JPH0374478A - Oil-based ink composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific phosphoric acid ester dye, having excellent solubility in alcohols and glycols and high aging stability, etc., and useful as a pollution-free oil-based ink for ball point pen, alcoholic marker pen, printing ink. etc. CONSTITUTION:The objective composition contains a dye of formula I (D is residue of azo or anthraquinone dye free from sulfone and carboxyl group; Y is 2-12C alcohol residue, 2-12C glycol monoether residue; 2-4C glycol residue, polybutyral resin residue, PVA residue, phenolic resin residue or cellulose residue; X is 0 or methylene; m is 0 or 1) (preferably the compound of formula II to IV [A is coupling component residue free from sulfone and carboxyl group; -B- is (substituted) phenylene or naphthylene; R is OH or (methyl)amino]}.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an oil-based ink composition that has excellent solubility in alcohols and glycols, and stability over time.

(Conventional technology) Generally, oil-based ballpoint pens and marker pens have color and
Solvsntdye listed in the index
(oil-based dyes) are used, but few dyes dissolve in high concentrations in low-toxic alcohol-based solvents.

For this reason, leuco base basic dyes are used to develop color by adding an organic acid, basic dye bases are salt-formed with acid dyes, and acid dyes are made into amine salts.

On the other hand, oil-based inks using pigments are also known, but pigments are originally hardly soluble in solvents or resins, so those that have been dispersed are used. When this type of ink is used as an ink for writing instruments, the pigments tend to aggregate or settle over time, and there are few inks with excellent writing performance.

Furthermore, since erasability of written characters and the like is important in marker inks for writing boards, pigments are mostly used as colorants.

[Problem to be solved by the invention]

In view of the current situation, the present invention aims to provide an oil-based ink that solves the above-mentioned problems and comprehensively improves the characteristics required of this type of oil-based ink, such as excellent writing characteristics and stability over time. This was done to provide a composition.

[Means to solve the problem]

That is, the present invention is based on the general formula: %Formula % (1) [wherein, D represents a residue of an azo or anthraquinone dye having no sulfone group or carboxyl group, and Y represents C1□
, alcohol residue of C*-+*, glycol monoether residue of C,-, glycol residue of C,-, polybutyral resin residue, polyvinyl alcohol residue, phenolic resin residue, or cellulose residue, represents an oxygen atom or a methylene group, and 驴 represents O or l. ] It is related with the oil-based ink composition containing the dye represented by these.

The dye represented by the general formula [1] according to the present invention is a dye represented by the general formula % (hereinafter referred to as a phosphoric acid dye in the present invention) containing alcohol, glycol monoether, glycol, or at least a hydroxyl group. It is an oil-soluble dye obtained by esterification with a specific resin.

Examples of phosphoric acid dyes include azo dyes or anthraquinone dyes having a water-soluble group such as OHOH0H -P=O-0-P=O-CH, -P=○OHOHOH. Such dyes are known and described in various dye-related literature.

Next, preferred examples [a), [b] and [c] of the oil-soluble dye (hereinafter referred to as phosphate ester dye in the present invention) constituting the composition of the present invention will be described.

It is a phosphoric acid ester compound of an azo dye, and the compound represented by the general formula (b) is represented by the following formula [b゛] (however, XSY and m
has the same meaning as above, A represents a coupling component residue having no sulfone group or carboxyl group, and -B- represents an unsubstituted or 0 yen (')7)'v kyl group (CHs, Cz
H5), alkoxy groups of cl-1 (OCHs, OCt,
Ha) Oh, Jbi/*,? , : represents a phenylene group or naphthylene group which may be substituted with a hydroxyl group, and R represents a hydroxyl group, an amino group or a methylamino group. ) The compound represented by the general formula [a] is a phosphoric acid acidic monoYO-, (-O
It is a phosphoric acid ester compound of a phosphoric acid disazo dye containing a monoazo dye represented by H as a diazo component.

Residue A of the coupling component in general formulas (a) and [b] is a compound that is normally used as a coupling component of a dye during the synthesis of an azo dye (however, in the present invention, a sulfone group and (limited to compounds without carboxyl groups). A is a phenol having no sulfone group or carboxyl group, naphthol, pyrazolone derivative, pyrazole derivative, acetoacetanilide derivative, perimidine derivative, phenylenediamine or 3-carbamoyl-4-methyl-6-hydroxy-N-butylpyridone, etc. Coupling component residues selected from: Specific examples of such coupling components include 3-methyl-1-phenyl-5-pyrazolone, 5-amino-3
-Methyl-1-phenylpyrazole, β-naphthol,
1-amino-7-naphthol, l-amino-5-naphthol, phenol, resorcinol, (o-, to-,
p-)aminophenol, p-phenylphenol, m
-phenylenediamine, acetoacetanilide, perimidine derivatives, 3-carbamoyl-4-methyl-6-hydroxy-N-butylpyridone, and the like.

-B- in general formula [b] is, for example, Fresamine,
p-cresidine, (o-, m-p-)phenetidine, (
o-, n-p-) anisidine, 2,5-dimethoxyaniline, (o-, ts-, p-) aminophenol, (o
-, m -, p-) Toluidine, p-xylidine,
It can be introduced with 2.4-xylidine, 8-amino-2-naphthol, naphthylamine, etc.

Further, the compound represented by the general formula [c] is a phosphoric acid ester compound of an anthraquinone dye obtained by reacting an anthraquinone derivative, for example, 1-amino-4-bromoanthraquinone and 3-aminobenzenephosphonic acid.

The esterified product of the phosphoric acid dye contained in the oil-based ink composition of the present invention is a phosphoric acid dye containing a C2-11 alcohol (for example, a C1-4 lower alcohol, amyl alcohol,
Hexyl alcohol, octyl alcohol, nonyl alcohol, benzyl alcohol, CtO-+* higher alcohols), glycols (e.g. glycols such as ethylene glycol, propylene glycol, butylene glycol), glycol monoethers (e.g. ethylene glycol monoethyl ether, Obtained by reacting Cellosolve M) such as propylene glycol monoethyl ether and ethylene glycol monophenyl ether at 100°C to 150°C in the presence of a catalyst (e.g., guanidine phosphate, dicyandiamide, cyanamide, amidinothiourea, etc.) .

When esterifying using a resin having a hydroxyl group (e.g., butyral resin, polyvinyl alcohol, phenolic resin, and cellulose), the above catalyst is used in 1,3-dimethyl-2-imidazolidinone, dimethylformamide, or formamide as a solvent. It is obtained by reacting at 100°C to 150°C in the presence of.

Specific examples of the phosphoric acid ester dyes of the present invention are illustrated below along with their hues; Compound 6 (red) Compound 7 (brown) Compound 3 (orange) Compound 4 (orange) Compound 5 (red) H Compound 11 (blue) Compound 12 (purple) Compound 13 (black) 0 Compound 14 (black) Compound 15 (black) Two or more of the dyes represented by the above general formula [1] may be used in combination as desired.

The amount of the dye represented by the general formula CI] depends on the purpose of use of the ink composition and is not particularly limited, but it is usually 8 to 20% by weight for ballpoint pens, preferably 10 to 15% by weight, and 10 to 15% by weight for ballpoint pens. For pens, the amount is 3 to 15% by weight, preferably 5 to 10% by weight.

The base of the oil-based ink composition according to the present invention is an oil-based medium containing an organic solvent as a main component, and optionally containing a binder resin that is soluble or compatible with the organic solvent.

Such organic solvents include monohydric alcohols (e.g. methanol, ethanol, propanol, benzyl alcohol, etc.), polyhydric alcohols (e.g. ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, propylene glycol, dipropylene glycol, etc.). ), hydroxyethers (e.g. monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and ethylene glycol monophenyl ether), esters of hydroxy ethers (e.g. ethylene glycol monomethyl ether acetate,
diethylene glycol monoethyl ether acetate, etc.) formamide, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, 1.
Examples include 3-dimethyl-2-imidazolidinone.

Examples of the binder resin include phenol resin, ketone resin, sulfamide resin, polyvinyl butyral, polyvinyl alcohol, polyethylene glycol, cellulose resin, and the like.

In addition to the above-mentioned ingredients, the oil-based ink composition according to the invention may contain, within the scope of the intended purpose of the invention, conventional additives suitable for various writing instrument inks, such as surfactants, humectants, etc. agent, viscosity modifier, p) (modifier, rust preventive agent, release agent, etc.) may be blended as appropriate.

The surfactant is preferably a nonionic surfactant,
For example, fluorine-based surfactants [Unidyne DS-401 and DS-402 (manufactured by Daikin Industries, Ltd.), Megafac P-1420 and F-177 (manufactured by Dainippon Ink Chemical Co., Ltd.], etc.), silicon-based surfactants [ Silicone L-7607 (manufactured by Nippon Unicar Co., Ltd.)] and phosphate ester surfactant [Plyserve A208 S (
(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)] and the like.

Wetting agents include polyalkylene glycols (e.g. polyethylene glycol, polypropylene glycol, etc.);
Alkylene glycols (e.g. ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, etc.), lower alkyl ethers of diethylene glycol (e.g. diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc.),
Examples include cellosolve and glycerin.

Examples of the viscosity modifier include polyvinyl alcohol and polyvinylpyrrolidone.

Examples of the pH adjuster include lower alkanolamines (eg, ethanolamine, jetanolamine, propanolamine, etc.).

An example of the rust preventive agent is benzotriazole.

In addition, in order to suitably use the phosphoric ester dye according to the present invention in various oil-based inks, the phosphoric ester residue Y should be
It is preferable to use something similar to the solvent or resin of the ink in view of solubility, compatibility, and stability over time of the ink.

For example, when used in an alcohol marker ink, the phosphoric acid ester residue Y is preferably a residue of an alcohol component having 3 to 10 carbon atoms.

When used in a ballpoint pen ink, it is preferably a residue of a glycol having 2 to 4 carbon atoms or a glycol monoether having 3 to 12 carbon atoms.

In addition, when using it as a marker ink for writing boards,
It is preferable that the resin has a composition in which the phosphoric acid ester residue Y is a butyral resin and the polyvinyl alcohol component is 20 to 50% (wt%). If the content of hydroxyl groups is low, the reactivity will be poor, and if the content is high, the solubility in alcohol will decrease.

In particular, when the phosphoric acid ester dye according to the present invention is used as the marker ink for writing boards, an alcohol with a relatively low boiling point is used as the solvent, and an alcohol that is soluble in the solvent and has a vapor pressure higher than that of the solvent is used as the release agent. Volatile or non-volatile liquids (e.g. higher fatty acid esters, phthalic acid esters, higher alkyl ethers of ethyl non-glycol, higher alkyl ethers of diethylene glycol, higher alcohols, liquid paraffin, etc.), as well as sucrose esters, surfactants, etc. A desired ink is prepared by adding or using them together.

(Effect of the invention) The phosphoric acid ester dye according to the present invention obtained by esterifying water-soluble phosphoric acid has excellent solubility in alcoholic solvents and good stability over time, so it can be used as a non-polluting oil-based ink for ballpoint pens. It can be used in inks for various writing instruments, such as inks for pencils and alcohol marker pens, as well as printing inks and stamp inks.

Furthermore, when the (specific) oil-based ink composition of the present invention is used as an alcohol marker ink for writing boards, the erasability of written characters is significantly improved compared to conventional oil-soluble dyes.

On the other hand, the ink has superior stability over time compared to pigment-dispersed markers for writing boards.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited by these Examples.

Dye Synthesis Reference Example 1 20.8 g of 3-aminobenzenephosphonic acid (012 m
o1), was dispersed in an aqueous solution of 100 ml of water and 18 g of hydrochloric acid, heated to 0°C with ice, and diazotized by adding 8.5 g of sodium nitrite. On the other hand, 5-amino-3-methyl-
1-phenylpyrazole 20.8g (0.12mol)
was added to an aqueous solution of 300 mQ of water and 16 g of hydrochloric acid to completely dissolve it, and the above diazo solution was gradually added to it, p) (8,0
Stirred at ~8.5 and 5-10°C for 3 hours. By filtration, washing with water and drying, 40.6g of yellow monoazo compound was obtained.
I got it. Then 18g (about 0.05+ol) of this compound
was dispersed in 150 g of n-butanol, 2 g of ammonia was further added and dispersed, and then 20 g of dicyandiamide (0
, 24 mol) and stirred under heating under reflux until the reaction was completed. By adding water and washing several times with water, extracting the dye from the oil phase (upper layer) and powdering it, the phosphate ester dye (
20 g of compound 1) was obtained.

Reference example 2 3-aminobenzenephosphonic acid 20.8g (0.12m
ol) was diazotized in the same manner as in Reference Example 1.

On the other hand, 16.3 g (0.12 mol) of p-cresidine was added to an aqueous solution of 1000 nQ of water and 14 g of hydrochloric acid and completely dissolved.
After adding this to the diazo solution, add thiourea fig
was added and stirred overnight. After filtration and washing with water, the wet cake was taken out and dispersed in 800 d of water. Then,
After adding 24g of hydrochloric acid, add 10g of sodium nitrite,
The mixture was stirred at ~40°C for 3 hours to prepare a monoazodiazo liquid. Next, 20.8 g of 3-methyl-1-phenyl-5-pyrazolone was added to 300 g of water and 7 g of sodium hydroxide.
The above monoazodiazo solution was added thereto, and the mixture was stirred at pH 8, 0 to 8.5, and 5 to 10°C for 3 hours. By filtering, washing with water, and drying, 60 g of an orange disazo compound was obtained.

Next, 18 g (about 0.05 mol) of this disazo compound
was dispersed in 100 g of ethylene glycol, and further, 3 g of ammonia was added and dispersed. 10 g of cyanamide was added, and the mixture was stirred at 150±2° C. until the reaction was completed. This reaction solution was poured into 500 ml of water, salted out, filtered,
Phosphate ester dye (compound 3) 27 by drying
I got g.

3-aminobenzenephosphonic acid t7.3g (0゜1mo
l), 70m of water! 2 and 8 g of sodium hydroxide to completely dissolve the mixture. To this was added 8 g of bicarbonate of soda and 16 g of 1-amino-4-promoanthraquinone (0.04 m
ol) and further added 0.6 g of copper chloride to 70-7
The mixture was stirred at 5°C until the reaction was completed. The reaction solution is filtered, the filtrate is acidified, excess 3-aminobenzenephosphonic acid is recovered, salt is added to the filtrate for acid salting out, filtration and drying, and then this is purified with alcohol to obtain a blue color. 20 g of anthraquinone compound was obtained. Next, 20 g (about 0.04 nol) of this anthraquinone compound was dispersed in 150 g of 1,3-dimethyl-2-imidazolidinone, and further,
After adding and dispersing 3 g of ammonia, butyral resin (
15 g of Nisrex BL-3 (manufactured by Tsukisui Kagaku Co., Ltd.) and 15 g of cyanamide were added, and the mixture was stirred at 110 to 115° C. until the reaction was completed. This reaction solution was poured into 50 ol IIQ water, filtered and dried to produce a phosphoric ester dye (
30 g of compound 9) was obtained.

Preparation Example 1 of Oil-Based Ink Composition for Alcohol Marker Pen A yellow ink was obtained by stirring and dissolving the composition shown in Table 1 at 50 to 60°C and filtering the mixture using Toyo Roshi N002. This ink was tested for stability over time and handwriting density, and the results are shown in Table 1 along with the hue of the ink.

Raiou Rui 1 A brown ink was obtained in the same manner as in Example 1, except that the mixture was stirred and dissolved at 40'C. This ink was tested for stability over time and handwriting density, and the results are shown in Table 1 along with the hue of the ink.

Example 3 The formulation shown in Table 1 was stirred and dissolved at 60 to 70°C, and the same procedure as in Example 1 was carried out to obtain an orange ink. When the stability of the ink over time was investigated, no precipitation of dye or the like was observed. Furthermore, when the writing performance was examined 3 hours after removing the cap, no dry-up was observed at the pen tip, and writing continued. Table 1 shows the stability over time, handwriting density, and ink hue.
Shown below.

Blue ink was obtained using the above-mentioned formulation in the same manner as in Example 3. The stability over time and writing performance of the ink were as good as in Example 3.

Example 5 The formulation shown in Table 1 was treated in the same manner as in Example 3 to obtain black ink. When the obtained ink was placed in a marker container and a writing test was conducted using a commercially available OHP sheet, no ink repellency was observed and clear, translucent handwriting was obtained. The stability over time and handwriting density were tested, and the results are shown in Table 1 along with the hue of the ink.

Example 6 A red ink was obtained in the same manner as in Example 1 by stirring and dissolving the formulation shown in Table 1 at 50 to 60°C. The stability over time and writing performance of the ink were tested, and the results are shown in Table 1 along with the hue.

Example 7 The formulation shown in Table 1 was dissolved with stirring at 90 to 95°C, and precoated filtration was performed using diatomaceous earth (#9000, manufactured by Showa Kagaku Co., Ltd.) to obtain a red ink. The resulting ink was filled into a ballpoint pen pipe and tested at 50° C. and 80% RH for two months, followed by a writing test, which showed the same writing performance as normal.

Further, no precipitation of dye or the like was observed in the ink in the pipe. Table 1 shows the stability over time, writing density, and hue of the ink.

Example 8 The formulation shown in Table 1 was treated in the same manner as in Example 7 to obtain a blue ink. The stability over time and writing performance of the ink were as good as in Example 7. These results are shown in Table 1 along with the hue of the ink.

Example 9 Preparation of oil-based ink composition for marker pen for writing board The formulations shown in Table 2 were mixed and dissolved at 40 to 45°C to obtain black ink. When the resulting ink was placed in a marker container and a writing test was conducted using a PP-coated white board, handwriting dried in 10 to 20 seconds and could be easily erased with an eraser without leaving any stains. Moreover, the stability of the ink over time was good. Table 2 shows the stability over time, handwriting density, ink hue and erasability.

Example 10 The formulations shown in Table 2 were mixed and dissolved at 40 to 45°C to obtain blue ink. When the obtained ink was placed in a marker container and a writing test was conducted using a white board coated with polyester, the handwriting dried in 10 to 20 seconds and could be easily erased with an eraser without leaving any stains. The stability over time, handwriting density, and erasability were tested, and the results are shown in Table 2 along with the hue.

Comparative Example 1 An ink was obtained in the same manner as in Example 9 using the formulation shown in Table 2. When this ink was subjected to a writing test in the same manner as in Example 9, the erasability was good, but the writing became blurred over time. Table 2 shows the stability over time, handwriting density, ink hue and erasability.

Comparative Example 2 An ink was obtained in the same manner as in Example 9 using the formulation shown in Table 2. When this ink was subjected to a writing test in the same manner as in Example 9, handwriting could not be easily erased. Table 2 shows the stability over time, handwriting density, ink hue and erasability.

1); Hilac llOH, manufactured by Hitachi Chemical Co., Ltd.

2); Santorite MSP, manufactured by Monsanto Company.

3); In an incubator (INCUBATOR, manufactured by Sanyo Electric Co., Ltd.), the temperature was alternately kept at -5°C and 50°C for 1 hour each for 3 months.

4);◎Double layer O: Normal △：Thin 5); Solmix A-2, manufactured by Nippon Kaseihin Co., Ltd.

6); MA-100, manufactured by Mitsubishi Chemical Industries, Ltd.

7); Manufactured by Orient Chemical Industry Co., Ltd.

8) Nibliserv A-20881 manufactured by Dai-Kogyo Seiyaku Co., Ltd.

9); Excellent; Can be easily erased.

Good: Can be erased normally.

Possible: Can be deleted.

Impossible: Difficult to erase.

Procedural amendment August 15, 1990 Chitose 1 year Patent Application No. 210997 2, Name of invention Oil-based ink composition 3, Relationship with the person making the amendment Name of patent applicant Orient Chemical Industry Co., Ltd. 4, Agent Voluntary action 6, “Claims” and “Detailed Description of the Invention” columns of the specification subject to amendment

Claims (1)

[Claims] 1. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [1] [In the formula, D represents a residue of an azo or anthraquinone dye that does not have a sulfonic group or a carboxyl group. , Y is C_2
_-_1_2 alcohol residue, C_2_-_1_2 glycol monoether residue, C_2_-_4 glycol residue, polybutyral resin residue, polyvinyl alcohol residue, phenol resin residue, or cellulose residue, and X is It represents an oxygen atom or a methylene group, and m represents 0 or 1. ] An oil-based ink composition containing a dye represented by: 2. The dye represented by the general formula [1] has the following general formula [a]
, [b] or [c]. The oil-based ink composition according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[c] (However, , X, Y and m have the same meanings as above, A represents a coupling component residue having no sulfone group or carboxyl group, and -B- represents an unsubstituted or C_1_-_2 alkyl group (CH_3, C_2H_5 ), C_1_-_2
represents a phenylene group or naphthylene group which may be substituted with an alkoxy group (OCH_3, OC_2H_5) and/or a hydroxyl group, and R represents a hydroxyl group, an amino group or a methylamino group. 3. The oil-based ink composition according to claim 1, comprising a dye represented by the general formula [1] and an organic solvent. 4. The oil-based ink composition according to claim 1, comprising a dye represented by the general formula [1], a binder resin, and an organic solvent. 5. An oil-based ink for ballpoint pens containing the composition according to any one of claims 1 to 4. 6. An oil-based ink for marker pens containing the composition according to any one of claims 1 to 4. 7. An oil-based ink for writing boards containing the composition according to any one of claims 1 to 4.