WO2003091348A1 - Composition d'encre a base d'eau pour stylo-bille - Google Patents

Composition d'encre a base d'eau pour stylo-bille Download PDF

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Publication number
WO2003091348A1
WO2003091348A1 PCT/JP2003/005083 JP0305083W WO03091348A1 WO 2003091348 A1 WO2003091348 A1 WO 2003091348A1 JP 0305083 W JP0305083 W JP 0305083W WO 03091348 A1 WO03091348 A1 WO 03091348A1
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WO
WIPO (PCT)
Prior art keywords
water
ink composition
general formula
organic solvent
ink
Prior art date
Application number
PCT/JP2003/005083
Other languages
English (en)
Japanese (ja)
Inventor
Atsushi Ito
Naoshi Murata
Yumi Hirose
Original Assignee
Sakura Color Products Corporation
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 Sakura Color Products Corporation filed Critical Sakura Color Products Corporation
Priority to AU2003227453A priority Critical patent/AU2003227453A1/en
Publication of WO2003091348A1 publication Critical patent/WO2003091348A1/fr
Priority to US10/973,190 priority patent/US7241335B2/en

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Classifications

    • 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

Definitions

  • Aqueous ink composition for ball pens for ball pens
  • the present invention relates to an aqueous ink composition for a ballpoint pen. More specifically, the present invention relates to a water-based ink composition for a ball-point pen, which has excellent lubricating properties of a ball-point pen tip and does not cause problems such as blurring of handwriting and line breakage during writing.
  • An object of the present invention is to provide a water-based ink composition for a ball-point pen containing at least a coloring agent and water, which ensures lubricity of a ball-point pen tip and does not cause problems such as blurring of handwriting and line breakage during writing.
  • An object of the present invention is to provide a water-soluble ink composition. Disclosure of the invention As a result of intensive studies to solve these drawbacks, the present inventor has found that a compound containing water and a colorant as essential components, a compound represented by the following general formula (1) and a branched hydrophobic group If the ink contains at least one water-soluble organic solvent of alcohols, glycols, and glycol ethers having the following, the compound represented by the following general formula (1) is used alone. It has been found that lubricating properties are ensured and smooth writability can be obtained as compared with the water-based ink contained in, and that problems such as blurring of handwriting and line breakage do not occur during writing.
  • the compound represented by the following general formula (1) used in the present invention is used to improve the lubricity of a ball-point tip, and its action is not clear. It is considered that a thin film is formed in the gap between the two to improve the lubricity.
  • ⁇ (Ri— is 100 X or R 2 — 0— (CH 2 CH 20 ) n —, R 2 — is a C 8 to Ci 8 alkyl group or alkenyl group or alkylphenyl group, n is 1 to 30, X is Alkali metal or amine or alkanolamine) More specifically, alkali metal salts of monoesters of phosphoric acid of polyoxyethylene alkyl ether, metal salts of monoesters of phosphoric acid of polyoxyethylene alkyl phenyl ether And metal salts of phosphoric acid diesters of polyoxyethylene alkyl ethers, and metal salts of phosphoric acid diesters of polyoxyethylene alkylphenyl ether.
  • examples of the alkali metal include sodium and potassium.
  • amine salts of polyoxyethylene alkyl ether phosphate monoesters, polyoxyethylene alkyl phenyl ether monoester phosphate amine salts, and polyoxethylene alkyl ether phosphate ester amine salts There is an amide salt of a phosphoric diester of polyoxyethylene alkylphenyl ether.
  • alkanolamine salts of lucanolamine salts and phosphoric acid diesters of polyoxyethylene alkylphenyl ether There are alkanolamine salts of lucanolamine salts and phosphoric acid diesters of polyoxyethylene alkylphenyl ether.
  • the content of the compound represented by the general formula (1) used in the present invention is preferably 0.05 to 10% by weight based on the whole ink composition.
  • the compound represented by the general formula (1) is used in an amount of 0. If the amount is less than 0% by weight, the lubricating effect is not sufficient, so that it is not possible to write smoothly, and line breaks occur. If the content is more than 10% by weight, the viscosity becomes too high and the writeability decreases, and the surface tension value of the ink becomes low, causing blurring of the handwriting. From the viewpoint of preventing handwriting bleeding, the content of the compound represented by the general formula (1) is preferably 0.1 to 5.0% by weight based on the total weight of the ink composition, and the content is optimal. The amount is 0.2 to 2.0% by weight.
  • the colorant used in the present invention may be any as long as it has an effect of arbitrarily coloring the ink, and pigments, dyes and the like which are usually used for ballpoint pen inks can be used. From the viewpoint of the effects of the present invention, it is preferable to use a pigment.
  • the pigment various known pigments can be used. Specific examples thereof include azo pigments, condensed polyazo pigments, phthalocyanine pigments, and quinacridone pigments.
  • Aqueous dispersion of polymer fine particles having an average particle size of 0.1 to ⁇ ⁇ obtained by emulsion polymerization using metal powder pigments such as aluminum pigments, styrene resin, acrylic resin, or acrylonitrile resin alone or in combination of two or more. Examples thereof include a colored resin emulsion colored with a basic dye, a fluorescent basic dye, and azo or a fluorescent whitening agent.
  • scaly glittering particles having a smooth particle surface such as a metal reflecting surface
  • a metal reflecting surface for example, glass flakes, inorganic particles, and resin film pieces coated with a metal or metal oxide. It can. These may be used alone or in combination of two or more.
  • the content of these coloring agents is selected in the range of preferably 1 to 30% by weight, more preferably 3 to 15% by weight, based on the whole ink composition. If the amount used is small, the handwriting becomes thin, and if it is large, the viscosity increases and the writing Gets worse. (Pigment dispersant)
  • the pigment dispersant at least one kind is selected from commonly used water-soluble resins and surfactants, and the water-soluble resin may be any of natural products, semi-synthetic products, and synthetic products.
  • the problem is that synthetic products are optimal in terms of viscosity characteristics as ink for ballpoint pens.
  • These synthetic products include, for example, water-soluble acrylyl resin, water-soluble maleic acid resin, water-soluble styrene resin, water-soluble styrene acrylic resin, water-soluble styrene maleic resin, polyvinylpyrrolidone, polyvinyl alcohol, water-soluble urethane resin, etc. Can be exacerbated.
  • the surfactant is selected from anionic, cationic, nonionic and amphoteric surfactants.
  • the amount of these pigment dispersants to be used is preferably selected within the range of 0.05 to 2 parts by weight per 1 part by weight of the pigment. If the amount used is small, the dispersion stability of the pigment deteriorates.
  • the water-soluble organic solvent at least one of alcohols, glycols and glycol ethers having a branched hydrophobic group is used.
  • the “having a branched hydrophobic group” structure in the water-soluble organic solvent of the present invention means a structure in which a hydrophobic group is bonded to a main chain as a side chain in a chain compound.
  • the type of the hydrophobic group may be any of a methyl group, an ethyl group, and the like.
  • the molecule may have one or more hydrophobic groups in the molecule, and when it has two or more, they may be the same or different. For example, in the case of hexylene glycol represented by the following chemical formula (1), a structure having a methyl group in a dotted frame corresponds to a structure having “a branched hydrophobic group”.
  • alcohols having a branched hydrophobic group include, for example, isopanol, S-butanol, t-butanol (C4), isopenenol, and s-pentanol.
  • glycols and glycol ethers having a branched hydrophobic group examples include 1,3-octylene glycol, hexylene glycol, dipropylene glycol, propylene glycol, polypropylene glycol, and poly (oxyethylene propylene) derivatives.
  • dipropylene glycol alkyl ether can be particularly preferably used.
  • the content of the water-soluble organic solvent can be appropriately determined according to the type of the water-soluble organic solvent, etc., but is usually about 1 to 50% by weight, preferably 1 to 30% by weight in the ink composition of the present invention. % By weight. If the content of the water-soluble organic solvent is more than 50% by weight, the solubility of the water-soluble resin may be reduced, and precipitation may occur. is there. If the content of the water-soluble organic solvent is less than 1% by weight, sufficient permeation and diffusion may not be obtained.
  • a pH adjuster a protective colloid-forming agent, a pseudoplasticity-imparting agent, an antibacterial agent, an antiseptic fungicide and the like can be appropriately selected and used.
  • a pH adjuster caustic soda, sodium carbonate, alkanolamine, ammonia and the like can be used.
  • a cross-linked acrylic acid polymer such as alkenylamine or an ammine or alkanolamine salt
  • specific examples thereof include rheodix 250H, Junron PW100 (Nippon Pure Chemical Industries, Ltd.), Carbopol # 934, # 940 (BF Goodrich), PEMULEN, TR_1, TR-2 ( ⁇ F Godrich) are available.
  • natural polysaccharides and semi-synthetic cellulose-based polymers can be used as pseudoplasticity-imparting agents that impart pseudoplastic flow characteristics (thixotropic properties) to inks.
  • examples of natural polysaccharides include guar gum, locust bean gum, perlan gum, ramzan gum, and xansu which have a high molecular chemical structure composed of monosaccharides such as glucose, galactose, rhamnose, mannose, and glug monophosphate.
  • semi-synthetic cellulosic polymers such as methylcellulose, ethylcellulose, and carboxymethylcellulose, which are made water-soluble by esterifying or etherifying the hydroxyl groups of cellulose. Etc. can be used.
  • Penzotriazole and its derivative dicyclohexyl ammonium nitrate can be used as the protective agent.
  • potassium sorbate, sodium benzoate, pentanaphthalene, sodium dihydroacetate, 1,2-pentisothiazoline-1-one, and the like can be used.
  • the aqueous ink composition for a ballpoint pen described above can be used for a ballpoint pen.
  • it can be suitably used for an aqueous gel ink ballpoint pen.
  • Examples 1 to 4 and Comparative Examples 1 to 4 fill ink directly into an ink storage tube made of polypropylene or the like filled in the main container (the same type as an oil-based ballpoint pen), and use polybutene at the rear end of the ink.
  • the base material is filled with a backflow inhibitor made by gelling it with a gelling agent if necessary.Furthermore, the tip of the ink is connected to a stopper with a stainless steel ball nipple.
  • the present invention relates to a ballpoint pen having a refillable ink-in-liquid type structure.
  • compositions and contents (parts by weight) shown in Table 1, the respective aqueous ink compositions were obtained by the following production methods.
  • the dispersion method, defoaming method, and filtration method used heretofore were known methods.
  • Aropirenque's recall 11 5.00 Ion pulse 12 85.18 85.18 87.18 87.18 90.68 90.18 85.68 85.18 Mouth 1 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Listen
  • composition of each raw material is as follows.
  • the codes correspond to the codes in the table.
  • Monoazo red pigment C. I. Pigment 2 58, trade name "Simla Fast Tread 41 27", manufactured by Dainippon Inki Chemical Industry Co., Ltd.
  • xanthan gum To 30 parts of water little by little so as to prevent mako, dissolve completely by stirring, and add carbon black, sodium salt of styrene acrylic acid copolymer and 40.2 parts of water to a sand mill. After stirring and dispersing for 1 hour, the remaining components were added and dissolved by stirring. The mixture was stirred for 1 hour, the pH was adjusted to 9 with an aqueous sodium hydroxide solution, and the mixture was filtered to obtain a black ink composition.
  • xanthan gum To 30 parts of water little by little so as to prevent mako, dissolve completely by stirring, and add sodium hydroxide, sodium salt of styrene acrylic acid copolymer and 40.2 parts of water. After stirring and dispersing with a sand mill for 1 hour, add the remaining components and stir and dissolve, add and stir for 1 hour, adjust the pH to 9 with aqueous sodium hydroxide, and filter to obtain a black ink composition.
  • Example 3 Example 3
  • xanthan gum to 30 parts of water little by little so as not to form mako, stir and dissolve completely, and add red pigment, sodium salt of styrene acrylic acid copolymer and 40.2 parts of water to a sand mill. After stirring and dispersing for 1 hour, add the remaining components, stir and dissolve, add and stir for 1 hour, adjust the pH to 9 with aqueous sodium hydroxide, and filter to obtain a red ink composition.
  • xanthan gum to 30 parts of water little by little so as not to form mako, stir and dissolve completely, and add red pigment, sodium salt of styrene acrylic acid copolymer and 40.2 parts of water to a sand mill. After stirring and dispersing for 1 hour, add the remaining components, stir and dissolve, add and stir for 1 hour, adjust the pH to 9 with aqueous sodium hydroxide, and filter to obtain a red ink composition.
  • a black ink composition was obtained in the same manner as in Example 1, except that the compound of the general formula (1) and the water-soluble organic solvent of glycol ether having a branched hydrophobic group in the ink component of Example 1 were replaced with the same amount of water.
  • a black ink composition was obtained in the same manner as in Example 1, except that the water-soluble organic solvent of glycol ether having a branched hydrophobic group in the ink component of Example 1 was replaced with the same amount of water.
  • the compound of the general formula (1) in the ink component of Example 1 was replaced with the same amount of water, and a black ink composition was obtained in the same manner.
  • a glycol ether having a branched hydrophobic group in the ink component of Example 1 was replaced with the same amount of a water-soluble organic solvent of a glycol having no branched hydrophobic group. Black ink set by method A product was obtained.
  • Table 1 shows the results of these evaluations.
  • handwriting was performed on commercially available loose-leaf paper, and the taste was evaluated. Those with a smooth writing taste were marked as ⁇ , those with a hard writing taste as ⁇ , and those with a catch were rated as X.
  • Comparative Example 1 and Comparative Example 3 do not contain a lubricant, and therefore have poor lubricity, have poor writing quality, and cause line breaks.
  • the ink of Comparative Example 2 which contains the compound represented by the general formula (1) and does not contain the water-soluble organic solvent having a branched hydrophobic group
  • the ink of Comparative Example 1 has a higher moisture content than that of Comparative Example 1.
  • there was no noticeable line break in the written test due to the lubricity there was a part of line break due to insufficient permeability by the water-soluble organic solvent.
  • Comparative Example 4 although lubricity was ensured, linear penetration occurred in some parts due to insufficient permeability by the water-soluble organic solvent. Industrial applicability
  • the present invention comprises water and a colorant as essential components
  • the ink contains at least one water-soluble organic solvent of alcohols, glycols and glycol ethers having a hydrophobic group branched from the compound represented by (1),
  • the lubricating properties of the conventional water-based ball ink composition can be ensured to obtain a smooth writing taste, and at the same time, blurring of handwriting during writing and occurrence of line breaks can be eliminated.
  • the compound represented by the general formula (1) in combination with at least one water-soluble organic solvent of alcohols, glycols and glycol ethers having a branched hydrophobic group, the compound represented by the general formula (1) 1)
  • the lubrication and the prevention of handwriting should be ensured even if the amount of the lubricant required to secure the lubrication and prevent handwriting is reduced only by using the compound shown in 1) alone. Therefore, the addition of a large amount of lubricant has the effect of preventing bleeding of handwriting and leakage of ink from the writing instrument container.

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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)

Abstract

La présente invention concerne une composition d'encre à base d'eau destinée à un stylo-bille qui est excellente pour lubrifier la pointe d'un stylo-bille à base d'eau et empêcher les coulures au moment de l'écriture. La composition d'encre comprend de l'eau et un colorant en tant que constituants principaux et se caractérise également en ce qu'elle renferme un composé représenté par la formule (1) et au moins un solvant organique soluble dans l'eau sélectionné parmi les alcools comprenant des groupes hydrophobes ramifiés, les glycols et les éthers glycoliques. Formule (1)
PCT/JP2003/005083 2002-04-25 2003-04-22 Composition d'encre a base d'eau pour stylo-bille WO2003091348A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003227453A AU2003227453A1 (en) 2002-04-25 2003-04-22 Water-base ballpoint ink composition
US10/973,190 US7241335B2 (en) 2002-04-25 2004-10-25 Aqueous ink for ball point pens

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-123580 2002-04-25
JP2002123580 2002-04-25

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/973,190 Continuation-In-Part US7241335B2 (en) 2002-04-25 2004-10-25 Aqueous ink for ball point pens

Publications (1)

Publication Number Publication Date
WO2003091348A1 true WO2003091348A1 (fr) 2003-11-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/005083 WO2003091348A1 (fr) 2002-04-25 2003-04-22 Composition d'encre a base d'eau pour stylo-bille

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AU (1) AU2003227453A1 (fr)
WO (1) WO2003091348A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018105151A1 (fr) * 2016-12-05 2018-06-14 ぺんてる株式会社 Composition d'encre, instrument d'écriture et procédé de production de composition d'encre

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060666A (ja) * 2000-08-23 2002-02-26 Sakura Color Prod Corp 二重発色インキ組成物及びそれを用いた筆記具

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060666A (ja) * 2000-08-23 2002-02-26 Sakura Color Prod Corp 二重発色インキ組成物及びそれを用いた筆記具

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018105151A1 (fr) * 2016-12-05 2018-06-14 ぺんてる株式会社 Composition d'encre, instrument d'écriture et procédé de production de composition d'encre
JPWO2018105151A1 (ja) * 2016-12-05 2019-10-24 ぺんてる株式会社 インキ組成物及び筆記具並びにインキ組成物の製造方法
US11697743B2 (en) 2016-12-05 2023-07-11 Pentel Kabushiki Kaisha Ink composition, writing instrument and method for producing ink composition

Also Published As

Publication number Publication date
AU2003227453A1 (en) 2003-11-10

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