JP2000160071A - Water-base correction liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a correction liquid excellent in resistance to an oily ink blot by compounding at least a masking material, a binder material comprising a polyethyleneimine and a solvent. SOLUTION: Preferably, a masking material is titanium oxide and its amount is 15-80 wt.% based on the total amount of a correction liquid. A binder material comprising a polyethyleneimine is desirably used in an amount of 2-20 wt.% based on the same. The amount of a solvent used is desirably 20-70 wt.% based on the same. Preferably, the solvent comprises water and an alcoholic solvent and the amount of the alcoholic solvent used is 10-30 wt.% based on the total amount of the solvents. Further preferably, a solid acid (e.g. acid clay) is incorporated and the amount used is desirably 1-40 wt.% based on the total amount of the correction liquid. When this correction liquid is coated on characters written with an oily ink, the polyethyleneimine contacts with a dye to effect electron donation-acceptance between them to insolubilize the dye, thereby improving resistance to blot.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a correction liquid, and more particularly, to an aqueous correction liquid having excellent bleeding resistance to oil-based ink handwriting.

[0002]

2. Description of the Related Art A correction liquid is used to cover and conceal such errors by applying them on the errors written on paper or film. Further, the correction liquid is also used for correcting erroneous writing or the like by writing on a dry coating film formed by drying the applied film.

[0003] Conventionally, correction fluids have a concealing material, a binder, and a solvent as main components. The concealing material is for concealing erroneous characters and the like, and a high concealing pigment having a high refractive index of 2.0 or more is used as a main concealing material. The binder is used to fix the concealing material on paper or film to form a coating film, and various resins and elastomers are used.

When correcting handwriting of water-based ink such as a fountain pen and a water-based felt-tip pen, organic solvents such as toluene, xylene, 1,1,1-trichloroethane and trichloroethylene, which hardly dissolve the handwriting of the water-based ink, are used as a main solvent. It is called oil-based correction fluid. When correcting handwriting with oil-based ink such as oil-based ballpoint pens and oil-based markers, printing with a typewriter, and copying images with a dry copying machine, these handwritings, printing, copied images, etc. (hereinafter collectively referred to as handwriting) are dissolved. Difficult water is used as the main solvent and is called an aqueous correction fluid. In recent years, cyclohexane-based organic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane, which have low solubility in handwriting with aqueous and oil-based inks, have been used to eliminate the complexity of using different solvents depending on the type of handwriting. It is called liquid. The most widely used correction fluid among the three is a dual-use correction fluid. However, the solvent used in the above oil-based correction fluid and the dual-use correction fluid is ultimately an organic solvent, and it cannot be denied that its safety is inferior to water in comparison with water. Has a drawback in that when applied to heat-sensitive paper or pressure-sensitive paper, color is developed. In this regard, the aqueous correction fluid has the advantage of being highly safe because of the low toxicity of the aqueous organic solvent used in combination as necessary, and has the advantage that it does not develop color when applied to thermal paper or pressure-sensitive paper. Is expensive.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the bleeding resistance of an aqueous correction liquid to an oil-based ink. The blur described in the present invention refers to a phenomenon in which, when a correction liquid is applied on a handwriting to be concealed, the handwriting is dissolved by the correction liquid and the concealed handwriting is dissolved in the coating film of the correction liquid. If the bleeding resistance is poor, the dye in the oil-based ink handwriting dissolves in the aqueous correction liquid, diffuses and floats on the surface of the coating film, so that sufficient hiding properties cannot be obtained. As described above, the correction liquid is used in a combination that does not dissolve the handwriting to be concealed, such as using an oil-based correction liquid for water-based ink handwriting and using an aqueous correction liquid for oil-based ink handwriting. However, handwriting with oil-based ink has a difference in the water resistance of the handwriting depending on the dye used, and the bleeding resistance of the aqueous correction liquid to the oil-based ink handwriting decreases as the water resistance of the handwriting decreases. However, the user of the aqueous correction fluid cannot judge the water resistance of the handwriting to be corrected at all. Therefore, it is necessary to improve the bleeding resistance to the oil-based ink handwriting so that the water-based correction liquid can obtain a sufficient concealing property even when the handwriting by the oil-based ink having low water resistance is concealed.

[0006]

According to the present invention, there is provided an aqueous correction solution containing at least a concealing material, a binder, and a solvent, wherein the binder is polyethyleneimine. .

Hereinafter, the description of the present invention will be described. As the concealing material, a pigment having a high concealing property such as titanium oxide or zinc oxide is used. In order to obtain the necessary hiding power and dry film strength as a correction liquid, use titanium oxide as a hiding material,
It is preferable to adjust the blending amount to 15% by weight or more and 80% by weight or less based on the total amount of the correction liquid. If the amount is less than 15% by weight, the concealing property of the correction liquid is small, and if it exceeds 80% by weight, the strength of the dried coating film of the aqueous correction liquid is weak, so that writing on the dried coating film cannot be performed. Commercial products of titanium oxide include Tytone SR-1, R-650, R-62N, and R-62.
3L, A-110, A-100, CR-58 (all manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-310, KR-380, KR-480, KA-10, KA
-20 and KA-30 (all manufactured by Titanium Industry Co., Ltd.)
Thai Pure R-900, R-931 (Dupon Japan Limited), Titanics JR-3
00, the same JR-800, the same JR-602 (all manufactured by Teica Corporation) and the like. These concealing materials can be used alone or in combination of two or more.

It is necessary to use polyethyleneimine as a binder. Polyethyleneimine used in the present invention is a polymer compound obtained by cationic polymerization of ethyleneimine having an imine group having a three-membered ring structure,
In particular, it is a polymer compound having a side chain or forming a three-dimensional structure by containing a tertiary amino nitrogen in the molecule. Polyethyleneimine is used not only for forming a coating film containing the above-mentioned concealing material and the like, but also for improving bleeding resistance to oil-based ink handwriting.

A specific example of polyethyleneimine is Lu.
pasolFG (molecular weight: about 800), G20 water
rfree (molecular weight about 1300), PR8515 (molecular weight about 2000), WF (molecular weight about 25000), F
C (molecular weight of about 800), G20 (molecular weight of about 1300),
G35 (molecular weight about 2000), G100 (molecular weight about 5)
000), HF, (molecular weight about 25,000), P (molecular weight about 750,000), PS (molecular weight about 750,000), SK (molecular weight about 2,000,000), SN (molecular weight about 1,000,000),
BSF Japan, Ltd.), Epomin SP-0
03 (molecular weight: about 300) and SP-006 (molecular weight: about 6)
00), SP-012 (molecular weight: about 1200), SP
-018 (molecular weight of about 1800), SP-103 (molecular weight of about 500 to 1500), SP-110 (molecular weight of about 5)
000-15000) and SP-20 (molecular weight of about 1).
And SP-1000 (molecular weight of about 70,000), and (Nippon Shokubai Co., Ltd.). These binders can be used alone or in combination of two or more. The amount of the binder used is preferably from 2% by weight to 20% by weight based on the total amount of the aqueous correction liquid.

The solvent used is water and, if necessary, a water-soluble organic solvent. Specific examples of the water-soluble organic solvent include alcoholic organic solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol. These water-soluble solvents can be used alone or in combination of two or more. The amount of the solvent used is 2 to the total amount of the aqueous correction fluid.
The content is preferably from 0% by weight to 70% by weight. Further, water and an alcohol-based organic solvent are used in combination, and the use ratio of the alcohol-based organic solvent is 10% by weight or more and 30% by weight based on the total amount of the solvent.
By adjusting as follows, the bleeding resistance to oil-based ink can be further improved. If the amount of the alcohol-based organic solvent is less than 10% by weight, the evaporation of the solvent is slow, and the bleeding resistance is not improved. If the content exceeds 30% by weight, the handwriting of the oil-based ink is dissolved in the alcoholic organic solvent, so that the bleeding resistance may decrease.

The aqueous correction fluid according to 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 the like.

In addition to the above components, if necessary,
Various additives can be used in combination. For example, the addition of a solid acid improves bleeding resistance to oil-based ink handwriting. This is because when the dye in the oil-based ink comes into contact with the solid acid, electrons are donated and accepted between the dye and the solid acid, and the dye becomes an unnecessary aggregate in water. Specific examples of solid acids include Mizuka Ace # 20 and # 20 as acidic clay.
0, # 300, # 400 (above, Mizusawa Chemical Industry Co., Ltd.), SA-10, SA-1, R-
15, R-5, Nikkanite G-36, G-153
(The above is made by Japan Active Shirato Co., Ltd.) Galleon Earth V2
R, V1, NV, NS, GSF, NF-2,
KYOWARD 700 as aluminum silicate (or more,
(Kyowa Chemical Industry Co., Ltd.). Other solid acids include calcium sulfate and the like. These solid acids can be used alone or in combination of two or more.
The amount used is preferably 1 to 40% by weight based on the total amount of the aqueous correction liquid.

Further, extender pigments such as calcium carbonate, and color pigments for matching the color tone with the writing surface can be used in combination. Also, polyethyleneimine and another resin can be used in combination as a binder. In this case, the anionic resin reacts with the polyethyleneimine to coagulate and solidify,
Use a nonionic water-soluble resin or a cationic water-soluble resin. Specifically, examples of the nonionic water-soluble resin include polyvinyl alcohol, and examples of the cationic water-soluble resin include an amine-added acrylic resin. However, in order to obtain the effect of the present invention, the amount is limited to a small amount. In addition, a dispersing agent and a thickening agent can be appropriately used for dispersion stability. In this case, a nonionic or cationic dispersant or dispersion stabilizer is used as in the case of the other resins. Commercially available cationic dispersants include Cotamine 60W and 86W (Kao Corporation). Commercially available cationic dispersion stabilizers include Neovisco GC (Sansei Co., Ltd., cationic thickener).

[0014]

The reason why the bleeding resistance to oil-based ink is improved by the aqueous correction liquid of the present invention is presumed to be as follows. When an aqueous correction liquid using polyethyleneimine is applied on the oil-based ink handwriting, the polyethyleneimine and the dye come into contact. Then, electron donation and acceptance are performed between the dye and the polyethyleneimine, and the bleeding resistance is improved by insolubilizing the dye. As described above, the aqueous correction liquid of the present invention can improve bleeding resistance to oil-based ink.

[0015]

EXAMPLES Examples of the present invention will be described below using a correction fluid, but the present invention is not limited to the examples. Example 1 Kronos KR-380 (manufactured by Titanium Industry Co., Ltd., titanium dioxide) 40 parts by weight Lupasol HF (manufactured by BSF Japan Co., Ltd.) polyethyleneimine (60% by weight aqueous solution of nonvolatile content) 8 parts by weight Water 51 parts by weight SA-10 (manufactured by Nippon Activated Shirato Co., Ltd., activated clay) 4 parts by weight Coatamine 60W (Kao Co., Ltd., dispersant) 1 part by weight Neovisco GC (manufactured by Sansei Co., Ltd., cationic guar gum) 3 parts by weight 6% by weight aqueous solution Among the above components, components other than the 3% by weight aqueous solution of Neovisco GC are dispersed in a ball mill for 24 hours, and the 3% by weight aqueous solution of Neobisco GC is added to this dispersion, and the mixture is stirred and dissolved to obtain an aqueous correction solution. Obtained.

Example 2 Titanics JR-300 (manufactured by Teica Co., Ltd., titanium dioxide) 43 parts by weight Lupasol PS (manufactured by BSF Japan Co., Ltd.), polyethyleneimine (33% by weight aqueous solution of nonvolatile content) 15 parts by weight water 40 parts by weight Coatamine 60W (described above) 2 parts by weight The above components were dispersed in a ball mill for 24 hours to obtain an aqueous correction liquid.

Example 3 Titanics JR-800 (manufactured by Teica Co., Ltd., titanium dioxide) 40 parts by weight Lupasol SK (manufactured by BSF Japan Co., Ltd., polyethyleneimine (24% by weight aqueous solution of nonvolatile content)) 21 parts by weight Water 28 parts by weight Ethanol 10 parts by weight Coatamine 86W (manufactured by Kao Corporation, 1 part by weight) 1 part by weight The above components were used in the same manner as in Example 2 to obtain an aqueous correction liquid.

Example 4 Taipure R900 (titanium oxide, manufactured by DuPont Japan Limited) 40 parts by weight Lupasol SN (manufactured by BSF Japan Co., Ltd.) 21 parts by weight of polyethylene imine (24% by weight aqueous solution of non-volatile content) Water 33 5 parts by weight Mizuka Ace # 200 (manufactured by Mizusawa Chemical Industry Co., Ltd., acid clay) 5 parts by weight Coatamine 60W (described above) 1 part by weight The above components were made in the same manner as in Example 2 to obtain an aqueous correction liquid.

Comparative Example 1 Kronos KR-380 (manufactured by Titanium Industry Co., Ltd., titanium dioxide) 30 parts by weight Joncryl 450 (manufactured by Johnson Polymer Co., Ltd., styrene-acrylic emulsion (42% by weight aqueous solution of nonvolatile content)) 23 parts by weight Water 38 parts by weight SA-10 (manufactured by Nippon Activated Shirato Co., Ltd., activated clay) 4 parts by weight Nikkor TL-10 (manufactured by Nikko Chemical Co., Ltd., monococo oil fatty acid polyoxyethylene sorbitan, dispersant) 1 part by weight 10 parts by weight of a 6% by weight aqueous solution of Kelzan AR (Zansan Gum, an anionic thickener manufactured by Sansei Co., Ltd.) 10 parts by weight A component excluding the 6% by weight aqueous solution of Kelzan AR in the above components is mixed and dispersed in a ball mill for 24 hours. . To this dispersion was added a 6% by weight aqueous solution of Kelzan AR, and the mixture was stirred and dissolved to obtain an aqueous correction liquid.

Comparative Example 2 Titanics JR-800 (manufactured by Teica Co., Ltd., titanium dioxide) 40 parts by weight Joncryl 61J (manufactured by Johnson Polymer Co., Ltd., styrene-acrylic resin (non-volatile content 31% by weight aqueous solution) 32 Parts by weight Water 25 parts by weight Ethanol 2 parts by weight Nikkor TL-10 (described above) 1 part by weight The above components were used in the same manner as in Example 2 to obtain an aqueous correction liquid.

Comparative Example 3 Titanics JR-800 (manufactured by Teica Co., Ltd., titanium dioxide) 40 parts by weight Joncryl 61J (described above) 32 parts by weight Water 7 parts by weight Ethanol 20 parts by weight Nikkor TL-10 (described above) 1 part by weight Part The above components were made in the same manner as in Example 2 to obtain an aqueous correction fluid.

The aqueous correction solutions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were tested for bleeding resistance and coating film drying time. Table 1 shows the results.

[0023]

[Table 1]

* 1 Bleeding resistance: An oil-based ballpoint pen (BK70, manufactured by Pentel Co., Ltd.) was used.
Write six straight lines. Next, the above-mentioned correction fluid was added to the gap 0.1.
Using a 52 mm applicator, apply the oil-based ballpoint pen at right angles to the handwriting. After standing for 24 hours, 45 °,
The 0 ° diffuse reflectance was measured, and the concealing rate was calculated to obtain the bleeding resistance. The higher the value, the better the bleeding resistance. * 2 Drying time of coating film: 0.152 of the above correction liquid on high quality paper
It was applied with an applicator of mm, and was written on the coating film with an oil-based ballpoint pen (BK70, manufactured by Pentel Co., Ltd.), and the time when the film became a writable coating film was measured.

[0025]

As described above in detail, the correction liquid of the present invention has a sufficient concealing property and is excellent in bleeding resistance to oil-based ink, so that it can be used practically as a correction liquid or a primer paint. It has excellent quality.

Claims (4)

[Claims] 1. An aqueous correction liquid containing at least a concealing material, a binder, and a solvent, wherein the binder is polyethyleneimine. 2. The aqueous correction fluid according to claim 1, wherein the concealing material is titanium oxide, and its use amount is 15 to 80% by weight based on the total amount of the correction fluid. 3. The aqueous correction fluid according to claim 1, further comprising a solid acid. 4. The method according to claim 1, wherein the solvent contains at least water and an alcohol solvent, and the amount of the alcohol solvent used is 10 to 30% by weight based on the total amount of the solvent. An aqueous correction fluid according to any of the above.