WO2011070966A1 - 水性ボールペン用インキ組成物及び水性ボールペン - Google Patents

水性ボールペン用インキ組成物及び水性ボールペン Download PDF

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Publication number
WO2011070966A1
WO2011070966A1 PCT/JP2010/071576 JP2010071576W WO2011070966A1 WO 2011070966 A1 WO2011070966 A1 WO 2011070966A1 JP 2010071576 W JP2010071576 W JP 2010071576W WO 2011070966 A1 WO2011070966 A1 WO 2011070966A1
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WO
WIPO (PCT)
Prior art keywords
water
ballpoint pen
ink composition
based ballpoint
microcapsule pigment
Prior art date
Application number
PCT/JP2010/071576
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English (en)
French (fr)
Japanese (ja)
Inventor
英明 遠見
昌尚 矢野
剛史 早川
秀寿 市川
Original Assignee
三菱鉛筆株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三菱鉛筆株式会社 filed Critical 三菱鉛筆株式会社
Priority to US13/514,766 priority Critical patent/US8562235B2/en
Priority to EP10835887.0A priority patent/EP2511353B1/de
Priority to CN201080063095.1A priority patent/CN102753632B/zh
Publication of WO2011070966A1 publication Critical patent/WO2011070966A1/ja

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/18—Writing inks specially adapted for ball-point writing instruments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks

Definitions

  • the present invention relates to a water-based ballpoint pen ink composition containing a microcapsule pigment and an aqueous ballpoint pen, and more specifically, a sufficient line density can be obtained even when a thermochromic microcapsule pigment having a small average particle diameter is used,
  • the present invention relates to a water-based ballpoint pen ink composition and a water-based ballpoint pen excellent in ink storage stability and writing performance.
  • thermochromic microcapsule pigments utilizing the development and decoloring mechanisms of leuco dyes.
  • an electron-donating color-forming organic compound that is a leuco dye (b) an electron-accepting compound that is a developer, and (c) a color-change temperature adjusting agent that determines the temperature at which the color reaction occurs.
  • a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising the reaction medium, and at least water, and the average particle size of the reversible thermochromic microcapsule pigment is 2.5-4.
  • a water-based ink composition for reversible thermochromic writing instruments characterized in that particles in the range of 0.0 ⁇ m and 2.0 ⁇ m or less are 30% by volume or less in the total microcapsule pigment (see, for example, Patent Document 1) ), Water, (a) an electron-donating color-forming organic compound that is a leuco dye, (b) an electron-accepting compound that is a developer, and (c) a color change that determines the temperature at which the color reaction occurs. Is the reaction medium a temperature regulator?
  • thermochromic microcapsule pigment encapsulating a reversible thermochromic composition
  • a polymer flocculant a polymer flocculant
  • a comb polymer dispersant having a carboxyl group in the side chain and a water-soluble resin.
  • a water-based ink composition for reversible thermochromic writing instruments having an average maximum outer diameter of capsule pigments of 0.5 to 5.0 ⁇ m is known (for example, see Patent Document 2).
  • the above microcapsule pigment tends to be unfavorable because the color density decreases as the average particle size decreases. It is described that it is difficult to exhibit the color developability of density, and it is described that particles having a size of 2.0 ⁇ m or less are 30% by volume or less, more preferably 10% by volume or less in the total microcapsule pigment. Also, in the above-mentioned Patent Document 2, it is described that the average value of the maximum outer diameter of the microcapsule pigment is 0.5 to 5.0 ⁇ m. 5 ⁇ m microcapsule pigment is used. This is because the capsule thickness in the microcapsule pigment is relatively increased.
  • the microcapsule pigment when used in an aqueous ballpoint pen, it is preferable to use a pigment having a small average particle diameter from the viewpoint of writing property and ink storage stability.
  • a pigment having a small average particle diameter from the viewpoint of writing property and ink storage stability.
  • JP 2008-280440 A (Claims, Examples, etc.)
  • JP 2009-227954 A (Claims, Examples, etc.)
  • an object of the present invention is to provide a water-based ballpoint pen ink composition and a water-based ballpoint pen which can provide a sufficient drawn line density and are excellent in ink storage stability and writing performance.
  • the present invention resides in the following (1) to (4).
  • a water-based ballpoint pen ink composition comprising at least a chemical substance having an acid value of 3 to 40 (mgKOH / g).
  • thermochromic microcapsule pigment having a small average particle size of 0.1 to 1.0 ⁇ m is used, a sufficient line density can be obtained, and the storage stability of the ink can be obtained.
  • An aqueous ballpoint pen ink composition and an aqueous ballpoint pen excellent in writing performance are provided.
  • the ink composition for water-based ballpoint pens of the present invention comprises a microcapsule pigment having a wall film formed of an amino resin having an average particle size of 0.1 to 1.0 ⁇ m, a polymer having a ketone as the main chain, It contains at least a chemical substance having an acidic functional group in the structure and an acid value of 3 to 40 (mgKOH / g).
  • the microcapsule pigment used in the present invention has a wall film having an average particle size of 0.1 to 1.0 ⁇ m formed of an amino resin, and is composed of at least a leuco dye, a developer, and a color change temperature adjusting agent. Encapsulating a thermochromic composition.
  • the leuco dye that can be used is not particularly limited as long as it is an electron-donating dye and functions as a color former.
  • pyridine compounds, quinazoline compounds, bisquinazoline compounds and the like that develop yellow to red color development can also be used.
  • These leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, etc., and develop color when these skeletons (rings) are opened.
  • Developers that can be used are those that develop leuco dyes, such as inorganic acids, aromatic carboxylic acids and anhydrides or metal salts thereof, organic sulfonic acids, other organic acids, and phenolic compounds. It is done. Particularly preferred are compounds having a phenolic hydroxyl group such as bisphenol A.
  • the color change temperature adjusting agent that can be used is one that causes the reaction between the leuco dye and the developer to reversibly occur in a specific temperature range, and is not particularly limited as long as it has this function. Examples include esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.
  • the microcapsule pigment used in the present invention comprises a thermochromic composition comprising at least the above leuco dye, a color developer, and a color change temperature adjusting agent so that the average particle diameter is 0.1 to 1.0 ⁇ m and a wall film.
  • a thermochromic composition comprising at least the above leuco dye, a color developer, and a color change temperature adjusting agent so that the average particle diameter is 0.1 to 1.0 ⁇ m and a wall film.
  • the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and can be appropriately selected according to the application.
  • a leuco dye, a developer, and a color change temperature adjusting agent are heated and melted, then charged into an emulsifier solution, heated and stirred to disperse into oil droplets, and then as a capsule film agent.
  • a resin raw material that can be formed of an amino resin for the wall film for example, after adding amino resin solution, specifically, methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc.
  • the desired thermochromic microcapsule pigment can be produced by filtering the dispersion.
  • the content of these leuco dyes, developers, and color change temperature adjusters varies depending on the type of leuco dye, developer, color change temperature adjuster used, microencapsulation method, etc.
  • the developer is 0.1 to 100 developer and 1 to 100 color changing temperature adjusting agent in mass ratio.
  • the capsule membrane agent is 0.1 to 1 in mass ratio with respect to the capsule contents.
  • it is possible to obtain the color of each pigment, an arbitrary color development temperature, and a decoloration temperature by suitably combining the types and amounts of the leuco dye, the developer, and the color change temperature adjusting agent. .
  • the wall film needs to be formed of an amino resin, and is preferably formed of, for example, a melamine resin, a urea resin, a benzoguanamine resin, and more preferably, a manufacturability and storage. It is desirable to form with a melamine resin from the point of stability and writing property.
  • a resin other than an amino resin such as a urethane resin or an epoxy resin
  • at least one of drawn line density, storage stability, and writing property is inferior.
  • the thickness of the wall film of the microcapsule pigment is appropriately determined according to the required strength of the wall film and the drawn line density.
  • a suitable amino resin raw material melamine resin, urea resin, benzoguanamine resin, etc.
  • dispersant a protective colloid Select etc.
  • the average particle size of the obtained microcapsule pigment is more preferably 0.1 to 1.0 ⁇ m, from the viewpoints of colorability, color developability, easy decolorization, stability, and suppression of adverse effects on writability. Is preferably 0.2 to 0.9 ⁇ m.
  • the “average particle size” defined in the present invention is a value obtained by measuring the average particle size with a particle size distribution measuring device [particle size measuring instrument N4Plus (manufactured by COULTER)]. If the average particle size is less than 0.1 ⁇ m, sufficient drawn line density cannot be obtained. On the other hand, if it exceeds 1.0 ⁇ m, the writability is deteriorated and the dispersion stability of the microcapsule pigment is decreased.
  • the microcapsule pigment having an average particle diameter in the above range varies depending on the microencapsulation method.
  • the microcapsule pigment is produced by It can be prepared by suitably combining stirring conditions.
  • the content of the microcapsule pigment is preferably 5 to 30% by mass (hereinafter simply referred to as “%”), more preferably 10 to 25%, based on the total amount of the ink composition. desirable. If the content of the colorant (developed particles) is less than 5%, the coloring power and color developability become insufficient. On the other hand, if it exceeds 30%, blurring tends to occur, which is not preferable.
  • the chemical substance used in the present invention is a polymer having a ketone as the main chain, has an acidic functional group in the chemical structure, and has an acid value of 3 to 40 (mgKOH / g). It exhibits functions such as improving the line density by interacting with the capsule pigment.
  • the chemical substance that can be used is a polymer having a ketone as the main chain, and examples of the acidic functional group in the chemical structure include a carboxylic acid group and a phosphoric acid group. If the acid value is less than 3 mgKOH / g, the writing property tends to be blurred, whereas if it exceeds 40 mgKOH / g, the stability of the ink is lowered and precipitates are easily generated, which is not preferable. A more preferred acid value is 5 to 15 mg KOH / g.
  • Solsperse 44000 main chain: ketone, acidic functional group: carboxylic acid, acid value of about 12 mg KOH / g, manufactured by Nippon Lubrizol
  • Solsperse 46000 main chain: ketone, acidic functional group: carboxylic acid, acid
  • 12 mg KOH / g manufactured by Nippon Lubrizol Co., Ltd.
  • the content of this chemical substance is preferably 0.1 to 10%, more preferably 0.3 to 5%, based on the total amount of the ink composition.
  • the content is less than 0.1%, a satisfactory drawn line density cannot be obtained, and the stability of the microcapsule pigment is lowered. On the other hand, if it exceeds 10%, blurring tends to occur during writing, which is not preferable.
  • the polyoxyethylene aliphatic amine (hereinafter referred to as “POE aliphatic amine”) used in the present invention has an aliphatic carbon number of 10 to 20, and exhibits functions such as dispersion stabilization of microcapsule pigments. is there. If the aliphatic carbon number is less than 10, the adsorptivity to the pigment is deteriorated and the pigment dispersion effect is insufficient. On the other hand, if the carbon number exceeds 20, the solubility in water becomes insufficient. It is not preferable.
  • Preferable POE aliphatic amines are preferably those having an addition mole number of POE in the POE aliphatic amine of 10 to 50, more preferably 10 to 20 mol, from the viewpoint of solubility in water and writing property.
  • Examples of the POE aliphatic amine that can be used include POE (15) oleylamine and POE (15) stearylamine, and at least one of them can be used.
  • the content of these POE aliphatic amines is preferably 0.1 to 10%, more preferably 0.3 to 5%, based on the total amount of the ink composition.
  • the content is less than 0.1%, the pigment dispersion effect is insufficient.
  • the content exceeds 10%, blurring tends to occur during writing, which is not preferable.
  • the water-based ink composition for ballpoint pens of the present invention in addition to the microcapsule pigment, the chemical substance, the POE aliphatic amine, and the balance as water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) As long as the effects of the present invention are not impaired, a water-soluble solvent, a thickener, a lubricant, a rust inhibitor, a preservative, or a fungicide can be appropriately contained.
  • water-soluble solvents examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. These can be used alone or in combination.
  • the thickener for example, at least one selected from the group consisting of synthetic polymers, natural rubber, cellulose, and polysaccharides is desirable.
  • gum arabic ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, starch glycolic acid and its salts, propylene glycol alginate
  • Lubricants include nonionics such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, and alkyl phosphates, which are also used in pigment surface treatment agents, and alkyl sulfonic acids of higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkyl allyl sulfonates, polyalkylene glycol derivatives, fluorosurfactants, and polyether-modified silicones.
  • benzotriazole As rust preventives, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins, etc., as preservatives or fungicides, phenol, sodium omadin, sodium benzoate, benzimidazole compounds, etc. Can be mentioned.
  • the water-based ink composition for ballpoint pens of the present invention conventionally known methods can be employed. For example, a predetermined amount of each of the above components is blended and stirred and mixed with a stirrer such as a homomixer or a disper. It is obtained by doing. Furthermore, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.
  • a stirrer such as a homomixer or a disper. It is obtained by doing.
  • coarse particles in the ink composition may be removed by filtration or centrifugation.
  • a microcapsule pigment in which a wall film having an average particle size of at least 0.1 to 1.0 ⁇ m is formed of an amino resin, and a ketone as a main chain A polymer containing an acidic functional group in the chemical structure and a chemical substance having an acid value of 3 to 40 (mgKOH / g) and containing a microcapsule pigment having a small average particle size Even when writing on paper or the like with a ballpoint pen equipped with the ink to be used, a sufficient drawing line density can be obtained, and an ink composition for water-based ballpoint pens excellent in ink storage stability and writing performance can be obtained. .
  • the ink composition for water-based ballpoint pens of the present invention uses a small microcapsule pigment having an average particle size of 0.1 to 1.0 ⁇ m, a sufficient line density can be obtained, and the storage stability of the ink can be obtained. It is assumed that the writing performance is excellent for the following reasons. That is, in the present invention, the chemical substance improves the drawn line density by causing gradual aggregation with respect to the microcapsule pigment, and further, the polyoxyethylene aliphatic amine serves to keep this aggregation state stable. It is.
  • the water-based ballpoint pen of the present invention has a general configuration as a water-based ballpoint pen, for example, a resin-made ink storage tube provided with a metal tip, and the water-based ink composition for a ballpoint pen of the present invention incorporated therein and Various types of ballpoint pen configurations of a knock type and a non-knock type (cap type) including a writing instrument main body (shaft body) can be adopted, and the production thereof can be performed according to a conventional method.
  • the ink composition for water-based ballpoint pens having the above configuration is mounted, it is preferable to employ various ballpoint pen configurations on which an ink follower is mounted.
  • the ink follower used in the aqueous ballpoint pen of the present invention is pre-kneaded at room temperature with all ink follower components such as a base oil and a surfactant, A very simple method of kneading with a disperser such as a roll mill or a kneader can be adopted.
  • a disperser such as a roll mill or a kneader
  • it can be heated, stirred, kneaded, and the like, if necessary.
  • It is also possible to adjust the manufactured ink follower by re-kneading with a disperser such as a roll mill or a kneader, or by heating.
  • Example 1 to 8 and Comparative Examples 1 and 2 [Microcapsule pigment: formulation of A-1 to A-6] (Pigment A-1) Leuco dye: 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone 1 part, developer: 2 parts of bisphenol A, and a color change temperature adjusting agent : 24 parts of 4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate heated and melted, then adjusted to 95 ° C.
  • Leuco dye 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone 1 part
  • developer 2 parts of bisphenol A
  • a color change temperature adjusting agent 24 parts of 4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate heated and
  • aqueous solution of methyl vinyl ether / maleic anhydride copolymer (GANTREZAN-179: manufactured by GAF CHEMICALS) The mixture was heated and stirred to disperse into oil droplets, and then 20 parts of a 50% methylolmelamine aqueous solution was gradually added as a capsule film agent, followed by reaction for 1 hour. The dispersion was filtered to obtain a microcapsule pigment.
  • the finished microcapsule pigment had an average particle size of 0.3 ⁇ m.
  • Pigment A-2 A microcapsule pigment having an average particle size of 0.6 ⁇ m was obtained by changing the stirring conditions in accordance with the formulation of Pigment A-1.
  • Pigment A-3 A microcapsule pigment having an average particle size of 0.9 ⁇ m was obtained by changing the stirring conditions in accordance with the formulation of Pigment A-1.
  • a solution obtained by adding 17 parts of formalin (formaldehyde 37% aqueous solution) to 10 parts of urea and 73 parts of water was added to the liquid dispersed in the above-mentioned oil droplets and adjusted to 80 ° C., and then a 20% acetic acid aqueous solution was added. 5 parts were added and reacted for 2 hours.
  • the dispersion was filtered to obtain a microcapsule pigment.
  • the finished microcapsule pigment had an average particle size of 0.8 ⁇ m.
  • microcapsule pigment had an average particle size of 0.8 ⁇ m.
  • a methyl vinyl ether / maleic anhydride copolymer heavy resin GANTREZAN-179: GAF CHEMICALS
  • the finished microcapsule pigment had an average particle size of 0.6 ⁇ m.
  • each water-based ink composition for water-based ballpoint pens was prepared by a conventional method.
  • a water-based ballpoint pen was produced using each ink composition obtained above. Specifically, a ball pen [Mitsubishi Pencil Co., Ltd., trade name: Signo UM-100] shaft is used, an inner diameter of 3.8 mm, a length of 113 mm, a polypropylene ink containing tube, and a stainless tip (carbide) Each ink is filled in a refill comprising a ball, a ball diameter of 0.5 mm) and a joint connecting the receiving tube and the tip, and an ink follower mainly composed of mineral oil is loaded at the rear end of the ink. Produced. Using the obtained aqueous ballpoint pens of Examples 1 to 8 and Comparative Examples 1 to 3, the drawing density, storage stability, and writing property were evaluated by the following evaluation methods. These results are shown in Table 1 below.
  • Examples 1 to 8 according to the present invention are superior in line density, storage stability, and writing properties as compared with Comparative Examples 1 to 3 that are outside the scope of the present invention.
  • Comparative Examples 1 and 2 even when a microcapsule pigment having an average particle size of 0.1 to 1.0 ⁇ m is used, the wall film is formed of a urethane resin other than an amino resin or an epoxy resin. Therefore, the target effect cannot be exhibited, and even in the case of Comparative Example 3, the microcapsule pigment of the present invention does not contain a chemical substance composed of a polymer having the ketone of the present invention as a main chain, so that the target effect is exhibited. I knew it was possible.
  • microcapsule pigments with an average particle size of 0.1 to 1.0 ⁇ m are used, excellent line drawing density is achieved, and ink storage stability and writing performance are excellent. It is most suitable for ink compositions and water-based ballpoint pens.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)
PCT/JP2010/071576 2009-12-08 2010-12-02 水性ボールペン用インキ組成物及び水性ボールペン WO2011070966A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/514,766 US8562235B2 (en) 2009-12-08 2010-12-02 Ink composition for aqueous ink ball point pen and aqueous ink ball point pen
EP10835887.0A EP2511353B1 (de) 2009-12-08 2010-12-02 Tintenzusammensetzung für einen kugelschreiber auf wasserbasis sowie kugelschreiber auf wasserbasis
CN201080063095.1A CN102753632B (zh) 2009-12-08 2010-12-02 水性墨圆珠笔用墨组合物和水性墨圆珠笔

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009278763A JP5534794B2 (ja) 2009-12-08 2009-12-08 水性ボールペン用インキ組成物及び水性ボールペン
JP2009-278763 2009-12-08

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WO2011070966A1 true WO2011070966A1 (ja) 2011-06-16

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US (1) US8562235B2 (de)
EP (1) EP2511353B1 (de)
JP (1) JP5534794B2 (de)
KR (1) KR101576329B1 (de)
CN (1) CN102753632B (de)
WO (1) WO2011070966A1 (de)

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JP5444061B2 (ja) * 2010-03-18 2014-03-19 パイロットインキ株式会社 感温変色性色彩記憶性トナー及びそれを収容したカートリッジ、画像形成装置、カートリッジセット、画像形成装置セット
JP5885965B2 (ja) * 2011-08-19 2016-03-16 株式会社パイロットコーポレーション 水性ボールペン用インキ組成物およびそれを用いた水性ボールペン
JP6231351B2 (ja) * 2013-09-03 2017-11-15 三菱鉛筆株式会社 マイクロカプセル色材及び筆記具用インク組成物
CN104130627B (zh) * 2014-07-23 2016-12-07 王勇 稳定的变色墨水
CN108139279B (zh) * 2015-10-21 2020-07-03 株式会社日立制作所 温度检测体
KR102668466B1 (ko) * 2016-01-06 2024-05-24 미쓰비시 엔피쯔 가부시키가이샤 마이크로 캡슐 안료 및 필기구용 수성 잉크 조성물
JP6626369B2 (ja) * 2016-02-29 2019-12-25 三菱鉛筆株式会社 筆記具用水性インク組成物
JP6888925B2 (ja) * 2016-08-24 2021-06-18 三菱鉛筆株式会社 筆記具
JP6964080B2 (ja) * 2016-08-29 2021-11-10 三菱鉛筆株式会社 筆記具用水性インク組成物
JP6763746B2 (ja) * 2016-10-28 2020-09-30 株式会社パイロットコーポレーション 熱変色性筆記具インキ組成物及びそれを内蔵した筆記具
JP6811626B2 (ja) * 2017-01-25 2021-01-13 三菱鉛筆株式会社 ボールペン用水性インク組成物
EP4083148A4 (de) * 2019-12-24 2024-01-03 Mitsubishi Pencil Company, Limited Tintenzusammensetzung für kugelschreiber auf wasserbasis
EP3858925B1 (de) * 2020-01-28 2023-01-11 Société BIC Irreversibel löschbare tintenzusammensetzung mit einem verfärbungsmittel
EP3904468B1 (de) 2020-04-30 2022-10-19 Société BIC Verfahren zur herstellung von thermochromen wasserbasierten geltintenzusammensetzungen und thermochrome wasserbasierte geltintenzusammensetzungen daraus
JP2021181515A (ja) * 2020-05-18 2021-11-25 三菱鉛筆株式会社 水性ボールペン用インク組成物
CN116426163B (zh) * 2023-04-04 2024-07-09 合肥金龙浩科技有限公司 一种温致变色油墨及其应用

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CN102753632B (zh) 2014-04-09
EP2511353B1 (de) 2015-09-16
US20120251222A1 (en) 2012-10-04
KR101576329B1 (ko) 2015-12-09
CN102753632A (zh) 2012-10-24
JP2011122010A (ja) 2011-06-23
JP5534794B2 (ja) 2014-07-02
US8562235B2 (en) 2013-10-22
KR20120103685A (ko) 2012-09-19
EP2511353A1 (de) 2012-10-17

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