JPH02150472A - Oily ink composition - Google Patents

Abstract

PURPOSE:To provide the subject odorless composition composed of a specific colorant, an alkylphenol novolak resin and an aliphatic saturated hydrocarbon solvent and giving a written mark free from tackiness. CONSTITUTION:The objective composition is composed of (A) a colorant produced by reacting a basic dye (e.g. C.I. Basic Yellow 2 of formula I) with a laurylsulfuric acid (salt), (B) an alkylphenol novolak resin soluble in an aliphatic saturated hydrocarbon solvent [e.g. the resin of formula II (R is 1-15C alkyl substituted at o-, m- or p-position; n is 0-9)] and (C) an aliphatic saturated hydrocarbon (e.g. n-hexane) as a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to an oil-based ink composition. More specifically, the present invention relates to an oil-based ink composition in which a basic dye is modified and dissolved in an aliphatic saturated hydrocarbon solvent, and is particularly used for feltben inks.

(B) Conventional technology Oil-based inks that have been used for marking paper, plastic, glass, etc. are manufactured by dissolving oil-soluble dyes, film-forming agents, etc. in aromatic hydrocarbon solvents such as toluene and xylene. was. However, the above-mentioned oil-based ink has a drawback that the odor of the solvent is strong, and it has been desired to develop an oil-based ink using a low-toxicity and odorless aliphatic hydrocarbon solvent instead of the above-mentioned solvent.

When looking at basic dyes as coloring agents for oil-based ink compositions, basic dyes have high coloring power per unit weight, are sold in large quantities on the market as dyes for dyeing textiles, and are available in inexpensive and abundant varieties. Not only can the number of colorants be utilized, but also the colorants have excellent compatibility with each other, so by blending colorants, it is possible to provide colorants with various hues and brightnesses. It cannot be used as a coloring agent, and must be modified to be oily in order to be used as a coloring agent in oil-based inks.

The oil-based ink composition using a coloring agent of a basic dye modified to be oil-based is a coloring agent obtained by reacting C,1, Basic Plue 3 with a mixture of sodium cetyl sulfonate and sodium stearyl sulfonate, and petroleum oil. Ink for felt-tip pens obtained by dissolving resin in ligroin, coloring agent obtained by reacting C, 1, Basic Red 12 with sodium azelate, and felt-tip pen ink obtained by dissolving pentaester resin in ligroin. A felt-tip pen made by dissolving a colorant such as ink obtained by reacting a basic dye with an anionic surfactant and a resin soluble in petroleum-based solvents, mainly aliphatic hydrocarbons, in the petroleum-based solvent. (Japanese Patent Application Laid-open No. 49-2
No. 8424).

(c) Problems to be Solved by the Invention In the conventional oil-based ink compositions using basic dyes, the solubility of the colorant in aliphatic hydrocarbon solvents is low, and solid components may remain during dissolution. Many of them are prone to post-precipitation or gelation, and even if a colorant is selected and used in which a basic dye is modified to increase its solubility, it has the disadvantage that handwritten marks become sticky and difficult to dry.

This invention was made to solve the above problem, and provides an oil-based ink composition that uses a basic dye and has good solubility in a resin solution dissolved in an aliphatic hydrocarbon solvent, and does not leave sticky marks. It tries to provide something.

(d) Means for Solving the Problems The inventors have discovered that the coloring agent obtained by reacting a basic dye with an alkyl compound has organic properties that are greatly influenced by the chemical structure of the alkyl compound. If the organic colorant is strong, the softening point will be lowered and it will become oily, and oil-based ink made with such a colorant will cause sticky marks. On the other hand, if the organic colorant is weak, the solubility and compatibility with the resin/solvent mixture will decrease. After discovering this fact, we conducted intensive research on the balance between organic and inorganic properties in order to solve the problems of "stickiness" and "solubility" described in F+ at the same time, resulting in this invention.

According to this invention, at least one coloring agent obtained by reacting a basic dye with lauryl sulfate or a salt thereof, an alkylphenol novolac resin soluble in an aliphatic saturated hydrocarbon solvent, and an aliphatic saturated solvent as a solvent. An oil-based ink composition comprising a hydrocarbon solvent is provided.

In this invention, at least one coloring agent obtained by reacting a basic dye with lauryl sulfate or a salt thereof is used.

The basic dyes are, for example, C,1, Basic Yellow 2 CI 41000 C,1, Basic Blue CI 42595 C,! , Basic Red 1 CI 45160 C1! , Basic Violet 10CI 4517
0 etc. can be used.

As the lauryl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, etc. can be used, for example.

The coloring agent can be produced, for example, by dropping the aqueous solution of the basic dye into an aqueous solution of lauryl sulfate or its salt, filtering the generated precipitate, washing with water, and drying. It is a colored substance whose absorbance near the wavelength has decreased by an amount corresponding to the increase in molecular weight caused by the reaction of lauryl sulfate with respect to the basic dye used as the raw material.

These colorants can be used singly or in combination of two or more, and the amount used is usually 2 to 100% of the oil-based ink composition. 2
% by weight is suitable, with 3 to 8% by weight being preferred.

The alkylphenol novolac resin in the present invention is obtained by condensing alkylphenol and formaldehyde with an acidic catalyst, and is soluble in an aliphatic saturated hydrocarbon solvent, and has the formula (where R is ortho, meta, or para carbon number 1-
15, preferably an alkyl group of 4 to 8, and n is an integer of 0 to 9, preferably 3 to 6) can be used. This usage amount is 3% compared to normal oil-based ink.
~35% by weight is suitable, among which 7~25% by weight
is preferred.

Examples of the aliphatic saturated hydrocarbon solvent in this invention include normal hexane, isohexane, normal heptane,
Normal octane, isooctane, normal decane, Isopar E (manufactured by Exxon Chemical Co., Ltd., aliphatic saturated hydrocarbon,
Aniline point: 74° C.), Isopar G (same as above, aniline point: 80° C.), etc. can be used alone or in an appropriate mixture. The amount used is usually 45 to 80% by weight based on the oil-based ink, and preferably 70 to 80% by weight.

In the oil-based ink composition of the present invention, since the alkylphenol novolac resin acts as a dissolution aid for the colorant,
In order to mix uniformly, it is preferable to first dissolve the alkylphenol novolac resin in an aliphatic hydrocarbon solvent, and then add and dissolve the colorant into this solution.

The oil-based ink composition of the present invention contains 3% by weight or less of a fatty acid of 012 or higher, such as oleic acid or stearic acid, which imparts smoothness in writing, and 3% by weight or less of a fatty acid of 012 or higher, such as oleic acid or stearic acid, and 3% by weight or less of a fatty acid of 012 or higher, such as oleic acid or stearic acid. Resins that are soluble in aliphatic saturated hydrocarbon solvents, such as Japanese hydrocarbon resins, rosin esters, and alkylphenol resol resins, may also be added.

Note that the oil-based ink composition of the present invention may be mixed with other dyes that do not disintegrate the solution state to obtain a desired color tone.

(e) Action Lauryl sulfate or its salt reacts with basic dyes to modify the basic dyes into oil-based coloring agents that do not leave sticky marks. When mixed into a resin solution, the alkylphenol novolac resin acts as a solubilizing agent, so that the colorant is uniformly dissolved, and the aliphatic saturated hydrocarbon solvent replaces solvents such as toluene and xylene, making it odorless.

(f) Example In the example of this invention, the following materials are used as main raw materials.

Flexo Yellow 110: BASF, basic dye, C,1, Basic Yellow 2゜Rhodamine 6 GCP: Kuchigai Kagaku, basic dye, C,1, Basic Red 10 Bassonil Red 540...manufactured by BASF, basic dye, C,1, Basic Violet 10° Bassonil Blue 636...manufactured by BASF, C,
1, Basic Bruch, C, I, 42595°Monogen LH...Daiichi Kogyo Seiyaku Co., Ltd., lauryl sulfate.

Tamanol 510...manufactured by Arayo Kagaku Co., Ltd., butylphenol novolac resin, softening point (ring and ball method) 75-95℃
.

Isopar E: Manufactured by Exxon Chemical Co., aliphatic saturated hydrocarbon solvent, aniline point 75°C.

Isopar G...manufactured by Exxon Chemical Co., aliphatic saturated hydrocarbon solvent, aniline point 80°C.

Example 1 3250 parts by weight of a 1.5% by weight aqueous solution of Rhodamine 6GCP is added dropwise over 3 hours to 1880 parts by weight of a 3% by weight aqueous solution of Monogen L H4 at 25 to 30°C. The resulting water-insoluble precipitate was filtered, washed with water, and dried to obtain 67 parts by weight of lauryl sulfate of C, 1, Basic Red I.

In addition, c, r, basic red! and c, r, i - about 5 each of lauryl sulfate of basic red l.
Maximum absorption wavelength (528 am) as ppm methanol solution
As shown in Table 1, the lauryl sulfate in Table 1 C, 1, Basic Red 1 has a molecular weight increase due to salt formation compared to the raw material C, 1, Basic Red 1. The absorbance (528 nm) showed a low value corresponding to .

Example 2 20 parts by weight of monogen LHIO in 47.8 parts by weight aqueous solution
Type 2 dish 20% aqueous solution of Alexoero-110 at ~25°C
0 parts by weight is added dropwise over 3 hours. The precipitate obtained by dropping was filtered, washed with water, and dried to obtain 5.2 parts by weight of lauryl sulfate of C, 1, Basic Yellow 2.

Example 3 Monogen LH 60 to 1040 parts by weight of 4% by weight aqueous solution
At 70° C., 1525 parts by weight of a 6% by weight aqueous solution of Bathonil Red 540 are added dropwise. The obtained precipitate was filtered, washed with water, dried, and C,1, basic violet lO
26.4 parts by weight of lauryl sulfate was obtained.

Example 4 Add 25 parts by weight of Tamanol 510 to 120 parts by weight of Isopar 8 and dissolve by stirring at 25° C. for 30 minutes to prepare a uniform resin solution. This resin solution was heated to 60°C, and therein were added C obtained in Examples 1, 2 and 3, 1. basic·
Yellow 2 lauryl sulfate 4.4 parts by weight, C, 1, Basic Red 1 lauryl sulfate 3.3 parts by weight, c,
r, basic violet 10 lauryl sulfate 3
．． 3 parts by weight were added and dissolved by stirring to obtain a transparent red oil-based ink.

Example 5 25 parts by weight of Tamanol 51O was added to a mixed solution of 100 parts by weight of Isopar E and 18 parts by weight of Isopar 0.
Stir for 30 minutes at ℃ to dissolve and create a homogeneous resin solution.

This resin solution was heated to 40°C and put into this Example! and C obtained in 2, 1. 8.3 parts by weight of lauryl sulfate of Basic Yellow 2 and 0.03 parts of lauryl sulfate of C, 1, Basic Red L were added and stirred to uniformly dissolve to obtain a transparent yellow oil-based ink. .

Example 6 C, t, 3 parts by weight of lauryl sulfate of Basic Yellow 2, C, I obtained in Examples 1.2 and 3.

2.3 parts by weight of lauryl sulfate from Basic Red L;
A combination of 2.3 parts by weight of lauryl sulfate of C.1, Basic Violet 10, and 1 part of Tamanol 510.
Add 7 parts by weight and 8 parts by weight of Isopar 0, and make 15~
Stir at 20°C for 1 hour, then at 35-40°C for 1 hour,
A transparent red oil-based ink was obtained.

Example 7 25 parts by weight of Tamanol 51O was added to a mixed solution of 102 parts by weight of Isopar E and 18 parts by weight of Isopar 0.
℃ for 30 minutes to dissolve, and this homogeneous resin solution was
C1 obtained in Examples I and 2 was maintained at 0-60°C. , Basic Yellow 2 Lauryl Sulfate 5.
8 parts by weight and 1.9 parts by weight of lauryl sulfate of C.1 and Basic Red 1 were added and stirred for 1 hour to uniformly dissolve, thereby obtaining a transparent orange oil-based ink.

Example 8 Iso p
Stir and dissolve at ℃ for 30 minutes to prepare a resin solution. C obtained in Examples 2 and 3, 1. 5.7 parts by weight of lauryl sulfate from Basic Red 1 and 2.5 parts by weight of lauryl sulfate from Basic Red 1O were blended and dissolved with stirring at 60°C to obtain a transparent pink oil-based ink.

Example 9 A solution is prepared by dissolving 1000 parts by weight of Bassonil Blue 636 in 50 parts by weight of methanol and 500 parts by weight of water.

Next, in 214 parts by weight of a 5% by weight aqueous solution of Monogen LH, 4
The Basonil Blue 636 solution is added dropwise over 40 minutes at 5-50°C. The obtained pasty precipitate was washed with water and dried, and C,1, basic bruch lauryl sulfate 5
, 7 parts by weight. Although this material has a low softening point, it can be handled as a solid at room temperature. Next, 100 parts by weight of the same resin solution as in Example 4 was added with the above C,! , 3.8 parts by weight of lauryl sulfate of Basic Blue was dissolved with stirring at 60°C to obtain a transparent blue oil-based ink.

Example 1O Example 1.2 was added to 100 parts by weight of the same resin solution as Example 4.
．． C1!6 Basic Yellow 2 obtained in 3 and 9
2.6 parts by weight of lauryl sulfate, C, 1, basic?
1.4 parts by weight of lauryl sulfate of Red 1, 1.4 parts of lauryl sulfate of C,1, Basic Violet 1O, lauryl sulfate of C,1, Basic Blue 2
．． 8 Ryoyabu was stirred and dissolved at 60°C to obtain a uniform black oil-based ink.

When the oil-based inks obtained in Examples 4 to 10 were impregnated into felt to make felt-tip pens and a writing test was conducted, it was confirmed that the writing marks in all cases were non-sticky and odorless.

Comparative Example 1 In Example 4, petroleum resin (manufactured by Tokushima Oil Co., Ltd., pentaester resin) was used in place of Tamanol 510, and even if the same procedure as in Example 4 was carried out, no resin solution was obtained, and a colorant was added. When the mixture was stirred, the colorant did not dissolve.

Comparative Example 2 In Example 6, petroleum resin (manufactured by Yasseki Kagaku Co., Ltd., Nisseki Polymer #120 resin) was used instead of Tamanol 51O,
Other than this, a resin solution was prepared in the same manner as in Example 6, and a colorant was added thereto and stirred. However, the colorant did not dissolve, and when the resin solution was cooled to 20°C, only a portion of the dissolved material remained. part was precipitated.

(G) Effects of the Invention According to the present invention, it is possible to provide an odorless oil-based ink composition that uses a basic dye, has good solubility in aliphatic hydrocarbon solvents, and does not leave sticky marks.

Claims (1)

[Claims] 1. At least one coloring agent obtained by reacting a basic dye with lauryl sulfate or its salt, an alkylphenol novolac resin soluble in an aliphatic saturated hydrocarbon solvent, and an aliphatic saturated hydrocarbon as a solvent. An oil-based ink composition.