JPS6058478A - Aqueous ink composition - Google Patents

Abstract

PURPOSE:To provide titled composition of high drying resistance and storage stability through retarding evaporation, for use in writing utensils, stamps, recorders, printing, etc., comprising an aqueous dye solution containing specific polyethylenepolyamine derivative. CONSTITUTION:The objective composition can be obtained by dissolving in water (A) a dye (e.g., acid dye such as Eisen eosin CH) and (B) a polyethylenepolyamine derivative of formula I [n is 1-4, R1-R5 are each of formula II (m is 0, 1-3)] (e.g., pentaoxypropylenediethylenefriamine) in a weight ratio 1/10-10/1.

Description

[Detailed description of the invention] The present invention is for writing instruments, stamps, and recorders.

The present invention relates to an aqueous ink composition suitable for printing and the like.

More specifically, the present invention relates to an aqueous ink composition that suppresses evaporation, has excellent drying resistance, and has excellent storage stability.

Traditionally, fountain pens, water-based ballpoint pens, and writing instruments with pen nibs made of fiber, felt, or monofilament have been used for long-term storage, or when the cap is removed from the body of the writing instrument and the nib is exposed to the atmosphere for a long period of time. However, there are problems such as evaporation of the ink, which causes clogging of the ink flow path at the nib of the pen, and the dye in the ink coagulates and precipitates, resulting in a decrease in concentration. To solve this problem, glycols and glycol ethers are used in water-based ink compositions.

Additions of water-soluble organic solvents such as glycol ether esters and hygroscopic inorganic compounds such as calcium chloride and lithium chloride have been carried out, but these are not always fully satisfactory in terms of long-term storage stability and drying resistance. I haven't gotten what I wanted. This is because glycols have a high viscosity, which increases the viscosity of the ink, making it difficult for the ink to flow out, and also has a high boiling point, which can dry handwriting.Therefore, the amount added is sufficient to satisfy the drying resistance of the ink. Second, glycol ethers and togelicol ether esters have a low surface tension, so the ink from handwriting easily bleeds onto the front and back sides of the paper, and the solubility of water-soluble dyes is low, so it is difficult to obtain sufficient color density. b.
In addition, calcium chloride and lithium chloride react with dyes to form salts1, reducing the solubility of dyes, making it difficult to obtain inks with high color density. This is due to the fact that the added amount cannot be adjusted.

Furthermore, not only water-based inks for writing instruments but also water-based inks for stamps, recorders, printing, etc. have not been sufficiently obtained.

Therefore, the present inventors conducted extensive research to solve these problems with water-based inks, and as a result, we added the following general formula (+) [(■), where n is an integer from 1 to 4, to an aqueous solution of dye. C, R1, R2゜R,, R4 and R7 are -(3H,,OH(OH2)mH
(m is 0 and OH is an integer of 1 to 3), and each group may be the same or at least one group may be different. ]
It was discovered that by adding the polyethylene polyamine derivative represented by the above, the above-mentioned problems could be solved, and a water-based ink composition with good drying resistance, excellent dye solubility, and no dye precipitation could be obtained. As a result, the present invention was completed.

Next, each component of the aqueous ink composition of the present invention will be explained in more detail.

Most dyes such as water-soluble acid dyes, direct dyes, and basic dyes can be used as the dyes used in the present invention, but specific examples include Eiseneosin OH (○, ■ .

45380), water black +21 (0, engineering, 1
5985゜42090, 42745 mixed dye), Nigrosine NB cone (a, engineering, 42090)
, Water Pink +2 (06E.

45410), Kayaftatrazine (C, Engineering, 1)
'B40).

Kayasil Pure Blue'FGA (0, engineering, 42080
), acid violet 6 B (0,1,42
640), etc. Direct dyes include water black ÷ 100 (0, engineering, 35255), direct deep black XAconC (o, engineering, 2772
0), Direct First Black AB (0, Engineering, 35440), Kayaras Black G cone
(0, engineering, 35225), water pink ÷ 1
53 (manufactured by Orient Chemical Co., Ltd.), basic dyes include Victoria Blue F4R (0, engineering, 42
565).

Victoria Blue FB (0,1,44045),
Methyl Reno (Iolet FN (0, engineering, 42535
), Rhodamine B ((:!, Eng.

45170), Rhodamine 6GOP (0, Eng, 4
5160). These water-soluble dyes are used alone or in combination with other water-soluble dyes, and the amount used varies depending on the purpose of the ink and the type and amount of other additives used as appropriate. Usually, it is preferably 0.1 to 30% by weight of the ink composition.

Further, as the polyethylene polyamide derivative represented by the general formula (I), pentaoxypropylene diethylene triamine, pentaoxyethylene diethylene triamine,
Examples include hexaoxypropylene triethylenetetramine, hexaoxyethylene triethylenetetramine, etc., and the amount used varies depending on the purpose of ink use, the type and amount of dye, or the type and amount of additives used as appropriate, but usually For example, when used as an ink for writing instruments, it is preferably 0.01 to 70% by weight of the ink composition. Furthermore, the blending ratio of the dye and the polyethylene polyamine derivative is in the range of 1/100 to 100/1, preferably in the range of 1/10 to 10/1, by weight.

The ink composition of the present invention may optionally contain water-soluble organic solvents such as glycols, /IJ coal ethers + licol ether esters, hygroscopic inorganic compounds such as calcium chloride and lithium chloride, and benzoic acid. )
Addition of preservatives such as IJum, sodium pentachlorophenol, potassium sorbate phenol, formalin, rust inhibitors such as hensitriazole, penetrants such as anionic or nonionic surfactants, or other known additives. be able to.

The ink composition according to the present invention can be prepared by adding, for example, the polyethylene polyamine derivative represented by the above formula (I), a dye, and other additives used as necessary to water simultaneously or sequentially at room temperature to about 50°C. It can be manufactured by stirring until a uniform composition is obtained.

The ink composition according to the present invention has the following excellent properties.

0 It dries and maintains good writability during long-term storage in a writing instrument or container.

0 Even if the cap is removed from the writing instrument body and left in the atmosphere for a long period of time, the ink does not evaporate from the pen tip, and the writing instrument has excellent drying resistance and maintains good writing performance.

0 Since the solubility of the dye is high, the concentration can be increased, and it also has excellent storage stability at high concentrations, so no blurring due to dye precipitation occurs.

The aqueous ink composition according to the present invention can be applied not only to writing instruments as described above, but also to stamps, recorders, printing, etc.

Next, the water-based ink composition of the present invention will be explained in more detail with reference to Examples, but the present invention is not necessarily limited to the following Examples. In addition, in the examples, all parts simply indicate parts by weight.

Example 1 Eiseneosin GH (0, Engineering, 45380, manufactured by Hodogaya Chemical Industry Co., Ltd.) 5.0 parts Pentaoxypropylene diethylene triamine 2s,
0 parts Water 70.0 parts The above components were added to water, dye, and pentaoxypropylene diethylene triamine, and the mixture was stirred and mixed at about 30° C. for 2 hours to obtain a red ink.

When the obtained red ink was used as an ink for a felt-tip pen, the pen tip did not dry even after removing the cap of the sign-pen at 20° C. and 65% RH for 10 days, and showed good writing performance. Even when used in a ballpoint pen, it showed stable and good writing properties over a long period of time.

On the other hand, an ink in which pentaoxypropylene diethylene triamine was removed from the above formulation and water was added in the same amount was dried in about one day under the same conditions.

Example 2 Water black ÷ 100 6.0 parts (a, work, 3
5255, manufactured by Orient Chemical Industry Co., Ltd.) Sodium pentachlorophenol (preservative) 1.0 parts Pentaoxyethylene diethylene triamine 27.0 parts Water 66
．． 0 parts Water, dye, pentaoxyethylene diethylene triamine, and pentachlorophenol sodium were added to each of the above components in this order, and the mixture was stirred and mixed at about 55° C. for 2 hours to obtain a black ink.

When the obtained black ink was used as an ink for felt-tip pens, the pen tip did not dry out and showed good writing performance even after removing the cap of the signature pen at 20°C and 65% RH and leaving it for 10 days. . Even when used in a ballpoint pen, it showed stable and good writing properties over a long period of time.

On the other hand, an ink obtained by removing pentaoxyethylene diethylene triamine from the above formulation and adding that amount of water dried under the same conditions in about one day.

Example 3 Water Blue φ9 4.0 parts (a, engineering, 42090, manufactured by Orient Chemical Industry Co., Ltd.) Sodium pentachlorophenol (preservative) 1.
0 parts ethylene glycol 15.0 parts pentaoxypropylene diethylene triamine 20.
0 parts Water 60.0 parts Water, ethylene glycol, dye, pentaoxypropylene diethylene triamine, and sodium pentachlorophenol were added to each of the above components in this order, and the mixture was stirred and mixed at about 40° C. for 2 hours to obtain a blue ink.

When the obtained blue ink was used as an ink for a felt-tip pen, the cap of the felt-tip pen was removed under the conditions of 20° C. and 654 RH, and even after being left for 10 days, the pen tip did not dry and showed good writing performance. Even when used in a ballpoint pen, it showed stable and good writing properties over a long period of time.

On the other hand, an ink obtained by removing pentaoxypropylene diethylene triamine from the above formulation and adding that amount of water dried under the same conditions in about 5 days.

Example 4 Sodium pentachlorophenol (preservative) 1.0
parts ethylene glycol 15.0 parts hexaoxane 7 propylene triethylenetetramine 20 parts
．． 0 parts Water 59.0 parts Water, ethylene glycol, dye, hexaoxypropylene triethylene tetramine, and sodium pentachlorophenol were added to each of the above components in this order, and the mixture was stirred and mixed at about 40° C. for 2 hours to obtain a purple ink.

When the obtained purple ink was used as an ink for a felt-tip pen, the pen tip did not dry even after removing the cap of the felt-tip pen at 20°C and 65% RH for 10 days, showing good writing performance. . Even when used in a ballpoint pen, it showed stable and good writing properties over a long period of time.

On the other hand, an ink obtained by removing hexaoxypropylene triethylenetetramine from the above formulation and adding that amount of water dried under the same conditions in about 3 days.

Example 5 Water Black + 100 6.0 parts (0,000 g, 3
Sodium pentachlorophenol (lIjJ agent) 1.0 parts ethylene glycol 20.0 parts pentaoxyethylene diethylene triamine x, o parts water 70.0 parts Each of the above components was mixed with water and ethylene glycol. , dye, pentaoxyethylene diethylene triamine, and 1 noum of pentachlorophenol sodium were added in this order and mixed with stirring at about 35° C. for 2 hours to obtain a black ink.

When the obtained black ink was used as an ink for a felt-tip pen, the cap of the felt-tip pen was removed under the conditions of 20°C and 65t4RH.1. ．． ．． Even after being left for 10 days, the pen tip did not dry out and showed good brush stroke consistency. Even when used in a ballpoint pen, it showed stable and good writing properties over a long period of time.

On the other hand, an ink obtained by removing pentaoxyethylene diethylene triamine from the above formulation and adding that amount of water dried under the same conditions in about one day.

Claims (1)

[Scope of Claims] 1. An aqueous ink composition comprising a polyethylene polyamine derivative represented by the following general formula (1) added to an aqueous solution of a dye. [In formula (I), n is an integer of 1 to 4, R1, R2゜R, R, and R5 are expressed as -OH20H (OH21,H (m is an integer of 1 to 3) 2. The aqueous dye according to claim 1, wherein the dye and the polyethylene polyamine derivative are mixed in a weight ratio of 1710 to 10/1. Ink composition.