JP2008500421A - Concentrated dye solution - Google Patents

Abstract

One or more cationizable dyes, concentrated dye aqueous solutions comprising organic acids and water, and their use for dyeing and / or printing organic substrates and for producing ink jet printing inks. Formula (I) wherein each A is independently —NH— or —O—, B is a polyvalent group or atom, n ′ and n ″ are natural numbers, and n ′ and n The sum of ″ is ≧ 2 and m is a group having the formula (c ₁ ) or (c ₂ ).

Description

  The present invention relates to a storage-stable concentrated dye aqueous solution, and more particularly to a storage-stable concentrated dye aqueous solution having no solubilizing agent content. The invention further relates to the use of the concentrated dye solution of the invention (if appropriate after dilution with water), in particular for dyeing and printing paper (including cardboard and board).

  Industrial dyeing and printing are typically performed in an aqueous medium. Thus, pulverulent dyes must first be dissolved (usually in hot or hot water) in order to be usable for printing and dyeing.

  Metering systems developed for this purpose utilize weighing or volumetric methods to control the metering of dyes, and they require stable dye solutions instead of powders and granules.

  Such dye solutions have the advantage that they are easily meterable, do not scatter dust and do not require costly dissolution operations.

  Such solutions should have optimal stability so that they do not precipitate during transport or storage. Typically, they should be stable for a long time between 0 and 5 degrees Celsius, but also at about 50 ° C. Similarly, the frozen solution should be stable after injection and should not present any stability problems during pumping. Precipitates can cause interruptions in pumping or metering systems and can lead to unacceptable machine shutdowns and costly cleaning and maintenance.

  One problem with known aqueous dye solutions is the large amount of additive solubilizers, which leads to high carbon content in the effluent of dyeing or paper mills. This leads to high total organic carbon (TOC) and chemical oxygen demand (COD) effluents and thus causes high water treatment costs. Accordingly, it is an object of the present invention to provide a concentrated dye aqueous solution that does not require the dye to be isolated and dried (high energy cost!) And that contains little or no solubilizer. That is.

  Concentrated dye aqueous solutions without the addition of solubilizers do not isolate the dye but concentrate it and make it unreactive for solubilizing agents (such as 1-methyl-2-pyrrolidone or dimethylacetamide) based on the reaction. It has now been found that it is stable when ultrafiltered to include.

  The concentrated dye aqueous solution of the present invention comprises one or more cationizable dyes, an organic acid and water.

〔ここで、
各Ａは独立して、−ＮＨ−または−Ｏ−であり、
Ｂは、多価の基または原子であり、
ｎ′およびｎ″は自然数であり、しかもｎ′およびｎ″の総和は≧２であり、
ｍは、≧０の自然数であり、
ＣＣは、式（ｃ₁）または（ｃ₂）

を有する基であり、
各Ｒ₁₀は独立して、Ｈ、Ｃ_1~4アルキル、Ｃ_5~6シクロアルキル、フェニル、ベンジルまたはフェニルエチルであり、
各Ｒ₁₀′は独立して、Ｈ、−ＯＨまたはＣ_1~4アルキルであり、
各Ｔ₁は独立して、Ｈ、−ＣＮ、−ＣＯＯＲ₁₅、ＣＯＮＲ₁₆Ｒ₁₇、ＳＯ₂ＮＲ₁₆Ｒ₁₇、

であり、
Ｇは、Ｈ、−Ｒ₁₁ＮＨＲ₁₂または−Ｒ₁₁ＮＲ₁₃Ｒ₁₄であり、
Ｒ₁₁は、Ｃ_1~6アルキレンまたはＣ_2~6アルケニレンであり、
Ｒ₁₂およびＲ₁₃は独立して、Ｈ；非置換Ｃ_1~6アルキル；ＯＨ、ＣＮもしくはハロゲンにより置換されたＣ_2~6アルキル；フェニル−Ｃ_1~3アルキル（ここで、フェニル基は、随意に、塩素、Ｃ_1~4アルキルまたはＣ_1~4アルコキシから成る群から選択された置換基により一回、二回または三回置換されている）；非置換Ｃ_5~6シクロアルキル；またはＣ_1~4アルキル基により一回、二回もしくは三回置換されたＣ_5~6シクロアルキルであり、
Ｒ₁₄は、Ｒ₁₂もしくはＲ₁₃についてのとおりの意味を有するかまたは水素原子であり、
Ｒ₁₅は、Ｃ_1~6アルキル基またはフェニル−Ｃ_1~3アルキル基であり、
Ｒ₁₆およびＲ₁₇は独立して、ＨまたはＣ_1~4アルキル基であり、
Ｒ₁₈は、各出現において独立して、Ｈ、Ｃ_1~4アルキル基、−ＮＲ₁₆Ｒ₁₇−（ＣＨ₂）_2~4−ＮＲ₁₆Ｒ₁₇または−ＣＯＮＲ₁₆Ｒ₁₇であり、
Ｒ₁₉は、Ｃ_1~4アルキル基またはヒドロキシ−Ｃ_1~4アルキル基であり、
Ｒ₂₀は、−Ｓ−または−Ｏ−であり、
Ｒ₂₁は、水素原子またはＣ_1~4アルキル基であり、そして
Ａｎ^-は、無色アニオンであり、
但し
（ｉ）ｎ′、ｎ″およびｍの総和は、Ｂの結合価数より小さく、
（ｉｉ）ｎ′およびｎ″の総和＝２であるときは、ｍは≧１であり、
（ｉｉｉ）ｎ′およびｎ″の総和＝３でありそしてＡ＝ＮＨであるときは、ｍは≧１である
ことを条件とする〕
の染料、有機酸および水を含む。 In a further preferred embodiment, the concentrated dye aqueous solution of the present invention has the formula (I)

〔here,
Each A is independently —NH— or —O—;
B is a polyvalent group or atom;
n ′ and n ″ are natural numbers, and the sum of n ′ and n ″ is ≧ 2,
m is a natural number ≧ 0,
CC represents the formula (c ₁ ) or (c ₂ )

A group having
Each R ₁₀ is independently H, C _1-4 alkyl, C _5-6 cycloalkyl, phenyl, benzyl or phenylethyl;
Each R ₁₀ ′ is independently H, —OH or C _1-4 alkyl;
Each T ₁ is independently H, —CN, —COOR ₁₅ , CONR ₁₆ R ₁₇ , SO ₂ NR ₁₆ R ₁₇ ,

And
G is H, —R ₁₁ NHR ₁₂ or —R ₁₁ NR ₁₃ R ₁₄ ;
R ₁₁ is C 1 _{~ 6} alkylene or C _{2 ~ 6} alkenylene,
R ₁₂ and R ₁₃ are independently, H; unsubstituted C _{1 ~ 6} alkyl; OH, CN or C _{2 ~ 6} alkyl substituted by halogen; phenyl -C 1 _{~ 3} alkyl (where the phenyl group is Optionally substituted once, twice or three times with a substituent selected from the group consisting of chlorine, C _1-4 alkyl or C _1-4 alkoxy); unsubstituted C _5-6 cycloalkyl; or once with C 1 _{~ 4} alkyl group, a twice or three times substituted C _{5 ~ 6} cycloalkyl,
R ₁₄ has the meaning as for R ₁₂ or R ₁₃ or is a hydrogen atom,
R ₁₅ is a C _1-6 alkyl group or a phenyl-C _1-3 alkyl group,
R ₁₆ and R ₁₇ are independently H or a C _1-4 alkyl group,
R ₁₈ is independently at each occurrence H, C _1-4 alkyl, —NR ₁₆ R ₁₇ — (CH ₂ ) ₂ —4-NR ₁₆ R ₁₇ or —CONR ₁₆ R ₁₇ ;
R ₁₉ is a C _1-4 alkyl group or a hydroxy-C _1-4 alkyl group,
R ₂₀ is —S— or —O—;
R ₂₁ is a hydrogen atom or a C _1-4 alkyl group, and An ⁻ is a colorless anion,
Where (i) the sum of n ′, n ″ and m is smaller than the valence of B,
(Ii) when the sum of n ′ and n ″ = 2, m is ≧ 1;
(Iii) When the sum of n ′ and n ″ = 3 and A = NH, m must be ≧ 1]
Including dyes, organic acids and water.

  The storage-stable high concentration solution of the dyes of formula (I) of the present invention may also contain a plurality of different dyes, whose formulas fall within formula (I).

の置換基である。 In preferred dyes of formula (I), T ₁ is of the formula

Is a substituent.

の置換基である。 In further preferred dyes, the CC group has the formula

Is a substituent.

Preferably, B is a group _{B'C [(CH 2) 0 ~} 4] 1 ~ or a _4, or B is a group _{[- (CH 2) 1 ~} 4 -O- (CH 2) 1 ~ 4] 4 C or [— (CH ₂ ) _1-3 O— (CH ₂ ) _1-3 O— (CH ₂ ) _1-3 ] ₄ C or [— (CH ₂ ) _1-2 O— (CH ₂ ) _1-2 -O- (CH ₂ ) _1-2 -O- (CH ₂ ) _1-2 ] ₄ C or [(-CH ₂ ) _1-4 ] ₂ N (CH ₂ ) _1-4 N [( —CH ₂ ) _{1 to 4} ] ₂ . It is particularly preferred that B is a carbon atom.

〔ここで、
ＣＣは、式（ｃ₁）または（ｃ₂）の置換基であり、そして
ｎ″は、１、２、３または４であり、
但し
ｎ″＝１であるときは、Ｂ″はＣ（ＣＨ₂ＯＨ）₃であり、
ｎ″＝２であるときは、Ｂ″はＣ（ＣＨ₂ＯＨ）₂であり、
ｎ″＝３であるときは、Ｂ″はＣ（ＣＨ₂ＯＨ）であり、
ｎ″＝４であるときは、Ｂ″はＣ、［−（ＣＨ₂）_1~4−Ｏ−（ＣＨ₂）_1~4］₄Ｃ、［−（ＣＨ₂）_1~3−Ｏ−（ＣＨ₂）_1~3−Ｏ−（ＣＨ₂）_1~3］₄Ｃ、［−（ＣＨ₂）_1~2−Ｏ−（ＣＨ₂）_1~2−Ｏ−（ＣＨ₂）_1~2−Ｏ−（ＣＨ₂）_1~2］₄Ｃまたは［（−ＣＨ₂）_1~4］₂Ｎ（ＣＨ₂）_1~4Ｎ［（−ＣＨ₂）_1~4］₂である
ことを条件とする〕
を有する。 Particularly preferred compounds of the formula (I) are those of the formula (Ia)

〔here,
CC is a substituent of formula (c ₁ ) or (c ₂ ) and n ″ is 1, 2, 3 or 4;
However, when n ″ = 1, B ″ is C (CH ₂ OH) ₃ ,
When n ″ = 2, B ″ is C (CH ₂ OH) ₂ ,
When n ″ = 3, B ″ is C (CH ₂ OH),
When n ″ = 4, B ″ represents C, [— (CH ₂ ) _{1 to 4} —O— (CH ₂ ) _{1 to 4} ] ₄ C, [— (CH ₂ ) _{1 to 3} —O— ( CH ₂ ) _1-3 O- (CH ₂ ) _1-3 ] ₄ C, [— (CH ₂ ) _1-2 O— (CH ₂ ) _1-2 O— (CH ₂ ) _1-2 O- (CH ₂ ) _{1 to 2} ] ₄ C or [(—CH ₂ ) _{1 to 4} ] ₂ N (CH ₂ ) _{1 to 4} N [(— CH ₂ ) _{1 to 4} ] ₂ To do]
Have

A compound of the formula of formula (Ia), wherein CC is a substituent of formula (c ₁ ) or (c ₂ ) and n ″ is 1, 2, 3 or 4;
However, when n ″ = 1, B ″ is C (CH ₂ OH) ₃ ,
When n ″ = 2, B ″ is C (CH ₂ OH) ₂ ,
When n ″ = 3, B ″ is C (CH ₂ OH),
When n ″ = 4, the compounds that require B ″ to be C are very special.

  The high storage stability solution of the dye of formula (I) of the present invention has a dye of formula (I) dye content up to 40% by weight, calculated on the total weight of the solution. Preferred dye solutions are dyes having a dye content in the range of 5% to 40% by weight or dyes having a dye content in the range of 10% to 35% by weight and most preferably in the range of 15% to 25% by weight. Having a dye with a dye content.

  The level of organic acid in the storage-stable concentrated solution of the dye of formula (I) of the present invention is between 0.5% and 25% by weight calculated on the total weight of the solution. Preferred dye solutions contain from 1% to 15% added organic acid by weight or from 2% to 10% added organic acid by weight and most preferably from 3% to 7% added organic acid by weight.

Preferred organic acids, in the formula A (-COOH) _n (where, A is C _{1 ~ 12} alkanyl or C _{1 ~ 12} alkenyl, yet may be interrupted by each their nitrogen atoms and / or oxygen atom And each additionally hydroxyl or NR′R ″, wherein R ′ and R ″ are independently C _1-6 alkanyl or C _1-6 alkenyl or C _1-6 hydroxyalkanyl or C _1-6 hydroxyalkenyl. or unsubstituted phenyl or hydroxyl - or sulfur - or C _{1 ~ 18} alkanyl - or C _{1 ~ 18} alkenyl - substituted phenyl) may be substituted by, and n is a natural number of 2 or 3) Of acid. n is preferably = 1 or 2 and more preferably = 1.

  Particularly preferred are formic acid, acetic acid, malonic acid, propionic acid, lactic acid, tartaric acid, benzoic acid and succinic acid. Acetic acid is the most preferred organic acid. These acids are present in a partially deprotonated (dissociated) state, as expected from their pK value and from the pH value of the dye solution.

  Examples of preferred colorless anions are chloride, bromide, sulfuric acid, bisulfuric acid, methosulfuric acid, aminosulfonic acid, perchloric acid, benzenesulfonic acid, oxalic acid, malonic acid, maleic acid, acetic acid, propionic acid, lactic acid, succinic acid Tartaric acid, malic acid, methanesulfonic acid and benzoic acid. But also complex anions such as zinc chloride double salts and the anions of boric acid, citric acid, glycolic acid, diglycolic acid and adipic acid or addition products of orthoboric acid with polyalcohol and at least one An anion of an addition product having a cisdiol group. These anions can of course also be exchanged, for example by ion exchangers or conventional precipitation reactions. Ions can also be exchanged by diafiltration or ultrafiltration. Chloride and bromide halides are particularly preferred anions, and chloride is most preferred.

  In principle, the salts of the added organic acid can also perform an anionic function. In a particularly preferred embodiment, the anion is chloride and the added organic acid is acetic acid.

  Preferred dye solutions according to the invention consist of up to 40% by weight of dye, 0.5% to 25% organic acid by weight and water to 100% by weight, but in particular 10% to 35% dye by weight. Consisting of 1% to 15% organic acid by weight and water made up to 100% by weight, however, particularly preferred dye solutions are 15% to 25% dye by weight, 2% to 10% organic acid by weight and Consists of water made up to 100% by weight.

  Particularly preferred dye solutions according to the invention consist of up to 40% by weight of dye as chloride, 0.5% to 25% organic acid by weight and water made up to 100% by weight, but in particular 10% by weight. To 35% of the dye as chloride, 1% to 15% by weight of organic acid and 100% by weight of water, and particularly preferred dye solutions are 15% to 25% by weight of chloride. Dye, consisting of 2% to 10% organic acid by weight and water to 100% by weight.

  Very particularly preferred dye solutions according to the invention consist of up to 40% by weight of dye as chloride, 0.5% to 25% acetic acid by weight and 100% by weight water, but in particular 10% by weight. % To 35% of the dye as chloride, 1% to 15% acetic acid by weight and 100% water by weight, however, a particularly preferred dye solution is 15% to 25% chloride by weight. Dyes, consisting of 2% to 10% acetic acid and 100% water by weight.

  The present invention also provides a method of producing a dye solution of the present invention, wherein an aqueous solution or suspension of at least one crude cationic dye is forced through a semipermeable membrane by applying pressure to form salts and less than 500. A method is provided that comprises removing a synthetic byproduct having a molecular weight as well as some water.

  In a preferred embodiment, the permeate is continuously or intermittently replaced or made up with water or buffer solution so that the batch volume (if any) changes minimally. In other words, the dye concentration remains constant or substantially constant. The permeate dye concentration does not vary more than 20% in a preferred embodiment, more than 10% in a particularly preferred process and more than 5% in a very particularly preferred process.

  Following this diafiltration or ultrafiltration, the dye solution is brought to the desired concentration by concentration.

Membranes used in the method of the present invention are TFM ^™ membranes such as G10, G20, G50 or DL5 membranes from GE Osmonics Desal (595 O Clearwater Drive, Minnetonka, Minnesota 55343, GE Osmonics Inc. of United States). Of these, the DL5 film is particularly preferred.

  In a further preferred variant, prior to diafiltration, the counterion of the cationic dye is exchanged or further anions are added. These newly added anions mean that the original anions can be easily removed by ultrafiltration or diafiltration. The counter ion of the cationic functional group is exchanged by a halide in a particularly preferred embodiment and by a chloride in a very particularly preferred embodiment.

  The present invention further provides the production of stable liquid formulations of anionic dyes by ultrafiltration of an aqueous solution or suspension of crude dyes.

  Ultrafiltration or diafiltration of the reaction solution, such as by the examples of WO 02/062902, where the dye is not isolated, makes the reaction solution free of further undesirable additives. Can be used to The absence of unwanted additives should be understood in particular as meaning that after ultrafiltration or diafiltration the solution contains less than 1% by weight and preferably less than 0.5% by weight of further substances. It is. Further undesirable substances are in particular alkali metal or alkaline earth metal salts such as ammonium, magnesium chloride, magnesium sulfate, magnesium bisulfate, sodium chloride, sodium sulfate, sodium bisulfate, potassium chloride, potassium sulfate or potassium bisulfate, Inactive salts and electrolytes, such as sodium chloride, that arise from the synthesis stage when used to neutralize and / or salt out dyes and are carried together in a synthesis solution or suspension is there.

  This is followed by the addition of the required amount of organic acid. In principle, the organic acid can also be added before or during ultrafiltration or diafiltration.

  In addition to the identified water-soluble organic acids, the dye solutions of the present invention may contain a biocide.

  Any biocide is suitable. However, preferred are biocides that have FDA approval. Any biocide capable of controlling the growth of gram positive or gram negative bacteria, yeast or fungi can be used in the solutions of the present invention. Suitable biocides are, for example, 3-thiazolone derivatives (eg alkylated and / or chlorinated or used as a mixture). Typically, the biocide is added in an amount up to 0.15% by weight per ready-made composition.

  The concentrated solutions can also be diluted again with water before they are used for staining. The concentrated solution can also be recolored with additional dyes before use. However, the concentrated solution can also be used to recolor other dyes.

  Dyes that are particularly useful for recoloring or being recolored have a color index of C.I. I. Basic Red or C.I. I. Basic brown or C.I. I. Basic blue or C.I. I. Any dye identified as basic violet is included, and in particular one or more of the following dyes can be used to recolor. That is, C.I. I. Basic Brown 23 or C.I. I. Basic Red 12 or C.I. I. Basic Blue 1 or C.I. I. Basic Red 14 or C.I. I. Basic violet 10 or C.I. I. Basic blue 26.

  The dyes of formula (II) and / or formula (III) are likewise useful for recoloring or being recolored.

  The concentrated solution can also be used to recolor the brown dye of formula (II), or the concentrated solution can be recolored with the dye of formula (II).

〔ここで、
Ｂ₁およびＢ₂は独立して−ＯＨおよびＮＨ₂であり、そしてＤ₃＝Ｈまたは式

の残基であり、そして
Ｒ₆、Ｒ₇、Ｒ₈またはＲ₉は独立して、Ｈまたは−ＳＯ₃Ｈであり、そして
Ｍ_aまたはＭ_bは独立して、Ｍ₁からＭ₁₀の意味を有し、
Ｍ₁は、Ｈであり、
Ｍ₂は、−（ＣＨ₂）₃Ｎ（ＣＨ₃）₂であり、
Ｍ₃は、−（ＣＨ₂）₂Ｎ（ＣＨ₂ＣＨ₃）₂であり、
Ｍ₄は、

であり、
Ｍ₅は、

であり、
Ｍ₆は、

であり、
Ｍ₇は、

であり、
Ｍ₈は、

であり、
Ｍ₉は、

であり、
Ｍ₁₀は、−（ＣＨ₂）₂ＮＨ₂であり、そして
Ｒ_aまたはＲ_bは独立して、Ｒ₁からＲ₅の意味を有し、
Ｒ₁は、Ｈであり、
Ｒ₂は、

であり、
Ｒ₃は、

であり、
Ｒ₄は、ＣＮであり、
Ｒ₅は、

である〕
を有する。 The dye of formula (II) has the following structure

〔here,
B ₁ and B ₂ are independently —OH and NH ₂ and D ₃ = H or the formula

And R ₆ , R ₇ , R ₈ or R ₉ is independently H or —SO ₃ H, and M _a or M _b is independently the meaning of M ₁ to M ₁₀ Have
M ₁ is H,
M ₂ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ ,
M ₃ is — (CH ₂ ) ₂ N (CH ₂ CH ₃ ) ₂ ,
M ₄ is

And
M ₅ is

And
M ₆ is

And
M ₇ is,

And
M ₈ is

And
M ₉ is,

And
M ₁₀ is — (CH ₂ ) ₂ NH ₂ and R _a or R _b independently has the meaning of R ₁ to R ₅ ;
R ₁ is H;
R ₂ is

And
R ₃ is

And
R ₄ is CN,
R ₅ is

Is)
Have

  The dyes of the formula (II) are known per se and can be prepared as described in DE 3715066.

  The concentrated solution can also be used to recolor the brown dye of formula (III), or the concentrated solution can be recolored with the dye of formula (III).

〔ここで、
Ｒ¹、Ｒ²またはＲ³は独立して、Ｈ、ＣＨ₃、Ｃ₂Ｈ₅、ｎ−Ｃ₃Ｈ₇、ｉ−Ｃ₃Ｈ₇、ｎ−Ｃ₄Ｈ₉、ｉ−Ｃ₄Ｈ₉、ｓｅｃ−Ｃ₄Ｈ₉であり、
Ｒⁿは、−Ｃ₂Ｈ₄−、−Ｃ₃Ｈ₆−、−ＣＨ（ＣＨ₃）ＣＨ₂−または−Ｃ₄Ｈ₆−であり、
Ｙは、水素またはニトロであり、
ｑは、１または２である〕
を有する。 The dye of formula (III) has the following structure

〔here,
R ¹ , R ² or R ³ is independently H, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , i-C ₃ H ₇ , n-C ₄ H ₉ , i-C ₄ H _9. a sec-C ₄ H _9,
R ⁿ is —C ₂ H ₄ —, —C ₃ H ₆ —, —CH (CH ₃ ) CH ₂ — or —C ₄ H ₆ —,
Y is hydrogen or nitro,
q is 1 or 2]
Have

  The dyes of the formula (III) are known and can be prepared as described in EP 162409 or EP 1352928.

  Recoloring is done at a ratio of 2% to 98% by weight of the dye of formula (I) and 98% to 2% by weight (based on the dye) of the recoloring dye, ie 0 / 98.0, 2.5 / 97.5, 12.5 / 87.5, 22.5 / 77.5, 32.5 / 67.5, 42.5 / 57.5, 50.0 / 50.0, 57.5 / 42.5, 67.5 / 32.5, 77.5 / 22.5, 80.0 / 20.0, 87.5 / 12.5, 90.0 / 10. It can be performed at a ratio of 0, 95.0 / 5.0, 97.5 / 2.5 or 98.0 / 2.0.

  The concentrated dye solution of the present invention is used for dyeing and printing paper (including paperboard and cardboard), especially after dilution with water where appropriate, where these materials are for example in pulp, It can be dyed by coating or by dipping. In addition, such liquid formulations can also be used in continuous or batch dyeing methods for dough materials, especially cellulose. The concentrated dye solution of the present invention can be used as a base for making ink jet inks or other inks and formulations for contactless printing of substrates such as paper or fabric. The formulations of the present invention can also be used for contactless printing of substrates such as paper or fabric without further modification.

  The invention further provides the use of the dye preparations according to the invention of anionic dyes for the production of wood stains for coloring solid wood or wood chips or chipboard or wood fiberboard. It is a preferred use of the wood stain according to the invention to color wood in the form of finished objects such as beams, planks or furniture, building parts. Application of the liquid formulation according to the invention can be carried out on all or part of the wood surface (to compensate for color defects in the wood or veneer). The liquid formulations according to the invention can be used for aqueous stains (the main solvent water), solvent stains (about 30-95% organic solvent) or chemical stains (generally dilutable with water).

  The following examples illustrate the invention. Unless otherwise stated, in these examples as well as throughout this application, parts are by weight and percentages are always weight percentages.

成分１ｂ

成分１ｃ

成分１ｄ

Production Example 1
To a mixture of 118 parts pentaerythritol and 8.7 parts sodium carbonate in 434 parts N, N-dimethylacetamide, 425 parts isatoic anhydride is added in portions at 50 ° C. The suspension is stirred for 2 hours and diluted with 4340 parts of water. This is followed by filtration, washing with water and drying at 60 ° C. under reduced pressure to give a white powder which is a mixture of four components having the formula (1a, 1b, 1c, 1d). That is,
Ingredient 1a

Ingredient 1b

Ingredient 1c

Ingredient 1d

成分２ｂ

成分２ｃ

成分２ｄ

Production Example 2
To a mixture of 1736 parts ice, 781 parts 30% HCl, 694 parts acetic acid and 260 parts N, N-dimethylacetamide is added 434 parts of the amino component of Example 1 and 182 parts 4N sodium nitrite solution. To diazotize. The temperature is maintained at 0-5 ° C. by addition of 870 parts ice. To the resulting diazo solution is added 3281 parts of an approximately 20% aqueous solution of 6-hydroxy-4-methyl-3-pyridonyl-3'-methylpyridinium chloride. The pH is adjusted to 3 at a temperature of 10-20 ° C. by addition of 130 parts of 30% sodium hydroxide solution. Subsequently, after stirring for 1 hour, 50 parts of Hyflo Supercell filter soil is added and then filtered through a magnetic suction filter equipped with an absorbent pad. The resulting clarified dye solution (9700 g, 8900 ml) is filtered in a laboratory ultrafiltration system with DL5 membrane at 40-45 ° C. and 15 bar pressure until the conductivity in the permeate remains constant. Filter. In this way, the capacity is kept substantially constant. This required about 33,000 parts (ml) of demineralized water. The pH is maintained at 4.0-4.5 during ultrafiltration by addition of acetic acid. The retentate is concentrated to 5180 parts (g) at a pressure of 12-15 bar and then mixed with 140 parts of acetic acid to give about 20% by weight of a component having the formula (2a, 2b, 2c, 2d) A solution having a total dye content is obtained. That is,
Ingredient 2a

Ingredient 2b

Ingredient 2c

Component 2d

This solution (20.7% dye as chloride, 5.5% acetic acid, 73.8% water) dyes paper with a bright yellow hue (λ _max = 423 nm in dimethylformamide). Moreover, this concentrated solution can be diluted if necessary. The resulting dyeing has excellent wet fastness (for fresh water, alcohol, milk, soapy water, acetic acid, urine, etc.).

Production Example A1
A mixture of 7.7 g of 4-aminoacetanilide and 22.9 g of 3-aminoacetanilide was diazotized with sodium nitrite by known methods, and 58.5 g of 6-hydroxy-4-methyl was added to the resulting diazonium salt mixture. -1- (3'-Dimethylamino) propyl-3-pyridinio-2-pyridone betaine base is added as a coupling component and these are coupled by known methods at a pH of 1.8-2.2.

  The acetylamino group was then hydrolyzed with 57.5 g of 30% hydrochloric acid by known methods, and then these two aminoazo compounds were diazotized with 13.8 g of sodium nitrite by known methods and obtained. The diazonium salt is coupled with 11 g resorcinol at 0-5 ° C.

の染料を含む茶色溶液がもたらされ、しかしてこの茶色溶液は木材含有紙を茶色の色合いにて染色する。 This gives 11.2 g of formula

Resulting in a brown solution containing the dye, which dyes wood-containing paper in a brown shade.

の化合物を０〜５℃にて塩酸媒質中で３．４５部（１／２０ｍｏｌ）の亜硝酸ナトリウムでジアゾ化し、そして１〜３のｐＨにて５．４部（１／２０ｍｏｌ）の１，３−ジアミノベンゼン上にカップリングして、式（Ａ２ａ）

の染料が得られる。 Production Example A2
22.1 parts (1/20 mol) formula

Of diazotized with 3.45 parts (1/20 mol) sodium nitrite in hydrochloric acid medium at 0-5 ° C. and 5.4 parts (1/20 mol) 1,3 at a pH of 1-3. Coupling onto 3-diaminobenzene to obtain a compound of formula (A2a)

Is obtained.

の化合物（公知方法により１−アミノ−３−アセチルアミノベンゼン−６−スルホン酸のジアゾ化およびピリドン上へのカップリング並びに引き続くケン化によって作製された）のジアゾニウム塩を式（Ａ２ａ）の染料上にカップリングすると、式

の染料の異性体混合物がもたらされる（可能なカップリング部位は矢印により印されている）。 26.1 parts (1/20 mol) of formula (A2b)

A diazonium salt of a compound of the formula (made by diazotization of 1-amino-3-acetylaminobenzene-6-sulfonic acid and coupling onto pyridone and subsequent saponification by known methods) on a dye of formula (A2a) When coupled to the formula

Resulting in an isomer mixture of the following dyes (possible coupling sites are marked by arrows).

  This isomer mixture dyes wood-containing paper in a brown shade.

〔ここで、Ｂ₁およびＢ₂は独立して−ＯＨおよびＮＨ₂であり、そしてＤ₃＝Ｈまたは式

の残基である〕
に一致する。 Table 1 below points out the construction of further dyes that can be prepared according to Preparation Example A2. They are expressions

Wherein B ₁ and B ₂ are independently —OH and NH ₂ and D ₃ = H or the formula

It is a residue of
Matches.

Production Example A36
Preparation of the diazo component: To 326 parts of isatoic anhydride in 1000 parts of dioxane, 187 parts of dimethylaminoethanol are added dropwise at 60 ° C. Subsequent stirring for 1 hour is followed by concentration in a water-flow vacuum apparatus and distillation in a precision vacuum apparatus. 402 parts of 2′-dimethylaminoethyl anthranilate are distilled at 160 ° C./0.1 Torr.

に一致する。 21 parts of 2'-dimethylaminoethyl anthranilate are dissolved in a mixture of 50 parts of water, 25 parts of glacial acetic acid and 30 parts of concentrated hydrochloric acid and cooled to 5 ° C before being added dropwise. Mix with 6 parts of 23% aqueous sodium nitrite. After 3 hours, excess nitrite is destroyed by addition of sulfamic acid. A solution of 11 parts resorcinol in 30 parts warm water is then added, the pH is raised to pH 5 with sodium acetate, and the batch is stirred overnight at room temperature. After cooling to 0 ° C., the batch is gradually adjusted to pH 7 with 5N sodium hydroxide. After 4 hours, the dye obtained is completely crystallized and can be filtered off with suction and washed with water. Air drying yields 22 g of dye powder. The dye can be dissolved with glacial acetic acid and water to form a stable 20% liquid formulation. This dye dyes paper in a yellow hue. The hue is No. in the color index hue display diagram. 4. The effluent is minimally colored. The dyed paper can be bleached with hydrosulfite. The dissolved compound has the formula

Matches.

Production Example A37
Preparation of the diazo component: To 326 parts of isatoic anhydride in 1000 parts of dioxane, 187 parts of dimethylaminoethanol are added dropwise at 60 ° C. Following the subsequent 1 hour stirring, the solvent was removed in a vacuum apparatus and distilled to distill off 402 parts of 2'-dimethylaminoethyl anthranilate at 160 ° C / 0.1 Torr.

に一致する。 275 parts of 2'-dimethylaminoethyl anthranilate are dissolved in a mixture of 190 parts of water and 230 parts of methanesulfonic acid and after cooling to 5 ° C, 150 parts of 40% nitrous acid added dropwise. Mixed with aqueous sodium solution. After 3 hours, excess nitrite was destroyed by the addition of sulfamic acid. A solution of 44 parts resorcinol in 160 parts water was then added, the batch was raised to pH 5 with sodium acetate and subsequently stirred at room temperature for about 12 h to form a homogeneous solution. This dissolved dye has the formula

Matches.

Production Example 3
1.25 kg of the dye solution of Preparation Example 2 is mixed with 7.75 kg of a liquid formulation of approximately 10% of the dye of Preparation Example A1 at RT (= room temperature). This results in a stable dye solution that dyes paper in a yellowish brown hue (λ _max = 433 nm in water / acetic acid).

Production Example 4
4.2 kg of the dye solution of Production Example 2 is mixed with 2.5 kg of the dye solution of Production Example A36 at RT. The resulting stable dye solution dyes paper in a reddish yellow hue (λ _max = 450 nm in water / acetic acid).

Dyeing prescription
Dyeing prescription A
70 parts of chemically bleached pinewood sulfite cellulose and 30 parts of chemically bleached birch sulfite cellulose are beaten into 2000 parts of water in a beater. To this stock is added 1.5 parts of the liquid dye preparation of Production Example 2. After a mixing time of 20 minutes, paper is made from this. The absorbent paper obtained in this way has a yellow color.

Dyeing prescription B
To 100 parts chemically bleached sulfite cellulose beaten with 2000 parts water in a beater, 1.5 parts of the liquid dye preparation of Production Example 2 are added. After thorough mixing for 15 minutes, conventional sizing is performed using resin size and aluminum sulfate. Paper made from this material exhibits a yellow hue in each case.

Dyeing prescription C
Pass the absorbent web of non-size paper at 40-50 ° C. through an aqueous dye solution comprising 95 parts of water and 5 parts of the inventive dye solution of Preparation Example 2.

  Excess dye solution is squeezed out by two rolls. This dried paper web has a yellow color in each case.

  The dye preparations of Preparation Examples 3, 4 and A1-A37 can be used for dyeing in the same way as formulations A to C.

Dyeing prescription D
Weigh 5 parts of the dye formulation of Preparation 2 into 4000 parts of softened water at room temperature. 100 parts of a prewet cotton fabric are introduced into the bath and then heated to boiling for 30 minutes. The bath is kept boiled for 1 hour, during which time evaporating water is occasionally made up. The dyeing is then removed from the liquor, rinsed with water and dried. The dyed product obtained has a yellow color.

  The dye preparations of Preparation Examples 3, 4 and A1-A37 can be used to dye cotton in a similar manner.

Dyeing prescription E
In a float of 250 parts of water at 55 ° C. and 0.5 part of a dye preparation made according to Preparation Example 2, 100 parts of freshly tanned and neutralized chromium silver skin are drummed for 30 minutes, It is then treated for a further 30 minutes with 2 parts of an anionic milk greasing agent based on sulfonated fish oil in the same bath. These leathers are conventionally dried and finished. The resulting leather has a uniform yellow hue.

  Further low-affinity plant rename leather can also be dyed according to known methods.

  Dyeing can be done in a similar manner with the dyes of Preparation Examples 3, 4 and A1-A37.

Use Case F
15 kg of waste paper (wood), 25 kg of bleached ground wood and 10 kg of unbleached sulfate pulp were beaten with a pulper to form a 3% aqueous pulp suspension. This pulp suspension was diluted to 2% in a dyeing vat. This suspension was then mixed by stirring with 5% kaolin and 1.25 kg of 5% dyestuff acetic acid solution of Preparation 2 calculated on the basis of dry total fiber. After 20 minutes, the pulp in the mixing vat was mixed with 1% (based on absolutely dry fibers) resin size dispersion. This homogeneous pulp suspension was adjusted to pH 5 with alum immediately upstream of the headbox in a paper machine.
Using a paper machine, yellow bag paper of 80 g / m ² was produced with mechanical finishing.

  Dyeing can be done in a similar manner with the dyes of Preparation Examples 3, 4 and A1-A37.

Example G
A dry stock containing 60% groundwood and 40% unbleached sulfite pulp is beaten in a beater with enough water so that the dry content is just over 2.5% and 40SR freeness And then adjusted with water to exactly 2.5% dryness for the high density pulp.

  200 parts of this high density pulp is mixed with 5 parts of 0.25% aqueous dye solution of Preparation 2 and stirred for about 5 minutes and mixed with 2% resin size and 4% alum based on dry stock. , And stir again for several minutes until homogeneous. This material is diluted with about 500 parts of water to 700 parts by volume and used in a known manner to make a paper sheet by draining in a sheet forming machine. These paper sheets have a deep yellow color.

  Dyeing can be done in a similar manner with the dyes of Preparation Examples 3, 4 and A1-A37.

Use case H
The ink composition for inkjet printing is
6 parts of the dye of Production Example 2
It consists of 20 parts glycerol and 74 parts water. This ink composition is then transferred into and used with commercially available ink jet printer ink containers for printing on paper, paper-like substrates, textile fiber materials and plastic films / sheets. Used by generating a monochromatic test print on the identified sheet-like material.

  Dyeing can be done in a similar manner with the dyes of Preparation Examples 3, 4 and A1-A37.

Example I
A narrow plate of softwood (European spruce) and a narrow plate of hardwood (beech), each cut into approximately 5 cm pieces and diluted dye solution according to Example 2 (10 parts water and 1 part according to Example 2) After being soaked in the dye solution for several minutes and dried for 10 hours, a light brownish narrow strip was obtained.

  Dyeing can be done in a similar manner with the dyes of Preparation Examples 3, 4 and A1-A37.

Claims (9)

In a concentrated aqueous dye solution comprising one or more cationizable dyes, an organic acid and water, the cationizable dye is of the formula (I)

〔here,
Each A is independently —NH— or —O—;
B is a polyvalent group or atom;
n ′ and n ″ are natural numbers, and the sum of n ′ and n ″ is ≧ 2,
m is a natural number ≧ 0,
CC represents the formula (c ₁ ) or (c ₂ )

A group having
Each R ₁₀ is independently H, C _1-4 alkyl, C _5-6 cycloalkyl, phenyl, benzyl or phenylethyl;
Each R ₁₀ ′ is independently H, —OH or C _1-4 alkyl;
Each T ₁ is independently H, —CN, —COOR ₁₅ , CONR ₁₆ R ₁₇ , SO ₂ NR ₁₆ R ₁₇ ,

And
G is H, —R ₁₁ NHR ₁₂ or —R ₁₁ NR ₁₃ R ₁₄ ;
R ₁₁ is C 1 _{~ 6} alkylene or C _{2 ~ 6} alkenylene,
R ₁₂ and R ₁₃ are independently, H; unsubstituted C _{1 ~ 6} alkyl; OH, CN or C _{2 ~ 6} alkyl substituted by halogen; phenyl -C 1 _{~ 3} alkyl (where the phenyl group is Optionally substituted once, twice or three times with a substituent selected from the group consisting of chlorine, C _1-4 alkyl or C _1-4 alkoxy); unsubstituted C _5-6 cycloalkyl; or C C _5-6 cycloalkyl substituted once, twice or three times by _1-4 alkyl groups;
R ₁₄ has the meaning as for R ₁₂ or R ₁₃ or is a hydrogen atom,
R ₁₅ is a C _1-6 alkyl group or a phenyl-C _1-3 alkyl group,
R ₁₆ and R ₁₇ are independently H or a C _1-4 alkyl group,
R ₁₈ is independently at each occurrence H, C _1-4 alkyl, —NR ₁₆ R ₁₇ — (CH ₂ ) ₂ —4-NR ₁₆ R ₁₇ or —CONR ₁₆ R ₁₇ ;
R ₁₉ is a C _1-4 alkyl group or a hydroxy-C _1-4 alkyl group,
R ₂₀ is —S— or —O—;
R ₂₁ is a hydrogen atom or a C _1-4 alkyl group, and An ⁻ is a colorless anion,
Where (i) the sum of n ′, n ″ and m is smaller than the valence of B,
(Ii) when the sum of n ′ and n ″ = 2, m is ≧ 1;
(Iii) When the sum of n ′ and n ″ = 3 and A = NH, m must be ≧ 1]
A concentrated dye aqueous solution, characterized in that Formula (II)

〔here,
B ₁ and B ₂ are independently —OH and NH ₂ and D ₃ = H or the formula

And R ₆ , R ₇ , R ₈ or R ₉ is independently H or —SO ₃ H, and M _a or M _b is independently the meaning of M ₁ to M ₁₀ Have
M ₁ is H,
M ₂ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ ,
M ₃ is — (CH ₂ ) ₂ N (CH ₂ CH ₃ ) ₂ ,
M ₄ is

And
M ₅ is

And
M ₆ is

And
M ₇ is,

And
M ₈ is

And
M ₉ is,

And
M ₁₀ is — (CH ₂ ) ₂ NH ₂ and R _a or R _b independently has the meaning of R ₁ to R ₅ ;
R ₁ is H;
R ₂ is

And
R ₃ is

And
R ₄ is CN,
R ₅ is

Is)
Dyes of formula (III)

〔here,
R ¹ , R ² or R ³ is independently H, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , i-C ₃ H ₇ , n-C ₄ H ₉ , i-C ₄ H _9. a sec-C ₄ H _9,
R ⁿ is —C ₂ H ₄ —, —C ₃ H ₆ —, —CH (CH ₃ ) CH ₂ — or —C ₄ H ₆ —,
Y is hydrogen or nitro,
q is 1 or 2]
The concentrated dye aqueous solution according to claim 1, comprising Organic acids, in the formula A (-COOH) _n (where, A is C _{1 ~ 12} alkanyl or C _{1 ~ 12} alkenyl, yet as well may be interrupted by each their nitrogen atoms and / or oxygen atom Each additionally hydroxyl or NR′R ″, wherein R ′ and R ″ are independently C _1-6 alkanyl or C _1-6 alkenyl or C _1-6 hydroxyalkanyl or C _1-6 hydroxyalkenyl or unsubstituted phenyl or hydroxyl - or sulfur - or C _{1 ~ 18} alkanyl - or C _{1 ~ 18} alkenyl - may be substituted by a substituted phenyl), and n is a natural number of 1, 2 or 3) of The concentrated dye aqueous solution according to claim 1, which is an organic acid.   4. Dye solution according to claim 1, characterized in that it contains up to 40% by weight of dye, 0.5% to 25% organic acid by weight and is made up to 100% by weight with water. The concentrated dye aqueous solution according to Item.   A method for producing a dye solution according to claim 1, wherein an aqueous solution or suspension of at least one crude cationic dye of formula (I) is forced through a semipermeable membrane by applying pressure to form salts and Removing a synthetic by-product having a molecular weight of less than 500, as well as some water.   6. The permeate is continuously or intermittently replaced or made up with water or a buffer solution so that the permeate dye concentration does not change more than 20%. A method of producing the described dye solution.   Use of a storage-stable concentrated dye aqueous solution according to claim 1 for dyeing and / or printing cellulosic material, in particular paper and / or paperboard and / or cardboard.   Use of a storage-stable concentrated dye aqueous solution according to claim 1 for the production of inks and formulations for contactless printing, especially for inkjet printing.   A substrate, characterized in that it is dyed or printed with a storage-stable concentrated dye aqueous solution according to claim 1.