JP2011127031A - Correction fluid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a correction fluid that prevents delayed drying of writing while preventing the writing from permeating the coating film and fading when writing down on the coating film with water-based ink. <P>SOLUTION: The correction fluid contains titanium oxide, a liquid medium, a film-forming resin, and chitosan with a molecular weight of 10,000 or more. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a correction liquid that conceals and erases typographical errors and the like, and more particularly, to a correction liquid that has a handwriting density that is unlikely to become thin when writing with water-based ink on a coating film and that is quick to dry.

  Conventionally, a correction liquid comprising at least a concealing material such as titanium oxide, a hydrocarbon solvent such as methylcyclohexane or water as a solvent, and a resin soluble or dispersible in the hydrocarbon solvent or water is known. . When an organic solvent such as methylcyclohexane is used as the solvent, a resin such as an acrylic resin or a styrene-butadiene thermoplastic elastomer is used. When water is used as the main solvent, a water-soluble acrylic resin or an acrylic emulsion is used. And vinyl acetate emulsions (see Patent Document 1, Patent Document 2, and Patent Document 3).

  In order to correct typographical errors, it is preferable that the color tone of the character rewritten on the coating film applied on the written character, etc. is the same as the color tone written on the paper, but titanium oxide and hydrocarbon organic The correction liquid consisting of a solvent and a resin soluble in the hydrocarbon-based organic solvent has a hydrophobic coating film itself, so when rewritten with a water-based ink such as a fountain pen or sign pen, The ink has been repelled, the drying time of the handwriting is delayed, and the ink has penetrated into the coating film over time, resulting in a problem that the handwriting density is reduced.

  In order to solve these problems, an ethylene oxide-added fluorine-based surfactant is added to reduce the surface tension of the coating film and improve the penetration of water-based ink into the coating film (see Patent Document 4), polyamine or water-soluble There have been proposed correction liquids and solid correction agents that use a cationic water-soluble resin such as water-soluble chitosan and adsorb the dye of water-based ink to prevent the handwriting density from becoming thin. (See Patent Documents 5 and 6)

Japanese Patent Application No. 55-65277 Japanese Patent Application No. 55-157485 JP 58-23863 A Japanese Patent Application No. 56-173925 JP-A-3-192168 Japanese Unexamined Patent Publication No. 7-97538

However, the correction liquid to which the ethylene oxide-added fluorine-based surfactant is added has no problem in repelling or drying characters rewritten on the dried coating film, but the ink penetrates due to the low surface tension of the coating film, There is a problem that a so-called color sink phenomenon occurs in which a handwritten character becomes thin.
In addition, acid dyes and direct dyes are generally used as dyes used for water-based dye inks for writing instruments. These dyes have a salt such as sodium acid group in the molecule, and this part is dissolved in water.
The correction liquid using the cationic water-soluble resin can suppress to some extent the handwriting density is reduced by adsorbing the acid group of the dye of the aqueous dye ink to the cationic group of the resin. However, since the resin is water-soluble, it is dissolved in the aqueous dye ink, and the viscosity of the aqueous dye ink is increased. For this reason, there is a problem in that penetrating into the coating film is difficult and the ink is held in the vicinity of the coating film surface for a long time, so that the handwriting drying property becomes slow.

  As an improvement measure, the present invention provides a correction liquid containing at least titanium oxide, a liquid medium, a film-forming resin, and chitosan having a molecular weight of 10,000 or more.

  Chitosan having a molecular weight of 10,000 or more used in the present invention is a linear glucosamine polysaccharide having an amino group in the molecule. When writing with a water-based dye ink on the coating film of the correction liquid containing this, the acid group of the dye and the amino group of chitosan having a molecular weight of 10,000 or more in the vicinity of the coating film surface are adsorbed to insolubilize the dye. Furthermore, chitosan itself that has adsorbed the dye does not flow because it is fixed to the correction liquid dry coating film with resin. For this reason, the dye does not penetrate into the correction liquid coating film, and the handwriting density does not decrease. In addition, chitosan having a molecular weight of 10,000 or more does not dissolve in the aqueous dye ink, so that it does not thicken and penetrates into the coating film quickly. It is presumed that, due to these things, it is possible to achieve both prevention of color settling and handwriting dryness.

  Titanium oxide is the white pigment having the highest hiding power in consideration of the most white color on the paper surface and covering the ground as a correction liquid, and has a particle size of approximately 0.15 to 0.5 μm. Specific examples of the product include TITON SR-1 (specific gravity 4.1, particle size 0.30 μm), R-650 (specific gravity 4.1, particle size 0.25 μm), R-62N (specific gravity 3.9). , Particle diameter 0.25 μm), R-42 (specific gravity 4.1, particle diameter 0.29 μm), R-7E (specific gravity 3.9, particle diameter 0.23 μm), R-21 (specific gravity 4. 0, particle size 0.20 μm (above, manufactured by Sakai Chemical Industry Co., Ltd.), Taipure R-900 (specific gravity 4.0, particle size 0.22 μm), R-902 (specific gravity 4.0, particle size 0.8. 21 μm), R-960 (specific gravity 3.9, particle size 0.21 μm) (above, manufactured by DuPont Japan Limited), TITANIX JR-301 (specific gravity 4.1, particle size 0.30 μm), JR- 805 (specific gravity 3.9, particle size 0.29 μm), JR-603 (specific gravity 4.0, particle size 0.28 μm), same JR800 (specific gravity 3.9, particle size 0.27 μm), JR-403 (specific gravity 4.0, particle size 0.25 μm), JR701 (specific gravity 4.1, particle size 0.27 μm) The amount of titanium oxide added is preferably 30 to 60% by weight based on the total amount of ink.

As the solvent, an organic solvent and / or water is used.
Correction fluids that use organic solvents as the main solvent mainly use hydrocarbon solvents. Considering the drying property of the coating film, a solvent having a boiling point of 40 to 150 ° C. is preferable. Specifically, normal pentane (boiling point 36.0 ° C.), cyclopentane (boiling point 49.2 ° C.), methylcyclopentane (boiling point 71.8 ° C.) normal hexane (boiling point 68.7 ° C.), isohexane (boiling point 62 ° C.) ), Normal heptane (boiling point 98.4 ° C), aliphatic hydrocarbon solvents such as normal octane, cyclohexane (boiling point 80.0 ° C), methylcyclohexane (boiling point 100.9 ° C), ethylcyclohexane (boiling point 132 ° C), etc. In addition, a mixture of aliphatic hydrocarbon solvents such as Exol DSP 100/140 (initial boiling point 102 ° C., dry point 138 ° C.) (exxon chemical Co., Ltd.) may be used. These can be used alone or in combination.
In addition to water, the correction liquid using water as the main solvent can be used in combination with ethanol (boiling point 78.4 ° C), isopropyl alcohol (boiling point 82.4 ° C), etc., in order to improve the drying property of the coating film. .
The amount of solvent used is preferably 30 to 60% by weight based on the total amount of ink.

For example, when the above-mentioned hydrocarbon organic solvent is used as the resin, the pigment is dispersed or the correction liquid is fixed on the paper surface. Alkyd resins, thermoplastic elastomers, and the like can be used, but acrylic resins are preferable in consideration of pigment dispersibility, fixability on paper, and the like.
Hereinafter, the acrylic resin will be described. Usable monomers are methyl acrylate, ethyl acrylate, isopropyl acrylate, normal butyl acrylate, 2-ethylhexyl acrylate as acrylate ester, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl as methacrylic acid ester. Examples include methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. Cationic monomers include N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (Meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-di-tert-butylaminoethyl (meth) acrylate, N, N-dicyclohexylaminoethyl (meth) acrylate, N, N dimethylamino Examples include ethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. In addition to these monomers, vinyl acetate, styrene, vinyl toluene, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, hydroxypropyl acrylate, acrylamide, N- A copolymerizable vinyl monomer such as methylolacrylamide, diacetoneacrylamide, or glycidylmethacrylate can also be contained.
When water is used as the main solvent, water-soluble acrylic resins, acrylic emulsions, vinyl acetate emulsions and the like can be used.
The amount of the resin used is preferably 3 to 15% by weight of the total solid content of the ink.

The chitosan used in the present invention adsorbs the dye of the aqueous dye ink, and it is necessary that the chitosan itself is not dissolved and thickened in the aqueous dye ink at the time of adsorption. That is, it needs to be chitosan having a molecular weight of 10,000 or more.
The addition amount is preferably 0.5 to 15% by weight.
Here, the molecular weight is an average molecular weight of the polymer substance and is a value measured by GPC (Gel Permeation Chromatography) analysis method, and a polyhydroxymethacrylate column was used as a packed column.

  Furthermore, other extender pigments, resin particles, and the like can be used as appropriate, and their shapes are not particularly limited. Specific examples of spherical and massive particles include fine carbon dioxide titanium oxide, crosslinked polymethyl methacrylate, benzoguanamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, silica, calcium carbonate, needles. Shaped particles include silicon nitride whisker, silicon carbide whisker, aluminum borate whisker, zinc oxide whisker, potassium titanate whisker, whisker-like calcium carbonate, whisker-like titanium oxide, alumina diameter whisker, magnesia whisker, mullite whisker, boric acid Magnesium whisker, titanium boride whisker, alumina and alumina silica short fiber, silica short fiber, zirconia fiber (short fiber), kaolin-based ceramic short fiber, plate The particles, mica, talc, boron nitride, molybdenum disulfide.

  For pigment dispersion stability, nonionic surfactants such as alkyl sulfate ester salts, alkyl phosphate salts, polycarboxylic acid polymers, polyethylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene fatty acid esters, etc. Dispersing agents such as ionic surfactants, quaternary ammonium salts and alkylamine salts can be added.

  The correction fluid of the present invention can be obtained by dispersing and mixing the above components using a stirring and dispersing machine such as a ball mill, an attritor, a sand grinder, and an impeller.

Example 1
TITANIX JR701 (titanium oxide, manufactured by Teika Co., Ltd.) 45.0 parts by weight Methylcyclohexane 44.3 parts by weight Dynal BR105 (acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd.) 8.7 parts by weight chitosan (molecular weight 3.5 million) 1 1.0 part by weight Disperbyk 101 (surfactant, manufactured by BYK Chemie, Germany) 1.0 part by weight Each of the above components was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 2
TITANIX JR701 (mentioned above) 43.0 parts by weight water 27.0 parts by weight
JONCRYL61J (water-soluble styrene acrylic resin, non-volatile content 30.5%, BASF (Germany))
10.0 parts by weight
JONCRYL711 (styrene acrylic emulsion, nonvolatile content 42.0%, manufactured by BASF (Germany)) 15.0 parts by weight chitosan (molecular weight 5 million) 5.0 parts by weight
Each component except JONCRYL711 was dispersed for 24 hours with a ball mill, then JONCRYL711 was added and stirred for 1 hour with a three-one motor to obtain a correction solution.

Example 3
TITANIX JR800 (titanium oxide, manufactured by Teika Co., Ltd.) 40.0 parts by weight Methylcyclohexane 20.3 parts by weight Cyclopentane 20.0 parts by weight Dianal BR1122 (previously described) 8.7 parts by weight chitosan (molecular weight 200,000) 10. 0 part by weight Disparon PW-36 (surfactant, manufactured by Enomoto Kasei Co., Ltd.) 1.0 part by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 4
10. TITANIX JR800 (titanium oxide, manufactured by Teika Co., Ltd.) 40.0 parts by weight Methylcyclohexane 20.8 parts by weight Cyclopentane 20.0 parts by weight Dianal BR1122 (previously described) 8.7 parts by weight chitosan (molecular weight 200,000) 0 part by weight FT 251 (ethylene oxide-added fluorine surfactant, manufactured by Neos Co., Ltd.)
0.5 parts by weight Each of the above components was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 5
TITANIX JR800 (previously described) 35.0 parts by weight methylcyclohexane 40.3 parts by weight Dianal BR105 (previously described) 8.7 parts by weight chitosan (molecular weight 15000) 15.0 parts by weight Disperbyk101 (previously described) 1.0 part by weight Was subjected to a dispersion treatment with a ball mill for 24 hours to obtain a correction liquid.

Comparative Example 1
TITANIX JR701 (previously described) 40.0 parts by weight Methylcyclohexane 50.0 parts by weight Dynal BR115 (previously described) 10.0 parts by weight Each of the above components was dispersed for 24 hours using a ball mill to obtain a correction liquid.

Comparative Example 2
TITANIX JR701 (previously described) 40.0 parts by weight Methylcyclohexane 49.5 parts by weight Dynal BR115 (previously described) 10.0 parts by weight Footent 251 (previously described) 0.5 parts by weight Each of the above components was dispersed in a ball mill for 24 hours. A correction fluid was obtained.

Comparative Example 3
TITANIX JR701 (previously described) 45.0 parts by weight water 34.0 parts by weight PAA-HCl-10L (polyallylamine aqueous solution, non-volatile content 40%, manufactured by Nitto Boseki Co., Ltd.) 20.0 parts by weight Cotamine 60W (Kao Corporation) Manufactured, dispersing agent) 1.0 part by weight Each of the above components was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Comparative Example 4
TITANIX JR701 (mentioned above) 35.0 parts by weight water 38.0 parts by weight
JONCRYL61J (mentioned above) 10.0 parts by weight
JONCRYL 711 (described above) 15.0 parts by weight chitosan (molecular weight 7000) 2.0 parts by weight
Each component except JONCRYL711 was dispersed for 24 hours with a ball mill, then JONCRYL711 was added and stirred for 1 hour with a three-one motor to obtain a correction solution.

Comparative Example 5
TITANIX JR800 (titanium oxide, manufactured by Teika Co., Ltd.) 40.0 parts by weight Methylcyclohexane 20.3 parts by weight Cyclopentane 20.0 parts by weight Dianal BR1122 (previously described) 8.7 parts by weight chitosan (molecular weight 5000) 10.0 Part by weight Disparon PW-36 (surfactant, manufactured by Enomoto Kasei Co., Ltd.) 1.0 part by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid.

Handwriting dryness test The correction fluid obtained in each of the Examples and Comparative Examples is applied to fine paper with a 250 μm applicator and dried at room temperature for 24 hours. Thereafter, a straight line was written with a ball Pentel B100-A (black aqueous black dye ink, manufactured by Pentel Co., Ltd.), and the handwriting was rubbed with fine paper every 10 seconds. did.

Color sink test The correction liquid obtained in each of Examples and Comparative Examples is applied to fine paper with a 250 μm applicator and dried at room temperature for 24 hours. Thereafter, Ball Pentel B100-A (black aqueous black dye ink, manufactured by Pentel Co., Ltd.), 50 straight lines were written without gaps, and the Y value of the handwriting was measured with a color computer after 24 hours.

Claims (1)

A correction liquid containing at least titanium oxide, a liquid medium, a film-forming resin, and chitosan having a molecular weight of 10,000 or more.