GB2387389A - Crystal modification of disazo pigment derived from 1,4-bis(acetoacetylamino)-2,5-dimethylbenzene & methyl 2-amino-4-[N-substituted-aminocarbonyl]benzoate - Google Patents
Crystal modification of disazo pigment derived from 1,4-bis(acetoacetylamino)-2,5-dimethylbenzene & methyl 2-amino-4-[N-substituted-aminocarbonyl]benzoate Download PDFInfo
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- GB2387389A GB2387389A GB0208443A GB0208443A GB2387389A GB 2387389 A GB2387389 A GB 2387389A GB 0208443 A GB0208443 A GB 0208443A GB 0208443 A GB0208443 A GB 0208443A GB 2387389 A GB2387389 A GB 2387389A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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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
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0028—Crystal modifications; Special X-ray patterns of azo compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The pigment is preferably, characterized by its x-ray diffraction pattern which exhibits two strong peaks corresponding to Ò 0.2 two theta double glancing angles of 7.9 and 25.7, four medium strength peaks corresponding to Ò 0.2 two theta double glancing angles of 5.2, 12.3, 12.8 and 18.6 and eight relatively weak peaks corresponding to Ò 0.2 two theta double glancing angles of 6.8, 10.7, 14.0, 15.7, 17.2, 21.1, 23.1 and 28.3. (see figure 2). The beta form crystal modification is obtained by treating the amorphous form of the pigment with N-methyl pyrrolidone, eg at 80{ - 160{C for 2-10 hours. The pigment may be used to colour a high molecular weight organic material.
Description
NEW CRYSTAL MODIFICATION OF A DISAZO CONDENSATION PIGMENT
The present invention relates to a disazo condensation pigment, in particular to a novel 5 form of a pigment of the formula (I) having distinct color characteristics and x-ray diffraction pattern, to a method for the preparation of said pigment form and the use of the pigment in high molecular weight organic materials.
HNX O H CO2CH3
CH NO
O O ( I)
NON CH3
H3CO2C::
:,N: O NH The pigment of the formula (I) was first described in the U.S. Pat. 4,866,1 13 as a yellow pigment. U.S. Pat. 4,866,113 discloses a method for its preparation and describes the resulting pigment as reddish yellow with good pigment properties.
15 In comparison to the known products of the formula (I), the new pigment form according to the invention shows a significantly yellower hue and a different X-ray diffraction pattern.
., ,. ,.
An organic pigment as of the invention, having a yellower hue is attractive because it can compete with existing yellow pigments like P.Y. 95, a state of the art pigment in this area of shade. The alpha form of formula (I), as known in the art, provides a reddish yellow shade and good pigment properties. Surprisingly, the beta-phase of formula (I) 5 additionally provides a different, greenish yellow shade. Due to the unique color characteristics, the outstanding fastness properties and its excellent theological properties, the pigment form of the invention is highly suited for use in plastics and coating applications, particularly in automotive coating systems.
10 The invention provides a pigment of formula (I) in the beta form crystal modification having color characteristics in the CIELAB system of chrome (C) around 76.5 and hue (H) around 85 measured in HDPE at a pigment concentration of 0.26 per cent.
The pigment as of the invention can be characterized by an x-ray diffraction pattern as 15 shown in figure 2. The x-ray diffraction pattern of the beta form crystal modification of formula (I) exhibits two strong peaks corresponding to double glancing angles of 7.9 and 25.7, four medium strength peaks corresponding to double glancing angles of 5.2, 12.3, 12.8 and 18.6 and eight relatively weak peaks corresponding to double glancing angles of 6.8, 10.7, 14.0, 15.7, 17.2, 21.1, 23.1 and 28. 3.
20 The x-ray diffraction pattern is measured with Cu K alpha radiation. It will be understood that the d-value and the double glancing angle (2 Theta) are of course subject to fluctuation due to experimental error of + /- 0.2 (double glancing angle).
The present invention further relates to a process for the preparation of the particular 25 beta form of the pigment of formula (I). The process includes the steps of synthesizing the amorphous form of the pigment, followed by a conversion into the beta form by an after treatment in an organic solvent. The beta form of the pigment of the formula (I) is obtained by after treatment in N-methylpyrrolidone. The alpha form of the pigment of the formula (I) is obtained by after treatment in orthodichlorobenzene or in N,N 30 dimethylforrnamide.
d'... Q
Preferably the after treatment in N-methylpyrrolidone is carried out at elevated temperatures from 80 to 160 C for 2 to 10 hours, most preferably at temperatures around 1 50 C for around 4 to 6 hours.
5 Description of Figures
Figure 1 shows the x-ray diffraction pattern of a pigment of the formula (I) designated as alpha form crystal modification.
Figure 2 shows an x-ray diffraction pattern of the pigment of the formula (I) designated as beta form crystal modification, prepared according to the process of the invention.
10 The two x-ray diffraction patterns were measured with Cu K alpha radiation.
The pigment according to the invention is excellently suited for the coloring of polymer compositions, by which are meant solvent-free and solvent-containing compositions comprising plastics or synthetic resins. Such compositions are applied in oil-based or 15 water-based paints, in coating materials, for the spin dyeing of viscose or cellulose acetate, or for pigmenting plastics, such as polyamide, polyethylene, polystyrene, polyvinyl chloride, rubber and artificial leather. The pigment according to the invention can also be used in printing inks for the graphical industry, for the coloring of paper pulps, for the coating of textiles or for pigment printing. The resulting colorations are 20 notable for their outstanding heat, light and weather fastness, chemical resistance, color strength and very good application properties, examples being their crystallization fastness and dispersing fastness, and in particular their fastness to migration, bleeding, overcoating and solvents.
25 In addition, the pigment of the invention is suitable as colorant in electrophotographic toners and developers, such as one- or two-component powder toners (also known as one- or two-component developers), magnetic toners, liquid toners, polymerization toners and further speciality toners.
30 A further area of application for the pigment of the invention is its use as colorant in powders and powder coating materials, especially triboelectrically or electrokinetically sprayed powder coating materials, which are used to coat the surfaces of articles made, i. i . -
for example, from metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.
Powder coating resins employed are typically epoxy resins, carboxyl- and hydroxyl 5 containing polyester resins, polyurethane resins and acrylic resins, together with customary hardeners. Combinations of resins are also used. For example, epoxy resins are frequently employed in combination with carboxyl- and hydroxyl-containing polyester resins. Examples of typical hardener components (depending on the resin system) are acid anhydrides, imidazoles and dicyandiamide and derivatives thereof, 10 blocked isocyanates, bisacylurethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.
Typical toner binders are addition polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrenebutadiene, acrylate, polyester and phenolic-epoxy resins, polysulphones, polyurethanes, individually or in combination, 15 and also polyethylene and polypropylene, in or to which further ingredients, such as charge control agents, waxes or flow assistants may be present or may be added subsequently. The pigment of the invention is suitable, moreover, as colorant in inkjet inks, both 20 aqueous and non-aqueous, and in inks which operate in accordance with the hot-melt process. The pigment of the invention is further suitable for cosmetics, like nail varnishes or makeup. In the following examples the parts and percentages are by weight. The temperatures are indicated in degrees Celsius. One part by volume corresponds to the volume of one part by weight of water.
c i. c - .
s EXAMPLES
Example 1: Preparation of the crude pigment of formula (I! In a I liter beaker, 66.6 parts of benzoic acid 2-amino-4-[[2,2,6,6-tetramethyl-4 5 piperidinyl)amino]carbonyl]-methyl ester of the formula (II) \/ HN O N Jq (11) CO2CH3
NH2 are stirred for 15 minutes in 200 parts of water at room temperature. Then 93.7 parts of cone. HCI are added in the beaker within 20 minutes and the reaction mixture is further 10 stirred for one hour. The mixture is then cooled to 0-5 C by immersing the reaction vessel in an ice/water bath. 45.6 parts of aqueous sodium nitrite solution 33.3% part by volume are slowly added over a period of 30 minutes. The mixture is further stirred for 40 minutes at 0-5 C. The resulting diazonium chloride solution is then clear-filtered.
30.4 parts of 1,4-bis-acetoacetylamino-2,5-dimethylbenzene are stirred in 200 parts of 15 water, in a beaker. Then 25.7 parts of cone. NaOH are added within 10 minutes, in order to dissolve the coupling component. This solution is then dropped within 15 minutes, into a stirred 5 liter beaker containing 200 parts of water, 12 parts of acetic acid and 3.2 parts by volume of a dispersing agent, e.g. Sandopan 2N (a Trademark of CLARIANT). Then 57.2 parts of sodium acetate are added to the suspension of the 20 precipitated coupling component. This suspension is further stirred at room temperature for 30 minutes.
The diazonium solution, kept at 0-5 C, is then slowly pumped into the coupling component over a period of 3 hours, whilst stirring. The resulting yellow suspension is further stirred for 2 hours.
25 The suspension is then heated to 80 C and further heated at this temperature for one hour. Then a solution of 66.8 part of sodium carbonate in 200 parts of water are pumped in the yellow suspension over a period of 90 minutes. The pigment suspension is further .. O.,.
heated for 1 hour at 80 C. Then it is filtered on a Buchner filter and washed with 2000 parts of hot water.
The resulting wet cake is dried in an oven at 100 C overnight, to give 94. 2 parts of dry pigment of the formula ( D, which is amorphous.
Comparative Example 2: Preparation of the alpha-form 40 parts of the previously prepared crude pigment of the formula (I) is stinted in 220 parts of N,N-dimethylformamide for 2 hours. The suspension is then heated to 150 C within one hour, whilst stirring, and further stirred at this temperature for 5 hours. The 10 suspension is then cooled to 80 C, filtered and washed with 50 parts of N,N-
dimethylforrnamide (at 80 C) and then with 150 parts of hot water. The resulting wet cake is dried in an oven at 100 C overnight, to give 35.9 parts of dry pigment of the formula (I),which is the alpha form.
The x-ray diffraction pattern of the alpha form is displayed in figure 1 and corresponds 15 to the following numeric data: d-spacing (Angstrom) double glancing angle(2 Theta) relative intensity ( %) 29.93 2.94
17.23 5.12 37.56
14.65 6.02 17.81
10.80 8.17 100
7.97 11.09 5.57
7.28 12.14 19.80
6.76 13.08 31.74
6.02 14.69 45.47
5.14 17.22 16.90
4.82 18.38 15.83
4.39 20.18 12.27
4.18 21.21 19.82
4.00 22.16 45.85
3.58 24.84 - 32.43
3.43 25.95 47.01
_ 27.15 42.45
3.18 - 27.97 15.43 -
3.06 29.06 9.04
...DTD:
r 7 Example 3: Preparation of the beta-form 40 parts of the previously prepared crude pigment of the formula (I) is stirred in 220 parts of Nmethylpyrrolidone for 2 hours. The suspension is then heated to 150 C within one hour, whilst stirring, and further stirred at this temperature for 5 hours. The 5 suspension is then cooled to 80 C, filtered and washed with 50 parts of N-
methylpyrrolidone (at 80 C) and then with 150 parts of hot water. The resulting wet cake is dried in an oven at 100 C overnight, to give 35.2 parts of dry pigment of the formula (I),which is the beta form.
The x-ray diffraction pattern of the beta form is displayed in the figure 2 and 10 corresponds to the following numeric data: d-spacing ( Angstrom) double glancing angle(2 Theta) relative intensity ( %) 16.99 5.19 25.1
12.92 6.83 12.49
11.18 7.89 100
9.48 9.31 1.31
8.22 10.74 11.66
7.19 12.29 31.57
7.13 12.39 28.44
6.92 12.76 28.24
6.46 13.67 13.20
6.299 14.04 21.85
6.25 14.15 14.63
5.64 15.68 18.15
5.32 16.63 13.19
5.15 17.18 19.52
4.77 18.57 39.71
4.62 19.16 9.13
4.41 20.11 12.28
4.21 21.06 29.09
4.05 21.91 12.03
3.84 23.13 - - 22.42
3.i8 23.46 17.06 3.6i- 24.21 14.26 3.45 25.74 63.93
:. ....
3.41 26.10 31.46
3.30 26.98 9.17
3.15 28.3 29.61
3.12 28.56 18.88
3.03 29.42 11.0g _, 2.92 30.58 10.63
2.73 32.76 4.29
2.64 33.87 5.81
_ _ 2.50 35.77 2.07
2.38 37.75 9.90
2.15 41.81 --- 7.89
_ 45.42 - 3.24 - --=
Example 4. Application in HDPE The pigments prepared in the comparative example 2 and in example 3 are mixed at 5 0.26% pigment concentration into a high density polyethylene, e.g. Hostalen GC 7260 (a Trademark of TICONA), stabilized with 0.1% of a phosphorus containing additive, e.g. Sandostab49 P-EPQ (a Trademark of CLARIANT).
The following data on color characteristics are measured in the CIELAB system: P.Y. 110 Comp.Example 2 Example 3 H (hue) 68.4 77 84.9 85.4 _ _ C (chrome) 73.8 75.8 76.5 75.8 _ The data clearly shows that the beta-phase of pigment (I) as of example 3 is much greener compared to the alphaphase of pigment (I) as of the comparative example 2.
. -
Claims (8)
1. A pigment of formula (I) CO2CH3
ON CH N'
/JN' O O
NAN CH3
H3CO2C
In O NH s characterized in that it is in the beta form crystal modification and by its color characteristics in the CIELAB system of chrome (C) around 76.5 and hue (H) around 85 measured in HDPE at a pigment concentration of 0.26 per cent.
2. A pigment according to claim 1, characterized by its x-ray diffraction pattern which exhibits two strong peaks corresponding to + 0.2 two theta double glancing angles of 7.9 and 25.7, four medium strength peaks corresponding to + 0.2 two 15 theta double glancing angles of 5.2, 12.3, 12.8 and 18.6 and eight relatively weak peaks corresponding to + 0.2 two theta double glancing angles of 6.8, 10.7, 14.0, 15.7, 17.2, 21.1, 23.1 and 28.3.
, .
3. A pigment according to claim 1 which exhibits an x-ray diffraction pattern corresponding substantially to figure 2.
4. A process for the preparation of a pigment of formula (I) according to claim 1, characterized in that the amorphous pigment form is conversed into the beta form crystal modification by after treatment in N-methyl pyrrolidone.
5. A process for the preparation according to claim 4, characterized in that the amorphous pigment is prepared by diazotising a compound of formula (II) --J\HJ (11)
\CO2CH3
NH2 and reacting the intermediate product with 1,4-bis-aeetoacetyl-amino2,5 dimethylbenzene in a molar ratio of around 2:1.
20
6. A process for the preparation according to claims 4 or 5 characterized in that the after treatment in N-methyl pyrrolidone is carried out at temperatures from 80 to 160 C for 2 to 10 hours.
25
7 A p it; t c; mation according to claims 6 characterized in that the after treatment in N-methyl pyrrolidone is carried out at temperatures around 150 C for around 4 to 6 hours.
,
8. A process for coloring a high molecular weight organic material, which comprises incorporating an effective pigment amount of the pigment according to claim I 5 into the high molecular weight organic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0208443A GB2387389A (en) | 2002-04-12 | 2002-04-12 | Crystal modification of disazo pigment derived from 1,4-bis(acetoacetylamino)-2,5-dimethylbenzene & methyl 2-amino-4-[N-substituted-aminocarbonyl]benzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0208443A GB2387389A (en) | 2002-04-12 | 2002-04-12 | Crystal modification of disazo pigment derived from 1,4-bis(acetoacetylamino)-2,5-dimethylbenzene & methyl 2-amino-4-[N-substituted-aminocarbonyl]benzoate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0208443D0 GB0208443D0 (en) | 2002-05-22 |
| GB2387389A true GB2387389A (en) | 2003-10-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0208443A Withdrawn GB2387389A (en) | 2002-04-12 | 2002-04-12 | Crystal modification of disazo pigment derived from 1,4-bis(acetoacetylamino)-2,5-dimethylbenzene & methyl 2-amino-4-[N-substituted-aminocarbonyl]benzoate |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2387389A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2085433A1 (en) * | 2008-01-23 | 2009-08-05 | Clariant International Ltd. | New crystal modifications of a disazo condensation pigment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866113A (en) * | 1986-04-10 | 1989-09-12 | Sandoz Ltd. | Compounds useful as pigments containing one or more 2,2,6,6-tetraalkylpiperidine groups |
| EP1081184A1 (en) * | 1999-08-31 | 2001-03-07 | Clariant Finance (BVI) Limited | Pigment for warpage-free polyolefins coloration |
-
2002
- 2002-04-12 GB GB0208443A patent/GB2387389A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866113A (en) * | 1986-04-10 | 1989-09-12 | Sandoz Ltd. | Compounds useful as pigments containing one or more 2,2,6,6-tetraalkylpiperidine groups |
| EP1081184A1 (en) * | 1999-08-31 | 2001-03-07 | Clariant Finance (BVI) Limited | Pigment for warpage-free polyolefins coloration |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2085433A1 (en) * | 2008-01-23 | 2009-08-05 | Clariant International Ltd. | New crystal modifications of a disazo condensation pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0208443D0 (en) | 2002-05-22 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |