JP6572014B2 - Oil-based ink composition for marking pen and marking pen containing the same - Google Patents

Description

  The present invention relates to an oil-based ink composition for marking pens and a marking pen containing the same. Furthermore, it is related with the oil-based ink composition which can form the handwriting excellent in water resistance, and the marking pen which accommodated it.

Conventionally, dyes are used as colorants in oil-based inks because of their excellent color developability. However, since they are poor in water resistance, they cause blurring of the handwriting that oozes out of the handwriting due to water adhesion and stains the surroundings. Therefore, as a countermeasure against bleeding, it is applied to use a metal-containing dye or to increase the amount of resin, but with a metal-containing dye, the color developability is inferior, and when the resin is increased, the ink viscosity increases and the writing performance deteriorates. It was something to end up with.
In order to solve the above problems, addition of various compounds has been studied. For example, a technique of adding a sucrose fatty acid ester having an HLB value of 8 or 9 or 9 to 11 has been disclosed (for example, patent document). 1 and 2).
However, even if the sucrose fatty acid ester has a prescribed HLB value, depending on the type of dye used and the material of the writing surface, sufficient effects are not exhibited, and the water resistance of the handwriting cannot be improved. It was. In particular, the handwriting on the paper surface deteriorates because water spreads around the handwriting. Therefore, it is necessary to improve the water resistance especially on the paper surface where the handwriting blur becomes clear.

JP 2001-200196 A JP 2012-214611 A

  The present invention can form handwriting on various writing surfaces even with oil-based inks using dyes, and is excellent in water resistance that does not bleed due to water adhesion even when written on paper. The present invention provides an oil-based ink composition for marking pens that provides a handwriting.

The present invention requires an oil-based ink composition for a marking pen comprising at least a solvent dye composed of a basic dye, an organic solvent, and an alkyl ester of gallic acid having an alkyl group having 1 to 18 carbon atoms. .
Furthermore, the gallic acid alkyl ester is required to be contained in an amount of 0.5 to 10% by mass based on the total amount of the ink composition.
Further, the marking pen containing the oil-based ink composition for a marking pen according to any one of the above requirements, and a structure in which the ink is impregnated with an ink occlusion body composed of a fiber bundle accommodated inside the shaft cylinder, or It is a requirement that the ink is directly stored inside the shaft cylinder and the ink flow rate adjusting member is interposed.

  According to the present invention, it is possible to form handwriting with excellent color developability on various writing surfaces, and even when oil-based ink using a dye is written on a paper surface, the water resistance does not bleed due to adhesion of water. Since a handwriting with excellent properties can be obtained, an oil-based ink composition excellent in convenience and practicality and a marking pen containing it can be provided.

式中のｎは１〜１８の自然数であり、上記化合物のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｉｓｏ−ペンチル基、ｓｅｃ−ペンチル基、ｔｅｒｔ−ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、２エチルヘキシル基、ノニル基、デシル基、ラウリル基、セチル基、ステアリル基、アリル基等が挙げられる。
前記エステル化合物はフェノール基が強い電子供与性を呈するため、油性インキ中に添加することで染料に対して作用し、染料が水に溶解することを抑制する。そのため、筆跡の耐水性が向上して水の付着による滲みが抑制される。前記効果は、特に耐水性が弱い塩基性染料を原料とするソルベント染料に対して有効に作用するため、染料の種類によらず水に滲み難い鮮明な筆跡を形成できる。 The alkyl ester of gallic acid is an ester compound composed of gallic acid represented by the following general formula (1) and an aliphatic alcohol having 1 to 18 carbon atoms, and has three phenol groups and an ester bond in an aromatic ring. .

In the formula, n is a natural number of 1 to 18, and the alkyl group of the above compound includes methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl. Group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, lauryl Group, cetyl group, stearyl group, allyl group and the like.
In the ester compound, since the phenol group exhibits a strong electron donating property, when it is added to the oil-based ink, it acts on the dye and suppresses the dye from being dissolved in water. Therefore, the water resistance of the handwriting is improved and bleeding due to water adhesion is suppressed. Since the above-mentioned effect effectively acts on a solvent dye made of a basic dye having a weak water resistance as a raw material, it is possible to form a clear handwriting that hardly permeates water regardless of the type of the dye.

The ester compound is used in an amount of 0.5 to 10% by mass, preferably 1 to 8% by mass, based on the total amount of the ink composition.
If it is less than 0.5% by mass, it is difficult to improve the water resistance of the handwriting, and even if added in excess of 10% by mass, no improvement in water resistance is observed, so no further addition is required.

Examples of the dye used as the colorant include organic solvent-soluble dyes classified as solvent dyes in the color index.
Specific examples of the solvent dye include Bali First Black 3806 (CI Solvent Black 29), Spirit Black SB (CI Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Nigrosine Base EX (CI Solvent Black 7), Spiron Pink BH (CI Solvent Red 82), Neozapon Blue 808 (CI Solvent Blue 70), Spiron Violet CRH (CI Solvent Violet 8-1), Bali First Red 1308 (salt formation of CI Basic Red 1 and CI Acid Yellow 23), Spirit Red 102 (CI Basic Red 1 and CI Acid Yellow) 42 salt formation), Bali First Violet 17 1 (salt formation of CI Basic Violet 1 and CI Acid Yellow 42), Bali First Violet 1702 (Salt Formation of CI Basic Violet 3 and CI Acid Yellow 36), Spiron Red CGH (CI basic red 1 and salt form of dodecyl (sulfophenoxy) -benzenesulfonic acid), oil blue 613 (mixture of CI solvent blue 5 and resin) and the like.
Usually, those composed of basic dyes are highly soluble in water, so they tend to cause handwriting blur due to water adhesion, but when used in the ink of the present invention, since handwriting bleeding is suppressed, especially The effect of improving water resistance becomes clear.
In addition, when using a mixed dye or a salt-forming dye of a basic dye and an acidic component as the dye, the dye is poor in light resistance, so 2- (3-t-butyl-5-octyloxycarbonylethyl) is used as a light resistance imparting agent. By using together with a benzotriazole derivative such as 2-hydroxyphenyl) benzotriazole, fading of the dye can be suitably prevented, and handwriting with various desired tones excellent in light resistance can be formed.

Moreover, a pigment can also be used together. Examples of pigments include inorganic pigments such as carbon black, ultramarine, and titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, selenium pigments, quinacridone pigments, anthraquinone pigments, stron pigments, and diketopyrrolopyrrole. -Based pigments, dioxazine-based pigments, perylene-based pigments, perinone-based pigments, isoindolinone-based pigments, and other organic pigments, aluminum pigments, metal pigments whose surfaces are treated with colored resins, and transparent or colored transparent films with metal-deposited films Examples include metallic luster pigments, fluorescent pigments, luminous pigments, and natural mica, synthetic mica, glass pieces, alumina, and pearl pigments in which the surface of transparent film pieces is coated with a metal oxide such as titanium oxide. .
The colorant containing the dye may be used singly or in combination of two or more, and is used in the range of 3 to 40% by mass in the ink composition.

As the organic solvent used in the ink, a conventional general-purpose solvent can be used, and it is used in the range of 40 to 80% by mass in the ink composition.
Examples of the organic solvent include benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, benzyl glycol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monophenyl ether Methyl lactate, ethyl lactate, and γ- butyrolactone and the like.
In addition, when a solvent having a vapor pressure of 5.0 to 50 mmHg, more preferably 10 to 50 mmHg, which is easily volatile as an organic solvent, is used as a main solvent, the handwriting has excellent drying properties. Good handwriting can be formed without causing problems such as dry ink adhering to the hand and contamination of blank areas on the writing surface where the handwriting is not formed.
Examples of the organic solvent having a vapor pressure of 5.0 to 50 mmHg (20 ° C.) include ethyl alcohol (45), n-propyl alcohol (14.5), isopropyl alcohol (32.4), and n-butyl alcohol (5.5). ), Alcohol organic solvents such as isobutyl alcohol (8.9), sec-butyl alcohol (12.7), tert-butyl alcohol (30.6), tert-amyl alcohol (13.0), ethylene glycol monomethyl ether (8.5), glycol ether organic solvents such as ethylene glycol diethyl ether (9.7), ethylene glycol monoisopropyl ether (6.0), propylene glycol monomethyl ether (7.6), n-heptane (35. 0), n-octane (11.0), isooctane (41.0 Hydrocarbon organic solvents such as methylcyclohexane (37.0), ethylcyclohexane (10.0), toluene (24.0), xylene (5.0 to 6.0), ethylbenzene (7.1), methyl Ketone organic solvents such as isobutyl ketone (16.0), methyl n-propyl ketone (12.0), methyl n-butyl ketone (12.0), di-n-propyl ketone (5.2), formic acid n- Butyl (22.0), isobutyl formate (33.0), n-propyl acetate (25.0), isopropyl acetate (48.0), n-butyl acetate (8.4), isobutyl acetate (13.0) And ester organic solvents such as ethyl propionate (28.0), n-butyl propionate (45.0), methyl butyrate (25.0) and ethyl butyrate (11.0).
In addition, the number in a parenthesis shows the vapor pressure of each organic solvent in 20 degreeC.
Of the organic solvents, preferably alcohols having 4 or less carbon atoms and / or glycol ethers having 4 or less carbon atoms, more preferably ethyl alcohol, n-propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether are used. It is suitable because it has excellent quick-drying properties and excellent solubility of various resins and additives used in combination.
The organic solvent having a vapor pressure of 5.0 to 50 mmHg at 20 ° C. is added in an amount of 50% by mass or more in the solvent.
Two or more solvents may be used in combination.
Furthermore, in a system using an alcohol having 3 or less carbon atoms and / or a glycol ether having 4 or less carbon atoms as a main solvent, an organic solvent having a boiling point of 160 ° C. to 250 ° C. can be used in combination to adjust the handwriting drying speed. preferable.
Benzyl alcohol is suitable as the organic solvent having a boiling point of 160 ° C to 250 ° C.

Furthermore, it is preferable to add a resin in the ink, and it can be applied without limiting what is usually soluble in the organic solvent used in the oil-based ink composition, suppression of blotting of handwriting, improvement of fixability, fastness, etc. Can be given.
Specific examples of the resin include ketone resin, amide resin, alkyd resin, rosin modified resin, rosin modified phenol resin, phenol resin, xylene resin, polyvinyl butyral resin, terpene resin, coumarone-indene resin, polyvinyl pyrrolidone, polyethylene oxide. , Polymethacrylic acid ester, ketone-formaldehyde resin, α- and β-pinene / phenol polycondensation resin, polyvinyl butyral resin, maleic acid resin, acrylic resin, polyacrylic acid polymethacrylic acid copolymer and the like.
These resins may be used alone or in combination of two or more, and are used in the range of 0.5 to 40% by mass, preferably 1 to 35% by mass in the ink composition.

Further, if necessary, a shear thinning agent can be added.
By adding the shear thinning agent, it is possible to suppress bleeding of the handwriting, so that even if writing on a fiber material such as a highly penetrating cloth as well as paper, the handwriting does not bleed and a good handwriting is achieved. Can be formed.
Examples of the shear thinning agent include cross-linked acrylic resins, cross-linked acrylic resin emulsion types, non-cross-linked acrylic resins, cross-linked N-vinylcarboxylic acid amide polymers or copolymers, and non-cross-linked N-vinyl carvone. Acid amide polymer or copolymer, hydrogenated castor oil, fatty acid amide wax, wax such as oxidized polyethylene wax, fatty acid metal salt such as stearic acid, palmitic acid, octylic acid, lauric acid aluminum salt, dibenzylidene sorbitol, Examples thereof include N-acylamino acid compounds, smectite inorganic compounds, montmorillonite inorganic compounds, bentonite inorganic compounds, hectorite inorganic compounds and the like.

The ink composition has a good writing feeling, and is put to practical use by filling a marker pen with a marker chip that can be written on various writing objects on the writing tip.
The structure and shape of the marking pen itself are not particularly limited. For example, a fiber chip, a felt chip, or a plastic chip is attached to a writing tip, and ink is stored in an ink occlusion body that is a fiber bundle accommodated inside a shaft cylinder. Structure that supplies ink to the tip of writing, ink is stored directly inside the shaft tube, and is written by interposing a valve mechanism, comb-groove-shaped ink flow rate adjustment member, ink flow rate adjustment member consisting of fiber bundles, etc. A marking pen having a structure for adjusting the amount of ink supplied to the tip portion can be mentioned. In addition, as the shaft cylinder, a metal processed body such as a resin molded product or an aluminum can is used.

  The ink compositions of Examples and Comparative Examples are shown in the following table. In addition, the numerical value of the composition in a table | surface shows a mass part.

The contents of the raw materials in the table are explained according to the note numbers.
(1) Product name: Nigrosine Base EX, manufactured by Orient Chemical Industry Co., Ltd.
(2) Product name: Bali Fast Red 1308, manufactured by Orient Chemical Co., Ltd.
(3) Product name: Oil Blue 613, manufactured by Orient Chemical Co., Ltd.
(4) Hodogaya Chemical Co., Ltd., trade name: Spiron Yellow CGNH
(5) Arakawa Chemical Industries, Ltd., trade name: Ketone Resin K-90
(6) Arakawa Chemical Industries, Ltd., trade name: Rosin WW
(7) Daiichi Kogyo Seiyaku Co., Ltd., trade name: DK ester F-110 (HLB: 11)
(8) Product name: Ryoto Sugar Ester S-570 (HLB: 5), manufactured by Mitsubishi Chemical Foods Corporation
(9) Product name: Bisphenol A, manufactured by Mitsubishi Chemical Corporation

Preparation of ink Each raw material was mixed by the compounding quantity of the said Example and a comparative example, and the oil-based ink composition was obtained by stirring and dissolving at 20 degreeC for 3 hours.

Production of marking pen By filling 5 g of the obtained ink composition into a shaft cylinder of a marking pen exterior (manufactured by Pilot Corporation; equipped with a WMBM-12L, polyester chip and containing a fiber bundle inside the shaft cylinder) An oily marking pen was obtained.

The following tests were conducted using the marking pen.
Immersion test Using each marking pen that was confirmed to be writable, a hand-written spiral circle was continuously written on JIS P3201 writing paper A in an environment of 20 ° C. Then, the writing paper was immersed for 30 minutes so that the handwriting was immersed in water, and the state of the handwriting which was taken out and dried was visually confirmed.
The results of the test are shown in the following table.

The evaluation of the test results is as follows.
Immersion test ○: Handwriting blur does not occur.
X: Dye oozes around the handwriting or the entire paper and the immersion liquid are colored.

Claims (4)

An oil-based ink composition for a marking pen, comprising at least a solvent dye composed of a basic dye, an organic solvent, and an alkyl gallate having a C 1-18 alkyl group.   The marking pen oil-based ink composition according to claim 1, wherein the gallic acid alkyl ester is contained in an amount of 0.5 to 10% by mass based on the total amount of the ink composition. The marking pen which accommodated the oil-based ink composition for marking pens of Claim 1 or 2. 4. The structure according to claim 3, wherein the ink occlusion body comprising a fiber bundle accommodated in the shaft tube is impregnated with ink, or the ink is directly stored in the shaft tube and an ink flow rate adjusting member is interposed. Marking pen.