JPH08333517A - Salt-forming dye of new triphenylmethane and ink composition - Google Patents

Abstract

PURPOSE: To obtain a blue new dye excellent in solubility against an alcoholic solvent and color fastness. CONSTITUTION: This is a dye of formula I [R<1> is a 3-6C alkyl; R<2> is H or methyl; R<3> is a 1-4C alkyl or a 1-4C alkyloxy; M<+> is a 6-20C organic ammonium; (n)=1, 2]. The dye is obtained by condensing 1mol of benzaldehyde with 2mol of N-benzyl-N-R<1> -m-R<2> -aniline of formula II, sulfonating the condensate with sulfuric acid, subsequently oxidizing with manganese dioxide and further reacting the reaction product with p-R<3> -aniline. The obtained anion component is easily separated from the reaction system in a form of an acid by acid precipitation. Further, the anion component can be converted into an acid form, a sodium salt or a potassium salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a triphenylmethane salt forming dye and an ink composition containing the same, and more particularly to a blue triphenylmethane salt forming dye having excellent solubility in an alcohol solvent.

[0002]

2. Description of the Related Art Conventionally, an ink composition has been used for recording on a recording material such as paper. As the ink composition, a composition in which various dyes or pigments are dissolved or dispersed in a liquid medium or a binder is generally used.

[0003] Among these, in the organic pigment dispersion type ink, the pigment easily precipitates and aggregates with time. Therefore, a complicated alteration preventing treatment such as dispersion processing is required in the manufacturing process, and the manufacturing cost is high.

On the other hand, the ink in which the dye is dissolved does not require dispersion processing in the manufacturing process. Therefore, the dye-dissolving ink can be manufactured more easily than the pigment-dispersing ink. However, the dye-dissolving oil-based ink has solvent toxicity, and the dye-dissolving water-based ink has a problem that it is slow to dry and lacks versatility. Therefore, in recent years, dyes having excellent solubility in alcoholic solvents have been demanded.

Alcohol-soluble dyes have hitherto been known as Victria Pure Blu.
e) and salt-forming dyes of basic dyes and acid dyes such as Methyl Violet, salt-forming dyes of basic dyes and fatty acids or resin acids, CI Direct Blue 87 and CI Acid Salt-forming dyes of acid dyes such as Blue 158 and organic amines are known.

However, such conventional alcohol-soluble dyes have insufficient solubility in alcoholic solvents and insufficient light resistance. Therefore, the ink composition using these is inferior in stability over time, and the solid content of the dye tends to be deposited when environmental conditions such as temperature and humidity are changed. In addition, the handwriting is inferior in water resistance and light resistance, that is, fastness.

[0007]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to provide a dye having excellent solubility in alcoholic solvents and excellent fastness, and An object is to provide an ink composition containing the same.

[0008]

The present invention is based on the formula

[0009]

Embedded image

[In the formula, R ¹ is an alkyl group having 3 to 6 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is 1 carbon atom.
Is an alkyl group having 4 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms, M ⁺ is an organic ammonium having 6 to 20 carbon atoms or a basic dye, and n is 1 or 2. ] To provide a triphenylmethane salt forming dye represented by
Thereby, the above object is achieved.

The triphenylmethane salt forming dye of the present invention has the formula

[0012]

Embedded image

[In the formula, R ¹ , R ² and R ³ have the same meanings as described above, and X is a hydrogen atom or an alkali metal. ] A triphenylmethane type water-soluble dye having a sulfone group having the structure shown in (hereinafter referred to as "anion component") is obtained by salt formation with a cation component such as an organic amine and a basic dye.

The anionic component used in the present invention is a water-soluble dye. As a general synthetic method, first, 1 mol of benzaldehyde and ² mol of N-benzyl-NR ¹ -mR ² -aniline are condensed, sulfonated with sulfuric acid, oxidized with manganese dioxide, and further reacted with pR ³ -aniline. This synthetic method is represented by the following formula.

[0015]

[Chemical 4]

The obtained anion component can be easily separated from the reaction system in the acid form by acid precipitation. Further, this anion component can be converted into an acid form, sodium salt and potassium salt by a conventional method.

The organic amine used as the cation component in the present invention has a total carbon number of 6 to 20, preferably 6 to 17,
More preferably, there are aliphatic or alicyclic amines in the range of 6 to 13, alkanolamine derivatives, diamine derivatives and guanidine derivatives. For example, dimethylamine,
When an amine having a carbon number of less than 6 such as diethylamine, propylamine and ethanolamine is used, the resulting salt-forming dye has too high hydrophilicity. 20 carbons
When an amine exceeding the above range is used, the solubility of the resulting salt-forming dye in an alcohol solvent is deteriorated.

Specific examples of the organic amine which can be preferably used as the cation component of the present invention include, in the form of free amine,
Hexylamine, Pentylamine, Octylamine, 2-
Aliphatic amines such as ethylhexylamine, di- (2-ethylhexyl) amine and dodecylamine; cycloaliphatic amines such as cyclohexylamine and di-cyclohexylamine; 3-propoxypropylamine, di- (3-ethoxy) Propyl) amine, 3-butoxypropylamine,
Alkoxyalkylamines such as octoxypropylamine and 3- (2-ethylhexyloxy) propylamine; containing alkanol groups such as N-cyclohexylethanolamine, N-dodecylethanolamine and N-dodecylimino-di-ethanol Amines; diamines such as diethylaminopropylamine and dibutylaminopropylamine; and 1,3-diphenylguanidine, 1-
Examples thereof include guanidine (derivative) such as o-tolylguadinine and di-o-tolylguadinine.

Aliphatic amines such as cyclohexylamine and di-cyclohexylamine as the cation component of the present invention; 3-propoxypropylamine, di- (3-ethoxypropyl) amine, 3-butoxypropylamine, octoxy. Alkoxyalkylamines such as propylamine and 3- (2-ethylhexyloxy) propylamine are especially preferred.

Also, various basic dyes can be used as the cation component of the present invention. The basic dye used in the present invention is not particularly limited as long as it has a vivid color and excellent light resistance. Examples of the basic dye that is preferably used include triphenylmethane-based dyes. Particularly preferably usable are "Victoria Blue BOH", "Victoria Blue BH" and "Victoria Blue BOH" manufactured by Hodogaya Chemical Co., Ltd.
Pure Blue BOH "and the like.

The salt forming dye of the present invention is produced by a method well known to those skilled in the art. For example, 1 mol of an anion component is dissolved in water to form a 2 to 10% solution, and then an aqueous solution of a cation component in a molar number corresponding to the number of acid groups of the water-soluble anionic dye is added dropwise to the solution. By stirring in an atmosphere for 1 to 5 hours, the triphenylmethane salt forming dye of the present invention can be obtained.

At this time, with respect to 1 mol of the anion component,
Up to about 2.2 moles of cationic component can be used. If the amount of the cation component used exceeds 2.2 moles, a water washing step such as desalting is required to remove the unreacted cation component, which is complicated.

When an organic amine is used as the cation component, the cation component is generally used in the form of an inorganic acid (eg hydrochloric acid or sulfuric acid) salt or an organic acid (eg formic acid or acetic acid) salt. However, it is also possible to react by adding the free organic amine directly.

The present invention also provides an ink composition containing a triphenylmethane salt forming dye represented by formula (I) and an alcohol solvent. As used herein, the term "alcoholic solvent" refers to water-miscible alcohols and glycols (including glycol ethers and esters). The present invention provides a non-polluting ink mainly containing an alcohol solvent as an ink liquid medium.

Examples of alcoholic solvents used in the oily liquid medium of the present invention include monohydric alcohols (for example, ethanol, n-propanol, isopropanol, n-butanol, amyl alcohol, benzyl alcohol, cyclohexanol and diacetone alcohol). Alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monoethyl ether; Glycol monoacetate such as acetate and propylene glycol monoacetate etc.), and dihydric alcohol ( For example, ethylene glycol, diethylene glycol, trimethylene glycol,
Triethylene glycol, tetraethylene glycol,
Glycols such as polyethylene glycol, propylene glycol and butanediol).

In the present invention, by appropriately mixing an organic solvent such as low toxicity or nontoxic ethanol, n-propanol, isopropanol, benzyl alcohol, ethylene glycol, phenyl glycol, propylene glycol monoalkyl ether and lactic acid ester, It is possible to prepare an ink that does not cause a sanitary problem.

In the oily liquid medium of the present invention, 2-pyrrolidone, N-methylpyrrolidone, N- (2-
Hydrophilic organic solvents such as hydroxyethyl) pyrrolidone, methyl lactate, ethyl lactate, and butyl lactate can be used together in an amount of less than 30% by weight based on the total weight of the ink composition.

The ink composition of the present invention contains 1 to 30% by weight, preferably 5 to 20% by weight, of the salt-forming dye of the present invention, based on the total amount of the ink composition, and 60 to 90% by weight, preferably 75 to 85% by weight of alcoholic solvent and 5-15% by weight, preferably 8
It can be obtained by (heating) dissolution in a liquid medium composed of ˜12% by weight of the resin for ink and then filtration. At this time, if necessary, a small amount of additives such as nonionic surfactants and rust preventives may be added.

The amount of the salt-forming dye contained in the ink composition of the present invention varies depending on the use of the ink. Generally, it is used in an amount of 15 to 25% by weight for a ballpoint pen, 5 to 15% by weight for a marking pen, and 3 to 10% by weight for an inkjet recording.

The ink resin which can be preferably used in the ink composition of the present invention is not particularly limited as long as it is soluble in alcohol. Examples thereof include low-condensation products of vinylpyrrolidone, which are widely used as resins for this type of ink, alkyd resins, acrylic resins, phenol resins, styrene-maleic acid resins, ketone resins and rosin resins.

[0031]

EXAMPLES Examples 1 to 14 describe the production of the salt-forming dye of the present invention.

Example 1 Synthesis of anion component By the method disclosed in the document BIOS 1157,53 described below,
The anion component was synthesized. First, 106 g of benzaldehyde
(1 mol) of N-benzyl-N-butyl-m-toluidine 508g (2mo
l) was condensed and sulfonated to introduce trisulfonic acid groups. After oxidizing this with manganese dioxide (MnO ₂ ), it was reacted with 137 g (1 mol) of p-phenetidine to give the formula

[0033]

Embedded image

500 g of the anion component shown in was obtained.

Synthesis of triphenylmethane salt forming dye 91 g (0.1 mol) of the obtained anion component was dissolved in water having a water temperature of 60 ° C. to obtain a 3% aqueous solution. This was adjusted to pH 7 and filtered. While stirring this filtrate, the cationic component 3- (2-
Ethylhexyloxy) propylamine 22.5 g (0.12 mol)
The acetic acid aqueous solution of was added dropwise over 40 minutes. After reacting at room temperature for 2 hours, the pH was adjusted to 5 to 6 and heated to 40 ° C. to coarsen particles. After that, it is filtered, washed with water, and dried to give 97g of blue salt-forming dye.
I got

Then, the dye is gradually added to 100 ml of ethanol at room temperature with stirring, and spotted on filter paper No. 2 (manufactured by Advantic) to determine the solubility (g / g) depending on whether the dye is deposited or not. 100 ml) was measured.

The structure of the obtained dye is shown in Table 1, and the hue, maximum absorption wavelength (λmax) and solubility in ethanol are shown in Table 4.
Visible absorption spectrum (dye concentration in methanol solvent 10 ^-5 g / m
l) is shown in FIG.

Examples 2 to 6 Instead of 3- (2-ethylhexyloxy) propylamine, the cation components M ⁺ (0.15mo) shown in Tables 1 and 2 respectively.
Example 2 is performed in the same manner as in Example 1 except that (l) is used.
~ 6 salt-forming dyes were obtained. The structures of the obtained dyes are shown in Tables 1 and 2, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Example 7 N-benzyl-N-butyl-m-toluidine was replaced by N-benzyl-N-butylaniline (2 mol), and the cation was replaced by 3- (2-ethylhexyloxy) propylamine. A salt-forming dye was obtained in the same manner as in Example 1 except that 3-ethylheptylamine (0.15 mol) as a component was used. The structure of the obtained dye is shown in Table 2, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Example 8 Instead of p-phenetidine, p-ethylaniline (1 mol)
In place of 3- (2-ethylhexyloxy) propylamine, butoxypropylamine (0.1
A salt-forming dye was obtained in the same manner as in Example 1 except that 5 mol) was used. The structure of the obtained dye is shown in Table 2, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Example 9 N-benzyl-N-hexylaniline (2 mol) was used instead of N-benzyl-N-butyl-m-toluidine, and p-butoxyaniline (1 mol) was used instead of p-phenetidine. A salt-forming dye was obtained in the same manner as in Example 1 except that it was used. The structure of the obtained dye is shown in Table 2, and the hue and maximum absorption wavelength (λma
x) and ethanol solubility are shown in Table 4.

Example 10 N-benzyl-N-propyl-m-toluidine was replaced by N-benzyl-N-propylaniline (2 mol), and p-phenetidine was replaced by p-butylaniline (1 mol). Use 3- (2-
A salt-forming dye was obtained in the same manner as in Example 1 except that butoxypropylamine (0.15 mol) as a cationic component was used instead of ethylhexyloxy) propylamine. The structure of the obtained dye is shown in Table 2, the hue and the maximum absorption wavelength.
(λmax) and ethanol solubility are shown in Table 4.

Example 11 Instead of 3- (2-ethylhexyloxy) propylamine, the cation component Victoria Pure Blue Base (C.
A salt-forming dye was obtained in the same manner as in Example 1 except that 0.15 mol of I.Base Blue 7) was used. The structure of the obtained dye is shown in Table 3, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Example 12 N-benzyl-N-butyl-m-toluidine was replaced with N-benzyl-N-butylaniline (2 mol), and the cation was replaced with 3- (2-ethylhexyloxy) propylamine. Ingredient Victoria Blue Base 0.15mo
A salt-forming dye was obtained in the same manner as in Example 1 except that 1 was used. The structure of the obtained dye is shown in Table 3, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Example 13 N-benzyl-N-butyl-m-toluidine was replaced by N-benzyl-N-butylaniline (2 mol), and the cation was replaced by 3- (2-ethylhexyloxy) propylamine. Ingredient methyl violet base (CI Base Violet 1) 0.1
A salt-forming dye was obtained in the same manner as in Example 1 except that 5 mol was used. The structure of the obtained dye is shown in Table 3, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Example 14 Instead of p-phenetidine, p-butylaniline (1 mol)
Was used in the same manner as in Example 1 except that 0.15 mol of the cation component, Crystal Violet 3 (CIBase Violet 3), was used instead of 3- (2-ethylhexyloxy) propylamine. . The structure of the obtained dye is shown in Table 3, and the hue, maximum absorption wavelength (λmax) and ethanol solubility are shown in Table 4.

Comparative Example 1 The anionic component obtained in Example 1 was used as a comparative dye. Table 4 shows the hue, maximum absorption wavelength (λmax) and solubility of this dye in ethanol.

Comparative Example 2 Formula

[0049]

[Chemical 6]

Victoria Pure Blue BOH (CIBase Blue 7), which is commercially available from Hodogaya Chemical Co., Ltd., was used as a comparative dye. Hue of this dye, maximum absorption wavelength (λmax)
And the solubility in ethanol is shown in Table 4.

Comparative Example 3 The same procedure as in Example 1 was repeated except that Kayanol Cyanine G (CI Acid Blue 90) commercially available from Nippon Kayaku Co., Ltd. was used in place of the anion component.

[0052]

[Chemical 7]

A salt-forming dye shown by was obtained. Table 4 shows the hue, maximum absorption wavelength (λmax) and solubility of this dye in ethanol.

Comparative Example 4 Instead of the anion component, Kayanol Cyanine G (CIAcid Blue 90) commercially available from Nippon Kayaku Co., Ltd. was used.
-(2-Ethylhexyloxy) propylamine instead of Victoria Pure Blue Base (CIBase Blue 7)
In the same manner as in Example 1 except that

[0055]

Embedded image

A salt-forming dye shown by was obtained. Table 4 shows the hue, maximum absorption wavelength (λmax) and solubility of this dye in ethanol.

Comparative Example 5 Instead of the anion component, Kayanol Cyanine 6B (CIAcid Blue 83) commercially available from Nippon Kayaku Co., Ltd. was used.
Example except that butoxypropylamine was used instead of 3- (2-ethylhexyloxy) propylamine
Similar to 1, the expression

[0058]

[Chemical 9]

A salt-forming dye shown by was obtained. Table 4 shows the hue, maximum absorption wavelength (λmax) and solubility of this dye in ethanol.

Comparative Example 6 Instead of the anion component, Kayanol Cyanine 6B (CIAcid Blue 83) commercially available from Nippon Kayaku Co., Ltd. was used,
In the same manner as in Example 1 except that methyl violet base (CI Basic Violet 1) was used instead of 3- (2-ethylhexyloxy) propylamine, the formula

[0061]

[Chemical 10]

A salt-forming dye according to Comparative Dye Example 6 shown in the above was obtained.
Table 4 shows the hue, maximum absorption wavelength (λmax) and solubility of this dye in ethanol.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4] Hue, maximum absorption wavelength and solubility of the salt-forming dye of the present invention Example No. Hue Maximum absorption wavelength (nm) Ethanol solubility (g / 100ml) 1 Blue 610 25 2 Blue 610 20 3 Blue 610 20 4 Blue 610 20 5 Blue 610 20 6 Blue 610 17 7 Blue 605 20 8 Blue 600 20 9 Blue 600 30 10 Blue 600 25 11 Blue 605 17 12 Blue 605 17 13 Blue Purple 580 20 14 Blue Purple 580 20 Comparative Example 1 Blue 610 5 Comparative Example 2 Blue 608 2 Comparative Example 3 Blue 610 15 Comparative Example 4 Blue 600 10 Comparative Example 5 Blue 610 15 Comparative Example 6 Blue Purple 580 10

Examples 15-27 describe ink compositions prepared from the novel salt-forming dyes obtained in Examples 1-14 and comparative dyes.

In Examples 15 to 20 and Comparative Examples 7 to 9, blue ink compositions for marker pens were prepared and evaluated.

Example 15

[Table 5] Salt-forming dye (Example 1) 7 g Ethanol 68 g Benzyl alcohol 5 g Ethyl lactate 10 g Ketone resin (trade name: SYNTHETIC RESINS, manufactured by Huls) 5 g Phenol resin (trade name: Tamanol 510, manufactured by Arakawa Chemical Co., Ltd.) 5 g

The above-mentioned composition was put in a 200 ml closed container and dissolved by stirring at 50 to 60 ° C. for 3 hours. After that, the solution obtained was filtered through a membrane filter of 1 μm to prepare a blue ink composition for a marker pen. By evaluating the temporal stability of this ink composition and the water resistance and light resistance of handwriting,
The obtained results are shown in Table 13.

Example 16

[Table 6] Salt-forming dye (Example 2) 7 g Ethanol 61 g Propylene glycol monomethyl ether 10 g Ethyl lactate 10 g Ketone resin (trade name: SYNTHETIC RESINS, manufactured by Huls) 7 g Phenol resin (trade name: Hitanole 1501, Hitachi Chemical Co., Ltd.) Made) 5g

A blue ink composition for a marker pen was prepared in the same manner as in Example 15. The stability with time of this ink composition and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 13.

Example 17

[Table 7] Salt-forming dye (Example 3) 8 g Ethanol 57 g Propylene glycol monomethyl ether 10 g Ethyl lactate 10 g Phosphanol RA-600 (manufactured by Toho Chemical Co., Ltd.) 5 g Ketone resin (trade name: SYNTHETIC RESINS, manufactured by Huls) 5 g Phenol Resin (Brand name: Hitanol 1501, Hitachi Chemical Co., Ltd.) 5g

A blue ink composition for a marker pen was prepared in the same manner as in Example 15. The stability with time of this ink composition and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 13.

Example 18

[Table 8] Salt-forming dye (Example 4) 8g Ethanol 10g Propylene glycol monomethyl ether 65g Benzyl alcohol 5g Ketone resin (trade name: SYNTHETIC RESINS, manufactured by Huls) 10g Phenol resin (trade name: Tamanol 510, Arakawa Chemical Co., Ltd.) Made) 2g

A blue ink composition for a marker pen was prepared in the same manner as in Example 15. The stability with time of this ink composition and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 13.

Example 19

[Table 9] Salt-forming dye (Example 8) 7 g Ethanol 68 g Benzyl alcohol 5 g Ethyl lactate 10 g Ketone resin (trade name: SYNTHETIC RESINS, manufactured by Huls) 5 g Phenol resin (trade name: Tamanol 510, manufactured by Arakawa Chemical Co., Ltd.) 5 g

A blue ink composition for a marker pen was prepared in the same manner as in Example 15. The stability with time of this ink composition and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 13.

Example 20

[Table 10] Salt-forming dye (Example 11) 7g Ethanol 61g Propylene glycol monomethyl ether 10g Ethyl lactate 10g Ketone resin (Product name: SYNTHETIC RESINS, manufactured by Hüls) 7g Phenolic resin (Product name: Hitanol 1501, Hitachi Chemical Co., Ltd.) Made) 5g

A blue ink composition for a marker pen was prepared in the same manner as in Example 15. The stability with time of this ink composition and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 13.

Comparative Example 7 A blue ink composition for a marker pen was prepared in the same manner as in Example 15 except that the salt-forming dye obtained in Comparative Example 3 was used instead of the salt-forming dye of Example 1. By evaluating the temporal stability of this ink composition and the water resistance and light resistance of handwriting,
The obtained results are shown in Table 13.

Comparative Example 8 A blue ink composition for a marker pen was prepared in the same manner as in Example 20 except that the salt-forming dye obtained in Comparative Example 4 was used instead of the salt-forming dye of Example 11. By evaluating the temporal stability of this ink composition and the water resistance and light resistance of handwriting,
The obtained results are shown in Table 13.

Comparative Example 9 Instead of the salt forming dye of Example 1, a salt forming dye of an acid dye and a basic dye (trade name: Varifast Blue
st Blue) 1603, manufactured by Orient Chemical Industry Co., Ltd.), and a blue ink composition for a marker pen was prepared in the same manner as in Example 15. The stability with time of this ink composition and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 13.

[0084]

[Water resistance test and evaluation] The ink composition was set in an ink container for various purposes, written on filter paper No. 2 (manufactured by Advantic), and immersed in water for 1 hour. After pulling the test paper from water and air-drying, the handwriting was observed and evaluated.

[0085]

[Table 11] Evaluation criteria 5: 100% to 90% of handwriting before the test remains 4: 90% to 70% of handwriting before the test 3: 70% to 50% of handwriting before the test 2: 50% handwriting before the test ~ 30% remaining 1: 30 to 10% of handwriting before the test 0: 10 to 0% of handwriting before the test

[0086]

[Light resistance test and evaluation] Set the ink composition in ink containers for various purposes, and use art paper (trade name: Art Post 24
No. 0, manufactured by Kanzaki Paper Co., Ltd.), irradiated with light for 5 hours in a fade meter (carbon arc method), observed the handwriting, and evaluated by the same evaluation criteria as the water resistance test.

[0087]

[Stability test and evaluation over time] Take 30 ml of the ink composition in a glass bottle, put it in a low temperature-high temperature constant temperature tank (model name: incubator, manufactured by Sanyo Electric Co., Ltd.) and test for 3 months (test condition: temperature range -10 ~ After repeating (at 50 ° C. for 60 minutes), the presence or absence of precipitation of solid components such as dyes and increase in viscosity of the ink composition was observed and evaluated.

[0088]

[Table 12] Evaluation criteria ⊚: Thickening of ink composition and no precipitation of solids ○: Thickening of ink composition but no precipitation of solids ×: Thickening of ink composition and precipitation of solids

[0089]

[Table 13] ^a Water resistance was evaluated by printing on art paper.

In Examples 21 to 23 and Comparative Examples 10 to 12, blue ink compositions for ballpoint pens were prepared and evaluated.

Example 21

[Table 14] Salt-forming dye (Example 5) 25 g Phenyl glycol 45 g Benzyl alcohol 12 g Oleic acid 5 g Polyvinylpyrrolidone 1 g Ketone resin (trade name: Hilac 111, manufactured by Hitachi Chemical Co., Ltd.) 12 g

The above-mentioned composition was put in a 200 ml closed container and dissolved by stirring at 70 to 80 ° C. for 3 hours. After that, the obtained solution was filtered through diatomaceous earth to prepare a blue ink composition for a ballpoint pen. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the results obtained are shown in Table 18.

Example 22

[Table 15] Salt-forming dye (Example 7) 25 g Phenyl glycol 45 g Benzyl alcohol 12 g Oleic acid 5 g Polyvinylpyrrolidone 1 g Ketone resin (trade name: Hilac 111, manufactured by Hitachi Chemical Co., Ltd.) 12 g

A blue ink composition for a ballpoint pen was prepared in the same manner as in Example 21. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in a table.
Shown in 18.

Example 23

[Table 16] Salt-forming dye (Example 13) 25g Phenyl glycol 45g Benzyl alcohol 12g Oleic acid 5g Polyvinylpyrrolidone 1g Ketone resin (trade name: Hilac 111, manufactured by Hitachi Chemical Co., Ltd.) 12g

A blue ink composition for a ballpoint pen was prepared in the same manner as in Example 21. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in a table.
Shown in 18.

Comparative Example 10 A blue ink composition for a ballpoint pen was prepared in the same manner as in Example 22 except that the salt-forming dye obtained in Comparative Example 5 was used instead of the salt-forming dye of Example 7. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the results obtained are shown in Table 18.

Comparative Example 11 A blue ink composition for a ballpoint pen was prepared in the same manner as in Example 23, except that the salt-forming dye obtained in Comparative Example 6 was used instead of the salt-forming dye of Example 13. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the results obtained are shown in Table 18.

Comparative Example 12

[Table 17] Organic salt of copper phthalocyanine acid dye (trade name: Varifast Blue 2605, manufactured by Orient Chemical Industry Co., Ltd.) 11g Victoria Pure Blue Base 8g Methyl Violet Base 6g Phenylglycol 45g Benzyl Alcohol 12g Oleic Acid 5g Polyvinylpyrrolidone 1g Ketone resin (Product name: Hirac Hitachi Chemical Co., Ltd.) 12g

A blue ink composition for a ballpoint pen was prepared in the same manner as in Example 21. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in a table.
Shown in 18.

[0101]

[Table 18] ^a Water resistance was evaluated by printing on art paper.

In Examples 24 to 27 and Comparative Examples 13 to 15, blue ink compositions for inkjet recording were prepared and evaluated.

Example 24

[Table 19] Salt-forming dye (Example 1) 7g Ethanol 67g Ethyl lactate 10g 2-Pyrrolidone 10g Ketone resin (Product name: SYNTHETIC RESINS, manufactured by Hüls) 13g Phenolic resin (Product name: Hitanol 1501, manufactured by Hitachi Chemical Co., Ltd.) ) 3g

The above-mentioned formulation was put in a 200 ml closed container, and dissolved by stirring at 50-60 ° C. for 3 hours. After that, the resulting solution was filtered with a membrane filter of 1 μm to prepare a blue ink composition for inkjet recording. Inkjet printers (model name: JET
-A-MAR, manufactured by Mattheus) is used to print on neutral paper (trade name: P (A4), Xerox Co., Ltd.) and corrugated paper, and the stability of the ink composition over time and the handwriting The water resistance and light resistance were evaluated, and the obtained results are shown in Table 23.

Example 25

[Table 20] Salt-forming dye (Example 3) 7g Ethanol 64g Benzyl alcohol 12g Ethyl lactate 10g Phosphanol RA-600 (manufactured by Toho Chemical Co., Ltd.) 2g Phenolic resin (trade name: Hitanol 1501, manufactured by Hitachi Chemical Co., Ltd.) 5g

A blue ink composition for inkjet recording was prepared in the same manner as in Example 24. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 23.

Example 26

[Table 21] Salt-forming dye (Example 9) 7 g Ethanol 67 g Ethyl lactate 10 g 2-Pyrrolidone 10 g Ketone resin (trade name: SYNTHETIC RESINS, manufactured by Hüls) 13 g Phenol resin (trade name: Hitanole 1501, manufactured by Hitachi Chemical Co., Ltd.) ) 3g

A blue ink composition for inkjet recording was prepared in the same manner as in Example 24. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 23.

Example 27

[Table 22] Salt-forming dye (Example 11) 7 g Ethanol 64 g Benzyl alcohol 12 g Ethyl lactate 10 g Phosphanol RA-600 (trade name manufactured by Toho Chemical Co., Ltd.) 2 g Phenol resin (trade name: Hitanol 1501 manufactured by Hitachi Chemical Co., Ltd.) 5 g

A blue ink composition for inkjet recording was prepared in the same manner as in Example 24. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 23.

Comparative Example 13 A blue ink composition for inkjet recording was prepared in the same manner as in Example 24 except that the salt-forming dye of Comparative Example 3 was used instead of the salt-forming dye of Example 1. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 23.

Comparative Example 14 A blue ink composition for ink jet recording was prepared in the same manner as in Example 27 except that the salt-forming dye of Comparative Example 4 was used in place of the salt-forming dye of Example 11. By evaluating the temporal stability of this ink composition and the water resistance and light resistance of handwriting,
The results obtained are shown in Table 23.

Comparative Example 15 A blue ink composition for inkjet recording was prepared in the same manner as in Example 24 except that Victoria Pure Blue Base was used instead of the salt-forming dye of Example 1. The stability of this ink composition over time and the water resistance and light resistance of handwriting were evaluated, and the obtained results are shown in Table 23.

[0114]

[Table 23] Example No. Light resistance ^a Water resistance A ^b Water resistance B Stability over time 24 4 5 5 ◎ 25 4 5 5 ◎ 26 4 5 5 ◎ 27 4 4 4 ◎ Comparative example 13 4 4 4 × Comparative example 14 3 4 4 ○ Comparative example 15 2 2 2 ○ ^a Water resistance A is the result of evaluation by printing on Xerox paper. ^b Water resistance B is the result of evaluation by printing on cardboard paper.

[0115]

EFFECT OF THE INVENTION A dye having excellent solubility in alcoholic solvents and excellent fastness, and an ink composition containing the same are provided. The ink composition using the novel salt-forming dye of the present invention is excellent in environmental resistance to changes in temperature, humidity, etc., stability over time, and in water resistance and light resistance of handwriting, as compared with conventional salt-forming dyes. Excel. Therefore, it can be optimally used as a quick-drying blue ink composition for various applications such as inks for writing instruments, (industrial) ink jet recording inks, and stamp inks.

[0116]

[Brief description of drawings]

1 is a visible absorption spectrum of the novel salt-forming dye of the present invention obtained in Example 1. FIG.

Claims (3)

[Claims] (1) Formula (1) [In the formula, R ¹ is an alkyl group having 3 to 6 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is an alkyl group having 1 to 4 carbon atoms or an alkyloxy group having 1 to 4 carbon atoms. And M ⁺ is an organic ammonium having 6 to 20 carbon atoms, and n is 1 or 2
Is. ] A triphenylmethane salt forming dye represented by the following formula. 2. The triphenylmethane salt-forming dye according to claim 1, wherein the M ⁺ is a basic dye. 3. An ink composition containing the triphenylmethane salt-forming dye according to claim 1 or 2 and an alcohol solvent.