JP2005187486A - Correction liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a correction liquid forming a coating film which does not cause no cissing of handwriting and allows fast drying of the handwriting when aqueous ink is used for writing. <P>SOLUTION: The correction liquid comprises at least a masking material such as titanium oxide, a hydrocarbon solvent, a resin soluble in the solvent and a needle-like particle. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an oil-based correction liquid that conceals and erases typographical errors and the like, and particularly relates to an oil-based correction liquid that has excellent handwriting dryness when written with aqueous ink on a coating film.

Conventionally, the correction liquid mainly contains a concealing material such as titanium oxide, a liquid medium that is water or an organic solvent, and a resin that is soluble in the water or organic solvent to be used.
The correction liquid that uses water as the liquid medium dissolves the handwriting of the water-based ink, so the coating film may become dirty with the color of the handwriting. Correction of handwriting with oil-based ink and characters with a dry copier The target to be corrected is limited.
On the other hand, a correction liquid using a solvent such as methylcyclohexane or isooctane as a solvent can be used regardless of the object to be corrected, such as handwriting of oil-based ink, handwriting of water-based ink, and characters by a dry copying machine. (See Patent Documents 1 and 2)
Japanese Patent Laid-Open No. 52-12040 JP 57-24765 A

The correction liquid may correct typographical errors and re-write on the coating film, and it is preferable that the drying time of the handwriting is short. In the case of an aqueous correction liquid using a water-soluble resin as a material for forming a coating film, the coating film is hydrophilic, so there is no problem in repelling or drying when writing on the coating film with aqueous ink. In the case of an oil-based correction liquid that can be corrected regardless of the target to be corrected, since a hydrophobic resin is used as the material for forming the coating film, the coating film after drying is hydrophobic. In some cases, the written handwriting of the water-based ink is repelled, or the handwriting is not easily dried, and when the handwriting is rubbed, the ink that has not been dried is spread and the paper surface is soiled.
In the case of oil-based correction fluid, a volatile hydrocarbon solvent is used, so that the surface of the coating film is dried first and the skin is stretched (skinning phenomenon), and the inside of the coating film is dried. As a result, the drying property of the entire coating film may be delayed. When writing with a hard pen tip such as a ballpoint pen on a coating film with only such a surface dried and undried inside, the dried film on the surface is broken and the undried surface is exposed, so that handwriting cannot be formed. It will be. This phenomenon occurs remarkably when the coating film thickness is increased or when a solvent having a lower boiling point is used.

  As an improvement measure, the present invention provides an oily correction liquid comprising at least a masking material, a hydrocarbon solvent, a resin soluble in the solvent, and needle-like particles.

The problem to be solved is that when writing on the coating film with water-based ink, the water-based ink is repelled and a clear handwriting cannot be formed, or the handwriting does not dry easily and the paper surface is rubbed. It is to prevent the stain from occurring and a skinning phenomenon in which only the surface of the coating film is dried first, thereby preventing the formation of clear handwriting on the coating film.
Therefore, the present invention adds needle-like particles to prevent the needle-like particles from being entangled in the coating film in a complex manner and preventing the concealing material from overlapping closely, and to form a large number of fine voids that open on the coating film surface. The water-based ink easily penetrates into the coating film, resulting in faster drying of the water-based handwriting, and the solvent inside the film can evaporate from the gap even if the coating surface surface dries first. Therefore, it is speculated that the decrease in the drying time of the coating film is reduced, and it is possible to suppress the formation of clear handwriting on the coating film.

  In the present invention, when writing on the coating film with water-based ink, in order to prevent the handwriting from being repelled, rubbing the handwriting because the handwriting does not dry easily, and to smudge the paper surface, This was realized by preparing a correction liquid comprising at least a hydrocarbon solvent, a resin soluble in the solvent, and needle-like particles.

  The correction liquid is used to conceal handwriting and figures that are difficult to erase with an eraser such as a fountain pen or ballpoint pen. The correction liquid covers typographical characters and re-writes on it if necessary. The basic composition is composed of a coloring component that becomes a masking material, a fixing component for the writing surface, and a liquid medium that dissolves and / or disperses them.

  As the masking material, a white pigment is used in consideration of the most white color on the paper surface. Titanium oxide is mainly used. Specific examples of products include TITON SR-1 (specific gravity 4.1), R-650 (specific gravity 4.1), and R-62N (specific gravity 3. 9), R-42 (specific gravity 4.1), R-7E (specific gravity 3.9), R-21 (specific gravity 4.0) (above, Sakai Chemical Industry Co., Ltd.), Kronos KR- 310 (specific gravity 4.2), KR-380 (specific gravity 4.2), 480 (specific gravity 4.2) (above, manufactured by Titanium Industry Co., Ltd.), Taipure R-900 (specific gravity 4.0), R-902 (specific gravity 4.0), R-960 (specific gravity 3.9), R-931 (specific gravity 3.6) (manufactured by DuPont Japan Limited), TITANIX JR-301 (specific gravity 4. 1), JR-805 (specific gravity 3.9), JR-603 (specific gravity 4.0), JR800 (specific gravity 3. 9), JR-403 (specific gravity 4.0), JR701 (specific gravity 4.1) (manufactured by Teika Co., Ltd.), and the like. The amount of titanium oxide added is preferably 30 to 60% by weight based on the total amount of ink.

  In addition, pigments such as carbon black, iron oxide, silica, alumina, calcium carbonate, mica, aluminum silicate, and resin particles that are insoluble in the solvent used to adjust the color tone and gloss of the correction liquid coating Can also be used together. The amount used is preferably 0.01 to 20% by weight based on titanium oxide.

  The solvent preferably has a boiling point of 40 to 150 ° C. in consideration of the drying property of the coating film. 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 60.2 ° C), normal heptane (boiling point 98.4 ° C), normal hydrocarbon such as normal octane, cyclohexane (boiling point 80.0 ° C), methyl In addition to cyclohexane (boiling point 100.9 ° C.), ethylcyclohexane (boiling point 132 ° C.), etc., aliphatics such as Exol DSP 100/140 (initial boiling point 102 ° C., dry point 138 ° C.) (manufactured by Exxon Chemical Co., Ltd.) Examples include a mixture of hydrocarbon solvents. These can be used alone or in combination. The amount of solvent used is preferably 30 to 60% by weight based on the total amount of ink.

  Resins that are soluble in the above hydrocarbon-based solvents bring about dispersion of pigments and fixing of correction liquids on the paper surface. For example, alkyd resins and thermoplastic elastomers can be used, but pigment dispersibility In view of the fixing property on the paper surface, an acrylic resin is preferable.

  Needle-like particles are used to increase the voids in the coating film, make it easier for water-based ink to penetrate into the coating film, and to accelerate the drying of the coating film by being intertwined in a dry coating film. It is. Specifically, 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, magnesium borate Whisker, titanium boride whisker, alumina and alumina silica short fiber, silica short fiber, zirconia fiber (short fiber), kaolin-based ceramic short fiber, etc., and the amount added varies depending on the specific gravity and length of the ink, Approximately 2 to 20% by weight is preferable based on the total amount. The preferred particle size (major axis) of the acicular particles is 3 to 40 μm, and the preferred aspect ratio (major axis / minor axis) is 10 or more.

  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. A dispersant such as an ionic surfactant, a quaternary ammonium salt, or an alkylamine salt can be added.

  The ink is 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.

Hereinafter, the present invention will be described in detail based on examples.
Example 1
TITANIX JR701 (titanium oxide, manufactured by Teika) 35.0 parts by weight Acryloid B67 (acrylic resin, manufactured by Rohm and Haas) 9.0 parts by weight methylcyclohexane 10.0 parts by weight cyclopentane 35.0 parts by weight Anti- Terra-P (Long Polyamide Phosphate, manufactured by BYK Chemie)
1.0 part by weight whiscal A (calcium carbonate whisker, major axis 20-30 μ, minor axis 0.5-1.0 μ, manufactured by Maruo Calcium Co., Ltd.) 10.0 parts by weight Each of the above components except for whiscal A was mixed with a ball mill. After the time dispersion treatment, Whiscal A was added and dispersed for 5 minutes with a homogenizer to obtain a correction solution.

Example 2
TITONE R62N (titanium oxide, manufactured by Sakai Chemical Co., Ltd.) 40.0 parts by weight Acryloid B67 (previously described) 10.0 parts by weight methylcyclohexane 22.0 parts by weight cyclopentane 22.0 parts by weight homogenol L18 (polycarboxylic acid type high Molecular surfactant (manufactured by Kao Corporation) 1.0 parts by weight Wiscal A (previously described) 5.0 parts by weight Each of the above components excluding Wiscal A was dispersed for 24 hours with a ball mill, then added with Whiscal A, and then homogenized. A correction solution was obtained by dispersing for 5 minutes.

Example 3
TITANIX JR301 (titanium oxide, manufactured by Teika Co., Ltd.) 35.0 parts by weight Acryloid B67 (previously described) 10.0 parts by weight methylcyclohexane 15.0 parts by weight cyclopentane 21.0 parts by weight Anti-Terra-P (previously described) 1 0.0 parts by weight of whiscal A (described above) 18.0 parts by weight The above components except for whisker A were dispersed for 24 hours with a ball mill, then added with whiscal A, and dispersed with a homogenizer for 5 minutes to obtain a correction solution.

Example 4
TITANIX JR701 (titanium oxide, manufactured by Teika Co., Ltd.) 35.0 parts by weight Acryloid B67 (previously described) 10.0 parts by weight methylcyclohexane 36.0 parts by weight Anti-Terra-P (previously described) 1.0 part by weight FTL-200 (Acicular titanium oxide, minor axis 0.05 to 0.15 μ, major axis 4 to 12 μ, manufactured by Ishihara Sangyo Co., Ltd.) 18.0 parts by weight The above components except for FTL-200 were dispersed for 24 hours in a ball mill, FTL-200 was added and dispersed with a homogenizer for 5 minutes to obtain a correction solution.

Comparative Example 1
A correction fluid was obtained in the same manner as in Example 2 except that Wiscal A was omitted from Example 2.

Comparative Example 2
TITANIX JR701 (mentioned above) 40.0 parts by weight Acryloid B67 (acrylic resin, manufactured by Rohm and Haas) 17.0 parts by weight methylcyclohexane 35.0 parts by weight Homogenol L18 (polycarboxylic acid type polymer surfactant, Kao Corporation )) 1.0 part by weight calcigros-GU (calcium carbonate, average particle size 0.9 μ, manufactured by Clariant Polymer Co., Ltd.) 7.0 parts by weight The above components except calcigros-GU were dispersed for 24 hours in a ball mill. Calcigros-GU was added and dispersed with a homogenizer for 5 minutes to obtain a correction solution.

Comparative Example 3
TITANIX JR301 (previously described) 45.0 parts by weight Jonkrill 61J (water-soluble styrene-acrylic copolymer, nonvolatile content 30.5%, manufactured by Johnson Polymer) 4.0 parts by weight Jonkrill 734 (styrene-acrylic copolymer emulsion) Non-volatile content: 42.0%, manufactured by Johnson Polymer) 8.0 parts by weight Wiscal A (previously described) 5.0 parts by weight water 38.0 parts by weight Disperse the above components except Jonkrill 734 and Wiscal A for 24 hours using a ball mill. After the treatment, Joncrill 734 and Wiscal A were added and dispersed with a homogenizer for 5 minutes to obtain a correction solution.

Aqueous ink handwriting hiding test Written on high-quality paper with a water-based ballpoint pen (Ball Pentel B100-A) with a correction pen filled with the Pentel pen correction liquid ZL21-W in the correction liquid obtained in each Example and Comparative Example. A correction fluid was applied on the letters. After the coating film was dried, the coloration (dirt) of the correction liquid coating film due to dissolution of the aqueous handwriting was visually observed.

Coating film drying test The correction liquid obtained in each Example and Comparative Example was applied to fine paper with an applicator of 250 μm, and the time until writing was possible with an aqueous ballpoint pen (Ball Pentel B100-A), and the repelling of handwriting It was confirmed whether there was. In addition, the coating film before drying was written with a water-based ballpoint pen, and it was visually confirmed whether or not a skinning phenomenon occurred on the coating film surface.

Overwriting handwriting dryness test The correction liquid obtained in each Example and Comparative Example was applied to fine paper with a 50 μ applicator, and a straight line was written on the coating film with a water-based ballpoint pen (Ball Pentel B100-A) one day later. The handwriting was rubbed with a finger every hour, and the time when the handwriting of the water-based ballpoint pen was not extended with the finger after writing was defined as the handwriting drying time.

  As described above in detail, the coating film of the correction liquid of the present invention has no water-based ink repellency, fast handwriting dryness, and the coating film surface is covered with skin during the coating drying process. Even the coating film is fast and dry.

Claims (3)

An oily correction liquid comprising at least a masking material, a hydrocarbon solvent, a resin soluble in the solvent, and needle-like particles. The oily correction fluid according to claim 1, wherein the major axis of the acicular particles is 3 to 40 µm. The oily correction liquid according to claim 1 or 2, wherein the boiling point of the hydrocarbon solvent is 72 ° C or lower.