JP4934461B2 - 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 a writing instrument and a marking pen containing the same. More specifically, the present invention relates to an oil-based ink composition for a writing instrument that can form a handwriting with excellent adhesion and no repelling on a writing surface with poor wettability, and a marking pen containing the same.

Conventionally, oil-based inks used for marking pens include a colorant, an organic solvent, a resin, and, if necessary, a surfactant, and require adhesion of handwriting formed on the writing surface of various materials. However, when writing on a material with poor wettability, for example, a synthetic resin film, paper with a resin coating on the surface, metal, etc., adhesion was insufficient and good handwriting could not be obtained.
In order to solve the above problems, by adding a silicone-based active agent such as polyether-modified silicone or trimethylsiloxysilicic acid, the fixability of the coating film when writing on the non-absorbing surface of metal, plastic, etc. was improved. Oil-based marking pen inks are disclosed (for example, see Patent Documents 1 and 2).
However, in the oil-based ink, when a polyethylene film is coated on a synthetic resin film or a paper base material such as a craft tape and is further written on a material covered with a silicone film, the repelling is seen and good. Some handwriting cannot be formed. Even if the handwriting can be formed, the obtained handwriting has poor adhesion after drying, and the handwriting is peeled off only by light rubbing, and the cap-off performance is deteriorated.
Japanese Patent Laid-Open No. 11-21492 JP-A-8-302261

  The present invention is intended to solve the problems of the ink composition containing this type of silicone-based active agent, that is, without reducing the cap-off performance, a synthetic resin film, and a paper whose surface is resin-coated. In addition to metal, we provide oil-based ink compositions for writing instruments that can produce handwriting with excellent adhesion even when writing on the surface of poorly wettable materials such as craft tape for packing. There is to do.

The present invention comprises a colorant, an organic solvent, and a resin, and contains at least at both ends modified polyether-modified silicone was substituted for the main-terminated groups linear dimethyl polysiloxane polyether group, the two A marking pen in which the polyether of the terminal-modified polyether-modified silicone is composed of polyoxyethylene and polyoxypropylene, the polyoxyethylene content is 50% by mass or more in the polyether, and the HLB is 3 to 8. An oil-based ink composition is required.
Furthermore, it contains 0.5 to 10% by mass of the both-end-modified polyether-modified silicone in the total amount of the ink composition, and alcohols having 4 or less carbon atoms and / or glycol ethers having 4 or less carbon atoms as a main solvent. And the main solvent is any of ethyl alcohol, n-propyl alcohol, and isopropyl alcohol.
Furthermore, the marking pen which accommodated the said oil-based ink composition for writing instruments is required.

  In the present invention, the handwriting formed on the writing surface of various materials is not repelled without deteriorating the cap-off performance, a good writing can be formed, and practicality excellent in adhesion after writing. A rich oil-based ink composition for writing instruments and a marking pen containing the same can be provided.

The both-end-modified polyether-modified silicone is one in which both ends of the main chain of a linear dimethylpolysiloxane are substituted with a polyether group, and when written on a non-absorbing surface of metal, plastic, etc. Used to form no clear handwriting. The polyether group is represented by —R ¹ (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ² [wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms, and R ² Represents any one of hydrogen, an alkyl group having 1 to 50 carbon atoms, and an aryl group. A represents an integer of 1 to 50, and b represents an integer of 1 to 50].
In particular, the polyether group is composed of at least polyoxyethylene and polyoxypropylene, and the content of the polyoxyethylene is preferably 50% by mass or more in the polyether. This is because the solubility in polar solvents such as alcohol solvents and glycol ether solvents improves as the content of polyoxyethylene increases, so that dissolution stability and stability over time are advantageous.

As the both terminal-modified polyether-modified silicone, manufactured by Dow Corning Toray Silicone Co., Ltd. trade name: Peinta' de 8 142, the 8331, the 8353, the 8388A, the 8388B, the 8417, DK Q8-8211 And trade names manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-4952, X-22-4272, X-22-6266, KF-6004, and the like.

The both terminal-modified polyether-modified silicone is used in the range of 0.5 to 10% by mass, preferably 0.5 to 5% 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 prevent bleeding. If the amount exceeds 10% by mass, the handwriting may be faded or left unwritten when left for a long time with the writing tip exposed to the outside air. It becomes easy.
In addition, the both-end-modified polyether-modified silicone has a HLB of 1 to 10, preferably 3 to 8.
If HLB is less than 1, it is difficult to dissolve in the solvent, and if it is more than 10, ink repellency is likely to occur when writing on the non-absorbing surface.

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),
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, 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 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 general-purpose solvent can be used conventionally, 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 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, 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),
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.
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 in various resins and various 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.
In an organic solvent having a boiling range of less than 160 ° C., both ends-modified polyether-modified silicone is dried before forming a homogeneous handwriting, so that it becomes difficult to obtain a clear handwriting. It tends to occur. An organic solvent having a boiling point of more than 250 ° C. has a low drying rate and tends to impair quick drying.
Benzyl alcohol is suitable as the organic solvent having a boiling point of 160 ° C to 250 ° C.

As the resin, a resin that is usually soluble in an organic solvent used in an oil-based ink composition can be applied without limitation, and it is possible to impart handwriting blurring 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 thereof include acid esters, ketone-formaldehyde resins, α- and β-pinene / phenol polycondensation resins, polyvinyl butyral resins, maleic 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 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.
In particular, 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.
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, waxes such as oxidized polyethylene wax, stearic acid, palmitic acid, octylic acid, fatty acid metal salts such as aluminium salt of lauric acid, 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 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, 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 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.
Further, the ball is 0.3 to 3 mm, preferably 0.4 to 2.0 mm, more preferably 0.5 to 1.0 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, and rubber. Things can be applied.

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.
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 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: Bali Fast Black 3810, manufactured by Orient Chemical 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) Arakawa Chemical Industries, Ltd., trade name: Marquide 33
(5) Arakawa Chemical Industries, Ltd., trade name: Ketone Resin K-90
(6) Product name: John Crill 68, manufactured by Johnson Polymer Co., Ltd.
(7) Both-end modified polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name: DK Q8-8221, active ingredient 50%
(8) Both-end modified polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name: Paintad 8388A
(9) Carboxy-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-3710
(10) Trimethylsiloxysilicic acid, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-7312J, active ingredient 50%
(11) Side chain-modified polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name: DC 57 Additive
(12) Sakamoto Pharmaceutical Co., Ltd., trade name: SY Glister TS-3S

Preparation of marking pen Inks and inks in Examples and Comparative Examples are provided in the ink pens in the marking pen provided with a chip in which an acrylic fiber bundle that is in communication with the ink occlusion body is bound with a resin at the tip. A marking pen was obtained by impregnating the composition and attaching a cap.

The following tests were performed using each marking pen.
Written test Written on the surface of a polypropylene film and a craft tape [manufactured by Nichiban Co., Ltd., product number: KF-37], the repelling of the handwriting was visually observed.
Scratch test After the handwriting obtained in the writing test was dried, the adhesiveness of the handwriting when moved over the handwriting with a tissue paper on which a 200 g weight was placed was observed.
Cap-off test After the cap was removed and the chip was exposed, the sample was allowed to stand at a temperature of 20 ° C. for 1 hour, and then the handwriting on the JIS P3201 writing paper A was continuously written by hand by hand.

The following table shows the results of each test.

The evaluation symbols in the table are as follows.
Written test ○: Handwriting repelling is not seen.
X: Repelling is seen in the handwriting.
Scratch test ○: Excellent ink adhesion to the writing surface, and the handwriting did not peel off.
X: The ink adhesion to the writing surface was poor, and the handwriting was peeled off.
Cap-off test ○: Writing is possible from writing.
X: Scratch is seen in writing.

Claims (5)

A colorant, an organic solvent, a resin, and a both-end-modified polyether-modified silicone in which both ends of the main chain of the linear dimethylpolysiloxane are substituted with a polyether group ; The ether-modified silicone polyether comprises polyoxyethylene and polyoxypropylene, the content of the polyoxyethylene is 50% by mass or more in the polyether, and the HLB is 3-8. object. The oil-based ink composition for marking pens according to claim 1, wherein the both-end-modified polyether-modified silicone is contained in an amount of 0.5 to 10% by mass based on the total amount of the ink composition.   The oil-based ink composition for a marking pen according to claim 1 or 2, wherein an alcohol having 4 or less carbon atoms and / or a glycol ether having 4 or less carbon atoms is used as a main solvent.   The oil-based ink composition for a marking pen according to claim 3, wherein the main solvent is one of ethyl alcohol, n-propyl alcohol, and isopropyl alcohol.   The marking pen which accommodated the oil-based ink composition for marking pens as described in any one of Claims 1 thru | or 4.