JP2008208290A - Oil-based ink composition for writing implement and marking pen containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-based ink composition for writing implements which gives writings being free of cissing, clear, highly wear-resistant, and highly practicable on writing surfaces of various types of materials and to provide a marking pen containing the same. <P>SOLUTION: The oil-based ink composition comprises at least a colorant, an organic solvent, a resin, and a silicone surfactant, wherein a dry coating film prepared by applying the ink composition to a polyethylene terephthalate film has a coefficient of static friction of 0.01-0.2 and a coefficient of dynamic friction of 0.01-0.15 when rubbed at a load of 500 g with a 30 mm×30 mm cotton cloth for color fastness test. The marking pen contains the ink composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an oil-based ink composition for writing instruments 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 clear handwriting on a writing surface with poor wettability and has excellent handwriting scratch resistance, and a marking pen containing the same.

Conventionally, oil-based inks used for marking pens include a colorant, an organic solvent, a resin, and optionally a surfactant, and it is required to form clear handwriting on the writing surface of various materials. When writing on a material having poor wettability, for example, a synthetic resin film, paper coated with a resin, metal, etc., the handwriting is repelled.
In order to solve the above problem, an ink that contains a colorant, an organic solvent, a resin, and a silicone-based surfactant and can be written on a metal or a synthetic resin film is disclosed (for example, Patent Document 1). reference). The ink to which the silicone surfactant is added can form a clear handwriting on the synthetic resin film, but depending on the surface state of the handwriting, the handwriting tends to be easily peeled off by rubbing with a finger or the like and the films rubbing each other. Moreover, it was not possible to write on a material covered with a silicone coating such as kraft tape.
Japanese Patent Laid-Open No. 11-21492

  The present invention is intended to solve the problems in the conventional ink composition, that is, even if writing on the surface of a material having poor ink wettability such as craft tape for packing, there is no repellency and good An object of the present invention is to provide an oil-based ink for a writing instrument capable of forming a handwriting and capable of forming a handwriting having scratch resistance against a synthetic resin film, and a marking pen containing the ink.

The present invention is an oil-based ink composition for a writing instrument comprising at least a colorant, an organic solvent, a resin, and a silicone surfactant, which is applied to a polyethylene terephthalate film using the ink composition. The static friction coefficient when the dried coating film obtained by rubbing with a cotton cloth for dyeing fastness test of 30 mm × 30 mm with a load of 500 g is 0.01 to 0.2, and the dynamic friction coefficient is 0.01. An oil-based ink composition for a writing instrument that is ˜0.15 is a requirement.
Furthermore, the silicone surfactant is selected from a block copolymer of dimethylpolysiloxane and polyalkylene oxide, an acrylic-silicone graft copolymer, and the block copolymer of dimethylpolysiloxane and polyalkylene oxide is dimethylpolysiloxane. It is selected from a linear block copolymer in which polyalkylene oxide is repeatedly bonded, and a block copolymer in which both ends of dimethylpolysiloxane are modified with polyalkylene oxide, and the silicone surfactant is added in an amount of 0.01 to 10 in the total amount of the ink composition. Containing 4% by mass, using as a main solvent an alcohol having 4 or less carbon atoms and / or glycol ethers having 5 or less carbon atoms, and using ethyl alcohol and / or propyl alcohol as a main solvent. Is referred to as requirements, etc. be used.
Furthermore, the marking pen which accommodated the said oil-based ink composition for writing instruments is required.

  The present invention is an oil-based ink composition for a writing instrument having excellent practicality and excellent scratch resistance of the handwriting, as well as being able to form clear handwriting on the writing surface formed of various materials. A contained marking pen can be provided.

  Examples of the silicone surfactant include polyether-modified silicone, carboxy-modified silicone, and amino-modified silicone. Preferably, a block copolymer of dimethylpolysiloxane and polyalkylene oxide, and an acrylic-silicone graft copolymer are used.

As the block copolymer of dimethylpolysiloxane and polyalkylene oxide, a linear block copolymer [(AB) n-type] in which dimethylpolysiloxane and polyalkylene oxide are alternately and repeatedly bonded, or both ends of dimethylpolysiloxane are made of poly (ethylene) and poly (alkylene oxide). A block copolymer (ABA type) modified with alkylene oxide is preferably used.
Examples of the linear block copolymer of dimethylpolysiloxane and polyalkylene oxide include a linear block copolymer of dimethylpolysiloxane and polyethylene oxide and / or polypropylene oxide, manufactured by Toray Dow Corning Silicone Co., Ltd. Product names: FZ 2203, FZ 2207, FZ 2208, FZ 2222 can be exemplified.

The block copolymer obtained by modifying both ends of the dimethylpolysiloxane with polyalkylene oxide is obtained by substituting both ends of the main chain of the linear dimethylpolysiloxane with a polyether group, and the polyether group includes polyoxyethylene and It is preferably composed of polyoxypropylene.
Specifically, 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 is an alkyl group having 1 to 10 carbon atoms. 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].
The content of polyoxyethylene is preferably 50% by mass or more in the polyether group, and the solubility in polar solvents such as alcohol solvents and glycol ether solvents is high due to the large content of polyoxyethylene. It improves and is excellent in dissolution stability and stability over time.
Examples of block copolymers in which both ends of dimethylpolysiloxane are modified with polyalkylene oxide include trade names of Toray Dow Corning Silicone Co., Ltd .: Paintad 29, 8142, 8331, 8353, 8353A, and 8388B. 8417, DK Q8-8211, and trade names: X-22-4952, X-22-4272, X-22-6266, and KF-6004 manufactured by Shin-Etsu Chemical Co., Ltd. can be exemplified.

（式中、Ｒ_１はメチル基又は水素原子、Ｒ_２は場合によりエーテル結合１個又は２個で遮断されている直鎖状又は分岐状の炭素鎖を有する炭素原子１〜１０個の２価の飽和炭化水素基、Ｒ_３はメチル基又はブチル基、ｍは３〜３００の整数を示す。）
で表されるものが挙げられる。
一方、アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマーは、ラジカル重合性不飽和結合を分子中に１個有する化合物を意味し、使用されるアクリレート及び／又はメタクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート、フルオロ炭素鎖１〜１０のパーフルオロアルキル（メタ）アクリレートを例示することができる。
なお、前記アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマーは、一種又は二種以上を併用して用いることができる。
また、アクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマーにおいて、アクリレート及び／又はメタクリレート以外に必要に応じて種々の重合性モノマー化合物を使用することができる。これらの化合物としては、スチレン、置換スチレン、酢酸ビニル、（メタ）アクリル酸、無水マレイン酸、マレイン酸エステル、フマル酸エステル、塩化ビニル、塩化ビニリデン、エチレン、プロピレン、ブタジエン、アクリロニトリル、フッ化オレフィン、Ｎ−ビニルピロリドン等を例示することができる。
分子鎖の片末端にラジカル重合性基を有するジメチルポリシロキサン化合物（Ａ）とアクリレート及び／又はメタクリレートを主体とするラジカル重合性モノマー（Ｂ）との共重合体は、重合比率（Ａ）：（Ｂ）＝１：１９〜２：１の範囲内で、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アゾビスイソブチロニトリル等の通常のラジカル重合開始剤の存在下で行われ、溶液重合法、乳化重合法、懸濁重合法、バルク重合法のいずれの方法の適用も可能である。
市販品としては、溶剤に溶解したものとして、信越化学工業（株）製の商品名：ＫＰ５４１（６０％イソプロピルアルコール溶液）、ＫＰ５４３（酢酸ブチル溶液）、ＫＰ５４５（３０％デカメチルシクロペンタシロキサン溶液）等が挙げられる。 The acrylic-silicone graft copolymer is a copolymer of an organopolysiloxane compound having a radical polymerizable group at one end of a molecular chain and a radical polymerizable monomer mainly composed of acrylate and / or methacrylate.
As an organopolysiloxane compound having radical polymerizability at one end of a molecular chain, the following formula (1)

(Wherein R ₁ is a methyl group or a hydrogen atom, R ₂ is a divalent valence of 1 to 10 carbon atoms having a linear or branched carbon chain optionally blocked by one or two ether bonds. A saturated hydrocarbon group, R ₃ is a methyl group or a butyl group, and m is an integer of 3 to 300.)
The thing represented by is mentioned.
On the other hand, the radical polymerizable monomer mainly composed of acrylate and / or methacrylate means a compound having one radical polymerizable unsaturated bond in the molecule, and the acrylate and / or methacrylate used is methyl (meth). Alkyl (meth) acrylates such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Examples thereof include hydroxyalkyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and perfluoroalkyl (meth) acrylate having 1 to 10 fluorocarbon chains.
In addition, the radically polymerizable monomer mainly composed of the acrylate and / or methacrylate can be used alone or in combination of two or more.
Moreover, in the radically polymerizable monomer mainly composed of acrylate and / or methacrylate, various polymerizable monomer compounds can be used as required in addition to acrylate and / or methacrylate. These compounds include styrene, substituted styrene, vinyl acetate, (meth) acrylic acid, maleic anhydride, maleic acid ester, fumaric acid ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefins, Examples thereof include N-vinyl pyrrolidone.
A copolymer of a dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of a molecular chain and a radically polymerizable monomer (B) mainly composed of acrylate and / or methacrylate has a polymerization ratio (A) :( B) = 1: 19 to 2: 1 in the presence of a normal radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, solution polymerization method, emulsion weight Any of a combination method, a suspension polymerization method, and a bulk polymerization method can be applied.
As commercial products, those dissolved in a solvent, trade names manufactured by Shin-Etsu Chemical Co., Ltd .: KP541 (60% isopropyl alcohol solution), KP543 (butyl acetate solution), KP545 (30% decamethylcyclopentasiloxane solution) Etc.

The silicone surfactant is added in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total amount of the ink composition.
If it is less than 0.01% by mass, the handwriting formed on the kraft tape can be repelled, or the handwriting formed on the synthetic resin film will have poor scratch resistance. On the other hand, when the amount exceeds 10% by mass, when the writing tip is exposed to the outside air for a long time, the handwriting tends to become dull or it becomes impossible to write.

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).
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 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 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 using a solvent having a vapor pressure of 5.0 to 50 mmHg, preferably 10 to 50 mmHg, which easily evaporates as an organic solvent, as a main solvent, the handwriting has excellent drying properties. A good handwriting can be formed without causing problems such as undried ink adhering to the hand or contaminating 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),
Ethylene glycol monomethyl ether (8.5), ethylene glycol diethyl ether (9.7), ethylene glycol monoisopropyl ether (6.0), propylene glycol monomethyl ether (7.6), propylene glycol monoethyl ether (4.0) ) Glycol ether organic solvents such as
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.
Among the organic solvents, preferably alcohols having 4 or less carbon atoms and / or glycol ethers having 5 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 as the main solvent, it is preferable to adjust the handwriting drying speed by using an organic solvent having a boiling point of 160 ° C. to 250 ° C. in combination.
In an organic solvent having a boiling range of less than 160 ° C., the silicone-based surfactant is dried before forming a uniform handwriting, so that it becomes difficult to obtain a clear handwriting, and the handwriting whitening phenomenon easily occurs under high humidity. . In an organic solvent having a boiling point of more than 250 ° C., the drying speed is slow and the quick drying property is easily impaired.
As the organic solvent having a boiling point of 160 ° C. to 250 ° C., benzyl alcohol is suitable.

  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, maleic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, etc., and are used for fixing to writing materials 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. Therefore, even if writing on a highly permeable material as well as the paper surface, the handwriting does not bleed and a good handwriting 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.
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 handwriting (dried coating film) formed by the ink composition has a static friction coefficient with a cotton cloth of 0.01 to 0.2, preferably 0.01 to 0.15, and a dynamic friction coefficient of 0.00. When it is 01 to 0.15, preferably 0.01 to 0.1, the surface of the handwriting exhibits good slipping characteristics, so that the handwriting is hardly peeled off from the surface to be written and sufficiently satisfies the scratch resistance.
Even if the silicone-based surfactant is included in the ink, if both the static friction coefficient and the dynamic friction coefficient are not satisfied, the handwriting is easily peeled off from the writing surface, and it is difficult to maintain a good handwriting permanently.
The static friction coefficient is the maximum resistance immediately before the movement starts on the contact portion when the handwriting is rubbed. The lower the numerical value, the more effectively it works against scratching. Specifically, when the static friction coefficient is 0.2 or less, it is possible to effectively prevent the handwriting from peeling off against discontinuous abrasion.
Further, when the friction is repeated, the lower the dynamic friction coefficient, which is the resistance applied to the contact portion continuously, functions more effectively against abrasion. Specifically, when the coefficient of dynamic friction is 0.15 or less, it is possible to effectively prevent the handwriting from peeling off against continuous abrasion.
Regarding the peeling of handwriting by rubbing, the fact that the coefficient of static friction and the coefficient of dynamic friction satisfy the above-mentioned ranges means that scratches caused by various discontinuous or continuous contacts such as finger contact, clothing contact, film-to-film contact, etc. This is an important requirement for maintaining a good handwriting.
The friction coefficient is measured by coating the ink composition on a polyethylene terephthalate film and drying it to provide a dry coating film to produce a test piece. The test piece is fixed to a moving table of a surface property measuring machine (HEIDON-14D), and a white cloth cotton cloth (according to JIS L0803) for JIS dyeing fastness test is used as a sliding piece on the flat indenter part of the measuring machine. The contact area is set to 30 mm × 30 mm. A flat indenter to which a cotton cloth is attached is set on the test piece, a static friction coefficient and a dynamic friction coefficient are measured by rubbing the dry coating film with a load of 500 g at a moving distance of 5 cm and a moving speed of 100 mm / min.
The static friction coefficient and the dynamic friction coefficient are calculated from the average value obtained by measuring a test piece of the same lot five times.

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 balls are 0.3 to 3 mm, preferably 0.4 to 2.0 mm, more preferably 0.5 to 1.5 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.

The non-volatile liquid and / or the hardly volatile liquid is preferably added with a gelling agent to increase the viscosity to a suitable viscosity. , 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: Nigrosine Base EX, manufactured by Orient Chemical Industry Co., Ltd.
(2) Arakawa Chemical Industries, Ltd., trade name: Ketone Resin K-90
(3) Polyoxyethylene alkyl ether phosphate ester, manufactured by Toho Chemical Industry Co., Ltd., trade name: Phosphanol RA-600
(4) Shin-Etsu Chemical Co., Ltd., trade name: KP543, active ingredient 50%
(5) Toray Dow Corning Co., Ltd. Product name: DK Q8-8111 Active ingredient 50%
(6) Toray Dow Corning Co., Ltd. Product name: FZ-2208
(7) Toshiba Silicone Co., Ltd., trade name: TSF4460

Measurement of Friction Coefficient Each ink was coated on a polyethylene terephthalate film having a thickness of 100 μm using a 10 mil wire bar and dried, and a dry coating film was provided to prepare a test piece.
The test piece is fixed to a moving table of a surface property measuring instrument [HEIDON-14D manufactured by Shinto Kagaku Co., Ltd.], and a white cloth cotton cloth for JIS dyeing fastness test conforming to JISL0803 is used as a sliding piece. The contact area with the test piece was set to 30 mm × 30 mm on the indenter part.
Next, a flat indenter attached with a cotton cloth was placed on the dry coating film of the test piece, and a friction coefficient was measured at a moving distance of 50 mm and a moving speed of 100 mm / min with a load of 500 g.
The same test piece was measured 5 times, and the average value was used as the static friction coefficient and the dynamic friction coefficient of each test piece.

Preparation of marking pen The ink composition of the marking pen is provided with a chip in which each ink composition is filled with an ink in a shaft cylinder and an acrylic fiber bundle communicating with the ink storage is attached to a tip portion with a resin. A marking pen was obtained by impregnation.

The following tests were performed using each marking pen.
Written test Written on craft tape [manufactured by Nichiban Co., Ltd., product number: KF-37] and polyethylene terephthalate film, the repellency of the handwriting was visually observed.
Abrasion test After writing on a polyethylene terephthalate film and a polyethylene film and drying, the writing surface was fixed to a stage of a friction tester [FR-2 type manufactured by Suga Test Instruments Co., Ltd.], and compliant with JISL0803 as a sliding piece. Attached white cloth for JIS dyeing fastness test was fixed to the curved part of the measuring machine, and after reciprocating 20 times the arm part to which the sliding piece was attached under a load of 500 g, the state of the handwriting on the film was visually observed. Observed.

The following table shows the results of the coefficient of friction, writing test, and scratch 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 ○: The handwriting on the film was kept almost the same as the initial stage.
Δ: About half of the handwriting on the film was peeled off (visible).
X: The handwriting on the film was almost peeled off.

Claims (7)

  An oil-based ink composition for a writing instrument comprising at least a colorant, an organic solvent, a resin, and a silicone-based surfactant, which is obtained by coating a polyethylene terephthalate film using the ink composition. The static friction coefficient when the dried coating is rubbed with a cotton cloth for dyeing fastness test of 30 mm × 30 mm with a load of 500 g is 0.01 to 0.2, and the dynamic friction coefficient is 0.01 to 0.15. An oil-based ink composition for a writing instrument.   The oil-based ink composition for a writing instrument according to claim 1, wherein the silicone surfactant is selected from a block copolymer of dimethylpolysiloxane and polyalkylene oxide, and an acrylic-silicone graft copolymer.   The block copolymer of dimethylpolysiloxane and polyalkylene oxide is selected from a linear block copolymer in which dimethylpolysiloxane and polyalkylene oxide are repeatedly bonded, and a block copolymer in which both ends of dimethylpolysiloxane are modified with polyalkylene oxide. 2. An oil-based ink composition for a writing instrument according to 2.   The oil-based ink composition for writing instruments as described in any one of Claims 1 thru | or 3 formed by containing the said silicone type surfactant 0.01-10 mass% in the ink composition whole quantity.   The oil-based ink composition for a writing instrument according to any one of claims 1 to 4, wherein an alcohol having 4 or less carbon atoms and / or a glycol ether having 5 or less carbon atoms is used as a main solvent.   The oil-based ink composition for writing instruments according to claim 5, wherein ethyl alcohol and / or propyl alcohol is used as a main solvent.   The marking pen which accommodated the oil-based ink composition for writing instruments as described in any one of Claims 1 thru | or 6.