CA2208740C - Monoazo pigments - Google Patents
Monoazo pigments Download PDFInfo
- Publication number
- CA2208740C CA2208740C CA002208740A CA2208740A CA2208740C CA 2208740 C CA2208740 C CA 2208740C CA 002208740 A CA002208740 A CA 002208740A CA 2208740 A CA2208740 A CA 2208740A CA 2208740 C CA2208740 C CA 2208740C
- Authority
- CA
- Canada
- Prior art keywords
- salt
- compound
- sulphonic acid
- formula
- azo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Paints Or Removers (AREA)
- Coloring (AREA)
- Developing Agents For Electrophotography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An azo pyrazolone compound of formula (1) in the form of a salt, and its use as a pigment.
Description
5i2oq-s MOflOA20 PI~ME_NTS
This invention relates to monoazo pigments and more particularly to orange pigments of the azo pyrazolone series.
J. of Chromatography, 665, 197 (1994) discloses certain sulphonated azo pyrazolones and the corresponding sodium an~i potassium salts.
European patent.EP 0 225 553 discloses certain isomeric azo pyrazolones as the calcium salts.
The use of pigments for the colouring o~f plastics matatials is well known.
For the produdian of orange cobrations. It has lean traditions! to employ Inorganic ~ pigments such as cadmiums, lead chromes and molybdate oranges but these are new being phased out because of environmental pre~sssures. Organic pigmec~s that have been proposed as replacements for these inorganic materials have not been found entirely satisfactory in sit of the major polymer types, especially in respect of their heat stabulty.
It has new been found that certain organic pigments o~f the azo pyrazolane series are characterised by excellent heat stability, light stability, and bleed fastness when used in a wide range of plastic materials.
Accordingly, the invention provides an azo pyrazoione compound of the fom~uia N =N
/ \
t~coaS C1) \ /
in the form of a salt.
1a According to one aspect of the present invention, there is provided an azo pyrazolone compound of the formula:
in the toms of a salt except for CNs HO~S ~ ~ tvl=N I
HO N'N
O~H
and HO~S ~ ~ --N
In the form of their sodium and potassium salt:~.
The salts of the compounds o1 Formula 1 may exhibit polyphormism and, where this is the case, the various polymorphic forms are regarded as within the scope of the invention.
Particularly advantageous compounds of Formula 1 in terms of superior heat and light stability are cxmpounds in which the sulphonic acid group of the naphthalene nucteus is present in the 4- or E3-position relative to the azo link and the sulphonic acid group of the benzene ring is present in the 3- or 4-position relative to the pyrazolyl group.
This invention relates to monoazo pigments and more particularly to orange pigments of the azo pyrazolone series.
J. of Chromatography, 665, 197 (1994) discloses certain sulphonated azo pyrazolones and the corresponding sodium an~i potassium salts.
European patent.EP 0 225 553 discloses certain isomeric azo pyrazolones as the calcium salts.
The use of pigments for the colouring o~f plastics matatials is well known.
For the produdian of orange cobrations. It has lean traditions! to employ Inorganic ~ pigments such as cadmiums, lead chromes and molybdate oranges but these are new being phased out because of environmental pre~sssures. Organic pigmec~s that have been proposed as replacements for these inorganic materials have not been found entirely satisfactory in sit of the major polymer types, especially in respect of their heat stabulty.
It has new been found that certain organic pigments o~f the azo pyrazolane series are characterised by excellent heat stability, light stability, and bleed fastness when used in a wide range of plastic materials.
Accordingly, the invention provides an azo pyrazoione compound of the fom~uia N =N
/ \
t~coaS C1) \ /
in the form of a salt.
1a According to one aspect of the present invention, there is provided an azo pyrazolone compound of the formula:
in the toms of a salt except for CNs HO~S ~ ~ tvl=N I
HO N'N
O~H
and HO~S ~ ~ --N
In the form of their sodium and potassium salt:~.
The salts of the compounds o1 Formula 1 may exhibit polyphormism and, where this is the case, the various polymorphic forms are regarded as within the scope of the invention.
Particularly advantageous compounds of Formula 1 in terms of superior heat and light stability are cxmpounds in which the sulphonic acid group of the naphthalene nucteus is present in the 4- or E3-position relative to the azo link and the sulphonic acid group of the benzene ring is present in the 3- or 4-position relative to the pyrazolyl group.
2 The salt of the azo pyrazolone compound of Formula 1 may be a metal salt, for example, an alkali metal, alkaline earth metal or heavy metal salt, or a salt of a nitrogenous base, for example a primary, secondary or tertiary amine or quaternary ammonium salt, particularly useful pigments being the salts of barium, strontium, manganese, magnesium, sodium and, especially, calcium.
The most preferred compounds of the invention have the formula N =N
/ \
6\ /
4 ~2+ (2) wherein the sulphonate group of the naphthalene nucleus is in the 4- or 6-position relative to the azo group.
The azo pyrazolone compounds of the invention may be prepared by diazotising a naphthylamine sulphonic acid of the formula NHZ
/ \
H03S (3) \ /
and coupling the resulting diazo compound with a sulphonated 3-methyl-1-phenylpyrazol-5-one of the formula (4) ~ ~ : : : °:xf.r~=...~ . ~a. .., ,. ., . . <. . 4 . . . . ~ , WO 96!22334 PCT/GB95/02833
The most preferred compounds of the invention have the formula N =N
/ \
6\ /
4 ~2+ (2) wherein the sulphonate group of the naphthalene nucleus is in the 4- or 6-position relative to the azo group.
The azo pyrazolone compounds of the invention may be prepared by diazotising a naphthylamine sulphonic acid of the formula NHZ
/ \
H03S (3) \ /
and coupling the resulting diazo compound with a sulphonated 3-methyl-1-phenylpyrazol-5-one of the formula (4) ~ ~ : : : °:xf.r~=...~ . ~a. .., ,. ., . . <. . 4 . . . . ~ , WO 96!22334 PCT/GB95/02833
3 and converting the resulting monoazo compound to the desired salt form.
The diazotisation and coupling reactions may be performed in a conventional manner appropriate to the classes of compound being used.
The preferred naphthylamine sulphonic acids for use in preparing the ,f compounds of the invention are 1-naphthylamine-4-sulphonic acid and 1-naphthylamine-6-sulphonic acid whilst the preferred coupling components are 3-methyl-1-(4'-sulphophenyl)pyrazol-5-one and, especially 3-methyl-1-(3'-sulphophenyl)pyrazol-5-one.
It is often convenient to prepare the compound of Formula 1 in the form of a sodium salt and then convert the sodium salt to, for example, an alkaline earth or heavy metal lake by adding the required amount of a water-soluble alkaline earth metal or heavy metal salt, usually in the form of an aqueous solution.
Surface active agents and/or organic solvents may optionally be present during the synthesis of the compound of Formula 1 and/or during precipitation of the pigment.
The compounds of the invention, which may be subjected to conventional milling operations and/or thermal treatments in order to provide products of the desired particle size and/or crystal structure, are useful orange pigments which may be used in conventional manner. In particular, they may be used alone or in conjunction with other pigments for the coloration of plastics materials, for example polyvinyl chloride, polyolefins, polystyrene and ABS where they exhibit excellent properties. The compounds of the invention are also valuable for the pigmentation of surface coatings.
The invention is illustrated but not limited by the following Examples.
1-Naphthylamine-6-sulphonic acid (4.46g), de-ionised water (50m1) and hydrochloric acid (5.1 ml) were stirred together in a vessel surrounded by an ice-bath, followed by sufficient 48% sodium hydroxide solution to form a solution alkaline to Brilliant Yellow paper. The solution was then cooled to 0-5°C and a further amount (5.1 ml) of hydrochloric acid was added. A solution of sodium nitrite (1.56g) in de-ionised water (5ml) was added all at once and the mixture was stirred at 0-5°C
for 30 mins.
i Excess nitrite was then removed by adding a few ml of 10% sulphamic acid solution.
3-Methyl-1-(3'-sulphophenyl) pyrazol-5-one (5.4g) was added to de-ionised water (50m1) and the pH was adjusted to 6.5 by the addition of 48%
sodium hydroxide solution. The solution was then stirred at 0-5°C and the diazo suspension WO 96!22334 PCTlGB95l02833
The diazotisation and coupling reactions may be performed in a conventional manner appropriate to the classes of compound being used.
The preferred naphthylamine sulphonic acids for use in preparing the ,f compounds of the invention are 1-naphthylamine-4-sulphonic acid and 1-naphthylamine-6-sulphonic acid whilst the preferred coupling components are 3-methyl-1-(4'-sulphophenyl)pyrazol-5-one and, especially 3-methyl-1-(3'-sulphophenyl)pyrazol-5-one.
It is often convenient to prepare the compound of Formula 1 in the form of a sodium salt and then convert the sodium salt to, for example, an alkaline earth or heavy metal lake by adding the required amount of a water-soluble alkaline earth metal or heavy metal salt, usually in the form of an aqueous solution.
Surface active agents and/or organic solvents may optionally be present during the synthesis of the compound of Formula 1 and/or during precipitation of the pigment.
The compounds of the invention, which may be subjected to conventional milling operations and/or thermal treatments in order to provide products of the desired particle size and/or crystal structure, are useful orange pigments which may be used in conventional manner. In particular, they may be used alone or in conjunction with other pigments for the coloration of plastics materials, for example polyvinyl chloride, polyolefins, polystyrene and ABS where they exhibit excellent properties. The compounds of the invention are also valuable for the pigmentation of surface coatings.
The invention is illustrated but not limited by the following Examples.
1-Naphthylamine-6-sulphonic acid (4.46g), de-ionised water (50m1) and hydrochloric acid (5.1 ml) were stirred together in a vessel surrounded by an ice-bath, followed by sufficient 48% sodium hydroxide solution to form a solution alkaline to Brilliant Yellow paper. The solution was then cooled to 0-5°C and a further amount (5.1 ml) of hydrochloric acid was added. A solution of sodium nitrite (1.56g) in de-ionised water (5ml) was added all at once and the mixture was stirred at 0-5°C
for 30 mins.
i Excess nitrite was then removed by adding a few ml of 10% sulphamic acid solution.
3-Methyl-1-(3'-sulphophenyl) pyrazol-5-one (5.4g) was added to de-ionised water (50m1) and the pH was adjusted to 6.5 by the addition of 48%
sodium hydroxide solution. The solution was then stirred at 0-5°C and the diazo suspension WO 96!22334 PCTlGB95l02833
4 obtained as described above was added over 10 mins whilst maintaining the pH
at 6.5 by the addition of 48% sodium hydroxide solution. The coupling mixture was then stirred overnight at room temperature.
The reaction mixture was then heated to 90°C and a solution of calcium chloride (32g CaCl2 in 40m1 water) was added all at once and the mixture stirred for a further 3 hours at 90°C. The mixture was then filtered hot and the product was washed chloride-free with de-ionised water (1000m1) and dried giving 7.3g of an orange solid.
1-Naphthylamine-4-sulphonic acid, sodium salt (6.14g), deionised water (50m1) and hydrochloric acid (5.1 ml) were stirred together in a vessel surrounded by an ice bath, followed by sufficient 48% sodium hydroxide solution to form a solution alkaline to Brilliant Yellow paper. The solution was then cooled to 0-5°C and a further amount (5.1 ml) of hydrochloric acid was added. A solution of sodium nitrite (1.56g) in deionised water (5m1) was added all at once and the mixture was stirred at 0-5°C
for 30 mins.
Excess nitrite was then removed by adding a few ml of 10% sulphamic acid solution.
3-Methyl-1-(3'-sulphophenyl)pyrazol-5-one (6.08g) was added to deionised water (50m1) and the pH was adjusted to 6.5 by the addition of 48% sodium hydroxide solution. The solution was then stirred at 0-5°C and the diazo suspension obtained as described above was added over 10 mins whilst maintaining the pH at 6.5 by the addition of 48% sodium hydroxide solution. The coupling mixture was then stirred overnight at room temperature.
The reaction mixture was then heated to 90°C and a solution of calcium chloride (32g CaCl2 in 40m1 water) was added all at once and the mixture stirred for a further 3 hours at 90°C. The mixture was then filtered hot and the product was washed chloride-free with deionised water (1000m1) and dried giving 8.4g of a orange solid.
1-Naphthylamine-4-sulphonic acid, sodium salt (5.74g), deionised water (50m1) and hydrochloric acid (5.1 ml) were stirred together in a vessel surrounded by an ice bath, followed by sufficient 48% sodium hydroxide solution to form a solution alkaline to Brilliant Yellow paper. The solution was then cooled to 0-5°C and a further amount (5.1m1) of hydrochloric acid was added. A solution of sodium nitrite (1.56g) in deionised WO 96!22334 PCTlGB95102833 water (5ml) was added all at once and the mixture was stirred at 0-5°C
for 30 mins.
Excess nitrite was then removed by adding a few ml of 10% sulphamic acid solution.
' 3-Methyl-1-(4'-sulphophenyl)pyrazol-5-one (5.6g) was added to deionised water (50m1) and the pH was adjusted to 6.5 by the addition of 48% sodium hydroxide v
at 6.5 by the addition of 48% sodium hydroxide solution. The coupling mixture was then stirred overnight at room temperature.
The reaction mixture was then heated to 90°C and a solution of calcium chloride (32g CaCl2 in 40m1 water) was added all at once and the mixture stirred for a further 3 hours at 90°C. The mixture was then filtered hot and the product was washed chloride-free with de-ionised water (1000m1) and dried giving 7.3g of an orange solid.
1-Naphthylamine-4-sulphonic acid, sodium salt (6.14g), deionised water (50m1) and hydrochloric acid (5.1 ml) were stirred together in a vessel surrounded by an ice bath, followed by sufficient 48% sodium hydroxide solution to form a solution alkaline to Brilliant Yellow paper. The solution was then cooled to 0-5°C and a further amount (5.1 ml) of hydrochloric acid was added. A solution of sodium nitrite (1.56g) in deionised water (5m1) was added all at once and the mixture was stirred at 0-5°C
for 30 mins.
Excess nitrite was then removed by adding a few ml of 10% sulphamic acid solution.
3-Methyl-1-(3'-sulphophenyl)pyrazol-5-one (6.08g) was added to deionised water (50m1) and the pH was adjusted to 6.5 by the addition of 48% sodium hydroxide solution. The solution was then stirred at 0-5°C and the diazo suspension obtained as described above was added over 10 mins whilst maintaining the pH at 6.5 by the addition of 48% sodium hydroxide solution. The coupling mixture was then stirred overnight at room temperature.
The reaction mixture was then heated to 90°C and a solution of calcium chloride (32g CaCl2 in 40m1 water) was added all at once and the mixture stirred for a further 3 hours at 90°C. The mixture was then filtered hot and the product was washed chloride-free with deionised water (1000m1) and dried giving 8.4g of a orange solid.
1-Naphthylamine-4-sulphonic acid, sodium salt (5.74g), deionised water (50m1) and hydrochloric acid (5.1 ml) were stirred together in a vessel surrounded by an ice bath, followed by sufficient 48% sodium hydroxide solution to form a solution alkaline to Brilliant Yellow paper. The solution was then cooled to 0-5°C and a further amount (5.1m1) of hydrochloric acid was added. A solution of sodium nitrite (1.56g) in deionised WO 96!22334 PCTlGB95102833 water (5ml) was added all at once and the mixture was stirred at 0-5°C
for 30 mins.
Excess nitrite was then removed by adding a few ml of 10% sulphamic acid solution.
' 3-Methyl-1-(4'-sulphophenyl)pyrazol-5-one (5.6g) was added to deionised water (50m1) and the pH was adjusted to 6.5 by the addition of 48% sodium hydroxide v
5 solution. The solution was then stirred at 0-5°C and the diazo suspension obtained as described above was added over 10 mins whilst maintaining the pH at 6.5 by the addition of 48% sodium hydroxide solution. The coupling mixture was then stirred overnight at room temperature.
The reaction mixture was then heated to 90°C and a solution of calcium chloride (32g CaCl2 in 40m1 water) was added all at once and the mixture stirred for a further 3 hours at 90°C. The mixture was then filtered hot and the product was washed chloride-free with deionised water (1000m1) and dried giving 3.4g of an orange solid.
i , . . . ''-- " ,:'t:r:.', -.
The reaction mixture was then heated to 90°C and a solution of calcium chloride (32g CaCl2 in 40m1 water) was added all at once and the mixture stirred for a further 3 hours at 90°C. The mixture was then filtered hot and the product was washed chloride-free with deionised water (1000m1) and dried giving 3.4g of an orange solid.
i , . . . ''-- " ,:'t:r:.', -.
Claims (8)
1. An azo pyrazolone compound of the formula ;
in the form of a salt except for in the form of their sodium and potassium salts.
in the form of a salt except for in the form of their sodium and potassium salts.
2. A compound according to claim 1 wherein the sulphonic acid group in the naphthalene nucleus is in the 4- or 6- position relative to the azo link and the sulphonic acid group in the benzene ring is in the 3- or 4-position relative to the pyrazolyl group.
3. A compound according to claim 1 or claim 2 wherein the salt is a metal salt or a salt of a nitrogenous base.
4. A compound according to claim 3 wherein the salt is a calcium salt.
5. A compound according to claim 4 having the formula wherein the sulphonate group in the naphthalene nucleus is in the 4- or 8-position relative to the azo link.
8. A method for the preparation of an azo pyrazolone compound as defined in claim 1 which comprises diazotising a naphthylamine sulphonic acid of the formula :
and coupling the resulting diazo compound with a sulphonated 3-methyl-1-phenylpyrazol-5-one of the formula:
and converting the resulting monoazo compound to the desired salt form.
and coupling the resulting diazo compound with a sulphonated 3-methyl-1-phenylpyrazol-5-one of the formula:
and converting the resulting monoazo compound to the desired salt form.
7. A method according to claim wherein the naphthylamine sulphonic acid comprises 1-naphthylamine-4-sulphonic acid and/or 1-naphthylamine-6-sulphonic acid.
8. A method according to claim 6 or claim 7 wherein the sulphonated 3-methyl-1-phenylpyrazol-5-one comprises 3-methyl-1-(4'-sulphophenyl)pyrazol-5-one and/or 3-methyl-1-(3'-sulphophenyl)pyrazol-5-one.
8. A method according to claim 6 or claim 7 wherein the sulphonated 3-methyl-1-phenylpyrazol-5-one comprises 3-methyl-1-(4'-sulphophenyl)pyrazol-5-one and/or 3-methyl-1-(3'-sulphophenyl)pyrazol-5-one.
8. The use of an azo pyrazolone compound as defined in claim 1 as a pigment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9501089.8A GB9501089D0 (en) | 1995-01-20 | 1995-01-20 | Monoazo pigments |
| GB9501089.8 | 1995-01-20 | ||
| PCT/GB1995/002833 WO1996022334A1 (en) | 1995-01-20 | 1995-12-05 | Monoazo pigments |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2208740A1 CA2208740A1 (en) | 1996-07-25 |
| CA2208740C true CA2208740C (en) | 2005-11-15 |
Family
ID=35530900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002208740A Expired - Fee Related CA2208740C (en) | 1995-01-20 | 1995-12-05 | Monoazo pigments |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2208740C (en) |
-
1995
- 1995-12-05 CA CA002208740A patent/CA2208740C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2208740A1 (en) | 1996-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5997628A (en) | Heat stable laked monoazo pigment compositions | |
| EP0804510B1 (en) | Monoazo pigments | |
| CA2208740C (en) | Monoazo pigments | |
| EP0804509B1 (en) | Monoazo pigments | |
| EP1472317B1 (en) | Mono- or bisazo copper complex dyestuffs | |
| US2274717A (en) | Azo derivatives of carboxylic acid amides and method of making | |
| CA1172250A (en) | Azo coupling process | |
| GB2031927A (en) | Dyestuffs | |
| US5731422A (en) | 2:1 Aluminum complexes of monoazo compounds | |
| US2653150A (en) | Morpholine azo dyestuffs | |
| US4212647A (en) | Water-insoluble azo dyestuffs which are derivatives of 1-aryl-3-trifluoromethyl-5-pyrazolones | |
| US4211697A (en) | Azoanilino-toluene sulfonamidoalkyleneamine cationic dyes for paper | |
| MXPA97005128A (en) | Mono pigments | |
| US2014450A (en) | Azo dye and method for its preparation | |
| US20040059099A1 (en) | Reactive azo dyes | |
| JPH0798907B2 (en) | Azo compound and its manufacturing method | |
| US1910690A (en) | Azo dyestuffs and process of preparing the same | |
| US4204994A (en) | Azoanilino-toluene sulfonamidoalkyleneamine cationic disazo dyes for paper | |
| MXPA00012016A (en) | Heat stable laked monoazo pigment compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |