JPS61225267A - Dye solution composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent solubility and stability, can exhibit quickly water resistance and is black and suitable for use in writing ink, and the coloration of paper, containing one of two dyes or a mixture thereof. CONSTITUTION:A dis-azo dye (a) of formula I (wherein R1 is H, lower alkyl, alkoxy; R2 is H, a group of formula II or III, etc.) is reacted with a diazo compd. (b) of aniline having a 4-18C alkyl (excluding 12C) group at the p- position to obtain a dye (A) of formula IV [wherein R is a 4-18C alkyl (excluding 12C)]. Component (b) is reacted with a monoazo dye (c) of formula V (wherein X is R1; Y is NO2, NH2, NHR2) to obtain a dye (B) of formula VI. The dye A and/or the dye B are/is dissolved in a mixture of a hydrophilic solvent such as glycol monoalkyl ether and water. If desired, polyamino or polyhydroxy compd. such as (alkyl)urea or alkylcellulose, water-soluble high- molecular compd. such as PVA, surfactant, anti-foaming agent, inorg. salt, etc., may be added.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a stable black dye solution composition that has good water resistance when coloring paper or writing on paper.

(b) Conventional technology Traditionally, water-based inks using water-soluble dyes such as direct dyes, acid dyes, and basic dyes have the excellent property of being less likely to bleed or set-off when written on paper. On the other hand, it has the disadvantage of poor water resistance, which is an important issue to be improved in, for example, water-based felt-tip pens and water-based ballpoint pens.

In order to improve the water resistance of water-based inks, for example, by dispersing finely divided pigments in water-based resin emulsions, or by adding counterions such as basic dyes or polymeric amino compounds to reduce the excessive water solubility of direct dyes and acid dyes. how to adjust,
Methods of bonding or adding paper-reactive groups or water-dispersible polymer chains to water-soluble dyes are being studied.

(c) Problems to be solved by the invention Despite attempts to improve the conventional methods as described above, the pigment dispersion method has drawbacks such as high ink viscosity and deterioration of writing performance due to sedimentation of particles. However, other methods have not yielded satisfactory results.

For example, the present inventors discovered C, which is often used in water-based inks.
1. Attempts were made to improve water resistance by introducing reactive groups and water-dispersible polymer chains into Diract Black 154 or similar dyes, but as is known, C, 1, Dira
Since it is not easy to obtain the dye shown as ct Black 154 with a constant composition, it is difficult to control the equivalence relationship between the pigment and the reagent to be reacted or added in the process of modifying it, resulting in poor water resistance and writing resistance. It contained undesirable components that impaired properties, and the stability and reproducibility of water resistance of inks using it were insufficient. Another problem is that the dye is an undesirable tolidine dye.

That is, one object of the present invention is to provide a dye that does not require secondary means that require reproducibility, such as the addition of reactive groups or polymer chains, in order to improve the drawbacks of the conventional water-based ink compositions.
In other words, its inorganic/organic value is essentially compatible with water and a hydrophilic organic solvent mixture system and has good solubility, but on the other hand, it can rapidly exhibit water resistance in response to changes in the ink composition due to writing. An object of the present invention is to provide a dye and to provide an improved dye solution composition using the same.

(d) Means for Solving the Problems The present inventors have previously studied in order to improve the drawbacks of the above-mentioned conventional water-based ink compositions, and found that in formulas (I) and (II), R is C□ It was discovered that a dye solution composition containing a dye of 2H11N achieves the object, and a patent application was filed. (Japanese Patent Application No. 60-105) The present invention has been completed by studying the surrounding areas of this prior invention and discovering a group of dye solution compositions that achieve similar effects.

The dye solution composition of the present invention has formulas (I) and (II) (
In the formula, R is an alkyl group of 04 to cis (excluding C12), R1 is H1 lower alkyl, an alkoxy group, R
2 is Hl (in the formula, R is an alkyl group of 04 to 01 (excluding C1□), X is H1 lower alkyl or alkoxy group, Y is NO8゜NH,, NHR, where R2 is the same as that shown in formula (I)).

Dyes having no R group in general formulas (I) and (If) are known, and the dyes used in the present invention can be produced according to their production methods. Specifically, as shown in the examples,
For example, dyes of formula (I) may be dyes of formula (III) (wherein R1, R
, indicates the same as formula (I). ) has a C9-C11 alkyl group at the p-position (however, C1
It is obtained by reacting a diazo compound of aniline with □). Moreover, the dye of formula (II) is the dye of formula (
rV) An aniline diazo compound having a C4 to CtS alkyl group (excluding C10) at the P-position is added to the monoazo dye represented by the formula (where x and Y are the same as those in formula (n)). Obtained by reaction. C4 at p-position
Preferred examples of the aniline having an alkyl group of ~CtS (excluding C1) include p-n-butylaniline, p-t-butylaniline, p-n-hexylaniline, p-n-octylaniline, Examples include p-n-nonylaniline, p-n-decylaniline, p-stearylaniline, and the like.

The dye solution composition of the present invention is prepared using a known method, that is, the dye obtained as described above is mixed with gelcols.

Glycol monoanosyl ethers, Impropatool, dimethyl sulfoxide, dimethylformua, mido,
Dissolve urea, if necessary, in a mixture of water and a hydrophilic solvent such as trihydroxyfuran.

polyamino or polyhydroxy compounds such as alkylureas, dextrins, alkylcelluloses, popal,
It can be easily obtained by adding a water-soluble polymer compound such as polyvinylpyrrolidone, various surfactants, inorganic salts such as Glauber's salt, antifoaming agents, defoaming agents, etc.

(e) Actions and Effects The dye used in the present invention is a black direct dye with long chain alkyl groups C, ~ C, as shown in general formulas (I) and (It).
This is an alkyl group of ZS (excluding C-2).

etc. are only known as so-called milling-type acid dyes that dye wool and nylon to produce dyed products that are extremely durable against washing and have excellent build-up properties; black direct dyes have not been previously known. It is.

As for the dyes represented by formulas (I) and (II) according to the present invention, surprising findings such as the present method have been obtained.

1. It has unexpectedly good solubility in hydrophilic solvents or mixtures of water and hydrophilic solvents.

2. Colored articles obtained by coloring or writing on paper with water-based ink using the dye of the present invention have extremely excellent water resistance.

3. Since the water-based ink using the dye of the present invention has extremely good covering power, the dye concentration used can be low, and therefore a water-based ink with low viscosity and excellent stability can be prepared.

Since the dye used in the present invention has such excellent properties, the dye solution composition of the present invention containing it is useful as an ink for coloring paper or writing, particularly for water-based felt-tip pens or water-based ballpoint pens.

(f) Examples Next, the effects of the present invention will be illustrated by Examples, but the present invention is not limited only to Examples.

Example 1 56 g of a disazo dye represented by the following formula (V) is dissolved in 700 ml of water to a pH of 9 using soda ash. p-n-butylaniline 1
5 g was diazotized by a conventional method and 300 ml of an aqueous solution neutralized to pi(4) was converted into a disazo dye solution.

The pH of the reaction solution is adjusted to 8 to 9 using soda ash. After stirring for about 3 hours, the selectively precipitated dye was filtered off and purified by a conventional method to obtain 60 g of the following formula (VI) dye.

A water-based ink having the following composition was prepared using this dye.

Dye of formula (Vl) 5g diethylene glycol 30g Plysurf-A212E (surfactant) 0.5g butyl hydroxybenzoate (antifungal agent) 0.1g water
70
g This black ink was used in a ballpoint pen to write on paper. After 5 minutes, it was immersed in water, but almost no elution was observed even after 24 hours.

Comparative Example 1 In the ink preparation of Example 1, 7 g of the dye of formula (■) below was used in place of the dye of formula (VI), and the paper was written in the same manner with a ballpoint pen, and 5 minutes later, the paper was immersed in water. Significant elution was observed and the handwriting became fainter.

Examples 2 to 5 A water-based ink was prepared according to the ink composition of Example 1 using 5 g of dye in which R, R1 and R3 in formula (I) are the groups shown in Table 1, used for a ballpoint pen, and applied to paper. I wrote it down. After 5 minutes, it was immersed in water, and Table 1 shows the hue and elution state of the handwritten marks 24 hours later.

Table 1 Example 6 47g of dye represented by the following formula (■) was added to 500ml of water with soda.
l (dissolved in 9.300ml of an aqueous solution in which 20g of p-n-octylaniline was diazotized by a conventional method and neutralized to pH 4.
The reaction solution which converts 1 into a monoazo dye solution is adjusted to p) 18-9 with soda ash. After stirring for about 3 hours, the precipitated dye was filtered and purified by a conventional method to obtain the following formula (■)
50 g of dye was obtained.

A water-based ink having the following composition was prepared using this dye.

Dye of formula (IX) 4g ethylene glycol 10°glycerin 10g sodium pentachlorophenol 0.5g anhydrous sodium sulfate
0.5g water
80g of this blue-black ink was used in a felt-tip pen to write on paper. After 30 minutes, it was immersed in water for 24 hours, but there was very little elution and clear handwriting was obtained.

Comparative Example 2 In the ink preparation of Example 6, 4 g of the dye of the formula (X) below was used instead of the dye of the formula (ff), and after 5 minutes of writing on paper with a felt-tip pen, the paper was immersed in water. Significant elution was observed and only a few handwritings were observed.

Examples 7 to 11 Using 4 g of dye in which R, I wrote it down. After 30 minutes, it was immersed in water, and Table 2 shows the hue and elution state of the handwritten marks after 24 hours.

Table 2 Example 12 In place of the disazo dye used in Example 1, 60 g of Banko-shita dye was used to obtain 75 g of purified dye of the following formula (xn).

Using this dye, a water-based ballpoint pen ink having the following composition was prepared.

Dye of formula (xn) 5g diethylene glycol 20g polyvinylpyrrolidone 1g Neugen P (
Surfactant) 0.1. .

Butyl parahydroxybenzoate 0.1g water

80g of this black ink was used in a ballpoint pen to write on paper, and after 5 minutes it was immersed in water. Almost no elution was observed even after 24 hours.

Comparative Example 3 In the ink preparation of Example 12, 5 g of the dye of formula (X) was used and written on paper with a ballpoint pen in the same manner.
After a minute it was soaked in water. Elution was observed, and handwriting became fainter.

28 g of the dye of the formula (X V ) and 23 g of the dye of the formula (X V ) are dissolved in 700 ml of water to pH 9 with soda ash. Diazotize 20 g of p-n-octylalinine by a conventional method and add dropwise 300 ml of an aqueous solution neutralized to pi(4). The pH of the reaction solution is adjusted to 8-9 with soda ash. After stirring for about 3 hours, the precipitated dye A black dye mixture represented by the following formulas (XVI) and (X■) is obtained.

Using this dye, an ink having the following composition was prepared.

Mixed dyes of formulas (XVI) and (X■) 4
g Ethylene glycol 10g Glycerin 10g Sodium pentachlorophenol 0.5g Water
80g of this black ink was used for a felt-tip pen. After 30 minutes of writing, it was immersed in water for 24 hours, but there was little elution and clear handwriting was obtained.

Comparative Example 4 In preparing the ink of Example 13, formulas (XVI) and (X
In place of the mixed dye ((2)), 4 g of a mixture of dyes of the following formulas (X) and (XIK) was used. After writing with a felt-tip pen for 30 minutes, it was immersed in water for 24 hours. Significant elution was observed.

29 g of the dye of the formula (XXI) and 24 g of the dye of the formula (XXI) are dissolved in pFI9 in 700 ml of water with soda ash. 300 ml of an aqueous solution prepared by diazotizing 18 g of p-n-hexylaniline and neutralizing it to pH 4 by a conventional method is added dropwise. The pH of the reaction solution is adjusted to 8 to 9 with soda ash. After stirring for about 3 hours, the precipitated dye was filtered out and expressed by the following formula (XX
A mixture of dyes of II) and (XXII[) is obtained.

Using this dye, an ink having the following composition was prepared.

Mixed dye of formula (xx n ) and (XXI[I)
5g ethyl cellosolve
30g Neugen PO
,1゜butyl parahydroxybenzoate 0.1
gAnhydrous mirabilite 0.5g water
70g of this black ink was used for a felt-tip pen. After 30 minutes of writing, it was immersed in water for 24 hours, but there was little elution and clear writing was obtained.

Claims (1)

[Claims] Formulas (I) and (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an alkyl group of C_4 to C_1_8 (excluding C_1_2), R_1 is H, Lower alkyl, alkoxy group, R_2 is H, CH_2SO_3H, CH_
2CO_2H, C_2H_4CO_2H, COCH_3
shows. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R is an alkyl group of C_4 to C_1_8 (excluding C_1_2), X is H, lower alkyl, alkoxy group, Y is NO_2, NH_2, NHR_2, where R_2 is the same as shown in formula (I).