JP6645865B2 - Oil-based ink composition for writing implement and writing implement containing the same - Google Patents

Description

  The present invention relates to an oil-based ink composition for a writing implement and a writing implement containing the composition. Furthermore, the present invention relates to an oil-based ink composition for writing implements capable of forming handwriting with excellent water resistance, and a writing implement containing the same.

Conventionally, dyes have been used as colorants in oil-based inks because of their excellent color developability. However, because of poor water resistance, the adhesion of water causes bleeding of handwriting that oozes out of handwriting and stains the surroundings. Therefore, as a countermeasure against bleeding, the use of a gold-containing dye or increasing the amount of resin has been applied.However, the coloring property of gold-containing dye is inferior, and when the amount of resin is increased, ink viscosity increases and writing performance deteriorates. It was something to do.
In order to solve the above problem, addition of various compounds has been studied. For example, a technique of adding a ketone resin having a softening point of 60 ° C to 100 ° C or an alkylphenol resin having 5 or more carbon atoms has been disclosed ( For example, see Patent Documents 1 and 2.
However, since the ketone resin and the alkylphenol resin have a low effect of imparting water resistance, a sufficient effect is not exhibited depending on the material of the writing surface, and sufficient water resistance cannot be imparted to the handwriting. In addition, when the amount of addition was increased to improve the effect, the dry-up resistance was reduced.
In particular, in the handwriting formed on the paper surface, the adhesion of water causes bleeding around the handwriting and deteriorates the appearance, so that a technique for improving the water resistance superior to the above-described conventional technique is required.

JP-A-5-17717 JP 2006-56946 A

  The present invention is capable of forming handwriting on various surfaces to be written even with an oil-based ink using a dye, and was written on papers that require particularly high performance without lowering dry-up resistance. Even in such a case, an object of the present invention is to provide an oil-based ink composition for a writing implement and a writing implement that can obtain a handwriting excellent in water resistance that does not bleed due to adhesion of water.

〔式中のｎは繰り返し数を表し、０〜５の正数である〕
更に、前記フェノール化合物の軟化点が１０５〜１６５℃であることを要件とする。
更には、前記筆記具用油性インキ組成物を収容した筆記具を要件とする。 The present invention, dye and an organic solvent and following general formula (1) Ri greens and contains at least a phenol compound represented by the phenolic compound for a writing instrument you 0.5 to 10 mass% in the total amount of the ink composition Require oil-based ink composition.

[N in the formula represents the number of repetitions and is a positive number from 0 to 5]
Further, the softening point of the phenol compound is required to be 105 to 165 ° C.
Further, a writing implement containing the oil-based ink composition for a writing implement is required.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to form a handwriting excellent in coloring property on various to-be-written surfaces, high water resistance can be provided, without impairing the dry-up performance of a pen tip. Therefore, even when writing on paper with an oil-based ink using a dye, it is possible to obtain handwriting with excellent water resistance that does not bleed due to adhesion of water. An oil-based ink composition and a writing instrument containing the same can be provided.

  The phenolic compound represented by the general formula (1) is a triphenolmethane-type phenolic resin, and a plurality of phenolic hydroxyl groups exhibit strong electron donating properties. Acts to inhibit the dye from dissolving in water. Therefore, the water resistance of the handwriting is improved, and bleeding due to the adhesion of water is suppressed. The above-mentioned effect is effective particularly for an oil-soluble dye made from a basic dye having a low water resistance, so that a clear handwriting which does not easily bleed into water can be formed regardless of the type of the dye.

The compound is a triphenolmethane-type phenol resin in which n in the general formula (1) represents a positive number of 0 to 5, preferably 1 to 3, and more preferably 1.3 to 2.5. is there.
The weight average molecular weight is not particularly limited, but is preferably 500 to 1000, more preferably 550 to 900, more preferably 600 to 800, and most preferably 600 to 700.
The softening point is not particularly limited, but those having a range of 105 to 165 ° C, preferably 105 to 145 ° C have a particularly high water resistance effect and are more suitable.
Examples of commercially available products of the compound include MEH-7500 and MEH-7500H (manufactured by Meiwa Kasei Co., Ltd.).

The phenol 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 the amount is less than 0.5% by mass, it is difficult to improve the water resistance of the handwriting. Even if the amount exceeds 10% by mass, no improvement in the water resistance is recognized, so no further addition is required.

Examples of the dye used as the colorant include organic solvent-soluble dyes classified as solvent dyes in a color index.
Specific examples of the solvent dye include Balifast Black 3806 (CI Solvent Black 29), Balifast Black 3807 (trimethylbenzylammonium salt of CI Solvent Black 29), and 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 Fast Red 1308 (a salt-forming body of CI Basic Red 1 and CI Acid Yellow 23) , Spirit Red 102 CI Basic Red 1 and CI Acid Yellow 42 salt-forming product), Balifast Violet 1701 (CI Basic Violet 1 and CI Acid Yellow 42 salt-forming product), Balifast Violet 1702 (a salt form of CI Basic Violet 3 and CI Acid Yellow 36), Spiron Red CGH (a salt form of CI Basic Red 1 and dodecyl (sulfophenoxy) -benzenesulfonic acid), oil Blue 613 (a mixture of CI Solvent Blue 5 and a resin).
Usually, those composed of basic dyes have high solubility in water, so handwriting bleeding due to adhesion of water is easy to occur, but when used in the ink of the present invention, handwriting bleeding is suppressed, so The effect of improving the water resistance becomes clear.
When a mixed dye of a basic dye and an acidic component or a salt-forming dye is used as the dye, the dye has poor light fastness. Therefore, 2- (3-t-butyl-5-octyloxycarbonylethyl) is used as a light fastness imparting agent. By using a benzotriazole derivative such as (-2-hydroxyphenyl) benzotriazole in combination, it is possible to suitably prevent the fading of the dye, and to form handwriting of various desired colors having excellent light fastness.

Further, a pigment can be used in combination. Examples of pigments include inorganic pigments such as carbon black, ultramarine blue, and titanium dioxide pigments, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, threne pigments, quinacridone pigments, anthraquinone pigments, sulphone pigments, and diketopyrrolopyrroles. Organic pigments, such as organic pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, metal powders obtained by treating the surface of aluminum powder or aluminum powder with a coloring resin, and a metal deposition film on a transparent or colored transparent film. Metallic luster pigments, fluorescent pigments, luminous pigments formed, natural mica, synthetic mica, glass flakes, alumina, pearl pigments whose transparent film pieces are coated with a metal oxide such as titanium oxide as a core substance. .
The coloring agent containing the dye may be used alone 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, and 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.
When a solvent having a vapor pressure of 5.0 to 50 mmHg, more preferably 10 to 50 mmHg at 20 ° C., which is easily volatilized as an organic solvent, is used as a main solvent, the dryness of the handwriting is excellent. Good handwriting can be formed without causing troubles such as the dry ink adhering to the hand and contaminating blank areas where the handwriting is not formed on the writing surface.
Organic solvents 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), ethylene glycol diethyl ether (9.7), glycol ether organic solvents such as ethylene glycol monoisopropyl ether (6.0), propylene glycol monomethyl ether (7.6), and n-heptane (35. 0), n-octane (11.0), isooctane (41.0 , Methylcyclohexane (37.0), ethylcyclohexane (10.0), toluene (24.0), xylene (5.0-6.0), hydrocarbon-based organic solvents such as 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), n-formic acid 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) , Ethyl propionate (28.0), n-butyl propionate (45.0), methyl butyrate (25.0), and ethyl butyrate (11.0).
The numbers in parentheses indicate the vapor pressure of each organic solvent at 20 ° C.
Of the organic solvents, preferably used are 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, and propylene glycol monomethyl ether. It is suitable because it is excellent in quick drying property and excellent in 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.
Further, 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, it is possible to adjust the handwriting drying rate by using an organic solvent having a boiling point of 160 ° C to 250 ° C in combination. preferable.
Benzyl alcohol is preferred as the organic solvent having a boiling point of 160 ° C to 250 ° C.

Further, it is preferable to add a resin to the ink, and it is possible to apply a resin which is soluble in an organic solvent usually used in an oil-based ink composition without limitation. Can be provided.
Specific examples of the resin include a ketone resin, an amide resin, an alkyd resin, a rosin-modified resin, a rosin-modified phenol resin, a phenol resin, a xylene resin, a polyvinyl butyral resin, a terpene-based resin, a cumarone-indene resin, a polyvinyl pyrrolidone, and a polyethylene oxide. And polymethacrylic acid esters, ketone-formaldehyde resins, α- and β-pinene-phenol polycondensation resins, polyvinyl butyral resins, maleic acid resins, acrylic resins, polyacrylic acid polymethacrylic acid copolymers and the like.
These resins may be used alone or in combination of two or more, and are used in an amount 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. Can be formed.
In particular, when the writing implement filled with the ink is in the form of a ball-point pen, it is possible to prevent the ink from leaking from the gap between the ball and the chip when not in use, or to prevent the ink from being left when the writing tip is left upward (upright state). Backflow can be prevented.
Examples of the shear thinning agent include a crosslinked acrylic resin, an emulsion type of a crosslinked acrylic resin, a non-crosslinked acrylic resin, a crosslinked N-vinylcarboxylic acid amide polymer or copolymer, and a noncrosslinked N-vinylcarboxylic acid. Acid amide polymers or copolymers, hydrogenated castor oil, fatty acid amide waxes, waxes such as oxidized polyethylene wax, stearic acid, palmitic acid, octylic acid, fatty acid metal salts such as aluminium salts of lauric acid, dibenzylidene sorbitol, Examples thereof include N-acylamino acid-based compounds, smectite-based inorganic compounds, montmorillonite-based inorganic compounds, bentonite-based inorganic compounds, and hectorite-based inorganic compounds.
In addition, the said shear-thinning agent can also be used together.

  When the ink composition of the present invention is used by filling it into a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, a thiophosphorous acid tri (alkoxycarbonylmethyl ester) ) Or thiophosphorous acid triesters such as triphosphorous acid tri (alkoxycarbonylethyl ester); phosphoric acid monoesters of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether; polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether It is preferable to add a lubricant such as a phosphoric diester or a metal salt, an ammonium salt, an amine salt, or an alkanolamine salt thereof to impart an effect of preventing wear of the ball seat.

The ink composition is put into practical use by filling it into a marking pen or a ball-point pen having a tip attached to a writing tip, but it is particularly preferable to use it with a marking pen because of its good writing feel. Further, since the marking pen has a structure in which the pen tip dries easily, the ink of the present invention which does not adversely affect the dry-up resistance becomes more useful.
When filling the marking pen, the structure and shape of the marking pen itself is not particularly limited.For example, a fiber chip, a felt chip, and a plastic chip are attached to the writing tip, and a fiber bundle stored inside the barrel is used. A structure in which ink is impregnated into an ink occluding body and ink is supplied to a writing tip portion, ink is directly accommodated in a barrel, and an ink flow rate adjusting member formed of a comb groove or a fiber bundle is interposed. Structured marking pens. In addition, as the shaft cylinder, a metal molded body such as a resin molded product or an aluminum can is used.

  When filling into a ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited. For example, ink is impregnated into an ink occluding body composed of a fiber bundle housed inside a barrel, and ink is supplied to a writing tip. Structure, containing ink directly inside the barrel, interposing an ink flow rate adjusting member in the form of a comb groove or an ink flow rate adjusting member consisting of a fiber bundle, and having an ink storage tube filled with an ink composition in the barrel. The ink storage tube communicates with a tip having a ball mounted on the tip, and a liquid stopper for preventing backflow is in close contact with the end surface of the ink (a solid ink backflow prevention body may be used together). Ballpoint pen). In addition, a resin molded product or a metal workpiece is used as the shaft cylinder or the ink storage tube.

  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 will be described along the note numbers.
(1) Orient Chemical Co., Ltd., trade name: Nigrosine base EX
(2) Orient Chemical Industry Co., Ltd., trade name: Varifast Red 1308
(3) Hodogaya Chemical Industry Co., Ltd., trade name: Spiron Yellow CGNH
(4) Arakawa Chemical Industry Co., Ltd., trade name: Rosin WW
(5) Daiichi Kogyo Seiyaku Co., Ltd., trade name: DK Ester F-110 (HLB: 11)
(6) MEH-7500 (softening point 110 ° C), manufactured by Meiwa Kasei Co., Ltd.
(7) Trade name: MEH-7500H (softening point 125 ° C), manufactured by Meiwa Kasei Co., Ltd.
(8) Arakawa Chemical Industry Co., Ltd., trade name: Tamanoru 510
(9) Arakawa Chemical Industries, Ltd., trade name: Ketone Resin K-90
(10) Kao Corporation, trade name: Neoperex GS

Preparation of Ink The raw materials were mixed at the compounding amounts of the above Examples and Comparative Examples, and stirred and dissolved at 20 ° C. for 3 hours to obtain an oil-based ink composition.

Preparation of Marking Pen 5 g of the obtained ink composition was placed in a shaft cylinder of a commercially available cap-type marking pen exterior (manufactured by Pilot Corporation; equipped with SCAP-F, an acrylic chip and containing a fiber bundle inside the shaft cylinder). By filling, an oil-based marking pen was obtained.

The following tests were performed using the marking pen.
Immersion Test Using each of the marking pens confirmed to be writable, a spiral circle was continuously written by hand on JIS P3201 writing paper A in an environment of 20 ° C. and 65% RH. Thereafter, the writing paper was immersed in the water for 30 minutes so that the handwriting was immersed in water, and the state of the handwriting and the immersion liquid taken out and dried were visually checked.
Cap-off test Each marking pen confirmed to be writable was placed in a state where the pen tip was exposed to the air, left in a horizontal state at 20 ° C. and 65% RH for 24 hours, and then at room temperature. Twelve spiral circles were continuously written by hand on JIS P3201 writing paper A. The handwriting state at that time was visually checked.
The results of the test are shown in the table below.

The evaluation of the test results is as follows.
Immersion test ：: Handwriting bleeding does not occur.
×: The dye oozes around the handwriting, or the entire paper and the immersion liquid are colored.
Cap-off test ：: No blurring occurs.
×: Scratching occurs during writing, or writing is impossible.

Claims (3)

Dye and an organic solvent and following general formula (1) Ri greens and contains at least a phenol compound represented by the phenolic compound for writing instruments oily ink composition you 0.5 to 10 mass% in the total amount of the ink composition .

[N in the formula represents the number of repetitions and is a positive number from 0 to 5]   The oil-based ink composition for a writing instrument according to claim 1, wherein the phenol compound has a softening point of 105 to 165C. A writing implement containing the oil-based ink composition for a writing implement according to claim 1.