JP2006124456A - Oil-based ink composition for writing utensil and writing utensil containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-based ink composition for writing utensil having excellent wettability of the ink to a non-penetrating face such as glass, plastics and metal, fixability of the written mark and dryability of the ink and forming a good written mark and provide a writing utensil such as ball-point pen containing the ink composition. <P>SOLUTION: The oil-based ink composition for writing utensil contains a coloring agent, an organic solvent and a polyglycerol-modified silicone as essential components. The amount of the polyglycerol-modified silicone is 0.1-10 wt.% based on the total amount of the ink composition. The invention further provides a writing utensil such as ball-point pen containing the oil-based ink composition. The oil-based ink composition for writing utensil incorporated with a shear viscosity depressant is directly held in a pipe-formed ink holding tube and a back-flow prevention device is placed at the rear end of the tube to obtain a ball-point pen having a simple structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an oil-based ink composition for a writing instrument and a writing instrument incorporating the same. More specifically, the present invention relates to an oil-based ink composition for a writing instrument having excellent wettability of ink to a non-penetrating surface, dryness and fixing property of handwriting, and a writing instrument incorporating the same.

Conventionally, as a writing instrument oil-based ink having stickiness of handwriting on a non-penetrating surface, an organic solvent such as a hydrocarbon, alcohol or glycol ether having a high vapor pressure is used as a main solvent, a modified phenol resin, a modified terpene resin, an acrylic resin, Ink compositions containing a ketone resin or the like as a fixing agent are frequently used. In addition to these oil-based inks for writing instruments, a silicone-based surfactant such as polyether-modified silicone (see Patent Document 1) and a glass transition temperature are used in order to further improve the wettability of ink on non-penetrating surfaces and the fixability of handwriting. It has been proposed to add a copolymer (see Patent Document 2) containing cyclohexyl methacrylate at -25 ° C to 10 ° C.
JP-A-6-271803 Japanese Patent Laid-Open No. 11-286636

  In the case of the oil-based ink to which the polyether-modified silicone is added, the wettability of the handwriting on the non-penetrating surface is improved, but the adhesion and the drying property of the handwriting are not improved at all. When a resin having a low glass transition temperature is used, the adhesion of the handwriting is improved, but a resin having a low glass transition point is in a semi-liquid state at room temperature and has adhesiveness. Therefore, the handwriting has a problem that a sticky feeling (tack) remains even after drying.

  As a result of intensive studies to solve the problems of the conventional oil-based ink for writing instruments, the present inventors have found that even when writing on a non-penetrating surface by blending polyglycerin-modified silicone, the wettability and adhesion of handwriting. Has been found to be significantly improved, and the present invention has been completed.

The present invention requires an oil-based ink composition for a writing instrument comprising a polyglycerin-modified silicone in an oil-based ink composition comprising at least a colorant, an organic solvent and a resin.
In addition, it is a requirement that the oil-based ink composition for writing instruments contains 0.1 to 10.0% by weight of the polyglycerin-modified silicone in the total amount of ink.
Furthermore, it is required that the writing instrument containing the oil-based ink for the writing instrument and the writing instrument are in the form of a ballpoint pen.

  The present invention includes a polyglycerin-modified silicone that significantly improves the wettability, adhesion, and drying properties of the handwriting on the non-penetrating surface, and can form a good handwriting oil-based ink composition for writing instruments and A writing instrument incorporating the same can be provided.

  As the polyglycerin-modified silicone used in the present invention, a compound represented by the following formula (1) is preferably used.

（式中、ｍ，ｎはそれぞれ１以上の整数を示し、Ｒ１ はアルキル基、アルケニル基、シクロアルキル基、アリール基、これらの基の水素原子が部分的にハロゲン原子で置換された基、ポリオキシアルキレン基を示し、そのうち少なくとも１つ以上は下記式（２）〜（８）から選ばれるポリグリセリン基である。）

（式中、Ｑは炭素数１〜１０のアルキレン基を示し、Ｒ２ は水素又は炭素数１〜３０のアルキル基を示し、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖはそれぞれ１以上の整数を示す。）

(In the formula, m and n each represent an integer of 1 or more, R1 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a group in which hydrogen atoms of these groups are partially substituted with halogen atoms, poly An oxyalkylene group, at least one of which is a polyglycerin group selected from the following formulas (2) to (8).

(In the formula, Q represents an alkylene group having 1 to 10 carbon atoms, R 2 represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and p, q, r, s, t, u, v are each 1 or more. Indicates an integer.)

The polyglycerin-modified silicone is added to the ink composition in an amount of 0.1 to 10.0% by weight, preferably 0.2 to 5.0% by weight, more preferably 0.5 to 3.0% by weight.
If it is less than 0.1% by weight, it is difficult to obtain a desired effect, and a sufficient effect is obtained with an addition amount of 10.0% by weight or less, so that no further addition is required.
The oil-based ink composition for writing instruments to which the polyglycerin-modified silicone is added has a feature that the wettability, stickiness and drying property of the handwriting are remarkably improved even when writing on a non-penetrating surface such as glass, plastic film or metal. Have.

Examples of the dye used as the colorant include organic solvent-soluble dyes classified as solvent dyes in the color index.
As a specific example of the solvent dye,
Bali First Black 3806 (CI Solvent Black 29),
Bali First Black 3807 (Trimethylbenzylammonium salt of 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),
Neo Zapon Blue 808 (CI Solvent Blue 70),
Bali First Red 1308 (salt structure of CI Basic Red 1 and CI Acid Yellow 23),
Spirone violet CRH (CI Solvent Violet 8-1),
Bali First Red 1308 (salt structure of CI Basic Red 1 and CI Acid Yellow 23),
Spirit Red 102 (salt structure of CI Basic Red 1 and CI Acid Yellow 42),
Bali First Violet 1701 (salt structure of CI Basic Violet 1 and CI Acid Yellow 42),
Bali First Violet 1702 (salt structure of CI Basic Violet 3 and CI Acid Yellow 36),
Spiron Red CGH (CI basic red 1 and dodecyl (sulfophenoxy) -benzenesulfonic acid salt),
And oil blue 613 (a mixture of CI Solvent Blue 5 and resin).
In addition, when using a mixed dye or a salt-forming dye of a basic dye and an acidic component as a dye, the dye is poor in light resistance, so that 2- (3-tert-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.

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, 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 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.

As the organic solvent used in the ink, a conventionally used solvent can be used, and it is used in the range of 40 to 80% by weight 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 mono Ethyl 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, γ -Butyrolac The emissions and the like.
In addition, when a solvent having a vapor pressure of 5.0 to 50 mmHg at 20 ° C., which is easily volatile as an organic solvent, is used as the main solvent, the handwriting has excellent drying properties. Therefore, when the handwriting is touched, undried ink adheres to the hand. And a good handwriting can be formed without causing problems such as contamination of a blank portion on which the handwriting on the writing surface 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),
Glycol ether organic solvents such as ethylene glycol monomethyl ether (8.5), 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), methylcyclohexane (37.0), ethylcyclohexane (10.0), toluene (24.0), xylene ( 5.0-6.0), hydrocarbon organic solvents such as ethylbenzene (7.1),
Ketone organic solvents such as methyl isobutyl ketone (16.0), methyl n-propyl ketone (12.0), methyl n-butyl ketone (12.0), di-n-propyl ketone (5.2),
N-butyl formate (22.0), isobutyl formate (33.0), n-propyl acetate (25.0), isopropyl acetate (48.0), n-butyl acetate (8.4), isobutyl acetate (13 0.0), ethyl propionate (28.0), n-butyl propionate (45.0), methyl butyrate (25.0), ethyl butyrate (11.0), and other organic organic solvents.
The numbers in parentheses indicate the vapor pressure of each organic solvent at 20 ° C.
Two or more solvents may be used in combination.

Moreover, resin can also be added as needed.
Examples of the resin include ketone resins, ketone-formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinylpyrrolidone, α- and β-pinene / phenol polycondensation resins, polyvinyl Examples include butyral resin, acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and the like, which are used for fixing to a writing material and imparting viscosity.

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.
Furthermore, when the writing instrument to be filled with the ink is in the form of a ballpoint pen, it prevents ink leakage from the gap between the ball and the tip when not in use, or the ink when the writing tip is left upward (upright state). Backflow can be prevented.
The viscosity of the ink composition to which the shear thinning agent is added is such that the ink viscosity is 10 mPa · s (20 ° C.) or more at a shear rate of 3.84S ⁻¹ by an E-type viscometer at 20 ° C., preferably 10 to 1000 mPa · s and a shear thinning index of 0.3 to 0.99, preferably 0.5 to 0.99.
The shear thinning index (n) is expressed by an empirical formula T = Kj ⁿ (K is a non-Newtonian viscosity coefficient) obtained from rheological measurement using a viscometer such as a shear stress value (T) and a shear rate value (j). It is a value calculated by fitting.

〔式中、Ｒ１ は炭素数１乃至１２のアルキル基を示し、Ｒ２ は炭素数１乃至２４のアルキル基を示し、ｍ、ｎは数千乃至数十万の重合度を示す。〕
アクリル酸又はメタクリル酸と、下記一般式（１１）又は（１２）で示されるアクリル酸エステル又はメタクリル酸エステルの共重合体、

（式中、Ｒ１ は炭素数１乃至１２のアルキル基を示す。）

（式中、Ｒ２ は炭素数１乃至１２のアルキル基を示す。）
等を例示できる。
なお、前記剪断減粘性付与剤は併用することもできる。 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, N-acyl amino acid compound, smectite inorganic compound, montmorillonite inorganic compound, bentonite inorganic compound, hectorite inorganic compound, silica, acrylic copolymer of the following general formula (9) and the following general formula (10),

[Wherein, R1 represents an alkyl group having 1 to 12 carbon atoms, R2 represents an alkyl group having 1 to 24 carbon atoms, and m and n represent a degree of polymerization of several thousand to several hundred thousand. ]
A copolymer of acrylic acid or methacrylic acid and an acrylic ester or methacrylic ester represented by the following general formula (11) or (12):

(In the formula, R1 represents an alkyl group having 1 to 12 carbon atoms.)

(Wherein R 2 represents an alkyl group having 1 to 12 carbon atoms.)
Etc. can be illustrated.
The shear thinning agent can be used in combination.

  When the ink composition of the present invention is used by filling 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) ) And thiophosphite triester (alkoxycarbonylethyl ester), etc., polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether It is preferable to add a lubricant such as a phosphoric acid diester or a metal salt, an ammonium salt, an amine salt, an alkanolamine salt thereof to give the ball seat an antiwear effect.

The ink composition is put into practical use by filling a marking pen or ballpoint pen with a tip attached to the writing tip.
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, plastic tip is attached to the writing tip, and the fiber bundle contained in the shaft cylinder 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 The marking pen of structure is mentioned.
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 chip having a ball attached to the tip, and a ballpoint pen having a structure in which a liquid stopper for backflow prevention is in intimate contact with the end surface of the ink.

The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip is moved forward by a spring body Energized items can be applied.
The ball may be about 0.2 to 3 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, or rubber.
In addition, the writing instrument filled with the ink of the present invention includes those provided with a rolling mechanism such as a roller at the tip of the writing for forming a handwriting by the same rolling operation as that of the ball.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is used as the ink storage tube that stores the ink composition.
Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a refill type in which the refill is accommodated in the shaft cylinder, or the shaft cylinder itself having a tip mounted on the tip is used as an ink container to directly fill the shaft cylinder with ink. May be.

The back end of the ink composition accommodated in the ink accommodating tube may be filled with an ink backflow prevention body.
The ink backflow prevention body composition is composed of a non-volatile liquid or a hardly volatile liquid.
Specifically, petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more can be used in combination.

It is preferable to add a gelling agent to the nonvolatile liquid and / or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface of the silica is hydrophobized, the surface is methylated fine particle silica, and aluminum silicate. , Swellable mica, hydrophobic thickeners such as bentonite and montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide modified Examples include dextrin compounds such as polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid ink backflow prevention body composition can be used in combination.

The following table shows the formulations of Examples and Comparative Examples.

The contents of the raw materials in the table will be explained according to the note numbers.
(1) Product name: Bali Fast Black 3806, manufactured by Orient Chemical Co., Ltd.
(2) Toyo Aluminum Co., Ltd., trade name: Alpaste 5680NS
(3) Product name: Picolastic A75, manufactured by Rika Hercules Co., Ltd.
(4) Product name: Synthetic Resin SK, manufactured by Impex Chemical Co., Ltd.
(5) Clariant Polymer Co., Ltd., trade name: Biscalex HV30
(6) Product name: Prisurf A212C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
(7) Shin-Etsu Silicone Co., Ltd., trade name: KF6100
(8) Shin-Etsu Silicone Co., Ltd., trade name: KF6104
(9) Product name: KF615, manufactured by Shin-Etsu Silicone Co., Ltd.

Preparation of writing instrument for performance test The fiber bundle is polyester in a shaft cylinder having a tip of a fiber chip having a diameter of 2 mm obtained by binding the polyester fiber bundle with a resin to the inks of Examples 1 and 2 and Comparative Examples 1 and 2. It was poured into a marking pen with a built-in ink occlusion body covered with a film to prepare a test writing instrument.
The inks of Example 3 and Comparative Example 3 are made of a polypropylene pipe in which a chip having a 0.5 mm cemented carbide ball rotatably held in a metal pipe is fitted via a chip holder. The ink was then poured into an ink storage tube, and an ink backflow preventer was closely placed at the rear end of the ink to provide a test writing instrument (ball pen).

[Handwriting dryness test]
Using each of the writing tools, writing was performed on a PET film, the handwriting was rubbed with a tissue paper every 10 seconds, and the time until the handwriting was not peeled was measured.
(Handwriting test)
Written on PP film using each of the above writing instruments, dried at room temperature for 24 hours, put a 1000 g weight on two layers of gauze (cotton), and visually observed the state of the handwriting when it was rubbed back and forth 10 times. Observed at.
The test results are shown in the following table.

The criteria for evaluation in the table are as follows.
A: There is no change in the state of the handwriting before the test.
○: There is no defect in the handwriting, but there is an abrasion on the surface.
Δ: There is a defect in the handwriting.
X: The handwriting was erased.

Claims (4)

  An oil-based ink composition for a writing instrument, comprising a polyglycerin-modified silicone in an oil-based ink composition comprising at least a colorant, an organic solvent, and a resin.   The oil-based ink composition for a writing instrument according to claim 1, wherein the polyglycerin-modified silicone is contained in an amount of 0.1 to 10.0% by weight in the ink composition.   A writing instrument comprising the oil-based ink composition according to claim 1 or 2.   The writing instrument according to claim 3, wherein the writing instrument is in the form of a ballpoint pen.