JPS6123826B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous ink composition suitable for writing instruments, stamps, printing, and recorders, and more specifically, it suppresses evaporation, has excellent drying resistance even when exposed to the atmosphere for a long time, and has a high concentration. The present invention relates to an aqueous ink composition having the following characteristics. Traditionally, for example, writing instruments, specifically writing instruments with pen nibs made of fiber, felt, or monofilament,
Or, in a capillary writing instrument of a fountain pen, even if the pen tip is exposed to the atmosphere for a long time during storage or when the cap is removed from the writing instrument body, the ink always flows out smoothly without clogging the ink flow path of the pen tip. There was a need for a water-based ink that would allow for extremely smooth writing. In order to meet this demand, water-soluble organic solvents such as glycol solvents, glycol ether solvents, and glycol ether ester solvents, or hygroscopic inorganic compounds such as lithium chloride and calcium chloride, are included in the aqueous solution of water-soluble dyes to improve dryness resistance. Although water-based inks with improved dryness resistance have been known, none have been able to provide sufficient drying resistance. The reason for this is that glycol solvents generally have a high viscosity and a high boiling point, which increases the viscosity of the ink, and when used in writing instruments that require low viscosity, the outflow of the ink is inhibited, causing the ink to run out. Furthermore, it has drawbacks such as the handwriting is difficult to dry and the abrasion resistance after writing is poor, and there is a limit to the amount used, and it is not possible to add it in an amount sufficient to satisfy the drying resistance. Glycol ether solvents and glycol ether ester solvents generally have low surface tension, so handwriting tends to smear, and the ink may penetrate to the back side of the paper or smudge on the surface, making it impossible to obtain clear handwriting. It has disadvantages such as its low ability to dissolve dyes, making it impossible to obtain a uniform color, increasing the viscosity of the ink, and having a strong odor.As mentioned above, it is necessary to add an amount sufficient to satisfy drying resistance. I can't do that. In addition, lithium chloride and calcium chloride react with dyes to form salts and reduce the solubility of dyes, making it difficult to prepare inks with high concentrations and making it impossible to add them in amounts sufficient to satisfy drying resistance. Furthermore, inks other than those for writing instruments, such as inks for stamps, have not yet been sufficiently developed. Therefore, the present inventors have conducted various studies to solve the conventional problems described above, and as a result, the present inventors have used a substituted benzenesulfonic acid morpholide derivative, a substituted benzenesulfonic acid piperazide derivative, or an alkylsulfonylmorpholinyl morpholide derivative in an aqueous solution of a water-soluble dye. It was discovered that when a ride derivative or an alkylsulfonylpiperazide derivative is blended, an aqueous ink composition having good drying resistance and good dye solubility without causing a sudden increase in viscosity can be obtained, and the present invention has been achieved. It is completed. That is, the present invention provides an aqueous solution of a water-soluble dye containing a substituted benzenesulfonic acid morpholide derivative represented by the following general formula (1a), a substituted benzenesulfonic acid piperazide derivative represented by the general formula (1b), or a substituted benzenesulfonic acid piperazide derivative represented by the general formula (1b). Alkylsulfonylmorpholide or general formula (b)
This is an aqueous ink containing an alkylsulfonylpiperazide derivative represented by: General formula: [In the formula, R ₁ is hydrogen or an alkyl group represented by C _n H _2n+1 (m is an integer of 1 to 5), R ₂ is hydrogen, C _n H ₂
It represents an alkyl group or halogen represented by _n+1 (m is an integer of 1 to 5). _R3 is

[Formula] (n is an integer of 1 to 5, R ₄ is hydrogen or a methyl group). ] The compound represented by the general formula (1a) or (a) can be easily obtained by reacting substituted benzenesulfonyl chloride or alkylsulfonyl chloride with morpholine. Further, the compound represented by the general formula (1b) or (b) can also be easily obtained by adding, for example, ethylene oxide or propylene oxide to the reaction product of substituted benzenesulfonyl chloride or alkylsulfonyl chloride and piperazide. . Examples of the substituted benzenesulfonic acid morpholide derivatives of the general formula (1a) include benzenesulfonylmorpholide, toluenesulfonylmorpholide, isopropylbenzenesulfonylmorpholide, chlorotoluenesulfonylmorpholide, and the like; Examples of the alkylsulfonylmorpholide in a) include methanesulfonylmorpholide, ethanesulfonylmorpholide, propanesulfonylmorpholide, isopropanemorpholide, and the like. Examples of substituted benzenesulfonic acid piperazide derivatives of general formula (1b) include addition products of benzenesulfonylpiperazide, toluenesulfonylpiperazide, isopropylbenzenepiperazide, chlorotoluenepiperazide, etc. and ethylene oxide or propylene oxide. Examples of the alkylsulfonylpiperazide derivatives of general formula (b) include methanesulfonylpiperazide, ethanesulfonylpiperazide, propanesulfopiperazide, isopropanesulfopiperazide, and ethylene oxide or propylene oxide. Examples include addition products with. Next, each component of the aqueous ink composition of the present invention will be explained in more detail. As water-soluble dyes, most dyes such as water-soluble acid dyes, direct dyes, and basic dyes can be used. Specific examples of acid dyes include Eiseneosin GH (CI45380), Water Black # 21 (mixed dye of CI15985, 42090, 42745), Nigrosine NBconc (CI50420), Water Blue #9 (CI42090), Water Pink #2 (CI45410), Kayactatrazine (C.
Direct dyes include Water Black #100 (CI35255), Direct Deep Black XA (manufactured by Sumitomo Chemical), Direct Deep Black EX (CI35225), and Direct First Black conc (CI27720). ,
Victoria Blue F4B (C.
I.42563), Victoria Blue FB (CI44045), Methyl Violet FN (CI42535), Rhodamine
6GCP (CI45160), etc., and these are used alone or in combination with other water-soluble dyes.
The amount of the water-soluble dye to be used may be varied depending on the purpose; for example, when used as an ink for writing instruments, suitable results can be obtained when it is used in an amount of 0.5 to 30% by weight of the ink composition. Substituted benzenesulfonic acid morpholide derivatives or substituted benzenesulfonic acid piperazide derivatives represented by general formula (1a) or (1b), or alkylsulfonylmorpholide or alkylsulfonylpiperazide represented by general formula (a) or (b) The amount of the derivative used varies depending on the purpose, but for example, when used as an ink for writing instruments, the amount of the derivative used is 5 to 70% of the ink composition.
Suitable results are obtained when using % by weight. The solubility of the dye is increased and its hygroscopicity is good, and the dye in the ink does not coagulate at room temperature, and the ink at the tip of the pen evaporates even if the cap is removed and left in the air for a long time. It is possible to obtain an ink composition with excellent drying resistance. The solubility of all acidic, direct, and basic dyes can be increased, and in particular, direct dyes, which were traditionally poorly soluble and rarely used, can be used, so the use of direct dyes can improve water resistance and drying resistance. A good ink composition is obtained. As mentioned above, the present invention greatly improves drying resistance by adding and blending a compound represented by general formula (1a) or (1b), or (a) or (b) into an aqueous solution of a water-soluble dye. However, if necessary, glycol type, glycol ether type glycol, ether ester type, dimethyl oxide, 2-pyrrolidone, N-methyl-
A solvent such as 2-pyrrolidone and a preservative may be appropriately selected and used. EXAMPLES Hereinafter, ink for writing instruments will be described with reference to Examples of the present invention. In the examples, parts simply refer to parts by weight. Example 1 Eiseneosin GH (CI45380, manufactured by Hodogaya Chemical Industry Co., Ltd.) 4.0 parts Sodium pentachlorophenol (preservative)
1.0〃 Ethylene glycol 20.0〃 Benzenesulfonylmorpholide (or methanesulfonylmorpholide) 25.0〃 Water 50.0〃 Among the above components, ethylene glycol and water are mixed first, and then the remaining components are mixed into the mixed solution for about The ink is prepared by stirring while heating at 40-50°C for 1 hour. This ink has good color strength and has good adhesion properties on writing paper without bleeding or bleeding when used on writing paper. In addition, the drying resistance of this ink was tested by leaving the cap on a writing instrument made of fiber, felt, or monofilament and having a porous or capillary tip for 10 days at a temperature of 20°C and a humidity of 65%. The pen tip did not dry out and writing was possible even after leaving the pen in place. Incidentally, an ink in which benzenesulfonylmorpholide or methanesulfonylmorpholide was removed from this formulation and water was added in the same amount was dried in about one day under the same conditions. Example 2 Water black #21 (CI15985, 42090,
42745 mixed dye, manufactured by Orient Chemical Industry Co., Ltd.)
6.5 parts Nigrosine NBconc (CI50420, manufactured by Sumitomo Chemical) 1.0〃 Formalin (preservative) 1.0 parts Ethylene glycol 20.0〃 Benzenesulfonyl β-hydroxyethylpiperazide (or methanesulfonyl β-hydroxyethylpiperazide) 20.0〃 Water 51.5〃 The above ink has good writing characteristics, and Example 1
Even if the cap was removed and left for 10 days under the same conditions as above, the pen tip did not dry out and writing was possible. Furthermore, excluding benzenesulfonyl β-hydroxyethylpiperazide or methanesulfonyl β-hydroxyethylpiperazide from this formulation,
The ink with that amount of water added under the same conditions is approximately 1
It dried up in the sun. Example 3 Water black #100 (CI35255, manufactured by Orient Chemical Industry Co., Ltd.) 6.5 parts Sodium pentachlorophenol (preservative)
1.0〃 Ethylene glycol 20.0〃 Benzenesulfonyl β-hydroxy isopropyl piperazide or methane sulfonyl β-hydroxyisopropyl piperazide 15.0〃 Water 57.5〃 The above ink has good writing characteristics, and Example 1
Even if the cap was removed and left for 10 days under the same conditions as above, the pen tip did not dry out and writing was possible. Furthermore, from this formulation, benzenesulfonyl β
The ink except for -hydroxyisopropylpiperazide or methanesulfonyl β-hydroxyisopropylpiperazide and to which that amount of water was added dried under the same conditions in about one day. Although the present invention has been mainly described above with respect to a water-based ink composition for writing instruments, it can also be applied to water-based ink compositions for stamps, printing, recorders, and the like.

Claims (1)

[Scope of Claims] 1 A substituted benzenesulfonic acid morpholide derivative represented by the following general formula (1a), a substituted benzenesulfonic acid piperazide derivative represented by the general formula (1b), or an alkylsulfonyl represented by the general formula (a) An aqueous ink composition comprising a morpholide or an alkylsulfonylpiperazide derivative represented by the general formula (b). [In the formula, R ₁ is hydrogen or an alkyl group represented by C _n H _2n+1 (m is an integer of 1 to 5), R ₂ is hydrogen, C _n H ₂
It represents an alkyl group or halogen represented by _n+1 (m is an integer of 1 to 5). R ₃ represents the formula (n is an integer of 1 to 5, R ₄ is hydrogen or a methyl group). ]