JPH0570675B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an ink composition suitable for writing instruments, printing, recording, stamping, and paper coloring. Prior Art Conventionally, various water-soluble dyes have been used in water-based inks. Although these water-based inks have good solution stability, they have the disadvantage of poor water resistance of handwriting and printed images. In particular, the reality is that there are almost no water-based inks that provide good water resistance to handwriting immediately after writing. Various inks have been studied to overcome the poor water resistance of water-based inks. For example, inks using direct dyes have insufficient water resistance and have poor solubility unless the pH of the solution is high. If the pH is high, for example, acetate fibers used in the storage body of felt-tip pen containers will undergo hydrolysis, and the physical properties of the ink, including the dye, will deteriorate. In addition, there are no other dyes with good color tone other than black, and black dyes tend to thicken and gel. Inks made by dissolving oil-soluble dyes in aromatic solvents are water resistant, but tend to smudge and have a pungent odor. Furthermore, inks prepared by dissolving alcoholic dyes, such as amine salts of water-soluble dyes, in alcoholic solvents have inferior water resistance compared to oil-soluble dyes. Emulsion inks and dispersion inks using water-insoluble dyes or pigments have poor stability over time and are prone to capillary clogging. There are also inks in which handwriting becomes water-insoluble over time due to the action of light or oxygen in the air, but these inks have the disadvantage that it takes time to develop water resistance and that the handwriting discolors. Furthermore, there are inks made by adding additives (including resins, etc.) to water-soluble dyes for the purpose of improving water resistance, but they have almost no water resistance immediately after writing, and currently known additive inks are stable against pH changes. It is difficult to maintain pH within a narrow range. In addition, the more water-resistant additive ink is, the less storage stability it has. For the above reasons, there is no existing ink that satisfies ink stability and water resistance of handwriting and printed images immediately after writing, and it is desired to develop an ink that has both of these properties. Problems to be Solved by the Invention It is an object of the present invention to provide a water-based ink composition and an alcohol-based ink composition that have excellent color tone and water resistance not only for black but also for other colors. The purpose of the present invention is to provide an ink composition that has good water resistance even immediately after printing and has excellent ink stability. Means to Solve the Problem That is, the present invention consists of the following three components: (a) a water-soluble dye having active hydrogen; (b) a general formula:

[Formula] [In the formula, R is a C ₁ to C ₄ alkyl group or -
CH ₂ OR ₁ (R ₁ is hydrogen, C ₁ may be branched)
~ _C5 alkyl group, _C1 - _C5 alkenyl group,
(meth)acrylic acid group, propyltrimethoxysilane, or a polyhydric alcohol residue with a molecular weight of 300 or less)] and (c) an ink containing a reaction mixture of an amine compound as a colorant. A composition is provided. According to the present invention, an ink composition excellent in stability over time, water resistance of handwriting, and light resistance can be obtained. The reason why water resistance is improved by using the colorant of the present invention is that by reacting a water-soluble dye with a compound containing an epoxy group, a colorant similar to a polymeric dye with an -OH group is obtained, and It is believed to improve dissolution stability, light resistance and compatibility with paper. In addition, the amine residue is thought to suppress the water solubility of sulfonic acid groups and the like that impart water solubility to dyes, and further improve affinity with paper. Water-soluble dye (a) having active hydrogen in the present invention
Examples include -NH-, -NH ₂ , - in the dye structure.
Direct dyes with COOH, _{-SO2NH2 ,} -OH, etc.
Examples include acidic dyes and basic dyes. These dyes are not limited and can be used without being limited to the type of color, so it is possible to use red dyes, which have traditionally been difficult to impart water resistance. becomes. The epoxy compound (b) used in the present invention has the following formula:

[Formula] [In the formula, R is a C ₁ to C ₄ alkyl group or -
CH ₂ OR ₁ (R ₁ is hydrogen, C ₁ - which may be branched)
_C5 alkyl group, _C1 to _C5 alkenyl group, (meth)acrylic acid group, propyltrimethoxysilane, or a polyhydric alcohol residue with a molecular weight of 300 or less)]. As the epoxide, both monoepoxide and polyepoxide can be used, but monoepoxide and diepoxide are particularly preferred. Examples of monoepoxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-pentene oxide, glycidol, methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, γ-glycidoxypropyl trimethoxy. Examples include silane. Examples of diepoxides include polyhydric alcohols with a molecular weight of 300 or less, such as ethylene glycol, diethylene glycol, polyethylene glycol,
1,2-propylene glycol, 1,4-butylene glycol, neopentyl glycol, 2,
2'-dibromo-neopentyl glycol, 1,
Examples include diglycidyl ethers derived from 2,6-hexanetriol, glycerol, and the like. The amine compound (c) used in the present invention includes aromatic amines such as 1,3-diphenylguanidine, 1-o-tolylbiguanide, and di-o-tolylguanidine; alicyclic amines such as cyclohexylamine and dicyclohexylamine; aliphatic amines such as 2-ethyl-hexylamine; and tetraethylurea, trimethylthiourea, N,
Examples include urea-based amines such as N'-diphenylthiourea. The above three components may be reacted simultaneously or sequentially. For example, () the dye (a) and the epoxy compound (b) may be reacted, and then a salt may be formed with the amine compound (c), or () the reaction product of the dye (a) and the amine compound (c) may be may be reacted with the epoxy compound (b). Furthermore, the dye (a) may be reacted with the reaction product of the epoxy compound (b) and the amine compound (c). These reactions result in a mixture of various reactants or unreacted substances depending on the type of starting materials, reaction conditions, etc., but the coloring agent containing all of them exhibits the effects of the present invention, and the presence of these substances is Not hinder. In the case of () above, the reaction between the active hydrogen-containing compound and the epoxy group-containing compound may be carried out by a conventional method. For example, the reaction is carried out in a solvent in the presence or absence of a catalyst (eg, acid or alkali). The reaction is carried out at room temperature or under heating. When using low-boiling epoxides such as ethylene oxide or propylene oxide, the process may be carried out in an autoclave. It is preferable that 1 to 4 epoxy groups are bonded to one molecule of the epoxide; if 5 or more epoxy groups are bonded, the product becomes highly viscous or becomes insoluble in water and alcoholic solvents, resulting in coloring of the ink composition. unsuitable as a drug. In addition, in the epoxy addition compound, two or more types of epoxides may be reacted with one type of dye.
Furthermore, by using epoxide and reacting it with two or more kinds of dyes, it is also possible to obtain a color intermediate between the two. The obtained epoxide addition compound may be isolated after the reaction to form a salt with the amine compound (c), or the reaction product may be prepared as a solution and then added to the amine compound (c).
After salt formation, it may be isolated and purified to obtain a powder or the like. Alternatively, after forming a salt with the amine compound (c), the reaction product may be directly adjusted to a solution. The amines to be salt-formed are:
Preferably, 0.2 to 1 mole is reacted. When obtained as a colored composition, the solution or the like is preferably one that can be used in the final composition to be formed, since it can be used without isolating the compound. Acid residues that do not form amine salts can be formed into various alkali salts. As the alkali source, sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia, water-soluble organic amines such as ethanolamine, etc. are used. In reaction method (2), dye (a) is salt-formed with amine compound (c) in advance, and then reacted with epoxy compound (b).
The reaction with the amine and the reaction with the epoxy compound are carried out in the same manner as in the method () above. In this case, the epoxy compound (b) reacts with the active hydrogen of the dye (a), and
It may also react with active hydrogen present in the amine compound (c) residue. Therefore, the product of this method has a complex composition and when used with a colorant,
Shows good stability. In the case of reaction method (), the amine compound (c) and the epoxy compound (b) are reacted in advance, and this is reacted with the dye (a). The conditions for the epoxidation reaction and amine addition reaction are the same as in method (). The simultaneous reaction of the three components is carried out under the conditions of sequentially completely dissolving each component in the same reactor in the presence of water or a water-soluble organic solvent, then adding a catalyst and heating. It is expected that the reaction products obtained in the present invention will be a mixture of various reaction products, for example when the dye has a plurality of groups having active hydrogen. However, as long as the same starting materials are used, even if the reaction conditions are changed, products having substantially the same properties in terms of hue, water resistance, stability, etc. can be obtained. Specific examples of typical reaction products of reaction method () are shown below. Compound example

[ka]

[ka]

[Chemical Formula] The above reaction product is blended with a solvent as a coloring agent and a suitable additive to form an ink composition. When used in a water-based ink composition, a water-soluble organic solvent is usually used in addition to water as the solvent. The water-soluble organic solvent is preferably a solvent that is compatible with water and has the property of dissolving dyes and additives well, has appropriate hygroscopicity, and can appropriately control ink evaporation, such as ethylene glycol, Glycol solvents such as diethylene glycol and thiodiglycol, alcohol solvents, cellosolve solvents, carbitol solvents, pyrrolidone solvents,
Examples include alkanolamines. Examples of solvents used in alcoholic ink compositions include, in addition to normal alcohol solvents, glycol solvents such as ethylene glycol, diethylene glycol, and thioglycol, cellosolve solvents, carbitol solvents, pyrrolidone solvents, and alkanolamines. It will be done. Also, due to the nature of the solvent,
It may contain a small amount of water (up to 10% by weight), and acetone, xylene, ethyl acetate, etc. may be used as a co-solvent. Note that when a ballpoint pen ink is prepared using benzyl alcohol and/or phenyl glycol, an ink with a good writing feel can be obtained. The ink composition of the present invention can be obtained by mixing and dissolving various additives, if desired, in addition to the above-mentioned components, and filtering if necessary. As additives, PH regulators, anionic and nonionic activators, or amphoteric activators are used,
Depending on the purpose, a preservative, a rust preventive agent, a metal sequestering agent, etc. can be added. Furthermore, if necessary, natural or synthetic water-soluble and alcohol-soluble resins are mixed. The amount of the additive in the aqueous ink composition is preferably 0.1 to 5% by weight based on the total amount of the ink composition. Effects of the Invention The ink composition of the present invention has extremely good stability over time and has a wide stable dissolution pH range, making it possible to prepare inks in a more neutral range. Furthermore, an ink with almost no corrosion or capillary clogging can be obtained, and the ink's handwriting and images have extremely excellent water resistance. The ink composition of the present invention is extremely suitable for writing instruments, printing, recording, and stamps. The present invention will be explained below with reference to Examples. Production Example 1 (Production of Compound Example 1) 500 equipped with stirrer, thermometer and cooler
Add 150 parts of water and 7.5 parts (0.1 mol) of glycidol to a ml four-necked flask, then add 41 parts (0.1 mol) of CI Acid Violet 41, stir and disperse at room temperature for 30 minutes, then gradually add 10 parts of 50% caustic potassium. Increase temperature. The mixture was stirred at 95-100°C until the reaction was completed.
The reaction mixture was filtered and the solution was diluted with 500 g of sulfuric acid containing 15 parts of sulfuric acid.
Pour into water and disperse well. The precipitated crystals were filtered, washed with 50 parts of a 1% aqueous sulfuric acid solution, then 50 parts of water, and dried. 32.5 parts of glycidol-added acid violet was obtained. Glycidol added acid violet 25g
(0.05 mol) in a 500 ml beaker, add 200 parts of water containing 5 parts of caustic soda, dissolve by heating at 70-80°C, and then cool to 40°C. Next, 10 parts (0.05 mol) of 1-o-tolyl biguanide was added to 100 parts of water containing 5 parts of hydrochloric acid, completely dissolved, and added dropwise to the above solution.
After dropping, adjust the pH to 3 and raise the temperature to 40°C. The precipitate was collected by filtration, washed with 100 parts of water, and dried. 35 parts of a coloring agent containing Compound Example 1 as a main component was obtained. Production Example 2 (Production method for Compound Example 2) 150 parts of water and 13 parts (0.1 mol) of butyl glycyl ether were added to the reactor used in Production Example 1, and then 77 parts (0.1 mol) of free acid type CI Direct Black 154 was added. ) and disperse well, then add diethanolamine.
Add 20 parts and gradually raise the temperature. The reaction was stirred at 80-85°C until completion. After the reaction was completed, the mixture was allowed to cool to room temperature. Next, 10 parts (0.05 mol) of 1-o-tolyl biguanide was added to 100 parts of water containing 5 parts of hydrochloric acid, completely dissolved, and added dropwise to the above solution. After dropping, adjust the pH to 3 and heat at 40°C.
Increase the temperature to. The precipitate was collected by filtration, washed with 100 parts of water, and dried. The yield was 80%. Production Example 3 (Production method for Compound Example 3) 150 parts of water and 7.5 parts (0.1 mol) of glycidol were added to the reactor used in Production Example 1, and then 70 parts (0.1 mol) of free acid type CI acid red 87 was added. Add triethanolamine after stirring and dispersing for 30 minutes at room temperature.
Add 25 parts and gradually raise the temperature. Stir at 85-90°C until reaction completion. After the reaction is complete, add 90 parts of warm water and 1,3-
Add 10.6 parts (0.05 mol) of diphenylguanidine,
After stirring until homogeneous, the pH was adjusted to 8 to 9 with a 10% aqueous solution of caustic soda, and after filtration, water was added to make a total of 360 parts to obtain a solution with a colorant concentration equivalent to a 20% solution of CI Acid Red 87. Production Example 4 (Production method of Compound Example 4) A diphenylguanidine adduct of CI acid yellow-9 was produced by the following method. Place 1000 parts of water and 200 parts of CI Acid Yellow 9 in a flask No. 31, heat to 70°C while stirring to dissolve, and allow to cool after complete dissolution. Completely dissolve 106 parts of 1,3-diphenylguanidine in 500 parts of water containing 90 parts of sulfuric acid, dropwise add to the above solution at below 30°C while stirring, adjust the pH to 3, and heat to 40°C. The precipitate was collected by filtration and dried to obtain 270 parts of a diphenylguanidine adduct of CI acid yellow-9. Into the reactor used in Production Example 1, 150 parts of water and 8.7 parts (0.1 mol) of methyl glycidyl ether were added, followed by 56.6 parts (0.1 mol) of diphenylguanidine adduct of CI acid yellow-9, and the mixture was heated at room temperature for 30 minutes.
After stirring and dispersing, add 10 parts of 50% caustic soda and gradually raise the temperature. The mixture was stirred at 95-100°C until the reaction was completed. The reaction mixture is poured into 500 parts of water containing 15 parts of sulfuric acid and is well dispersed. Filter the precipitate and add 100 parts to 1%
It was washed with sulfuric acid water, then 100 parts of water, and dried.
60 parts of colorant compound were obtained. When the obtained colorant compound was analyzed by high performance liquid chromatography (HLC), it was found to have the following composition. The colorant compound contains the following four component interactants. Methyl glycidyl ether adduct of CI acid yellow 9 approx. 35% CI acid yellow 9 approx. 30% Methyl glycidyl ether adduct of diphenylguanidine approx. 20% Diphenyl guanidine approx. 15% (Note) High performance liquid chromatography conditions: Machine Seed: Manufactured by Waters, 6000A ABS-440 type column: RP-18 7μ Carrier: Acetonitrile-water-based detector: Abs-254 Production example 5 (Production method of compound example 5) Into the reactor used in production example 1, 150 parts of water, Add 6 parts (0.05 mol) of trimethylthiourea, then add 56 parts (0.1 mol) of free acid type CI Direct Black 90, disperse well, add 8.7 parts (0.05 mol) of ethylene glycol siglycidyl ether, and then add diethanolamine. Add 20 parts and gradually raise the temperature. The reaction was stirred at 80-85°C until completion. After the reaction was completed, 100 parts of warm water was added, the pH was adjusted to 10 to 10.5 with a 10% aqueous solution of caustic soda, and water was added to make a total of 280 parts. The benefits obtained are CI Direct Black 90
It was a concentrated solution of the colorant compound corresponding to a 20% solution. Production Example 6 (Production method for Compound Example 6) 150 parts of n-propyl alcohol and 19.8 parts (0.2 mol) of cyurohexylamine were added to the reactor used in Production Example 1, and then 83.2 parts of free acid form CI Acid Blue 90 was added. (0.1 mol) was added and dispersed well, then 13 parts (0.1 mol) of butyl glycidyl ether was added and dispersed, and then 20 parts of diethanolamine was added and the temperature was gradually raised. The reaction was stirred at 90-95°C until completion. After the reaction was completed, 100 parts of n-propyl alcohol was added to adjust the pH to 7 to 8, followed by addition of n-propyl alcohol to make a total of 417 parts. The resulting solution was prepared using CI Acid Blue 90 20
% solution of the colorant compound. Compound Examples 7 to 13 In Production Examples 1 to 9, dyes, epoxy compounds,
The compound was prepared by replacing the amine compound. The reaction composition conditions are shown in Table-1.

[Table] (Note) Production Example Number Example 1 8 parts of the coloring agent of Compound Example 2 was dispersed in 40 parts of distilled water, and the pH was adjusted to 8 to 9 with a 10% aqueous lithium hydroxide solution to obtain a solution. Then ethylene glycol 10
10 parts of diethylene glycol, 5 parts of thiodiglycol, 0.3 parts of preservative, 0.2 parts of activator and distilled water to make a total of 100 parts, heated and dissolved at 60 to 70°C, and filtered through industrial paper. A black ink was obtained. When the resulting ink composition was placed in a felt-tip pen container and a writing test was performed, there was no ink blurring at the pen tip, the ink always flowed out smoothly, and the handwriting was clear in tone. After 30 minutes of writing,
A water resistance test was performed by immersing it in distilled water, and it was found to be good. Furthermore, it remained stable even when left at room temperature for more than 6 months. Example 2 Concentrated solution of colorant of Compound Example 3 40 parts ethylene glycol 10 parts diethylene glycol 10 parts propylene glycol 5 parts preservative 0.3 parts activator 0.2 parts distilled water 34.5 parts The above formulation was heated at 60-70°C.・Dissolved and passed through industrial paper to obtain red ink. The resulting ink composition was placed in a felt-tip pen container and tested and found to be good. Example 3 Colorant for Compound Example 4 4 parts Diethylene glycol 10 parts 2-pyrrolidone 10 parts Diethanolamine 4 parts Preservative 0.3 parts Activator 0.3 parts Distilled water 71.4 parts The above formulation was heated and dissolved at 60 to 70°C. , and passed through industrial paper to obtain a yellow ink. Example 4 Colorant of Compound Example 1 Tri-glycidol-added CI acid Violet 41
2 parts ethylene glycol 10 parts diethylene glycol 10 parts N-methylpyrrolidone 5 parts triethanolamine 2 parts preservative 0.3 parts activator 0.2 parts distilled water 67.5 parts A purple ink was obtained by passing it through paper. Example 5 Concentrated solution of colorant of Compound Example 8 40 parts diethylene glycol 10 parts propylene glycol 5 parts glycerin 5 parts activator 0.2 parts Distilled water 39.8 parts The above mixture was heated and dissolved at 60 to 70°C, and industrial An orange ink was obtained by passing it through paper. Example 6 Concentrated solution of colorant of Compound Example 11 25 parts Glycerin 10 parts Ethylene glycol 5 parts Trimethylolpropane 5 parts Preservative 0.5 part Activator 0.1 part Distilled water 54.4 parts The above formulation was heated at 60-70°C. It was heated and dissolved and passed through industrial paper to obtain blue ink. Example 7 N-propyl alcohol solution of the colorant of Compound Example 6 30 parts Ethanol 40 parts Methyl cellosolve 20 parts Tamanol 100-S (manufactured by Arakawa Chemical Industries; phenolic resin) 10 parts The above formulation was heated at 60 to 70°C. The mixture was heated, dissolved, and passed through industrial paper to obtain blue ink. Example 8 Coloring agent for Compound Example 9 7 parts Coloring agent for Compound Example 7 1 part Ethanol 40 parts N-propyl alcohol 32 parts Methyl cellosolve 10 parts Halon 100H (ketone resin) 10 parts The above mixture was prepared in the same manner as in Example 7. After processing, a red alcoholic ink was obtained. Example 9 Coloring agent for Compound Example 13 9 parts Coloring agent for Compound Example 7 1 part Ethanol 40 parts N-propyl alcohol 20 parts Methyl cellosolve 20 parts Sulfamide resin 10 parts The above mixture was treated in the same manner as in Example 7 to obtain a black color. An alcoholic ink was obtained. Example 10 Concentrated solution of colorant of Compound Example 5 25 parts diethylene glycol 5 parts 2-pyrrolidone 5 parts triethalolamine 5 parts Preservative 0.2 parts Distilled water 59.8 parts The above formulation was thoroughly mixed at 60-70°C. After heating and dissolving, it was overpurified using a membrane filter with a pore size of 0.8μ to obtain a black jet printing ink. Example 11 Concentrated solution of colorant of Compound Example 10 40 parts Methyl cellosolve 20 parts Scorerol 900 (manufactured by Kao Soap Co., Ltd., activator) 10 parts Lithium hydroxide 4 parts Distilled water 34.5 parts The above formulation was heated at 70 to 80°C. The mixture was heated and dissolved in a microwave oven, and passed through industrial paper to obtain a pink OHP ink. Example 12 Concentrated solution of coloring agent of Compound Example 12 50 parts Glycerin 45 parts Gum arabic 5 parts The above formulations were thoroughly mixed, heated and dissolved at 70-80°C, and filtered through industrial filter paper to obtain a black color. I got the stamp ink. Example 13 Colorant for Compound Example 1 5 parts Colorant for Compound Example 2 15 parts Colorant for Compound Example 9 5 parts Phenyl glycol 45 parts Benzyl alcohol 10 parts Triethanolamine 5 parts Polyvinylpyrrolidone 5 parts Halon 100H (ketone resin) ) 10 parts or more of the mixture was heated and dissolved at 80 to 90°C and filtered through diatomaceous earth precoat to obtain a black ballpoint pen ink. After placing the ink in a felt-tip pen container or ballpoint pen container, write continuously on JIS P 3201 paper using a writing tester, and after 30 minutes have passed, soak the handwriting in distilled water.
After soaking for 24 hours, taking it out and air-drying it, the handwriting was observed and evaluated. The results are shown in Table-2. Comparative Examples 1 to 6 and 10 to 12 Each ink was prepared using a sodium salt of the raw material dye in place of the coloring agent used in each Example and using a formulation having the same composition. Comparative Examples 7 to 9 and 13 Each ink was prepared using a diphenylguanidine salt of the raw material dye in place of the coloring used in each Example, and a formulation having the same composition. After setting the ink in a felt-tip pen container or a ball-point pen container, a water resistance test was conducted in the same manner as in the examples. The results are shown in Table-2.

【table】

Claims (1)

[Scope of Claims] 1 The following three components; (a) a water-soluble dye having active hydrogen; (b) general formula: [Formula] [wherein R is a C ₁ to C ₄ alkyl group or -
CH ₂ OR ₁ (R ₁ is hydrogen, C ₁ may be branched)
~ _C5 alkyl group, _C1 - _C5 alkenyl group,
(meth)acrylic acid group, propyltrimethoxysilane, or a polyhydric alcohol residue with a molecular weight of 300 or less)] and (c) an ink containing a reaction mixture of an amine compound as a colorant. Composition. 2. The ink composition according to item 1, wherein the reaction mixture is obtained by reacting two of the three components (a), (b) and (c), and then reacting with the remaining one component.