JP2000336315A - Aqueous correction fluid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous correction fluid which is an aqueous correction fluid hardly causing a hard precipitate even after long-term preservation forms a coating film for suppressing the rise of direct dye and acidic dye to the surface of coating film in opacified handwriting. SOLUTION: In this aqueous correction fluid comprising at least water, an opacifying material and a cationic resin, the opacifying material is titanium oxide coated with silica and alumina. The amount of silica used in the treatment is larger than that of alumina.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous correction liquid for concealing and correcting handwriting of oil-based ink or water-based ink, printing by a typewriter, a thermal printer or an ink-jet printer, or an image copied by a dry copying machine. . More specifically, the present invention relates to an aqueous correction liquid which prevents direct dyes and acid dyes in oil-based inks or water-based inks from floating on the surface of a coating film and hardly causes hard sediment even after long-term storage.

[0002]

2. Description of the Related Art Heretofore, a correction liquid has been used to cover and conceal such errors by applying them on the errors written on paper, film or the like. In addition, the correction fluid
It is also used to correct mistakes and the like by writing on a dry coating film formed by drying the coating film.

[0003] Aqueous correction fluids are based on concealing materials, binders, and water. 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, mainly titanium oxide, is used as a main concealing material. The binder fixes the concealing material on paper or a film to form a coating film, and various water-soluble resin emulsions and the like are used.

[0004] An aqueous correction liquid containing water as a main solvent is used to conceal and correct handwriting of oil-based ink, printing by a typewriter, a thermal printer, and the like, and a copy image by a dry copying machine (hereinafter simply referred to as handwriting). Had been. However, when this aqueous correction liquid is used to conceal handwriting with oil-based ink using a dye, and even handwriting with water-based ink, the dye in the handwriting is dissolved, and the handwriting concealed by the coating film is coated on the surface of the coating film. There was a problem that it came out above.

To cope with this problem, an aqueous correction liquid has been proposed which uses a cationic resin to suppress the dissolution of the dye and prevent the ink from floating on the surface of the coating film.
For example, Japanese Unexamined Patent Publication (Kokai) No. 10-502688 discloses an aqueous correction liquid comprising at least water, a cationic resin, and alumina-treated titanium oxide, wherein the titanium oxide has an alumina treatment amount of 4.5% or more. I have.

[0006]

However, in the case of the aqueous correction liquid as described above, titanium oxide precipitates over time, and the precipitate becomes a hard sediment which is difficult to re-disperse. There is a problem that can not be. SUMMARY OF THE INVENTION It is an object of the present invention to provide an aqueous correction liquid that prevents an ink using a direct dye or an acid dye from floating on the surface of a coating film and hardly causes hard sediment even after long-term storage.

[0007]

According to the present invention, there is provided an aqueous correction solution comprising at least water, a concealing material and a cationic resin, wherein the concealing material is coated with silica and alumina,
In addition, the gist of the present invention is an aqueous correction liquid that is a titanium oxide in which a silica treatment amount is larger than an alumina treatment amount.

Hereinafter, description of the present invention will be described. Titanium oxide used as a concealing material is usually coated with alumina or alumina and silica to improve its dispersibility and light resistance. The treatment ratio of the surface treating agent greatly affects the dispersion of the ink. The titanium oxide used in the present invention is coated with silica and alumina, and the silica processed amount is larger than the alumina processed amount.
This is because, by combining with a cationic resin, dispersion is stabilized, sedimentation of titanium oxide is suppressed as much as possible, and hard sediment hardly occurs even after long-term storage. In addition, the blending amount is not less than 15% by weight based on the total amount of the correction liquid.
It is preferable to adjust it to 0% by weight or less. As a commercially available product of titanium oxide, Thai Pure R-960 (oil absorption 18.
0 (g / 100 g) TiO2: 89.0% or more, alumina: 3.6%, silica: 6.5%), R-931 (oil absorption: 36.0 (g / 100 g) TiO2: 80.0%) Above, alumina: 8.0%, silica: 9.5%) (both manufactured by DuPont Japan Limited), Titanics JR
-800 (oil absorption 30.0 (g / 100 g) TiO2:
91.0% or more, alumina: 2.7%, silica: 4.1
%) And JR-801 (oil absorption 40.0 (g / 100
g) TiO2: 83.9% or more, alumina: 4.7%,
Silica: 7.1%) and JR-805 (oil absorption 22.0)
(G / 100 g) TiO2: 89.5% or more, alumina: 2.9%, silica: 5.3%), JR-809
(Oil absorption 22.0 (g / 100 g) TiO2: 88.0
% Or more, alumina: 4.0%, silica: 5.0%) (all manufactured by Teika Co., Ltd.). These concealing materials can be used alone or in combination of two or more. The figures in parentheses (excluding the oil absorption figures)
Is a representative value of the titanium oxide composition, and the unit is% by weight.

The amount of oil absorption is as follows: 2 g of titanium oxide is placed on a glass plate, oil is added dropwise to the boiled sesame little by little, mixed well with a metal spatula, and the mixture of oil and titanium oxide is putty-shaped. 100 g of titanium oxide added until it has moldability
It is the amount (g) of boiled linse oil converted as.

As the binder, a cationic resin is used. The cationic resin is used to form a coating film containing the concealing material and the like, and when the correction liquid is applied on the handwriting to be concealed, the correction liquid causes the correction ink to be used in the handwriting of an oil-based ink or a water-based ink. It is also used for preventing the contained direct dye and acidic dye from dissolving and the handwriting concealed in the coating film from floating on the coating film surface.

Examples of the cationic resin include an acrylic copolymer containing an amine-functional monomer, an acrylic-urethane microemulsion, polyethyleneimine, polyallylamine, polyallylamine hydrochloride, and polyallylamine acetate. These binders can be used alone or in combination of two or more. The amount of the binder used is preferably from 5% by weight to 20% by weight based on the total amount of the aqueous correction liquid. Specific examples of acrylic copolymers containing an amine-functional monomer include Worlecryl 77
12W, 7712 (Worleycryl-C
Acryt UW-319S as an acrylic-urethane microemulsion
X (manufactured by Taisei Kako Co., Ltd.). Specific examples of polyethyleneimine include Lupasol FG and G
20waterfree, same PR8515, same WF, same FC, same G20, same G35, same G100, same HF, same P, same PS, same SK, same SN, (all manufactured by BSF Japan Ltd.), Epomin SP- 003, SP
-006, SP-012, SP-018, SP-
103, SP-110, SP-20, SP-10
00 (all manufactured by Nippon Shokubai Co., Ltd.).
Specific examples of polyallylamine include PAA-15 and PA-15.
AA-15B, PAA-10C and the like. Specific examples of polyallylamine hydrochloride include PAA-HCl-
3L, PAA-HCl-10L, PAA-HCl-3
S, PAA-HCl-10S and the like. Specific examples of polyallylamine acetate include PAA-CH3CO
OH-L, PAA-D11-HCl (Nitto Boseki
Co., Ltd.). The water-insoluble resin is used in the form of an aqueous emulsion.

As the solvent, water and, if necessary, a water-soluble organic solvent are used. 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 70% by weight to 70% by weight.

The aqueous correction liquid 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, and a sand grinder.

[0014] In addition to the above components, if necessary,
Various additives can be used in combination. For example, the addition of a solid acid prevents the ink handwriting from bleeding.
This is because when the acid dye in the ink or the dye directly contacts 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 as acid clay,
# 200, # 300, and # 400 (all manufactured by Mizusawa Chemical Industry Co., Ltd.), SA-10 and SA- as activated clay
1, R-15, R-5, Nicanite G-36, G-36
153 (all manufactured by Nippon Activated Shirato Co., Ltd.), Galleon Earth V2R, V1, NV, NS, NS, GSF, NF
-2 (above, manufactured by Mizusawa Chemical Industry Co., Ltd.), KYOWARD 700 (Kyowa Chemical Industry Co., Ltd.) as aluminum silicate
Manufactured). 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 of the solid acid 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. In addition, humectants, defoamers, preservatives, rust inhibitors,
Dispersants and thickeners can also be appropriately used for dispersion stability. In this case, a nonionic or cationic dispersant or dispersion stabilizer is used.

[0016]

The aqueous correcting solution containing at least titanium oxide, a cationic resin and water according to the present invention has a pH of 4.0 to 4.0.
The pH becomes 7.0. Since the surface of the titanium oxide used at this time is coated with alumina and silica in an amount equal to or greater than this alumina, the titanium oxide has an excellent affinity for water,
In the H region, it is presumed to be negatively charged. Cationic resins dissolve and ionize in water. Positively charged cationic resin preferentially adsorbs to the surface of the titanium oxide particles to form an outer coating of diffused charge. As a result, the electrostatic repulsion between the particles increases, and the dispersion state is stabilized. further,
The dispersion state becomes stable due to the dispersion effect caused by the steric hindrance between the chains of the adsorbed cationic resin. This makes it difficult for hard sediments to occur over time.

[0017]

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 Thai Pure R960 (titanium dioxide, manufactured by Dupont Japan Limited) 40 parts by weight Worlecryl 7712W (Worlecryl-Chemie GmbH, Germany) (25% by weight aqueous solution of non-volatile components) 40 parts by weight Water 20 parts by weight For 24 hours to obtain an aqueous correction liquid.

Example 2 Titanics JR-800 (Titanium Co., Ltd., titanium dioxide) 40 parts by weight Worlecryl 7712W (Worlecryl-Chemie GmbH, Germany) (25% by weight aqueous solution of nonvolatile components) 40 parts by weight Water 20 parts by weight The above components were made in the same manner as in Example 1 to obtain an aqueous correction fluid.

Example 3 Titanics JR-805 (manufactured by Teica Co., Ltd., titanium dioxide) 40 parts by weight PAA-HCl-3L (manufactured by Nitto Boseki Co., Ltd., polyallylamine hydrochloride (non-volatile content 50% by weight aqueous solution)) 20 parts by weight water 40 parts by weight The above components were made in the same manner as in Example 1 to obtain an aqueous correction liquid.

Example 4 Thai Pure R931 (Titanium Dioxide, DuPont Japan Limited) 40 parts by weight Worlecryl 7712W (Worlecryl-Chemie GmbH, Germany) (25% by weight aqueous solution of non-volatile content) 40 parts by weight Water 15 parts by weight SA-10 (Activated clay, manufactured by Nippon Activated Shirato Co., Ltd.) 5 parts by weight The above components were made in the same manner as in Example 1 to obtain an aqueous correction fluid.

Comparative Example 1 TYPURE R902 (oil absorption 17.0 (g / 100 g) TiO ₂ : 91.0% by weight or more, alumina: 4.7% by weight, silica: 2.0% by weight, Dupont Japan Limited) 40 parts by weight Worlecryl 7712W (Worlecryl-Chemie GmbH, Germany) (25% by weight aqueous solution of non-volatile components) 40 parts by weight Water 20 parts by weight The above components were made in the same manner as in Example 1 to obtain an aqueous correction liquid. Was.

Comparative Example 2 Titanics JR-301 (oil absorption 18.0 (g / 100 g) TiO2: 93.0% or more, only alumina treatment, manufactured by Teica Co., Ltd., titanium dioxide) 40 parts by weight PAA-HCl— 3 L (manufactured by Nitto Boseki Co., Ltd., polyallylamine hydrochloride (non-volatile content 50% by weight aqueous solution)) 20 parts by weight Water 40 parts by weight The above components were made in the same manner as in Example 1 to obtain an aqueous correction liquid.

Comparative Example 3 Titanics JR-602 (oil absorption 21.0 (g / 100 g) TiO2: 93.0% or more, only alumina treatment. Titanium Co., Ltd., titanium dioxide) 40 parts by weight Worrecryl 7712W (Worrecryl) -Chemie GmbH, Germany) (25% by weight aqueous solution of non-volatile content) 20 parts by weight Water 35 parts by weight SA-10 (manufactured by Japan Activated Shirato Co., Ltd., activated clay) 5 parts by weight The above components were used in the same manner as in Example 1. An aqueous correction fluid was obtained.

With respect to the aqueous correction liquids obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the hiding ratio, sedimentation separation, and hardness test of the ink sedimentation layer with time were performed. Table 1 shows the results.

[0025]

[Table 1]

Oil-based hiding factor Oil-based ballpoint pen (BK102-A, manufactured by Pentel Co., Ltd.)
And write 16 straight lines with a width of 1 mm on high quality paper. Next, the correction liquid is applied by an applicator having a gap of 0.152 mm so as to intersect the handwriting of the high-quality paper at right angles. After leaving it for 24 hours, 45 ° and 0 ° diffuse reflectances were measured with an SM color computer (manufactured by Suga Test Instruments Co., Ltd.) to calculate the concealment ratio.

Aqueous concealment ratio: Using an aqueous ballpoint pen (B50-AD, manufactured by Pentel Co., Ltd.), 16 straight lines of 1 mm width are written on wood free paper. Next, the correction liquid is applied by an applicator having a gap of 0.152 mm so as to intersect the handwriting of the high-quality paper at right angles. After leaving it for 24 hours, SM color computer (manufactured by Suga Test Instruments Co., Ltd.)
, The 45 ° and 0 ° diffuse reflectances were measured, and the concealment ratio was calculated.

Sedimentation separation test: An aqueous correction solution was sampled at 50 mm into a screw cap bottle (S-5, manufactured by Nidec Rika Glass Co., Ltd.).
Leave at room temperature in a sealed state, and set the height of the separated liquid to 2
Measured after months.

Aged ink sedimentation layer hardness test: Aqueous correction liquid was placed in a screw-neck bottle (S-5, manufactured by Nichiden Kagaku Glass Co., Ltd.) for 50 times.
mm, and after standing for 30 days in a thermostat at 60 ° C. in a sealed state, the hardness of the sedimentation layer was measured with a rheometer (Fudo Kogyo Co., Ltd.)
Manufactured).

[0030]

As described in detail above, the aqueous correction liquid of the present invention can prevent the ink using the direct dye and the acidic dye from floating on the surface of the coating film and can also be used with time. It is stable and has practically excellent quality as a correction fluid and a primer.

Claims (2)

[Claims] 1. An aqueous correction liquid comprising at least water, a concealing material, and a cationic resin, wherein the concealing material is coated with silica and alumina, and the silica treatment amount is titanium oxide larger than the alumina treatment amount. Aqueous correction fluid. 2. The titanium oxide has an oil absorption of 22.0 (g).
/ 100 g) or less.