JP5802562B2 - Oil-based ink composition for marking pen and marking pen incorporating the same - Google Patents

Description

The present invention relates to an oil-based ink composition for marking pens . More specifically, the present invention relates to an oil-based ink composition for a marking pen excellent in dry-up resistance in a state where the pen tip is exposed for a long time, and a marking pen incorporating the same.

Conventionally, in oil-based inks for writing instruments, a volatile (low boiling point) organic solvent such as a lower alcohol is used as a medium in order to obtain quick drying of handwriting. For this reason, when the cap is removed, the pen tip is dried, and the resin and colorant in the ink are dried and hardened.
In order to solve the above problem, 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 less is disclosed (for example, see Patent Document 1).

JP 2001-200196 A

  Although the addition of the sucrose fatty acid ester can provide a slight dry-up performance, it is difficult to obtain a sufficient effect when applied to a writing pen in the form of a marking pen having severe use conditions.

  The present invention is not only a general-purpose writing instrument, but also a writing instrument that can exhibit excellent dry-up resistance over a long period of time, even when applied to a marking pen-shaped writing instrument used in severe environmental conditions. An oil-based ink composition and a writing instrument are provided.

〔式（１）中のｎは１以上の整数であり、Ｒは炭素数１２〜２０のアルキル基である。〕
更に、前記アルキルグルコシドの融点が３０℃以上であることを要件とする。
更には、前記油性インキ組成物を内蔵してなるマーキングペンを要件とし、ポリエステル繊維束の樹脂加工体であるポリエステルチップを筆記先端部に備えたマーキングペンであることを要件とする。
The present invention relates to an oil-based ink composition for a marking pen comprising a colorant, an organic solvent selected from glycol ethers or aliphatic alcohols having 5 or less carbon atoms, a resin, and an alkyl glucoside represented by the following general formula (1). Things are a requirement.

[N in Formula (1) is an integer greater than or equal to 1, and R is a C12-C20 alkyl group. ]
Furthermore, it is a requirement that the melting point of the alkyl glucoside is 30 ° C. or higher.
Furthermore, the marking pen formed by incorporating the oil-based ink composition is a requirement, and it is a requirement that the marking pen is provided with a polyester chip, which is a resin processed body of a polyester fiber bundle, at the writing tip.

According to the present invention, even when ink using a highly volatile organic solvent is applied to a writing instrument in the form of a marking pen used under severe environmental conditions such as outdoors, it has excellent resistance to light without deteriorating handwriting performance. An oil-based ink composition capable of exhibiting dry-up performance over a long period of time and a marking pen incorporating the oil-based ink composition can be provided.

  The oil-based ink composition of the present invention is good by adding the alkyl glucoside given by the general formula (1) when an organic solvent selected from aliphatic alcohols and glycol ethers having 5 or less carbon atoms is used as a solvent. It exhibits high dry-up resistance for a long period of time in a state where a good handwriting can be formed.

The alkyl glucoside given by the general formula (1) is one in which maltose and a higher alcohol having 12 to 20 carbon atoms are glucoside-bonded, and has high solubility in the organic solvent used in the present invention. In particular, those bonded with higher alcohols having 16 to 20 carbon atoms are more useful because they produce high effects even in a small amount.
Examples of commercially available products of the alkyl glucoside include Emulgard PL68 / 50 (R = C ₁₆ / C ₁₈ ), Glucopone 50G (R = C ₁₂ / C ₁₄ ), and Glucopone 215 CSUP (R = C ₈ / C) manufactured by Cognis. ₁₀ ), Mydoll 12 (R = C ₁₂ ) manufactured by KAO, and the like.
In particular, those having a melting point of 30 ° C. or higher, preferably 40 ° C. or higher are more useful because they have good film-forming properties on the chip surface and high resistance to dry-up.
The alkyl glucoside is added to the ink in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
If it is less than 0.1% by weight, it is difficult to obtain the desired effect, and a large amount can be added, but if it is 10% by weight or less, the desired effect is sufficiently obtained.

As the organic solvent, at least one selected from aliphatic alcohols and glycol ethers having 5 or less carbon atoms is used. As the alcohol, a lower aliphatic alcohol having 1 to 5 carbon atoms is applied. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol , T-butyl alcohol, pentyl alcohol and the like.
Examples of the glycol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol diethyl 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 and the like.
The organic solvent may be used singly or in combination of two or more in the ink composition in the range of 40 to 95% by weight. At that time, compatible general-purpose solvents can be used in combination.

As the colorant, general-purpose dyes and pigments conventionally applied to oil-based inks are appropriately used.
Examples of the dye include organic solvent-soluble dyes classified as solvent dyes in the color index.
Specific examples of the solvent dye include Balifast Black 3806 (CI Solvent Black 29), 3807 (Trimethylbenzylammonium salt of the dye of CI Solvent Black 29), Spirit Black SB (C.I. Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Bali Fast Red 1308 (Salt Form of Dye of CI Basic Red 1 and Dye of CI Acid Yellow 23), Bali Fast Yellow AUM (Salt of CI Basic Yellow 2 dye and CI Acid Yellow 42 dye), Spiron Yellow C2GH (organic acid salt of CI Basic Yellow 2 dye) Ron Violet CRH (CI Solvent Violet 8-1), Balifu Strioviolet 1701 (salt salt of CI Basic Violet 1 and CI Acid Yellow 42 dyes), Spiron Red CGH (organic acid salt of CI Basic Red 1 dye), Spiron Pink BH (C.I. CI Solvent Red 82), Nigrosine Base EX (CI Solvent Black 7), Oil Blue 613 (CI Solvent Blue 5), Neozapon Blue 808 (CI Solvent Blue 70) and the like. It is done.
Examples of the pigment 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, selenium pigments, diketopyrrolo Organic pigments such as pyrrole pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, aluminum pigments, metal pigments whose surfaces are treated with colored resins, transparent or colored transparent films such as aluminum Metallic pigment, gold, silver, platinum, copper, with a thickness of 0.01 to 0.1 μm, obtained by peeling a metallic vapor deposited film such as aluminum formed on a substrate such as a metallic luster pigment, film, etc. Colloidal particles with an average particle size selected from 5 to 30 nm, fluorescent pigments, luminous pigments, thermal discoloration Pigments, natural mica as a core material, synthetic mica, glass pieces, alumina, pearl pigment and the like to the surface of the transparent film pieces were coated with a metal oxide such as titanium oxide.
The colorant may be used alone or in combination of two or more, and is used in the range of 3 to 40% by weight in the ink composition.

The resin is not particularly limited as long as it is soluble in the above organic solvent, and can be added to the ink for the purpose of imparting handwriting suppression, fixing property improvement, fastness, and the like. .
Specifically, 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, polymethacryl Examples include acid esters, ketone-formaldehyde resins, α- and β-pinene / phenol polycondensation resins, polyvinyl butyral resins, acrylic resins, and polyacrylic acid-polymethacrylic acid copolymers.
These resins may be used singly or in combination of two or more, and are used in the range of 0.5 to 40% by weight, preferably 1 to 35% by weight in the ink composition. If the amount is less than 0.5% by weight, sufficient effects such as suppression of handwriting on paper, improvement of fixing property, imparting fastness and the like cannot be exerted. If the amount exceeds 40% by weight, the solubility of the resin in the solvent decreases. In addition, the fluidity of the ink may be reduced.

Furthermore, the oil-based ink composition for a writing instrument of the present invention contains, in addition to the above components, an antioxidant, an ultraviolet absorber, a rust inhibitor, a lubricant, a viscosity modifier, a release agent, a pigment dispersant, an anti-oxidant, as necessary. Various additives such as a foaming agent, a shear thinning agent, and a surfactant can be used.
The additive is a so-called conventional additive, and can be appropriately used as necessary from known compounds.

As the rust inhibitor, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin and the like can be used.
As the antioxidant, dibutylhydroxytoluene, nordihydroxytoluene, flavonoids, butylhydroxyanisole, ascorbic acid derivatives, α-tocopherol, catechins and the like can be used.
As UV absorbers, 2- (2'-hydroxy-3'-t-butyl 5'-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole, p-benzoic acid-2-hydroxybenzophenone, and the like can be used.
As the antifoaming agent, dimethylpolysiloxane or the like can be used.

  Any release agent may be used as long as it is a compound that can provide release properties contained in an ink composition used for a writing board (white board) made of materials such as enamel, glass, metal, or thermoplastic or thermosetting plastic. For example, carboxylic acid esters, silicone surfactants, nonionic surfactants, and the like can be mentioned. Examples of suitable release agents include polyoxyalkylene alkyl ether sulfates, polyoxyalkylenes. Alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate or salt thereof, aliphatic dibasic acid ester, aliphatic monobasic acid ester, polyalkylene glycol ester, a compound selected from one or more Can also be used in combination.

  When the oil-based ink composition of the present invention is applied to 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 thiophosphite tri (alkoxycarbonyl) A lubricant such as a thiophosphite triester such as a methyl ester) or a thiophosphite triester (alkoxycarbonylethyl ester) can be added if necessary. Particularly, a polyoxyethylene alkyl ether or a polyoxyethylene alkyl aryl ether Use of phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid diester, or their metal salts, ammonium salts, amine salts, alkanolamine salts, etc., will prevent wear of the ball seat. Excel

Furthermore, by adding a shear thinning agent, ink leakage from the gap between the ball and the tip when not in use is prevented, or the ink flows backward when the writing tip is left facing upward (upright state). Can be prevented.
As the shear thinning agent, a conventionally known compound can be used. For example, a crosslinkable acrylic resin, a crosslinkable acrylic resin emulsion type, a crosslinkable N-vinylcarboxylic acid amide polymer or a copolymer. Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer aqueous solution, hydrogenated castor oil, fatty acid amide wax, oxidized polyethylene wax and other waxes , Fatty acid metal salts such as aluminum stearate, aluminum palmitate, aluminum octylate, aluminum laurate, dibenzylidene sorbitol, dextrin fatty acid ester, N-acyl amino acid compound, smectite inorganic compound, montmorillonite inorganic compound, bentonite inorganic Compound, Kutoraito phosphate mineral, silica and the like.

The ink composition is practically used by filling a ballpoint pen or a marking pen with a tip attached to a writing tip.
When filling the ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited. For example, an ink occlusion body composed of a fiber bundle housed in the shaft tube is impregnated with ink and supplied to the writing tip. Structure, ink is stored directly inside the shaft cylinder, and there is an ink storage tube filled with the ink composition in the shaft cylinder, with a comb groove-shaped ink flow control member and an ink flow control member consisting of fiber bundles interposed The ink storage tube communicates with a tip having a ball attached to the tip, and a ballpoint pen having a structure in which an ink follower such as a liquid stopper or a solid stopper is in close contact with the end face of the ink to prevent backflow it can.
When filling the marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a fiber tip, felt tip, or plastic tip is attached to the writing tip and the fiber bundle accommodated inside the shaft tube is used. The ink occlusion body is impregnated with ink, the ink is supplied to the tip of the writing, the ink is directly stored inside the shaft cylinder, and the ink flow rate adjustment member consisting of a comb groove-like ink flow rate adjustment member or fiber bundle is interposed Examples include a marking pen having a structure in which ink is directly stored in the shaft cylinder and a predetermined amount of ink is supplied to the writing tip portion by a valve mechanism.
In particular, when a polyester chip that is a resin processed body of a polyester fiber bundle is used as a chip applied to the marking pen, the writing feeling is soft and the ink following property is good, but it is disadvantageous in dry-up resistance. The effect of the ink is easily expressed and effective.

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

The contents of the raw materials in the table are explained according to the note numbers.
(1) C.I. I. Pigment Black 7 20%, polyvinyl butyral 20%, ethanol 60% dispersion (2) C.I. I. Pigment Blue 60 50%, polyvinyl butyral 50% processed pigment (3) C.I. I. Acid Yellow 42 and C.I. I. Salt formation body of Basic Red 1 (4) Rosin-modified styrene-maleic acid copolymer

Preparation of Ink Each raw material of the above Examples and Comparative Examples was mixed and stirred with a disper at 40 ° C. for 2 hours to obtain an oil-based ink composition for writing instruments.

Production of Marking Pen An oil-based marking pen was obtained by filling 5 g of the obtained ink composition into a commercially available marking pen exterior (manufactured by Pilot Corporation; provided with WMBM-12L, polyester tip).

Dry-up resistance test Using each marking pen, leave the pen tip in an exposed state in an environment of 20 ° C and 65% humidity, then spirally write on the coated paper every hour (total 3 hours) The state of the handwriting was confirmed visually.
The test results are shown in the following table.

The evaluation of the test results is as follows.
○: Handwriting better than writing is obtained.
Δ: Wrinkles are found in the writing, but it recovers within 10 circles.
X: Scratch of handwriting does not recover within 10 circles.

Claims (4)

An oil-based ink composition for a marking pen comprising a colorant, an organic solvent selected from glycol ethers or aliphatic alcohols having 5 or less carbon atoms, a resin, and an alkyl glucoside represented by the following general formula (1).

[N in Formula (1) is an integer greater than or equal to 1, and R is a C12-C20 alkyl group. ] The oil-based ink composition for a marking pen according to claim 1, wherein the melting point of the alkyl glucoside is 30 ° C or higher. Claim 1 or marking pen comprising a built-in marking pen oil-based ink composition according to 2. 4. A marking pen according to claim 3, wherein the marking pen is a marking pen provided with a polyester chip, which is a resin processed body of a polyester fiber bundle, at a writing tip.