties are obtained.
Example 5: The procedure described in Example 4 is repeated, excep-t that 2.5 parts of C.I. Pigment Red 177 (anthraquinone derivative) are used in place of -the 2,9~
dichloroquinacridone, affording a reddish yellow pigmen-t ;
alloy with equally good properties.
Example 6: The procedure described in Example 4 is ~
repeated, except that 2.5 parts of 1,4,9,10--tetrachloro-2,6-dimethoxy-triphendioxazine are used in place of the 2,9-dichloroquinacridone, affording a reddish yellow pig-ment alloy with equally good properties.
Example 7: The procedure described in Example 4 is repeated, excep-t tha-t 2 5 par-ts of 2,9-dimethylquin-acridone are used in place of the 2,9-dichloroquin-acridone, af~ording a reddish yellow pigmen-t alloy with equally good proper-ties.
Example 8: The procedure described in Example 4 is I 16~02 repea-ted, except that polys-tyrene granules having a dia-meter of 1 - 1.5 mm are used in place of glass spheres, affording a reddish yellow pigment alloy with equally good properties.
Example 9: In a glass-bead mill with a capacity of 500 parts by volume, 12 parts of C.I. Pigment Yellow 110, 3 parts of C.I. Pigmen-t Blue 15:3 (~-Cu phthalocyanine) and 1.7 parts of finely divi~ed hydrogenated abietic acid are s-tirred well, for 30 minutes, in 130 parts of water.
400 pa~rts of glass spheres having a diameter of 3.5 -
4.0 mm are added to the pigment suspension and the pigment mixture is ground together with the resin for 8 hours at a stirring speed of 320 rpm and with external water-cooling. The pigment suspension is separated off from the glass spheres, which are subsequently washed with a littlewater,and is then filtered. The press-cake is washed with water an~ dried at 70-80 in a vacuum drying cabinet This gives 15.6 parts of a green pigment alloy containing about 10% of hydrogenated abietic acid, which, when converted to a powder and used for colouring plasticised PVC milled sheets, gives intense, clear, transparent, uniform, bottle-green colorations with very good fastness properties. The pigment alloy exhibits an excellent dispersibility and equal dispersibility at low as at high shear strength.
~ ompared with the mixture, prepared in the con-ventional manner,withthe sameproportions of the pigments ground individually in the same way, the pigment alloy does no-t exhibit any blue streaks of the phthalocyanine pigment in the PVC sheet.
Example 10: The procedure of Example 9 is repeated, except that 13.5 parts of C.I. Pigment Yellow 110 are used in place of 12 parts, and 1.5 par-ts of C.I. Pigmen-t Blue 15:3, No 74,160, are used in place of 3 parts, affording a pigmen-t alloy which, when used for colouring plastics and lacquers, gives ligh-t green colorations with equally good properties.
Example 11. In a glass-bead mill, 4 5 parts of C I.
Pigment Brown 23 (disazopigment), 10.5 parts of C I
Pigment Yellow 110 and 1.7 parts of finely divided hydrogena-ted abietic acid are initially ground well to-gether, for 30 minutes, in 130 parts of water, at room temperature 400 parts of glass spheres having a dia-meter of 3.5 - 4.0 mm are then added to the pigment sus-pension, and the pigment mixture is ground together with the resin for 9 hours at a stirring speed of 320 r~m and with external water-cooling, The ground pigment sus-pension is separated from the glass spheres, which are subsequently washed with water, and is then filtered.
The press-cake is washed with water and dried a-t 70 - 80 in a vacuum drying cabine-t. This gives 15.6 parts of a brown pigment alloy containing about lO~o of hydrogena-ted abietic acid, which, when converted to a powder and used for colouring plas-ticised PVC milled sheets, gives intense, clear, transparent, neutral brown colorations with excellent fastness properties The pigment alloy exhibits an excellent disPersibility and equal disper-sibility at low as at high shear strength. Compared with the mixture, prepared in the conventional manner, withthe sameproportions of the individual pigments, the pigment alloy no longer exhibits any brown streaks of the ~azo pigment in the PVC sheet.
Example 12- The procedure described in Example 11 is repeated,except tha-t13.5 par-tsof s-tabilised~-Cuph-thalocyanine pigment are used in place of 4.5 parts of C.I Pigment Brown 23 (disazopigment), and 1.5 parts of perylenetetra-carboxylic acid diimide are used in place of 10 5 parts of C I. Pigment Yellow 110, affording a pigment alloy which, when used for colouring plasticised PVC milled sheets, gives very transparent, clear, very intense, uni-formly reddish blue colora-tions with excellent fastness properties, This is surprising becausewiththe same pig-men-t propor-tions of pigment mix-tures prepared in the con-ventional manner, non-uniform and dull colorations are l 1604~2 obtained as a result of the poor dispersibility of the individual pigments.
Example 13: The procedure described in Example 11 is re-peated,except that 12 parts of C.I.~gLent Brown 23 are used in place of 4.5 parts, and 3.0 parts of C.I. Pigment Red 88, No. 73,312 (tetrachlorothioindigo), are used in place of the C.I. Pigment Yellow 110, and the mixture is ground for 90 minutes instead of 9 hours, affording a pigment alloy which, when used for colouring plasticised PVC
milled sheets, gives intense, clear, uniformly reddish brown colorations with very good fastness properties.
Compared with a pigment mixtureprepared withthe samepig-ment proportions but in the conventional manner, the pig-ment alloy has a better dispersibility and gives more transparent, clearer and more intense colorations.
Example 14: In a glass-bead mill with a capacity of 500 parts by volume, 5.0 parts of C.I. Pigment Yellow 83 (d~azo pigment), 9.0 parts of C.I. Pigment Red 144 (disazo pigment) and 1 part of C.I Pigment Blue 15:3, No. 74,160 (~-Cu phthalocyanine), together with 1.7 parts of finely divided hydrogenated abietic acid, are initially stirred well, for 30 minutes, in 130 parts of water. 400 parts of glass spheres having a diameter of 3.5 - 4.0 mm are then added to the pigment suspension, and the pigment mixture is ground together with the added, finely divided hydrogenated abietic acid, for 3 hours, at a stirring speed of about 320 rpm and with external water-cooling.
The ground pigment suspension is separated off from the glass spheres, which are subsequently washedtosome extent withwater~andis thenfiltered. Thepress-cake issubsequently washed with water and dried at 70 - 80 in a vacuum drying cabinet. After conversion to a powder, 15.9 parts of a brown pigment alloy containing about 10% of hydrogenated abietic acid are obtained, which can satisfac'orily be incorporated into DOP pastes In comparison with DOP
pastes into which the individual pigments have been mixed separately, the LOP pastes coloured with the pigment alloy -l 160402 have, on application, substantially more intense, clearercolorations which, in particular, have a constant hue.
Exam~le~ In a glass-bead mill with a capacity of 500 parts by volume, 6 parts of the 1:2 zinc complex of the isoindoline of the formula cW ,/ ~, ~' ~ c l! 1 and 1.5 parts o~ -the yellow metal complex of the formula ,-~ ,N C;d, '' !
together with 7.5 parts of finely divided hexachloroethane, are thoroughly ground for 24 hours in 130 parts of water, with 400 parts of glass spheres having a diameter of 3.5~-4.0 mm, at a stirring speed of 320 rpm and with external water-cooling The glass spheres are separated off from the suspension and subsequently washed to some extent with water. In a stirred vessel, the hexachloroethane is distilled off by passing steam into the suspension.
The pigment suspension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70 - 80 and powdered. This gives 6.5 parts of a pigment alloy which, when used for colouring plasti-cised PVC milled sheets, gives intense, clear, trans-parent yellow colorations with substantially better fast-ness properties than the pigment mixture prepared in the conventionalmanner withthe samepigment proportions.
Example 16: The procedure described in Example 15 is re-peated,except that7.~ parts of naphthaleneare usedin place of 7.5 parts of hexachloroethane as the grinding aid, which is separated off by sublimation during the drying of the pigment press-cake instead o~ by steam distillation, l 160~02 a~fording a pigme~t alloy with equally good properties.
Exam~le 17: The procedure described in Example 15 is repeated, except that 7.5 parts of p-dichlorobenzene are used in place of 7.5 parts of hexachloroethane as the grinding aid, which is separated off by sublimation during the drying of the pigment press-cake instead o~ by steam distillation, affording a pigment alloy with equall~ good properties Example 18: In a glass-bead mill with a capacity of 500 parts by volume, 8.0 parts of C.I. Pigment Yellow 83, 6.o parts of C.I. Pigment Red 144 and 1 part of C.I.
Pigment Blue 15:3, No. 74,160 are thoroughly ground together for 90 minutes in 125 parts of water, with 400 parts of glass spheres having a diameter of 3.5 - 4.0 mm, at a stirring speed of 320 rpm and with external water-cooling. The ground pigment suspension is separated off from the glass spheres, which are subsequently washed to some extent with water, and is then filtered. The press-cake is subsequently washed with water and dried at 70 - 80 in a vacuum drying cabinet and the dry material is powdered. This gives 14 parts of a brown pigment alloy which can satisfactorily be incorporated into DOP pastes.
In comparison with DOP pastes into which the indi~idual pigments are mixed separately, the DOP pastes coloured with the pigment alloy have, on application, substantially more intense, clearer colorations which, in particular, have a constant hue.
_l~! In a beaker with a capacity o~ 500 parts by volume, 5 parts of C,I. Pigment Yellow 83, 9 parts of C.I
Pigment Red 14~ and l part of C.I. Pigment Blue 15:3, No.
74,160, are thoroughly ground for 4 hours in 85 parts of water, with 150 parts by volume of sand (Ottawa sand with a diameter of 2 - 3 mm), using a nylon disc stirrer, at a stirring speed of 2,000 rpm, with external water-cooling.
The ground pigment suspension is separated off from the sand, which is subsequently washed to some extent with water, and is then filtered. The press-cake is sub-sequently washed with water and dried at 70 - 80 in a vacuum drying cabinet and the dry material is powdered.
This gives 14.4 parts of a brown pigment alloy which, when used for colouring plasticised PVC milled sheets, gives very intense, uniform colorations with good fastness properties. Compared with a mixture prepared in the conventionalmanner withthe sa~ pigment proportions, the pigment alloy gives, on application, more intense, clearer and more uniform, brown colorations.
Example 20: The proce*ure of Example 11 is repeated, except that 1.7 parts of finely divided stearic acid are used in place of 1.7 parts of hydrogenated abietic acid, affording 15.7 parts of a pigment alloy containing about 10~ of stearic acid and having equally good properties.
Example 2 _ In a glass-bead mill with a capacity of 500 parts by volume, 6 parts of the polyanthrimide pigment Vat Black 9, listed in the third edition of the Color Index, and 1.5 parts of the anthraquinone pigment prepared in Example 138 of ~ritish Patent Specification 1,415,037, by condensing 1 mol o~ 4,4~-dibromobenzophenone with 2 mols of l-amino-4-p-nitrophenylaminoanthraquinone, together with 7.5 parts of finely divided hexachloroethane, are thoroughly ground for 24 hours in 130 parts of water, with 400 parts of glass spheres having a diameter of 3.5 - 4.0 mm, at a stirring speed of 320 rpm and with external water-cooling, The glass spheres are then separated off from the suspen-sion and subsequently washed to some extent with water.
In a stirred vessel, the hexachloroethane is distilled off by passing steam into the suspension. The pigment sus-pension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70-80 and powdered. This gives 6.5 parts of a black pigment alloy which, in the manner described in U.S.
Patent Specification 4,191,566~can be used with excellent results as a black toner for electrophotographic image processes.
"~:
1 160~02 Example 22- In a glass-bead mill with a capacity of 500 parts by volume, 5.4 parts of 1,5,9,10-tetrachloro-2,~-dimethoxytriphendioxazine and 2.1 parts o~ the ~-modifica-tion of perylenetetracarboxylic acid N,N'-bis-(3,5-dimethylphenyl)-imide, together with 7.5 parts of finely divided hexachloroethane, are thoroughly ground for 24 hours in 130 parts of water, with 400 parts of glass spheres having a diameter of 3.5-4.0 mm at a stirring speed of 320 rpm and with external water-cooling. The glass spheres are then separated off from the suspension and subsequently washed to some extent with water. In a stirred vessel, the hexachloroethane is distilled off b~ passing steam into the suspension. The pigment sus-pension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70-80 and powdered This gives 6.6 parts of a magenta-coloured pigment alloy which, in the manner described in U.S. Patent Specification 4,191,566, can be used with excellent results as a magenta toner for electrophoto-graphic image processes. Compared~with the pigment mix-ture prepared in the conventional manner and consisting of the 5.4 parts of dioxazine pigment and 2 1 parts of peryl-ene pigment listed above, the pigment alloy prepared according to the invention has a significantly higher photoelectrophoretic sensitivity ExampleZ3 In a glass-bead mill with a capacity of 500 parts by volume, 13.2 parts of coarse crystalline ~-Cu phthalocyanine pigment and 1.8 parts of chloranil are thoroughly ground together for 24 hours in 125 parts of water, with 400 parts of glass spheres having a diameter of 3 5 to 4.0 mm, at a stirring speed of 320 rpm and with e~ternal water-cooling. The ground pigment suspension is separated off from the glass spheres, which are sub-sequently washed to some extent with water, and is then filtered. The press-cake is subsequently washed wi-th water and dried to constant weight at room temperature in ' I 160~02 a desiccator over concentrated sulfuric acid, and the dry material is powdered. This gives 14 parts of a blue mixture (A), the semiconductor properties of which were investigated by measuring the electrical resistance.
By way of comparison, the electrical resistance of pure Cu phthalocyanine pigment (C), and also o~ a powder mixture of the same percentage composition, (B), obtained in the customary manner by mixing finely divided Cu phthalocyanine pigment for 20 minutes with chloranil in a Turbula mixer from Willy A. Bachofen, Basel, was measured.
The electrical resistances (~) measured on the compressed powders gave the following result:
P*
alloy sample (A) 8,5.105 mixture (B) 4.4.108 Cu phthalocyanine pigment (C) 4.9.101 * specific electrical resistance: + 0.3r~.cm at 25C.
The specific resistance of the alloy sample (C) is several powers of ten lower than that of the comparison samples. By thorough grinding of the donor component (Cu phthalocyanine) and the acceptor component (chloranil), it was possible to prepare a charge-transfer compound with semiconductor properties.
Example_24: In a glass-bead mill with a capacity of 500 parts by volume, 12 parts of coarse crystalline ~-Cu phthalocyanine pigment, 3 parts of carbazoledioxazine (C.I. Pigment Violet 23) and 1.7 parts of finely divided hydrogenated abietic acid are initially stirred well for 30 minutes in 130 parts of water. 400 parts of glass spheres having a diameter of 3.5 to 4.0 mm are then added to the pigment suspension, and the pigment mixture is ground together with the resin for 5 hours, at a stirring speed of 320 rpm and with external water-cooling. The pigment suspension is separated off from the glass spheres, which are subsequently washedwith alittlewater, ~f~
~-l 160~02 and is then filtered. The press-cake is washed with water and dried at 70-80 in a vacuum drying cabinet.
This gives 15.7 parts of a blue pigment alloy containing about lGyo 0l hydrogenated abietic acid, which, when con-verted to a powder and used for colouring lacquers and plastics, gives intense, clear blue colorations. The dispersibility in plasticised PVC milled sheets is excellent Example 25: The procedure described in Example 11 is repeated, except that 7 5 parts of C.I, Pigment Brown 23 are used in place of 4.5 parts, and 7.5 parts of C.I. Pig-ment Yellow 110 are used in place of 10.5 parts, af~ording a pigment alloy which, when used for colouring unplasti-cised PVC window profiles, gives neutral brown colorations with excellent weathering fastness.
A mixture of 130 parts of steatite spheres having a diameter of 8 mm, 47 5 parts of alkyd-melamine stoving lacquer, consisting of 60 parts of Beckosol 27-320 ~ , 60% in xylene ~Reichhold Chemie AG), 36 parts o~
Super-Beckamin 13-501 ~ s 50/o in a 1:1 mixture of xylene and butanol (Reichhold Chemie AG), 2 parts of xylene and 2 parts of ethylene glycol monomethyl ether, and 2.5 parts of the pigment alloy obtained according to Example 1 is dispersed in a 200 ml glass flask with a twist-of~ stopper, for 120 hours on a roller stand. After separating off the steatite spheres, 2.4 parts of the full shade mixture dispersed in t~is way and 6.o parts of titanium dioxide (Kronos RN 59 ~ from Kronos Titan GmbH) are mixed with 24.0 parts of the above alkyd-melamine stoving lacquer and the mixture is sprayed onto aluminium sheets and then stoved for 30 minutes at 130. This gives orange-red colorations with excellent ~astness properties.
ExamE~Le 27~.; A mixture of 1 0 part of the pigment alloy obtained according to Example 4, 1.0 part of antioxidant l 160402 _ 20 -(IRGANOX 1010 ~ from CIBA-GEIGY AG) and 1,000.0 part high-density polyethylene granula~ ~estolen A 60-16 ~
from H~ls) is premixed for 15 minutes in a glass flask on a roller stand. The mixture is then extruded in two passes on a single-screw extrud~r and converted to granules, the granules thus obtained are moulded on an Allround Aarburg 200 injection-mouiding machine, at 220, to form plaques, and the plaques are subsequently compression-moulded for 5 minutes at 180. The moulded plaques have intense reddish yellow hues with excellent fastness properties.
Example 28: 2.0 parts of a 50% pigment preparation con-sisting o~ 1.0 part of -the pigment alloy obtained accord-ing to Example 4 and 1.0 part of Mg behenateareused in place of 1.0 part of t~e pure pigment alloy, and the pro-cedure is otherwise as described in Example 28, affording reddish yellow moulded plaques with equally good proper-ties.
Example 29: For colouring PVC, a mixture of 65 parts of stabilised PVC, 35 parts of dioctyl phthalate and 0 2 part of the pigment alloy obtained according to Example 12 is prepared and worked between two rolls of a mill at about 150 for 5 minutes. The plasticised PVC sheet thus obtained has a transparent, clear reddish blue coloration with excellent fastness to light.
~$E~a~ A mixture of 92.0 parts of vinyl resin Vinnol H65D~-J(from Wacker9 ~nich), 8.0 parts of vinyl copolymer Vestolit HIS 7,~87 ~ ~rom HUELS), 1.5 parts of plasticiser Reoplast 39 ~ (from CIBA-GEIGY AG), 1.4 parts of stabiliser IRGASTAB BC-10 ~ (rom~CIBA-GEIGY AG), 1.4 parts of stabiliser IRGASTAB BC-29 ~ from CIBA-GElGY AG), 0.7 part of auxiliary stabiliser IRGASTAB CH-300 ~ ~rom CIBA-GEIGY AG), 0.4 part of lubricant IRGAWAX 370 ~ (~rom CIBA-GEIGY AG), 0.2 part of lubricant IRGAWA% 360 ~ ~rom CIBA-GEIGY AG~ and 0.25 part of ligh~ stabiliser TIN W IN 320 ~ ~rom CIBA-GEIGY AG) is prepared in a Fluid mixer (from Papenmeier K.G., Detmold) by stirring for about ~`~`i ~ 160~02
~ ompared with the mixture, prepared in the con-ventional manner,withthe sameproportions of the pigments ground individually in the same way, the pigment alloy does no-t exhibit any blue streaks of the phthalocyanine pigment in the PVC sheet.
Example 10: The procedure of Example 9 is repeated, except that 13.5 parts of C.I. Pigment Yellow 110 are used in place of 12 parts, and 1.5 par-ts of C.I. Pigmen-t Blue 15:3, No 74,160, are used in place of 3 parts, affording a pigmen-t alloy which, when used for colouring plastics and lacquers, gives ligh-t green colorations with equally good properties.
Example 11. In a glass-bead mill, 4 5 parts of C I.
Pigment Brown 23 (disazopigment), 10.5 parts of C I
Pigment Yellow 110 and 1.7 parts of finely divided hydrogena-ted abietic acid are initially ground well to-gether, for 30 minutes, in 130 parts of water, at room temperature 400 parts of glass spheres having a dia-meter of 3.5 - 4.0 mm are then added to the pigment sus-pension, and the pigment mixture is ground together with the resin for 9 hours at a stirring speed of 320 r~m and with external water-cooling, The ground pigment sus-pension is separated from the glass spheres, which are subsequently washed with water, and is then filtered.
The press-cake is washed with water and dried a-t 70 - 80 in a vacuum drying cabine-t. This gives 15.6 parts of a brown pigment alloy containing about lO~o of hydrogena-ted abietic acid, which, when converted to a powder and used for colouring plas-ticised PVC milled sheets, gives intense, clear, transparent, neutral brown colorations with excellent fastness properties The pigment alloy exhibits an excellent disPersibility and equal disper-sibility at low as at high shear strength. Compared with the mixture, prepared in the conventional manner, withthe sameproportions of the individual pigments, the pigment alloy no longer exhibits any brown streaks of the ~azo pigment in the PVC sheet.
Example 12- The procedure described in Example 11 is repeated,except tha-t13.5 par-tsof s-tabilised~-Cuph-thalocyanine pigment are used in place of 4.5 parts of C.I Pigment Brown 23 (disazopigment), and 1.5 parts of perylenetetra-carboxylic acid diimide are used in place of 10 5 parts of C I. Pigment Yellow 110, affording a pigment alloy which, when used for colouring plasticised PVC milled sheets, gives very transparent, clear, very intense, uni-formly reddish blue colora-tions with excellent fastness properties, This is surprising becausewiththe same pig-men-t propor-tions of pigment mix-tures prepared in the con-ventional manner, non-uniform and dull colorations are l 1604~2 obtained as a result of the poor dispersibility of the individual pigments.
Example 13: The procedure described in Example 11 is re-peated,except that 12 parts of C.I.~gLent Brown 23 are used in place of 4.5 parts, and 3.0 parts of C.I. Pigment Red 88, No. 73,312 (tetrachlorothioindigo), are used in place of the C.I. Pigment Yellow 110, and the mixture is ground for 90 minutes instead of 9 hours, affording a pigment alloy which, when used for colouring plasticised PVC
milled sheets, gives intense, clear, uniformly reddish brown colorations with very good fastness properties.
Compared with a pigment mixtureprepared withthe samepig-ment proportions but in the conventional manner, the pig-ment alloy has a better dispersibility and gives more transparent, clearer and more intense colorations.
Example 14: In a glass-bead mill with a capacity of 500 parts by volume, 5.0 parts of C.I. Pigment Yellow 83 (d~azo pigment), 9.0 parts of C.I. Pigment Red 144 (disazo pigment) and 1 part of C.I Pigment Blue 15:3, No. 74,160 (~-Cu phthalocyanine), together with 1.7 parts of finely divided hydrogenated abietic acid, are initially stirred well, for 30 minutes, in 130 parts of water. 400 parts of glass spheres having a diameter of 3.5 - 4.0 mm are then added to the pigment suspension, and the pigment mixture is ground together with the added, finely divided hydrogenated abietic acid, for 3 hours, at a stirring speed of about 320 rpm and with external water-cooling.
The ground pigment suspension is separated off from the glass spheres, which are subsequently washedtosome extent withwater~andis thenfiltered. Thepress-cake issubsequently washed with water and dried at 70 - 80 in a vacuum drying cabinet. After conversion to a powder, 15.9 parts of a brown pigment alloy containing about 10% of hydrogenated abietic acid are obtained, which can satisfac'orily be incorporated into DOP pastes In comparison with DOP
pastes into which the individual pigments have been mixed separately, the LOP pastes coloured with the pigment alloy -l 160402 have, on application, substantially more intense, clearercolorations which, in particular, have a constant hue.
Exam~le~ In a glass-bead mill with a capacity of 500 parts by volume, 6 parts of the 1:2 zinc complex of the isoindoline of the formula cW ,/ ~, ~' ~ c l! 1 and 1.5 parts o~ -the yellow metal complex of the formula ,-~ ,N C;d, '' !
together with 7.5 parts of finely divided hexachloroethane, are thoroughly ground for 24 hours in 130 parts of water, with 400 parts of glass spheres having a diameter of 3.5~-4.0 mm, at a stirring speed of 320 rpm and with external water-cooling The glass spheres are separated off from the suspension and subsequently washed to some extent with water. In a stirred vessel, the hexachloroethane is distilled off by passing steam into the suspension.
The pigment suspension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70 - 80 and powdered. This gives 6.5 parts of a pigment alloy which, when used for colouring plasti-cised PVC milled sheets, gives intense, clear, trans-parent yellow colorations with substantially better fast-ness properties than the pigment mixture prepared in the conventionalmanner withthe samepigment proportions.
Example 16: The procedure described in Example 15 is re-peated,except that7.~ parts of naphthaleneare usedin place of 7.5 parts of hexachloroethane as the grinding aid, which is separated off by sublimation during the drying of the pigment press-cake instead o~ by steam distillation, l 160~02 a~fording a pigme~t alloy with equally good properties.
Exam~le 17: The procedure described in Example 15 is repeated, except that 7.5 parts of p-dichlorobenzene are used in place of 7.5 parts of hexachloroethane as the grinding aid, which is separated off by sublimation during the drying of the pigment press-cake instead o~ by steam distillation, affording a pigment alloy with equall~ good properties Example 18: In a glass-bead mill with a capacity of 500 parts by volume, 8.0 parts of C.I. Pigment Yellow 83, 6.o parts of C.I. Pigment Red 144 and 1 part of C.I.
Pigment Blue 15:3, No. 74,160 are thoroughly ground together for 90 minutes in 125 parts of water, with 400 parts of glass spheres having a diameter of 3.5 - 4.0 mm, at a stirring speed of 320 rpm and with external water-cooling. The ground pigment suspension is separated off from the glass spheres, which are subsequently washed to some extent with water, and is then filtered. The press-cake is subsequently washed with water and dried at 70 - 80 in a vacuum drying cabinet and the dry material is powdered. This gives 14 parts of a brown pigment alloy which can satisfactorily be incorporated into DOP pastes.
In comparison with DOP pastes into which the indi~idual pigments are mixed separately, the DOP pastes coloured with the pigment alloy have, on application, substantially more intense, clearer colorations which, in particular, have a constant hue.
_l~! In a beaker with a capacity o~ 500 parts by volume, 5 parts of C,I. Pigment Yellow 83, 9 parts of C.I
Pigment Red 14~ and l part of C.I. Pigment Blue 15:3, No.
74,160, are thoroughly ground for 4 hours in 85 parts of water, with 150 parts by volume of sand (Ottawa sand with a diameter of 2 - 3 mm), using a nylon disc stirrer, at a stirring speed of 2,000 rpm, with external water-cooling.
The ground pigment suspension is separated off from the sand, which is subsequently washed to some extent with water, and is then filtered. The press-cake is sub-sequently washed with water and dried at 70 - 80 in a vacuum drying cabinet and the dry material is powdered.
This gives 14.4 parts of a brown pigment alloy which, when used for colouring plasticised PVC milled sheets, gives very intense, uniform colorations with good fastness properties. Compared with a mixture prepared in the conventionalmanner withthe sa~ pigment proportions, the pigment alloy gives, on application, more intense, clearer and more uniform, brown colorations.
Example 20: The proce*ure of Example 11 is repeated, except that 1.7 parts of finely divided stearic acid are used in place of 1.7 parts of hydrogenated abietic acid, affording 15.7 parts of a pigment alloy containing about 10~ of stearic acid and having equally good properties.
Example 2 _ In a glass-bead mill with a capacity of 500 parts by volume, 6 parts of the polyanthrimide pigment Vat Black 9, listed in the third edition of the Color Index, and 1.5 parts of the anthraquinone pigment prepared in Example 138 of ~ritish Patent Specification 1,415,037, by condensing 1 mol o~ 4,4~-dibromobenzophenone with 2 mols of l-amino-4-p-nitrophenylaminoanthraquinone, together with 7.5 parts of finely divided hexachloroethane, are thoroughly ground for 24 hours in 130 parts of water, with 400 parts of glass spheres having a diameter of 3.5 - 4.0 mm, at a stirring speed of 320 rpm and with external water-cooling, The glass spheres are then separated off from the suspen-sion and subsequently washed to some extent with water.
In a stirred vessel, the hexachloroethane is distilled off by passing steam into the suspension. The pigment sus-pension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70-80 and powdered. This gives 6.5 parts of a black pigment alloy which, in the manner described in U.S.
Patent Specification 4,191,566~can be used with excellent results as a black toner for electrophotographic image processes.
"~:
1 160~02 Example 22- In a glass-bead mill with a capacity of 500 parts by volume, 5.4 parts of 1,5,9,10-tetrachloro-2,~-dimethoxytriphendioxazine and 2.1 parts o~ the ~-modifica-tion of perylenetetracarboxylic acid N,N'-bis-(3,5-dimethylphenyl)-imide, together with 7.5 parts of finely divided hexachloroethane, are thoroughly ground for 24 hours in 130 parts of water, with 400 parts of glass spheres having a diameter of 3.5-4.0 mm at a stirring speed of 320 rpm and with external water-cooling. The glass spheres are then separated off from the suspension and subsequently washed to some extent with water. In a stirred vessel, the hexachloroethane is distilled off b~ passing steam into the suspension. The pigment sus-pension is filtered at about 70 and the press-cake is washed with water, dried in a vacuum drying cabinet at 70-80 and powdered This gives 6.6 parts of a magenta-coloured pigment alloy which, in the manner described in U.S. Patent Specification 4,191,566, can be used with excellent results as a magenta toner for electrophoto-graphic image processes. Compared~with the pigment mix-ture prepared in the conventional manner and consisting of the 5.4 parts of dioxazine pigment and 2 1 parts of peryl-ene pigment listed above, the pigment alloy prepared according to the invention has a significantly higher photoelectrophoretic sensitivity ExampleZ3 In a glass-bead mill with a capacity of 500 parts by volume, 13.2 parts of coarse crystalline ~-Cu phthalocyanine pigment and 1.8 parts of chloranil are thoroughly ground together for 24 hours in 125 parts of water, with 400 parts of glass spheres having a diameter of 3 5 to 4.0 mm, at a stirring speed of 320 rpm and with e~ternal water-cooling. The ground pigment suspension is separated off from the glass spheres, which are sub-sequently washed to some extent with water, and is then filtered. The press-cake is subsequently washed wi-th water and dried to constant weight at room temperature in ' I 160~02 a desiccator over concentrated sulfuric acid, and the dry material is powdered. This gives 14 parts of a blue mixture (A), the semiconductor properties of which were investigated by measuring the electrical resistance.
By way of comparison, the electrical resistance of pure Cu phthalocyanine pigment (C), and also o~ a powder mixture of the same percentage composition, (B), obtained in the customary manner by mixing finely divided Cu phthalocyanine pigment for 20 minutes with chloranil in a Turbula mixer from Willy A. Bachofen, Basel, was measured.
The electrical resistances (~) measured on the compressed powders gave the following result:
P*
alloy sample (A) 8,5.105 mixture (B) 4.4.108 Cu phthalocyanine pigment (C) 4.9.101 * specific electrical resistance: + 0.3r~.cm at 25C.
The specific resistance of the alloy sample (C) is several powers of ten lower than that of the comparison samples. By thorough grinding of the donor component (Cu phthalocyanine) and the acceptor component (chloranil), it was possible to prepare a charge-transfer compound with semiconductor properties.
Example_24: In a glass-bead mill with a capacity of 500 parts by volume, 12 parts of coarse crystalline ~-Cu phthalocyanine pigment, 3 parts of carbazoledioxazine (C.I. Pigment Violet 23) and 1.7 parts of finely divided hydrogenated abietic acid are initially stirred well for 30 minutes in 130 parts of water. 400 parts of glass spheres having a diameter of 3.5 to 4.0 mm are then added to the pigment suspension, and the pigment mixture is ground together with the resin for 5 hours, at a stirring speed of 320 rpm and with external water-cooling. The pigment suspension is separated off from the glass spheres, which are subsequently washedwith alittlewater, ~f~
~-l 160~02 and is then filtered. The press-cake is washed with water and dried at 70-80 in a vacuum drying cabinet.
This gives 15.7 parts of a blue pigment alloy containing about lGyo 0l hydrogenated abietic acid, which, when con-verted to a powder and used for colouring lacquers and plastics, gives intense, clear blue colorations. The dispersibility in plasticised PVC milled sheets is excellent Example 25: The procedure described in Example 11 is repeated, except that 7 5 parts of C.I, Pigment Brown 23 are used in place of 4.5 parts, and 7.5 parts of C.I. Pig-ment Yellow 110 are used in place of 10.5 parts, af~ording a pigment alloy which, when used for colouring unplasti-cised PVC window profiles, gives neutral brown colorations with excellent weathering fastness.
A mixture of 130 parts of steatite spheres having a diameter of 8 mm, 47 5 parts of alkyd-melamine stoving lacquer, consisting of 60 parts of Beckosol 27-320 ~ , 60% in xylene ~Reichhold Chemie AG), 36 parts o~
Super-Beckamin 13-501 ~ s 50/o in a 1:1 mixture of xylene and butanol (Reichhold Chemie AG), 2 parts of xylene and 2 parts of ethylene glycol monomethyl ether, and 2.5 parts of the pigment alloy obtained according to Example 1 is dispersed in a 200 ml glass flask with a twist-of~ stopper, for 120 hours on a roller stand. After separating off the steatite spheres, 2.4 parts of the full shade mixture dispersed in t~is way and 6.o parts of titanium dioxide (Kronos RN 59 ~ from Kronos Titan GmbH) are mixed with 24.0 parts of the above alkyd-melamine stoving lacquer and the mixture is sprayed onto aluminium sheets and then stoved for 30 minutes at 130. This gives orange-red colorations with excellent ~astness properties.
ExamE~Le 27~.; A mixture of 1 0 part of the pigment alloy obtained according to Example 4, 1.0 part of antioxidant l 160402 _ 20 -(IRGANOX 1010 ~ from CIBA-GEIGY AG) and 1,000.0 part high-density polyethylene granula~ ~estolen A 60-16 ~
from H~ls) is premixed for 15 minutes in a glass flask on a roller stand. The mixture is then extruded in two passes on a single-screw extrud~r and converted to granules, the granules thus obtained are moulded on an Allround Aarburg 200 injection-mouiding machine, at 220, to form plaques, and the plaques are subsequently compression-moulded for 5 minutes at 180. The moulded plaques have intense reddish yellow hues with excellent fastness properties.
Example 28: 2.0 parts of a 50% pigment preparation con-sisting o~ 1.0 part of -the pigment alloy obtained accord-ing to Example 4 and 1.0 part of Mg behenateareused in place of 1.0 part of t~e pure pigment alloy, and the pro-cedure is otherwise as described in Example 28, affording reddish yellow moulded plaques with equally good proper-ties.
Example 29: For colouring PVC, a mixture of 65 parts of stabilised PVC, 35 parts of dioctyl phthalate and 0 2 part of the pigment alloy obtained according to Example 12 is prepared and worked between two rolls of a mill at about 150 for 5 minutes. The plasticised PVC sheet thus obtained has a transparent, clear reddish blue coloration with excellent fastness to light.
~$E~a~ A mixture of 92.0 parts of vinyl resin Vinnol H65D~-J(from Wacker9 ~nich), 8.0 parts of vinyl copolymer Vestolit HIS 7,~87 ~ ~rom HUELS), 1.5 parts of plasticiser Reoplast 39 ~ (from CIBA-GEIGY AG), 1.4 parts of stabiliser IRGASTAB BC-10 ~ (rom~CIBA-GEIGY AG), 1.4 parts of stabiliser IRGASTAB BC-29 ~ from CIBA-GElGY AG), 0.7 part of auxiliary stabiliser IRGASTAB CH-300 ~ ~rom CIBA-GEIGY AG), 0.4 part of lubricant IRGAWAX 370 ~ (~rom CIBA-GEIGY AG), 0.2 part of lubricant IRGAWA% 360 ~ ~rom CIBA-GEIGY AG~ and 0.25 part of ligh~ stabiliser TIN W IN 320 ~ ~rom CIBA-GEIGY AG) is prepared in a Fluid mixer (from Papenmeier K.G., Detmold) by stirring for about ~`~`i ~ 160~02
5 minutes at a speed of 1,400 rpm.
1.5 parts of the unplasticised PVC mixture pre-pared in this way and 0.075 part of the pigment alloy prepared according to Example 11 are mixed in a Henschel mixer (Henschelwerke G.M.B.H., Kassel) at a speed of about 2,000 rpm, at room temperature, ~or about 3 minutes.
The unplasticised PVC mixture pigm~nted in this way is calendered on mixing rolls at 190 ~or 6 minutes, at 25 rpm and with a speed ratio of 1:1.2, and compression-moulded at 190 ~or 6 minutes on a B~rkle press, between chrome-plated steel platens, to a layer thickness of about 1 mm. This gives a uniformly brown-coloured moulding ~hich has outstanding fastness to light and weathering fastness.
`.~J
1.5 parts of the unplasticised PVC mixture pre-pared in this way and 0.075 part of the pigment alloy prepared according to Example 11 are mixed in a Henschel mixer (Henschelwerke G.M.B.H., Kassel) at a speed of about 2,000 rpm, at room temperature, ~or about 3 minutes.
The unplasticised PVC mixture pigm~nted in this way is calendered on mixing rolls at 190 ~or 6 minutes, at 25 rpm and with a speed ratio of 1:1.2, and compression-moulded at 190 ~or 6 minutes on a B~rkle press, between chrome-plated steel platens, to a layer thickness of about 1 mm. This gives a uniformly brown-coloured moulding ~hich has outstanding fastness to light and weathering fastness.
`.~J
Claims (9)
1. A process for the preparation of a pigment alloy, which comprises subjecting a mixture consisting of at least two pigments from different groups of the perylene, phthalocyanine, perinone, quinacridone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinoid, thioindigo, methine or azomethine series, or of the monoazo or disazo series of the 2,3-hydroxynaphthoic acid arylide, acetoacetic acid arylide, pyrazolone or benzimidazolone group, to thorough wet-grinding in water until the pigments are alloyed with one another on the microscopic scale.
2. A process according to claim 1, which comprises using 0.1 - 50 parts by weight of the pigment o one of the groups and 50-99.9 parts by weight of at least one pigment of the other group per 100 parts by weight of the pigment mixture.
3. A process according to claim 1, which comprises carrying out the wet-grinding in the presence of a grind-ing aid which is subsequently to be removed.
4. A process according to claim 3, which comprises using hexachloroethane as the grinding aid.
5. A process according to claim 3, which comprises using 0.5 - 1.5 parts by weight of the grinding aid per 1 part by weight of the pigment mixture.
6. A process according to claim 3, which comprises removing the grinding aid by steam distillation or sublimation, after the grinding.
7. A process according to claim 1, which comprises carrying out the wet grinding in the presence of a grind-ing aid remaining in the product.
8. A process according to claim 7, which comprises using 0.01 to 0.15 part by weight of an organic additive, per 1 part by weight of the pigment mixture, as the grind-ing aid remaining in the product.
9. A process according to claim 8, which comprises using abietic acid, hydrogenated abietic acid or stearic acid as the organic additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4718/80-6 | 1980-06-19 | ||
| CH471880 | 1980-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160402A true CA1160402A (en) | 1984-01-17 |
Family
ID=4281302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000379969A Expired CA1160402A (en) | 1980-06-19 | 1981-06-17 | Process for the preparation of pigment alloys |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0042816B1 (en) |
| JP (1) | JPS5730765A (en) |
| CA (1) | CA1160402A (en) |
| DE (1) | DE3163191D1 (en) |
| DK (1) | DK269181A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391507B1 (en) * | 1999-06-18 | 2002-05-21 | Clariant Gmbh | Cyan pigments in electrophotographic toners and developers |
| US6989056B2 (en) | 2003-09-26 | 2006-01-24 | Ciba Specialty Chemicals Corporation | IR reflective pigment compositions |
| US7029526B2 (en) | 2001-10-19 | 2006-04-18 | Ciba Specialty Chemicals Corporation | Process for making green pigment compositions useful for color filters and LCD's |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5951950A (en) * | 1982-09-17 | 1984-03-26 | Mitsubishi Chem Ind Ltd | Blended dye composition having ultrahigh light fastness |
| DE3584138D1 (en) * | 1984-11-07 | 1991-10-24 | Ciba Geigy Ag | PIGMENT MIXTURES. |
| JPS61178717U (en) * | 1985-04-27 | 1986-11-07 | ||
| US4801702A (en) * | 1985-11-06 | 1989-01-31 | Ciba-Geigy Corporation | Process for the preparation and conditioning or organic pigments |
| DE3602182A1 (en) * | 1986-01-25 | 1987-07-30 | Hoechst Ag | COLORS FOR ELECTROPHOTOGRAPHIC RECORDING METHODS |
| EP0408499A3 (en) * | 1989-07-13 | 1992-08-19 | Ciba-Geigy Ag | Method of conditioning organic pigments |
| FR2681329B1 (en) * | 1991-09-18 | 1995-06-23 | Oreal | FINE DISPERSION OF MELANIC PIGMENTS, ITS PREPARATION AND ITS USE IN COSMETICS. |
| US5516770A (en) * | 1993-09-30 | 1996-05-14 | American Home Products Corporation | Rapamycin formulation for IV injection |
| US5387281A (en) * | 1993-12-01 | 1995-02-07 | Ciba-Geigy Corporation | Compositions based on 2,9-Dichloroquinacridone pigments |
| US5753030A (en) * | 1996-05-13 | 1998-05-19 | Bayer Corporation | Crystal growth modifiers for perylene pigments |
| JPH11256061A (en) * | 1998-03-10 | 1999-09-21 | Mitsubishi Paper Mills Ltd | New mixed crystal of phthalocyanine and production of electrophotographic photoreceptor by using the same |
| US20050039636A1 (en) * | 2001-12-20 | 2005-02-24 | Yasumasa Matsumoto | Heat shielding surface layer |
| WO2003080742A1 (en) * | 2002-03-25 | 2003-10-02 | Ciba Specialty Chemicals Holding Inc. | Black pigment compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1209852B (en) * | 1959-09-29 | 1966-01-27 | Ciba Geigy | Process for conditioning pigments |
| FR1274676A (en) * | 1959-09-29 | 1961-10-27 | Ciba Geigy | Crystallization and flocculation stable alpha variety of copper phthalocyanine, containing manganiferous phthalocyanine, process for its preparation |
| DK131789C (en) * | 1970-03-20 | 1976-03-22 | Koege Kemisk Vaerk | PROCEDURE FOR PREPARING COPPER PHTHALALYANINE PIGMENTS |
| US3772048A (en) * | 1972-06-14 | 1973-11-13 | Chemetron Corp | Method for reducing oil absorption of pigment containing beta-copper phthalocyanine and composite green pigment |
| GB1502884A (en) * | 1974-08-21 | 1978-03-08 | Hoechst Ag | Process for the preparation of easily dispersible pigments of the beta-modification of phthalocyanine |
| AT355149B (en) * | 1978-01-24 | 1980-02-11 | Basf Farben & Fasern | METHOD FOR PRODUCING GLOSSY OR CAPACITY IMPROVED PIGMENT COMPOSITIONS |
| DE2842468A1 (en) * | 1978-09-29 | 1980-04-10 | Hoechst Ag | CHINACRIDONE PIGMENT MIXTURES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
-
1981
- 1981-06-15 DE DE8181810241T patent/DE3163191D1/en not_active Expired
- 1981-06-15 EP EP19810810241 patent/EP0042816B1/en not_active Expired
- 1981-06-17 CA CA000379969A patent/CA1160402A/en not_active Expired
- 1981-06-18 DK DK269181A patent/DK269181A/en not_active Application Discontinuation
- 1981-06-19 JP JP9516981A patent/JPS5730765A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391507B1 (en) * | 1999-06-18 | 2002-05-21 | Clariant Gmbh | Cyan pigments in electrophotographic toners and developers |
| US6406528B1 (en) | 1999-06-18 | 2002-06-18 | Clariant Gmbh | Use of improved cyan pigments in inkjet inks |
| US7029526B2 (en) | 2001-10-19 | 2006-04-18 | Ciba Specialty Chemicals Corporation | Process for making green pigment compositions useful for color filters and LCD's |
| US6989056B2 (en) | 2003-09-26 | 2006-01-24 | Ciba Specialty Chemicals Corporation | IR reflective pigment compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5730765A (en) | 1982-02-19 |
| DE3163191D1 (en) | 1984-05-24 |
| DK269181A (en) | 1981-12-20 |
| EP0042816A3 (en) | 1982-01-13 |
| EP0042816A2 (en) | 1981-12-30 |
| EP0042816B1 (en) | 1984-04-18 |
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