JPS6366869B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-based ink, and more particularly to a water-based ink that has extremely good water resistance. Conventionally, water-based inks that use 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, etc. In comparison, it had a problem of poor water resistance. Although oil-based inks that use oil-soluble dyes have extremely good water resistance compared to water-based inks that use water-soluble dyes, they have the problem of bleeding and set-off when written on paper, etc. An aromatic solvent is used to dissolve the dye.
There was a problem with toxic odor. As a result of various studies on the above-mentioned problems, the present inventors have come to the knowledge that there is the following relationship between conventional ink compositions and water resistance. With conventional inks that use water-soluble dyes, when you write on paper, even if the dye is once dyed on the paper, when the paper is immersed in water, the dye is water-soluble and the dye dissolves from the paper surface, causing the handwriting to change. Poor water resistance. With conventional oil-based inks that use oil-soluble dyes, the oil-soluble dyes are insoluble in water, so once the dye is dyed onto the paper, even if the paper is immersed in water, the dye will not dissolve into the water from the surface of the paper. Therefore, the water resistance of handwriting is improved. Therefore, the present inventors believe that by using a water-insoluble substance as a colorant and using a water-soluble organic solvent that dissolves the substance, a water-based ink with excellent water resistance can be created while maintaining solubility as much as possible. Based on the idea that oil-soluble dyes, water-soluble organic solvents, and water can be obtained, the water-soluble organic solvent has a dielectric constant of 8 or more and a boiling point of 80 to 300℃ at normal pressure. An application was filed for a water-based ink using a water-soluble organic solvent. (Japanese Patent Application No. 55-135558) The above-mentioned water-based inks exhibit extremely good water resistance compared to water-based inks that use water-soluble dyes, but among them, water-based inks that use yellow oil-soluble dyes had the problem of inferior water resistance compared to water-based inks using other oil-soluble dyes. For this reason, water-based inks that use yellow oil-soluble dyes as coloring agents tend to dissolve in water more easily than other oil-soluble dyes when soaked in water after writing on paper, resulting in discolored handwriting. I had a problem with it. The present inventors discovered that because most of the yellow oil-soluble dyes are produced using acidic dyes as a base material, the SO ₃ H or SO ₃ Na groups in the dye molecules increase the solubility in water, resulting in water resistance. Based on the knowledge that water resistance deteriorates, we believe that using a yellow oil-soluble dye that does not contain SO ₃ H or SO ₃ Na groups will improve water resistance. As a result of various studies regarding the soluble groups of dyes, the present invention was finally completed. Namely, the present invention consists of an oil-soluble dye which is an acid esterified product of a compound represented by the following general formula and a sugar or a sugar derivative. Or a colorant combined with other oil-soluble dyes and a dielectric constant of 8 or higher and a boiling point at normal pressure.
The gist is a water-based ink consisting of at least a water-soluble organic solvent having a temperature of 80 to 300°C and water. [In the formula, R is an alkyl group, X is a substitutable aryl group, Y is a hydrogen atom, a halogen atom, a hydroxyl group,
Indicates an alkyl group. ] The oil-soluble dye used in the present invention has improved water resistance because it does not contain SO ₃ Na groups in the dye molecule, and
Because it has sugar or sugar derivative residues (polar groups),
It is thought that it becomes soluble in the specific organic solvent of the present invention and can be used as a water-based ink. The present invention will be explained in detail below. The oil-soluble dye, which is an acid ester of the compound represented by the above general formula and sugar or sugar derivative, is prepared by diazotizing an aryl compound having at least an amino group and a carboxyl group, and then coupling it with a pyrazolone compound containing active methylene by a conventional method. The resulting chromogen is reacted with an acid chloride agent such as chlorosulfonic acid, sulfuryl chloride, thionyl chloride, etc., the carboxyl group of the chromogen is converted into an acyl chloride group, and the sugar or sugar derivative is converted into an acyl chloride group under alkaline conditions using a conventional method. It is obtained by reacting and purifying the resulting product by washing with water and filtering. Examples of the above-mentioned aryl compounds having an amino group and a carboxyl group include p-aminobenzoic acid, 3
-Amino-4-chlorobenzoic acid, p-aminohippuric acid, m-dimethylaminobenzoic acid, 4-aminosalicylic acid, anthranilic acid, 3-amino-4-methylbenzoic acid, etc., and pyrazolone containing active methylene As a compound, 1-phenyl-
3-Methyl-5-pyrazolone, 1-(4'-tolyl)
-3-methyl-5-pyrazolone, 1-phenyl-
3-isopropyl-5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 3-methyl-
Examples of the sugar or sugar derivative include 1-(4-methylphenyl)-5-pyrazolone, and examples of the sugar or sugar derivative include fructose, sucarose, mannitol, sorbitol, and glucose. Almost all other oil-soluble dyes can be used, but
Alcohol-based oil-soluble dyes and metal-containing oil-soluble dyes are particularly preferred for inks that require density, such as ink for writing instruments, but are not limited to these. , CI Solvent Orange 1, CI 2, CI 5, CI 6, CI 11, CI
14, 27, 37, 40, 44, 45, 59, CI
Solvent Red 1, 3, 7, 8, 9,
23, 24, 25, 27, 30, 49, 81, 25
82, 83, 84, 100, 109, 121, 125,
Same 127, Same 130, Same 131, Same 132, CI Disperse Thread 9, CI Solvent Violet 8, Same
13, 14, 21, 24, 27, CI Daysverse Violet 1, CI Solvent Blue 2, Same
11, 12, 25, 35, 36, 48, 49,
51, 53, 55, 67, 73, CI Solvent Green 3, CI Solvent Brown 3, 5, Same
20, 34, 35, 37, 42, 43, 44, CI
Solvent Black 2, 3, 5, 6, Solvent Black
22, 23, 28, 29, etc., as well as various commercially available oil-soluble dyes for resin coloring, which can be used alone or in combination, and the amount used varies depending on the type of dye. For the total amount of ink,
0.3 to 15% by weight is preferred. Examples of water-soluble organic solvents include glycols and their derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and glycerin, monoethanolamine, diethanolamine, isopropanolamine, and −
Methyldiethanolamine, NN-dimethylethanolamine, 2-(2-aminoethylamino)
N-alkanolamines such as ethanol,
Alcohols such as 2-chloroethanol and tetrahydrofurfuryl alcohol, acetamide, formamide, N-methylacetamide, N
- Amides such as methylformamide, N-methylpropylamide, NN-dimethylamide,
Sulfolane, 2-pyrrolidone, N-methyl-2-
Examples include pyrrolidone, 1,1,3,3-tetramethylurea, etc., which have a dielectric constant (ε) of 8 or more and a boiling point (bp) of 80 to 300°C at normal pressure.
They can be used alone or in combination, and the amount used is preferably 1 to 45% by weight based on the total amount of the ink. The amount of water used is preferably 35 to 85% by weight based on the total amount of ink. In addition, known rust preventives, preservatives, and antifungal agents can be used as appropriate, and urea and small amounts of water-soluble organic solvents that do not meet the above conditions can also be used as solubilizers. Next, to briefly describe the method for producing the water-based ink of the present invention, it is important to first stir and mix the oil-soluble dye and the water-soluble organic solvent. After dissolving it in a solvent, add other ingredients including water,
Mix and stir to make ink. Incidentally, the mixing and stirring may be carried out while heating, or if there are any insolubilized substances when the ink is formed, the insolubilized substances may be removed by filtration or the like. Hereinafter, the present invention will be described in more detail with reference to Examples, in which "parts" indicate "parts by weight". Example 1 Acid ester of fructose (yellow oil-soluble dye) [carboxyl group in the above structural formula obtained by diazotizing p-aminobenzoic acid and coupling reaction with 3-methyl-1-phenyl-5-pyrazolone It was converted into an acyl chloride group, reacted with fructose, and was then washed and filtered with water. ] Tetrahydrofurfuryl alcohol (ε=13.61,
bp = 178℃) 25.0 parts Sulfolane (ε = 43.3, bp = 285℃) 5.0 parts Water 64.5 parts Sodium pentachlorophenol (preservative, antifungal agent) 0.5 parts Tetrahydrofurfuryl alcohol for the yellow oil-soluble dye of the above ingredients and sulfolane and heated to 50℃
The mixture was stirred and mixed for 1 hour, and other components were added and mixed for 1 hour to obtain a yellow water-based ink. Comparative Example 1 A yellow water-based ink was prepared in the same manner as in Example 1, except that a yellow oil-soluble dye such as Solvent Yellow RLSN (CI Solvent Yellow 83, manufactured by Sandoz Co., Ltd.) was used instead of the oil-soluble dye in Example 1. I got it. Example 2 Acid esterified product of satucarose (yellow oil-soluble dye) It was obtained by changing to a chloride group, reacting with sutucarose, washing with water and filtering. ] Astra Blue 6GLL Split Soluble (CI
Solvent Blue 51, Bayer) 2.5 parts Tetrahydrofurfuryl alcohol (ε=13.61,
bp=178℃) 20.0 parts N-methyl-2-pyrrolidone (ε=32.0, bp=
202℃) 5.0 parts Water 72.0 parts Among the above ingredients, add tetrahydrofurfuryl alcohol to the yellow oil-soluble dye and Astra Blue 6GLL split soluble, stir for 2 hours, then add other ingredients for 1 hour. A green water-based ink was obtained by stirring and mixing. Comparative Example 2 The procedure was the same as in Example 2 except that a yellow oil-soluble dye such as Irizole Fast Yellow GRE (CI Solvent Yellow 65, manufactured by Bayer AG) was used instead of the yellow oil-soluble dye in Example 2. A green water-based ink was obtained. Example 3 Acid ester of sorbitol (yellow oil-soluble dye) [The above structural formula obtained by diazotizing p-aminobenzoic acid and coupling it with 3-methyl-1-(4-methylphenyl)-5-pyrazolone] It was obtained by changing the carboxyl group to an acyl chloride group, reacting with sorbitol, washing with water, and filtering. Lake Black (CI Solvent Black 3, manufactured by Bayer) 3.5 parts Tetrahydrofurfuryl alcohol 15.5 parts Sulfolane (ε=43.3, bp=285℃) 10.0 parts Ethylene glycol (ε=37.7, bp=197.6℃)
5.0 parts water 60.7 parts urea (solubilizer) 5.0 parts sodium pentachlorophenol (preservative, antifungal agent) 0.3 parts Mix the yellow oil-soluble dye and lake black from the above ingredients with tetrahydrofurfuryl alcohol, sulfolane, and urea. Add to the solution and warm to 50℃,
Stir and mix for 1 hour, add other ingredients, stir and mix for another 2 hours, filter to remove insolubilized materials,
A black water-based ink was obtained. Comparative Example 3 Instead of the yellow oil-based dye in Example 3,
A black water-based ink was obtained in the same manner as in Example 3, except that Irizol Fast Yellow GRE was used. Table 1 shows the water resistance tests of the inks obtained in Examples 1 to 3 and Comparative Examples 1 to 3.

[Table] As explained above, the water-based ink of the present invention has good water resistance and is suitable as an ink for writing instruments, printing, recorders, stamps, jet printing, etc. be.

Claims (1)

[Scope of Claims] 1. A coloring material comprising a compound represented by the following general formula and an oil-soluble dye which is an acid ester of sugar or a sugar derivative alone or in combination with other oil-soluble dyes, and having a dielectric constant of 8 or more, A water-based ink comprising at least water and a water-soluble organic solvent having a boiling point of 80 to 300°C at normal pressure. [In the formula, R is an alkyl group, X is a substitutable aryl group, Y is a hydrogen atom, a halogen atom, a hydroxyl group,
Indicates an alkyl group. ]