JPS64429B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to water-based inks, and more particularly to water-based inks that use acidic dyes and have improved water resistance. Conventionally, water-based inks using acidic dyes have been widely used because the dye has good solubility and clear handwriting can be obtained, but they have had the problem of poor water resistance of handwriting. Therefore, an object of the present invention is to provide a water-based ink with improved water resistance while maintaining as much as possible the advantages of inks using acid dyes. be. That is, the present invention provides SO ₃ Na groups and/or
or a water-based ink consisting of at least a colorant that is an alkali metal salt of an acid amide derivative obtained by reacting a COONa group with an amino group of an aminocarboxylic acid, a water-soluble organic solvent, and water. It is something. It is not clear why the aqueous ink of the present invention has excellent water resistance, but the alkali metal salt of the acid amide derivative has a sulfonic acid amide bond and/or a carboxylic acid amide bond in the molecule that the acid amide derivative has. It is thought that water resistance improves because it has affinity with polar groups on the paper surface. Furthermore, alkali metal salts of acid amide derivatives are poorly soluble in water, but readily soluble in water-soluble organic solvents alone or in mixtures with water, so that they can be made into inks. The present invention will be explained in detail below. Acidic dyes serve as colorants for coloring materials; examples include CI Acid Yellow 11, CI Acid Yellow 17,
23, 25, 29, 36, 38, 40, 42, 42
44, 76, CI acid orange 7, 8, same
10, 19, 20, 24, 28, 41, 45, 20
51, 56, CI Assisted Red 1, 6, 8,
13, 14, 18, 26, 27, 32, 35, 18
37, 42, 51, 80, 82, 83, 85,
87, 88, 89, 92, 94, 106, 111,
114, 115, CI Assist Violet 7, same
41, 43, 51, CI acid blue 1, 7,
9, 15, 22, 23, 25, 27, 29, 22
40, 41, 43, 45, 62, 78, 80,
92, 93, 113, 117, 138, CI Assisted Green 3, 9, 16, 19, 20, 25, CI Assisted Green
27, 36, 41, 44, CI Assisted Brown 2, 4, 13, 14, 27, CI Assisted Black 1, 7, 24, 26, 31, etc.
Furthermore, acidic dyes obtained by treating lake pigments with sulfuric acid can also be used. Specific examples of aminocarboxylic acids to be reacted with acidic dyes include monoaminomonocarboxylic acids such as valine and alanine, oxyamino acids such as serine, and sulfur-containing amino acids such as cysteine.
Monoaminodicarboxylic acids such as aspartic acid, aliphatic α-amino acids such as diaminomonocarboxylic acids such as lysine, aliphatic amino acids such as δ-aminobutyric acid, amino acids with an aromatic nucleus such as phenylalanine, and histidine. , amino acids with heterocycles such as proline, anthranilic acid,
Examples include aromatic amino acids such as P-aminobenzoic acid. Acid amide derivatives are the acid dyes mentioned above.
SO ₃ Na group and/or COONa group are treated with chlorinating agents such as phosphorus pentachloride, phosphorus oxychloride, and thionyl chloride to form SO ₂ Cl group and/or COOl group, which is then usually used as an acid amide synthesis method. being given
It can be obtained by reacting with the amino group of an aminocarboxylic acid by the Schotten-Bauman method or the like. The -COOH group of this acid amide derivative is converted into an alkali metal salt such as lithium, sodium, potassium, etc. by a conventional method and used as the coloring material of the present invention. The amount used is preferably 5 to 20% by weight based on the total amount of ink. As an example of a specific method for synthesizing the coloring material of the present invention, CI acid red 13 having two SO ₃ Na groups is used. and valine

To describe the reaction with [formula], a 300ml four-necked flask was equipped with a ball condenser, a thermometer, a dropping funnel, and a stirrer.
50.2g (0.1mol) of CI acid-dried 13 and N,
Add 100 ml of N-dimethylformamide, and gradually dropwise add 26.2 g (0.22 mol) of thionyl chloride while stirring. At this time, heat is generated, so the liquid temperature is 10℃.
Cool from front to back. When the heat generation stops after dropping, stop cooling.
The reaction was heated at 100°C for 2 hours, then cooled to around 20°C, and gradually added to a mixture of this cooled solution, 500 g of ice, and 200 ml of water.
13 sulfonic acid chlorides)

[Formula] is produced, and the precipitate is filtered off, washed with water, and purified. The obtained purified precipitate was dispersed in ice water, and 25.8 g of valine adjusted to pH 8-9 with soda carbonate was added to this dispersion.
Gradually add 50ml aqueous solution of (0.22mol), then
The temperature is raised to around 20°C, and the reaction is allowed to proceed slowly for 10 hours while appropriately adding a 5% aqueous solution of sodium hydroxide to maintain the pH at 8 to 9. then gradually
The temperature was raised to 50°C, and the reaction was stopped when the pH of the reaction solution stopped decreasing. Hydrochloric acid was added. The precipitate formed was separated, washed with water, and dried in vacuum to form an acid amide derivative of CI acid red 13 and valine. 49.9g (0.076mol) of is obtained. The coloring material of the present invention is obtained by converting the COOH group of this acid amide derivative into an alkali metal salt by a conventional method. The water-based ink of the present invention is obtained by adding at least a water-soluble organic solvent and water to the above-mentioned coloring material to form an ink. The water-soluble organic solvent may be one that is compatible with water; specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1.3-butylene glycol, thiodiglycol, ethylene glycol monomethyl ether, and ethylene glycol. Monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetin, glycerin, etc. can be used alone or in combination, and the amount used is based on the total amount of ink. It is preferably 5 to 50% by weight. Water is used as the main solvent, and the amount used is preferably 50 to 95% by weight based on the total amount of the ink. In addition, surfactants, preservatives, and the like may be used as appropriate. Hereinafter, the present invention will be described in detail according to Examples, where "parts" in the Examples indicate "parts by weight." Example 1

[Table] The above components were mixed and stirred to obtain a red water-based ink. Comparative Example 1 A red water-based ink was obtained in the same manner as in Example 1, except that CI Acid Red 13 was used instead of the coloring material in Example 1. Example 2

[Table] The above components were mixed and stirred while being heated to 50°C to obtain a blue water-based ink. Comparative Example 2 A colored water-based ink was obtained in the same manner as in Example 2, except that CI Acid Blue 45 was used instead of the colorant in Example 2. Example 3

[Table] The above components were mixed and stirred to obtain a yellow water-based ink. Comparative Example 3 A yellow water-based ink was obtained in the same manner as in Example 3, except that CI Acid Yellow 23 was used instead of the colorant in Example 3. Example 4

[Table] The above components were mixed and stirred to obtain a black water-based ink. Comparative Example 4 CI Acid Black 1 of the colorant in Example 4
A black water-based ink was obtained in the same manner as in Example 4, except that . Example 5

【table】

[Table] Stir and mix the above ingredients while heating to 50℃.
A red water-based ink was obtained. Comparative Example 5 A red water-based ink was obtained in the same manner as in Example 5, except that CI Ash Dred 87 was used instead of the colorant in Example 5. Fill a commercially available felt-tip pen with the obtained inks of Examples 1 to 5 and Comparative Examples 1 to 5, write on JISP3201 writing paper A using this felt-tip pen, and after 5 minutes soak the writing paper in water for 1 hour. As a result, the handwritings made with the inks of Examples 1 to 5 remained clear, whereas the handwritings made with the inks of Comparative Examples 1 to 5 flowed out and were illegible. Also, in order to check the solubility of the inks of Examples 1 to 5,
After the felt-tip pens filled with Examples 1 to 5 were left in a constant temperature room at -5° C. for one week with the cap facing upward, clear handwriting was obtained when writing on paper. As described above, the water-based ink of the present invention has excellent water resistance and good solubility, and is suitable as an ink for writing instruments, stamps, jet printing, printing, and recorders.

Claims (1)

[Claims] 1. A coloring material that is an alkali metal salt of an acid amide derivative obtained by reacting the SO ₃ Na group and/or COONa group of an acidic dye with the amino group of an aminocarboxylic acid, a water-soluble organic solvent, and water. A water-based ink consisting of at least