JPS6375068A - Alcohol-soluble dye composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition by reacting a specific active hydrogen- containing dye (precursor) with an epoxy compound, capable of exhibiting a solubility of a high concentration in a lower alcohol, e.g. propyl alcohol, etc., and capable of giving ink with low toxicity for woodworking, writing, printing and recording. CONSTITUTION:A composition, containing a reaction mixture obtained by reacting a dye (precursor) having active hydrogen, preferably amino group, imino group, OH or COOH linked to N atom or O atom without any other active hydrogen with a compound having epoxy group, preferably monoepoxide or diepoxide and forming a dye in the case of a dye precursor and particularly soluble in propyl alcohol, butyl alcohol, propylene glycol monoalkyl ether, etc., in a high concentration.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dye composition that exhibits high solubility in lower alcohols, particularly propyl alcohol, butyl alcohol, propylene glycol monoalkyl ether, and the like.

(Prior Art and its Problems) Recently, the use of highly toxic solvents such as xylene has been restricted in various fields from the viewpoint of air pollution, toxicity to the human body, and the like. There is also a demand for ink for writing instruments to shift to less toxic solvents than xylene solvent type and methyl cellosolve solvent type.

Conventionally, dyes that are soluble in methyl alcohol and ethyl alcohol are mostly salt-formed salts of basic dyes and acid radicals or water-soluble dyes, or amine salt-formed water-soluble dyes, but n-propyl alcohol, i - There is very little solubility in propyl alcohol, and current commercially available products have low solubility even if dissolved, and even when used in markers and other inks, problems such as clogging occur due to precipitation of precipitates over time. There is almost nothing that is easily satisfying.

Furthermore, there are many dyes that are soluble in ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, but the solubility in propylene glycol monoether is poor and there are no satisfactory dyes.

(Means for Solving the Problems) The present inventors have discovered that existing dyes treated with epoxy compounds dissolve in lower alcohols at high concentrations.

That is, in the present invention, a dye or a dye precursor having an active hydrogen bonded to a nitrogen or oxygen atom and no other active hydrogen is reacted with a compound having an epoxy group, and in the case of a dye precursor, this is An alcohol-soluble dye composition containing a reaction mixture obtained by dyeing is provided.

Active hydrogens bonded to nitrogen or oxygen atoms are present, for example, in amino, imino, hydroxyl or carboxyl groups. The dye has at least one of these active hydrogens and does not have other active hydrogens (eg, sulfonic acid groups).

Examples of such dyes include commercially available oil-soluble dyes, mordant dyes, and xanthine acid dyes, but these dyes are not particularly limited and can be used without being limited to the type of color.

In the present invention, precursors of the above dyes can also be used. A precursor becomes a dye by, for example, a coupling reaction, and when a precursor is used, it is first reacted with an epoxy compound and then converted into a dye.

These dyes (including precursors) are reacted with epoxides having epoxy groups. As the epoxide, both monoepoxide and polyepoxide can be used, but monoepoxide and jepoxide are particularly preferred. It is preferable that 1 to 4 epoxy groups of these epoxides are bonded to one molecule of the dye, and if the epoxy groups are bonded on 5 epoxy groups, the product becomes highly viscous or insoluble.

Examples of monoepoxides include ethylene oxide propylene oxide, 1,2-butylene oxide, 1,2-pentene oxide, glycidol, methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, γ-glycidoxypropyl trimester. Examples include toquinsilan and the like.

Examples of dieboxides include polyhydric alcohols with a molecular weight of 300 or less, such as ethylene glycol, diethlene glycol, polyethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, neopentyl glycol, 2,2'- Examples include diglycidyl ethers that can be derived from bromoneopentyl glycol, 1,2,6-hexandriol, glycerol, and the like.

The reaction between the dye having active hydrogen and the compound having an epoxy group may be carried out by a conventional method. For example catalysts (e.g.
The reaction is carried out in a solvent in the presence or absence of an acid or alkali). The reaction is carried out at room temperature or heated (e.g. 60℃
~120°C).

When using a low-boiling epoxide such as ethylene oxide or propylene oxide, the reaction may be carried out in an autoclave.

The solvent used in the reaction is one that dissolves the raw material, such as ethanol, n-propyl alcohol, i
-Propyl alcohol, propylene glycol monomethyl ether, etc.

The reaction product may be isolated and purified after the reaction and obtained in the form of a powder or the like, but the reaction product may also be prepared as it is into a solution.

-Fl dye may be reacted with two or more types of epoxides. Also, 2FI on this using Noeboxide!
It is also possible to react the above dyes to obtain a color intermediate between the two.

The reactants obtained in the present invention are expected to result in a mixture of various reaction products, for example when the dye has multiple groups having active hydrogen. As described above, the mixture has a positive influence on the stability, hue, etc. of the dye composition, and it is impractical to completely isolate it as a single substance. Therefore, it is difficult in practice to specify the reaction product, but at least it has the following formula: (R, H1 is a C3-C2 alkyl group that may have a certain degree of skill, a C1-Cs alkenyl group,
(meth)acrylic acid group, propyltrimethoxysilane or polyhydric alcohol residue with a molecular weight of 300 or less),
Compounds are found in the dye compositions of the present invention, where m is 1 or 2 and m is a number from 1 to 4. Such specific examples are as shown in the examples below: [wherein, CuPc represents copper phthalocyanine]. ]H The dye composition of the present invention is blended with an alcoholic solvent together with suitable additives as a colorant to form an ink composition.

Additives that can be used are pH! It stabilizers, anionic and nonionic activators, or amphoteric activators are used, and depending on the application, preservatives, rust preventives, metal sequestering agents, etc. can also be added. Furthermore, if necessary, a natural or synthetic alcohol-soluble resin may be mixed.

The amount of additive in the ink composition is 0.0% of the total amount of the ink composition.
1 to 5% by weight is preferred.

Examples of alcoholic solvents include lower alcohols such as methanol, ethanol, propyl alcohol and butyl alcohol; or monoalkyl ethers of diols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the like.

(Effects of the Invention) The dye composition of the present invention is soluble in lower alcohols, especially propyl alcohol, butyl alcohol, or monoethers of diols, especially propylene glycol monomethyl ether, etc., and has low toxicity for woodworking, writing, etc. Ink for printing and recording can be obtained.

(Example) The present invention will be explained in more detail with reference to Examples.

Example 1 1-Phenyl-3-carboxy-5-pyrazolone 4 was added to 11 four-bottle flasks equipped with a stirrer, thermometer and condenser.
xg (0.2 mol) and 500 m of water were added, 22.2 g (0.6 mol) of glycidol and 20 g of triethanolamine were added, and the temperature was raised. Stir at 80-85°C until reaction completion. Filter after cooling. The filtrate is brought to 15°C with water.

On the other hand, 21.1 g (0.1 mol) of 0-tolidine was diazotized by a conventional method and gradually added dropwise to the filtrate to effect coupling. The temperature is maintained at 10-15°C, the pH is adjusted to 8-9, and the mixture is stirred for an additional 5 hours. Stir, warm to 40°C, and filter. The cake was washed with water and dried to obtain 60 g of an orange dye represented by formula (1).

The resulting 20% (w/w) n-propyl alcohol solution of the dye was stable during a 3 month storage test at -5°C and 60°C.

Example 2 Into the reactor used in Example 1, 37.6 g (0.2 mol) of 2-oxy-3-naphthoic acid, 2.4 g (0.6 mol) of ethylene glycol zig 11 cidyl ether IO, and triethanolamine were added. Add 15g and raise the temperature. 90-95℃
Stir for 10 hours. Filter, add 21.8 g (0.2 mol) of p-aminophenol and dissolve and disperse, then
Cool in an ice bath. 23 g of isoamyl nitrite is gradually added dropwise at a liquid temperature of 5° C. or lower. Furthermore, 1 at 5-20℃
After stirring for 0 hours, the solvent was recovered by filtration to obtain 70 g of a tar-like red dye represented by formula (II).

The resulting 30% (w/w) n-propyl alcohol solution of the dye was stable during a 3 month storage test at -5°C and 60°C.

Example 3 300 g of propylene glycol monomethyl ether was charged into the reactor used in Example 1, and 46.3 g (0.2 mol) of the following formula compound obtained by reacting with α-naphthylamine and methyl glycidyl ether, p-chloro Aniline 2
5.4 g (0.2 mol) was added, dispersed and dissolved, and then cooled in an ice bath. 23 g of isoamyl nitrite is gradually added dropwise at a liquid temperature of 5° C. or lower. Furthermore, 10 at 5-20℃
After stirring for an hour, the mixture was filtered and propylene glycol monomethyl ether was added to obtain a 20% solution of the orange dye represented by formula (I) with a total fli of 350 g.

The dye solution obtained was stable during a 3 month storage test at -5°C and 60°C.

Example 4 After stirring, 120 parts of n-propyl alcohol and 55.4 parts (0.2 mol) of a dye having the following were added to a 500 m (4-bottomed) flask equipped with a thermometer and a condenser, and after well dispersing, methyl glycidyl ether was added. 52.8 parts (0.6 mol) and 15 parts of triethanolamine were added, and after stirring at room temperature for 30 minutes, the temperature was gradually raised and the mixture was stirred at 70 to 75°C until the reaction was completed.

After cooling, the mixture was filtered with diatomaceous earth precoat, and the filtrate was made up to 240 parts with n-propyl alcohol. 30% of dye example 4
A concentrated solution composition was obtained. It was also stable in a 3 month storage test at -5°C and 60°C.

Examples 5 to 13 Reactions were carried out in the same manner as in Example 4 to obtain dye solutions. The reaction conditions are shown in Table 1, and the stability of the obtained dye solution over time is shown in Table 2.
It was shown to.

Table-20 = Good Example 14 (Alcohol Marker) Dye solution obtained in Example 4 30 parts Ethanol 10 parts N-propyl alcohol 50 parts Sulfonamide resin
10 parts or more of the blend was stirred and dissolved to obtain a yellow alcoholic ink.

1 Example 15 (OHP7-Car) Dye solution obtained in Example 4 5 parts Dye solution obtained in Example 7 20 parts Ethanol
50 parts n-propyl alcohol
15 parts ketone resin 1
0 parts or more of the formulation was stirred and dissolved to obtain a red OHl' ink.

1 (Marker for writing board) Dye solution obtained in Example I2 30 parts Butyral resin 3 parts Butyl oleate
6 parts nonionic activator
05 parts denatured alcohol 60.
5 parts or more of the blend was stirred and dissolved to obtain a black writing board ink.

Example 17 (erasable marker) White Millbase 20 parts Example IO
Dye solution obtained in 10 parts n-octyl stearate 8 parts refined sugar ester
A blend of 61 parts or more of 1 part denatured alcohol was stirred and dissolved to obtain a blue erasable ink.

White mill base is denatured alcohol 64 parts butyral resin 15 parts titanium oxide
20 part powder
One or more parts of the formulation were prepared by dispersing in a ball mill for 48 hours.

Claims (1)

[Claims] 1. A dye or a dye precursor having an active hydrogen bonded to a nitrogen or oxygen atom and no other active hydrogen is reacted with a compound having an epoxy group, and in the case of a dye precursor, is an alcohol-soluble dye composition containing a reaction mixture obtained by turning this into a dye. 2. The dye composition according to item 1, wherein the active hydrogen bonded to the nitrogen atom or oxygen atom is at least one of an amino group, an imino group, a hydroxyl group, or a carboxyl group. 3. The reaction mixture has the general formula: [where D is a dye residue, R is an alkyl group of C_1 to C_4 or -CH_2OR_1 (R_1 is H, an alkyl group of C_1 to C_5 which may be branched, C_1 ~C_
5), m is l or 2, n is a number from 1 to 4] 2. The dye composition according to claim 1, comprising: 4. The reaction occurs in the presence or absence of a catalyst between 60 and 120
2. The dye composition according to claim 1, which is carried out at <0>C.