CA1148955A - Cationic compounds of the naphthalimide series, process for their preparation and their use - Google Patents
Cationic compounds of the naphthalimide series, process for their preparation and their useInfo
- Publication number
- CA1148955A CA1148955A CA000364150A CA364150A CA1148955A CA 1148955 A CA1148955 A CA 1148955A CA 000364150 A CA000364150 A CA 000364150A CA 364150 A CA364150 A CA 364150A CA 1148955 A CA1148955 A CA 1148955A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- compounds
- alkyl
- cationic compounds
- denotes
- 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
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Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention provides cationic compounds of the formula (I) (I) in which R denotes alkyl, hydroxyalkyl, alkoxyalkyl, phenylalkyl, or phenoxyalkyl, R' denotes alkyl, hydroxyalkyl,benzyl, or allyl and X(-) denotes a colorless anion, a process for their manufacture and their use.
The compounds of the invention can be used for brightening organic materials such as cotton and synthetic fibers.
The invention provides cationic compounds of the formula (I) (I) in which R denotes alkyl, hydroxyalkyl, alkoxyalkyl, phenylalkyl, or phenoxyalkyl, R' denotes alkyl, hydroxyalkyl,benzyl, or allyl and X(-) denotes a colorless anion, a process for their manufacture and their use.
The compounds of the invention can be used for brightening organic materials such as cotton and synthetic fibers.
Description
~8~;5 Cation optical brighteners of the naphthalimide series containing quaternary nitrogen atoms are known. French Patent 1,557,945 describes cationic naphthalimide derivatives containing trialkylammonium radicals bound to the imide nitrogen via a chain of two or three methylene groups.
The present invention provides novel cationic compounds of the formula (1) CIH3 (+) / 3 lH2 C - CH2 - IN ~ CH3 X~
~j in which OR
R denotes alkyl, hydroxyalkyl, alkoxyalkyl,phenylalkyl,or phenoxyalkyl, Rl denotes alkyl, hydroxyalkyl, benzyl, or allyl and X( ) denotes a colorless anion.
The radicals R and R' preferably contain ] to 4 carbon atoms in the alkyl or alkoxy gIOUpS and are, for example, ethyl, propyl, butyl, hydroxyethyl, methoxyethyl, ethoxyethyl, propoxyethyl, phenoxyethyl, or benzyl and, in par-ticular, methyl because of the favorable manufacturing conditions. X( ) stands, for example, for a halide, alkyl sulfonate, alkyl sulfate, alkylphenyl sulfonate, or phenyl sulfonate ion.
Compounds of the formula (1) are manufactured in known manner by alkylation of a compound of the formula ~2) CIH3 ~ ~ CH3 CH2 Cl CH2 N ~ (2) o~N~ CH3 3 OR
: .
' . , ; :
, .
- 3 - ~OE 79/F 295 with a compound of the formula X - R'.
The alkylation is preferably carried out in a suitable inert organic solvent such as toluene, xylene, chlorobenzene, dimethylformamide, or tetralin, at a temperature in the range of from room temperature to 100C, preferably room temperature to 60C.
The naphthalimides of the formula (2) used as starting materials are obtained by reaction of the 4-chloro- or 4-bromo-naphthalic anhydrides with N,N,2,2-tetramethylpropane-1,3-diamine (dimethylamino-neopentylamine) to give the corresponding N-(2,2-dimethyl-3-dimethylaminopropyl)-4-halogenonaphthalimides with subsequent exchange of the halogen atoms by reaction with alcohols of the formula HOR
or their alkali metal salts.
The novel compounds can be used for brightening organic materials such as cotton and, above all, for synthetic fibers, for example of polyamides such as polymers on the basis of hexamethylene-diamino-adipate or caprolactam, cellulose esters such as cellulose-2 1/2 acetate and cellulose triacetate, and preferably polyacrylonitrile.
For brightening the organic materials a small amount of optical brightener according to the invention, preferably 0.001 to 1 ~, calculated on the material to be brightened, is incorporated therein, optionally together with other substances such as plasticizers, stabilizers or pigments. The brighteners can be incorporated, into the plastic material,for example, in the form of a solution in a plasticizer, for example dioctyl phthalate, or together with a stabilizer, for example dibutyl tin dilaurate or sodium pentaoctyl tripolyphosphate, or together with pig-ments, for example titanium dioxide. Depending on the material to be brightened, it is also possible to dissolve the brightener in the monomers prior to polymerization, in the polymer mass, or in a solvent together with the polymer.
The material pretreated in the above manner is then transformed into the desired final shape by processes known per se, such as spinning and drawing. Alternatively, the , . . .
' ' ' ' ' :, ~' :
~ . . ...................................................... .
, s brightener carl be incorporated into finishing agents, for example those ~or textile fibers, such as polyvinyl alcohol, or into resins or resin precondensates such as methylol compounds of ethylene urea, used for textile treatment.
The compounds of the invention are also suitable to br:Lghten the surface coat of paper. It is preferable, however, to brighten therewith colorless, high molecular weight organic materials in the form of fibers. For brightening , said fiber materials it proved advantageous to use an aqueous solution of the compounds of formula (1) according to the invention. The solutions preferably contain from 0.005 to 0.5 ~ of naphthalimides of the invention, calcu-lated on the fiber material. The solutions may further contain auxiliaries such as dispersing agents, for example condensation products of C10-C18 fatty alcohols or alkyl-phenols with 15 to 25 moles of ethylene oxide or condensation products,of, C16-C18alkyl,mono- or polyamines with at least 10 mols of ethylene oxide, organic acids such as formic acid, oxalic acid or acetic acid, detergents, swelling agents such as di- or trichlorobènzenes, wetting agents such as sulfo-succinic acid alkyl esters, bleaching agents such as sodium chlorite, peroxides or hydrosulfites, retarders and optionally other brighteners of the same or another series, for example derivatives of stilbene having an affinity for cellulose.
The fiber material is brightened with the aqueous brightener bath either by an exhaust process at temperatures preferably in the range of from 30 to 150C or by a padding process. In the latter case the material is impregnated, for example with a 0.2 to 0.5 % brightener solution and finished by a dry or moist heat treatment, for example by steaming under 2 atmospheres or, after drying, by a short dry heating to 180 to 220C, optionally with simultaneous thermofixation of the fabric. The fiber material treated in this manner is then rinsed and dried.
Colorless, high molecular weight, organic material which has be~n optically brightened according to the invention, in particular natural or synthetic fiber material ~ , ~ . , .
3~5 - 5 - HOE 7g/F 295 that has been briyntened by the exhausiion process, has a pleasant, pure white, blue-violet to blui~h, fluorescent aspect. When dyed light shades and whitened according to the invention the material is distinguished by a clear shade.
When textile fibers, for example of synthetic polyamide and cellulose ester fibers, in particular polyacrylonitrile fibers, are washed with washing liq~lors containing a naphthalimide of the formula (1), the material acquires a brilliant aspect in daylight.
It should ~e stressed that the compounds of the invention have a good stability to light, a high stability to chlorite, a high tinctorial strength and especially a high degree of whiteness and, on the whole, an outstanding tinctorial behavior.
The compounds of the formula (1) containing a quaterna-ry carbon atom in B-position with respect to the quaternary ammonium group-and--i-n B-position with respect to the imide nitrogen are extremely stable. They are distinctly superior as regards the brightening effect, especially in the one-bath chlorite bleaching of polyacrylonitrile fibers, to the above mentioned cationic naphthalimides containing tri-alkylammonium radicals bound to the imide nitrogen via a chain of two or three methylene groups.
The following examples illustrate the invention.
E X A M P L E
For preparing the compound CIH3 l+) CH2 - C~ - Cll2 N(CH3)3 CH30S03 o~; r N ~
3 "' 17 g of ~--methoxy-N-dimethylamino-neopentyl-naphthalimide are dissolved in 100 ml of acetone and 5.2 ml of dimethyl sulfate are added dropwise at room temperature. Stirring of , ~. ' . ' . ', , .
the mixture is continued for 18 hours at room temperature, the mixture is filtered with suction and the residue is washed with acetone. After drying in vacuo at 60C, 21.2 g of a yellowish crystalline powder are obtained, corres-ponding to 91 % of the theoretical. Melting point 231 to233C, sintering point 228C.
The 4-methoxy-N-dimethylamino-neopentyl-naphthalimide required as starting material is prepared as follows: An autoclave with stirrer is charged with 121 g of 4-chloro-naphthalic anhydride and 81.4 ml of dimethylamino-neopentyl-amine in 750 ml of methanol, the autoclave is heated to 70C and kept at said temperature for 5 hours. Next, the autoclave is cooled to 50C, 60 g of 40 ~ sodium hydroxide solution are added and the whole is heated to 100C. The reaction mixture is stirred for 2 hours at the indicated temperature, cooled to room temperature and the precipitated reaction product is filtered off with suction, washed in portions with 500 ml of methanol and then with water. The precipitate is dried in vacuo at 60C. 142.0 g of a yellow powder are obtained melting at 107 to 110C, corresponding to 83.5 ~ of the theoretical.
E X A M P L E _ 0.24 g of sodium chlorite, 0.1 g of a commercial bleaching auxiliary and 0.3 ml of 2N acetic acid are dissolved at 60C in 200 ml of water. A solution is prepared from the optical brightener obtained according to Example 1 by dissolving 0.02 g thereof in 1 ml of dimethyl formamide.
The solution is added to the aqueous bath and the pH of the bath is adjusted to 3,5 by adding dropwise acetic acid (10 ~ strength). 5 g of a polyacrylonitrile fabric are introduced into the aqueous bath containing the brightener and having a temperature of 60C. The fabric is first bleached for 30 minutes at 80C and then for 30 minutes at 100C, whereupon it is rinsed with hot and cold water and dried. The fiber material treated in this manner has a pleasant white aspect with a violet hue. A similar effect is obta~ned by bleaching in the absence of sodium chlorite and bleaching auxiliary and adjusting the pH of the bath to -8~
- 7 - HOE 79/F 2g5 4 with 10 ~ acetic acid.
0.12 ml of 85 ~ formic acid is added to 100 ml of water.
A solution of the optical brightener accordiny to Example 1 is prepared by dissolving 1 g thereof in 100 ml of water.
1.5 ml of the solution obtained are added to the above solution, the mixture obtained in heated to 60C and 3 g of a polyacrylonitrile fabric are introduced. The temperature is raised to 95 to 98C within 10 to 15 minutes and the fabric is treated at said temperature for 1 hour. It is then rinsed for 2 minutes in running cold water and dried at 60C. The treated fabric has a white brilliant aspect.
In the manner described in Example 1 the compounds listed in the following table are prepared .- -CH2 ' 3 CH - N ~ 3 CH3 X( ) O ~ N ~ C~3 ~ _ OR
:
, 8~3S5 R R' X(-)n reaction medium melting point reaction tempe- (purification rature _ agent) _ C2H5- COCH2CH2 Cl( ) 1 2-chloroethanol 204.5C with 128C decomp. (from _ pyridine) CH3CH2CH2 CH3 CH30S03( ) toluene 60C 184 - 192C
_ _. .
3 H2C 2 HOCH2CH2 Cl( ) 2-chloroethanol 113 - 116.5C
_ _ 128C (from ethanol) , ~ _ _ CH3- CH3- CH3C6H5S3 1 toluene 60C 222 - 225C
i ~ _ CH3- C2H5- C2H5S03~ J 1 diethyl sulfate 198 - 200C
50C (from methanol~
_ CH3- HOCH2CH2 Cl( ) 1 2_chloroethanol 218 - 220C with 128C decomp. (from ethanol~
_ CH3- CH3(CH2)3- Br( ) 1 n-butyl bromide 192 - 193C with 102C decomp. (from _ sopro~ol) C2H5- CH3- CH30S03( ) 1 toluene 60C 233 - 237C with decomp. (from n-butanol~
_ I
CH30CH2CH2- CH3 CH30S03( ) 1 ¦toluene 60C 220 - 225C
~ 8 . .
.
.
:
' '.
The present invention provides novel cationic compounds of the formula (1) CIH3 (+) / 3 lH2 C - CH2 - IN ~ CH3 X~
~j in which OR
R denotes alkyl, hydroxyalkyl, alkoxyalkyl,phenylalkyl,or phenoxyalkyl, Rl denotes alkyl, hydroxyalkyl, benzyl, or allyl and X( ) denotes a colorless anion.
The radicals R and R' preferably contain ] to 4 carbon atoms in the alkyl or alkoxy gIOUpS and are, for example, ethyl, propyl, butyl, hydroxyethyl, methoxyethyl, ethoxyethyl, propoxyethyl, phenoxyethyl, or benzyl and, in par-ticular, methyl because of the favorable manufacturing conditions. X( ) stands, for example, for a halide, alkyl sulfonate, alkyl sulfate, alkylphenyl sulfonate, or phenyl sulfonate ion.
Compounds of the formula (1) are manufactured in known manner by alkylation of a compound of the formula ~2) CIH3 ~ ~ CH3 CH2 Cl CH2 N ~ (2) o~N~ CH3 3 OR
: .
' . , ; :
, .
- 3 - ~OE 79/F 295 with a compound of the formula X - R'.
The alkylation is preferably carried out in a suitable inert organic solvent such as toluene, xylene, chlorobenzene, dimethylformamide, or tetralin, at a temperature in the range of from room temperature to 100C, preferably room temperature to 60C.
The naphthalimides of the formula (2) used as starting materials are obtained by reaction of the 4-chloro- or 4-bromo-naphthalic anhydrides with N,N,2,2-tetramethylpropane-1,3-diamine (dimethylamino-neopentylamine) to give the corresponding N-(2,2-dimethyl-3-dimethylaminopropyl)-4-halogenonaphthalimides with subsequent exchange of the halogen atoms by reaction with alcohols of the formula HOR
or their alkali metal salts.
The novel compounds can be used for brightening organic materials such as cotton and, above all, for synthetic fibers, for example of polyamides such as polymers on the basis of hexamethylene-diamino-adipate or caprolactam, cellulose esters such as cellulose-2 1/2 acetate and cellulose triacetate, and preferably polyacrylonitrile.
For brightening the organic materials a small amount of optical brightener according to the invention, preferably 0.001 to 1 ~, calculated on the material to be brightened, is incorporated therein, optionally together with other substances such as plasticizers, stabilizers or pigments. The brighteners can be incorporated, into the plastic material,for example, in the form of a solution in a plasticizer, for example dioctyl phthalate, or together with a stabilizer, for example dibutyl tin dilaurate or sodium pentaoctyl tripolyphosphate, or together with pig-ments, for example titanium dioxide. Depending on the material to be brightened, it is also possible to dissolve the brightener in the monomers prior to polymerization, in the polymer mass, or in a solvent together with the polymer.
The material pretreated in the above manner is then transformed into the desired final shape by processes known per se, such as spinning and drawing. Alternatively, the , . . .
' ' ' ' ' :, ~' :
~ . . ...................................................... .
, s brightener carl be incorporated into finishing agents, for example those ~or textile fibers, such as polyvinyl alcohol, or into resins or resin precondensates such as methylol compounds of ethylene urea, used for textile treatment.
The compounds of the invention are also suitable to br:Lghten the surface coat of paper. It is preferable, however, to brighten therewith colorless, high molecular weight organic materials in the form of fibers. For brightening , said fiber materials it proved advantageous to use an aqueous solution of the compounds of formula (1) according to the invention. The solutions preferably contain from 0.005 to 0.5 ~ of naphthalimides of the invention, calcu-lated on the fiber material. The solutions may further contain auxiliaries such as dispersing agents, for example condensation products of C10-C18 fatty alcohols or alkyl-phenols with 15 to 25 moles of ethylene oxide or condensation products,of, C16-C18alkyl,mono- or polyamines with at least 10 mols of ethylene oxide, organic acids such as formic acid, oxalic acid or acetic acid, detergents, swelling agents such as di- or trichlorobènzenes, wetting agents such as sulfo-succinic acid alkyl esters, bleaching agents such as sodium chlorite, peroxides or hydrosulfites, retarders and optionally other brighteners of the same or another series, for example derivatives of stilbene having an affinity for cellulose.
The fiber material is brightened with the aqueous brightener bath either by an exhaust process at temperatures preferably in the range of from 30 to 150C or by a padding process. In the latter case the material is impregnated, for example with a 0.2 to 0.5 % brightener solution and finished by a dry or moist heat treatment, for example by steaming under 2 atmospheres or, after drying, by a short dry heating to 180 to 220C, optionally with simultaneous thermofixation of the fabric. The fiber material treated in this manner is then rinsed and dried.
Colorless, high molecular weight, organic material which has be~n optically brightened according to the invention, in particular natural or synthetic fiber material ~ , ~ . , .
3~5 - 5 - HOE 7g/F 295 that has been briyntened by the exhausiion process, has a pleasant, pure white, blue-violet to blui~h, fluorescent aspect. When dyed light shades and whitened according to the invention the material is distinguished by a clear shade.
When textile fibers, for example of synthetic polyamide and cellulose ester fibers, in particular polyacrylonitrile fibers, are washed with washing liq~lors containing a naphthalimide of the formula (1), the material acquires a brilliant aspect in daylight.
It should ~e stressed that the compounds of the invention have a good stability to light, a high stability to chlorite, a high tinctorial strength and especially a high degree of whiteness and, on the whole, an outstanding tinctorial behavior.
The compounds of the formula (1) containing a quaterna-ry carbon atom in B-position with respect to the quaternary ammonium group-and--i-n B-position with respect to the imide nitrogen are extremely stable. They are distinctly superior as regards the brightening effect, especially in the one-bath chlorite bleaching of polyacrylonitrile fibers, to the above mentioned cationic naphthalimides containing tri-alkylammonium radicals bound to the imide nitrogen via a chain of two or three methylene groups.
The following examples illustrate the invention.
E X A M P L E
For preparing the compound CIH3 l+) CH2 - C~ - Cll2 N(CH3)3 CH30S03 o~; r N ~
3 "' 17 g of ~--methoxy-N-dimethylamino-neopentyl-naphthalimide are dissolved in 100 ml of acetone and 5.2 ml of dimethyl sulfate are added dropwise at room temperature. Stirring of , ~. ' . ' . ', , .
the mixture is continued for 18 hours at room temperature, the mixture is filtered with suction and the residue is washed with acetone. After drying in vacuo at 60C, 21.2 g of a yellowish crystalline powder are obtained, corres-ponding to 91 % of the theoretical. Melting point 231 to233C, sintering point 228C.
The 4-methoxy-N-dimethylamino-neopentyl-naphthalimide required as starting material is prepared as follows: An autoclave with stirrer is charged with 121 g of 4-chloro-naphthalic anhydride and 81.4 ml of dimethylamino-neopentyl-amine in 750 ml of methanol, the autoclave is heated to 70C and kept at said temperature for 5 hours. Next, the autoclave is cooled to 50C, 60 g of 40 ~ sodium hydroxide solution are added and the whole is heated to 100C. The reaction mixture is stirred for 2 hours at the indicated temperature, cooled to room temperature and the precipitated reaction product is filtered off with suction, washed in portions with 500 ml of methanol and then with water. The precipitate is dried in vacuo at 60C. 142.0 g of a yellow powder are obtained melting at 107 to 110C, corresponding to 83.5 ~ of the theoretical.
E X A M P L E _ 0.24 g of sodium chlorite, 0.1 g of a commercial bleaching auxiliary and 0.3 ml of 2N acetic acid are dissolved at 60C in 200 ml of water. A solution is prepared from the optical brightener obtained according to Example 1 by dissolving 0.02 g thereof in 1 ml of dimethyl formamide.
The solution is added to the aqueous bath and the pH of the bath is adjusted to 3,5 by adding dropwise acetic acid (10 ~ strength). 5 g of a polyacrylonitrile fabric are introduced into the aqueous bath containing the brightener and having a temperature of 60C. The fabric is first bleached for 30 minutes at 80C and then for 30 minutes at 100C, whereupon it is rinsed with hot and cold water and dried. The fiber material treated in this manner has a pleasant white aspect with a violet hue. A similar effect is obta~ned by bleaching in the absence of sodium chlorite and bleaching auxiliary and adjusting the pH of the bath to -8~
- 7 - HOE 79/F 2g5 4 with 10 ~ acetic acid.
0.12 ml of 85 ~ formic acid is added to 100 ml of water.
A solution of the optical brightener accordiny to Example 1 is prepared by dissolving 1 g thereof in 100 ml of water.
1.5 ml of the solution obtained are added to the above solution, the mixture obtained in heated to 60C and 3 g of a polyacrylonitrile fabric are introduced. The temperature is raised to 95 to 98C within 10 to 15 minutes and the fabric is treated at said temperature for 1 hour. It is then rinsed for 2 minutes in running cold water and dried at 60C. The treated fabric has a white brilliant aspect.
In the manner described in Example 1 the compounds listed in the following table are prepared .- -CH2 ' 3 CH - N ~ 3 CH3 X( ) O ~ N ~ C~3 ~ _ OR
:
, 8~3S5 R R' X(-)n reaction medium melting point reaction tempe- (purification rature _ agent) _ C2H5- COCH2CH2 Cl( ) 1 2-chloroethanol 204.5C with 128C decomp. (from _ pyridine) CH3CH2CH2 CH3 CH30S03( ) toluene 60C 184 - 192C
_ _. .
3 H2C 2 HOCH2CH2 Cl( ) 2-chloroethanol 113 - 116.5C
_ _ 128C (from ethanol) , ~ _ _ CH3- CH3- CH3C6H5S3 1 toluene 60C 222 - 225C
i ~ _ CH3- C2H5- C2H5S03~ J 1 diethyl sulfate 198 - 200C
50C (from methanol~
_ CH3- HOCH2CH2 Cl( ) 1 2_chloroethanol 218 - 220C with 128C decomp. (from ethanol~
_ CH3- CH3(CH2)3- Br( ) 1 n-butyl bromide 192 - 193C with 102C decomp. (from _ sopro~ol) C2H5- CH3- CH30S03( ) 1 toluene 60C 233 - 237C with decomp. (from n-butanol~
_ I
CH30CH2CH2- CH3 CH30S03( ) 1 ¦toluene 60C 220 - 225C
~ 8 . .
.
.
:
' '.
Claims (3)
1. Cationic compounds of the formula (1) (1) in which R denotes alkyl, hydroxyalkyl, alkoxyalkyl, phenyl-alkyl, or phenoxyalkyl, R' denotes alkyl, hydroxyalkyl, benzyl, or allyl and X(-)denotes a colorless anion.
2. Process for the manufacture of compounds of the formula (1) as claimed in claim 1, which comprises alkylating a compound of the formula (2) (2) with a compound of the formula X - R'.
3. Process of optical brightening which consists in apply-ing a compound as claimed in claim 1 onto the material to be brightened.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2944867.7 | 1979-11-07 | ||
| DE19792944867 DE2944867A1 (en) | 1979-11-07 | 1979-11-07 | CATIONIC COMPOUNDS OF THE NAPHTHALIMIDE SERIES, METHOD FOR THE PRODUCTION AND USE THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148955A true CA1148955A (en) | 1983-06-28 |
Family
ID=6085316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000364150A Expired CA1148955A (en) | 1979-11-07 | 1980-11-06 | Cationic compounds of the naphthalimide series, process for their preparation and their use |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0028777B1 (en) |
| JP (1) | JPS5676459A (en) |
| AR (1) | AR224787A1 (en) |
| AT (1) | ATE2896T1 (en) |
| AU (1) | AU534463B2 (en) |
| BR (1) | BR8007198A (en) |
| CA (1) | CA1148955A (en) |
| DE (2) | DE2944867A1 (en) |
| ES (1) | ES8200349A1 (en) |
| MX (1) | MX152119A (en) |
| PT (1) | PT72029B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3535496A1 (en) * | 1985-10-04 | 1987-04-16 | Bayer Ag | METHOD FOR FLUORESCENT EXTINGUISHING AND NEW CATIONIC NAPHTHALINE PERI DICARBONIC ACID IMID DERIVATIVES |
| DE3604827A1 (en) * | 1986-02-15 | 1987-08-20 | Bayer Ag | ELECTROPHOTOGRAPHIC TONER |
| DE3618458A1 (en) * | 1986-06-02 | 1987-12-03 | Hoechst Ag | NAPHTHALIMIDES CONTAINING SULFURIC ACID ESTER GROUPS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3635711A1 (en) * | 1986-10-21 | 1988-04-28 | Knoll Ag | 5-NITROBENZO (DE) ISOCHINOLIN-1,3-DIONE, THEIR PRODUCTION AND USE |
| JP5480991B1 (en) * | 2013-04-02 | 2014-04-23 | 美津濃株式会社 | Fluorescent whitening highly cross-linked polyacrylate fiber, method for producing the same, and fiber structure including the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB962019A (en) * | 1961-04-12 | 1964-06-24 | Mitsubishi Chem Ind | Naphthalimide optical whitening agents |
| FR1541050A (en) * | 1967-08-11 | 1968-10-04 | Ugine Kuhlmann | New optical brighteners, their preparation and applications |
| DE2430566A1 (en) * | 1974-06-26 | 1976-01-15 | Basf Ag | MIXTURES OF COMPOUNDS OF THE NAPHTHALIMIDE SERIES |
-
1979
- 1979-11-07 DE DE19792944867 patent/DE2944867A1/en not_active Withdrawn
-
1980
- 1980-10-31 EP EP80106703A patent/EP0028777B1/en not_active Expired
- 1980-10-31 AT AT80106703T patent/ATE2896T1/en not_active IP Right Cessation
- 1980-10-31 DE DE8080106703T patent/DE3062551D1/en not_active Expired
- 1980-11-03 ES ES496509A patent/ES8200349A1/en not_active Expired
- 1980-11-05 AR AR283132A patent/AR224787A1/en active
- 1980-11-06 AU AU64125/80A patent/AU534463B2/en not_active Ceased
- 1980-11-06 JP JP15525380A patent/JPS5676459A/en active Granted
- 1980-11-06 CA CA000364150A patent/CA1148955A/en not_active Expired
- 1980-11-06 PT PT72029A patent/PT72029B/en unknown
- 1980-11-06 MX MX184634A patent/MX152119A/en unknown
- 1980-11-06 BR BR8007198A patent/BR8007198A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE2896T1 (en) | 1983-04-15 |
| AU6412580A (en) | 1981-05-14 |
| AU534463B2 (en) | 1984-02-02 |
| PT72029A (en) | 1980-12-01 |
| JPS644544B2 (en) | 1989-01-26 |
| ES496509A0 (en) | 1981-10-16 |
| ES8200349A1 (en) | 1981-10-16 |
| MX152119A (en) | 1985-05-30 |
| JPS5676459A (en) | 1981-06-24 |
| BR8007198A (en) | 1981-05-12 |
| AR224787A1 (en) | 1982-01-15 |
| EP0028777A1 (en) | 1981-05-20 |
| DE2944867A1 (en) | 1981-05-27 |
| EP0028777B1 (en) | 1983-03-30 |
| DE3062551D1 (en) | 1983-05-05 |
| PT72029B (en) | 1982-01-26 |
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