JPH04103676A - Water-resistant ink composition and its production - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent water resistance on paper and stability with time by dissolving a specific anionic dye in water, adding a specific water resistance-imparting agent, an oil-soluble dye and a dispersive dye and mixing the resultant system with stirring at above room temperature. CONSTITUTION:(A) An anionic dye having <=60dyn/cm surface tension at 20 deg.C (in water) in the concentration of 0.1wt.% is added to water and completely dissolved, and (B) a water resistance-imparting agent containing a compound, hardly soluble in water and having aromatic ring or 6-12C aliphatic hydrocarbon as a lipophilic group and a group having O, N and S atoms as a hydrophilic group as an active ingredient, (C) an oil-soluble dye hardly soluble in water and having 2wt.% solubility at 20 deg.C when dissolving in ethyl alcohol and/or (D) a dispersing dye having same properties as the component C are added to said A solution, then the resultant mixture is stirred at above room temperature to afford the objective ink composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a water-based ink composition, and more specifically, to an ink for writing instruments, plotters, and inkjet printers that exhibits excellent water resistance on paper and stability over time. The present invention relates to an aqueous ink composition comprising:

[Prior art and issues to be solved by the present invention M] Compared to the conventional technology! Various research and developments are being carried out for the purpose of imparting water resistance on paper to marks. Pigment-based water-based inks using pigments are generally well known, but these pigment-based water-based inks have problems in stability over time, such as poor dispersion stability and sedimentation of pigment particles.

[Means for Solving the Problems] In order to solve the problems, the present inventors have developed a so-called dye system that has good water resistance on paper and uses water-soluble dyes that are superior in stability over time compared to pigments. We conducted research on water-based ink compositions.

The present inventors found that the present invention contains both a lipophilic group selected from an aromatic ring or an aliphatic hydrocarbon having 6 to 12 carbon atoms, and a hydrophilic group selected from a group having at least one O, N, or S atom. It has been found that anionic dye inks containing poorly water-soluble compounds have significantly improved water resistance on paper.

However, the above-mentioned compounds are poorly soluble in water, and only dispersion inks can be obtained.However, among the above-mentioned compounds, the only compound that shows a solubility in ethyl alcohol at 20°C of 5% by weight or more is 0.1% by weight in water. The surface chord force when melted is 20
A new finding has been obtained that anionic dyes having a viscosity of 60 dVn/cm or less at °C can be very suitably solubilized in water.

Taking advantage of this new knowledge, we invented a water-based ink that has excellent water resistance on paper and excellent stability over time.

This is the invention of Japanese Patent Application No. 1-277313 by the present inventor. This invention has excellent water resistance and stability over time, but (B) dye has a color [! There were some restrictions on the neck, and the color tone was somewhat unsatisfactory.

As a result of further research, the present inventor found that (B) the amount of dye in the ink composition is 2-301% by weight or more and 60% in the total dye of the ink.
jl amount % or more, the above-mentioned (D) R solubility in water and solubility when dissolved in ethyl alcohol is 2f at 20°C! The present invention was completed by discovering that it is possible to dissolve a dispersible dye similar to an oil-soluble dye in an amount of % or more.

(B) Dyes have a limited range of colors, so it is desirable to adjust the tone. Oil-soluble dyes and dispersible dyes come in a wide variety of colors and form water-resistant handwriting, but they cannot be used in inks because they are not soluble in water. be.

As described above, according to the present invention, specific oil-soluble dyes and dispersible dyes can be used as color tone adjusting agents in ink dyes, and it has been possible to further improve water resistance and obtain a wide variety of color tones.

The above-mentioned component (C) of the present invention and (D) and/or (E)
To solubilize the ingredients (B) Dye is in the ink sacrificial acid.
Outside this range, component (C) and components (D) and/or (B) cannot be completely solubilized.

Further, the amount of component (C) in the ink composition is suitably 0.5 to 5% by weight in order to impart water resistance.

The amount of component (D) and/or component (E) is preferably 40% by weight or less based on the total weight of the dye.

The present invention also provides the above-mentioned (F) as an auxiliary tone adjustment side.
A dye can be used in combination. (F) The dye has a wide variety of colors and has an excellent tone adjustment effect. The amount used must be no more than 5% by weight in the ink composition and no more than 9% by weight of the total dye weight of the ink; outside this range, water resistance will be adversely affected.

That is, the present invention provides: ``1゜ (A) water; (B) 2 to 30% by weight of indigo in the ink composition, and 60% by weight or more of the total dye weight of the ink, and 0.1% by weight of water; The surface tension when melted is 60 dyn at 20℃
/cm or less; and (C) an aromatic ring or an aliphatic hydrocarbon having 6 to 12 carbon atoms as a lipophilic group;
, N, a group having at least one S atom is a hydrophilic group,
Water resistance, which is a poorly water-soluble compound containing one or more of each of these two groups, and whose effective component is a water-soluble compound whose solubility when dissolved in ethyl alcohol is 5% by weight or more at 20°C. (D) an oil-soluble dye that is H-soluble in water and has a solubility of 211% or more when dissolved in ethyl alcohol at 20° C. as a color tone adjusting agent in an ink composition prepared by blending and dissolving the imparting agent and 2 or more and/or (E) 1. of a dispersible dye that is sparingly soluble in water and has a solubility in ethyl alcohol of 2% by weight or more at 20°C. A water-resistant ink composition containing two or more of the following.

2. The water resistance imparting agent (C) component is 0.5% in the ink composition.
The water-resistant ink composition according to claim 1, wherein the water-resistant ink composition is 51i% by weight.

3. The water-resistant ink composition according to claim 1 or 2, wherein the color tone adjusting agent (D) and/or (E) is present in an amount of 40 weight percent or less based on the total dye weight of the ink.

4. As an auxiliary color adjuster, (F) has a surface tension of 20℃ when dissolved in water at 0.1% by weight.
5. Anionic dyes exceeding 60 dyn/country in the ink composition. 4. The water-resistant ink composition according to claim 1, wherein the water-resistant ink composition is blended in an amount of not more than 9% by weight based on the total dye weight of the ink.

5. The anionic dye (B) described in claim 1 (
A) is added to water and completely dissolved, and then one or more of the oil-soluble dyes of (D) and/or one or more of the dispersible dyes of ([) and two or more of the water-resistant dyes of (C) are added. 1. A method for producing a water-resistant ink composition, which comprises adding a property imparting agent and stirring at a temperature of room temperature or higher, and then adding and mixing the remaining components.

Add 6iB) of the anionic dye and ([) of the anionic dye to the water of (A) and dissolve completely, then add one or more of the oil-soluble dyes of (0) and/or (E). A water-resistant ink composition, characterized in that one or more of the dispersible dyes (C) and the water resistance imparting agent (C) are added, stirred at a temperature above room temperature, and then the remaining components are added and mixed. ``Manufacturing method''.

As the aliphatic hydrocarbon group of the water resistance imparting agent, an alkylene group is suitable.

[Function] Regarding the improvement of water resistance on paper, academic elucidation is not necessarily sufficient, but since the present invention has repeatability, the present inventor thinks as follows.

That is, due to the presence of a poorly water-soluble compound containing one or more hydrophilic groups having at least one highly electronegative O, N, or S atom, the hydrogen bond between the paper and the dye is stronger than the conventional hydrogen bond between the paper and the dye. A stronger hydrogen bond is formed between the paper, the dye, and the poorly water-soluble compound, and furthermore, water B? It is thought that the water resistance of the ink on paper is improved due to the hydrophobicity of the octavalent gold compound with the soluble dye and/or the disperse dye.

In addition, regarding the solubilization of poorly water-soluble compounds and oil-soluble dyes and/or disperse dyes in water, the above-mentioned (B> anionic dye, especially when the surface tension when dissolved at 0.1% by weight in water is 20°C It is considered that those having a molecular weight of 60 dyn/cm or less form micelles in water and solubilize the poorly water-soluble compound and the oil-soluble dye and/or disperse dye.

In order to exhibit sufficient water resistance, this (B) dye must be present in an amount of 2 to 30% by weight in the ink composition and 60% by weight or more in the total dye weight of the ink. Water resistance imparting agents and oil-soluble dyes and/or
Alternatively, the ability to solubilize disperse dyes decreases, resulting in instability over time and decreased water resistance. Also 30% by weight
If the above is used, the dye will precipitate and become unstable over time, resulting in an increase in the viscosity of the ink.
It is unsuitable as an ink for inkjet printers. If the amount is less than 60% by weight of the total dye weight of the ink, the ink will not have good water resistance.

Among poorly water-soluble compounds, those having a solubility of 5% by weight or more in ethyl alcohol at 20°C are suitably solubilized.

The above-mentioned (B) dye used in the present invention is added to water at 0.1
The surface tension when dissolved by weight% is 60 at 20°C.
Examples of anionic dyes having dyn/(2) or less include the following.

Acid dye: C11, acid yellow 40 C9 summer, acid orange 51 C,1, acid red 114.249C,T, acid blue 83.90,103,127C,T, acid green 25.27 Direct dye: C,1, Direct Black 154 Epoxy Addition C,1, Direct Black 154 One or more of the above dyes can be used.

The above-mentioned component (C) used in the present invention is an aromatic ring or a lipophilic group selected from aliphatic hydrocarbons having 6 to 12 carbon atoms, and a group having at least one O, N, or S atom. Examples of poorly water-soluble compounds containing one or more of both hydrophilic groups include the following.

a) Compounds having a dicarboxylic acid ester skeleton b) Compounds having a benzophenone skeleton C) Compounds having a phenol skeleton d) Compounds having an imidazole skeleton e) Compounds having a benzothiazole skeleton (f) Compounds having a benzoin skeleton (9) Compounds having a benzoin skeleton ,! , one or more compounds selected from compounds having an aromatic ester skeleton, and particularly a compound having a solubility in ethyl alcohol of 5% by weight or more at 20°C.

Specific examples of (a) include diethyl sebacate, bis(2
, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-bentamethyl-4-
piperidyl) sebacate, etc.

Specific examples of (b) include benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxy-benzophenone.

Specific examples of (C) include 2,2-bis(4'-hydroxyphenyl)propane ethyl gallate, n-propyl gallate, isoamyl salicylaldoxime gallate, 4-
Hydroxy-1,2, diethyl phthalate, var.
Examples include t-butylphenol.

Specific examples of (d) include benzimidazole.

Specific examples of (e) include 2-chlorobenzothiazole, 2-methyl-5chlorobenzothiazole, and 2-mercaptobenzothiazole.

Specific examples of (f) include benzoin methyl ether.

Specific examples of (g) include propyl para-hydroxybenzoate and phenylbenzoate.

One or more of the above compounds can be used.

Examples of the oil-soluble dye of component (D) include the following.

C,1, Solvent Yellow 15.21.61C,1,
Solvent Orange 5.6.37C,1,'/Ruvent Red 8.30.49,82°83.84 C,1, Solvent Blue 2.55 One or more of the above compounds can be used.

Examples of the dispersible dye of component (E) include the following.

C1L Disperse Yellow 3.5.31C, L Disperse Orange 13C,! , Dispersed thread l, 4, 5, 11C, 1,
Disperse Blue 3,7 One or more of the above compounds can be used.

Examples of the dye of component (F) include the following.

Acid dye: C,1, Arashido Yellow 6.23 C,1, Ashido Red 1,37.73,87°C,1
, Assid Blue-80 Direct dye: C,1, Direct Yellow 44 C,1, Direct Red 4,9.23,31°C,1
, Direct Blue 1.15□86.87C, 1, Direct Black 19 ][! of the above compound] Or two or more types can be used.

The ink of the present invention uses water as a solvent component, and water is used to prevent the ink from drying, to improve dye solubility, and to solubilize poorly water-soluble compounds and oil-soluble dyes and/or disperse dyes. Dry-up resistance can be improved by adding substances such as those exemplified below for the purpose of increasing the amount.

Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, polyglycerin, polyethylene glycol, polypropylene glycol, methyl cellosolve, ethyl cellosolve, butyl seronulp, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol methyl Ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, 3 methyl 3 methoxybutanol, 2
-Pyrrolidone, triethanolamine, urea and its derivatives.

Examples of urea derivatives include thiourea, ethylene urea, hydroxyethyl urea, hydroxypropylurea, ethylene thiourea, and diethyl thiourea.

One or more of the above substances can be used.

In addition to the above-mentioned components, the ink of the present invention may optionally contain methyl P-oxybenzoate, 1,2-benzisothiazoline-
Antibacterial agents such as 3-one, rust inhibitors such as benzotriazole, butoxyethyl acid phosphate diethylamine salt, and water-soluble 1F such as polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives, maleic acid resin, etc.
Viscosity modifiers such as II fats, surface tension modifiers such as surfactants, and adhesion improvers such as polymer emulsions to improve adhesion to non-permeable supports such as polyester films are used to avoid impairing the performance of the ink. It can be added as appropriate within a certain range.

Next, to briefly describe the method for producing the water-based ink of the present invention, the anionic dye is completely dissolved in water, and then the poorly water-soluble compound is added and dissolved.

Note that it is preferable to stir and dissolve at room temperature or higher.

A temperature of 80°C or higher is particularly suitable.

After confirming that the poorly water-soluble compound has been completely solubilized, the other components are added and dissolved by stirring to produce ink.

[Example] Next, the present invention will be explained with reference to Examples and Comparative Examples.

For easy understanding, examples containing oil-based dyes are marked with the symbol I and then a number, such as 0, such as I-1.
Examples containing a dispersible dye are marked with ■.

In addition, examples in which both were used in combination are marked with a symbol ■, and examples in which an auxiliary tone adjusting dye was used in combination are marked with a symbol.

Example l-1 (B) C,1, acid blue 90 (surface tension 52
．． 36yn/cz) 3.60 parts by weight (D)
C, 1, Solvent Yellow 61 (ethyl alcohol solubility 2% by weight or more > 2.40f! parts (C
) 2.2-bis(4-hydroxyphenyl)propane (ethylal 1.00 parts by weight 10.00 parts by weight 1 part 10.00!! parts by weight 1.00 parts by weight 1, OO!lr parts by weight 71.00 parts by weight 100 Solvent Yellow 6 after completely dissolving Niazid Blue 90 in ion-exchanged water by stirring (60°C).
1. Add 2.2-bis(4'-hydroxyphenyl)propane and stir at 80°C for 1 hour. 1. Next, add the remaining ingredients and stir at room temperature for 1 hour. Leave to cool, then filtrate to remove acid. A green ink was obtained in which the blue color of Blue 90 was mixed with the yellow color of Solvent Yellow 61.

Cole solubility 5% by weight or more) Ethylene glycol diethylene glycol triethanolamine Proxel
．． 3dyn/cs) 3.60 parts by weight (D)
C, 1, Solvent Red 49 (ethyl alcohol solubility 2% by weight or more) 2.40 parts by weight (C)
2.2-bis(4°-hydroxyphenyl)propane (ethyl alcohol solubility: 5% by weight or more) 1.00 parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol 10.00 parts by weight Triethanolamine 1600 parts by weight Proxel XL-2
1,00 parts by weight <A) Ion 71.00 Amount 1
00.00 weight 1 part operation After completely dissolving Niazid Blue 90 in ion exchange water by stirring (60°C) Solvent Red 49
．． Add 2,2-bis(4'-hydroxyphenyl)propane and stir at 80°C for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour. After cooling Group 1, filtrate to obtain acid blue. 90 blue with Solventre Sodo 49
A reddish-purple ink with a toned red color was obtained.

Example l-3 (B) C,1, acid yellow 40 (surface tension 3
7.4dyn/cz) 5.00 parts by weight (D
) C,1, Solvent Orange 37 (ethyl alcohol solubility 2% by weight or more) 2.00 parts by weight (C
) Bis<2.2,6.6-tetramethyl-4-piperidyl) sebacate (ethyl alcohol solubility 5% by weight or more) 1.00 parts by weight Polyethylene glycol #200 20.00 parts by weight Triethanolamine 1.00 parts by weight Proxel XL-21.00 parts by weight (A) Ion 70.00 Jl
Loo, 00 parts by weight operation After completely dissolving Niazid Yellow 40 in ion-exchanged water by stirring (60°C), add Solvent Orange 37, Bis<2.2,6.6-tetramethyl-4-piperidyl) Sepagate. Heat and stir at 80°C for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour. Leave to cool and then filtrate to obtain a mixture of Acid Yellow 40 yellow and Solvent Orange 37 orange. Colored ink was obtained.

Example l-4 (B) C,1, acid yellow 40 (surface tension 3
7.4dyn/cx) 5.00 parts by weight (D
) C,l Solvent Blue 2 (Ethyl alcohol solubility 2% by weight or more') 2.00.1 parts by weight (
C) Benzoin methyl ether (ethyl alcohol solubility 5% by weight or more) 1.00 parts by weight Polyethylene glycol #200 20.00 parts by weight Triethanolamine i, ooij L parts Proxel XL-2 1,00 parts by weight (A) In
70.00 parts by weight 100.00 parts by weight Operation After completely dissolving Niazid Yellow 40 in ion exchange water by stirring (60°C) Solvent Blue 2
, add benzoin methyl ether and heat and stir at 80°C for 1 hour.Next, add the remaining ingredients and stir at room temperature for 1 hour, then leave to cool. A toned yellow-green ink was obtained.

Example l-5 (B) C,1, Acid Red 114 (Surface tension 5
4.4dyn/cz) 2.50 parts by weight (B
) C, 1, acid yellow 40 (surface tension 37.
4dyn/cm ) 2.50 parts by weight (D)
C, 1, Solvent Orange 5 (Ethyl alcohol solubility 2% by weight or more > 2.00 parts by weight (C)
Benzoin methyl ether (ethyl alcohol solubility 5% by weight or more) 1.00 parts by weight ethylene glycol 10.00 parts by weight diethylene glycol 10. OO 1 member Triethanolamine 1,00 parts by weight Proxel XL-2
1,00 parts by weight (A) Ion water 70.00 parts by weight 1
After completely dissolving Niazid Red 114 and Acid Yellow 40 in ion-exchanged water by stirring (60
°C) Add Solvent Orange 5 and benzoin methyl ether and heat and stir at 80°C for 1 hour.Next, add the remaining ingredients and stir at room temperature for 1 hour. Leave to cool and pass for a while to create the red color of Acid Red 114 and acid yellow. 40
A brown ink was obtained in which the yellow color of Solvent Orange 5 was toned.

Comparative Example I-1 ((D> Component oil-soluble dye with ethyl alcohol solubility of 2% by weight or more is 41% by weight or more in the total amount of dye) (B) C, 1, Acid Blue 90 (Surface tension 52
．． 3dyn/cz) 3.00 parts by weight (D)
C, 1, Solvent Yellow 61 (ethyl alcohol solubility 2x 1% or more) 3.00 parts by weight (C)
2.2-bis(4°-hydroxyphenyl)propane (ethyl alcohol solubility: 5% by weight or more) 1.00 parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol io, 00 parts by weight Triethanolamine 1,00 parts by weight Proxel XL -2
1,00 parts by weight (A) ion water exchange 71. ◇0 weight 10
0.00 weight 1 part operation After completely dissolving Niazid Blue 90 in ion exchange water by stirring (60°C) Solvent Yellow 6
1.2. Add 2-bis(4'-hydroxyphenyl)propane and heat and stir at 80°C for 1 hour. 1. Next, add the remaining ingredients and stir at room temperature for 1 hour, then leave to cool and pass. A green ink was obtained.

*A considerable amount of undissolved Solvent Yellow 61 remained on the paper.

Comparative Example I-2 (component (D), an oil-soluble dye with an ethyl alcohol solubility of 2% by weight or more, of 41% by weight or more in the total amount of dye) (B) C, ], Acid Blue 90 (surface tension 52%)
．． 3dyn/c+m) 3.00 weight 1 part (D
) C, 1, Solvent Red 49 (Ethyl alcohol solubility 2x % or more) 3.00 parts by weight (C)
2.2-bis(4-hydroxyphenyl)propane (ethyl alcohol solubility 5% or more in full view) 1.00 parts by weight ethylene glycol 10.00 parts by weight diethylene glycol 10.00 parts by weight Triethanolamine i, oo overlapping type Proxel XL-
21.00 parts by weight (A) Ion 71.00 parts by weight 10
After completely dissolving 0.00 parts by weight of Niazid Blue 90 in ion-exchanged water by stirring (60°C), Solvent Red 49
．． Adding 2,2-bis(4'-hydroxyphenyl)propane 7i01. F3: Heat and stir at Q°C for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour. After cooling, filter the mixture to obtain a reddish-purple ink.

*A considerable amount of undissolved Solvent Red 49 remained on the paper.

Comparative Example I-3+ Added oil-soluble dye with ethyl alcohol solubility of less than 2% by weight (D) component) CB)
C, 1, acid blue 90 (surface tension 52.3dy
n/cx) 4.00 parts by weight (D) C,
1, Solvent Yellow 33 (ethyl alcohol solubility less than 2 Jyusha %) 2.00 parts by weight (C)
2.2-Bis(4-hydroxyphenyl)propane (ethyl alcohol solubility: 5% by weight or more) 1.00 parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol 10.0 parts by weight Triethanolamine 1.00 parts by weight Proxel XL-
21,00 parts by weight (A> In-Kokinaga 71.00 parts by weight
oo, oout section operation After completely dissolving Niazid Blue 90 in ion exchange water by stirring (60℃) Solvent Yellow 3
3.2. Add 2-bis(4'-hydroxyphenyl)propane and heat and stir at 80°C for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour, then leave to cool and filter. .

*A large amount of undissolved matter of Solvent Yellow 33 remained on the paper, and the ink of the r connection turned blue, making it impossible to obtain the green ink that was originally planned.

Example ff-1 (B) C,1, acid blue 90 (surface tension 52
．． 3dyn/s+) 3.60 parts by weight (E)
C, 1, Disperse Yellow 3 (ethyl alcohol solubility 2% by weight or more) 2.40 parts by weight (C)
2.2-bis(4°-hydroxyphenyl)propane (ethyl alcohol solubility 5% by weight or more) 1.00 parts by weight ethylene glycol 10. OOt parts Diethylene glycol 10.00 parts by weight Triethanolamine 1,00 parts by weight Proxel XL-2 1,00 parts by weight (A) Ion 71.00 parts by weight 1
After completely dissolving Niazid Blue 90 in ion-exchanged water by stirring (60°C), add Dispurst Yellow 3.2.2-bis(4'-hydroxyphenyl)propane and dissolve 80 ℃Heat and stir for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour, then leave to cool. A green ink was obtained.

Example 11-2 (B) Acid Blue 90 (Surface tension 52.3 dyn/cz) 3.6
0 parts by weight (E) C, 1, Dispersed Red 4 (Ethyl alcohol solubility 2% by weight or more > 2.40 parts by weight (C)
2.2-Bis(4'-hydroxyphenyl)propane (ethyl alcohol solubility: 5% by weight or more) 1.00 parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol 10.00 parts by weight Triethanolamine 1.00 parts by weight Proxel XL -2
1,00 parts by weight (A) in
71.00 @ Amount 100.00 parts by weight Operation After completely dissolving Niazid Blue 90 in ion exchange water by stirring (60°C) Disper Red 4.2.2-Bis(4'-hydroxyphenyl)propane was added and heated and stirred at 80° C. for 1 hour. Next, the remaining components were added and stirred at room temperature for 1 hour. After cooling, the mixture was filtered to obtain a reddish-purple ink.

Example 11-3 (B) C,1, Acid Yellow 40 (Surface tension 3
7.4dyn/cz) 5.00 parts by weight (E
) C, 1, Disperse Orange 13 (Ethyl alcohol solubility 2% by weight or more > 2. OOt parts (C)
Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (ethyl alcohol solubility 5% by weight or more) 1.00 parts by weight Polyethylene glycol #200 20.001 parts by weight Triethanolamine 1.00 parts by weight Proxel XL-21,00 parts by weight (A) Ion 70.00 parts by weight ioo, oo parts by weight Operation After completely dissolving Niazid Yellow 40 in ion-exchanged water by stirring (60°C) Disperse Orange 13, Bis(2 , 2,6,6-tetramethyl-4-piperidyl) sebacate and heat and stir at 80°C for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour.
After being allowed to cool, a red-orange ink was obtained.

Example If-4 (B) C,1, acid yellow 40 (surface tension 3
7.4 dyn/am) 5.00 parts by weight (E
) C,! , Disperse Blue 3 (ethyl alcohol solubility 2% by weight or more) 2.00 parts by weight (C)
Benzoin methyl ether (ethyl alcohol solubility 51% or more) 1.00 parts by weight Polyethylene glycol #200 20.00 parts by weight Triethanolamine 1.00 parts by weight Proxel XL-2 1,00 parts by weight (A) Ion 70.00 parts by weight 10
Completely dissolve Niazid Yellow 40 in ion-exchanged water by stirring at 0.00 parts by weight.Add Disperse Blue 3 (60℃) and benzoin methyl ether and heat and stir at 80℃ for 1 hour.Remaining components After stirring at room temperature for 1 hour, the mixture was allowed to cool and then passed through to obtain a yellow-green ink.

Example I [-5 (B) C,1, Acid Red 114 (Surface tension 5
4.4dyn/cs) 2.50 parts by weight (B
) C, 1, acid yellow 40 (surface tension 37.
4dyn/cm ) 2.50 parts by weight (E)
C,! , Disperse Red 1 (ethyl alcohol solubility 2% by weight or more) 2.00 parts by weight (C)
Benzoin methyl ether (ethyl alcohol solubility 5% by weight or more) i, oo parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol 10.00 parts by weight Triethanolamine 1.00 parts by weight Proxel XL-21
,00 parts by weight (A) Ion 70.00 parts by weight 1
After completely dissolving Niazid Red 114 and Acid Yellow 40 in ion-exchanged water by stirring (60 parts by weight)
℃) Add Disper Red 1 and benzoin methyl ether. Heat and stir for 61 hours.Next, add the remaining ingredients, stir at room temperature for 1 hour, leave to cool, and filter 7 to obtain brown ink. Ta.

Comparative Example n-1+ (E) Component in which the disperse dye with an ethyl alcohol solubility of 2% by weight or more is 41% by weight or more in the total dye composition) (B) C, 1, Acid Blue 90 (Surface tension 52
．． 3dyn/CI+> 3.00 weight 1 part (E)
C, 1, Disperse Yellow 3 (Ethyl alcohol solubility 2% by weight or more > 3.00 parts by weight (C)
2.2-Bis(4°-hydroxyphenyl)propane (ethyl alcohol solubility 5111% or more) 1.00 parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol 10.0O11! Parts by weight Triethanolamine 1.00 parts by weight Proxel XL
-21.00 parts by weight (A) Ion water 71.00 parts by weight 1
00.00 parts by weight Operation Niazid Blue 90 was completely dissolved in ion exchange water by stirring f! (60℃) Disperse Yellow 3. Add 2,2-bis(4'-hydroxyphenyl)propane and heat and stir at 80℃ for 1 hour. Next, add the remaining ingredients and stir at room temperature for 1 hour, then leave to stand. After cooling, filtration was performed to obtain green ink.

*A considerable amount of undissolved matter of Disperse Yellow 3 remained on the paper.

Comparative Example 11-2+ Component (E), a disperse dye with an ethyl alcohol solubility of 2% by weight or more, was 41% by weight of the total amount of dye.
(B) C, 1, acid blue 90 (surface tension 52
．． 3 clyn/cm ) 3.001 parts (E
) C, 1, Disperse Red 4 <Ethyl alcohol solubility 2% by weight or more> 3.00 parts by weight (C)
2.2-bis(4°-hydroxyphenyl)propane (ethyl alcohol solubility 5% or more) 1.00 parts by weight Ethylene glycol 10.00 parts by weight Diethylene glycol 10.00 parts by weight Triethanolamine 1.0 parts by weight Proxel XL
-21.00 parts by weight (A) Ion Water 71.00 parts by weight 10O,00 Heavy-duty section operation After completely dissolving Niazid Blue 90 in ion-exchanged water by stirring (60°C) Dispersed Red 4
．． Add 2,2-bis(4'-hydroxyphenyl)propane and heat and stir at 80°C for 1 hour.Next, add the remaining ingredients and stir at room temperature for 1 hour, then leave to cool and filter to obtain reddish-purple ink. Obtained.

*Is there a lot of undissolved material in Dispersed Red 4? It remained on paper.

Comparative Example 11-3f (E) component containing a disperse dye with an ethyl alcohol solubility of less than 2% by weight) (B)
C, 1, acid blue 90 (surface tension 52.3d
Yn/cm) 4.00℃ parts (E) C
, 1, Disperse Yellow 64 (ethyl alcohol solubility 2fidan%: iA) 2.00 parts by weight (C) 2.2-bis(4゛-hydroxyphenyl)
Propane (ethyl alcohol solubility: 5% by weight or more) 1.00 parts by weight Ethylene glycol 10. OOi Parts by weight Diethylene glycol 10.00 parts by weight Triethanolamine 1゜00 parts by weight Proxel χt-
21,00 parts by weight (A) Ion exchange water 71.0 OFf J parts 10 O, 00 parts by weight Operation After completely dissolving Niazid Blue 90 in ion exchange water by stirring (60°C) Disperse Yellow 64.2.2 -Bis(4'-hydroxyphenyl)propane was added and the mixture was heated and stirred at 80 DEG C. for 1 hour. Next, the remaining ingredients were added and the mixture was stirred at room temperature for 1 hour. After cooling, the mixture was filtered.

* Undissolved matter of Disperse Yellow 64 remained on the poly J1 paper, and the ink after filtration turned blue, making it impossible to obtain the green ink that was originally planned.

Example I [[-1+ <Example containing component D) and component (E)] An ink having the composition shown in Table 3 was prepared in the same manner as in Example I-1.

Examples TV-4 to 3 ((F) component 60 d7
(Using an anionic dye of n/cz or higher) An ink having the composition shown in Table 3 was prepared in the same manner as in Example I-1.

Examples I, n, II [, IV and Comparative Examples I, II
The compositions are shown in Tables 1 to 3.

The ink compositions obtained in Comparative Test Examples and Comparative Examples were tested for stability over time and water resistance on paper using the following test methods.

The results were as shown in Tables 4 to 6.

(Test method) After water-resistant writing on paper VL, the handwriting is immersed in water for 1 minute, and the presence or absence of ink bleeding and staining of the writing paper is observed.

◎No ink bleeding or writing paper stains.

There is a slight ooze of O ink, but there is no stain on the writing paper.

△There is a lot of ink bleeding and the writing paper is stained.

× Almost no writing lines remain.

Stability over time The physical properties were measured after being left in a glass container at 50°C for 60 days, and the physical properties were compared with those before aging.

Further, the presence or absence of precipitation of dyes, water resistance imparting agents, etc. was observed using an optical microscope (100x magnification).

(speculum) ◎There is almost no change in physical properties before and after aging.

No precipitation.

There is a slight change in physical properties before and after O aging.

No precipitation.

× Large change in physical property values before and after aging.

Or there is precipitation.

Viscosity Measure the viscosity at 20°C using a B-type viscometer manufactured by Nitokyo Keiki Co., Ltd.

pH 2 Using a pH meter manufactured by Toa Denpa Kogyo Co., Ltd.
Measure H.

Surface tension meter CBuP manufactured by Kani Kyowa Kai Science Co., Ltd.
Measured at 20℃ using ^-3 type.

(Effects) As is clear from the above comparative test, the ink of the present invention has excellent water resistance on paper and stability over time, and is suitable as an ink for writing instruments, plotters, and inkjet printers. .

Claims (1)

[Claims] 1. (A) water; (B) an amount of 2 to 30% by weight in the ink composition and 60% by weight or more of the total dye weight of the ink, and 0.1% by weight in water; The surface tension when melted is 60 dyn/at 20°C.
cm or less, and (C) an aromatic ring or an aliphatic hydrocarbon having 6 to 12 carbon atoms as a lipophilic group, and a group having at least one O, N, or S atom as a hydrophilic group; A water resistance imparting agent whose effective component is a poorly water-soluble compound containing one or more of both groups, the solubility of which is 5% by weight or more at 20°C when the compound is dissolved in ethyl alcohol; (D) One or more oil-soluble dyes that are sparingly soluble in water and have a solubility of 2% by weight or more when dissolved in ethyl alcohol at 20°C. and/or (E) A water-resistant ink composition containing one or more dispersible dyes that are poorly soluble in water and have a solubility in ethyl alcohol of 2% by weight or more at 20°C. 2. The water resistance imparting agent (C) component is 0.5% in the ink composition.
5. The water-resistant ink composition of claim 1, wherein the water-resistant ink composition is 5% by weight. 3. The water-resistant ink composition according to claim 1 or 2, wherein the component (D) and/or the color tone adjusting agent (E) is 40% by weight or less based on the total dye weight of the ink. 4. As an auxiliary color tone adjusting agent, (F) has a surface tension of 20℃ when dissolved in water at 0.1% by weight.
The ink composition according to any one of claims 1 to 3, wherein the ink composition contains an anionic dye having a density of more than 60 dyn/cm in an amount of not more than 5% by weight and not more than 9% by weight of the total dye weight of the ink. Water-resistant ink composition. 5. The anionic dye (B) described in claim 1 (A
) and completely dissolve in water, then (C) the water resistance imparting agent and (D) one or more of the oil-soluble dyes and/or (E) one or two of the dispersible dyes. A method for producing a water-resistant ink composition, which comprises adding the above ingredients and stirring at a temperature higher than room temperature, and then adding and mixing the remaining ingredients. 6. Add the anionic dye (B) and the anionic dye (F) to the water (A) and dissolve them completely, then add the water resistance imparting agent (C) and the oil-soluble dye (D). 1 or 2 or more of (E) and/or 1 or 2 or more of the dispersible dyes (E) are added, stirred at a temperature of room temperature or higher, and then the remaining components are added and mixed. Method for producing the composition.