JPS62119281A - Ink composition for writing utensil - Google Patents

Abstract

PURPOSE:To provide the titled composition containing an alcohol-soluble resin, an alcohol-soluble resin containing sulfonic acid group and dyed with a basic dye and an alcoholic solvent and having excellent fixability, water-resistance, light-resistance, etc., and improved dry-up property. CONSTITUTION:The objective composition is composed of (A) an alcohol-soluble resin (preferably ketone resin, rosin-modified maleic acid resin, phenolic resin, etc.), (B) an alcohol-soluble resin having a sulfonic acid (salt) group and dyed with a basic dye [preferably a resin containing a monomer unit having a sulfonic acid (salt) group and a monomer unit such as (meth)acrylate] and (C) an alcoholic solvent (preferably 1-4C alcohol, ethylene glycol, etc.]. The amounts of the components A and B are 1-30(wt)% and 1-40%, respectively, and the component C accounts for the remaining part.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a writing ink composition containing alcohol as a main solvent component. More specifically, the present invention enables writing on glass, wooden products, plastics, paper, cloth, stone, etc., has excellent adhesion (friction fastness), water resistance, light resistance, etc., and is non-toxic. The present invention relates to a writing ink composition which has low dry-up properties and improved dry-up properties.

[Conventional technology]

Writing instrument inks are generally divided into water-based inks whose main solvent components are water and water-soluble solvents such as polyhydric alcohols, and oil-based inks whose main solvents are hydrocarbon-based, ketone-based, or ester-based solvents.

By the way, when using water-based ink, for example, if a writing instrument is left without a gap, the ink at the outflow hole will evaporate and dry, causing problems such as poor first-time writing, blurred letters, and the inability to write. It is also non-water resistant, so
There are disadvantages such as contamination and loss of handwriting when it gets wet.

On the other hand, since oil-based inks use organic solvents, the drawbacks of water-based inks caused by the use of water can be overcome to some extent;

In order to prevent backflow and smearing, resin is added to make it highly viscous, so when used in writing instruments with nib or capillary type writing instruments made of fibers, felt, monofilament, etc., the flow of ink will be hindered. In addition, the odor and toxicity of the organic solvents used are considered health problems, and when used in felt-tip pens, the solvent dries out from the tip of the pen, causing damage to the tip. There is also the problem of so-called dry-up, where dyes and resins precipitate and become impossible to write on.

As described above, water-based inks and oil-based inks each have their drawbacks, and to date, various alcohol-based ink compositions containing dyes, alcohol-soluble resins, and alcohol-based solvents have been developed to improve these drawbacks. proposed (Special Publication No. 54-37539, Special Publication No. 54-37539,
7-1555, JP-A-59-41369)
.

However, in the alcoholic ink compositions proposed so far, all alcohol-soluble resins include shellac, maleic acid resin, polyvinylpyrrolidone, and phenolic resin.

Ketone resins, polyvinyl butyral, etc. have been used, but these resins have insufficient adhesion (fixing power) to the writing material; Since it is merely dispersed in the resin, it has the disadvantage that when the handwriting gets wet with water, the color dissolves.

[Problem that the invention seeks to solve]

As described above, conventional alcoholic ink compositions are not satisfactory in terms of adhesion (friction fastness) and water resistance.

The purpose of the present invention is to improve the drawbacks of conventional alcohol-based ink compositions, and in particular, to have excellent adhesion and water resistance, good light resistance, no toxicity or odor problems, and to improve dry-up properties. An object of the present invention is to provide an improved alcoholic writing ink composition.

[Means for solving problems]

As a result of extensive research to achieve the above object, the present inventors have found that in alcoholic ink compositions, instead of directly blending dyes, alcoholic ink compositions containing sulfonic acid groups or their salts dyed with basic dyes have been developed. It was discovered that the objective could be achieved by blending a soluble resin, and the present invention was completed based on this knowledge.

That is, the present invention comprises (A) an alcohol-soluble resin, and (
The present invention provides a writing ink composition comprising: B) an alcohol-soluble resin having a sulfonic acid group or its salt dyed with a basic dye; and (C) an alcohol-based solvent.

The alcohol-soluble resin having a sulfonic acid group or a salt thereof used in the composition of the present invention can be produced by various methods known so far. For example, commonly known resins may be sulfonated, or ethylenic sulfonic acid monomers or salts thereof, or these may be copolymerized with monomers that provide alcohol-soluble resins.

Examples of the ethylenic sulfonic acid monomer or its salt include styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acryloyloxyethyl sulfonic acid, methacryloyloxypropylsulfonic acid, and 2-acrylamide. Unsaturated sulfonic acids such as -2-methylpropanesulfonic acid and salts thereof, such as lithium salts, sodium salts, potassium salts, ammonium salts, etc. can be mentioned.

Examples of monomers that can provide alcohol-soluble resins that can be copolymerized with these include evaporative hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

Polyethylene glycol monomethacrylate, ethyl acrylate, ethyl methacrylate, globyl acrylate, propyl methacrylate, butyl acrylate,
Examples include butyl methacrylate. In the present invention, one or more of these monomers and one or more of the ethylenically unsaturated sulfonic acid monomers or salts thereof are copolymerized, and although there is no particular restriction on the ratio of these monomers, ethylenically unsaturated If the proportion of the sulfonic acid monomer or its salt becomes too high, the solubility in alcohol will decrease, so in order to obtain a dark ink composition,
Its proportion is usually 0.1 to 70 weight-[
1, preferably 1. Selected in the range of Q to 5C1 heavy. Furthermore, other monomers copolymerizable with these may be copolymerized to the extent that the alcohol solubility of the polymer is not impaired. In this case, it is desirable that the proportion of the other monomers does not exceed 40% by weight based on the total amount of monomer components excluding the ethylenically unsaturated sulfonic acid monomer or its salt.

Examples of the other copolymerizable monomers include acrylic esters such as methyl acrylate, 2-ethylhexyl acrylate, and glycidyl acrylate; methacrylic esters such as methyl methacrylate, 2-ethylhexyl methacrylate, and glycidyl methacrylate; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; ethylenically unsaturated acids such as acrylic acid, methacrylic acid, maleic acid; acrylamide, methacrylamide, etc. and their derivatives, as well as styrene, butadiene, Examples include chlorobrene, vinyl chloride, and vinylidene chloride.

The alcohol-soluble resin having a sulfonic acid group or a salt thereof used in the present invention can be prepared, for example, in water or in a solvent such as alcohol, in the presence or absence of a basic dye, and if necessary, in the presence of a surfactant, a dispersant, etc. , a common radical polymerization initiator, such as a persulfate such as potassium persulfate or ammonium persulfate, or kiemene hydroperoside, together with an organic peroxide such as monobutyl hydroperoside, etc., are added to the above monomer components at once. Alternatively, it can be produced by introducing it into a polymerization vessel that is partially or continuously stirred and polymerizing it. In this case, the polymerization can be carried out at a temperature below the boiling point of the reaction medium.

The molecular weight of the polymer obtained by such a polymerization method depends on the concentration of monomers present in the polymerization system, the amount of radical polymerization initiator used, the polymerization temperature, and the like. The concentration of the monomer in the polymerization medium is not particularly limited, but is generally 3 to 50% by weight, usually 10 to 30% by weight.
Selected within a range of %. If this concentration is too high, the viscosity of the polymerization system will increase, making it difficult to remove the polymerization heat, which is undesirable.
Also, if it is too low, it is not desirable for economic reasons.

Of course, the method for producing the alcohol-soluble resin having the sulfonic acid group or its salt is not limited to the above method.

In the composition of the present invention, a basic dye (in a broad sense that also includes a cationic dye) is used as a coloring agent, and an alcohol-soluble resin having the sulfonic acid group or its salt dyed with this dye is used. is necessary.

Examples of basic dyes include triphenylmethane, azo, and methine.

Examples include oxazine dyes and anthraquinone dyes, and dyeing may be carried out in the presence of these basic dyes during polymerization of the resin, or may be carried out by the following method.

That is, the alcohol-soluble resin is treated with an organic acid such as formic acid, acetic acid, tartaric acid, or malic acid, or an inorganic acid such as hydrochloric acid or sulfuric acid, or with an aqueous solution such as sodium hydroxide or sodium carbonate, to a pH of 2 to 7, preferably. pH
3 to 5, add an aqueous dye solution, then dissolve this solution directly in an alcoholic solvent, or remove the polymerization solvent by a normal drying method such as spray drying or vacuum drying, and further dry if necessary. After washing and drying, the dyed polymer is dissolved in an alcohol solvent to obtain a colored polymer solution in the present invention. Alternatively, it can be obtained by adding an alcoholic solution of the dye to the polymer solution.

In addition, when polymerizing with a basic dye present in the polymerization system, the pH of the polymerization system should be adjusted to pH 2, taking into account the dye's discoloration and fading stability.
It is desirable to carry out the test between 7 and 7. In any case, in dyeing the polymer of the present invention with a basic dye, such dyeing conditions are not limited in any way from the spirit of the present invention.

There is no particular restriction on the content of the colored polymer dyed in this way in the ink composition, but it is usually 1 to 1.
It is selected in a range of 40% by weight, preferably from 5 to 50% by weight. If the amount of this bond is too large, the viscosity of the composition becomes too high, which is undesirable from a practical standpoint, and if it is too small, the color density becomes low, which is not preferable.

In the composition of the present invention, it is compatible with the colored polymer,
In addition, it is necessary to contain a resin soluble in an alcoholic solvent, such as a ketone resin, a rosin-modified maleic acid resin, a phenol resin, a polyvinyl butyral resin, and a shellac resin. These alcohol-soluble resins may be used alone or in combination of two or more, and the composition contains 1 to 30% by weight, preferably 3 to 30% by weight.
It is desirable to contain it in a range of 20% by weight.

The alcohol-soluble resin can be contained in various food materials such as paper, wood, and glass.

The adhesion (fixing force) of ink to stones, plastics, etc. is improved, and a synergistic effect on ink performance is observed.

If the content is too large, the viscosity of the composition becomes high (which is not preferred in practice), and if the content is too small, the above effects are not significant.

Examples of alcoholic solvents used in the composition of the present invention include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-methyl alcohol, 5ea-)f alcohol, ta
Monohydric alcohols such as rt-fluoric alcohol and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol and glycerol; and monomethyl ether or monoethyl of these polyhydric alcohols. Examples include those whose main solvent component is monoalkyl ether such as ether, and
Volatile organic solvents such as xylene, toluene, n-butyl acetate, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, methyl imbutyl ketone, N-methylpyrrolidone, and tetrahydrofuran can also be used as other solvent components.

The ink composition of the present invention has a level that does not interfere with drying.
Alternatively, when the composition is used as a drying rate regulator, for example, as an ink for overhead projector sheets, it may have a water content of 10% by weight or less. Furthermore, additives commonly used in monoalcoholic ink compositions, such as surfactants, preservatives, fragrances, etc., may be added as necessary.

〔Effect of the invention〕

The writing ink composition of the present invention is an alcohol-based ink that takes advantage of the richness and brightness of colors of conventionally known basic dyes, and has improved light resistance, which was the only drawback of basic dyes. Due to its composition, it has particularly excellent adhesion and water resistance, as well as improved dry-up properties.In addition, unlike conventional solvents such as xylene, toluene, or methyl ethyl ketone, which have safety concerns, it uses ethanol. We can also provide inks with high safety as the main ingredient for glass, wood products, plastics, paper, and cloth.

Suitable for writing on a wide range of materials such as stone.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

Example 1 40 g of ethyl acrylate, 2
-Acrylamido-2-methylpropanesulfonic acid2.
19. Pour 100 g of ethyl alcohol, heat it while stirring, and when it reaches 70°C, start dropping a catalyst solution in which 1 g of azobisisobutyronitrile is dissolved in 100 g of ethyl alcohol. The reaction was continued for 5 hours to obtain an ethanol solution with a polymer concentration of 164% by weight.

This solution ICl0C10 weight Sodium oxide aqueous solution 3g
After neutralization by adding cationic dye, Cachilon Prilliant Red 4cH (manufactured by Hodogaya Chemical Industry ■) 1.29
was dissolved in 200 g of water, the pH was adjusted to 55 using acetic acid, and the mixture was stirred at 60° C. for 1 hour.

This solution was dropped into water, and the colored polymer was precipitated and filtered, washed with water, and then dried under vacuum at 40°C.

Next, the dried colored polymer 52. Denka Butyral 2
000L (Denki Kagaku, polyvinyl butyral resin) 5
g was dissolved in a mixed solvent of 90 g of ethanol and 10 g of Improper Tool to prepare an ink composition.

It was possible to write on glass, polyvinyl chloride boards, polyethylene films, etc. with good quick-drying properties using a felt pen filled with the ink composition of the present invention. In addition, we made streaks on glass and hard vinyl chloride film, applied a load of 300g to a cotton swab, rubbed them, and examined the adhesive strength. Ta. Furthermore, although it was immersed in water for one day, no color was leached into the water, and when the adhesive strength of this product was examined in the same way, it was found to be rated 5. It was hard vinyl chloride film 2.

Example 2 99% of water was added to a polymerization container under a nitrogen stream. Ethyl alcohol 25
9 was prepared and the temperature was raised to 60°C without stirring.

Butyl methacrylate 34g, spinomer NaEE (p
- Sodium styrene sulfonate purity 82.0% by weight,
Dropwise addition of a sodium styrene sulfonate aqueous solution containing 7.49 (manufactured by Toyo Soda Kogyo ■) dissolved in 30 g of water and a catalyst solution containing 1.09 of azobisisobutyronitrile dissolved in ethyl alcohol Schiff 0 g/C was started, and the mixture was kept for 3 hours. Polymerization was carried out while the solution was added dropwise, and the reaction continued for 5 hours to obtain a polymer solution with a polymer concentration of 21.9% by weight.

Next, add 100 g of this polymer solution to 100 M of the cationic dye cationic dye cation brilliant flavin. A solution prepared by dissolving 55 g of 300% (manufactured by Hodogaya Kagaku ■) in 200 g of water was gradually added, the pH was adjusted to 4.1 using acetic acid, and the mixture was stirred at 60°C for 1 hour. This was poured into a large amount of water to precipitate the colored polymer, then separated, washed with water, and dried under vacuum at 40°C.

10g of colored polymer, 10g of Hilac 110E'I (manufactured by Mitsubishi Kasei ■, ketone resin), and 64g of ethyl alcohol.
, and 16 g of butanol were dissolved in a mixed solvent to prepare an ink composition of the present invention.

When this ink composition was filled in a felt-tip pen and written, lines were created on glass, hard vinyl chloride boards, polyethylene films, etc.

The adhesive strength of the dried lines was examined in the same manner as in Example f1, and the results shown in Table 1 were obtained. The adhesive strength after immersion in water was also examined in the same manner.

The results are shown in Table 1.

Comparative Example 1 The ink composition in Example 2 was prepared by mixing 10 g of colored polymer with 809.9 g of ethyl alcohol. An ink composition was produced in the same manner as in Example 2, except that it was dissolved in a mixed solvent of 10 g of n-butyl alcohol. When the adhesive strength was measured, the results shown in Table 1 were obtained.

Example 3 99% of water was added to a polymerization container under a nitrogen stream. Ethyl alcohol 23
g was prepared, and the temperature was raised to 60°C while stirring.

Butyl methacrylate) 24g, spinomer Na5S (purity 82.0% by weight) A sodium styrene sulfonate aqueous solution containing 19.59 dissolved in water 809 and a catalyst solution containing 1.09 of azobisisobutyronitrile dissolved in 200 g of ethyl alcohol. Each dropwise addition was started, and polymerization was carried out while dropping over a period of 3 hours, and the reaction was continued for 5 hours to obtain a polymer solution having a polymer concentration of 2 (L5% by weight).

Next, 100 g of this polymer solution was added with Cachilon Blue-CD-
A solution of PRLH (Hodogaya Chemical Industry Gm1J) a8 f' dissolved in 300 g of water was gradually added, and then paxa was prepared using acetic acid, followed by stirring at 60° C. for 1 hour. After pouring this into a large amount of water to precipitate a colored polymer, it was filtered, washed with water, and dried under vacuum at 40°C.

10 parts of colored polymer, 15 parts of Marquid High 51 (manufactured by Arayo Kagaku, rosin-modified maleic acid resin), 609 parts of ethyl alcohol. The ink composition of the present invention was prepared by dissolving it in a mixed solvent of 10 g of N-methylpyrrolidone and 5 g of isopropyl alcohol.

When this ink composition was filled in a felt-tip pen and written, lines were created on glass, hard vinyl chloride boards, polyethylene films, etc.

The adhesive strength of the dried lines was examined in the same manner as in Example 1, and the results shown in Table 2 were obtained. The adhesive strength after immersion in water was also examined in the same manner.

The results are shown in Table 2.

Comparative Example 2 The ink composition in Example 3 was prepared by adding 10 g of colored polymer to 809.9 g of ethyl alcohol. N-methylpyrrolidone 1159. An ink composition was prepared in exactly the same manner as in Example 3, except that the ink composition was dissolved in a mixed solvent of isopropyl alcohol and alcohol.

Stretching was performed in the same manner as in Example 5, and the adhesive strength was measured after drying and after immersion in water, and the results shown in Table 2 were obtained.

Example 4 Dimethylformamide C or less D was placed in a polymerization container under a nitrogen stream.
MF) 509 was charged, and the temperature was raised to 65°C while stirring.

Methyl methacrylate) 1 & 09. A monomer solution containing 17 g of ethyl methacrylate and 1,000 g of 2,3-dichlorobutadiene, Subinomer NaEE (sodium p-styrene sulfonate, purity 82.0% by weight, manufactured by Toyo Soda Kogyo ■) 7.49 was added to 90 g of DMF. Dissolved p-
Dropwise addition of a catalyst solution in which sodium styrene sulfonate solution and azobisin butyronitrile 1. % solution was obtained.

Next, add the cationic dye Cachilon Red T-BL to this solution.
A solution of 5 g of K (manufactured by Hodogaya Chemical Industry ■) dissolved in 200 g of water was gradually added, the pH was adjusted to 4.5 using acetic acid, and the mixture was stirred at 60°C for 1 hour.

After cooling to room temperature, the colored polymer was poured into a large amount of water to precipitate it, filtered, washed with water, and dried under vacuum at 40°C.

10g of colored polymer, 10g of Hytic 532 (Japanese Shellac ■, Shellac resin), 6 ml of ethyl alcohol.
89. The ink composition of the present invention was prepared by dissolving it in a mixed solvent of N-methylpyrrolidone 127.

When this ink composition was filled in a felt pen and written on it, streaks were created on glass, hard vinyl chloride boards, polyethylene films, etc.

The adhesive strength of the dried lines was examined in the same manner as in Example 1, and the results shown in Table 3 were obtained. We also investigated the adhesion strength after immersion in water.

The results are shown in Table 3.

Comparative Example 3 The ink composition in Example 4 was prepared by mixing colored polymer 109 with 71 h of ethyl alcohol and 59.9 h of ethyl alcohol. An ink composition was prepared in exactly the same manner as in Example 4, except that 155 g of N-methylpyrrolidone was dissolved in a mixed solvent. Stretching was performed in the same manner as in Example 4, and the adhesive strength was measured after drying and after immersion in water, and the results shown in Table 3 were obtained.

Example 5 (Lightfastness test) A lightfastness test was conducted on each of the ink compositions produced in Examples 1 to 4.

The light resistance test was carried out by measuring the color difference after 20 hours of exposure using a Sunshine Carbon Arc Fade Meter (manufactured by Suga Test Instruments) in accordance with the light test method specified for JIS B-6057 oil-based marking ink pens. This was carried out by

The results were as shown in Table-4.

Comparative Examples 4-7 All the ink compositions carried out in Examples 1-4 except that only dyes were dissolved instead of using colored polymers.
Ink compositions were prepared by following each example. However, some of the dyes used had low solubility and were thought to be impractical, but tests were conducted at concentrations at saturated solubility at room temperature of 23°C.

Color testing paper was prepared in the same manner as in Example 5, and a light fastness test was conducted. The test results were as shown in Table-4.

Claims (1)

[Scope of Claims] 1 Comprising: (A) an alcohol-soluble resin, (B) an alcohol-soluble resin having a sulfonic acid group or its salt dyed with a basic dye, and (C) an alcohol-based solvent. Writing ink composition. 2 Monomer units formed by introducing a sulfonic acid group or a salt thereof into an alcohol-soluble resin having a sulfonic acid group or a salt thereof, and units of ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. The writing ink composition according to claim 1, which contains at least one selected monomer unit. 3. The alcohol-soluble resin is at least one selected from ketone resin, rosin-modified maleic acid resin, phenol resin, polyvinyl butyral resin, and shellac resin.
The writing ink composition according to claim 1 or 2, which is a seed. 4 The alcohol solvent is a polyhydric alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and isobutyl alcohol, ethylene glycol, propylene glycol and glycerol. According to any one of claims 1 to 3, the main solvent component is at least one alcohol selected from monohydric alcohols and monomethyl ethers or monoethyl ethers of these polyhydric alcohols. The writing ink composition described. 5 Based on the weight of the ink composition, (A) component 1 to 30
% by weight and 1 to 40% by weight of component (B), the writing ink composition according to any one of claims 1 to 4.