JP2018009172A - Colorant and ink composition for writing instruments containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colorant having excellent solubility in an alcoholic solvent and excellent temporal stability.SOLUTION: A colorant contains: a salt-forming dye composed of a triphenylmethane basic dye represented by formula (5) and a disazo acidic dye such as C.I. Acid Red; and a salt-forming dye composed of a tris (4-diethylaminophenyl) methane basic dye and a disazo acidic dye (Ris H, C1-18 alkylphenylaminocarbonyl, C1-18 alkoxyphenylaminocarbonyl or halogen-substituted phenylaminocarbonyl; Ris H, C1-18 alkyl, C1-18 alkoxy, a halogen atom, amino, or nitro).SELECTED DRAWING: None

Description

  The present invention relates to a colorant and an ink composition for a writing instrument containing the colorant and used for a ballpoint pen, a marking pen, or the like.

Conventionally, pigments or dyes have been used as colorants used in oil-based inks. Although the pigment-based oil-based ink is excellent in fastness of handwriting, the pigment is aggregated or settled in the ink, so that the handwriting becomes thin or the handwriting is not formed easily. On the other hand, since dye-based oil-based inks are stably stored by dissolving the dye in a solvent, they do not cause problems with pigment-based oil-based inks, but tend to have poor water resistance and weather resistance of handwriting. As a method of improving the water resistance of dye-based oil-based inks, a method of improving the fixability of handwriting on a writing medium such as paper by adding a condensation resin of urea and aldehyde (Patent Document 1), or oil-based marking ink There is known a method of adding a silicone-based surfactant to (Patent Document 2). However, the effect is not always sufficient, and further improvement in water resistance has been desired.
In addition, xylene, ketones, and the like have been frequently used as solvents used in oil-based inks. Since these solvents have problems such as toxicity to human body and odor, alcohol solvents such as alcohol and glycol are used. However, since alcohol solvents are hydrophilic, inks in which dyes are dissolved in these solvents have poor water resistance, and the dyes ooze out when the handwriting gets wet with water. For this reason, it is difficult to read the written characters, or the dye appears on an unused recording medium.

  In order to eliminate such problems, oil-soluble salt-forming dyes are known in which a basic dye having high coloring power and an acid dye are combined, or a basic dye and a colorless or light-colored organic acid are combined. . In particular, triphenylmethane basic dyes have good hue and coloring power, and are combined with various anions to be used as coloring agents for writing instrument inks. As such a colorant, a colorant containing a triarylmethane basic dye and a salt forming dye of an azo yellow acidic dye is known (Patent Document 3). Part of the dye collapsed, resulting in the formation of precipitates and deterioration in writing quality. In addition, salt-forming dyes based on basic dyes (Patent Document 4) have good ink aging stability, but the surfactants included to improve the writing quality react with the basic dyes and precipitate. There was a problem of generating things.

JP-A-4-239071 JP-A-11-172185 Japanese Patent Laid-Open No. 9-165542 JP-A-8-134393

  The present invention has been made to solve the above-mentioned problems, and is a colorant excellent in solubility in alcohol solvents such as alcohol and glycol and stability over time, and contains this, and has high water resistance and time. An object is to provide an ink composition for a writing instrument having stability.

（化学式（１）中、ａは１〜２の正数であり、ｂは１〜２の正数であり、Ｙ^ｂ−は下記化学式（２）

（化学式（２）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子であり、Ｍ及びＮは互いに独立して水素原子又はアルカリ金属であり、ｍは０〜１の数であり、ｎは０〜１の数であり、ただしｍ及びｎがともに１の場合を除く）である）で表される造塩染料と、下記化学式（５）

（化学式（５）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子である）で表される造塩染料とを、含有するものである。なお本明細書において、前記化学式（１）で表される造塩染料を造塩染料Ｘと称し、前記化学式（５）で表される造塩染料を造塩染料Ｙと称する。
着色剤は、前記化学式（１）で表される造塩染料Ｘが、カチオンとアニオンとの当量比を２：１とし、下記化学式（４）

（化学式（４）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子である）で表されることが好ましい。
着色剤は、例えば、燃焼クーロメトリー法によって測定された前記造塩染料の全塩素量が、５０〜１０００ｐｐｍであるものが挙げられる。
着色剤は、前記造塩染料の鉄含有量が、最大で１００ｐｐｍであってもよい。
着色剤は、高速液体クロマトグラフィーによって測定された、前記化学式（４）で表される造塩染料と前記化学式（５）で表される造塩染料との存在比が９９．１〜８５．０：０．９〜１５．０％であるものであってもよい。
本発明の筆記具用インキ組成物は、上記いずれかの着色剤を含有するものである。
筆記具用インキ組成物は、液媒体、及び前記液媒体に溶解する樹脂を含有するものであってもよい。 The colorant of the present invention made to achieve the above object has the following chemical formula (1)

(In the chemical formula (1), a is a positive number of 1 to 2, b is a positive number of 1 to 2, and Y ^b− is the following chemical formula (2).

(In the chemical formula (2), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). , R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom, M and N are each independently a hydrogen atom or an alkali metal, m is a number from 0 to 1, n is a number from 0 to 1, except that m and n are both 1). And a salt-forming dye represented by the following chemical formula (5)

(In the chemical formula (5), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom) The salt-forming dye represented by these is contained. In this specification, the salt-forming dye represented by the chemical formula (1) is referred to as a salt-forming dye X, and the salt-forming dye represented by the chemical formula (5) is referred to as a salt-forming dye Y.
In the colorant, the salt-forming dye X represented by the chemical formula (1) has an equivalent ratio of cation to anion of 2: 1, and the following chemical formula (4)

(In the chemical formula (4), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom) It is preferable to be represented by
Examples of the colorant include those in which the total chlorine amount of the salt-forming dye measured by a combustion coulometry method is 50 to 1000 ppm.
The colorant may have a maximum iron content of 100 ppm.
The colorant has an abundance ratio of the salt-forming dye represented by the chemical formula (4) and the salt-forming dye represented by the chemical formula (5), measured by high performance liquid chromatography, of 99.1 to 85.0. : It may be 0.9 to 15.0%.
The ink composition for a writing instrument of the present invention contains any one of the above colorants.
The ink composition for writing instruments may contain a liquid medium and a resin that dissolves in the liquid medium.

Since the colorant of the present invention exhibits high solubility in alcohol solvents and has high compatibility with additives such as resins and surfactants, it is precipitated in the ink composition for writing instruments. It is difficult to achieve, and is excellent in stability over time, and it is possible to ensure the freedom of selection of additives and the mixing ratio thereof.
The ink composition for a writing instrument of the present invention does not produce a precipitate at a low temperature, is excellent in stability and water resistance, and does not cause bleed, bleeding and blurring of handwriting. In this ink composition for writing instruments, since the salt-forming dye, which is a colorant contained therein, has a disazo structure, it exhibits high fastness and is excellent in heat resistance and light resistance. Further, since the total chlorine amount measured by the combustion coulometry method is extremely low, the metal balls and ball tips used for the pen tip of the ballpoint pen do not corrode.

It is a figure which shows the ultraviolet visible spectral absorption spectrum of salt-forming dye A-1 to which this invention is applied. It is a figure which shows the ultraviolet visible spectral absorption spectrum of salt-forming dye A-5 to which this invention is applied. It is a figure which shows the ultraviolet visible spectral absorption spectrum of comparative salt-forming dye B-1 which is not applicable to this invention.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

（化学式（Ａ１）中、Ｚ^p−はアニオン、ｐは１〜２の正数である）
で表されるトリフェニルメタン系塩基性染料と、下記化学式（Ａ２）

（化学式（２）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子であり、Ｍ及びＮは互いに独立して水素原子又はアルカリ金属である）で表される酸性染料とから得られるものである。
この造塩染料Ｘは、前記化学式（Ａ１）で表されるトリフェニルメタン系塩基性染料から得られるカチオンと前記化学式（Ａ２）で表されるジスアゾ酸性染料から得られるアニオンとの当量比が２：１であることにより、下記化学式（４）

（化学式（４）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子である）で表されるものであることが好ましい。 [Salt-forming dye]
(Salt making dye X)
The salt-forming dye X which is a colorant contained in the ink composition for a writing instrument of the present invention has the following chemical formula (A1)

(In the chemical formula (A1), Z ^p- is an anion, and p is a positive number of 1 to 2)
And a triphenylmethane basic dye represented by the following chemical formula (A2)

(In the chemical formula (2), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). , R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom, M and N are each independently obtained from an acidic dye represented by a hydrogen atom or an alkali metal.
This salt-forming dye X has an equivalent ratio of a cation obtained from the triphenylmethane basic dye represented by the chemical formula (A1) and an anion obtained from the disazo acid dye represented by the chemical formula (A2). : 1, the following chemical formula (4)

(In the chemical formula (4), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom) It is preferable that it is represented by these.

The triphenylmethane basic dye represented by the chemical formula (A1) can be produced from diethylaniline and dimethylaniline by a known method for producing triphenylmethane. What is generally marketed is a triphenylmethane-based basic dye in which Z ^p- in the chemical formula (A1) is Cl ⁻ and p = 1.

（化学式（７）中、Ａ−Ｈはβ−ナフトール誘導体であるカップリング成分である） The disazo acid dye represented by the chemical formula (2) is a diazotized 4,4′-diaminodiphenyldisulfonic acid in an aqueous system using a known diazotization coupling reaction as shown in the following chemical formula (7), for example. It is obtained by alkaline coupling with a coupling component AH, which is a predetermined β-naphthol derivative.

(In the chemical formula (7), AH is a coupling component which is a β-naphthol derivative)

（化学式（８）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子である） A preferable structure of the β-naphthol derivative is represented by the following chemical formula (8).

(In the chemical formula (8), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). R ² is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom)

  Specific examples of the anion in the chemical formula (4) include the following chemical formulas (9) to (11). Of these, the following chemical formula (9) is preferred.

The following chemical formula (9) is C.I. I. It is an anion obtained from Acid Red 97.

The following chemical formula (10) is C.I. I. It is an anion obtained from Acid Red 144.

The following chemical formula (11) is C.I. I. It is an anion obtained from an Acid Red type disazo dye.

  The salt-forming dye X can be suitably used for a black colorant to be contained in a black writing instrument ink composition. In this case, if the salt-forming dye X has an anion obtained from a disazo acid dye exhibiting red, a black colorant exhibiting good jet black can be obtained from the viewpoint of matching of the hue blend. Thereby, it is possible to obtain an ink composition for a writing instrument that achieves both good writing taste and dark handwriting. A particularly preferable anion is a residue of a disazo acid dye represented by the chemical formula (9).

  The total chlorine content of the salt-forming dye X measured by the combustion coulometry method of total chlorine measurement is preferably 50 ppm to 1000 ppm, more preferably 50 ppm to 800 ppm, and even more preferably 100 ppm to 700 ppm. . When the total chlorine content of the salt-forming dye X is within this range, the ink composition for a writing instrument containing the salt-forming dye X exhibits a value within this range. Since the ink composition for writing instruments containing this salt-forming dye X does not corrode the metal ball and metal ball pedestal used for the pen tip, which is the tip of the ballpoint pen, It is not necessary to apply a structure. Therefore, according to the ink composition for a writing instrument containing the salt-forming dye X, a ballpoint pen having a good writing taste can be produced at a low cost. In addition, since the total chlorine content is in the above range, the salt-forming dye X does not dissolve and precipitate in the ink composition for writing instruments over a long period of time, so that writing defects such as blurring do not occur in the handwriting.

The method for producing the salt-forming dye X is as follows:
Step 1: Step of dissolving basic dye Step 2: Step of dissolving acidic dye Step 3: Step of synthesizing a salt-forming dye and precipitating crystals Step 4: Filtering and washing the crystals of the obtained salt-forming dye Step 5: At least a step of drying the filtered salt-forming dye. According to this production method, a high purity salt-forming dye X can be obtained. Hereinafter, each process will be described in detail.

[Step 1]
Step 1 is a step in which a triphenylmethane basic dye and an inorganic acid or an organic acid are added to a solvent and mixed while heating to dissolve the triphenylmethane basic dye. Examples of the solvent include water such as purified water, distilled water, and pure water, and hydrophilic solvents such as alcohol. Of these, water is preferable. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid, and examples of organic acids include acetic acid, lactic acid, and oxalic acid. Of these, hydrochloric acid is preferred. The amount of the inorganic acid or organic acid is not particularly limited as long as the triphenylmethane basic dye can be dissolved, but it is preferably 0.5 to 1.5 equivalents relative to the triphenylmethane basic dye. . The mixing / dissolving temperature is preferably from room temperature to 80 ° C.
[Step 2]
Step 2 is a step of mixing the acid dye and the basic substance in a solvent to dissolve the acid dye. Examples of the solvent include water and a hydrophilic solvent. Examples of basic substances include hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; carbonates such as sodium carbonate and sodium hydrogen carbonate; aqueous ammonia; Is preferred. The amount of the basic substance is not particularly limited as long as the acidic dye can be dissolved, but it is preferably 0.5 to 1.5 equivalents relative to the acidic dye. An acidic dye is easily dissolved in a solvent by setting to weak alkaline conditions (pH = 8 to 11). The mixing / dissolving temperature is preferably from room temperature to 90 ° C.
[Step 3]
Step 3 is a step in which the solution of Step 2 is added to the solution of Step 1 while heating while adjusting the pH to be weakly acidic or neutral to synthesize a salt-forming dye and precipitate crystals (Step 3-1). Alternatively, the solution of step 1 is added to the solution of step 2 while heating while adjusting the pH from weak alkalinity to weak acidity to synthesize a salt-forming dye and to make the pH weakly acidic to precipitate crystals (step 3- 2). The reaction in step 3 is represented by the following chemical formula (12).

（化学式（１２）中、Ａはβ−ナフトール誘導体から得られる残基であり、Ｐは下記化学式（１３）である）

(In the chemical formula (12), A is a residue obtained from a β-naphthol derivative, and P is the following chemical formula (13)).

In step 3, it is preferable that the equivalent amount of the disazo acid dye is equal to or slightly greater than that of the triphenylmethane basic dye. Specifically, it is preferably 1.0 to 1.5 equivalents, and more preferably 1.0 to 1.2 equivalents. For adjusting the pH, the inorganic acid or organic acid and the basic substance mentioned in Step 1 and Step 2 can be suitably used. A buffer solution may be prepared with an organic acid salt. In Step 3-1 and Step 3-2, it is preferable to synthesize a salt-forming dye at a temperature from room temperature to 90 ° C. In addition, when depositing a salt-forming dye, instead of acid precipitation that precipitates under weakly acidic conditions, salting-out may be performed by adding an inorganic salt such as sodium chloride. You may use together.
[Step 4]
Step 4 is a step of obtaining the salt-forming dye by filtering and washing the crystals of the salt-forming dye obtained in Step 3 with water. This is an important step for obtaining a salt-forming dye having a total chlorine content of 50 to 1000 ppm measured by a combustion coulometry method. In order to reduce the amount of the inorganic salt produced in Step 1 to Step 3, it is preferable to perform filtration so that the electric conductivity of the filtrate is 200 μS / cm or less. If necessary, the salt-forming dye may be dissolved, and the solution may be passed through an ion exchange membrane for desalting treatment. It is preferable that the salt-forming dye is redispersed and washed with water by adding washing water to the salt-forming dye crystals or wet cake obtained by filtration.
[Step 5]
Step 5 is a step of drying the salt-forming dye obtained in Step 4. Examples of the drying method include hot air drying, reduced pressure drying, freeze drying, and spray drying.
Since the obtained salt-forming dye X has a water-insoluble and oil-soluble dye structure, it is easy to remove impurities and raw materials, particularly inorganic salts.

As shown in the above chemical formula (4), the salt-forming dye X is a divalent anion derived from a triphenylmethane structure, which is a monovalent cation derived from a triphenylmethane-based basic dye, and a divalent anion derived from a disazo acid dye. It preferably has one disazo structure of 1 molar equivalent. Further, like the original acidic dye of the anion represented by the chemical formula (2), when the disazo acidic dye has two sulfonic acid groups in the diphenyl skeleton in one molecule, the cation and the anion Is more preferable because it is a salt-forming dye in which is strongly bound. The original acid dye of the anion may be a sulfonate.
Further, the salt-forming dye X has a triphenylmethane structure having a plurality of alkyl groups in one molecule, and thus exhibits excellent solubility in an alcohol solvent of the ink composition. More preferably, the disazo acid dye has two sulfonic acid groups. As a result, the coloring power of the amino (ammonium) skeleton of the triphenylmethane basic dye, which is the coloring portion, the coloring power of the azo coloring portion including two naphthalene structures, and the deepening effect of sulfonic acid Due to the synergistic effect, the salt-forming dye X develops at a high concentration. An ink composition for a writing instrument containing such a salt-forming dye X is suitable for black color matching, particularly by developing a deep purple color close to black. Therefore, it can be suitably used particularly for an ink composition for a ballpoint pen.
Further, by selecting a disazo acid dye having two β-naphthols in one molecule, the fastness of the salt-forming dye X is improved, and the heat resistance and light resistance are improved.
Furthermore, since the disazo acid dye used has two sulfonic acid groups in the diphenyl skeleton, it has high water solubility. For this reason, even if unreacted disazo acid dye remains in the production process of the salt-forming dye X, it can be easily removed by washing with water, and the purity of the salt-forming dye X can be increased.

  The iron content of the salt-forming dye X is preferably at most 100 ppm, more preferably from 5 ppm to 100 ppm, and even more preferably from 5 ppm to 70 ppm. When the iron content of the salt-forming dye X is within this range, the ink composition for a writing instrument containing the salt-forming dye X exhibits a value within this range. According to the ink composition for a writing instrument containing the salt-forming dye X, a complex of the salt-forming dye X and iron, a complex of the salt-forming dye X, an additive and iron, particularly a complex of a compound having a hydroxyl group and iron Precipitation can be prevented. As a result, the salt-forming dye X dissolves in the ink composition for writing instruments over a long period of time and does not crystallize, so that the long-term stability of the ink is improved and writing defects such as blurring do not occur in the handwriting. Moreover, the ink composition for writing implements containing such a salt-forming dye X improves the abrasion property with respect to the metal ball | bowl and metal ball | bowl base which are used for the pen tip which is a ball-point tip part.

（化学式（１４）中、Ｕ⁻はアニオン（例えばＣｌ及びＢｒのようなハロゲン原子から得られるアニオン、塩酸、硫酸、及び硝酸のような無機酸から得られるアニオン、並びに酢酸、乳酸、及びシュウ酸のような有機酸から得られるアニオン）である）で表されるトリフェニルメタン系塩基性染料と、下記化学式（Ａ２）

（化学式（２）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子であり、Ｍ及びＮは互いに独立して水素原子又はアルカリ金属である）で表されるジスアゾ酸性染料とから得られるものであり、下記化学式（５）

（化学式（５）中、Ｒ^１は水素原子又は下記化学式（３）

（化学式（３）中、Ｒ^３は炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、又はハロゲン原子である）であり、Ｒ^２は水素原子、炭素数１〜１８で直鎖若しくは分枝鎖のアルキル基、炭素数１〜１８で直鎖若しくは分枝鎖のアルコキシ基、アミノ基、ニトロ基又はハロゲン原子である）で表されるように、トリフェニルメタン系塩基性染料とジスアゾ酸性染料とがモル当量比２：１で構成されるものである。 (Salt making dye Y)
The salt-forming dye Y, which is a colorant contained in the ink composition for a writing instrument of the present invention, has the following chemical formula (14)

(In Formula (14), U ⁻ represents an anion (for example, an anion obtained from a halogen atom such as Cl and Br, an anion obtained from an inorganic acid such as hydrochloric acid, sulfuric acid, and nitric acid, and acetic acid, lactic acid, and oxalic acid) An anion obtained from an organic acid such as a triphenylmethane basic dye represented by the following formula (A2):

(In the chemical formula (2), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). , R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom, M and N are each independently a hydrogen atom or an alkali metal) and are obtained from a disazo acid dye represented by the following chemical formula (5):

(In the chemical formula (5), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom). R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom) As shown, the triphenylmethane basic dye and the disazo acid dye are configured in a molar equivalent ratio of 2: 1.

（化学式（１５）中、Ｂはβ−ナフトール誘導体から得られる残基であり、Ｑは下記化学式（１６）である）

The salt-forming dye Y of the present invention can be produced by the same production method as the salt-forming dye X as shown in the following chemical formula (15).

(In the chemical formula (15), B is a residue obtained from a β-naphthol derivative, and Q is the following chemical formula (16))

Examples of the anion in the chemical formula (5) derived from the disazo acid dye having a β-naphthol derivative include the chemical formulas (9) to (11), and the chemical formula (9) is particularly preferable.
The total chlorine content of the salt-forming dye Y measured by the combustion coulometry method for measuring total chlorine is preferably 50 ppm to 1000 ppm, more preferably 50 ppm to 800 ppm, and more preferably 100 ppm to 100 ppm. More preferably, it is 700 ppm.
The salt-forming dye Y has almost the same effect as the salt-forming dye X. Since the ink composition for writing instruments contains a small amount of polar salt-forming dye Y, the solubility of salt-forming dye X and salt-forming dye Y in the liquid medium is improved. The salt-forming dye Y does not precipitate in the ink composition for writing instruments. As a result, the ink composition for writing instruments does not cause defects such as blurring in the handwriting, and is therefore suitably used for a ballpoint pen ink composition containing a high concentration salt-forming dye. In such an ink composition for a writing instrument, the abundance ratio of the salt-forming dye X and the salt-forming dye Y measured by high performance liquid chromatography (HPLC) is: salt-forming dye X: salt-forming dye Y = 99.1- It is preferably 85.0: 0.9 to 15.0%, more preferably 94.5 to 85.5: 5.5 to 14.5%, and 90.5 to 86.0: 9. It is still more preferable that it is 0.5-14.0%.

(Blending colorant)
Since the salt-forming dye X and / or salt-forming dye Y of the present invention is a purple colorant, it can be suitably used as a black colorant. In order to prepare an ink composition for a black writing instrument, a combination of a salt-forming dye X and / or a salt-forming dye Y and a dye pigment of three colors of red, blue, and yellow (the three primary colors) It is preferable to prepare an agent. These colors and blending ratios are arbitrarily set according to the color to be expressed. For example, two basic colors of purple and yellow can be set and other dyes and pigments can be combined. As these dyes and pigments, known yellow, reddish yellow (orange), and red dyes and pigments can be used.

Specific examples of yellow dyes include C.I. I. Solvent Yellow 13, 15, 21, 30, 32, 34, 44, 54, 57, 60, 61, 62, 65, 83, 93, 105, 120, 136, 155, etc .; I. Examples thereof include Basic Yellow 28, 51 and the like.
Specific examples of reddish yellow (orange) dyes include C.I. I. Solvent Orange 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 19, 20, 37, 37.1, 40, 40: 1, 49, etc .; I. Basic Orange 2, 22 etc. can be mentioned.
Specific examples of the red dye include C.I. I. Solvent Red 8, 13, 14, 18, 30, 35, 36, 37, 38, 39, 46, 49, 52, 79, 81, 82, 83, 96, 99, 100, 102, 109, 112, 113, 115, 119, 122, 124, 127, 128, 142, 184, 185, 186, 187, 203, 204, 205, 206, etc .; I. Basic Red 1 etc. can be mentioned.

Specific examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 34, 42, 55, 73, 74, 79, 81, 83, 93, 94, 95, 97, 104, 109, 110, 111, 120, 128, 133, 136, 138, 139, 147, 151, 154, 155, 167, 173, 174, 175, 176, 180, 185, 191, 194, 213 and the like.
Specific examples of reddish yellow (orange) pigments include C.I. I. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 62, 68, 72, 74, and the like.
Specific examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 25, 30, 31, 32, 37, 38, 39, 40, 41, 42, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 49: 3, 50, 50: 1, 50: 2, 50, 52, 52: 1, 52: 2, 52: 3, 53: 1, 53: 2, 54, 55, 56, 57, 57: 1, 57: 2, 58, 58: 1, 58: 2, 58: 3, 58: 4, 59, 60, 60: 1, 101, 104, 112, 122, 144, 146, 149, 166, 170, 175, 176, 177, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 211, 21 , Mention may be made of the 214,242,253,254,255,256,257,264,266,268,270,272 and the like.

Further, in order to improve the fastness of the black colorant and adjust the blackness, an azine-based nigrosine oil-soluble dye (CI Solvent Black 5, 7), a black metal-containing dye, and a black pigment can be used in combination.
Specific examples of black metal-containing dyes include C.I. I. Solvent Black 15, 22, 22: 1, 23, 25, 26, 27, 28, 29, 30, 34, 35, 36, 37, 38, 40, 41, 42, 43, 45, 47, 48 etc. be able to.
Specific examples of black pigments include C.I. I. Pigment Black 1, 6, 7, 11, 28, 30 and the like.

The ink composition for writing instruments may contain a colorant such as a dye, pigment, or a mixture thereof showing a hue of yellow, orange, red, blue, purple, green, and black.
As such dyes, direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, salt-forming dyes, alcohol-soluble dyes, azoic dyes, sulfur dyes, sulfur vat dyes used in known dye ink compositions , Vat dyes, disperse dyes, oil-soluble dyes, food dyes, and metal complex dyes. Examples of these dyes include azo dyes, anthraquinone dyes, oxazine dyes, phthalocyanine dyes, quinacridone dyes, quinophthalone dyes, triphenylmethane dyes, perinone dyes, and perylene dyes. It is preferable that content of dye is 0.01-50 mass% with respect to the ink composition whole quantity for writing instruments.
The dye is preferably a salt-forming dye available on the market. As this salt-forming dye,
VALIFAST® YELLOW 1101, 1103, 1109, 3108, 3120, 3150, 3170, 3180, 4120, 4121, etc .;
VALIFAST ORANGE 1201, 2210, 3208, 3209, 3210, etc .;
VALIFAST RED 1308, 1320, 1364, 1388, 2303, 2320, 3304, 3306, 3311, 3312, 3320, etc .;
VALIFAST PINK 2310N, 2312, etc .;
VALIFAST BROWN 2402, 3402, 3405, etc .;
VALIFAST GREEN 1501 etc .;
VALIFAST BLUE 1605, 1613, 1621, 1631, 2620, 2670, 2680, etc .;
VALIFAST VIOLET 1701, 1702, 1704, 1705, etc .;
VALIFAST BLACK 1807, 1821, 3804, 3806, 3808, 3810, 3820, 3830, 3840, 3870, 3877, etc .;
OIL BLUE 613, etc .; OIL PINK 312 etc. (above, manufactured by Orient Chemical Industry Co., Ltd.)
C. I. B. Salt-forming dyes of Basic Red 1 and alkyl diphenyl ether disulfonic acid; I. B. Salt-forming dyes of Basic Red 1: 1 and alkyl diphenyl ether disulfonic acid; I. B. Salt-forming dyes of Basic Red 2 and organic acids; I. B. Salt-forming dyes of Basic Yellow 1 and organic acids; I. B. Salt-forming dyes of Basic Yellow 2 and organic acids; I. B. Salt yellow 51 and organic acid salt dye; I. B. Salt-forming dyes of Basic Yellow 52 and organic acids; I. Acid Black 51 and organic amine salt-forming dyes; C.I. I. Examples thereof include salt-forming dyes of Acid Black 52 and organic amines.

The pigment that can be used is preferably one that does not dissolve easily in the liquid medium and has an average particle diameter of 30 nm to 700 nm when dispersed in the liquid medium. The pigment content is preferably 0.5 to 25 mass%, more preferably 0.5 to 20 mass%, based on the total amount of the ink composition for writing instruments.
The pigments are inorganic facials such as carbon black, graphite and titanium dioxide pigments; constitutional facials such as talc, silica, alumina, mica and alumina silicate; azo pigments, condensed azo pigments, phthalocyanine pigments, anthraquinones Organic pigments such as pigments, quinacdrine pigments, isoindolinone pigments, diketopyrrolopyrrole pigments and various lake pigments; fluorescent pigments, pearl pigments, metallic pigments such as gold and silver.
Further, graphite (graphite) is preferable as the black pigment having lubricity. As the graphite, artificial graphite and natural graphite can be used, and graphite on scale, lump graphite, and earth graphite can be used in properties and sizes as required.
Other black pigments include Printex 3, 25, 30, 35, 40, 45, 55, 60, 75, 80, 85, 90, 95, 300, Special Black 4, 5, 100, 250, 550 (or more, Evonik Degussa Japan).
Mitsubishi Carbon Black # 2700, # 2650, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750 , # 650, # 260, # 95 # 52, # 50, # 47, # 45, # 45L, # 44, # 40, # 33, # 32, # 30, # 25, # 20, # 10, # 5 CF9, MCF88, MA600, MA77, MA7, MA11, MA100, MA100R, MA100S, MA220, MA230 (above, manufactured by Mitsubishi Chemical Corporation),
Talker Black # 8500 / F, # 8300 / F, # 7550SB / F, # 7400, # 7360SB / F, # 7350 / F, # 7270SB, # 7100 / F, # 7050 (above, manufactured by Tokai Carbon Co., Ltd.) Carbon black,
Examples thereof include aniline black such as diamond black N (manufactured by Jade Color Co., Ltd.), iron black such as bone black (manufactured by Mie Color Techno), and iron black KN-320 (manufactured by Nippon Iron Chemical Co., Ltd.).
As the yellow pigment, the reddish yellow (orange) pigment, and the red pigment, the same pigments as those contained in the black colorant can be used.
As a blue pigment, C.I. I. Pigment Blue 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 28, 29, 36, 60, 68, 76, 80 and the like.
As a green pigment, C.I. I. Pigment Green 7, 36, 37 and the like.
As a purple pigment, C.I. I. Pigment Violet 19, 23 and the like.
These pigments may be used alone or in combination.
A processed pigment to which a dispersion of an inorganic pigment or a dye is added may be used as necessary. Furthermore, the resin emulsion obtained by polymerizing monomers such as styrene, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, and olefin, and swollen in the ink composition for writing instruments A hollow resin emulsion or an organic multicolor pigment which is dyed resin particles obtained by dyeing these emulsions with a colorant may be used.

The dispersant for dispersing the pigment is appropriately selected according to the type of the pigment. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl ether, styrene-maleic acid copolymer, ketone resin, hydroxyethyl cellulose and derivatives thereof, synthetic resins such as styrene-acrylic acid copolymer, and EO thereof (Ethylene oxide) adduct, PO (propylene oxide) adduct, polyester amine oligomer and the like.
The pigment is mixed with a pulverizer such as a ball mill, a roll mill, a bead mill, a sand mill, or a pin mill, and then mixed and pulverized by centrifugal separation or filtration. It is preferable that the dissolved substance and the mixed solid are removed.

[Ink composition for writing instruments]
The ink composition for a writing instrument of the present invention contains at least one of a salt-forming dye X and a salt-forming dye Y, and is a blended colorant obtained by blending a colorant such as a dye and pigment as necessary. And a liquid medium and a resin that dissolves in the liquid medium, and is preferably used by being filled in a writing instrument such as a ballpoint pen, a marking pen, or a sign pen. The content of the writing tool dye or the blended colorant is preferably 0.10 to 30% by mass and more preferably 0.50 to 25% by mass with respect to the total amount of the writing instrument ink composition. If the content is less than 0.10% by mass, the coloring power and color developability of the ink composition for writing instruments will be insufficient. On the other hand, if it exceeds 30% by mass, the handwriting will be blurred.
According to this ink composition for a writing instrument, an oil-based ink containing at least one colorant of a salt-forming dye X, a salt-forming dye Y, and a blended colorant can be formulated, and handwriting by a writing instrument filled with this ink is Excellent water resistance and bleed resistance.

Examples of the liquid medium contained in the ink composition for writing instruments include solvents such as alcohol solvents, polyhydric alcohol solvents, glycol ether solvents, diether solvents, and ester solvents. Although content of a solvent is suitably set according to the kind of writing instrument, and the kind and content of dyeing pigment, it is preferable that it is 20-97 mass% with respect to the ink composition whole quantity for writing instruments, and 30- More preferably, it is 95 mass%.
The alcohol solvent is an aliphatic alcohol having 2 or more carbon atoms, specifically, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1-pentanol, isoamyl alcohol, sec -Amyl alcohol, 3-pentanol, tert-amyl alcohol, n-hexanol, methyl amyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethyl Hexanol, 3,5,5-trimethylhexanol, nonanol, n-decanol, undecanol, n-decanol, trimethylnonyl alcohol, tetradecanol, heptadecanol, cyclohexanol, 2-methylcyclohexanol, benzylal Lumpur, 2-phenoxyethanol.
As polyhydric alcohol solvents, ethylene glycol, diethylene glycol, 3-methyl-1,3-butanediol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentane Examples thereof include polyhydric alcohols having two or more carbons, two or more hydroxy groups in the molecule such as diol, hexylene glycol and octylene glycol, and derivatives thereof.
As glycol ether solvents, methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2 -Ethyl butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, 3-methyl 3-methoxy-1-butanol, 3-methoxy-1-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether, propylene glycol tertiary butyl ether, di- Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, among others, carbon Number 2-7 glycol ether Preferred.
Examples of the diether solvent include ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
As ester solvents, propylene glycol methyl ether acetate, propylene glycol diacetate, 3-methyl-3-methoxybutyl acetate, propylene glycol ethyl ether acetate, ethylene glycol ethyl ether acetate, butyl formate, isobutyl formate, isoamyl formate, propyl acetate, Butyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, iso Propyl butyrate, methyl valerate, ethyl valerate, propyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, trimethylacetic acid Chill, ethyl trimethyl acetate, propyl trimethyl acetate, methyl caproate, ethyl caproate, propyl caproate, methyl caprylate, ethyl caprylate, propyl caprylate, methyl laurate, ethyl laurate, methyl oleate, ethyl oleate, Examples include caprylic acid triglyceride, tributyl acetate citrate, octyl oxystearate, propylene glycol monoricinoleate, methyl 2-hydroxyisobutyrate, 3-methoxybutyl acetate, and diesters having no hydroxy group in the molecule.

The ink composition for writing instruments contains a resin for improving the fixing property of ink, preventing the show-through of handwriting, improving the solubility and dispersibility of the dye and pigment, and adjusting the viscosity. This resin is dissolved in the solvent which is the liquid medium. The content of the resin is preferably 0.50 to 35% by mass, and 1.0 to 20% by mass with respect to the total amount of the ink composition for writing instruments, from the viewpoint of adjusting the viscosity and adjusting the writing taste. Is more preferable. If the content is less than 0.50% by mass, the viscosity of the ink composition for writing instruments is insufficient, and the handwriting is likely to bleed, or the pen tip of the ballpoint pen is significantly worn. On the other hand, when it exceeds 35% by mass, the solvent or dye / pigment to be contained in the ink composition for writing instruments is insufficient, or the handwriting is dull and the writing quality is adversely affected.
Examples of such a resin include ketone-based resins such as polyether ketone and polyether ether ketone; styrene-based resins such as polystyrene; polyvinyl acetals such as polyvinyl butyral; polyvinyl pyrrolidone; rosin-modified maleic acid resins and styrene maleic acid resins. Rosin-modified phenolic resin, terpene phenolic resin, phenolic resin such as alkylphenol resin; acrylic resin such as styrene-acrylic resin; rosin resin; urea aldehyde resin; cyclohexanone resin Can be mentioned. Of these, polyvinyl butyral resin is preferred. Since the salt-forming dye X and the salt-forming dye Y do not have a free acid component such as an unreacted acid dye by washing with water in the production process, hydrolysis of the polyvinyl butyral resin by this acid component does not occur. The ink composition for writing instruments is excellent in aging stability and storage stability. Therefore, by selecting a polyvinyl butyral resin, it is possible to impart good film-forming properties and high thickening action to the ink composition for writing instruments.

Ink compositions for writing instruments are lubricants, shear thinning agents, viscosity modifiers, leveling agents, rust inhibitors, preservatives, surface tension modifiers, antioxidants, UV absorbers, antifoaming agents as necessary. , Wetting agents, dispersion aids, and pH adjusting agents.
Lubricants include higher fatty acids such as oleic acid, nonionic surfactants having a long chain alkyl group, polyether-modified silicone oil, polyoxyethylene alkyl ether, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, poly Oxyethylene sorbit fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylamine, N-acyl amino acid, polyoxyethylene alkyl ether or poly Phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether of oxyethylene alkyl aryl ether Of phosphoric acid diesters, phosphoric acid triesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, alkyl phosphoric acid esters, alkyl ether phosphoric acid esters or their metal salts, ammonium salts, amine salts, alkanolamine salts Examples thereof include phosphate ester surfactants. These lubricants may be used alone or in combination. An ink composition for a writing instrument containing a lubricant exhibits an effect of preventing wear of a ball receiving seat of a ball tip of a ballpoint pen.
Fine particles that further improve the lubricity may be contained in the ink composition for writing instruments. Examples of the fine particles include acrylic, silicone, and polyethylene resin fine particles, alumina fine particles, and silica fine particles. Of these, spherical silica fine particles are preferable. Since the fine particles enter the gap between the ball receiving seat of the ball chip and the ball, metal contact between the ball receiving seat and the ball is suppressed, so that the lubricity is improved.
As shear thinning agent, crosslinked acrylic resin, emulsion type of crosslinked acrylic resin, crosslinked N-vinylcarboxylic acid amide polymer or copolymer, non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer aqueous solution, hydrogenated castor oil, fatty acid amide wax, oxidized polyethylene wax and other waxes, aluminum stearate, aluminum palmitate, aluminum octylate, aluminum laurate And fatty acid metal salts such as dibenzylidene sorbitol, dextrin fatty acid ester, N-acyl amino acid compound, smectite inorganic compound, montmorillonite inorganic compound, bentonite inorganic compound, hectorite inorganic compound, and silica. By containing a shear thinning agent, the ink composition for writing instruments does not leak from the gap between the ballpoint ball and the ball tip, and when the ballpoint pen is left standing (upright) The ink composition for writing instruments does not flow backward.
Synthetic polymer materials such as ketone resins, terpene resins, alkyd resins, phenoxy resins, polyvinyl acetate, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polyethylene oxide, polyvinyl pyrrolidone as viscosity modifiers; guar gum, locust bean gum Seed polysaccharides and derivatives thereof; microbial polysaccharides and derivatives thereof such as xanthan gum, welan gum and rhamzan gum; seaweed polysaccharides and derivatives thereof such as carrageenan and alginic acid; resin polysaccharides such as tarragant gum; Resin; Pyrrolidone-based resin is exemplified.
Examples of the leveling agent include acetylene glycol, acetylene alcohol, and silicone-based surfactant.
Examples of the rust inhibitor include benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin, ethylenediaminetetraacetic acid, metal salt compounds, and phosphate ester compounds.
Examples of preservatives include benzoisothiazolin-3-one, sodium dehydroacetate, isothiazolone, and oxazolidine compounds.
Examples of the surface tension adjusting agent include a silicone surfactant and a fluorine surfactant.
Examples of the antioxidant include dibutylhydroxytoluene, nordihydroxytoluene, flavonoids, butylhydroxyanisole, ascorbic acid derivatives, α-tocopherol, and catechins.
As UV absorbers, 2- (2′-hydroxy-3′-t-butyl 5′-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzo And triazole and p-benzoic acid-2-hydroxybenzophenone.
Antifoaming agents include silicone compounds such as dimethylpolysiloxane, mineral oils, and fluorine compounds.
Examples of the wetting agent include glycerin, sorbitan compounds, polysaccharides, urea, ethylene urea, and derivatives thereof.
Examples of the dispersion aid include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the pH adjusting agent include alkalizing agents such as sodium hydroxide, alkanolamine, amine and ammonium.

A well-known method can be used for manufacturing the ink composition for writing instruments. For example, a predetermined amount of salt-forming dye X and / or salt-forming dye Y, a liquid medium solvent, a resin, and, if necessary, additives such as a lubricant are blended and put into a stirrer such as a homomixer or a disper. Obtained by stirring and mixing. Furthermore, if necessary, coarse particles may be removed by filtration or centrifugation. The ink composition for writing instruments thus manufactured is filled into a ballpoint pen or a marking pen.
The structure and shape of the ballpoint pen are not particularly limited. For example, an ink containing tube that connects a ball tip with a ball mounted on the ball seat at the tip to the tip is accommodated in the inner space of the shaft, and this tip is The ball-point pen which has the structure which protrudes from the front-end | tip of can be mentioned. After the ink composition for a writing instrument is filled from the open base end of the ink containing tube, the base end opening is closed with a backflow prevention liquid stopper or backflow prevention body. When the ball rolls on the writing medium, the ink composition for the writing instrument is supplied to the surface of the ball from the gap between the ball chip and the ball, and soaks into the writing medium to form handwriting. The shaft cylinder and the ink storage tube are a resin molded product or a metal processed body.
The structure and shape of the marking pen are not particularly limited.For example, in the inner space of the shaft tube, an ink occlusion body formed of a fiber bundle, and a structure in which a pen core integrated therewith protrudes from the tip of the shaft tube, In addition to this, a marking pen having a comb groove-shaped ink flow rate adjusting member formed of a fiber bundle at the tip of the shaft cylinder can be exemplified. The ink occlusion body is impregnated by filling the shaft cylinder with the ink composition for writing instruments. When the ink composition for a writing instrument is supplied to the pen core and the fiber chip is rubbed against a writing medium such as paper, the ink composition for the writing instrument soaks into the writing medium to form a handwriting. The pen core can be made of fiber bundle, felt, or plastic.

  The ink composition for writing instruments may be used for whiteboard marking pens made of enamel, glass, metal, thermoplastic resin, or thermosetting resin. In this case, it is preferable to include a release agent in the ink composition for writing instruments. Examples of the release agent include carboxylic acid esters, silicone surfactants, and nonionic surfactants. Specific examples of release materials that can be suitably used include sulfuric acid ester of polyoxyalkylene alkyl ether, sulfuric acid ester of polyoxyalkylene alkyl aryl ether, polyoxyethylene alkyl ether phosphate ester and salts thereof, aliphatic dibasic acid ester, Examples thereof include aliphatic monobasic acid esters and polyalkylene glycol esters. These release agents can be used alone or in combination.

で表されるトリフェニルメタン系塩基性染料を、トリフェニルメタン塩基性染料Ｃとし、下記化学式（１８）

で表されるトリフェニルメタン系塩基性染料を、トリフェニルメタン塩基性染料Ｄとする。
なお、製造例及び比較製造例で用いた水の電気伝導度は、全て２２．５℃において１４８μＳ／ｃｍである。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not limited only to these. In the examples, the following chemical formula (17)

The triphenylmethane basic dye represented by the formula is triphenylmethane basic dye C, and the following chemical formula (18)

The triphenylmethane basic dye represented by is represented by triphenylmethane basic dye D.
The electric conductivity of water used in the production examples and comparative production examples is 148 μS / cm at 22.5 ° C.

２Ｌビーカーに水１７００ｇを入れて７５℃に加熱し、３５．４ｇのトリフェニルメタン塩基性染料Ｃ（鉄含有量２５ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝３．１）。この溶液に５質量％の塩酸溶液を加えｐＨ＝２．７とした後濾過し、濾液を３Ｌビーカーへ移して、溶液−Ａとした。別な１Ｌビーカーに水４１０ｇを入れて７５℃に加熱し、２６．４ｇのＣ．Ｉ．Ａｃｉｄ Ｒｅｄ ９７をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝８．１）。この溶液に炭酸ナトリウム２．４ｇを加えｐＨ＝１０．１とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを４６分間で滴下し５０℃にて１時間反応した（ｐＨ＝７．６）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が１７３μＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、造塩染料Ａ−１を得た（収量＝５２．３ｇ）。
造塩染料Ａ−１を、塩素・硫黄分析装置（三菱化学アナリテック社製、製品名：ＴＯＸ−２１００Ｈ）にて全塩素の含有量を測定したところ、３５６ｐｐｍであった。
造塩染料Ａ−１の吸光度を次の条件で測定した。造塩染料Ａ−１を０．０５０ｇ秤量し、ベンジルアルコール１０ｍＬに溶解させ、１００ｍＬメスフラスコに入れ１−メトキシ−２−プロパノールで１００ｍＬとした。この溶液１ｍＬをホールピペットで秤量して１００ｍＬメスフラスコに移し、１−メトキシ−２−プロパノールを加えて１００ｍＬとした。この溶液の吸光度を、紫外線可視分光光度計（島津製作所社製、製品名：ＵＶ−１７００ ＵＶ−ＶＩＳＩＢＬＥ ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲ）にて測定した。結果を図１に示した。
造塩染料Ａ−１を、ＩＣＰ発光分光分析装置（サーモフィッシャーサイエンティフィック社製、製品名：ｉＣＡＰ７４００Ｄｕｏ）で、鉄の含有量を測定したところ、１１ｐｐｍであった。 (Production Example A-1)
Triphenylmethane basic dye C and disazo acid dye C.I. I. Synthesis of salt-forming dye A-1 with Acid Red 97 [salt-forming dye A-1]

1700 g of water was put in a 2 L beaker and heated to 75 ° C., and 35.4 g of triphenylmethane basic dye C (iron content 25 ppm) was gradually added thereto and dissolved over 2 hours (pH = 3.1). ). A 5% by mass hydrochloric acid solution was added to this solution to adjust the pH to 2.7, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 410 g of water was added and heated to 75 ° C., and 26.4 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.1). To this solution, 2.4 g of sodium carbonate was added to adjust to pH = 10.1, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 46 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.6). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 173 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and salt-forming dye A-1 was obtained (yield = 52.3g).
The total chlorine content of the salt-forming dye A-1 was measured using a chlorine / sulfur analyzer (product name: TOX-2100H, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and found to be 356 ppm.
The absorbance of the salt-forming dye A-1 was measured under the following conditions. 0.050 g of salt-forming dye A-1 was weighed and dissolved in 10 mL of benzyl alcohol, placed in a 100 mL volumetric flask, and made up to 100 mL with 1-methoxy-2-propanol. 1 mL of this solution was weighed with a whole pipette and transferred to a 100 mL volumetric flask, and 1-methoxy-2-propanol was added to make 100 mL. The absorbance of this solution was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-1700 UV-VISABLE SPECTROTOPOMETER). The results are shown in FIG.
When the iron content of the salt-forming dye A-1 was measured with an ICP emission spectroscopic analyzer (manufactured by Thermo Fisher Scientific, product name: iCAP7400Duo), it was 11 ppm.

(Production Example A-2)
Triphenylmethane basic dye C and disazo acid dye C.I. I. Synthesis of salt-forming dye A-2 with Acid Red 97 [salt-forming dye A-2]
The chemical formula of the salt-forming dye A-2 is the same as the chemical formula (A-1) of the salt-forming dye A-1.
1700 g of water was put in a 2 L beaker and heated to 75 ° C., 35.4 g of triphenylmethane basic dye C (iron content 65 ppm) was gradually added thereto and dissolved over 2 hours (pH = 3.0). ), Solution-A. In another 1 L beaker, 410 g of water was added and heated to 75 ° C., and 26.4 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.1) to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 42 minutes, and 10% by mass aqueous sodium hydroxide solution was gradually added to adjust to pH = 8.7. The reaction was performed at 50 ° C. for 1 hour. The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 199 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and salt-forming dye A-2 was obtained (yield = 49.4g).
About obtained salt-forming dye A-2, it was 387 ppm when content of total chlorine was measured similarly to salt-forming dye A-1, and it was 31 ppm when content of iron was measured.

(Production Example A-3)
Triphenylmethane basic dye C and disazo acid dye C.I. I. Synthesis of salt forming dye A-3 with Acid Red 97 [Salt forming dye A-3]
The chemical formula of the salt-forming dye A-3 is the same as the chemical formula (A-1) of the salt-forming dye A-1.
1700 g of water was put in a 2 L beaker and heated to 75 ° C., and 35.4 g of triphenylmethane basic dye C (iron content 39 ppm) was gradually added thereto and dissolved over 2 hours (pH = 3.3). ). A 5 mass% hydrochloric acid solution was added to this solution to adjust the pH to 2.8, followed by filtration. The filtrate was transferred to a 2 L beaker to obtain Solution-A. In another 1 L beaker, 410 g of water was added and heated to 75 ° C., and 26.4 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.0). To this solution, 2.4 g of sodium carbonate was added to adjust the pH to 10.0, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-A was added dropwise to Solution-B over 65 minutes, and reacted at 50 ° C. for 1 hour (pH = 8.1). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 205 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and salt-forming dye A-3 was obtained (yield = 50.5g).
About obtained salt-forming dye A-3, it was 401 ppm when content of all the chlorine was measured similarly to salt-forming dye A-1, and it was 18 ppm when content of iron was measured.

３Ｌビーカーに水１８３０ｇを入れて７５℃に加熱し、３５．４ｇのトリフェニルメタン塩基性染料Ｄ（鉄含有量３８ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝２．９）。この溶液に５質量％の塩酸溶液を加えｐＨ＝２．５とした後濾過し、濾液を５Ｌビーカーへ移して、溶液−Ａとした。別な１Ｌビーカーに水４４０ｇを入れて７５℃に加熱し、２８．０ｇのＣ．Ｉ．Ａｃｉｄ Ｒｅｄ ９７をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝８．２）。この溶液に炭酸ナトリウム２．５ｇを加えｐＨ＝１０．０とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを５５分間で滴下し５０℃にて１時間反応した（ｐＨ＝７．５）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が２０８μＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、造塩染料Ａ−４を得た（収量＝５３．１ｇ）。
得られた造塩染料Ａ−４について、造塩染料Ａ−１と同様に、全塩素の含有量を測定したところ３４１ｐｐｍであり、鉄の含有量を測定したところ１５ｐｐｍであった。 (Production Example A-4)
Triphenylmethane basic dye D and disazo acid dye C.I. I. Synthesis of salt-forming dye A-4 with Acid Red 97 [salt-forming dye A-4]

1830 g of water was put in a 3 L beaker and heated to 75 ° C., and 35.4 g of triphenylmethane basic dye D (iron content 38 ppm) was gradually added thereto and dissolved over 2 hours (pH = 2.9). ). A 5 mass% hydrochloric acid solution was added to this solution to adjust the pH to 2.5, followed by filtration. The filtrate was transferred to a 5 L beaker to obtain Solution-A. In another 1 L beaker, 440 g of water was added and heated to 75 ° C., and 28.0 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.2). To this solution, 2.5 g of sodium carbonate was added to adjust the pH to 10.0, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 55 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.5). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 208 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and salt-forming dye A-4 was obtained (yield = 53.1g).
About obtained salt-forming dye A-4, it was 341 ppm when content of all the chlorine was measured similarly to salt-forming dye A-1, and it was 15 ppm when content of iron was measured.

２Ｌビーカーに水１１００ｇを入れて７５℃に加熱し、２０．０ｇのトリフェニルメタン塩基性染料Ｃ（鉄含有量５２ｐｐｍ）及び２．６ｇのトリフェニルメタン塩基性染料Ｄ（鉄含有量４７ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝３．０）。この溶液に５質量％の塩酸溶液を加えｐＨ＝２．５とした後濾過し、濾液を３Ｌビーカーへ移して、溶液−Ａとした。別な１Ｌビーカーに水２５０ｇを入れて７５℃に加熱し、１６．２ｇのＣ．Ｉ．Ａｃｉｄ Ｒｅｄ ９７をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝８．０）。この溶液に炭酸ナトリウム１．４ｇを加えｐＨ＝１０．０とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを２４分間で滴下し５０℃にて１時間反応した（ｐＨ＝７．２）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が１９３μＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、造塩染料Ａ−５を得た（収量＝３４．０ｇ）。
得られた造塩染料Ａ−５について、造塩染料Ａ−１と同様に、全塩素の含有量を測定したところ３８６ｐｐｍであり、鉄の含有量を測定したところ３１ｐｐｍであった。
得られた造塩染料Ａ−５の吸光度を、造塩染料Ａ−１と同様に測定した。結果を図２に示した。
得られた造塩染料Ａ−５について、高速液体クロマトグラフィー（ＨＰＬＣ 島津製作所社製 検出器；ＳＰＤ−Ｍ２０Ａ、カラムオーブン；ＣＴＯ−２０Ａ、ポンプ；ＬＣ−２０ＡＴ、デガッサー；ＤＧＵ−２０Ａ_３）を用い、以下の測定条件にて測定を行い、トリフェニルメタン塩基性染料Ｃとトリフェニルメタン塩基性染料Ｄとの存在比を算出した。
サンプル０．００５ｇを溶離液３ｍＬに溶解させ、超音波洗浄器に３０分かけ、平均ポア径が０．５μｍのメンブランフィルターで濾過してサンプル溶液とし、以下の条件で測定した。カラム；Ｌ−Ｃｏｌｕｍｎ ＯＤＳ （４．６×２５０ｍｍ）、カラムオーブン温度；４５℃、流速；１．０ｍＬ／分、試料注入量；５μＬ、検出波長；２５４ｎｍ、溶離液；アセトニトリル：０．０１ｍｏｌ／Ｌ−ＫＨ_２ＰＯ_４：リン酸＝８：２：０．０３
測定結果を島津製作所社製の解析ソフトウエア「ＬＣ ｓｏｌｕｔｉｏｎ ＬＣ−Ａｓｓｉｓｔ」を用いて以下の条件で解析した。
Ｗｉｄｔｈ；５秒、ｓｌｏｐｅ；３００μＶ／分、Ｄｒｉｆｔ；０μＶ／分、Ｔ．ＤＢＬ；１０００分、最少面積／高さ；１００００
保持時間＝４〜７分に検出されたトリフェニルメタン塩基性染料Ｃ（前記化学式（１７）で表されるトリフェニルメタン系塩基性染料）、及び保持時間＝２〜４分に検出されたトリフェニルメタン塩基性染料Ｄ（前記化学式（１８）で表されるトリフェニルメタン系塩基性染料）の存在比を、各面積値の割合から算出した。その結果、トリフェニルメタン塩基性染料Ｃ：トリフェニルメタン塩基性染料Ｄ＝８８．１：１１．９％であった。 (Production Example A-5)
Triphenylmethane basic dye C: triphenylmethane basic dye D = 88: 12% and disazo acid dye C.I. I. Synthesis of salt-forming dye A-5 with Acid Red 97 [salt-forming dye A-5]

1100 g of water is put in a 2 L beaker and heated to 75 ° C., 20.0 g of triphenylmethane basic dye C (iron content 52 ppm) and 2.6 g of triphenylmethane basic dye D (iron content 47 ppm) are added. This was gradually added and dissolved over 2 hours (pH = 3.0). A 5 mass% hydrochloric acid solution was added to this solution to adjust the pH to 2.5, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 250 g of water was added and heated to 75 ° C., and 16.2 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.0). To this solution was added 1.4 g of sodium carbonate to adjust the pH to 10.0, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 24 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.2). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 193 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and salt-forming dye A-5 was obtained (yield = 34.0g).
About obtained salt-forming dye A-5, it was 386 ppm when content of all the chlorine was measured similarly to salt-forming dye A-1, and it was 31 ppm when content of iron was measured.
The absorbance of the obtained salt-forming dye A-5 was measured in the same manner as the salt-forming dye A-1. The results are shown in FIG.
About the obtained salt-forming dye A-5, high performance liquid chromatography (HPLC Shimadzu Corporation detector; SPD-M20A, column oven; CTO-20A, pump; LC-20AT, degasser; DGU-20A ₃ ) was used. The measurement was performed under the following measurement conditions, and the abundance ratio of triphenylmethane basic dye C and triphenylmethane basic dye D was calculated.
0.005 g of the sample was dissolved in 3 mL of the eluent, passed through an ultrasonic cleaner for 30 minutes, filtered through a membrane filter having an average pore diameter of 0.5 μm to obtain a sample solution, and measured under the following conditions. Column: L-Column ODS (4.6 × 250 mm), column oven temperature: 45 ° C., flow rate: 1.0 mL / min, sample injection amount: 5 μL, detection wavelength: 254 nm, eluent: acetonitrile: 0.01 mol / L -KH ₂ PO _4: phosphate = 8: 2: 0.03
The measurement results were analyzed under the following conditions using analysis software “LC solution LC-Assist” manufactured by Shimadzu Corporation.
Width: 5 seconds, slope: 300 μV / min, Drift: 0 μV / min, T.P. DBL; 1000 minutes, minimum area / height; 10,000
Triphenylmethane basic dye C (triphenylmethane basic dye represented by the above chemical formula (17)) detected at retention time = 4 to 7 minutes, and tritium detected at retention time = 2 to 4 minutes The abundance ratio of the phenylmethane basic dye D (triphenylmethane basic dye represented by the chemical formula (18)) was calculated from the ratio of each area value. As a result, triphenylmethane basic dye C: triphenylmethane basic dye D = 88.1: 11.9%.

(Production Example A-6)
Triphenylmethane basic dye C: triphenylmethane basic dye D = 91: 9% and disazo acid dye C.I. I. Synthesis of salt-forming dye A-6 with Acid Red 97 [salt-forming dye A-6]
The chemical formula of the salt-forming dye A-6 is the same as the chemical formula (A-5) of the salt-forming dye A-5.
1100 g of water is put in a 2 L beaker and heated to 75 ° C., 20.0 g of triphenylmethane basic dye C (iron content 31 ppm) and 1.9 g of triphenylmethane basic dye D (iron content 46 ppm) are added. This was gradually added and dissolved over 2 hours (pH = 3.2). A 5% by mass hydrochloric acid solution was added to this solution to adjust the pH to 2.7, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 250 g of water was added and heated to 75 ° C., and 15.7 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.2). Sodium carbonate 1.4g was added to this solution, and it was set to pH = 10.1, Then, it filtered, and it was set as the solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 27 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.7). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 175 μS / cm. Then, it dried for 3 days at 50 degreeC with the shelf type warm air dryer, and salt-forming dye A-6 was obtained (yield = 31.2g).
About obtained salt-forming dye A-6, it was 428 ppm when content of all the chlorine was measured similarly to salt-forming dye A-1, and it was 18 ppm when content of iron was measured.
About the obtained salt forming dye A-6, when abundance ratio was measured by HPLC similarly to salt forming dye A-5, triphenylmethane basic dye C: triphenylmethane basic dye D = 90.2: 9 8%.

(Production Example A-7)
Triphenylmethane basic dye C: triphenylmethane basic dye D = 70: 30% and disazo acid dye C.I. I. Synthesis of Salt-Forming Dye A-7 with Acid Red 97 [Salt-Forming Dye A-7]
The chemical formula of the salt-forming dye A-7 is the same as the chemical formula (A-5) of the salt-forming dye A-5.
1400 g of water is put in a 2 L beaker and heated to 75 ° C., 20.0 g of triphenylmethane basic dye C (iron content 35 ppm) and 8.1 g of triphenylmethane basic dye D (iron content 37 ppm) are added. This was gradually added and dissolved over 2 hours (pH = 3.1). A 5 mass% hydrochloric acid solution was added to this solution to adjust the pH to 2.5, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 320 g of water was added and heated to 75 ° C., and 20.4 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.2). To this solution, 1.8 g of sodium carbonate was added to adjust the pH to 10.0, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 37 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.2). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 271 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and salt-forming dye A-7 was obtained (yield = 34.7g).
About obtained salt-forming dye A-7, it was 423 ppm when content of all the chlorine was measured similarly to salt-forming dye A-1, and it was 17 ppm when content of iron was measured.
When the abundance ratio of the obtained salt-forming dye A-7 was measured by HPLC in the same manner as the salt-forming dye A-5, triphenylmethane basic dye C: triphenylmethane basic dye D = 71.3: 28 0.7%.

２Ｌビーカーに水１７００ｇを入れて７５℃に加熱し、３５．４ｇのトリフェニルメタン塩基性染料Ｃ（鉄含有量６４３ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝３．１）。この溶液に５質量％の塩酸溶液を加えｐＨ＝２．５とした後濾過し、濾液を３Ｌビーカーへ移して、溶液−Ａとした。別な１Ｌビーカーに水４１０ｇを入れて７５℃に加熱し、３８．７ｇのドデシルジフェニルエーテルジスルホン酸ナトリウム（５０質量％）をこれに徐々に加え２時間かけて溶解させた。この溶液に炭酸ナトリウム２．３ｇを加えｐＨ＝１０．０とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを４１分間で滴下し５０℃にて１時間反応した（ｐＨ＝７．４）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が１８５μＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、比較造塩染料Ｂ−１を得た（収量＝６０．５ｇ）。
得られた比較造塩染料Ｂ−１について、造塩染料Ａ−１と同様に、全塩素の含有量を測定したところ４６８ｐｐｍであり、鉄の含有量を測定したところ３２５ｐｐｍであった。
得られた比較造塩染料Ｂ−１の吸光度を、造塩染料Ａ−１と同様に測定した。結果を図３に示した。 (Comparative Production Example B-1)
Synthesis of Salt-Forming Dye B-1 with Triphenylmethane Basic Dye C and Dodecyl Diphenyl Ether Disulfonic Acid [Comparative Salt-Forming Dye B-1]

1700 g of water was put in a 2 L beaker and heated to 75 ° C., and 35.4 g of triphenylmethane basic dye C (iron content 643 ppm) was gradually added thereto and dissolved over 2 hours (pH = 3.1). ). A 5 mass% hydrochloric acid solution was added to this solution to adjust the pH to 2.5, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 410 g of water was added and heated to 75 ° C., and 38.7 g of sodium dodecyl diphenyl ether disulfonate (50 mass%) was gradually added thereto and dissolved over 2 hours. To this solution, 2.3 g of sodium carbonate was added to adjust the pH to 10.0, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 41 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.4). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 185 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and comparative salt-forming dye B-1 was obtained (yield = 60.5g).
As for the obtained comparative salt-forming dye B-1, the total chlorine content was measured to be 468 ppm, and the iron content was measured to be 325 ppm in the same manner as the salt-forming dye A-1.
The absorbance of the obtained comparative salt-forming dye B-1 was measured in the same manner as the salt-forming dye A-1. The results are shown in FIG.

２Ｌビーカーに水１０００ｇを入れて７５℃に加熱し、２０．０ｇのトリフェニルメタン塩基性染料Ｃ（鉄含有量４０ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた後（ｐＨ＝２．８）、濾過し、溶液−Ａとした。別な１Ｌビーカーに水２３０ｇを入れて７５℃に加熱し、７．７ｇのＣ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ３６をこれに徐々に加え２時間かけて溶解させた。この溶液に炭酸ナトリウム１．３ｇを加えｐＨ＝１０．２とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを２０分間で滴下し５０℃にて１時間反応した（ｐＨ＝６．８）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が１．３ｍＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、比較造塩染料Ｂ−２を得た（収量＝２９．０ｇ）。
得られた比較造塩染料Ｂ−２について、造塩染料Ａ−１と同様に、全塩素の含有量を測定したところ１５２４ｐｐｍであり、鉄の含有量を測定したところ２６ｐｐｍであった。 (Comparative Production Example B-2)
Triphenylmethane basic dye C and monoazo acid dye C.I. I. Synthesis of Comparative Salt-Forming Dye B-2 with Acid Yellow 36 [Comparative Salt-Forming Dye B-2]

After putting 1000 g of water in a 2 L beaker and heating to 75 ° C., 20.0 g of triphenylmethane basic dye C (iron content 40 ppm) was gradually added thereto and dissolved over 2 hours (pH = 2. 8) Filtered to Solution-A. In another 1 L beaker, 230 g of water was added and heated to 75 ° C., and 7.7 g of C.I. I. Acid Yellow 36 was gradually added thereto and dissolved over 2 hours. To this solution, 1.3 g of sodium carbonate was added to adjust to pH = 10.2, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 20 minutes, and reacted at 50 ° C. for 1 hour (pH = 6.8). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 1.3 mS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and comparative salt-forming dye B-2 was obtained (yield = 29.0g).
With respect to the obtained comparative salt-forming dye B-2, the total chlorine content was measured as in the case of the salt-forming dye A-1, and it was 1524 ppm, and when the iron content was measured, it was 26 ppm.

２Ｌビーカーに水１１７０ｇを入れて７５℃に加熱し、２０．０ｇのトリフェニルメタン塩基性染料Ｂａｓｉｃ Ｖｉｏｌｅｔ ３の塩酸塩（鉄含有量５３ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた後（ｐＨ＝２．５）、濾過し、溶液−Ａとした。別な１Ｌビーカーに水２８０ｇを入れて７５℃に加熱し、１８．８ｇのＣ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ４２をこれに徐々に加え２時間かけて溶解させた。この溶液に炭酸ナトリウム１．６ｇを加えｐＨ＝１０．５とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを２０分間で滴下し５０℃にて１時間反応した（ｐＨ＝７．１）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が９６０μＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、比較造塩染料Ｂ−３を得た（収量＝３１．２ｇ）。
得られた比較造塩染料Ｂ−３について、造塩染料Ａ−１と同様に、全塩素の含有量を測定したところ１１２０ｐｐｍであり、鉄の含有量を測定したところ３１ｐｐｍであった。 (Comparative Production Example B-3)
Triphenylmethane basic dye Basic Violet 3 and disazo acid dye C.I. I. Synthesis of Comparative Salt-Forming Dye B-3 with Acid Yellow 42 [Comparative Salt-Forming Dye B-3]

After putting 1170 g of water in a 2 L beaker and heating to 75 ° C., 20.0 g of the triphenylmethane basic dye Basic Violet 3 hydrochloride (iron content 53 ppm) was gradually added thereto and dissolved over 2 hours. (PH = 2.5) and filtered to make Solution-A. In another 1 L beaker, 280 g of water was added and heated to 75 ° C., and 18.8 g of C.I. I. Acid Yellow 42 was gradually added thereto and dissolved over 2 hours. To this solution was added 1.6 g of sodium carbonate to adjust the pH to 10.5, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 20 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.1). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 960 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and comparative salt-forming dye B-3 was obtained (yield = 31.2g).
With respect to the obtained comparative salt-forming dye B-3, the total chlorine content was measured as in the case of the salt-forming dye A-1, and it was 1120 ppm. The iron content was measured, and was 31 ppm.

２Ｌビーカーに水１７００ｇを入れて７５℃に加熱し、３５．４ｇのトリフェニルメタン塩基性染料Ｃのナトリウム塩（鉄含有量６５４ｐｐｍ）をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝３．２）。この溶液に５質量％の塩酸溶液を加えｐＨ＝２．５とした後濾過し、濾液を３Ｌビーカーへ移して、溶液−Ａとした。別な１Ｌビーカーに水４１０ｇを入れて７５℃に加熱し、２７．４ｇのＣ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ ４２をこれに徐々に加え２時間かけて溶解させた（ｐＨ＝８．０）。この溶液に炭酸ナトリウム２．３ｇを加えｐＨ＝１０．０とした後濾過し、溶液−Ｂとした。溶液−Ａ及び溶液−Ｂを５０℃に加熱し、溶液−Ａに溶液−Ｂを４９分間で滴下し５０℃にて１時間反応した（ｐＨ＝７．３）。７１℃まで加熱した後３０℃まで冷却し、濾過後、電気伝導度が１９６μＳ／ｃｍになるまで水洗した。その後、棚型温風乾燥機にて５０℃で３日間乾燥し、比較造塩染料Ｂ−４を得た（収量＝５５．１ｇ）。
得られた比較造塩染料Ｂ−４について、造塩染料Ａ−１と同様に、全塩素の含有量を測定したところ４２７ｐｐｍであり、鉄の含有量を測定したところ２２５ｐｐｍであった。 (Comparative Production Example B-4)
Triphenylmethane basic dye C and disazo acid dye C.I. I. Synthesis of Comparative Salt-Forming Dye B-4 with Acid Yellow 42 [Comparative Salt-Forming Dye B-4]

1700 g of water was put in a 2 L beaker and heated to 75 ° C., and 35.4 g of triphenylmethane basic dye C sodium salt (iron content 654 ppm) was gradually added thereto and dissolved over 2 hours (pH = 3.2). A 5 mass% hydrochloric acid solution was added to this solution to adjust the pH to 2.5, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 410 g of water was added and heated to 75 ° C., and 27.4 g of C.I. I. Acid Yellow 42 was gradually added thereto and dissolved over 2 hours (pH = 8.0). To this solution, 2.3 g of sodium carbonate was added to adjust the pH to 10.0, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 49 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.3). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 196 μS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and comparative salt-forming dye B-4 was obtained (yield = 55.1g).
With respect to the obtained comparative salt-forming dye B-4, the total chlorine content was measured to be 427 ppm and the iron content was measured to be 225 ppm in the same manner as the salt-forming dye A-1.

(Comparative Production Example B-5)
Triphenylmethane basic dye C and disazo acid dye C.I. I. Synthesis of Comparative Salt-Forming Dye B-5 with Acid Red 97 [Comparative Salt-Forming Dye B-5]
The chemical formula of the salt-forming dye B-5 is the same as the chemical formula (A-1) of the salt-forming dye A-1.
1700 g of water was put in a 2 L beaker and heated to 75 ° C., and 35.4 g of triphenylmethane basic dye C (iron content 265 ppm) was gradually added thereto and dissolved over 2 hours (pH = 3.1). ). A 5% by mass hydrochloric acid solution was added to this solution to adjust the pH to 2.7, followed by filtration. The filtrate was transferred to a 3 L beaker to obtain Solution-A. In another 1 L beaker, 410 g of water was added and heated to 75 ° C., and 26.4 g of C.I. I. Acid Red 97 was gradually added thereto and dissolved over 2 hours (pH = 8.1). To this solution, 2.4 g of sodium carbonate was added to adjust to pH = 10.1, followed by filtration to obtain Solution-B. Solution-A and Solution-B were heated to 50 ° C., Solution-B was added dropwise to Solution-A over 46 minutes, and reacted at 50 ° C. for 1 hour (pH = 7.6). The mixture was heated to 71 ° C., cooled to 30 ° C., filtered, and washed with water until the electric conductivity reached 1.2 mS / cm. Then, it dried at 50 degreeC with the shelf type warm air dryer for 3 days, and comparative salt-forming dye B-5 was obtained (yield = 52.7g).
With respect to the obtained comparative salt-forming dye B-5, the total chlorine content was measured as in the case of the salt-forming dye A-1, and it was 1399 ppm, and when the iron content was measured, it was 122 ppm.

(Preparation of ink composition for ballpoint pen)
Salt-forming dyes A-1 to A-7 and comparative salt-forming dyes B-1 to B-5 and commercially available dyes were mixed in powder form, and the blending colorants 1 to 7 for Examples shown in Table 1 were mixed. And the compounding colorant 8-13 for comparative examples was prepared. In Table 1, VALIFAST YELLOW 1103 (organic amine salt of CI Acid Yellow 42), VALIFAST RED 1308 (salt-forming dye of CI Basic Red 1 and CI Acid Yellow 42), VALIFAST BLACK 1815 (organic acid salt of CI Acid Black 1) and VALIFAST BLACK 1821 (organic acid salt of CI Solvent Black 7) are oil-soluble dyes manufactured by Orient Chemical Industries.

  The ink composition for ballpoint pens of Examples 1-7 using the blending colorants 1-7 for Examples, and the ink composition for ballpoint pens of Comparative Examples 1-6 using the blending colorants 8-13 for Comparative Examples, Each was prepared. Table 2 shows the composition of each ink composition. In Table 2, polyvinyl butyral BL-1 and BH-S are polyvinyl butyral resins manufactured by Sekisui Chemical, Hilac 111 is a ketone resin manufactured by Hitachi Chemical, and YP90L is a terpene phenol resin manufactured by Yashara Chemical. Polyvinylpyrrolidone K-90 is a polymer of vinylpyrrolidone manufactured by Nippon Shokubai Co., Ltd.

  The ink compositions for ballpoint pens of Examples 1 to 3 and 5 to 7 and Comparative Examples 1 to 3, 5, and 6 were stirred with a dissolver and dispersed. The ink compositions for ballpoint pens of Example 4 and Comparative Example 4 were dispersed by a bead mill. Then, the following evaluation was performed.

(Dissolution stability evaluation of ink composition for ballpoint pens)
The ink compositions for ballpoint pens of Examples 1 to 7 and Comparative Examples 1 to 6 were each placed in a 20 mL glass bottle, sealed, completely dissolved, and left in a thermostatic bath at 0 ° C. for 1 month. Then, the surface layer and lower layer of the ink composition for ball-point pens in a glass bottle were visually observed. Thereby, the presence or absence of a film-like substance and the presence or absence of precipitates were observed. The results were evaluated in the following four stages, and the results are shown in Table 3.

No film-like substance and precipitate were observed: ○
A slight amount of film-like substance and precipitate was observed: Δ
Film-like material and precipitates were observed: x
The ballpoint pen ink colorant did not dissolve and could not be evaluated:-

(Preparation of ballpoint pen for evaluation test)
An appropriate amount of the ink composition for ballpoint pens of Examples 1 to 7 and Comparative Examples 1 to 6 was filled in a polypropylene tube having an inner diameter of 1.6 mm, and a ball (made of cemented carbide, diameter 1.0 mm) was attached to the tip. Attached to a stainless steel ball chip. Further, an ink follower was placed at the base end of the tube, the tube was inserted into a shaft tube, a cap was fitted so as to cover the ball chip, and an evaluation test ballpoint pen was produced.

(Dry-up evaluation of ink composition for ballpoint pens)
The cap of the produced ballpoint pen was taken out and allowed to stand at 25 ° C. and 65% humidity for 1 hour, and then a circle was written on the PPC paper freehand. The blur of the handwriting was evaluated in the following four stages.
Scratch was difficult to occur: ○
Scratch slightly occurred: △
Scratch was easy to occur: ×
The ballpoint pen ink colorant did not dissolve and could not be evaluated:-

Table 3 shows the evaluation results of the ink composition for ballpoint pens.

(Preparation of ink composition for marking pen)
Salt-forming dyes A-1 to A-7 and comparative salt-forming dyes B-1 to B-5 and commercially available dyes were mixed in powder form, and the blending colorants 14 to 19 for Examples shown in Table 4 were used. And the mixing | blending colorant 20-25 for a comparative example was prepared.

Ink compositions for marking pens of Examples 8 to 13 using blending colorants 14 to 19 for Examples, and Ink compositions for marking pens of Comparative Examples 7 to 12 using blending colorants 20 to 25 for Comparative Examples Were prepared respectively. Table 5 shows the composition of each ink composition. In Table 5, Marquide No. 31 is a maleic acid resin manufactured by Arakawa Chemical Industries.

  The ink compositions for marking pens of Examples 8 to 10, 12, and 13 and Comparative Examples 7, 8, and 10 to 12 were stirred with a dissolver and dispersed. The marking pen ink compositions of Example 11 and Comparative Example 9 were dispersed by a bead mill. Then, the following evaluation was performed.

(Dissolution stability evaluation of ink composition for marking pen)
Each of the marking pen ink compositions of Examples 8 to 13 and Comparative Examples 7 to 12 was placed in a 20 mL glass bottle, sealed, and allowed to stand in a thermostatic bath at 0 ° C. for 1 month. Then, the surface layer and lower layer of the marking pen ink composition in the glass bottle were visually observed. Thereby, the presence or absence of a film-like substance and the presence or absence of precipitates were observed. The results were evaluated in the following four stages. The results are shown in Table 6.
No film-like substance and precipitate were observed: ○
A slight amount of film-like substance and precipitate was observed: Δ
Film-like material and precipitates were observed: x
The marking pen ink colorant could not be evaluated because it did not dissolve:-

(Production of marking pen for evaluation test)
An appropriate amount of the marking pen ink compositions of Examples 10 to 17 and Comparative Examples 5 to 8 is filled in a marking pen having a felt pen core (product name: oily piece marker) having a pen core made of felt. A cap was fitted so as to cover, and an evaluation marking pen was produced.

(Dry-up evaluation of ink composition for marking pen)
The cap of the produced marking pen was taken out and allowed to stand at 25 ° C. and 65% humidity for 1 minute, and then a circle was written on the PPC paper freehand. The blur of the handwriting was evaluated in the following four stages.
Scratch was difficult to occur: ○
Scratch slightly occurred: △
Scratch was easy to occur: ×
The marking pen ink colorant could not be evaluated because it did not dissolve:-

The evaluation results of the marking pen ink composition are shown in Table 6.

  As is clear from Tables 3 and 6, the ball-point pen ink compositions of Examples 1 to 7 and the marking ink compositions of Examples 8 to 13 to which the present invention was applied were comparative examples outside the scope of the present invention. It was confirmed that the ink composition was excellent in performance as compared with the ink compositions 1 to 12.

(Evaluation of ball chip corrosivity of ink composition for ballpoint pens)
The ink compositions for ballpoint pens of Examples 14 to 16 and Comparative Examples 13 to 15 were prepared and subjected to the following tests.
The salt-forming dyes A-1, A-5, and A-6 and a commercially available dye (VALIFAST BLACK 1815) were each powder-mixed to prepare a blended colorant. Further, the blended colorant, the resin, and the liquid medium were stirred with a disper to prepare ink compositions for ballpoint pens of Examples 14 to 16. In the same manner, comparative ink compositions for ballpoint pens of Comparative Examples 13 to 15 were prepared using comparative salt-forming dyes B-2, B-3, and B-5.
45 mL of the ink compositions for ballpoint pens of Examples 14 to 16 and Comparative Examples 13 to 15 were placed in a 50 mL glass bottle, and all stainless steel plates (1 cm square, 3 mm in thickness) made of the same material as the ball tip of the above ballpoint pen were dipped. It was. After leaving for 1 month in a thermostatic bath at 30 ° C., the stainless steel plate was taken out, washed with methanol, the surface was observed, the degree of surface gloss loss due to corrosion was visually observed, and the following three stages were evaluated.
No surface corrosion (decrease in surface gloss): ○
Slight surface corrosion (degree of surface gloss loss) was confirmed: △
Surface corrosion (decrease in surface gloss) was clearly confirmed: ×

Table 7 shows the compositions of the ink compositions for ballpoint pens of Examples 14 to 16 and Comparative Examples 13 to 15 and the results of the corrosive evaluation.

  The ink compositions for ballpoint pens of Examples 14 to 16 did not corrode the stainless steel plate.

(Evaluation of crystal generation of ink composition for ballpoint pen)
The ink compositions for ballpoint pens of Examples 17 to 20 and Comparative Examples 16 and 17 were prepared and subjected to the following tests.
The salt-forming dyes A-1 and A-5 to A-7 and a commercially available dye (VALIFAST BLACK 1815) were powder-mixed to prepare a blended colorant. Further, the blended colorant, resin, and liquid medium were stirred with a disper to prepare ink compositions for ballpoint pens of Examples 17-20. In the same manner, ballpoint pen ink compositions of Comparative Examples 16 and 17 were prepared using comparative salt-forming dyes B-4 and B-5.
45 mL of the ink compositions for ballpoint pens of Examples 17 to 20 and Comparative Examples 16 and 17 were placed in a 50 mL glass bottle and left in a thermostatic bath at 60 ° C. for 1 month. Each of the ink compositions for ballpoint pens of Examples and Comparative Examples was placed on a slide, and the generation of crystals was observed with an optical microscope (400 times) and evaluated in the following three stages.
There was no crystal at all: ○
Slight crystals were confirmed: △
A large amount of crystals was confirmed: ×
(Writing evaluation of ink composition for ballpoint pen)
Using the ink compositions for ballpoint pens of Examples 17 to 20 and Comparative Examples 16 and 17 obtained above, ballpoint pens for evaluation tests were produced in the same manner as in Examples 1 to 7. Using the produced ballpoint pen, a circle was written freehand on PPC paper. The blur of the handwriting was evaluated in the following four stages.
I was able to write smoothly, and it was hard for wrinkles to occur: ○
I was able to write, but some blurring occurred: △
It was difficult to write and a lot of blurring occurred: ×
Could not write: XX

Table 8 shows the compositions of the ink compositions for ballpoint pens of Examples 17 to 20 and Comparative Examples 16 and 17, and the results of crystal generation evaluation and writing property evaluation.

  The ink compositions for ballpoint pens of Examples 17 to 20 did not precipitate crystals.

  The salt-forming dye which is the colorant of the present invention, and writing tool dyes and black colorants containing the same are used as coloring agents for ink compositions for writing tools such as ballpoint pens and marking pens together with desired dyes and pigments. The ink composition for a writing instrument of the present invention is used by being filled in a writing instrument.

Claims (7)

The following chemical formula (1)

(In the chemical formula (1), a is a positive number of 1 to 2, b is a positive number of 1 to 2, and Y ^b− is the following chemical formula (2).

(In the chemical formula (2), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom)
R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom. And M and N are each independently a hydrogen atom or an alkali metal, m is a number from 0 to 1, n is a number from 0 to 1, except that m and n are both 1)
Is)
A salt-forming dye represented by the following chemical formula (5)

(In the chemical formula (5), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom)
R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom. is there)
The coloring agent characterized by containing the salt-forming dye represented by these. The salt-forming dye represented by the chemical formula (1) has an equivalent ratio of cation to anion of 2: 1 and the following chemical formula (4)

(In the chemical formula (4), R ¹ is a hydrogen atom or the following chemical formula (3)

(In the chemical formula (3), R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a halogen atom)
R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, an amino group, a nitro group, or a halogen atom. is there)
The colorant according to claim 1, wherein   The colorant according to claim 1 or 2, wherein a total chlorine amount of the salt-forming dye measured by a combustion coulometry method is 50 to 1000 ppm.   The colorant according to any one of claims 1 to 3, wherein the iron content of the salt-forming dye is 100 ppm at the maximum.   The abundance ratio of the salt-forming dye represented by the chemical formula (4) and the salt-forming dye represented by the chemical formula (5) measured by high performance liquid chromatography is 99.1 to 85.0: 0.9. The colorant according to claim 2, which is ˜15.0%.   An ink composition for a writing instrument, comprising the colorant according to any one of claims 1 to 5.   The ink composition for a writing instrument according to claim 6, comprising a liquid medium and a resin that dissolves in the liquid medium.

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