JPH0148303B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to new dyes containing imidazolyl methylene groups and their use. The new dye has the general formula [In the formula, R ¹ and R ² are independently a hydrogen atom or a C ₁ -C ₄ -alkyl group, R ³ is a hydrogen atom, and R ⁴ is a C ₁
~ _C4 -alkyl group or hydroxy- _C2 - _C4 -alkyl group, (n+m) is 1 to 4, X is the equivalent of the anion, F is (a) aromatic carbocyclic diamine, β-naphthol, its derivative or (b) A product obtained by coupling an aromatic carbocyclic diamine to a pyrazolone-5-compound; (c) A product obtained by coupling an optionally substituted aminoazobenzole to a pyrazolone-5-compound. The product coupled with (d) the following formula (In the formula, Q is the following formula

[Formula] or

Residue of [Formula], B ¹ is hydrogen atom or methyl group, B ² is hydrogen atom, methyl group or ethyl group, S′ is sulfonic acid or hydrogen atom, B ³
is a hydrogen atom, a hydroxyl group, an amino group, a 2-hydroxyethylamino group, a methylamino group or a phenylamino group, ^B4 is a hydrogen atom, an acetyl group or an N-phenylcarbamoyl group, ^B5 is a hydrogen atom, a hydroxyl group,
Methyl group, methoxy group, chlorine atom, bromine atom, 2
- means a hydroxyethylamino group or a dimethylamino group, in which case B ³ or B ⁵ is a hydroxyl group,
B ⁶ is a hydrogen atom, a methyl group or a methoxy group, B ⁷ is a hydroxyl group or an amino group, B ⁸ is a phenyl group or a 4-
Methoxyphenyl group, B ⁹ is hydrogen atom, methyl group or methoxy group, B ¹⁰ is hydrogen atom or chlorine atom,
B ¹¹ is a hydrogen atom or a methoxy group, and B ¹² is a methoxy group, a butoxy group, an amino group, a methylamino group, a phenoxy group, a 4-methylphenoxy group, or a 3-methyl-4-methoxyphenoxy group). The dye represented by (e) the following formula (In the formula, D is a chlorine atom, a nitro group, a methoxy group,
means a phenyl group optionally substituted by a methyl group, a phenylazo group or a tolylazo group, the phenyl group having one or two substituents, and the substituents being a nitro group, a phenylazo group and a tolylazo group. may be the same or different except for R ⁶ is a hydrogen atom, chlorine atom, bromine atom, nitro group, methyl group, trifluoromethyl group, carbalkoxy group, optionally substituted carbamoyl group or sulfamoyl group, sulfonic acid Aryl ester group, cyan group, alkanoylamino group or phenyl group, R ⁷ is a hydrogen atom, chlorine atom or bromine atom, R ⁸ and R ⁹ are independently a hydrogen atom, chlorine atom, bromine atom or together a fused ring , and R ¹⁰ means a methyl group or a phenyl group optionally substituted with a chlorine atom or a methoxy group), (f) 5,6-benzoquinophthalone, (g) 7-dialkylamino-3
-benzimidazolyl-(2)-coumarin, (h) condensation product of naphtholactam and barbituric acid or N-substituted barbituric acid, (i) triphenylmethane dye or xanthene dye, (k) phthalocyanine, (l) violanthrone , isoviolanthrone, pyrantrone, indanthrone, naphtoylenebenzimidazole or anthraquinone bisacridone, or (n+m)-valent residue derived from (m) perylene-3,4,9,10-tetracarboxylic acid diimide. [meaning a group]]. The novel compounds of the formula are readily soluble in water in their salt form and in dilute acids such as acetic acid, hydroxyacetic acid, propionic acid, lactic acid or methanesulfonic acid in their base form. Examples of the salt include zinc double salt, benzene sulfonate, _C1 - _C20 -alkylbenzene sulfonate, methyl sulfate, ethyl sulfate, chloride and sulfate. Compounds of the formula in the form of quaternary ammonium salts are readily to well soluble in water. The dyes are suitable as cationic dyes for dyeing cellulose fiber materials, especially for dyeing paper raw materials. Paper dyed with the new dye has high colorfastness. On the other hand, dyeings with dyes in which, for example, F is a phthalocyanine residue can be decolorized with sodium hypochlorite, which is particularly advantageous in the finishing of straw paper. When the dyes of the invention are used in the production of colored paper, colorless or virtually colorless wastewater is obtained. Substituents for R ¹ and R ² include, in addition to a hydrogen atom, individually, for example, a butyl group, a propyl group, an ethyl group, and a methyl group. R ¹ and R ² may be the same or different. As R ¹ ,
Particularly preferred are hydrogen atom, methyl group and ethyl group. R ⁴ is for example a butyl group, a propyl group, especially an ethyl or methyl group, or a hydroxy-C ₂
~ _C4 -alkyl group. As X, individually, for example, benzol sulfonate, o- or p
- Anion of toluene sulfonate, CH ₃ O -
Examples include SO ₃ , C ₂ H ₅ O—SO ₃ , Cl , 1/2SO ₄ 2 and 1/2ZnCl ₄ 2 . When (m+n)>1, the dye is (m+n)
=1, 2, 3 and/or 4 dyes, m and n can also be fractions as average values. In this case, m or n may be 0. Particular preference is given to dyes in which n=1 to 4 and m=0. As the (m+n)-valent dye residue for F,
Residues derived from the following may be mentioned. (1) Monoazo-, disazo- or polyazo dyes, (2) Quinophthalones, (3) Bisdioxazines, (4) 5,6-arylo-2-pyrone compounds, (5) Naphtholactam dyes, (6) triphenylmethane- and xanthene dyes, (7) phthalocyanines, (8) indigoids, (9) anthraquinone dyes containing phenyl or naphthyl groups, (10) highly ortho-condensed carbonyl dyes, and (11) carbonyl group-containing dyes. Dyes such as quinacridone and its derivatives, perylene-3,4,9,10-
Tetracarboxylic acid diimide and its derivatives, naphthalene-1,4,5,8-tetracarboxylic acid diimide derivative, naphthoazaline derivative, diaminonaphthoquinone derivative, anthrapyrimidine derivative and pyrazoloanthrone derivative. The new dye is based on a dye with the general formula F(H) _n+o (). The dye must be capable of being amidomethylated. Dyes can be manufactured by known methods. (1) As azo and disazo dyes, for example, German Patent Application No. 2810246, No. 30-
The one described on page 32 is used. The azo compounds described there belong essentially to the following two groups: (1.1) Compounds in which an aromatic carbocyclic monoamine or diamine is coupled to a carbocyclic or heterocyclic compound at the o-position relative to the hydroxyl group; (1.2) Aromatic carbocyclic monoamine or diamine or aminoazobenzole (which is further substituted) ) with an aromatic or heterocyclic amine or with a compound having an enolizable ketomethylene group, such as an arylamide of acetoacetic acid or a pyrazolone. Azo dyes are identified by the amine and coupling component underlying the diazo component according to conventional methods in the art, where the arrow indicates
For example, it refers to a coupling component such as aniline → β-naphthol. Examples of azo compounds of groups (1.1) and (1.2) are as follows. (1.1) 4-methoxyaniline → β-naphthol, 3,3′-dimethoxy-4,4′-diaminodiphenyl → β-naphthol, bis-(4-aminophenyl)-disulfide → β-naphthol, bis-(3 -amino-4-methoxyphenyl)-sulfone → β-naphthol, bis-(3-amino-4-methylphenyl)
-Sulfone → β-naphthol, 4,4′-diaminobenzanilide → β-naphthol, bis-(4-aminophenyl)-sulfone →
3-hydroxy-2-naphthoanilide, aniline → 3-hydroxy-2-naphthoanilide, 2-methoxyaniline → 3-hydroxy-
4'-chloro-2-naphthoanilide, 3-methoxyaniline → 3-hydroxy-
4'-Chloro-2-naphthoanilide, 2-chloroaniline → 3-hydroxy-4'-
Chlor-2-naphthoanilide, 4-methoxyaniline → 3-hydroxy-2
-Naphtho-o-anisidide, 2-chloroaniline → 3-hydroxy-2-
Naphtho-o-anisidide, 4-chloroaniline → 3-hydroxy-2-
Naphtho-o-anisidide, 5-(N-phenylsulfamoyl)-2-
Methoxyaniline → 3-hydroxy-2-naphtho-o-anisidide, bis-(4-aminophenyl)-sulfone →
3-hydroxy-2-naphtho-o-anisidide, bis-(3-amino-4-methoxyphenyl)-sulfone → 3-hydroxy-2-naphtho-o-anisidide, 3,4′-diaminobenzanilide → 3-hydroxy-2-naphtho-o-anisidide, 3',4-diaminobenzanilide → 3-hydroxy-2-naphtho-o-anisidide, 3,3'-dimethoxy-4,4'-diaminodiphenyl → 3-hydroxy-2-naphtho-o-anisidide, aniline → 3-hydroxy-2-naphtho-o
-Anisidide, 2-methoxyaniline → 3-hydroxy-2
-naphtho-o-anisidide, aniline → 3-hydroxy-5'-chlor-2
-naphtho-o-anisidide, o-toluidine → 3-hydroxy-5'-chloro-2-naphtho-o-anisidide, 2-methoxyaniline → 3-hydroxy-2
-Naphtho-o-toluidide, 2-chloroaniline → 3-hydroxy-2-
Naphtho-o-toluidide, 4-bromo-2-chloroaniline → 3-hydroxy-2-naphtho-o-toluidide, bis-(3-amino-4-methoxyphenyl)-sulfone → 3-hydroxy-2-naphtho -o-toluidide, bis-(3-amino-4-methylphenyl)
-Sulfone→3-hydroxy-2-naphtho-o
-Toluidide, bis-(4-aminophenyl)-disulfide → 3-hydroxy-2-naphtho-o-toluidide, 4-bromo-3-methylaniline → 4'-chloro-3-hydroxy-2-naphtho-o-toluidide , 3-ethylaniline → 3'-chloro-3-hydroxy-2-naphtho-o-toluidide, bis-(4-aminophenyl)-disulfide → 3-hydroxy-2-naphtho-o-phenetidide, aniline → 3-hydroxy -2-Naft-o
-phenetidide, o-toluidine → 3-hydroxy-2-naphtho-o-phenetidide, 2-methoxyaniline → 3-hydroxy-2
-Naphtho-o-phenetidide, 3-iodoaniline → 4'-chloro-3-hydroxy-2',5'-dimethoxy-2-naphthoanilide, 4-isopropylaniline → 3-hydroxy-2-naphtho-2, 4-xylidide, 2,5-dimethoxyaniline → 3'-chloro-
3-hydroxy-2-naphtho-p-anisidide, 2,4-difluoroaniline → 3-hydroxy-2'-methyl-2-naphtho-p-anisidide, 3,4-diethoxyaniline → 5'-chloro-
3-hydroxy-2',4'-dimethoxy-2-naphthoanilide, 2-methoxyaniline → 3-hydroxy-2
-Carbamoylnaphthalene, 4,4'-diaminobenzanilide → 3-hydroxy-2-carbamoylnaphthaline, 3,3'-diaminobenzanilide → 3-hydroxy-2-carbamoylnaphthaline, 3,4'-diaminobenzanilide Lead → 3-hydroxy-2-carbamoylnaphthalene, 3',4-diaminobenzanilead → 3-hydroxy-2-carbamoylnaphthalene, bis-(3-amino-4-methoxyphenyl)-sulfone → 3-hydroxy- 2-carbamoylnaphthalene, bis-(4-aminophenyl)-sulfone→
3-hydroxy-2-N-(3-dimethylaminopropyl)-carbamoylnaphthalene, bis-(3-amino-4-methoxyphenyl)-sulfone → 3-hydroxy-2-N-
(3-dimethylaminopropyl)-carbamoylnaphthaline, 2-methoxyaniline → N,N'-bis-
(3-hydroxy-2-naphthoyl)-diaminoethane. (1.2) 3,3'-dimethoxy-4,4'-diaminodiphenyl → 2-methoxyacetoacetanilide, 3,3'-dimethoxy-4,4'-diaminodiphenyl → 2-chloroacetoacetanilide , 3,3'-dimethoxy-4,4'-diaminodiphenyl → 4-methoxyacetoacetanilide, 4,4'-diaminobenzanilide → acetoacetanilide, 4,4'-diaminobenzanilide → 2-methylacetoacetanilide, 4,4'-diaminobenzanilide → 2-methoxyacetoacetanilide, bis-(4-aminophenyl)-disulfide → 2-methoxyacetoacetanilide, 3,3'-dimethoxy -4,4'-diaminodiphenyl → 1-phenyl-3-methyl-5-pyrazolone, bis-(3-amino-4-methylphenyl)
-Sulfone→1-(4-methylphenyl)-3
-Methyl-5-pyrazolone, bis-(4-aminophenyl)-disulfide→1-phenyl-3-methyl-5-pyrazolone, bis-(4-aminophenyl)-sulfone→
1-phenyl-3-methyl-5-pyrazolone, bis-(3-amino-4-methoxyphenyl)-sulfone → 1-phenyl-3-methyl-
5-pyrazolone, 4,4'-diaminobenzanilide → 1-phenyl-3-methyl-5-pyrazolone, 3,3'-diaminobenzanilide → 1-phenyl-3-methyl-5-pyrazolone, 4, 4'-Diaminobenzanilide → 1-
(4-methylphenyl)-3-methyl-5-pyrazolone, 4-aminoazobenzole→1-phenyl-
3-Methyl-5-pyrazolone, 4-amino-2',3-dimethylazobenzole → 1-phenyl-3-methyl-5-pyrazolone, 2,6-dichloro-4-nitroaniline → aminohydroquinone dimethyl ether → diethylamino- 4-phenyl-triazole-1,
3. (1.3) As a monoazo dye that is the basis of the compound of the formula, the following formula is further used: An azo dye represented by is used. In this formula, B ¹ is a hydrogen atom or a methyl group, B ² is a hydrogen atom, a methyl group, or an ethoxy group, and S' is -
It means SO ₃ H or a hydrogen atom, and the residue Q has the following meaning. (1.3.1) Naphthol residue of the following formula In this formula, ^B3 is a hydrogen atom, a hydroxyl group, an amino group,
2-hydroxyethylamino group, methylamino group or phenylamino group, ^B4 is a hydrogen atom, acetyl group or N-phenylcarbamoyl group,
B ⁵ is a hydrogen atom, hydroxyl group, methyl group, methoxy group, chlorine atom, bromine atom, 2-hydroxyethylamino group or dimethylamino group, B ⁶ is a hydrogen atom, methyl group or methoxy group, and S′ is a hydrogen atom or - means SO ₃ H, in which case B ³ or B ⁵
is a hydroxyl group; (1.3.2) a residue of the following formula In this formula, B ⁷ is a hydroxyl group or an amino group, and B ⁸ is

[Formula] or

means [formula]; (1.3.3) Residue of the following formula In this formula, A ¹ and A ² are independently a hydrogen atom or a methyl group, or one of A ¹ and A ² is a hydroxyl group, and A ³ is a hydrogen atom, a methyl group, a hydroxymethyl group, or a chlorine atom; (1.3 .4) Residues of the formula In this formula, A ⁴ means a hydrogen atom, a methyl group, or an amino group, and A ⁵ means a hydrogen atom, a methyl group, a hydroxyl group, a methoxy group, or a chlorine atom; (1.3.5) A residue of the following formula (1.3.6) Residues of the formula In this formula, B ⁹ means a hydrogen atom, a methyl group or a methoxy group, B ¹⁰ means a hydrogen atom or a chlorine atom, and B ¹¹ means a hydrogen atom or a methoxy group; (1.3.7) A residue of the following formula In this formula, B ¹² is -OCH ₃ , -OC ₄ H ₉ , -NH ₂ ,
-NH- _CH3 ,

[Formula] or

means [formula]; (1.3.8) Residue of the following formula In this formula B ¹ and B ² have the meanings given above; (1.3.9) Residues of the formula In this formula B ¹³ means -NH ₂ or -OCH ₃ ; or (1.3.10) a residue of the formula

【formula】

【formula】

or

[Formula] In these formulas, B ¹⁴ is a methyl group or an ethyl group,
B ¹⁵ is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a chlorine atom, a bromine atom, a cyan group or a trifluoromethyl group, B ¹⁶ and B ¹⁷ are independently a hydrogen atom, a C ₁ -C ₄ -alkyl group, 3-methoxypropyl group, 3-ethoxypropyl group or phenyl group, B ¹⁸ means a hydrogen atom, methyl group, ethyl group or C ₁ -C ₄ -alkoxy-C ₂ - or -C ₃ -alkyl group. (1.4) Furthermore, as a compound, the general formula An azo compound represented by is used. In this formula, D is the residue of a common disazo- or tetrazo compound, for example the residue of the compound described in German Patent Application No. 2843873, s is a number of 1 or 2, and R ⁵ is a hydrogen atom or an aromatic group. Residue, R ⁶ is hydrogen atom, chlorine atom, bromine atom, nitro group, methyl group, trifluoromethyl group, carbalkoxy group, optionally substituted carbamoyl group or sulfamoyl group, sulfonic acid aryl ester group, cyan group , an alkanoylamino group or a phenyl group, R ⁷ is a hydrogen atom, a chlorine atom or a bromine atom, R ⁸ and R ⁹ are independently a hydrogen atom,
chlorine atom or bromine atom or taken together to mean a fused ring; R ¹⁰ is a hydroxyl group, methyl group, carbalkoxy group, optionally substituted aryl group or alkanoylamino group, preferably a methyl group or a chlorine atom or methoxy It means a phenyl group which may be substituted with a group. (2) Dyes derived from quinophthalone include, for example, 2-[1,3-dioxo-hydroindyl-(2)]-quinoline and 2-[1,3-dioxo-hydroindyl-(2)]-5,6 - Benzoquinoline can be given. Quinophthalone compounds are obtained by condensing an aromatic o- or per-dicarboxylic acid anhydride with a compound having a methyl group or an active methylene group, such as optionally substituted quinaldine or γ-picoline. These dyes may have, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyan group, a nitro group, an alkanoylamino group, an alkylmercapto group and/or an arylmercapto group as a substituent. (3) As a bisdioxazine compound for F(H) _n+o , for example, CI Pigment Violet 23
(CINo.51319) is used. (4) As the 5,6-arylo-2-pyrone compound for the dye, one in which the 3-position of the pyran ring is substituted with a heterocyclic group residue is used. Compounds of this series which are suitable for the preparation of the dyes according to the invention are described, for example, in German Patent Application No. 1098125. (5) Further, as F(H) _n+o , a condensation product of naphtholactam and a barbituric acid or a derivative thereof, such as the compound described in German Patent No. 2428198, is used. Preferred naphtolactam dyes have the following formula: (In the formula, R ⁶ means a halogen atom, such as a chlorine atom or a bromine atom, or an optionally substituted thiophenyl group). (6) Furthermore, as dyes of the formula, triphenylmethane dyes such as CI Basic Blue 26, CI No.
51319, as well as xanthene dyes such as CI Solvent Violet 10 (CI No. 45190:1) and
CI Solvent Dye 45 (CI No. 45195) is used. (7) As the phthalocyanine for F(H) _n+o ,
For example, the following can be mentioned. Copper, cobalt, nickel, zinc, aluminum or iron phthalocyanines as well as metal-free phthalocyanine compounds. These phthalocyanines may contain up to two chlorine atoms in the molecule. (8) Indigoids for F(H) _n+o include, for example, indigo, dichlor-, tetrachlor- and dibromo-indigo, thioindigo and its dichloro- or dibrome derivatives, as well as mixed indigo-thioindigo derivatives and higher Indigoid vat dyes with fused ring systems are used. (9) As the anthraquinone dye for F(H) _n+o , one having at least one of the following substituents is used. Phenylamino group, phenylalkylamino group, phenoxy group, thiophenyl group, naphthylamino group, phenyl group or phenyltriazinyl group. These dyes may optionally contain up to four other substituents, such as the substituents common to anthraquinone dyes, such as amino, alkylamino, dialkylamino, alkoxyalkylamino, hydroxyl, alkoxy,
Alkyl group, chlorine atom, bromine atom, nitro group,
Sulfamoyl group, N-alkyl- and N,N
-Dialkylsulfamoyl group, carbamoyl group, N-alkyl- and N,N-dialkylcarbamoyl group, N-C-acylamino group, carboxyl group or -SO ₃ H. The phenylamino, phenylalkylamino, naphthylamino and phenyltriazinyl groups are preferably present in the α-position. Phenoxy and phenylthio groups are in the α-position and β-position.
Although it can be present in the - position, the phenyl group is usually in the β-
It exists in the position. (10) The group of highly ortho-fused carbonyl dyes includes (10.1) carbonyl group-containing dyes based on anthraquinones and benzanthrone, and (10.2) polycyclic carbonyl group-containing dyes based on naphthalene. As (10.1) dyes derived from violanthrone, isoviolanthrone, pyrantrone, benzanthronylaminoanthraquinone, acedianthrone, indanthrone, cis- and trans-dibenzopyrenequinone are used, for example. Individual examples of (10.1) include: violanthrone, isoviolanthrone, benzanthrone pyrazoleanthrone,
Bisbenzanthrone Perithiophene, pyrantrone, its chlorine and/or bromine atom-containing derivatives, indanthrone, chlorindanthrone containing 1 to 2 chlorine atoms in the molecule, cis- and trans-dibenzopyrenequinone, Brome derivatives, anthraquinone-monoacridone, anthraquinone-bisacridone and anthraquinonethioxanthone. As the naphthalene-based carbonyl group-containing dye in (10.2), those derived from anthoanthrone are used. Among the dyes of the formula, those derived from the following compounds are preferred. (a) Aromatic carbocyclic diamine with β-naphthol,
derivatives thereof or products coupled to acetoacetanilide; (b) products coupled to aromatic carbocyclic diamines to pyrazolone-5 compounds, particularly 1-phenyl-3-methylpyrazolone-5; (c) substituted Pyrazolone-5 compounds, especially 1-phenyl-3
-Product coupled to methylpyrazolone-5; (d) Q has the formula a, b, f, g, h, m
or the residue of o; (e) D means a phenyl group optionally substituted by a chlorine atom, a nitro group, a methoxy group, a methyl group, a phenylazo group or a tolylazo group, in which case phenyl The group may have one or two substituents, and the substituents include a nitro group,
Dyes of the formula which may be the same or different except for the phenylazo or tolylazo group; (f) quinophthalones, especially 5,6-benzoquinophthalone; (g) 7-dialkylaminocoumarins having a benzimidazolyl-(2) group in the 3-position; (h) condensation products of naphtholactam and barbituric acids or N-substituted barbituric acids; and (i) triphenylmethane- or xanthene dyes. Among the dye groups listed in (7) to (10), (k) copper phthalocyanine, (l) violanthrone, isoviolanthrone,
The naphtoylenebenzimidazole and anthraquinone bisacridone dye families are superior. For color and technical reasons, Example 1,
3, 64, 71, 73, 76, 78, 79, 81, 82, 84, 85,
The novel dyes described in 88, 91a, 91b and 92 and dyes derived from copper phthalocyanines are particularly suitable. A new compound of the formula where m=0 can be obtained by combining the dye of the formula F(H) _n+o () with anhydrous formaldehyde and the formula It can be obtained by reacting with an imidazole compound in the presence of an acidic reagent. In the formula, R ¹ is a hydrogen atom, a C ₁ -C ₆ -alkyl group or a C ₂ -C ₆ -alkenyl group, R ² and R ³ are independently a hydrogen atom,
A _C1 - _C5 -alkyl group or a _C2 - _C6 -alkenyl group is meant, the alkyl group being linear or branched. Formaldehyde can be used in the reaction in monomeric form or preferably in polymeric form, eg as paraformaldehyde or trioxane. As the imidazole, for example, 1-
Methyl-, 1-ethyl-, 1-m-propyl-,
1-isopropyl-, 1-n-butyl-, 1-isobutyl-, 1-tert-butyl-, 1-vinyl- and 1-allylimidazole, 4-methylimidazole, 2-methylimidazole, 1-butyl-2
-Methylimidazole, 1,2-dimethyl-, 1
-Ethyl-2-methyl- and 1-propyl-2-
Examples include methylimidazole, of which 4-methylimidazole is particularly preferred. Imidazole is used together with anhydrous formaldehyde in at least the stoichiometric amount required, particularly preferably in excess. The reaction for producing the compound is carried out using a C-
Hydroxymethylimidazole, such as 4-hydroxymethyl-5-methylimidazole or 4-
It can also be carried out using methyl-5-hydroxymethylimidazole. Imidazole can also be used in the form of salts with mineral acids. The reaction is generally carried out at a temperature of 0 to 140°C, preferably 0 to 100°C. The reaction time depends on the number of methylene imidazole groups introduced into the dye, the dye,
Depends on acidic reagent and reaction temperature. Reaction times are generally 1 to 48 hours. Acidic reagents for this method (which can also be used simultaneously as reaction medium) include e.g.
100% by weight of sulfuric or phosphoric acid is used, optionally together with water-eliminating agents such as sulfur trioxide (oleum), phosphorus pentoxide, meta- or polyphosphoric acid, acetic anhydride, benzol- or toluosulfonic acid. As an acidic reagent that also serves as a reaction medium, 96
~100% by weight sulfuric acid, up to 12% by weight fuming sulfuric acid, or
A mixture of 85% phosphoric acid and phosphorus pentoxide is preferred. In the reaction in sulfuric acid or fuming sulfuric acid, one or more sulfonic acid groups can be added to the reaction product by increasing the sulfuric acid concentration and/or increasing the temperature during or after the reaction with the imidazole compound, if desired. can be introduced into Dyes for paper dyeing should normally contain no more than one sulfonic acid group per molecule, preferably on average from 0 to 0.5 sulfonic acid groups. The reaction product with m=0 is precipitated by discharging the reaction mixture onto water or ice water and separated. If the product is partially or completely soluble in dilute aqueous acid, it is precipitated in the free base form by addition of a basic reagent such as caustic soda solution, caustic potash solution or ammonia, separated by filtration and dried. Alternatively, use in the form of a moistened press cake. Furthermore, to isolate the reaction product from dilute aqueous acid, it is also possible to precipitate it as a zinc double salt using zinc chloride and sodium chloride. If the reaction product contains sulfonic acid groups, these are usually present in the form of potassium, sodium or ammonium salts. Dyes of the formula derived from monoazo- or disazo dyes can also be obtained by coupling the corresponding diazo compound with a coupling component containing at least one imidazolyl methylene group. As a coupling component, for example, the following formula (In the formula, R is a hydrogen atom, a methyl group, an ethyl group, or
Examples include amines represented by C ₁ -C ₄ -alkoxy-C ₂ - or C ₃ -alkyl group, where n means the number 1 or 2). Diazo compounds suitable for this coupling component are obtained, for example, by diazotization of 2-(4'-aminophenyl)-6-methylbenzothiazole. A coupling component having an imidazolyl methylene group is prepared by combining a coupling component containing at least one aromatic ring with imidazole and paraformaldehyde of the formula in the same manner as in the case of dyes.
It is produced by condensation under the conditions described above. A compound of the formula containing a quaternary imidazolyl group,
That is, for compounds where m is a number from 1 to 5, m=0
By alkylation in a manner known per se from dyes containing methyleneimidazolyl groups, such as chloro-C ₂ -C ₄ -alkanols, corresponding sulfuric acid diesters such as dimethyl sulfate or diethyl sulfate or corresponding sulfonic acid esters such as toluene sulfone. They are obtained by reaction with acids-C ₁ -C ₄ -alkyl esters, particularly preferably methyl esters, ethyl esters, 2-chloroethanol and chloropropanol. The industrial advantage of the new imidazolyl group-containing dyes is that they can be obtained in a simple manner that is free from industrial hygiene and toxicological problems. On the other hand, U.S. Patent No. 3565570, which is considered to be at the latest state of the art,
The dyes described in German Patent Application No. 1569848 and German Patent Application No. 2508892 are as follows:
It is produced via the corresponding chloromethyl compound, using bis-chloromethyl ether in its production or forming it as a by-product. Parts and percentages in the examples below relate to weight. The absorption maximum value (λ _nax ) of the dye is 5 unless otherwise specified.
Measurements were made in a solution containing 0.02 g of dye in wt% acetic acid. The phthalocyanine residue is Pc
It is represented by Example 1 21.5 parts of 4-methylimidazole and 7.5 parts of paraformaldehyde in 165 parts of 96% sulfuric acid at 10-15°C
30 minutes at a time and the mixture is stirred at 40° C. for 30 minutes. After cooling to 0-5°C, 26.9 parts of 4,4'-diaminobenzanilide→β-naphthol (2 moles) are added little by little. The temperature is then gradually increased to 20°C and stirred at 20-25°C for 3 hours. The reaction mixture was drained onto ice water and the acid was neutralized with dilute caustic soda solution.
Filter the precipitate, wash with water until salt-free, and dry. The following formula 42 parts of disazo dye are obtained in the form of a red powder.
Color of dilute acetic acid solution: red; λ _nax 505nm. Elemental analysis: C ₄₈ H ₄₁ N ₁₁ O ₃ (M819) N Calculated value (%) 18.8 Actual value (%) 19.0 Colorless wastewater is obtained when dyeing paper raw materials. Raw dyeing of paper according to Application Example 3 gives a red paper with high gloss and very good water resistance. Example 2 By operating in the same manner as in Example 1, but using 28.7 parts of 4,4'-diamino-benzenesulfoanilide → β-naphthol as the compound, the following formula 42 parts of disazo dye are obtained. This dye powder is reddish-purple, and its dilute acetic acid solution is also reddish-purple. λ _nax 483nm. Example 3 4-methylimidazole in 165 parts of 96% sulfuric acid
20.5 parts and 7.5 parts of paraformaldehyde are added simultaneously at 0-5°C and the mixture is stirred at 40°C for 0.5 hour. After cooling to 0-5°C, 31.5 parts of dye from 4,4'-diamino-3,3'-dichlorodiphenyl→acetoacetani lead were added and the mixture was heated to 15°C at 20-25°C.
Stir for an hour. The reaction mixture was drained onto ice water, neutralized with dilute caustic soda solution, the precipitate was filtered, washed salt-free and dried at 50°C, giving the following formula: 47 parts of disazo dye are obtained. Color of dilute acetic acid solution: yellow. Elemental analysis: C ₂₄ H ₄₄ Cl ₂ N ₁₂ O ₄ (n=3) (M911) N Calculated value (%) 18.4 Actual value (%) 18.6 When paper is dyed with raw materials, yellow paper is obtained. The wastewater is colorless. The maximum absorption value is 398 nm. Example 4 Proceeding as in Example 3, but using 4,4'-diamino-3,3'-dichlorodiphenyl→2-methoxyacetoacetanilide as the dye, three imidazolyl methylene groups were dye with
You will get 50 copies. Elemental analysis: C ₄₉ H ₄₈ Cl ₂ N ₁₂ O ₆ (n=3) (M971) N Calculated value (%) 17.3 Actual value (%) 17.9 This dye dissolves in dilute acetic acid with a yellow color. Colorless wastewater is obtained in the dyeing of paper raw materials. The maximum absorption value is 422 nm. Examples 5 to 37 Proceeding as in Examples 1 to 3, but using the dyes indicated by the amine and coupling components in the table below, the corresponding dyes containing 4-methylimidazolyl methylene groups are obtained. These dyes are 1, 2
or 3 imidazolyl methylene groups, and 1
Mixtures of dyes having 1, 2 and 3 such groups may also be present. The resulting dye is diluted with acetic acid,
Dissolve propionic acid and methoxyacetic acid to the color shown in the table. A dyeing of the same shade is obtained on paper.

【table】

[Table] Example 38 In 270 parts of 96% sulfuric acid, 4-methylimidazole
21.5 parts and 10-15 parts of paraformaldehyde 7.5 parts
℃ and stirred at 50℃ for 2 hours. 2-(3′-phenyloxadiazolyl-1′,2′,
4') -4-Chloraniline→21.5 parts of the monoazo compound from 2,6-dihydroxy-3-methyl-4-cyanpyridine are added little by little. (This monoazo compound was prepared by the method described in German Patent No. 2457687, Example 64.) The mixture was stirred at 50°C for 4 hours, at 20-25°C for 16 hours, and then poured on ice water. to be discharged. The solution is neutralized with dilute caustic soda solution, the precipitate is filtered off with suction, washed salt-free and dried. 29 parts of a dye containing one imidazolyl methylene group are obtained. Maximum absorption value 400nm. If the other monoazo compounds described in DE 2457687 are reacted in a similar manner, yellow to red imidazolyl methylenated products are likewise obtained, which contain on average one or two imidazolyl methylene groups. Contains. These dyes are soluble in dilute acetic acid, emulsion or methanesulfonic acid. Examples 39 to 55 Working as in Example 38, but using the monoazo compounds indicated by the monoamines and coupling components in the following table, dyes having one 4-methylimidazolyl methylene group are obtained. These dyes are soluble in dilute acetic acid, propionic acid, lactic acid and methoxyacetic acid to the shades shown in the table. Paper is dyed to the same tone by dyeing the raw materials. A colorless to slightly colored wastewater is obtained.

【table】

[Table] Example 56 Add 23 parts of Solvent Black 3 (CI No. 26150) little by little to 276 parts of 96% sulfuric acid at 10 to 20°C, then add 4-methyl-5-hydroxymethyl-imidazole hydrochloride 18 at 20°C. Add part. reaction mixture 40
After stirring for 5 hours at °C, the mixture is poured onto 1000 parts of ice water, the insoluble matter is filtered off, and the liquid is neutralized with caustic soda solution. The precipitate is filtered off with suction, washed salt-free and dried. =1 imidazolyl methylated azo dye
17 parts are obtained, which is partially sulfonated. Example 57 2-(4'-aminophenyl)-6-methylbenzothiazole→β in 250 parts of sulfuric acid monohydrate
- 20 parts of naphthol dye and 16.4 parts of 4-methylimidazole are dissolved at 20°C, then 20~
Add 8.3 parts of paraformaldehyde in small portions within 3 hours at 25°C. The mixture is stirred for 16 hours at 20-25° C., drained onto 2000 parts of ice water and brought to pH 10 with 400 parts of 50% caustic soda solution. After separating the precipitate, washing it with neutral and salt-free water and drying it at 80℃, the following formula is obtained. 31.2 parts of imidazolyl methylated azo dye are obtained in the form of a red powder. Elemental analysis: C ₂₉ H ₂₃ N ₅ OS (489) N S Calculated value (%) 14.3 6.5 Actual value (%) 15.5 6.2 Color of 30% acetic acid solution: Red; λ _nax 499 nm. Examples 58-63 In the same manner as in Example 57, the monoazo compounds shown by the amines and couplings in the following table are reacted under the conditions shown in column 7 of the table. The dye obtained is isolated analogously to Example 57. The number of 4-methylimidazolyl methylene groups is shown in column 4. The color of the dilute acetic acid solution is shown in column 5. In raw paper dyeing, the paper is dyed the same color and the waste water is colorless or practically colorless.

【table】

[Table] Example 64 4-
17 parts of methylimidazole and 6 parts of paraformaldehyde are added simultaneously and stirred at 40°C. After 2 hours, 19.6 parts of 2-(4'-aminophenyl)-6-methylbenzimidazole→barbituric acid dye is added little by little. After 9 hours at 40°C, the solution was drained onto ice water, the precipitate was filtered off by suction, washed neutral with small portions of ice water, and dried under vacuum at 50°C. 24 parts of azo dye are obtained. Elemental analysis: C ₁₃ H ₁₉ N ₇ O ₃ S (473) N S Calculated value (%) 20.6 6.7 Actual value (%) 20.6 6.3 An acetic acid solution of this dye dyes paper in a glossy yellow tone. The light fastness of the paper dyeing is good. λ _nax 412 nm (0.01 g/in 5% acetic acid). When the raw material is dyed according to Use Example 3, a reddish-yellow paper is obtained, and this paper has good light fastness and bleed fastness. Example 65 In 125 parts of sulfuric acid monohydrate at 20-25°C, 3
-Chlor-4-aminoazobenzole→2-phenylpyrazolo[5,1-b]quinazolone dye
Add 12.5 parts and 8.2 parts of 4-methylimidazole,
Then 4.2 parts of paraformaldehyde are added little by little. The mixture was stirred at 20-25°C for 16 hours, then
Drain onto 1000 parts of ice water and PH with 50% caustic soda solution
10 (approximately 220 copies). The precipitate is filtered by suction, washed neutrally and dried at 80°C, resulting in the following formula: 15.9 parts of a mixture of mono-imidazolylmethylated disazo dyes are obtained. Elemental analysis: C ₃₃ H ₂₄ ClN ₉ O (597.5) Cl N Calculated value (%) 5.94 21.08 Actual value (%) 5.4 20.7 Color of 5% acetic acid solution: Red; λ _nax 471 nm. Examples 66-70 Analogously to Examples 38 or 56, the monoazo compounds indicated in the table below by amine and coupling component are reacted with 4-methylimidazole and the dye is isolated. The number of imidazolyl methylene groups is 4th
The color of the 30% acetic acid solution is shown in column 5, and the absorption maximum is shown in column 6.

[Table] Example 71 20.5 parts of 2-methylimidazole and 7.5 parts of paraformaldehyde are simultaneously added to 270 parts of 96% sulfuric acid at 20°C. Increase temperature to 50°C and hold for 2 hours. Then, at 45-50°C, 16.1 parts of 2-[1,3-dioxohydrinyl-(2)]-5,6-benzoquinoline are added in portions, and the mixture is subsequently stirred at 50°C for 1 hour. The reaction solution was drained onto ice water, neutralized with 50% caustic soda solution, and the yellow precipitate was filtered off with suction and washed salt-free. hydrinyl-(2)]
33 parts of -5,6-benzoquinoline are obtained. Elemental analysis: C ₂₇ H ₂₀ N ₃ O ₂ (417) N Calculated value (%) 10.07 Actual value (%) 10.3 λ _nax 418 nm. This yellow dye was dissolved in dilute acetic acid and used in Usage Examples 1 and 2.
Or when used for dyeing paper raw materials according to 3, paper dyed deep yellow can be obtained. The wastewater is colorless. Example 72 Proceed as in Example 71, but using 1-methylimidazole instead of 4-methylimidazole. The mixture was heated at 40°C for 5 hours and then at 60°C.
After holding for 12 hours and finishing treatment in the same manner as in Example 71, the following formula is obtained. 18 parts of dye are obtained. Color of dilute acetic acid solution: yellow; λ _nax 418nm. Example 73 65 parts of 2-[1,3-dioxohydrinyl-(2)]-5,6-benzoquinoline are added and dissolved in 100 parts of 96% sulfuric acid at 15-20°C. In this, 4-methyl-
5-Hydroxymethylimidazole (82.6%)72
Add portions little by little. The mixture was stirred for 2 hours at 20-25°C and 3 hours at 50°C, then drained onto ice water, neutralized with 50% caustic soda solution at 10-15°C, filtered with suction and washed salt-free. dry. imidazolylmethylated 2-[1,3-dioxohydrinyl-(2)]- with n=1 and 2;=1.3
99 parts of a mixture of 5,6-benzoquinolines are obtained. λ _nax 408nm. This yellow dye has the color properties on paper of Example 71.
It corresponds to the dye of The wastewater is colorless. Usage example 3
When used, a yellow paper is obtained which has high color density, high gloss and good smudge fastness. Example 74 In 275 parts of 96% sulfuric acid, 4-methylimidazole
20.5 parts and 7.5 parts of paraformaldehyde are stirred at 50°C for 2 hours, then cooled to 20-25°C. 2-[1,3-dioxo-4,7-dichloro-5,6-dithiophenyl-hydrindyl-(2)] in the mixture
-Add 28.7 parts of quinoline and heat at 50℃ for 2 hours and 20~
Stir at 25°C for 16 hours. The acid solution is drained onto ice water and the solution is neutralized with 50% caustic soda solution while cooling. Suction the precipitate, wash with salt-free water, and store at 50°C.
Vacuum drying yields 46 parts of yellow powder. This dye has two imidazolyl methylene groups. Colorless wastewater is obtained in the dyeing of paper raw materials. Example 75 4-
25.5 parts of methylimidazole and 9 parts of paraformaldehyde were added at the same time, stirred at 30-35°C for 1 hour, and then CI Pigment Violet 32 (CI No.
51319) Add 59 parts little by little. mix 30-35
Stir for 5 h at °C, drain onto ice water, and reduce the solution to 50%.
Neutralize with caustic soda solution. The purple precipitate was washed with salt-free water and dried at 80°C, yielding 96 parts of dye.
This is a mixture of dyes with n=1 and 2. The dye dissolves in dilute acetic or lactic acid with a purple color; λ _nax 570 nm. From this solution, the paper stock is dyed in a deep blue-violet shade according to use example 1, and the waste water is colorless. The bleed fastness is very good. Example 76 20.5 parts of 4-methylimidazole and then 7.5 parts of paraformaldehyde are added portionwise at 20-25 DEG C. into 270 parts of 96% sulfuric acid. The mixture was stirred for 2 hours at 50°C, cooled and heated at 15-20°C with 16.7 parts of 3-(benzimidazolyl-2')-7-diethylaminocoumarin (prepared according to German Patent Application No. 1098125, Example 2). and stir at 15-20°C for 8 hours. The mixture is drained onto ice water and neutralized with dilute caustic soda solution at 0-30°C. The precipitate is filtered off with suction, washed salt-free and dried to give 25 parts of imidazolylmethylated 3-(benzimidazolyl-2')-7-diethylaminocoumarin with n=1. Elemental analysis: C ₂₅ H ₂₄ N ₅ O ₂ (440) N Calculated value (%) 15.9 Actual value (%) 15.6 λ _nax 475 nm. Thin layer chromatography on silica gel plates (layer thickness 0.25 mm, 5 parts chloroform, 2 parts glacial acetic acid)
1 part methanol and 1 part methanol), the R _f value of the substance used is 0.99 and that of the imidazolyl methylated product is 0.1. The dye obtained no longer contains starting material. When paper is dyed as a raw material according to Use Example 2, paper dyed yellow is obtained, which has good smear fastness. Example 77 4-Methylimidazole in 270 parts of 96% sulfuric acid
21.5 parts and 7.5 parts of paraformaldehyde at the same time
Add at 10-15°C and stir at 35-40°C for 1 hour. 20
At ℃, add 20.6 parts of a monoazo compound of 2,5-dichloroaniline→N-phenylethyl-2-hydroxy-3-cyan-4-methylpyridone-(6),
Stir at ~25 °C for 18 h. Drain the mixture onto ice water and neutralize with dilute caustic soda solution. The precipitate is filtered off with suction, covered with a little water and dried to give 48 parts of dye (containing salt). This dye dissolves yellow in dilute acetic acid; λ _nax 423 nm. Using this imidazolyl methylation product,
The paper is raw dyed to a transparent yellow tone. Example 78 4-
12.8 parts of methylimidazole and 4.5 parts of paraformaldehyde are added simultaneously and stirred at 40°C for 2 hours.
Next, German Patent Application No. 2428198,
15.4 parts of the condensation product from naphtholactam and N,N'-dimethylbarbituric acid prepared according to Example 1 are added in portions and kept at a temperature of 40° C. for 3 hours. The solution is drained onto ice water, neutralized with ammonia, the precipitate is filtered off, washed and dried, giving the following formula: 23 parts of dye are obtained. Elemental analysis: C ₂₂ H ₁₉ N ₅ O ₃ (401) N Calculated value (%) 17.6 Actual value (%) 17.4 This dye dissolves in dilute acetic acid with a yellow color. Example 79 4-Methylimidazole in 270 parts of 96% sulfuric acid
17.1 parts and 6 parts of paraformaldehyde at 10-15℃
and stir at 40°C for 2 hours. Next, a small amount of 20.8 parts of the condensation product from 4-phenylmercaptonaphtholactam (1,8) and N,N'-dimethylbarbituric acid prepared according to DE 24 28 198, Example 7 was added. Add one by one,
Stir at 40°C until the reaction is complete. The solution was drained onto ice water, neutralized with 25% aqueous ammonia under cooling, and the precipitate was filtered off with suction, washed and dried at 50 °C, giving the following formula: 35 parts of dye are obtained. Elemental analysis: C ₃₃ H ₂₆ N ₇ O ₃ S (603) N S Calculated value (%) 16.53 5.3 Actual value (%) 15.3 5.4 λ _nax 475 nm. This dye gives a red paper with good wet fastness when raw dyeing of paper according to Application Example 1 from an acetic acid solution. Example 80 In 270 parts of 96% sulfuric acid, 4-methylimidazole
10-15 parts of 12.8 parts and 4.5 parts of paraformaldehyde
℃ and stirred at 40℃ for 2 hours. At this temperature,
Condensation product from 2,4-diphenylmercapto-naphtholactam-(1,8) and N,N'-dimethylbarbituric acid (German Patent Application No.
2428198) was added little by little and stirred at 40°C for 1 hour. The solution was drained onto ice water and worked up as in Example 1, giving the following equation: 48 parts of dye are obtained. Elemental analysis: C ₃₉ H ₃₄ N ₇ O ₃ S ₂ (711) (n=2) N Calculated value (%) 13.78 Actual value (%) 13.8 λ _nax 506 nm. This dye, when raw dyeing paper according to use example 1 from an acetic acid solution, gives a red-dyed paper which has good wet fastness properties. The wastewater is colorless. Example 81 In 250 parts of sulfuric acid monohydrate at 10-15°C, 4
-Amino-3,2'-dimethylazobenzole→1
-Phenyl-3-methyl-5-pyrazolone dye
Add 20.5 parts and 16.4 parts of 4-methylimidazole. Then 8.3 parts of paraformaldehyde were added in small portions over 30 minutes, the mixture was stirred at 20-25°C for 20 hours, poured onto 2000 parts of ice water, brought to pH 9-10 with 50% caustic soda solution, filtered off with suction and washed with water. , the following equation 25 parts of mono-imidazolylmethylated disazo dye are obtained. Elemental analysis: C ₂₈ H ₂₆ N ₈ O (490) N Calculated value (%) 22.8 Actual value (%) 22.6 Using this dye, from acetic acid solution to Usage Example 1~
3 gives a glossy yellowish-orange paper dyeing with high color density and very little coloration of the waste water. When the raw material is dyed in accordance with Use Example 1, a paper dyed in a yellowish orange color with good bleeding fastness, gloss, and high color density is obtained. Example 82 Proceed as in Example 81, but with 4 as the dye.
-Aminoazobenzole → Using 19.1 parts of 1-phenyl-3-methyl-5-pyrazolone, the following formula 26.8 parts of dye are obtained. Elemental analysis: C ₂₇ H ₂₃ N ₈ O (475) N Calculated value (%) 23.5 Actual value (%) 22.5 Color properties are similar to the dye of Example 81.
When paper is dyed as a raw material in accordance with Use Example 2, paper dyed in a yellowish-orange color with high color density and good bleeding fastness is obtained. Example 83 13.8 parts of 1-butyl-2-methylimidazole and paraformaldehyde in 130 parts of 96% sulfuric acid
Add 4.5 parts simultaneously at 5-10°C and stir at 20°C for 1 hour. Then 4-aminoazobenzole → 1-
Phenyl-3-methyl-5-pyrazolone dye 10
Add portions little by little. The reaction mixture was heated at 20-25 °C for 15
Stir for 6 hours at 40°C and then drain onto ice water and bring to PH10 with 50% caustic soda solution. The precipitate is filtered by suction, washed neutrally and dried at 80°C.
The following formula 14.9 parts of dye are obtained. Color of 5% acetic acid solution: yellow; λ _nax 417 nm (measured as 0.01 g/in 5% acetic acid). Example 84 9.7 parts of 1,2-dimethylimidazole and 4.2 parts of paraformaldehyde are added simultaneously to 130 parts of 96% sulfuric acid at 5-10°C and stirred for 30 minutes. then 3
-Chlor-4-aminoazobenzole→2-phenylpyrazolo[5,1-b]quinazolone dye
Add 12.5 parts little by little. Heat the reaction mixture to 40-45℃
Stir for 6 hours at 60℃ and 5 hours at 60℃, then add to ice water.
Drain over 1000 parts and bring the resulting solution to pH 7.5 with 25% aqueous ammonia. The precipitate is filtered by suction, washed salt-free and dried at 80°C, resulting in the following formula: 17.5 parts of disazo dye are obtained. Elemental analysis: C ₃₄ H ₂₆ ClN ₉ O (611.5) N Cl Calculated value (%) 23.5 5.8 Actual value (%) 20.6 5.3 Color of 5% acetic acid solution: Orange-red; λ _nax 461 nm. Example 85 10.9 parts of 2-ethyl-4-methylimidazole and paraformaldehyde in 130 parts of 96% sulfuric acid
Add 4.2 parts simultaneously at 20-25°C and stir for 30 minutes.
Then 3-chloro-4-aminoazobenzole→
Add 12.5 parts of 2-phenylpyrazolo[5,1-b]quinazolone dye little by little. mix 20-25
After stirring at °C for 72 hours, finishing treatment was performed in the same manner as in Example 84, resulting in the following formula 20.1 parts of disazo dye are obtained. λ _nax 455nm. Example 86 21.3 parts of 4-methylimidazole and 7.5 parts of paraformaldehyde in 165 parts of 96% sulfuric acid at 0-15°C
1 part at the same time and stirred at 40°C for 1 hour. 0-5
After cooling to 30°C, 30.6 parts of 2,6-dichloro-4-nitroaniline → aminohydroquinone dimethyl ether → 2-diethylamino-4-phenylthiazole-1,3 dye was added, and the mixture was heated to 30°C at 20-25°C.
Stir for 6 hours at 30-35°C. The reaction mixture was discharged onto ice water, the dissolved components were precipitated by adding 25% aqueous ammonia up to the neutralization point, the precipitate was filtered off by suction, washed and dried, and the following equation was obtained: 33 parts of disazo dye are obtained. Color of dilute acetic acid solution: reddish-blue. Example 87 21.4 parts of 4-methylimidazole and 7.5 parts of paraformaldehyde in 165 parts of 96% sulfuric acid at 0-15°C.
1 part at the same time and stirred at 40°C for 1 hour. After cooling to 30℃, CI Basic Blue 26 (CI No.
Add 25.3 parts of 44045) and stir at 40°C for 12 hours.
Drain the reaction mixture onto ice water and precipitate the dye with 25% aqueous ammonia. When the precipitate is filtered, washed salt-free and dried at 50℃, the following formula is obtained. 36 parts of triphenylmethane dye are obtained. Elemental analysis: C ₃₈ H ₃₉ N ₅ O (581) N Calculated value (%) 12.0 Actual value (%) 12.1 Acetic acid solution is blue; λ _nax 614 nm. When paper is dyed as raw material, blue paper is obtained. Example 88 21.3 parts of 4-methylimidazole and 7.5 parts of paraformaldehyde in 165 parts of 96% sulfuric acid at 0-15°C
1 part at the same time and stirred at 40°C for 2 hours. After cooling to 30℃, CI solvent die (CINo.45195)
Add 36.9 parts little by little and stir first at 40°C for 1 hour, then at 20-25°C for 20 hours. Drain the reaction mixture onto ice water, neutralize the solution with 25% aqueous ammonia,
After filtering the precipitate and washing it with salt-free water, the following formula is obtained: 42 parts of xanthene dye are obtained. Elemental analysis: C ₅₁ H ₄₈ N ₈ O ₃ (820) N Calculated value (%) 13.6 Actual value (%) 13.0 NMR spectrum (CF ₃ COOD): 2.2 ppm (broad s), 2.4 ppm (s), 4.2 ppm (broad s), as well as aromatic signals. Absorption maximum in ethanolic 5% acetic acid:
526nm. Using this dye according to Application Examples 1 and 2, a glossy red-dyed paper is obtained from an acetic acid solution. The coloration of the waste water is significantly less than with the corresponding dye (CI No. 45195) which does not contain imidazolyl methylene groups. Example 89 4 in sulfuric acid pre-operated as in Example 88
- Add 25.5 parts of CI Solvent Violet 10 (CI No. 45190: 1) in portions at 30°C to a mixture of methylimidazole and paraformaldehyde,
Stir at 40°C for 3 hours, then at 20-25°C for 15 hours. When the mixture is worked up as in Example 88, the formula 32 parts of xanthene dye are obtained. Elemental analysis: C ₃₉ H ₃₁ N ₄ O ₃ (n=1) (603)
C ₄₄ H ₃₈ N ₆ O ₃ (n=2) (697) Calculated value: N9.28% Calculated value: N12.05% Actual value: N10.0% Acetic acid solution is red; λ _nax 530 nm (5% ethanolic in acetic acid). Red paper is obtained by dyeing paper as a raw material. Example 90 4 in acetic acid pre-operated as in Example 88
- 30.6 parts of the condensation product of 2 mol of 2-chloroaniline and 3,6-dichlorofluorane are added in portions at 0-5°C to the reaction mixture of methylimidazole and paraformaldehyde, and then at 20-23°C.
Stir for 15 hours. When the mixture is worked up as in Example 88, the formula 38 parts of xanthene dye are obtained. Elemental analysis: C ₄₂ H ₃₂ Cl ₂ N ₆ O ₃ (740) Cl Calculated value (%) 9.59 Actual value (%) 9.56 The acetic acid solution is red. When paper is dyed as a raw material, red-dyed paper is obtained. Example 91 (a) Proceeding as in Example 90, but using 31.5 parts of the condensation product of 2 moles of mesidine and 3,6-dichlorofluorane as the dye, the formula 37 parts of dye are obtained. Acetic acid solution is red; λ _nax 528nm. From the acetic acid solution, paper dyed in red with high color intensity is obtained according to use examples 1 and 3. (b) 2 moles of 2,6-diethylaniline and 3,6-
Using the condensation product from dichlorofluorane,
Imidazolyl methylation analogously to Example 90 gives a dye which likewise has very good properties in use. Example 92 (a) 24 parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized with 7.6 parts of sodium nitrite in hydrochloric acid solution. A diazonium salt solution was prepared according to (b) in 400 parts of ice water and 60 parts of 30% acetic acid. In a solution containing 39 parts of a coupling component of
Add under stirring at 5°C. The pH value of the mixture is then brought to 5.5 with sodium acetate solution. Increase the temperature to 20-25 °C within 18 hours. The very finely precipitated dye is filtered off and the excess residue is dissolved by adding glacial acetic acid. Filter this solution and precipitate the dye in the solution using 25% aqueous ammonia at 50-60°C. The precipitate is filtered, washed salt-free with warm water and dried at 50°C to give 47.2 parts of a golden yellow powder. (b) Synthesis of coupling component: 20.5 parts of 4-methylimidazole and 10 parts of paraformaldehyde are simultaneously added to 130 parts of 96% sulfuric acid and stirred. After cooling to 0-5℃,
19.7 parts of N-methylbenzylaniline are added dropwise. The reaction mixture was heated at 2-5°C for 3 hours at 5-20°C.
Stir for 18 hours at 30°C and 6 hours at 30°C. Then drain onto ice water and PH the solution with 25% ammonia water.
Set it to 9.0. The precipitate is dissolved in butanol, the butanol phase is separated, washed with water and dried, and the butanol is distilled off. This residue is used as it is as a coupling component. The dye obtained according to (a) gives, from acetic acid solution, paper dyed golden yellow according to Application Examples 1, 2 or 3. The wastewater is colorless. Example 93 To a mixture of 1167 parts of 97.5% sulfuric acid and 115 parts of copper phthalocyanine are added portionwise at 20-35° C. 71.3 parts of imidazole and 45.3 parts of paraformaldehyde. The reaction mixture is then heated to 110° C. and stirred at this temperature for 15 hours. After cooling, place the reaction solution on ice 4000
and 1500 parts of water and the resulting solution is brought to pH 10 with 1900 parts of 50% caustic soda solution. The warm precipitate at 50°C is filtered by suction on a Nutsuchie, washed with neutral and salt-free water, and dried, resulting in the following formula: 153 parts of dye are obtained in the form of a dark red powder. This dye is a mixture of dyes with n=1, 2 and 3 and dissolves in 30% acetic acid to a brilliant blue color.
λ _nax 327 and 607nm. Example 94 To a mixture of 1300 parts of 100% sulfuric acid and 115 parts of copper phthalocyanine, 143.8 parts of 1-ethylimidazole and 76 parts of paraformaldehyde are added at 20-35°C. Gradually heat the mixture to 110 °C and at this temperature
Stir for 12 hours. The reaction solution obtained is poured onto 3000 parts of ice and 1000 parts of water. 900 parts of sodium chloride and 150 parts of zinc chloride are added to this solution and the suspension is stirred. After filtering the precipitate and washing the residue with 10% sodium chloride solution to make it sulfate-free and drying at 90°C, the following formula is obtained: 403 parts of dye are obtained in the form of a dark blue powder. This powder dissolves in water to a greenish-blue color. λ _nax 331 and
625nm. Example 95 Cobalt phthalocyanine in 200 parts of 100% sulfuric acid
Add 14.3 parts, 15.9 parts of 1-ethylimidazole, and 7.2 parts of paraformaldehyde, and heat at 100 to 105°C for 20 minutes.
Stir for an hour. The cooled reaction solution is drained onto ice water and 350 parts of 50% caustic soda solution are added to precipitate the reaction product. After separating the precipitate, washing with water and drying, the following formula is obtained. 13.4 parts of dye are obtained. Propionic acid solution is greenish-blue in color. From 14.3 parts of nickel phthalocyanine, the corresponding nickel phthalocyanine compound can be obtained by the same operation.
21.5 copies are obtained. Example 96 1670 parts of 0.5% oleum and 115 parts of copper phthalocyanine
86 parts of 1-methylimidazole and 45.4 parts of paraformaldehyde were simultaneously added to the mixture at 20-35° C. and stirred for 1 hour. Then the reaction mixture
Heat to 100°C and stir at this temperature for 18 hours. After cooling, the reaction mixture is drained onto ice water and the solution is brought to pH 10-11 with caustic soda solution. The precipitate is filtered by suction, washed to neutrality, and dried, resulting in the following formula: 144 parts of dye are obtained in the form of a dark blue powder. 30%
The color of the acetic acid solution is a shiny blue. λ _nax
325 and 607nm. Example 97 10.3 parts of metal-free phthalocyanine and 17.9 parts of 4-methyl-5-hydroxymethylimidazole hydrochloride were added to 160 parts of 98% sulfuric acid, and the mixture was gradually heated to 80°C for 2 hours at 80°C. Stir. Example
96 and isolated by draining onto water and precipitating the dye with caustic soda solution,
The following formula 3.6 parts of dye are obtained in the form of a blue powder. The color of the dilute propionic acid solution is linden green. Example 98 Working as in Example 97, but using 11.4 parts of iron phthalocyanine instead of the metal-free phthalocyanine and stirring at 80° C. for 5 hours, 7.6 parts of the corresponding iron phthalocyanine compound are obtained, which is Gives a blue-green solution in dilute acetic acid. Example 99 Copper phthalocyanine 15.3 in 200 parts of 100% sulfuric acid
part, add 7.1 parts of paraformaldehyde and 22.5 parts of 1-butyl-2-methylimidazole, and add 20 to 30 parts of
Stir for 1 hour at 100°C and then 18 hours at 100°C. After draining onto ice water and making alkaline with caustic soda solution, the dye is separated, washed with salt-free water and dried, resulting in the following formula: 21.5 parts of dye are obtained as a reddish-blue powder. 20
% acetic acid solution is a shiny blue color. Example 100 200 parts of 100% sulfuric acid, 14.3 parts of copper phthalocyanine, 2
- A mixture of 27.25 parts of isopropylimidazole and 12.75 parts of paraformaldehyde at 30-35°C.
Stir for 1 hour at 100°C and 24 hours at 100°C. Example 96
When isolation is performed in the same manner as 21.8 parts of dye are obtained. The color of the 20% propionic acid solution is a shiny blue. 1, instead of 2-isopropylimidazole
When 24 parts of 2-dimethylimidazole is used, the corresponding bis-(dimethylimidazolylmethylene)-
29.9 parts of copper phthalocyanine are obtained. Example 101 200 parts of 100% sulfuric acid, 15.3 parts of copper phthalocyanine, 1
-A mixture of 15.3 parts of vinylimidazole and 7.1 parts of paraformaldehyde is stirred at 100° C. for 18 hours. The reaction mixture is worked up as in Example 96 to give 20 parts of a pale blue dye which is easily dissolved in dilute acetic acid. Example 102 250 parts of 5% oleum, dibenzopyrenequinolene
A mixture of 16.6 parts, 24 parts of 1-ethylimidazole, and 12.8 parts of paraformaldehyde was added at 20 to 30°C.
Stir for 16 hours, then at 80°C for 10 hours, and at 90°C for 8 hours. The reaction mixture was drained onto ice water, the precipitate was filtered off by suction, washed with water and dried, resulting in the following formula: 25 parts of dye (=1.2, ie a mixture of dyes with n=1 and 2) are obtained. The color of the dilute acetic acid solution is yellowish brown. Example 103 20.3 parts of pyranthrone, 24 parts of 1-ethylimidazole and 12.8 parts of paraformaldehyde are added in small portions to 250 parts of 5% oleum. Mixture 20~
Stir at 25°C for 16 hours and at 80°C for 12 hours. After cooling, drain the reaction mixture onto ice water and reduce the mixture to 50%.
Adjust the pH to 7 with 395 parts of caustic soda solution. When the precipitate is suctioned, washed with water and dried, the following formula is obtained. 33 parts of dye are obtained. 10.3 parts of this dry powder are quaternized with 2.8 parts of dimethyl sulfuric acid in 100 parts of dioxane at 50° C. for 10 hours. The quaternary ammonium compound is isolated from the solution by distilling off the solvent (yield 14 parts). This product is readily soluble in water. Example 104 22.3 parts of 1,4-bis-phenylethylaminoanthraquinone and 4-methyl- in a mixture of 500 parts of 85% phosphoric acid and 197.5 parts of phosphorus pentoxide at 25-30°C.
28.1 parts of 5-hydroxymethylimidazole are added and the mixture is stirred at 60-65°C for 8 hours and at 110°C for 2 hours. After cooling, it is poured onto water, the reaction product is precipitated with caustic soda solution and filtered off with suction.
When the excess residue is mixed with 10% sodium carbonate solution, filtered by suction, and washed to neutrality, the following formula is obtained. 21 parts of dye are obtained. A blue solution is obtained in dilute acetic acid. Example 105 Indanthrone 22.2 parts in 250 parts of 98-99% sulfuric acid
and 18.6 parts of 4-methyl-5-hydroxymethylimidazole are added at 50-65°C.
The mixture was heated at 60-65°C for 2 hours, at 70°C for 6 hours and at 80°C.
Stir for 15 hours at °C. After cooling, transfer the reaction mixture to ice water.
Drain the mixture onto 1000 parts 50% caustic soda solution
Make PH10 with 300 copies. The precipitate is filtered by suction, washed to neutrality, and dried, resulting in the following formula: 30 parts of dye are obtained. This dye dissolves in dilute acetic acid to a dark blue color. Example 106 250 parts of 5% fuming sulfuric acid, 23.2 parts of perylenetetracarboxylic acid dimethylimide, paraformaldehyde
A mixture of 12.8 parts and 24 parts of 1-ethylimidazole is stirred at 20-25°C for 12 hours and at 100°C for 12 hours. The dye solution was drained onto ice water, the pH was adjusted to 7.0 with 50% caustic soda solution, the precipitate was filtered off by suction, washed with water to neutrality, and dried, resulting in the following formula: 37 parts of dye are obtained. The color in dilute propionic acid aqueous solution is red. Example 107 In 250 parts of 98% sulfuric acid, 13.6 parts of 4-methyl-5-hydroxymethylimidazole and the following formula Adding 21.4 parts of anthraquinone bisacridone,
The mixture is stirred at 60°C for 4 hours. After cooling, the reaction mixture is discharged onto water and the reaction product is precipitated by addition of 430 parts of 50% caustic soda solution (PH 10). The precipitate is filtered by suction, washed to neutrality, and dried, resulting in the following formula: 28 parts of dye are obtained. This dye dissolves in dilute acetic acid to a purple color. λ _nax 545nm (0.060g/in 5% acetic acid)
). 2-amino- instead of the above bis-acridone
Using 16.4 parts of 3,4-phthaloyl acridone and stirring at 60℃ for 3 hours and then at 80℃ for 8 hours, the following formula is obtained. 21 parts of dye are obtained. This dye dissolves in dilute acetic acid to give a blue color. Example 108 A mixture of 18.8 parts of 8,9-phthaloyl-benzo[a]acridone and 11.4 parts of 4-methyl-hydroxymethylimidazole was added to 190 parts of 96% sulfuric acid and the mixture was heated at 40-45°C for 5 hours and 60~65℃
Stir for 8 hours. When the dye is isolated in the same manner as in Example 107, the following formula 27.5 parts of dye are obtained. This dye dissolves in dilute acetic acid to an orange-red color. Example 109 220 parts of 99.8% sulfuric acid, 22.8 parts of violanthrone, 1
-A mixture of 20.5 parts of methylimidazole and 10.5 parts of paraformaldehyde is stirred at 100-105°C for 18 hours. Drain the reaction solution onto about 2000 parts of ice water,
Add 470 parts of 50% caustic soda solution and filter by suction.
After washing with water and drying, the following formula 40 parts of dye are obtained. This dye dissolves in dilute propionic acid to give a marine blue color. λ _nax 570nm. Example 110 Proceeding as in Example 109, but using the same amount of isoviolanthrone instead of violanthrone, the following formula 32.5 parts of dye (n=1.5, ie a mixture of dyes with n=1 and 2) are obtained. This dye dissolves in dilute propionic acid to a purple color. λ _nax 555nm. Example 111 Proceed as in Example 109, except that violanthrone is replaced by benzoantrone-pyrazoloanthrone.
Replaced with 21.1 parts and heated at 80°C for 4 hours, then at 90°C.
When stirred at ℃ for 7 hours, the following formula 31 parts of dye are obtained. This dye dissolves in acetic acid to give a blue color. Example 112 The following formula in 210 parts of 98% sulfuric acid To a solution of 23.7 parts of anthraquinone bisthiazole was added 16.8 parts of 4-methyl-5-hydroxymethylimidazole at 20 to 30°C. The reaction mixture is stirred at room temperature for 2 hours and then at 80° C. and 90° C. for 7 hours each. The cooled reaction mixture is placed in ice water and the reaction product is precipitated by neutralization with caustic soda solution. When the precipitate is filtered, washed with salt-free water and dried, the following formula is obtained. 34 parts of dye are obtained. This dye dissolves yellow in dilute acetic acid. λ _nax 266, 305 and 413nm. The main absorption band is at 305nm. Example 113 The following formula in 300 parts of sulfuric acid monohydrate To a solution of 27.2 parts of the compound is added 11.4 parts of 4-methyl-5-hydroxymethylimidazole and the mixture is stirred at 100°C for 7 hours and at 115°C for 12 hours. The dye is precipitated in ice water and caustic soda solution, washed neutral and dried at 80°C, giving the following formula: 40 parts of dye are obtained. This dye dissolves in acetic acid to an olive green color. Example 114 20.6 parts of naphthrenebenzimidazole are combined with 250 parts of sulfuric acid monohydrate and 11.4 parts of 4-methyl-5-hydroxymethylimidazole in 105
Stir at ℃ for 4 hours. The reaction solution is precipitated with ice water and caustic soda solution, filtered with suction, and washed salt-free, resulting in the following formula: 30.7 parts of dye are obtained. This dye dissolves in dilute acetic acid to an orange-red color. λ _nax 462nm. Elemental analysis: C ₃₆ H ₂₄ N ₈ O ₂ (600) N Calculated value (%) 18.6 Actual value (%) 18.6 Example 115 In 250 parts of sulfuric acid monohydrate at 55-60°C, 24.5 parts of dichlordibromoindigo and 4 -Methyl-
A mixture consisting of 23 parts of 5-hydroxymethylimidazole is added in portions and stirred at this temperature for 6 hours. After cooling, drain onto ice water, make alkaline with caustic potassium solution, filter through suction, and wash with water to neutralize. 33.3 parts of dye are obtained. This dye dissolves in dilute propionic acid to a dark blue color. Example 116 2,4-bis-(1-anthraquinoylamino)-6-phenyl-1,3,5-triazine 30
1 part was dissolved in 240 parts of 99% sulfuric acid, 10.3 parts of 1-methylimidazole and 4.5 parts of paraformaldehyde were added simultaneously, and the mixture was heated at 90°C for 10 hours and then at 100°C for 5 hours.
Stir for an hour. After cooling, drain it onto ice water, adjust the pH to 10 with caustic soda solution, and filter the precipitate by suction and wash with water. 35 parts of dye are obtained. This dye dissolves yellow in dilute acetic acid. Example 117 In 210 parts of 96% sulfuric acid, 21 parts of 1,5-di-p-toluidino-anthraquinone and 4-methyl-5-
Add 13.5 parts of hydroxymethylimidazole and 20
Stir at ~30 °C for 30 min, then at 70 °C for 90 min.
After cooling, drain onto ice water and pH with caustic soda solution.
10.0, suction filter the precipitate, wash it to neutrality and dry it, then the following formula is obtained. 27.5 parts of dye are obtained. This dye dissolves in 30% acetic acid to a crimson red color. Example 118 Proceed as in Example 117, except that 1,5-di-p-toluidinoanthraquinone is replaced by 1,4-di-p-toluidinoanthraquinone 21
When stirred for 20 hours at 20-25℃, the following formula dye (=3; n=mixture of 2, 3 and 4) 28
part is obtained. This dye has a blue-green solution color in dilute acetic acid. Example 119 Proceed as in Example 117, but instead of 1,5-di-p-toluidino-anthraquinone, 1
Using 20.4 parts of -amino-2-bromo-4-P-toluidino-anthraquinone and stirring at 40°C for 6 hours and then at 60-65°C for 7 hours, the following formula is obtained. 30.5 parts of dye are obtained. This dye dissolves in 30% acetic acid to a dark blue color. Example 120 23.8 parts of 1,4-bis-(2'-phenylpropylamino)-anthraquinone and 16.8 parts of 4-methyl-5-hydroxymethylimidazole are simultaneously added little by little to 210 parts of 98% sulfuric acid and stirred. . 20
After 20 hours at ~25°C, drain onto ice water, add caustic soda solution until precipitation is complete, filter the precipitate with suction, wash to neutral, and dry at 60°C. 32.2 parts of dye are obtained. This dye dissolves in dilute propionic acid to a clear blue color. Example 121 Proceed as in Example 120, but instead of 1,4-bis-(2'-phenylpropylamino)-anthraquinone, 1-nitro-8-o-toluidino-4,5-dihydroxyanthraquinone 19.5 When stirred at 90℃ for 7 hours and then at 100-102℃ for 15 hours, the following formula 28 parts of dye are obtained. This dye dissolves in dilute acetic acid to give a blue color. Example 122 12.2 parts of AlPc (aluminum phthalocyanine) of formula C ₃₂ H ₁₆ N ₈ AlCl.2H ₂ O, paraformaldehyde
4.2 parts and 8.2 parts of 1-methylimidazole were simultaneously added to 120 parts of sulfuric acid monohydrate under stirring,
Melt at 30℃. Heat the mixture to 100℃, 100℃
After stirring for 15 hours at
After washing and drying, 14.5 parts of imidazolyl methylene-aluminum phthalocyanine are obtained which dissolves in dilute acetic acid with a turquoise color. Example 123 Thioindigo in 420 parts of 96% sulfuric acid at 20-30°C.
A mixture of 29.8 parts and 28.2 parts of 4-methyl-5-hydroxymethylimidazole is added and stirred at this temperature for several hours. Then the mixture was heated to 40℃ and 60℃
Stir each for 7 hours. Drain the cooled solution onto ice water and transfer the reaction product to a 50% caustic soda solution.
Precipitate with 850 parts. The precipitate is filtered by suction, washed neutrally and salt-free, and dried at 60°C, resulting in the following formula: 45 parts of dye (=1.7, ie a mixture of n=1 and 2) are obtained. Example 124 19.9 parts of 1-amino-2-phenoxy-4-hydroxyanthraquinone and 4-methyl-5-hydroxymethylimidazole in 210 parts of 98% sulfuric acid
Add 21.5 parts and stir at 20-25°C for 20 hours. The reaction mixture was added to 2000 parts of ice water, the pH was adjusted to 10 with 400 parts of 50% caustic soda solution, the precipitate was filtered off by suction, and washed to neutrality. 26.5 parts of dye are obtained. Elemental analysis: C ₂₅ H ₁₈ N ₃ O ₄ (424) N Calculated value (%) 9.9 Actual value (%) 10.0 The color of the solution in dilute acetic acid is red. Example 125 Proceed as in Example 124, but using 21.9 parts of 1-amino-2-(4'-chlorophenyl)-4-hydroxyanthraquinone instead of 1-amino-2-phenoxy-4-hydroxyanthraquinone. When stirred at 60℃ for 12 hours, the following formula 10 parts of dye are obtained. Example 126 Proceed as in Example 124, but instead of 1-amino-2-phenoxy-4-hydroxyanthraquinone, 1-amino-2-thiophenyl-4
- Using 15 parts of hydroxyanthraquinone and stirring the mixture at 50°C for 8 hours, the following formula 20 parts of dye are obtained. Elemental analysis: C ₂₅ H ₁₈ N ₃ O ₃ S (440) N S Calculated value (%) 9.54 7.2 Actual value (%) 9.6 7.6 This dye dissolves in dilute acetic acid to a blue-red color. Example 127 220 parts of 100% sulfuric acid, 11.4 parts of 4-methyl-5-hydroxymethylimidazole and the following formula A mixture of 22.5 parts of benzanthrone derivative is stirred at room temperature for several hours and then at 60-70° C. for 7 hours. The reaction mixture is poured into 2000 parts of ice water and the reaction product is precipitated by addition of 320 parts of 50% caustic soda solution (PH 10). The precipitate is filtered by suction, washed neutrally and dried at 110°C, resulting in the following formula: 24.1 parts of dye are obtained. This dye dissolves in dilute acetic acid to a blue-green color. Example 128 A mixture of 220 parts of 1% oleum, 20.3 parts of acedianthrone and 13.6 parts of 4-methyl-5-hydroxymethylimidazole was heated at 30°C for 1 hour and at 90°C.
Stir for 2 hours. After cooling, drain onto ice water and neutralize with caustic soda solution. After the precipitate is filtered by suction, washed salt-free and dried, the following formula is obtained. 24.2 parts of dye are obtained. This dye dissolves in dilute acetic acid to a yellow-brown color. Example 129 250 parts of sulfuric acid monohydrate, 4-methyl-5-
15 parts of hydroxymethylimidazole and 9-
A mixture of 22.5 parts of (1'-anthraquinoylamino)-benzaantrone is stirred at 80° C. for 1 hour. After cooling, drain onto ice water and precipitate the reaction product with caustic soda solution. The precipitate is filtered by suction, washed to neutrality, and dried, resulting in the following formula: 27 parts of dye are obtained. This dye dissolves in dilute acetic acid to a brown color. Example 130 45 parts of water, 10 parts of 40% acetic acid and 16 parts of the dye obtained in Example 96 are heated to 45-50°C until completely dissolved. Then add 5.6 parts of dimethyl sulfate and heat to 50-52℃.
Stir for 2 hours. Decompose excess dimethyl sulfate with dilute aqueous ammonia. Propanol 119 at about 20℃
The dye is precipitated by adding 50% of 21 parts of quaternary ammonium compound are obtained. This compound dissolves in water with a clear turquoise color. Example 131 23.7 parts of anthraquinone bisthiazole of the formula are dissolved in 250 parts of sulfuric acid monohydrate. Then 16.4 parts of 4-methylimidazole and 8.3 parts of paraformaldehyde are added simultaneously. Mixture at 25℃
Stir for 20 hours and at 50°C for 7 hours. Drain the reaction solution onto ice water and bring to pH 10 with 50% caustic soda solution. The precipitate is filtered by suction, washed with neutral and salt-free water, and dried at 80°C, resulting in the following formula: 34.8 parts of dye are obtained. Elemental analysis: C ₃₈ H ₂₄ N ₆ O ₂ S ₂ (660) S N Calculated value (%) 9.7 12.7 Actual value (%) 9.1 12.2 λ _nax 266, 305, 413 nm The color of the solution in dilute acetic acid is yellow. Example 132 22.8 parts of isoviolanthrone is added to 220 parts of sulfuric acid monohydrate and dissolved. Then 20.5 parts of 4-methylimidazole and 10.5 parts of paraformaldehyde
Add parts at the same time. The mixture is stirred at 25-30°C for 1 hour and at 100°C for 5 hours. Pour the reaction solution into ice water 1500 ml
Drain to the top and adjust the pH to 10 with 50% caustic soda solution. When the precipitate is filtered by suction, washed with neutral and salt-free water, and dried, the following formula is obtained. 42.2 parts of dye are obtained. Elemental analysis: C ₄₉ H ₃₄ N ₆ O ₂ (738) N Calculated value (%) 11.4 Actual value (%) 11.1 The acetic acid solution has a reddish-blue color. λ _nax 557nm. Example 133 22.2 parts of 4-methylimidazole are added to 280 parts of sulfuric acid monohydrate, and then 8.3 parts of paraformaldehyde are added little by little. The mixture is stirred at 25° C. for 60 hours, then drained onto 2000 parts of ice water and brought to pH 10 with about 420 parts of 50% caustic soda solution. When the precipitate is filtered by suction and washed with neutral and salt-free water, the following formula is obtained. 31.7 parts of dye are obtained. Elemental Analysis: C ₃₃ H ₂₀ N ₄ O ₄ (536) N Calculated (%) 10.45 Found (%) 10.7 The solution in 25% acetic acid is blue in color. λ _nax 667nm
(0.040g/). Example 134 Copper phthalocyanine in 690 parts of sulfuric acid monohydrate
86.1 parts of 4-methylimidazole and 24.75 parts of paraformaldehyde were added simultaneously at 20-30°C. The mixture is stirred at 30-40°C for 30 minutes, then heated to 98-100°C and stirred at this temperature for 10 hours. After cooling, the reaction mixture was drained onto ice water and
Bring the solution to pH 10-11 with caustic soda solution. After separating the precipitate, washing it neutrally and without salt, and drying it at 100℃, the following formula is obtained. 42.4 parts of dye are obtained. Atomic ratio Cu:N=1:14. The acetic acid solution has a turquoise color. λ _nax 327 and
607nm. Example 135 8.6 4-methylimidazole in 140 parts of 96% sulfuric acid
1 part and 4.2 parts of paraformaldehyde, and heated to 40°C.
Stir for 30 minutes. Then, 4,4′-bis-(6-methylbenzothiazolyl-2)-azobenzole (Helvetica chimica acta No.
1944, p. 27) add 12 copies. mixture
Heat to 60°C for 30 minutes and stir at 60°C for 3 hours.
Drain the solution onto ice water and neutralize with 25% aqueous ammonia while cooling. Aspirate the precipitate, wash and heat at 70°C.
When dried with 15.7 parts of dye are obtained, which dissolves yellow in dilute acetic acid. λ _nax 237 and 380nm. Usage example 1 Disintegrate 50g of waste paper (containing wood fiber) in water (10°dH) at room temperature until it becomes a fiber suspension.
Then dilute with 1 part of the same water. In suspension, examples
A mixture of 2 g of a 10% acetic acid solution of the dye from No. 64 and 10 ml of water is added. The mixture is stirred gently for 15 minutes and then diluted to 0.5% solids with water. This suspension was used on a Frank laboratory paper sheet forming machine.
80g/ ^cm2 paper sheets are produced and the wet paper sheets are heated to 100℃.
Dry for 5 minutes. A red-dyed inferior paper is obtained. The wastewater is colorless. The smear fastness (according to DIN 53991) of this dyed paper is very good and the light fastness is likewise very good. The waste paper is made of (a) a mixture of 30% birch sulfate pulp and 70% pine sulfate pulp, (b) pine sulfite pulp or
(c) Similarly good results are obtained when replacing with pine sulfate pulp. An orange-red to red dyed paper is obtained which has excellent fastness properties. Usage example 2 Waste paper (contains wood fiber) 15Kg, bleached ground wood pulp 25Kg
Kg and 10Kg of unbleached sulphate pulp in a pulper.
% aqueous stock suspension. The stock suspension is diluted to 2% in the dye bath. The oxidatively degraded soluble corn starch is then added to this suspension with stirring.
0.5%, kaolin 5% (both calculated on the total amount of dry fiber) and 1.25 Kg of a 5% acetic acid solution of the dye from Example 64 are added in sequence. After 20 minutes, 1% (based on bone dry fiber) of resin size dispersion is added to the stock in a mixing tank. This homogeneous stock suspension is adjusted to pH 5 using alum in the paper machine just before the flow box. Bag paper weighing 80 g/m ² is machine produced on a paper machine. This paper exhibits a medium red shade with good smudge fastness according to DIN 53991. Usage example 3 In a pulper, 25 kg of catalog paper (recycled paper), bleached groundwood pulp (Shopper Riegler freeness)
65゜) 60Kg and 15Kg of unbleached sulfite pulp and 2500g of water
It disintegrates inside. Add 0.4% soluble starch, 16% kaolin and 2% talc (all calculated on dry fiber) to a 4% aqueous stock suspension. The stock suspension is then ground in a refiner to a Schottsper-Riegler freeness of 45°. In the stock suspension, Example 64
Add 12Kg of a 10% acetic acid solution of the dye from (1% dry red dye on bone dry fiber). After a transfer time of 15 minutes, a resin size dispersion (amount: 0.6% dry matter based on fiber) is added to the paper stock, and after 10 minutes the stock flowing out of the mixing tank is continuously mixed with water to form a 0.8% paper diluted to the desired content and _continuously tested
(SO ₄ ) _{3.18H 2} O] to adjust the pH to 4.5 (measured in screen water) and pump into the flow box. A yellowish-red catalog paper (60 g/m ² ) with good water resistance is obtained. In place of the dye from Example 64, Example 65 or
With dye No. 69, a red-orange to orange-dyed paper with good wet fastness properties is obtained. Example 136 75 parts of 2-chloroethanol (1) and 19 parts of the dye obtained in Example 96 were heated at 80°C for 1 hour and at 90-95°C.
Stir for 2 hours. After cooling to 20°C, 200 parts of acetone was added to precipitate the dye, which was filtered with suction.
After washing with acetone and drying at 30°C, the following formula 22.3 parts of quaternary ammonium compound are obtained. This compound dissolves in water with a clear turquoise color.
λ _nax 325 and 607nm. A dyeing of the same shade is obtained on the paper, and the waste water is not colored.

Claims (1)

[Claims] 1. General formula [In the formula, R ¹ and R ² are independently a hydrogen atom or a C ₁ -C ₄ -alkyl group, R ³ is a hydrogen atom, and R ⁴ is a C ₁
~ _C4 -alkyl group or hydroxy- _C2 - _C4 -alkyl group, (n+m) is 1 to 4, X is the equivalent of the anion, F is (a) aromatic carbocyclic diamine, β-naphthol, its derivative or (b) A product obtained by coupling an aromatic carbocyclic diamine to a pyrazolone-5-compound; (c) A product obtained by coupling an optionally substituted aminoazobenzole to a pyrazolone-5-compound. The product coupled with (d) the following formula (In the formula, Q is the following formula [Formula] or a residue of [Formula], B ¹ is a hydrogen atom or a methyl group, B ² is a hydrogen atom, a methyl group or an ethyl group, S' is a sulfonic acid group or a hydrogen atom,
B ³ is a hydrogen atom, hydroxyl group, amino group, 2-hydroxyethylamino group, methylamino group, or phenylamino group, B ⁴ is a hydrogen atom, acetyl group, or N
- Phenylcarbamoyl group, B ⁵ means a hydrogen atom, hydroxyl group, methyl group, methoxy group, chlorine atom, bromine atom, 2-hydroxyethylamino group or dimethylamino group, in which case B ³ or B ⁵ is a hydroxyl group Yes, ^B6 is a hydrogen atom, methyl group or methoxy group,
B ⁷ is a hydroxyl group or an amino group, B ⁸ is a phenyl group or 4-methoxyphenyl group, B ⁹ is a hydrogen atom, methyl group, or methoxy group, B ¹⁰ is a hydrogen atom or a chlorine atom, B ¹¹ is a hydrogen atom or a methoxy group , and B ¹²
means a methoxy group, butoxy group, amino group, methylamino group, phenoxy group, 4-methylphenoxy group or 3-methyl-4-methoxyphenoxy group), (e) a dye represented by the following formula: (In the formula, D is a chlorine atom, a nitro group, a methoxy group,
means a phenyl group optionally substituted by a methyl group, a phenylazo group or a tolylazo group, the phenyl group having one or two substituents, and the substituents being a nitro group, a phenylazo group and a tolylazo group. may be the same or different except for R ⁶ is a hydrogen atom, chlorine atom, bromine atom, nitro group, methyl group, trifluoromethyl group, carbalkoxy group, optionally substituted carbamoyl group or sulfamoyl group, sulfonic acid Aryl ester group, cyan group, alkanoylamino group or phenyl group, R ⁷ is a hydrogen atom, chlorine atom or bromine atom, R ⁸ and R ⁹ are independently a hydrogen atom, chlorine atom, bromine atom or together a fused ring , and R ¹⁰ means a methyl group or a phenyl group optionally substituted with a chlorine atom or a methoxy group), (f) 5,6-benzoquinophthalone, (g) 7-dialkylamino-3
-benzimidazolyl-(2)-coumarin, (h) condensation product of naphtholactam and barbituric acid or N-substituted barbituric acid, (i) triphenylmethane dye or xanthene dye, (k) phthalocyanine, (l) violanthrone , isoviolanthrone, pyrantrone, indanthrone, naphtoylenebenzimidazole or anthraquinone bisacridone, or (n+m)-valent residue derived from (m) perylene-3,4,9,10-tetracarboxylic acid diimide. A dye containing an imidazolyl methylene group represented by the following. 2 R ¹ and R ² are hydrogen atoms or C ₁ independently
~ _C4 -alkyl group, ^R3 is a hydrogen atom, n is 1-4,
The dye according to claim 1, wherein m is 0. 3 R ¹ and R ³ are hydrogen atoms, R ² is 4-methyl group,
A dye according to claim 1, characterized in that n is 1 to 4 and m is 0. 4 F is the following formula [In the formula, Q' is a barbituric acid residue, a N-methyl-N-benzylaniline residue, or a 4-(6'-
(n
Dye according to claim 2, characterized in that it is a residue with a valence of +m). 5 F is the following formula (In the formula, D' means a phenyl group substituted with a phenylazo group or a tolylazo group, and the phenyl group may be further substituted with a chlorine atom, a methoxy group, or a methyl group). A dye according to claim 2, characterized in that it is a group. 6 F is benzoquinophthalone (2-[1,3-
Claim 2, characterized in that it is a residue derived from dioxo-hydroindyl-(2)]-5,6-benzoquinoline) or a condensation product of naphtolactam and barbituric acid. dye. 7 F is derived from copper phthalocyanine (m
Dye according to claim 2, characterized in that it is a residue with a valence of +n). 8 General formula [In the formula, R ¹ and R ² are independently a hydrogen atom or a C ₁ -C ₄ -alkyl group, R ³ is a hydrogen atom, and R ⁴ is a C ₁
~ _C4 -alkyl group or hydroxy- _C2 - _C4 -alkyl group, (n+m) is 1 to 4, X is the equivalent of the anion, F is (a) aromatic carbocyclic diamine, β-naphthol, its derivative or (b) A product obtained by coupling an aromatic carbocyclic diamine to a pyrazolone-5-compound; (c) A product obtained by coupling an optionally substituted aminoazobenzole to a pyrazolone-5-compound. The product coupled with (d) the following formula (In the formula, Q is the following formula [Formula] or a residue of [Formula], B ¹ is a hydrogen atom or a methyl group, B ² is a hydrogen atom, a methyl group or an ethyl group, S' is a sulfonic acid group or a hydrogen atom,
B ³ is a hydrogen atom, hydroxyl group, amino group, 2-hydroxyethylamino group, methylamino group, or phenylamino group, B ⁴ is a hydrogen atom, acetyl group, or N
- Phenylcarbamoyl group, B ⁵ means a hydrogen atom, hydroxyl group, methyl group, methoxy group, chlorine atom, bromine atom, 2-hydroxyethylamino group or dimethylamino group, in which case B ³ or B ⁵ is a hydroxyl group Yes, ^B6 is a hydrogen atom, methyl group or methoxy group,
B ⁷ is a hydroxyl group or an amino group, B ⁸ is a phenyl group or 4-methoxyphenyl group, B ⁹ is a hydrogen atom, methyl group, or methoxy group, B ¹⁰ is a hydrogen atom or a chlorine atom, B ¹¹ is a hydrogen atom or a methoxy group , and B ¹²
means a methoxy group, butoxy group, amino group, methylamino group, phenoxy group, 4-methylphenoxy group or 3-methyl-4-methoxyphenoxy group), (e) a dye represented by the following formula: (In the formula, D is a chlorine atom, a nitro group, a methoxy group,
means a phenyl group optionally substituted by a methyl group, a phenylazo group or a tolylazo group, the phenyl group having one or two substituents, and the substituents being a nitro group, a phenylazo group and a tolylazo group. may be the same or different except for R ⁶ is a hydrogen atom, chlorine atom, bromine atom, nitro group, methyl group, trifluoromethyl group, carbalkoxy group, optionally substituted carbamoyl group or sulfamoyl group, sulfonic acid Aryl ester group, cyan group, alkanoylamino group or phenyl group, R ⁷ is a hydrogen atom, chlorine atom or bromine atom, R ⁸ and R ⁹ are independently a hydrogen atom, chlorine atom, bromine atom or together a fused ring , and R ¹⁰ means a methyl group or a phenyl group optionally substituted with a chlorine atom or a methoxy group), (f) 5,6-benzoquinophthalone, (g) 7-dialkylamino-3
-benzimidazolyl-(2)-coumarin, (h) condensation product of naphtholactam and barbituric acid or N-substituted barbituric acid, (i) triphenylmethane dye or xanthene dye, (k) phthalocyanine, (l) violanthrone , isoviolanthrone, pyrantrone, indanthrone, naphtoylenebenzimidazole or anthraquinone bisacridone, or (n+m)-valent residue derived from (m) perylene-3,4,9,10-tetracarboxylic acid diimide. A method of using a dye containing an imidazolyl methylene group represented by the following formula for dyeing a cellulose fiber-containing material.