JP3390228B2 - Water-based water-based ink composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous ink composition having water resistance using water as a solvent and an anionic dye as a colorant. More specifically, it is a writing tool such as a marking pen, and a brush for designing and pen. A water-based ink composition that can be suitably used for drawing inks that can be used for writing, air brushes, etc., and can be written on not only an absorptive surface but also a non-absorptive surface. The present invention relates to a water-based ink composition in which recording by a material (hereinafter, simply referred to as handwriting) has water resistance. In particular, the present invention relates to a water-based ink composition for writing that can be suitably used for a marking pen having a porous nib.

[0002]

2. Description of the Related Art Conventionally, oil-based inks and water-based inks have been generally used as recording inks having water resistance and light resistance of handwriting, especially writing inks. Among them, the oil-based ink is one in which an oil-soluble and water-insoluble dye is dissolved in an organic solvent, and not only on an absorptive surface such as paper, but also on a non-absorptive surface such as glass or plastic. While having the advantage of being able to write on it, there is concern about the toxicity of the aromatic hydrocarbons used as solvents, such as xylene and toluene, to the human body, and when writing on paper, the ink may reach the back of the paper. There is a so-called set-off problem that penetrates.

On the other hand, the water-based ink uses a pigment as a colorant, and although there is no problem with the oil-based ink as described above, the pigment segregates and segregates over time, causing color separation and marking pen. When used, there are problems such as clogging or a decrease in concentration. Therefore,
Conventionally, even in a water-based ink composition using a water-soluble dye as a colorant, in order to impart water resistance to the handwriting, it has been attempted to directly use the dye or to add an additive such as a penetrant. Even if the writing surface is an absorptive surface such as paper, a water-based ink composition that gives handwriting with sufficient water resistance has not yet been known.

[0004]

The present invention has been made in order to solve the above-mentioned problems in conventional water-based ink compositions, and it is a water-based ink composition in which the handwriting is water-resistant, and , Such as oil-based ink, it is possible to write not only on the absorptive surface but also on the non-absorptive surface, and even when writing on the absorptive surface such as paper,
It is an object of the present invention to provide a water-based ink composition that does not cause set-off and has no color change even after storage and can be suitably used as a marking pen ink or a drawing ink.

[0005]

An aqueous ink composition having water resistance according to the present invention uses water as a solvent and has a molecular weight of 15
It has an acid value of 150 to 300 in the range of 0 to 30000.
A semi-esterified styrene-maleic acid resin in the range of, and as a colorant, (a) an azo metal complex hydrochloric acid dye,
(b) CI Direct Black, and (c) CI Acid Yellow 110, CI Acid Yellow 127, CI Direct Yellow 100, CI20215, CI202
16, CI20230, CI23266, CI2363
5, CI40002, CI40215, CI42655
And at least one anionic dye selected from CI 42660, wherein the pH is adjusted to 6 to 9.5 by an alkaline substance which is volatile at room temperature.

In the present invention, the anionic dye means a dye having an acidic group such as a carboxyl group or a sulfonic acid group, and the direct dye is one of the anionic dyes which can dye cotton by a usual dyeing method. An acid dye is a dye that can be dyed and cannot dye cotton. On the other hand, the azo metal complex hydrochloric acid dye means, among acid dyes, particularly an azo dye and a metal complex salt. Also, according to the Color Index nomenclature, direct dyes, acid dyes and basic dyes (basic) are based on color: black, yellow, orange, red, violet, blue, green and It is classified into eight types of brown.

The ink composition according to the present invention can be preferably used as an ink for marking pens and an ink for drawing. The marking pen includes a porous nib made of felt, a fiber bundle, a plastic molding, and the like, and an ink storage means formed by impregnating the felt, the fiber bundle, and the like with ink in a hollow cylinder. A writing instrument capable of writing by supplying ink from a different ink storage means to a pen tip provided at the tip of the cylindrical body by utilizing a capillary phenomenon.

As described above, the ink composition for drawing is painted with a brush like paint, written with a pen, and surface-painted with an air brush (a kind of spray used for design), drawn, and dots. Used to do.

The half-esterified styrene-maleic acid resin used in the present invention is required to be dissolved together with an alkaline substance in water as a solvent having a pH in the range of 6 to 9.5. The above resin has an acid value of 150 to
It should be in the range of 300. When the acid value is less than 150, the amount of acid groups that give solubility to the resin is small, the resin does not have sufficient solubility in the ink composition, and as a result, the resulting handwriting has sufficient water resistance. It has no sex. When the acid value of the resin exceeds 300, since the resin itself has a considerable water solubility, the handwriting with the obtained ink composition does not have sufficient water resistance.

Further, the half-esterified styrene-maleic acid resin used in the present invention has a molecular weight of 15
It is necessary to be in the range of 00 to 30,000. When the molecular weight is less than 1500, the adhesiveness of the handwriting when writing on a non-absorbent surface such as glass or plastic is low, and the water resistance of the handwriting is insufficient. On the other hand, when the molecular weight is more than 30,000, the viscosity of the ink composition is excessively high, the writability is deteriorated, and the solubility of the resin itself is decreased, so that it is necessary to reduce the compounding amount of the resin. As a result, the adhesiveness of the handwriting on the writing surface is reduced. In particular, in the present invention, the semi-esterified styrene-maleic acid resin has an acid value of 180-250,
It preferably has a molecular weight of 1800 to 15000.

The half-esterified styrene-maleic acid resin used in the present invention is preferably one in which the maleic acid component is substantially half-esterified.

[0012]

[Chemical 1]

It has a repeating unit such as In the above formula, R is an alkyl group. A styrene-maleic anhydride resin in which the maleic acid component has a maleic anhydride structure,
Styrene-maleic acid resins in which all maleic acid components are free carboxyl groups have an acid value of more than 300 and are not suitable for use in the present invention.

The semi-esterified styrene-maleic acid resin used in the present invention may contain isobutylene as a monomer component. In the present invention, various commercially available products can be preferably used as the half-esterified styrene-maleic acid resin.

As the above-mentioned half-esterified styrene-maleic acid resin, commercially available products can be used. Examples of commercially available products of such a half-esterified styrene-maleic acid resin include the following. Product name Molecular weight Acid value High loss X-200 14000 190 High loss X-201 14000 200 High loss X-203 14000 220 High loss X-205 9000 205 High loss X-220 14000 155 High loss X-120 2S 14000 190 High loss X-1216S 14000 150 (above, HOSHIKO CHEMICAL CO., LTD. SMA resin 1440 2500 175 SMA resin 17352 1700 270 SMA resin 2625 1900 220 (above, ARCO Chemical Co., Ltd.)

The ink composition according to the present invention comprises 2 to 20 of the above-mentioned semi-esterified styrene-maleic acid resin.
It is contained in the range of% by weight. When the content of the resin is less than 2% by weight, the handwriting formed has no water resistance. On the other hand, when the resin content exceeds 20% by weight,
Since the viscosity of the ink composition is too high, the writability is poor and the writing is hindered. In the present invention, the content of the resin is
The preferred range is 5 to 15% by weight.

The anionic dyes used in the present invention include (a) azo metal complex hydrochloric acid dye, (b) CI direct black, and (c) CI acid yellow 110, CI acid yellow 127, CI direct yellow 10.
0, CI20215, CI20216, CI2023
0, CI23266, CI23635, CI4000
2, CI 40215, CI 42655 and CI 4266
It is at least one selected from 0.

Although it seems to be related to the mechanism of water resistance of handwriting of the ink composition according to the present invention, water resistance cannot be imparted to the handwriting of the ink composition obtained except for the above-mentioned anionic dye. Examples of the azo metal complex hydrochloric acid dye (a) include CI13900, CI18745, C.I.
I.12205, CI18762, CI13425, CI
15691, CI15711, CI18165 and the like.

Further, as the azo metal complex hydrochloric acid dye (a),
Other than the above, for example, CI Acid Yellow 59, C.
I. Acid Yellow 111, CI Acid Yellow 11
2, CI Acid Yellow 116, CI Acid Yellow 161, CI Acid Orange 82, CI Acid Orange 87, CI Acid Orange 88, CI Acid Orange 95, CI Acid Orange 122, CI Acid Orange 147, CI Acid Red 209, CI
Acid Red 211, CI Acid Red 215, C.
I. Acid Red 216, CI Acid Red 217,
CI Acid Red 256, CI Acid Red 26
2, CI Acid Red 317, CI Acid Red 3
55, CI Acid Violet 66, CI Acid Violet 75, CI Acid Violet 116, C.I.
I. Acid Blue 167, CI Acid Blue 168,
CI Acid Blue 171, CI Acid Blue 23
4, CI Acid Blue 250, CI Acid Blue 2
76, CI Acid Brown 30, CI Acid Brown 44, CI Acid Brown 45, CI Acid Brown 46, CI Acid Brown 224, CI Acid Brown 282, CI Acid Brown 283, CI Acid Brown 294, CI Acid Brown 295,
CI Acid Brown 296, CI Acid Brown 2
97, CI Acid Brown 333, CI Acid Brown 352, CI Acid Brown 353, CI Acid Brown 369, CI Acid Brown 368, CI
Acid Green 43, CI Acid Green 60, C.
I. Acid Green 76, CI Acid Green 77,
CI Acid Green 80, CI Acid Black 5
2: 1, CI acid black 107, CI acid black 110, CI acid black 132, CI acid black 155, CI acid black 179 and the like can be mentioned.

Examples of anionic dyes belonging to the category of the above CI direct black (b) include CI direct black 154, CI 27700 and CI 3525.
5, CI35435, CI35440, CI3023
5, CI27720, CI31600, CI30400
Etc. can be mentioned. The anionic dyes belonging to the above-mentioned group (c) are direct dyes and acid dyes which can be effectively used in the ink composition according to the present invention, although they are not included in the above-mentioned categories of the groups (a) and (b).

In the ink composition according to the present invention, the anionic dye is used in the range of 0.01 to 10% by weight. When the amount of the anionic dye compounded is too small, the coloration of the resulting ink composition is poor and the light resistance of the handwriting is also poor. On the other hand, when the amount is too large, the dye or resin may be precipitated in the ink composition, and the ink composition has an excessively high viscosity, resulting in poor writing performance. In particular, the blending amount of the anionic dye is preferably in the range of 0.05 to 8% by weight in the ink composition.

As described above, the ink composition according to the present invention is a water-based ink containing water as a solvent and the semi-esterified styrene-maleic acid resin and an anionic dye. It has been adjusted to ~ 9.5. When the pH of the ink composition is less than 6, the above-mentioned semi-esterified styrene-maleic acid resin is not stably dissolved in the ink composition. On the other hand, when the pH exceeds 9.5, the anionic dye in the ink composition becomes unstable, causing discoloration or precipitation due to the destruction of the dye, or the resin is hydrolyzed depending on the resin used. Due to the above, deterioration or precipitation of the ink composition may occur or may occur.

In the present invention, the alkaline substance is required to be water-soluble and volatile at room temperature. First, in the ink composition, the ink composition is alkaline. , Which serves to dissolve the semi-esterified styrene-maleic acid resin therein, and secondly, when writing is carried out using such an ink composition, as will be described later, the solvent evaporates from the handwriting, If the handwriting is dry, while wrapping the anionic dye,
It is expected that the handwriting will be water resistant as the resin forms a water insoluble colorant.

Therefore, examples of the alkaline substance that can be used in the present invention include ammonia water and water-soluble organic amine compounds such as trimethylamine and triethylamine, but ammonia water is particularly preferably used.

In the present invention, such an alkaline substance is 85 to 105% of the required amount for neutralizing the acid groups contained in the semi-esterified styrene-maleic acid resin.
It is preferable to use in the range of. The amount of the alkaline substance blended is 8 which is a necessary amount for neutralizing the acid groups of the resin.
When it is less than 5%, the resulting aqueous ink composition
The pH may be lower than 6, and in such a case, the solubility of the resin in water is lowered and it becomes difficult to obtain a uniform ink composition. On the other hand, when the blending amount of the alkaline substance is more than 105% of the required amount for neutralizing the acid group of the semi-esterified styrene-maleic acid resin, the pH of the resulting aqueous ink composition is 9%. In such a case, the ester structure of the resin is hydrolyzed to cause precipitation, or the anionic dye is decomposed to cause discoloration or precipitation.
The ink composition will be inferior in stability.

Further, in the present invention, a non-volatile alkaline substance can be added to the ink composition together with the volatile alkaline substance. Such a non-volatile alkaline substance maintains the required pH of the ink composition for a long period of time, thus ensuring long-term storage stability of the ink composition, or even when the cap is removed from the pen. It is useful for preventing the composition from drying, preventing ink scratches, etc., and ensuring good writability. However, the blending amount is up to 50% of the required amount for neutralizing the acid groups of the semi-esterified styrene-maleic acid resin, and usually in the range of 5 to 50%. As such a non-volatile alkaline substance, for example, an alkali metal hydroxide or an alkanolamine is used. Specifically, sodium hydroxide, potassium hydroxide, triethanolamine, ethyldiethanolamine, diethylmonoethanolamine, methyldiethanolamine, dimethylmonoethanolamine and the like are preferably used.

In the ink composition according to the present invention, water is used as the solvent. The amount of water is usually in the range of 40 to 85% by weight in the ink composition. Ion-exchanged water is preferably used.

In the present invention, in order to prevent water from evaporating from the ink composition and to enhance the solubility of the dye in the ink composition, the ink composition may be glycolic or glycol, if necessary. A monoether type water-soluble organic solvent can be blended. Such a water-soluble organic solvent is preferably of the general formula (I) H- (OR ¹ ) n-OR ² (wherein R ¹ is an ethylene group and R ² is hydrogen,
n represents an integer of 1 to 4, when R ¹ is an ethylene group, R ² is a methyl group, n represents 1 or 2, and when R ¹ is a propylene group, R ² is hydrogen or methyl. Shows a group, and n shows 1 or 2. ).

Examples of such water-soluble organic solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tetraethylene glycol (di,
Examples include (di) alkylene glycol monomethyl ethers such as (tri- or tetra) alkylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

Further, according to the present invention, aliphatic polyhydric alcohols such as glycerin and aliphatic lower alcohols such as ethanol, isopropyl alcohol, n-propyl alcohol and butanol can also be used as the water-soluble organic solvent. . Particularly, in the present invention, among the above-mentioned solvents, those having a boiling point in the range of 100 to 300 ° C. are preferable. When an organic solvent having a boiling point of more than 300 ° C. is written on the non-absorbing surface of the ink composition containing the organic solvent, almost all of the organic solvent remains in the handwriting, which deteriorates the water resistance of the handwriting. In particular, in the present invention, as the water-soluble organic solvent, those having a boiling point in the range of 120 to 250 ° C. are preferable, and therefore, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like are preferably used.

Such a water-soluble organic solvent is used in the ink composition in an amount of 40% by weight or less. Particularly, in the present invention, the ink composition has 3 to 3
A range of 0% by weight is preferred. When a high-molecular-weight water-soluble polyethylene glycol is used to write an ink composition containing the same on the non-absorbing surface, almost all of the organic solvent remains in the handwriting, deteriorating the water resistance of the handwriting, and further, the ink obtained. It excessively increases the viscosity of the composition and deteriorates the writability.

Further, in the present invention, in addition to the above-mentioned various components, if necessary, a preservative, a fungicide, a surfactant and the like can be appropriately blended. The surfactant is
It may be a nonion, anion or cation. The method for producing the ink composition according to the present invention is not particularly limited, but, for example, a resin is added to an aqueous solution of an alkaline substance, and if necessary, heated and stirred, and dissolved to obtain a dye, a water-soluble substance. An organic solvent, other additives, etc. are added, stirred and dissolved to obtain an ink composition.

[0033]

In the ink composition according to the present invention,
It is considered that the high acid value semi-esterified styrene-maleic acid resin dissolves in the aqueous solution while forming a salt with the alkaline substance at the acid group and encapsulating the anionic dye to form micelles. .

Further, according to the ink composition of the present invention, when writing on the writing surface, the solvent evaporates, and the handwriting is dried,
The alkaline substance that made the resin water-soluble evaporates to form a water-insoluble resin film, and at the same time, the anionic dye is wrapped and the acidic groups that make the anionic dye water-soluble are blocked, so the handwriting is water-soluble. It is presumed that the handwriting has water resistance even though it contains the anionic dye. Although the present invention is not limited by any theory, since water resistance is imparted to the handwriting by enclosing the anionic dye in the resin as described above, only a specific anionic dye can be effectively used. Seems to be possible.

Further, according to the present invention, when the non-volatile alkaline substance is contained together with the volatile alkaline substance, such non-volatile alkaline substance holds the required pH of the ink composition for a long period of time, Thus, the ink composition obtained not only has excellent long-term storability but also prevents the ink composition from drying even when the cap is removed from the pen when used in a marking pen, and prevents ink stains and the like. It is possible to prevent this and ensure good writability.

Further, the ink composition according to the present invention is excellent in stability because the anionic dye is wrapped in the resin and dissolved in the solvent as described above, and the ink composition precipitates even after long-term storage. It is possible to obtain a sufficient color density without causing blurring and having high storability and causing no blur during writing. Moreover, the ink composition according to the present invention forms a resin film on the surface of a non-absorbent writing surface quickly even when written on the surface, so that not only the absorbent surface but also the non-absorbent surface is written. be able to.

[0037]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In addition, below, the component amount shows a weight part. As the anionic dye, those using the azo metal complex hydrochloric acid dye (a) are Examples 1, 2, 15 and 16, and those using CI direct black are Examples 3, 4, 5 and.
9, 13 and 17, and other examples are described in (c) above.
Acid dyes or direct dyes belonging to the group are used.
Furthermore, among the examples, 13 to 15 are those in which the pH of the ink composition was adjusted with aqueous ammonia, and the others were those in which a non-volatile alkali was used in combination with ammonia.

Although various resin solutions are used in the following, the resin solution 1 is usually 105% neutralized and has a pH of 8.5.
.About.9.5, and Resin Solution 2 at 100% neutralization gives an ink composition of pH 7.7-8.6. In an ink composition containing a non-volatile alkali at room temperature, the percentage in parentheses after the amount of the non-volatile alkali compounded at room temperature neutralizes the acid groups of the half-esterified styrene-maleic acid resin. Means the ratio to the required amount for.

Example 1 A predetermined amount of 28% aqueous ammonia and triethanolamine were added to ion-exchanged water, and Hyros X-20 was added thereto with stirring.
3 was added, and the mixture was stirred at a temperature of 40 ° C or lower for 5 hours. After that, while continuing stirring, the liquid temperature was raised to 85 ° C., kept at that temperature for 1 hour, then cooled to room temperature, and a 25% aqueous solution of Hyros X-203 with a neutralization degree of 105% (resin Solution 1) was prepared. Resin solution 1 Ion-exchanged water 68.0 28% Ammonia water 4.8 Triethanolamine 2.2 (15.8%) Hyros X-203 25.0 (Ammonia / triethanolamine molar ratio is 85/15. )

Next, this resin solution 1 was mixed with the following components under stirring to prepare a black drawing ink at pH 8.7. Ethylene glycol 5.0 Ion-exchanged water 51.0 CI Acid Black 107 3.0 Sodium benzoate 1.0 Resin solution 1 40.0

Example 2 In the same manner as in Example 1, a brown marking pen ink having the following components and having a pH of 8.0 was prepared. Ethylene glycol 14.0 Ion-exchanged water 38.5 CI Acid Orange 122 6.5 Sodium benzoate 1.0 Resin solution 1 40.0

Example 3 In the same manner as the resin solution 1, a 25% resin solution 2 (neutralization degree 100%) of Hyros X-203 comprising the following components was prepared. Resin solution 2 Ion-exchanged water 67.1 28% ammonia water 4.4 Triethanolamine 3.5 (25.0%) Hyros X-203 25.0 (Ammonia / triethanolamine molar ratio is 75/25. )

Next, this resin solution 2 was mixed with the following components under stirring to prepare a black drawing ink at pH 8.1. Propylene glycol 3.0 Ion-exchanged water 66.4 CI35255 1.5 Resin solution 2 30.0

Example 4 In the same manner as in Example 3, a black marking pen ink having the following components and having a pH of 8.4 was prepared. Propylene glycol 15.0 Ion-exchanged water 52.5 CI Direct Black 154 4.0 Resin solution 2 30.0

Example 5 In the same manner as in Example 3, a black marking pen ink containing the following components at pH 8.1 was prepared. Propylene glycol 25.0 Ion-exchanged water 46.0 CI27700 4.0 Resin solution 2 30.0

Example 6 In the same manner as in Example 3, a red marking pen ink having the following components and having a pH of 8.2 was prepared. Propylene glycol 20.0 Ion-exchanged water 40.0 CI23266 5.0 Resin solution 2 35.0

Example 7 In the same manner as in Example 1 except that the above resin solution 1 was used,
A yellow marking pen ink was prepared at pH 9.1 comprising the following components. Propylene glycol 20.0 Ion-exchanged water 34.0 CI Acid Yellow 127 5.0 Sodium benzoate 1.0 Resin solution 1 40.0

Example 8 A predetermined amount of 28% ammonia water and methyldiethanolamine were added to ion-exchanged water, and Hyros X-was added thereto with stirring.
205 was added and the mixture was stirred at a temperature of 40 ° C. or lower for 5 hours.
After that, while continuing stirring, the liquid temperature was raised to 85 ° C., maintained at that temperature for 1 hour, then cooled to room temperature, and a 25% aqueous solution of Hyros X-205 with 100% neutralization degree (resin Solution 3) was prepared. Resin solution 3 Deionized water 68.8 28% Ammonia water 4.7 Methyldiethanolamine 5.4 (50%) HIROS X-205 25.0

Next, this resin solution 3 was mixed with the following components under stirring to prepare a red marking pen ink at pH 8.2. Diethylene glycol 15.0 Ethylene glycol monomethyl ether 5.0 Ion-exchanged water 34.0 CI 23635 5.0 Sodium benzoate 1.0 Resin solution 3 40.0

Example 9 In the same manner as in Example 8, Hyros X-having a neutralization degree of 100% was used.
A 25% aqueous solution of 201 (resin solution 4) was prepared. Resin solution 4 Ion-exchanged water 63.8 28% ammonia water 3.8 Dimethylmonoethanolamine 2.4 (30%) HIROS X-201 25.0

Next, this resin solution 4 was mixed with the following components with stirring to prepare a black marking pen ink at pH 9.1. Diethylene glycol 20.0 Ion-exchanged water 33.5 CI35255 5.5 Sodium benzoate 1.0 Resin solution 4 40.0

Example 10 In the same manner as in Example 8, Hyros X-having a neutralization degree of 100% was used.
A 25% aqueous solution of 200 (resin solution 5) was prepared. Resin solution 5 Ion-exchanged water 69.2 28% ammonia water 4.6 Ethyldiethanolamine 1.2 (10%) HIROS X-200 25.0

Next, this resin solution 5 was mixed with the following components under stirring to prepare a yellow marking pen ink at pH 8.8. Dipropylene glycol 20.0 Ion-exchanged water 34.0 CI Acid Yellow 110 5.0 Sodium benzoate 1.0 Resin solution 5 40.0

Example 11 In the same manner as in Example 8, a 25% aqueous solution of SMA resin 1440 (resin solution 6) having a neutralization degree of 100% was prepared. Resin solution 6 Ion-exchanged water 69.9 28% Ammonia water 4.5 Triethanolamine 0.6 (5%) SMA resin 1440 25.0

Next, this resin solution 6 was mixed with the following components under stirring to prepare a blue marking pen ink at pH 7.8. Propylene glycol 15.0 Diethylene glycol monomethyl ether 5.0 Ion-exchanged water 35.0 CI 42655 4.0 Sodium benzoate 1.0 Resin solution 6 40.0

Example 12 In the same manner as in Example 8, Hyros X-having a neutralization degree of 100% was used.
A 25% aqueous solution of 205 (resin solution 7) was prepared. Resin solution 7 Ion-exchanged water 69.2 28% Ammonia water 5.0 Sodium hydroxide 0.3 (10%) HIROS X-205 25.0

Next, this resin solution 7 was mixed with the following components under stirring to prepare a red marking pen ink at pH 8.5. Ethylene glycol 18.0 Ethylene glycol monomethyl ether 2.0 Ion-exchanged water 34.0 CI 23635 5.0 Sodium benzoate 1.0 Resin solution 7 40.0

Example 13 In the same manner as in Example 8, Hyros X-having a neutralization degree of 100% was used.
A 25% aqueous solution of 205 (resin solution 8) was prepared. Resin solution 8 Ion-exchanged water 69.5 28% ammonia water 5.5 Hyros X-205 25.0

Next, this resin solution 8 was mixed with the following components under stirring to prepare a black marking pen ink at pH 9.2. Ethylene glycol 20.0 Ion-exchanged water 33.5 CI35255 5.5 Sodium benzoate 1.0 Resin solution 8 40.0

Example 14 The resin solution 8 was mixed with the following components with stirring to adjust pH.
In 7.9, a blue marking pen ink was prepared. Dipropylene glycol 15.0 Propylene glycol monomethyl ether 5.0 Ion-exchanged water 35.0 CI 42655 4.0 Sodium benzoate 1.0 Resin solution 8 40.0

Example 15 The resin solution 8 was mixed with the following components under stirring to adjust pH.
A black marking pen ink was prepared in 8.7. Ethylene glycol 20.0 Ion-exchanged water 33.5 CI Acid Black 107 5.5 Sodium benzoate 1.0 Resin solution 8 40.0

Example 16 The resin solution 7 was mixed with the following components with stirring to adjust pH.
In 8.8, a brown marking pen ink was prepared. Propylene glycol 30.0 Ion-exchanged water 25.0 CI Acid Orange 122 5.0 Resin solution 7 40.0

Example 17 The resin solution 7 was mixed with the following components with stirring to adjust pH.
A black marking pen ink was prepared in 9.4. Ethylene glycol 25.0 Ion-exchanged water 34.0 CI53255 6.0 Resin solution 7 40.0

An ink composition as a comparative example will be given below. Comparative Examples 1, 2 and 6 use direct dyes which do not belong to the above (a) and (b) groups, and are not included in (c) group, and Comparative Examples 3, 4 and 5 are An acidic dye which does not belong to the groups (a) and (b) and is not included in the group (c) is used.

Comparative Example 1 Using the resin solution 1 described above, in the same manner as in Example 1,
A red felt pen ink having a pH of 8.0, which comprises the following components, was prepared. Ethylene glycol 20.0 Ion-exchanged water 34.0 CI29100 (Direct Red) 5.0 Sodium benzoate 1.0 Resin solution 1 40.0

Comparative Example 2 Using the resin solution 2 described above, in the same manner as in Example 1,
A blue felt-tip ink was prepared with the following components at pH 7.6. Ethylene glycol 20.0 Ion-exchanged water 34.5 CI24410 (direct blue) 4.5 Sodium benzoate 1.0 Resin solution 2 40.0

Comparative Example 3 Using the resin solution 1 described above, in the same manner as in Example 1,
An orange drawing ink having the following components was prepared at pH 9.0. Propylene glycol 3.0 Ion-exchanged water 66.5 CI22895 (Acid orange) 1.5 Resin solution 3 30.0

Comparative Example 4 Using the resin solution 2 described above, in the same manner as in Example 1,
A pink marking pen ink having a pH of 8.1 comprising the following components was prepared. Ethylene glycol 20.0 Ion-exchanged water 33.5 CI 45410 (Acid red) 5.5 Sodium benzoate 1.0 Resin solution 2 40.0

Comparative Example 5 Using the resin solution 8 described above, in the same manner as in Example 1,
A blue marking pen ink having the following components was prepared at pH 7.5. Ethylene glycol 27.0 Ion-exchanged water 25.0 CI42090 (Acid blue) 7.0 Sodium benzoate 1.0 Resin solution 8 40.0

Comparative Example 6 In the same manner as in Example 1 except that the resin solution 8 described above was used,
A blue marking pen ink having a pH of 8.0 composed of the following components was prepared. Propylene glycol 25.0 Ion-exchanged water 26.0 CI24110 (Direct Blue) 8.0 Sodium benzoate 1.0 Resin solution 8 40.0

Performance Evaluation of Ink Compositions Next, the performances of some of the ink compositions obtained as described above and conventional ink compositions were evaluated,
Compared. That is, a conventional water-based ink composition containing a pigment as a colorant, an oil-based ink composition, and a water-based ink composition containing an anionic dye other than those defined in the present invention as a colorant are prepared, and their storage stability is improved. In addition, the water resistance of the handwriting, the light resistance of the handwriting, and the presence or absence of set-off of the ink composition when written on the paper were examined in comparison with the ink composition of the present invention. As the ink composition according to the present invention, the ink compositions of Examples 4 and 11 were used as typical examples, and Comparative Examples 5 and 6 were used as water-based ink compositions containing an anionic dye other than those specified in the present invention as a colorant. I used the one.

Pigment ink A pigment base having the following composition was prepared.     Resin solution 3 4.0     Color Black SB-5 (Degussa's carbon bra       22.5     Ethylene glycol 10.0     Ion-exchanged water 27.5

Using this pigment base, a pigment ink composition having the following composition was prepared. Pigment base 33.3 Resin solution 3 11.3 Neocor YSK (Daiichi Kogyo Seiyaku Co., Ltd. sodium dialkyl sulfosuccinate) 0.4 Ethylene glycol 3.0 Ion-exchanged water 52.0

Oil-based ink The following ingredients were charged in a container and, if necessary, at 50-80 ° C.
Under heating, the mixture was stirred and dissolved to prepare an oil-based ink composition. Oil Blue 603 (oil-soluble dye made by Orient Chemical Industry Co., Ltd.) 5.0 Ester gum AAW (Rosin ester made by Arakawa Chemical Industry Co., Ltd.) 16.0 Ethylene glycol monoethyl ether 13.0 Xylene 66.0

Water resistance of handwriting When the handwriting was sprayed with water by spraying and dried, it was visually examined whether the handwriting was blurred. A coating sample was prepared using the ink composition of the light resistance test ink for handwriting, half of which was covered with black paper, and the change after 4 hours of the fade meter was examined.

Storability of ink composition Assembled in a felt pen filled with the ink composition, the pen tip was placed up, down or sideways, and the ink composition was put in a glass bottle and placed in a constant temperature bath at 40 ° C for 1 hour. In addition to the writing performance when left for a month, the presence or absence of discoloration or precipitation of the ink composition was examined. Bleeding of handwriting 10 sheets of high-quality paper are overlaid, and the pen tip of the writing instrument is loaded 50
The ink was soaked for 3 seconds at g to determine how many sheets the ink penetrated from the top and the ratio of the maximum diameter of the handwriting when the time for pressing the pen tip was 1 second.

The above results are shown in Table 1. In the table, ◎ means very good, ○ means good, and × means bad. Originally, an ink composition or an oil-based ink composition using a pigment as a colorant has excellent water resistance of the handwriting, but the handwriting of the ink composition according to the present invention has a water resistance comparable to that in the spray water resistance. However, there is no blur in the handwriting. However, as an anionic dye, CI 42090 shown in Comparative Example 5 and shown in Comparative Example 6
The ink composition using CI24110 does not have water resistance in handwriting. Further, the ink composition according to the present invention is excellent not only in storage stability but also in light resistance and does not bleed.

[0078]

[Table 1]

Resistance to Drying of Ink Composition The ink storage means of a marking pen with a cap provided with an ink storage means in a hollow cylinder, and a pen tip made of felt is filled with the ink composition for normal use. Then, the marking pen was left with the cap removed from the marking pen under the conditions of a temperature of 20 ° C. and a relative humidity of 65%, and the time during which writing was possible was measured.

As a result, the ink compositions of Examples 13 and 14 had a writable time of about 1 hour, while the ink compositions of Examples 4 and 11 had a writable time of about 3 hours. .

Claims (10)

(57) [Claims] 1. A water-based solvent having a molecular weight of 1500 to 300.
And a semi-esterified styrene-maleic acid resin having an acid value in the range of 150 to 300, and (a) an azo metal complex hydrochloric acid dye, (b) CI direct black, and ( c) CI Acid Yellow 110, CI Acid Yellow 127, CI Direct Yellow 100, CI202
15, CI20216, CI20230, CI2326
6, CI23635, CI40002, CI4021
5, an aqueous ink containing at least one anionic dye selected from CI 42655 and CI 42660 (not containing a basic dye) , the pH of which is adjusted to 6 to 9.5 by an alkaline substance which is volatile at room temperature . A water-based ink composition characterized in that 2. A water-based ink composition for writing according to claim 1, which contains a semi-esterified styrene-maleic acid resin in the range of 2 to 20% by weight based on the ink composition. 3. The water-based ink composition according to claim 1, which contains an anionic dye in a range of 0.01 to 10% by weight. 4. The aqueous ink composition according to claim 1, wherein the alkaline substance which is volatile at room temperature is ammonia. 5. The water-based ink composition according to claim 1, which contains an alkaline substance which is non-volatile at room temperature. 6. The non-volatile alkaline substance at room temperature is at least one alkanolamine selected from triethanolamine, ethyldiethanolamine, diethylmonoethanolamine, methyldiethanolamine and dimethylmonoethanolamine.
The water-based ink composition according to claim 5 . 7. The water-based ink composition according to claim 5 , wherein the alkaline substance which is non-volatile at room temperature is sodium hydroxide or potassium hydroxide. 8. A compound represented by the general formula (I) H- (OR ¹ ) n-OR ² (wherein R ¹ is an ethylene group and R ² is hydrogen,
n represents an integer of 1 to 4, when R ¹ is an ethylene group, R ² is a methyl group, n represents 1 or 2, and when R ¹ is a propylene group, R ² is hydrogen or methyl. Shows a group, and n shows 1 or 2. The water-based ink composition according to claim 1, which further comprises a water-soluble organic solvent represented by the formula (1). 9. A water-based ink composition for a marking pen according to claim 1. 10. A water-based ink composition for drawing according to claim 1.