CA1082832A - Perinone compounds, process for preparing them and their use as dyes - Google Patents
Perinone compounds, process for preparing them and their use as dyesInfo
- Publication number
- CA1082832A CA1082832A CA236,904A CA236904A CA1082832A CA 1082832 A CA1082832 A CA 1082832A CA 236904 A CA236904 A CA 236904A CA 1082832 A CA1082832 A CA 1082832A
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- lower alkyl
- conh
- substituted
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- 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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/32—1.3 azoles of the anthracene series
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/12—Perinones, i.e. naphthoylene-aryl-imidazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Coloring (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Indole Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention is a process for colouring a substance which comprises incorporating into the substance a pigment which is a perinone compound of the general formula (I) in which A represents an ortho- or peri-arylene radical selected from the benzene, napthalene or anthracene series or a 5- or 6-membered heterocyclic radical containing 1 or 2 nitrogen atoms, and X represents hydrogen or a direct bond or a straight or branched alkylene of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula -CO-, -CONH-, -NH-CO-NH-, -CO-?-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH
n represents the number 1 or 2 and m = 1 if n = 1, and m = 0 if n = 2, R re-presents hydrogen or lower alkyl and Y represents lower alkylene or phenylene.
The invention is a process for colouring a substance which comprises incorporating into the substance a pigment which is a perinone compound of the general formula (I) in which A represents an ortho- or peri-arylene radical selected from the benzene, napthalene or anthracene series or a 5- or 6-membered heterocyclic radical containing 1 or 2 nitrogen atoms, and X represents hydrogen or a direct bond or a straight or branched alkylene of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula -CO-, -CONH-, -NH-CO-NH-, -CO-?-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH
n represents the number 1 or 2 and m = 1 if n = 1, and m = 0 if n = 2, R re-presents hydrogen or lower alkyl and Y represents lower alkylene or phenylene.
Description
The present invention relates to a process for the dyeing of high molecular weight organic polymers wherein a pigment which is a perinone compound of thc gencral formula r in which A represents an ortho- or peri-arylene radical selected from the benzene, naphthalene or anthracene series or a 5- or 6-membered heterocyclic radical containing 1 or 2 nitrogen atoms, and X represents hydrogen or a direct bond or a straight or branched alkylene of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula R
-CO-, -CONH-, -NH-CO-NH-, -CO-N-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH-n represents the number 1 or 2 and m = 1 if n = 1, and m = O if n = 2, R re-presents hydrogen or lower alkyl and Y represents lower alkylene or phenylene, is incorporated into the polymer melt, spinning solution, lacquer, paint or printing ink.
¢~
~ , ~
- : :
Of particular interest is the use in the process of the invention of compounds of the formula II
o ~ N ~,,,N ~II) ~ H
C I -la-:`' ' . ' .
1082f~32 in which A1 represents phenylene radical which is unsubstituted or is sub-stituted by one or two substituents selected from the group consisting of fluorine, chlorine, bromine, lower alkyl groups such as methyl, ethyl, or propy.L groups, lower alkoxy groups such as methoxy, ethoxy or propoxy groups, hydroxy, phenyl, phenoxy, benzyloxy, lower aIkanoylamino groups such as acetyl, benzoylamino, lower alkyl-sulfonyl groups, nitro, nitrile, trifluoro-methyl, carboxy carbalkoxy of 2 to 5 carbon atoms or carboxylic or sulfonic acid amide which is unsubstituted or substituted at the nitrogen atom by one or two radicals selected from lower alkyl, phenyl or nitrophenyl, or wherein A, is a group of formu~La:
o ~ N ~ N
HO ~ OH
wherein A1 is phenylene which is unsubstituted or substituted by 1 or 2 sub-stituents selected from fluorine, chlorine, bromine, lower alkyl, lower alkoxy, phenyl, phenoxy, hydroxy, benzyloxy, lower alkanoylamino, benzoylamino, lower alkylsulfonyl, nitro, nitrile, trifluoromethyl, carboxy, carbaLkoxy of 2 to 5 carbon atoms and carboxylic or sulfonic acid amide which is unsubstituted or substituted at the nitrogen by 1 or 2 radicals selected from lower alkyl, phenyl or nitrophenyl; or wherein A1 is a group of the formula ~ , ~ , ~ or B
. . ..: .
- 1082b~32 ~ .' Of these mention is made of compounds in which A is a group of the formula .~ ~9 .
Also of particular interest are compounds of formula III
A
o _~N ~f~N
NO / ~ ON (III~
in which A2 represents a naphthalene or acenaphthene radical, which is unsub-stituted or is substituted by fluorine, chlorine, or bromine, lower alkyl such as methyl or ethyl groups, lower alkoxy such as methoxy or ethoxy groups, hydroxy, phenoxy, nitro, lower aIkanoyl such as acetyl, benzoyl, lower alkanoyl-amin~ suchdas acetylamino or benzoylamino or carbamoylor sulfamoyl, which are unsubstituted or are substituted at the nitrogen atom by one or two substituents selected from lower alkyl and phenyl.
; Further compounds of interest are compounds of the formNla IV
` ~ ' , . ~-, .
1082f~32 ~ , o ~ =~N ~N
HO / ~ \ OH (IV) in which B represents a bridge member forming together with the two carbon atoms to which it is linked a 5- or 6-membered ring, which bridge member con-sists of carbon and up to two nitrogen ato~s. Preferably the bridge member consists of two -NH- groups and two groups selected from -CO- and -CS-.
Yet further compounds useful in the invention are those of formula (V) ~X~
~ ~ O ~ N ~ (V) NO ~ QN ~O - ~ ~
in which X represents a direct bond, a straight or branched alkylene radical of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula R
-CO-, -CONH-, -NH-CO-NH-, -CO-N-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH-in which Y is lower alkylene or phenylene~ R is hydrogen or lower alkyl and the phenyl nuclei marked "a" are unsubstituted or are substituted by chlorine, lower alkyl ~r lower alkoxy.
B
: .
108Z~32 The dyestuffs may be obtained by reacting 1 or 2 moles of 3,6-di-hydroxynaphthalic acid anhydride with 1 mole of an aromatic or heterocyclic ortho- or peri-diamine or tetramine or the salts thereof, optionally in the presence of acid-binding agents.
The dyestuffs of the formula II may also be obtained by condensing 1 mole of the 3,6-dihydroxynaphthalic acid anhydride with 1 mole of ano-nitroaniline, then reducing the nitro group to an amino group and effecting the cyclization to the dyestuff of the formula II.
The aromatic diamines of the benzene, diphenyl, naphthalene, acena-phthene, anthraquinone, fluorene or phenanthene series, in particular the ortho-phenylene diamines or ortho- orperi-naphthylene-diamines and the o-nitra-nilines, used as the starting compounds may contain other substituents, for example halogen atoms, such as fluorine~ chlorine or bromine atoms, lower alkyl groups such as methyl, ethyl or propyl groups, hydroxy or lower alkoxy groups such as methoxy, ethoxy or propoxy groups, aryloxy groups e.g. option-ally substituted phenoxy groups, aralkoxy groups such as benzyloxy groups, acylamino groups such as acetyl or benzoylamino groups, alkyl-sulfonyl groups, nitro, nitrilej trifluoromethyl, carboxylic acid ester groups or carboxylic acid amide groups and optionally substituted sulfonic acid amide groups.
As tetramines, there may be used 1,2,4,5-tetraminobenzene, in parti-cular amines of the formula VI
-CO-, -CONH-, -NH-CO-NH-, -CO-N-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH-n represents the number 1 or 2 and m = 1 if n = 1, and m = O if n = 2, R re-presents hydrogen or lower alkyl and Y represents lower alkylene or phenylene, is incorporated into the polymer melt, spinning solution, lacquer, paint or printing ink.
¢~
~ , ~
- : :
Of particular interest is the use in the process of the invention of compounds of the formula II
o ~ N ~,,,N ~II) ~ H
C I -la-:`' ' . ' .
1082f~32 in which A1 represents phenylene radical which is unsubstituted or is sub-stituted by one or two substituents selected from the group consisting of fluorine, chlorine, bromine, lower alkyl groups such as methyl, ethyl, or propy.L groups, lower alkoxy groups such as methoxy, ethoxy or propoxy groups, hydroxy, phenyl, phenoxy, benzyloxy, lower aIkanoylamino groups such as acetyl, benzoylamino, lower alkyl-sulfonyl groups, nitro, nitrile, trifluoro-methyl, carboxy carbalkoxy of 2 to 5 carbon atoms or carboxylic or sulfonic acid amide which is unsubstituted or substituted at the nitrogen atom by one or two radicals selected from lower alkyl, phenyl or nitrophenyl, or wherein A, is a group of formu~La:
o ~ N ~ N
HO ~ OH
wherein A1 is phenylene which is unsubstituted or substituted by 1 or 2 sub-stituents selected from fluorine, chlorine, bromine, lower alkyl, lower alkoxy, phenyl, phenoxy, hydroxy, benzyloxy, lower alkanoylamino, benzoylamino, lower alkylsulfonyl, nitro, nitrile, trifluoromethyl, carboxy, carbaLkoxy of 2 to 5 carbon atoms and carboxylic or sulfonic acid amide which is unsubstituted or substituted at the nitrogen by 1 or 2 radicals selected from lower alkyl, phenyl or nitrophenyl; or wherein A1 is a group of the formula ~ , ~ , ~ or B
. . ..: .
- 1082b~32 ~ .' Of these mention is made of compounds in which A is a group of the formula .~ ~9 .
Also of particular interest are compounds of formula III
A
o _~N ~f~N
NO / ~ ON (III~
in which A2 represents a naphthalene or acenaphthene radical, which is unsub-stituted or is substituted by fluorine, chlorine, or bromine, lower alkyl such as methyl or ethyl groups, lower alkoxy such as methoxy or ethoxy groups, hydroxy, phenoxy, nitro, lower aIkanoyl such as acetyl, benzoyl, lower alkanoyl-amin~ suchdas acetylamino or benzoylamino or carbamoylor sulfamoyl, which are unsubstituted or are substituted at the nitrogen atom by one or two substituents selected from lower alkyl and phenyl.
; Further compounds of interest are compounds of the formNla IV
` ~ ' , . ~-, .
1082f~32 ~ , o ~ =~N ~N
HO / ~ \ OH (IV) in which B represents a bridge member forming together with the two carbon atoms to which it is linked a 5- or 6-membered ring, which bridge member con-sists of carbon and up to two nitrogen ato~s. Preferably the bridge member consists of two -NH- groups and two groups selected from -CO- and -CS-.
Yet further compounds useful in the invention are those of formula (V) ~X~
~ ~ O ~ N ~ (V) NO ~ QN ~O - ~ ~
in which X represents a direct bond, a straight or branched alkylene radical of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula R
-CO-, -CONH-, -NH-CO-NH-, -CO-N-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH-in which Y is lower alkylene or phenylene~ R is hydrogen or lower alkyl and the phenyl nuclei marked "a" are unsubstituted or are substituted by chlorine, lower alkyl ~r lower alkoxy.
B
: .
108Z~32 The dyestuffs may be obtained by reacting 1 or 2 moles of 3,6-di-hydroxynaphthalic acid anhydride with 1 mole of an aromatic or heterocyclic ortho- or peri-diamine or tetramine or the salts thereof, optionally in the presence of acid-binding agents.
The dyestuffs of the formula II may also be obtained by condensing 1 mole of the 3,6-dihydroxynaphthalic acid anhydride with 1 mole of ano-nitroaniline, then reducing the nitro group to an amino group and effecting the cyclization to the dyestuff of the formula II.
The aromatic diamines of the benzene, diphenyl, naphthalene, acena-phthene, anthraquinone, fluorene or phenanthene series, in particular the ortho-phenylene diamines or ortho- orperi-naphthylene-diamines and the o-nitra-nilines, used as the starting compounds may contain other substituents, for example halogen atoms, such as fluorine~ chlorine or bromine atoms, lower alkyl groups such as methyl, ethyl or propyl groups, hydroxy or lower alkoxy groups such as methoxy, ethoxy or propoxy groups, aryloxy groups e.g. option-ally substituted phenoxy groups, aralkoxy groups such as benzyloxy groups, acylamino groups such as acetyl or benzoylamino groups, alkyl-sulfonyl groups, nitro, nitrilej trifluoromethyl, carboxylic acid ester groups or carboxylic acid amide groups and optionally substituted sulfonic acid amide groups.
As tetramines, there may be used 1,2,4,5-tetraminobenzene, in parti-cular amines of the formula VI
2 ~ X ~ NH2 (VI) `' ~
~)82~3z in which X has the meanings given above and the benzene nuclei a may contain other substituents, for example halogen atoms such as chlorine atoms, lower alkyl groups or lower alkoxy groups.
The 3,6-dihydroxy-1,8-naphthalic acid anhydride used as the starting compound may be prepared by sulfonation of 1,8-naphthalic acid anhydride with about 20-30% oleum at 170 - 200C and by subsequent alkali melt of the 3,6-disulfonaphthalic acid formed (cf. Chemisches Zentralblatt 1936, II~ 4213-4214).
The dyestuffs are advantageously prepared in known manner by heating the components (3,6-dihydroxy- naphthalic acid anhydride and di- or tetraamine) in water optionally acidified with catalytical amounts of acid or a solvent, for example acetic acid, ethanol, dimethylformamide or N-methylpyrrolidone.
The reaction is completed after several hours at elevated temperature, pre-ferably at 80 - 150 C. It may be easily followed by chromatography. In general, the perinone compounds formed of the formula I precipitate from the reaction mixture and are isolated by filtration. The addition of water prior to the isolation may sometimes be of advantage, because some of the compounds ; of the invention show a tendency to delay crystallization.
In some cases, for example with very unstable aromatic di- or tetra-amines, it may be of advantage to condense, instead of the free base, a mineral acid salt thereof with 3,6-dihydroxynaphthalic acid anhydride, in which case the addition of an acid-binding agent, for example alkali metal carbonate or acetate, warrants a particularly smooth reaction.
In the same manner, a condensation of the 3,6-dihydroxynaphthalic acid anhydride under comparable reaction conditions with the o-nitroaniline ' 1082~32 from which the unstable diamino compound is derived to the resulting 3,6-dihydroxynaphthalic acid imide may be of advantage, whereupon a reaction of the nitro-group standing in ortho-position to the imide-nitrogen, for example by catalytical or iron reduction is followed and whereupon, in general, the o-amino-group formed spontaneously closes the imidazole ring under separation of water. Heating for several hours to elevated temperatures to effect cyclization has been found necessary only in some cases with kinetically partic-ularly disadvantageous conditions.
The perinones of formula I have been found to be valuable dyes, in particular valuable pigments that may be used in finely dispersed form, in-dividually or as mixtures, for the pigrnentation of high molecular organic materials, for example for cellulose ethers and cellulose esters, for example ethyl cellulose, cellulose acetate, cellulose butyrate, for polyamides or polyurethanes or polyesters, natural or synthetic resins such as those resins obtained by polymerization, for example aminoplasts, in particular urea-form-aldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, poly-carbonates, for polyolefins such as polystyrene, polyvinyl chloride, poly-ethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, for rubber, casein, silicone and silicon resins.
The perinones of formula I have already valuable tinctorial properties.
But in many cases, their properties regarding application may often be improved by an usual pigment finish~ for example by prolonged heating in water and/or solvents, by distribution by grinding or kneading in the presence of salts, solvents or dispersants.
The high molecular materials to be dyed may be masses of plastic in .~
. . -.
the form of melts or of spinning solutions, lacquers, paints or printing inks.
The pigments may be used in the form of a pure pigment powder or in ~he form of a dispersion of pigment in a resin. The resins which are suitable for use as carriers in pigment dispersions are natura] resins, for example abietic acid or the esters thereof, ethyl cellulose, cellulose acetobutyrate, alkaline earth metal salts of higher fatty acids~ fatty amines~ for example stearyl amine or colophonium-amine, vinyl chloride/vinyl-acetate copolymers, polyacrylonitrile or polyterpene resins or water-soluble resins, for example resins containi~g sulfonic acid groups or their alkaline earth metal salts.
The next comparable compound of the mono-hydroxy-naphthoylene-benzimidazole series(known from '~Journal of the Society of Dyers and Colour-ists", Vol. 85 (1969), page 249) is a typical disperse dyestuff and carnot be used as pigment because of its insufficient fastness to bleeding and to over-lacquering.
Thus~ it was surprising and not foreseeable that the introduction of an additional hydroxy group would result in such considerable modifications of the properties. In addition to a high tinctorial strength, the pigments are distinguished : B
- 1082~32 by an excellent fastness to light, very good purity of colour shade and, in general, valuable colouristic and utilization properties, in particular by a surprisingly high fastness to solvents and plastizisers, for example a very good fastness ~o bleeding, overlacquering, migration and blooming. In view of these properties and by reason of their easy accessibility, these com-pounds represent a considerable technical advance.
The following Examples illustrate the invention, parts are by weight.
EXAMPLE 1:
A mixture of 2700 parts of glacial acetic acid, 130 parts of 3,6-dihy-droxynaphthalic acid anhydride and 67.3 parts of o-phenylene-diamine was heated, while stirringJ for 5 - 6 hours, to the boiling temperature ~ ~ 115 - 120 C). The reaction mixture was allowed to cool, the dyestuff of the formula >~
Q N N
H0 ~ OH
that had precipitated was filtered off with suction, washed with water until neutrality and dried at 80 C. 165 Parts (= 97% of the theory) of a yellow pigment were obtained; the pigment was found to be excellently suitable for the dyeing of synthetics and plastic masses and yielded dyeings with excellent fastness properties.
Better fastness properties, in particular very good fastness to bleeding and overlacquering, were obtained when stirring the water-wet pigment before drying for 5 hours with the 5-fold amount of dimethylformamide at 100 - 110 C, . ~-.,. ,, ; , - -iO8Z~3Z
filtering it off while hot, washing it with water and drying it.
If, instead of glacial acetic acid, the same quantities of formic acicl were used, the pigment was formed with comparable yields and showed the same fastness properties.
~X~MPLe 2:
23 Parts o 3,6-dihydroxynaphthalic acid anhydride, 17.4 parts of 1,8-naphthylene-diamine and S parts of propionic acid were stirred consecu-tively into 250 parts of water and the mixture so obtained was heated for 8 hours in an autoclave to 130 - 140 C, whereupon a pressure of 3 - 4 atmos-pheres rose up. The mixture was then cooled, the pressure was released and - the compound formed of the formula ;; ~ .
~IO ~ OH
was filtered off with suction, washed with water and dried at 100 C. 35 Parts (= 99% of the theory) of a red pigment were obtained, which pigment was found to be excellently suitable for the preparation of printing inks, lac-quers and paints and permits, in these fields of application, dyeings with high colour intensity and excellent properties of fastness.
When the 1,8-naphthylene-diamine was replaced by a corresponding amount of 4-methoxy-1,8-naphthylene-diamine, there was obtained a somewhat more bluish pigment having comparable properties of fastness and higher tinctorial strength.
-::.
.
, Z~32 F:XA~JPLE 3:
23 Parts of 3,6-dihydroxynaphthalic acid anIIydride, 25,3 parts of 2,4-diaminoanisole-dicIIlorohydrate, 400 parts of iso-propanol and 20.5 par~s of sodium acetate were heat~ in an autoclave for 10 hours to 140 _ 145 C. After coolin~, the pressurc was rcleased and the dyestuf f obtained was filtered off with suction. Af~er washing with isopropanol and water, the dyestuff was dried at 80 C.
31 Parts (= 93.4 % of the theory) of an orange yellow pigment were obtained which was found to be suita~le for the preparation of light and weather fast lacquers as well as for the colouring of plastizised polyvinyl chloride. Subsequent heating for 5 hours of the water-wet filter cake with the 10-fold amound of a mixture of 9 parts of water and 1 part of isobutanol to 150 C yielded a pigment which had increased covering power and improved fastness to li~ht and to weather.
~ XA~IPLE 4:
23 Parts of 3,6-dihydroxynaphthalic acid anhydride and 18 parts of 3-nitro-4- aminobenzonitrile were introduced into 400 parts of 95% acetic acid and the mixture was then heated to 90 C. After 2 lIours~ the nitroimide of the formula CN
~2 0~0 ~ ~ ~ ~ ~ OH
separated. Then, 14 parts of iron po~rrder we-re added portionwise 1~)82832 within 2 nours. The reaction was exothermic and took place at 100 C. The wll~le was heated for 3 hours to 100 - 105 C, dliluted with 600 parts of water and filtered with suction while hlot, The filter cake which was still contaminated with basic iron ~c~tate was then introduced into 1000 parts o~ dimethyl~
formamide and heated to the boilin~ temperature. After addition of 5 parts of active carbon, the mixture was filtered with suction through a clarifying filter, the filtrate was cooled to 50 C while stirring and the compound of the formula CN
~ .
O ~ '~
}10 ~~ C'i whlch had precipitated was filtexed off, ~ashed with water and dried, 30 Parts of a greenish-yellow pigment (= 91.7% of the theory) were obtained; the pigment was found to have an excellent fastness to light and to be excellently suitable for : the preparation of lacquers, in particular lacquers with ` metallic effect.
The reduction of the intermediarily formed nitroimide may be effected with the sams result catalytically with hydrogen, which also induces spontaneous cyclization to th~ compound of the invention.
:: For this purpose, the o-nitroimide isolated ~y filtration .vas heated in 1500 parts of dimethylformamide with addi.tion of 1 part of a nickel catalyst and under a hydrogen pressure of 50 atmospheres gau~e to 130 C~, until no absorption of gas ~as 10~2~32 stated. The pressure was released, the mixture was filtered while hot to remove the catalyst and the filtrate was cooled, while stirring, to 50 C, whcroupon the pigment separated. Its isolation was effected as described abovo.
EXAMPLES 5 ~
When replacing in Example 4 the 3-nitro-4-amino-benzo-nitrile by aliquot amounts of other o-nitranilines and working in the manner described, there were obtained other pigments of the invention corresponding to the general formula ' ~ .
O N N
110 ~ 0}~
with the yields and shades indicated in table l.
T a b l e Example X Yield Shade Cl 96.3 % greenish yellow 6 -OC2H5 97.5 % orange 7 -NHCOCH3 98.5 % orange red 8 CH3 94.8 % yellow 9 Br 98.l % greenish yellow 2 3 96.5 % greenish yellow ll OH 93.0 % reddish yellow :
~08283Z
ExAr.lPLE 12:
23 Parts of 3,6-dihydroxynaphthallc acid anhydride, 18.3 parts o~ 3,4-diaminobenzoic acid and lS0 parts o~ N-methylpyrro-lidone were stirred, 5 parts of formic acid were added and the mlxture was heated for 5 hours to 120 - 130 C. The precipitate .
of the compound oi the ~ormula ~,OO
.' ~10 ~ Ojl formed was completed by the addition of 200 parts of water, the ocompound was filtered off with suction, washed witll water and dried.
33.8 Parts (97,7 % of the theory) of a greenish-yellow pigm::nt were obtained; after grinding with a salt, in particular with the 5-fold amount of sodium sul~ate, this pigment was found to be particularly suitable for the preparation of transparent lacquers.
- The following Tables 2 to 5 show other compounds of the ~ormulae II to V of the invention which had been prepared according to one o~ the processes of the invention, in particular in a manner analogous to that described in the foregoing Examples, and indicate also the corresponding yields and shades, _ 14 -. _ .
,.. ' ~ ~
108Z~32 T a b 1 e 2 (Dyestuffs of the formula II) Examplo A1 Yield Shade cll3 1.; ~ 96.8 % Yellow ~H3 14 ~ ~ 94.8 % yellow )~ , F
~ greenish ~ 91.9 % yellow : CH3-CH
16 ~ 89.5 % yellow :` .
- ., .
1082~32 Example Al Yield Shade Cl Cl 17 ~ 98.5 % greenish yellow 18 ll7C30 ~ 92.8 % yellow 19 ~ 97.0 % orange ~ .
~ 98.3 % reddish yellow . ~I
N2 ~
21 ~ 98.6 % greenish yellow 22 NHCO ~ 98.0 % orange ~ .,.
>=<
CN
23 ~ 94.8 % greenish yellow 24 ~ 9l.9 % g~eenish yellow .~ - 16 -1082~32 E.~an~ple Al Yield Shade _ . _ COOC4~l9 2S ~ 89.8 % greenish yellow 26 ~ 99.0 % greenish yellow.
,N 2 27 97.8 % greenish yellow - CONH
~, C 2H5 28 . S02N 96.9 % greenish yellow 2~1S' )~< ' ~: 29 ~ 94.5 % yellow ~ 92.8 % rellow 31 o = ~ o 93.7 % red orenge D
`
` -. ~ , .
~. ` .-.
- ~ . .
, . .
1082~32 Example Al Yield Shade /~
32 ~ -o 93.0 % y~llow ~, 33 ~ 94.5 % yellow 34 ~ ~ 94.~ % yellow T a b l e 3 Example A2 Yield Shade .
~ 35 ~ 96.8 % bluish red :~ CH2- CH2 36 ~ 95.5 % red . ' .
' :
10~2832 Example A2 Yield Shade 502N~ ~ 99.1 ~ bluish red OC2"5 38 ~ 95.8 ~ red T a b l e 4 (Dyestuffs of the formula IV) Example B Yield Shade N,H ~' 39 5 ~ H 95.0 ~ yel10w NH~
0 ~ NH 94.9 % yellow NH~
41 0 ~NH 98.3 % yellow :......................................... . . . .
., ` .
: ' .
1~lgZ~32 T a b 1 e 5 (Dyestuffs of the formula V) E~mple ~ X ~ Yield Shade 42 ~ 97.2 ~ yellow NHCO
43 ~ ~ 95.9 % orange ~ NHCONH ~
44 ~ ~ 98.7 % orange ~' ~ ~ 94.5 % greenish yellow 2 ~ ~ yellow -: , :, :
- - , : :.
.
~)82~3z in which X has the meanings given above and the benzene nuclei a may contain other substituents, for example halogen atoms such as chlorine atoms, lower alkyl groups or lower alkoxy groups.
The 3,6-dihydroxy-1,8-naphthalic acid anhydride used as the starting compound may be prepared by sulfonation of 1,8-naphthalic acid anhydride with about 20-30% oleum at 170 - 200C and by subsequent alkali melt of the 3,6-disulfonaphthalic acid formed (cf. Chemisches Zentralblatt 1936, II~ 4213-4214).
The dyestuffs are advantageously prepared in known manner by heating the components (3,6-dihydroxy- naphthalic acid anhydride and di- or tetraamine) in water optionally acidified with catalytical amounts of acid or a solvent, for example acetic acid, ethanol, dimethylformamide or N-methylpyrrolidone.
The reaction is completed after several hours at elevated temperature, pre-ferably at 80 - 150 C. It may be easily followed by chromatography. In general, the perinone compounds formed of the formula I precipitate from the reaction mixture and are isolated by filtration. The addition of water prior to the isolation may sometimes be of advantage, because some of the compounds ; of the invention show a tendency to delay crystallization.
In some cases, for example with very unstable aromatic di- or tetra-amines, it may be of advantage to condense, instead of the free base, a mineral acid salt thereof with 3,6-dihydroxynaphthalic acid anhydride, in which case the addition of an acid-binding agent, for example alkali metal carbonate or acetate, warrants a particularly smooth reaction.
In the same manner, a condensation of the 3,6-dihydroxynaphthalic acid anhydride under comparable reaction conditions with the o-nitroaniline ' 1082~32 from which the unstable diamino compound is derived to the resulting 3,6-dihydroxynaphthalic acid imide may be of advantage, whereupon a reaction of the nitro-group standing in ortho-position to the imide-nitrogen, for example by catalytical or iron reduction is followed and whereupon, in general, the o-amino-group formed spontaneously closes the imidazole ring under separation of water. Heating for several hours to elevated temperatures to effect cyclization has been found necessary only in some cases with kinetically partic-ularly disadvantageous conditions.
The perinones of formula I have been found to be valuable dyes, in particular valuable pigments that may be used in finely dispersed form, in-dividually or as mixtures, for the pigrnentation of high molecular organic materials, for example for cellulose ethers and cellulose esters, for example ethyl cellulose, cellulose acetate, cellulose butyrate, for polyamides or polyurethanes or polyesters, natural or synthetic resins such as those resins obtained by polymerization, for example aminoplasts, in particular urea-form-aldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, poly-carbonates, for polyolefins such as polystyrene, polyvinyl chloride, poly-ethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, for rubber, casein, silicone and silicon resins.
The perinones of formula I have already valuable tinctorial properties.
But in many cases, their properties regarding application may often be improved by an usual pigment finish~ for example by prolonged heating in water and/or solvents, by distribution by grinding or kneading in the presence of salts, solvents or dispersants.
The high molecular materials to be dyed may be masses of plastic in .~
. . -.
the form of melts or of spinning solutions, lacquers, paints or printing inks.
The pigments may be used in the form of a pure pigment powder or in ~he form of a dispersion of pigment in a resin. The resins which are suitable for use as carriers in pigment dispersions are natura] resins, for example abietic acid or the esters thereof, ethyl cellulose, cellulose acetobutyrate, alkaline earth metal salts of higher fatty acids~ fatty amines~ for example stearyl amine or colophonium-amine, vinyl chloride/vinyl-acetate copolymers, polyacrylonitrile or polyterpene resins or water-soluble resins, for example resins containi~g sulfonic acid groups or their alkaline earth metal salts.
The next comparable compound of the mono-hydroxy-naphthoylene-benzimidazole series(known from '~Journal of the Society of Dyers and Colour-ists", Vol. 85 (1969), page 249) is a typical disperse dyestuff and carnot be used as pigment because of its insufficient fastness to bleeding and to over-lacquering.
Thus~ it was surprising and not foreseeable that the introduction of an additional hydroxy group would result in such considerable modifications of the properties. In addition to a high tinctorial strength, the pigments are distinguished : B
- 1082~32 by an excellent fastness to light, very good purity of colour shade and, in general, valuable colouristic and utilization properties, in particular by a surprisingly high fastness to solvents and plastizisers, for example a very good fastness ~o bleeding, overlacquering, migration and blooming. In view of these properties and by reason of their easy accessibility, these com-pounds represent a considerable technical advance.
The following Examples illustrate the invention, parts are by weight.
EXAMPLE 1:
A mixture of 2700 parts of glacial acetic acid, 130 parts of 3,6-dihy-droxynaphthalic acid anhydride and 67.3 parts of o-phenylene-diamine was heated, while stirringJ for 5 - 6 hours, to the boiling temperature ~ ~ 115 - 120 C). The reaction mixture was allowed to cool, the dyestuff of the formula >~
Q N N
H0 ~ OH
that had precipitated was filtered off with suction, washed with water until neutrality and dried at 80 C. 165 Parts (= 97% of the theory) of a yellow pigment were obtained; the pigment was found to be excellently suitable for the dyeing of synthetics and plastic masses and yielded dyeings with excellent fastness properties.
Better fastness properties, in particular very good fastness to bleeding and overlacquering, were obtained when stirring the water-wet pigment before drying for 5 hours with the 5-fold amount of dimethylformamide at 100 - 110 C, . ~-.,. ,, ; , - -iO8Z~3Z
filtering it off while hot, washing it with water and drying it.
If, instead of glacial acetic acid, the same quantities of formic acicl were used, the pigment was formed with comparable yields and showed the same fastness properties.
~X~MPLe 2:
23 Parts o 3,6-dihydroxynaphthalic acid anhydride, 17.4 parts of 1,8-naphthylene-diamine and S parts of propionic acid were stirred consecu-tively into 250 parts of water and the mixture so obtained was heated for 8 hours in an autoclave to 130 - 140 C, whereupon a pressure of 3 - 4 atmos-pheres rose up. The mixture was then cooled, the pressure was released and - the compound formed of the formula ;; ~ .
~IO ~ OH
was filtered off with suction, washed with water and dried at 100 C. 35 Parts (= 99% of the theory) of a red pigment were obtained, which pigment was found to be excellently suitable for the preparation of printing inks, lac-quers and paints and permits, in these fields of application, dyeings with high colour intensity and excellent properties of fastness.
When the 1,8-naphthylene-diamine was replaced by a corresponding amount of 4-methoxy-1,8-naphthylene-diamine, there was obtained a somewhat more bluish pigment having comparable properties of fastness and higher tinctorial strength.
-::.
.
, Z~32 F:XA~JPLE 3:
23 Parts of 3,6-dihydroxynaphthalic acid anIIydride, 25,3 parts of 2,4-diaminoanisole-dicIIlorohydrate, 400 parts of iso-propanol and 20.5 par~s of sodium acetate were heat~ in an autoclave for 10 hours to 140 _ 145 C. After coolin~, the pressurc was rcleased and the dyestuf f obtained was filtered off with suction. Af~er washing with isopropanol and water, the dyestuff was dried at 80 C.
31 Parts (= 93.4 % of the theory) of an orange yellow pigment were obtained which was found to be suita~le for the preparation of light and weather fast lacquers as well as for the colouring of plastizised polyvinyl chloride. Subsequent heating for 5 hours of the water-wet filter cake with the 10-fold amound of a mixture of 9 parts of water and 1 part of isobutanol to 150 C yielded a pigment which had increased covering power and improved fastness to li~ht and to weather.
~ XA~IPLE 4:
23 Parts of 3,6-dihydroxynaphthalic acid anhydride and 18 parts of 3-nitro-4- aminobenzonitrile were introduced into 400 parts of 95% acetic acid and the mixture was then heated to 90 C. After 2 lIours~ the nitroimide of the formula CN
~2 0~0 ~ ~ ~ ~ ~ OH
separated. Then, 14 parts of iron po~rrder we-re added portionwise 1~)82832 within 2 nours. The reaction was exothermic and took place at 100 C. The wll~le was heated for 3 hours to 100 - 105 C, dliluted with 600 parts of water and filtered with suction while hlot, The filter cake which was still contaminated with basic iron ~c~tate was then introduced into 1000 parts o~ dimethyl~
formamide and heated to the boilin~ temperature. After addition of 5 parts of active carbon, the mixture was filtered with suction through a clarifying filter, the filtrate was cooled to 50 C while stirring and the compound of the formula CN
~ .
O ~ '~
}10 ~~ C'i whlch had precipitated was filtexed off, ~ashed with water and dried, 30 Parts of a greenish-yellow pigment (= 91.7% of the theory) were obtained; the pigment was found to have an excellent fastness to light and to be excellently suitable for : the preparation of lacquers, in particular lacquers with ` metallic effect.
The reduction of the intermediarily formed nitroimide may be effected with the sams result catalytically with hydrogen, which also induces spontaneous cyclization to th~ compound of the invention.
:: For this purpose, the o-nitroimide isolated ~y filtration .vas heated in 1500 parts of dimethylformamide with addi.tion of 1 part of a nickel catalyst and under a hydrogen pressure of 50 atmospheres gau~e to 130 C~, until no absorption of gas ~as 10~2~32 stated. The pressure was released, the mixture was filtered while hot to remove the catalyst and the filtrate was cooled, while stirring, to 50 C, whcroupon the pigment separated. Its isolation was effected as described abovo.
EXAMPLES 5 ~
When replacing in Example 4 the 3-nitro-4-amino-benzo-nitrile by aliquot amounts of other o-nitranilines and working in the manner described, there were obtained other pigments of the invention corresponding to the general formula ' ~ .
O N N
110 ~ 0}~
with the yields and shades indicated in table l.
T a b l e Example X Yield Shade Cl 96.3 % greenish yellow 6 -OC2H5 97.5 % orange 7 -NHCOCH3 98.5 % orange red 8 CH3 94.8 % yellow 9 Br 98.l % greenish yellow 2 3 96.5 % greenish yellow ll OH 93.0 % reddish yellow :
~08283Z
ExAr.lPLE 12:
23 Parts of 3,6-dihydroxynaphthallc acid anhydride, 18.3 parts o~ 3,4-diaminobenzoic acid and lS0 parts o~ N-methylpyrro-lidone were stirred, 5 parts of formic acid were added and the mlxture was heated for 5 hours to 120 - 130 C. The precipitate .
of the compound oi the ~ormula ~,OO
.' ~10 ~ Ojl formed was completed by the addition of 200 parts of water, the ocompound was filtered off with suction, washed witll water and dried.
33.8 Parts (97,7 % of the theory) of a greenish-yellow pigm::nt were obtained; after grinding with a salt, in particular with the 5-fold amount of sodium sul~ate, this pigment was found to be particularly suitable for the preparation of transparent lacquers.
- The following Tables 2 to 5 show other compounds of the ~ormulae II to V of the invention which had been prepared according to one o~ the processes of the invention, in particular in a manner analogous to that described in the foregoing Examples, and indicate also the corresponding yields and shades, _ 14 -. _ .
,.. ' ~ ~
108Z~32 T a b 1 e 2 (Dyestuffs of the formula II) Examplo A1 Yield Shade cll3 1.; ~ 96.8 % Yellow ~H3 14 ~ ~ 94.8 % yellow )~ , F
~ greenish ~ 91.9 % yellow : CH3-CH
16 ~ 89.5 % yellow :` .
- ., .
1082~32 Example Al Yield Shade Cl Cl 17 ~ 98.5 % greenish yellow 18 ll7C30 ~ 92.8 % yellow 19 ~ 97.0 % orange ~ .
~ 98.3 % reddish yellow . ~I
N2 ~
21 ~ 98.6 % greenish yellow 22 NHCO ~ 98.0 % orange ~ .,.
>=<
CN
23 ~ 94.8 % greenish yellow 24 ~ 9l.9 % g~eenish yellow .~ - 16 -1082~32 E.~an~ple Al Yield Shade _ . _ COOC4~l9 2S ~ 89.8 % greenish yellow 26 ~ 99.0 % greenish yellow.
,N 2 27 97.8 % greenish yellow - CONH
~, C 2H5 28 . S02N 96.9 % greenish yellow 2~1S' )~< ' ~: 29 ~ 94.5 % yellow ~ 92.8 % rellow 31 o = ~ o 93.7 % red orenge D
`
` -. ~ , .
~. ` .-.
- ~ . .
, . .
1082~32 Example Al Yield Shade /~
32 ~ -o 93.0 % y~llow ~, 33 ~ 94.5 % yellow 34 ~ ~ 94.~ % yellow T a b l e 3 Example A2 Yield Shade .
~ 35 ~ 96.8 % bluish red :~ CH2- CH2 36 ~ 95.5 % red . ' .
' :
10~2832 Example A2 Yield Shade 502N~ ~ 99.1 ~ bluish red OC2"5 38 ~ 95.8 ~ red T a b l e 4 (Dyestuffs of the formula IV) Example B Yield Shade N,H ~' 39 5 ~ H 95.0 ~ yel10w NH~
0 ~ NH 94.9 % yellow NH~
41 0 ~NH 98.3 % yellow :......................................... . . . .
., ` .
: ' .
1~lgZ~32 T a b 1 e 5 (Dyestuffs of the formula V) E~mple ~ X ~ Yield Shade 42 ~ 97.2 ~ yellow NHCO
43 ~ ~ 95.9 % orange ~ NHCONH ~
44 ~ ~ 98.7 % orange ~' ~ ~ 94.5 % greenish yellow 2 ~ ~ yellow -: , :, :
- - , : :.
.
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the dyeing of high molecular weight organic polymers wherein a pigment which is a perinone compound of the general formula (I) in which A represents an ortho- or peri-arylene radical selected from the benzene, naphthalene or anthracene series or a 5- or 6-membered heterocyclic radical containing 1 or 2 nitrogen atoms, and X represents hydrogen or a direct bond or a straight or branched alkylene of 1 to 6 carbon atoms, a vinylene radical or a bridging member of the formula -CO-, -CONH-,-NH-CO-NH-, -CO-?-CO-, -NH-CO-NH-CO-, -CONH-Y-NHCO-, -NHCO-Y-CONH-n represents the number 1 or 2 and m = 1 if n = 1, and m = 0 if n = 2, R re-presents hydrogen or lower alkyl and Y represents lower alkylene or phenylene, is incorporated into the polymer melt, spinning solution, lacquer, paint or printing ink.
2. A process as defined in claim 1 wherein the perinone compound is of the formula wherein A1 is phenylene which is unsubstituted or substituted by 1 or 2 sub-stituents selected from fluorine, chlorine, bromine, lower alkyl, lower alkoxy, phenyl, phenoxy, hydroxy, benzyloxy, lower alkanoylamino, benzoylamino, lower alkylsulfonyl, nitro, nitrile, trifluoromethyl, carboxy, carbalkoxy of 2 to 5 carbon atoms and carboxylic or sulfonic acid amide which is unsubstituted or substituted at the nitrogen by 1 or 2 radicals selected from lower alkyl, phenyl or nitrophenyl; or wherein A1 is a group of the formula , , or
3. A process as defined in claim 1, wherein the perinone compound is of the formula wherein A2 is naphthalene or acenaphthene which are unsubstituted or substi-tuted by fluorine, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy, phenoxy, nitro, lower alkanoyl, benzoyl, lower alkanoylamino or benzoylamino or carbamoyl or sulfamoyl, which are unsubstituted or substituted at the nitro-gen by 1 or 2 substituents selected from lower alkyl and phenyl.
4. A process as defined in claim 1, wherein the perinone compounds of the formula wherein B represents a bridge member forming together with the two carbon atoms to which it is linked a 5- or 6-membered ring which bridge member consists of carbon and up to 2 nitrogen atoms.
5. A process as defined in claim 4, wherein the bridge member consists of 2 -NH- and 2 groups selected from -CO- and -CS-.
6. A process as defined in claim 1, wherein the perinone compound is of the formula wherein X is a direct bond, alkylene of 1 to 6 carbon atoms, vinylene or a group of the formula -CO-, -CO-NH-, -NH-CO-NH-, -CO-NR-CO-, -NH-CO-NH-CO-, -CO-NH-Y-NH-CO- or -NH-CO-Y-CO-NH-in which R is hydrogen or lower alkyl, Y is lower alkylene or phenylene and wherein the phenyl nuclei marked with "a" may be substituted by chlorine, lower alkyl or lower alkoxy.
7. A process as defined in claim 2 wherein A1 is a group of the formula
8. A process as defined in claim 1, wherein the high molecular weight organic polymer to be dyed is a cellulose ether, cellulose ester, polyamide, polyurethane, polyester, resin, polycarbonate, polyolefin, poly-acrylonitrile, polyacrylic acid ester, plastic mass, lacquer, paint or printing ink.
9. A process as defined in claim 1, wherein the high molecular weight organic polymer to be dyed is a polyolefin, polyester; lacquer, paint or printing ink.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2447228.4 | 1974-10-03 | ||
| DE19742447228 DE2447228A1 (en) | 1974-10-03 | 1974-10-03 | PERINON COMPOUNDS, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE AS A COLOR |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082832A true CA1082832A (en) | 1980-07-29 |
Family
ID=5927449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,904A Expired CA1082832A (en) | 1974-10-03 | 1975-10-02 | Perinone compounds, process for preparing them and their use as dyes |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5163823A (en) |
| BR (1) | BR7506450A (en) |
| CA (1) | CA1082832A (en) |
| DE (1) | DE2447228A1 (en) |
| FR (1) | FR2286864A1 (en) |
| GB (1) | GB1522683A (en) |
| IT (1) | IT1043040B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH650523A5 (en) * | 1979-10-25 | 1985-07-31 | Sandoz Ag | Phthaloperinon dyes. |
| FR2620713B1 (en) * | 1987-09-23 | 1992-04-17 | Sandoz Sa | MASS DYEING PROCESS FOR SYNTHETIC POLYAMIDES |
| EP1453902A1 (en) * | 2001-07-26 | 2004-09-08 | Ciba Specialty Chemicals Holding Inc. | Method of mass-colouring synthetic materials |
-
1974
- 1974-10-03 DE DE19742447228 patent/DE2447228A1/en not_active Withdrawn
-
1975
- 1975-10-01 IT IT2785675A patent/IT1043040B/en active
- 1975-10-02 JP JP11830975A patent/JPS5163823A/en active Pending
- 1975-10-02 CA CA236,904A patent/CA1082832A/en not_active Expired
- 1975-10-03 BR BR7506450A patent/BR7506450A/en unknown
- 1975-10-03 FR FR7530316A patent/FR2286864A1/en active Granted
- 1975-10-03 GB GB4066575A patent/GB1522683A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2286864B1 (en) | 1980-08-14 |
| DE2447228A1 (en) | 1976-04-22 |
| IT1043040B (en) | 1980-02-20 |
| FR2286864A1 (en) | 1976-04-30 |
| GB1522683A (en) | 1978-08-23 |
| BR7506450A (en) | 1976-08-10 |
| JPS5163823A (en) | 1976-06-02 |
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