JP2002012824A - Covering-up liquid for reclaimed paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a covering-up liquid for reclaimed paper which forms dried coating film having homogeneous color tone. SOLUTION: The covering-up liquid consists of 20-70 wt.% of an alumina- silica treated titanium oxide, 0.01-5 wt.% of yellow iron oxide, 0.01-5 wt.% of low-order titanium oxide, 30-70 wt.% of a solvent and 5-20 wt.% of a resin soluble in the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a correction solution for recycled paper, and more particularly, to a dried coating film having a color that is inconspicuous when applied to light yellow recycled paper. The present invention relates to a correction liquid having a uniform color tone.

[0002]

2. Description of the Related Art A correction fluid is used to cover and conceal erroneous information by applying it on erroneous information 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, the correction fluid has a concealing material, a binder, and a solvent as main components. The concealing material is for concealing erroneous writing and the like, and a high refraction and high concealing pigment having a refractive index of 2.0 or more is used as a main concealing material.

Solvents disperse the concealing material, dissolve the binder,
Used for adjusting the viscosity of dispersion and correction fluids. fountain pen,
When correcting handwriting of water-based ink such as water-based felt-tip pens,
Organic solvents, such as toluene, xylene, 1,1,1-trichloroethane, and trichloroethylene, which hardly dissolve the handwriting by the aqueous ink are used as main solvents, and are called oil-based correction fluids. In addition, handwriting with oil-based ink such as oil-based ballpoint pens and oil-based markers, and printing with a typewriter,
When correcting a copy image or the like by a dry copying machine, these handwriting, printing, copy image, etc. (hereinafter, collectively referred to as handwriting)
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 inks and oil-based inks, have been used to eliminate the complexity of using different solvents depending on the type of handwriting. It is called correction fluid.

When an organic solvent is used as the binder, acrylic resin, vinyl alkyl ether resin, cyclized rubber, styrene-butadiene copolymer elastomer is used.
When water is used, a (meth) acrylate resin emulsion, a styrene-butadiene copolymer resin emulsion, an ethylene vinyl acetate resin emulsion, or the like is used.

When concealing erroneous information written on colored paper, the color tone of the dried coating film is matched with that of the colored paper, and carbon black,
Black pigments such as iron black, yellow clay, yellow pigments such as titanium yellow,
Use red pigments such as red iron and blue pigments such as ultramarine blue.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to make the color of a dry coating film uniform in a correction liquid for recycled paper. Recycled paper refers to at least general paper made from at least waste paper, but the recycled paper described in the present invention refers to at least writing paper used for office work made from waste paper. The color tone of such recycled paper is mainly pale yellow, although the whiteness and yellowish color vary depending on the used paper used as a raw material and the manufacturing method. When the correction liquid is applied, a dry coating film is formed on the paper surface to mask erroneous writing, but the dry coating film impairs the appearance of the paper surface. In order to improve the appearance of the paper surface on which the dried coating film is formed, it is necessary that there is no difference in the color tone between the coated paper surface and the dried coating film, and that the color tone of the dried coating film is uniform. Today, pigments having various color tones are commercially available, but there are limited colorants that can be used in combination with titanium dioxide as a concealing material to make the color of a dried coating film uniform.
That is, if there is a large difference in specific gravity or a difference in dispersibility from titanium oxide which is a concealing material, color unevenness occurs in the dried coating film.

The correction liquid for recycled paper uses a coloring material in order to adjust the color tone of the dried coating film to that of the recycled paper so that the corrected portion is not conspicuous. In order to make the color tone of the dried coating film pale yellow, there are a method of using a brown pigment as a coloring material and a method of mixing a yellow pigment and a black pigment. The type of coloring material used, considering uniform dispersibility,
It is desirable to minimize it. However, most of the brown pigments are soil pigments, and thus have hard particles and poor dispersibility.
Therefore, when titanium oxide and a brown pigment, which are concealing materials, are used, a dry coating film having a uniform color tone cannot be obtained. Accordingly, the present invention describes a method for obtaining a dry coating film having a uniform color tone when two types of coloring materials are used, particularly when a yellow pigment and a black pigment are used as the coloring materials.

The correction operation using the correction liquid is performed in the following steps. (1) Apply the correction liquid to the erroneous portion. (2) Dry until the solvent in the correction liquid evaporates to allow writing on the correction liquid coating film. (3) Rewriting is performed on the dried coating film which conceals a mistake. In the correction liquid using titanium oxide as the concealing material and the yellow pigment and the black pigment as the coloring material, that is, the correction liquid using two or more kinds of pigments having different color tones, the color tone of the dried coating film is not uniform. ) And (2), during the drying process, one of the two or more pigments having different color tones has a higher sedimentation rate at the bottom of the coating, and the other pigment has a lower sedimentation rate at the top of the coating. To do that. Therefore, the correction liquid using two or more kinds of pigments having different color tones can make the dried coating film uniform by selecting a pigment having a small difference in sedimentation speed. In order to reduce the difference in sedimentation velocity, it is necessary to reduce the difference in specific gravity and the difference in particle size. These are related to the intensity of the Brownian motion of the pigment in the coating film, and the more the Brownian motion, the harder the pigment settles. The Brownian motion is lighter in specific gravity and becomes more intense as the particle size is smaller. Therefore, the smaller the difference between the specific gravity and the particle size, the smaller the difference between the Brownian motions. As described above, in a correction liquid using two or more kinds of pigments having different color tones, it is necessary to select a pigment having a small specific gravity difference and a small particle size difference in order to obtain a dry coating film having a uniform color tone.

[0010]

SUMMARY OF THE INVENTION The present invention comprises a concealing material, a coloring material, a solvent, and a binder soluble in the solvent, wherein the concealing material has a surface treated with alumina-silica. Wherein the coloring material comprises at least yellow iron oxide and low-order titanium oxide.

Hereinafter, the composition of the present invention will be described. As the concealing material, at least titanium oxide treated with alumina-silica is used. Alumina-silica-treated titanium oxide is obtained by coating titanium and alumina with a thickness of several nm on the surface of primary particles of titanium oxide in order to impart hydrophilicity to titanium oxide. The type of treatment layer to be coated is a treatment phase in which alumina and silica are co-precipitated to form one layer, and a treatment layer in which a silica layer is formed and an alumina layer is further formed to form a double layer. There is a treatment layer in which a double layer is formed by forming a layer, an alumina layer, and further forming a silica layer. In addition, a treatment layer in which a silica layer or an alumina layer is made porous in order to impart concealing properties. On the contrary, there is a treatment layer in which a silica layer or an alumina layer is made dense in order to impart weather resistance. Commercially available products include Tytone R2
1, R-7E, R-3L, R62N (all manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-380, KR-4
80 (manufactured by Titanium Industry Co., Ltd.), Thai Pure R-9
31, R-902, R-960
Japan Limited, Titanics JR-40
3, JR-805 and JR-800 (all manufactured by Teica Co., Ltd.). Alumina-silica-zinc treated titanium oxide has light resistance and light discoloration resistance in order to provide primary particles of zinc oxide treated titanium oxide as a nucleus, and has a thickness of several nm on the surface to impart hydrophilicity to alumina. It is coated with silica. As the type of the treatment layer to be coated, there is a type similar to the above-mentioned alumina-silica treatment. Commercially available products include Tytone R-650 (manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-380N (manufactured by Titanium Industry Co., Ltd.), Titanics JR-701, and JRNC
(Both manufactured by Teika Co., Ltd.). These concealing materials can be used alone or in combination of two or more. The amount of these concealing materials used is 3
0-70% by weight is preferred.

The coloring material is used to obtain a target color tone. The yellow pigment uses yellow iron oxide. Commercially available products include Tarox LL-XLO, LL-100, and LE
MON, HY-100, HY-200, HY-2
50 (manufactured by Titanium Industry Co., Ltd.), Biferrox 415, 420, 1420, 3420, 142
0M, 910, 920, 930, 940, 9
43, 960, 3905, 3910, 392
0, 3950, 920Z, 1920 (all manufactured by Bayer K.K.), YP-200N, YP-100N, Y
P-50N (all manufactured by Tone Sangyo Co., Ltd.). The above yellow iron oxides can be used alone or in combination of two or more. The use amount of these yellow iron oxides is preferably 0.01 to 5% by weight based on the total amount of the correction liquid.

As the black pigment, low order titanium oxide is used. Lower titanium oxide is generally Ti _n O _2n - represented by substances ₁ expression, were mixed stoichiometrically so that the ratio of titanium and oxygen in the oxide for the purpose of the metal titanium and titanium dioxide And obtained by firing at 600 ° C. or higher in a nitrogen stream. Commercially available black conductive titanium oxide M
-1, S-1 (all manufactured by Ishihara Sangyo Co., Ltd.), Tila
ck D (manufactured by Ako Kasei Co., Ltd.). The lower titanium oxides can be used alone or in combination of two or more. The use amount of these low order titanium oxides is preferably 0.01 to 5% by weight based on the total amount of the correction liquid.

The solvent is used for dissolving the binder resin and adjusting the viscosity. Water is used as the solvent in the aqueous correction fluid, but a water-soluble organic solvent can be used in combination to adjust the drying property and the freeze resistance. Specific examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, alcohols such as normal propyl alcohol, glycols such as ethylene glycol and propylene glycol, glycerin, polyhydric alcohols such as sorbitol, methyl Glycol ethers such as cellosolve, ethyl cellosolve, butyl cellosolve, tertiary butyl cellosolve, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more. In the oil-based correction fluid, a water-insoluble organic solvent is used as a solvent. Specific examples of the water-insoluble organic solvent include toluene, xylene,
Examples thereof include 1,1,1-trichloroethane and trichloroethylene. These solvents can be used alone or in combination of two or more. In the dual-use correction fluid, a chain hydrocarbon having 6 to 9 carbon atoms and a cyclic hydrocarbon having 6 to 8 carbon atoms are used. Specific examples of the chain hydrocarbon having 6 to 9 carbon atoms include hexane, isohexane, heptane and the like. Examples of the cyclic hydrocarbon having 5 to 8 carbon atoms include cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. These solvents can be used alone or in combination of two or more. The amount of the concealing material used is preferably 30 to 70% by weight based on the total amount of the correction liquid.

The binder soluble in the solvent is used for forming a coating film. In the case of an aqueous correction fluid, gum arabic,
Natural or semi-synthetic water-soluble polymers such as tragacanth gum, dextrin, modified starch, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, water-soluble acrylic resin, water-soluble styrene-acrylic resin, water-soluble styrene-maleic acid Resins that dissolve in solvents such as synthetic water-soluble polymers such as resins, and resins that can be dispersed in solvents such as resin emulsions such as acrylic resins, alkyd resins, vinyl resins, polyester resins, styrene resins, maleic resins, and urethane resins. No. In the case of an oil-based correction fluid or a dual-use correction fluid, an acrylic resin such as an acrylate polymer, a methacrylic ester polymer, a copolymer of acrylic acid and methacrylic ester, and a vinyl alkyl ether resin, a cyclized rubber, and styrene-butadiene And the like. In particular, when an acrylic resin is used, the adhesion of the coating film to the surface to be coated is good, and the smoothness of the coating film is also good. Acryloid B-67 is a commercially available acrylic resin.
(Above, manufactured by Rohm & Haas Co., USA). These binders can be used alone or in combination of two or more. The amount of binder used is 5 to the total amount of correction fluid.
20% by weight is preferred.

[0016] In addition to the above components, extenders such as silica and calcium carbonate may be used in combination to improve the hiding power. Various additives such as a dispersant and an anti-settling agent for the dispersion stability of the pigment and a flow improver and a leveling agent for further improving the coating performance can be appropriately added.

[0017]

By using alumina-silica-treated titanium oxide as a concealing material, yellow iron oxide as a yellow pigment as a coloring material, and lower titanium oxide as a black pigment, a uniform color tone can be obtained by the following actions. it is conceivable that. Yellow iron oxide and lower titanium oxide have a smaller difference in specific gravity than titanium oxide, and when at least alumina-silica treatment is applied to titanium oxide, these three pigments all have hydrophilic surfaces. Then, since the pigments have similar wettability on the surface of the pigment, the dispersing force is evenly applied to the three types of pigments, and the particle diameters are substantially the same. Therefore, a dried coating film having a uniform color tone can be obtained.

[0018]

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., alumina-silica treated titanium oxide) 65.0 parts by weight Talox LL-100 (manufactured by Titanium Industry Co., Ltd., yellow iron oxide) 1.6 Parts by weight Tilack D (lower titanium oxide, manufactured by Ako Kasei Co., Ltd.) 0.8 parts by weight Cyclopentane (manufactured by Maruzen Petrochemical Co., Ltd.) 61.0 parts by weight Methyl acetyl linoleate (manufactured by Daihachi Chemical Co., Ltd.) 5.2 parts by weight Acryloid B-67 (Acrylic resin, manufactured by Rohm & Haas Company, USA) 12.0 parts by weight Mizukasil P-80 (Dispersant, manufactured by Mizusawa Chemical Industry Co., Ltd.) 12.0 parts by weight Homogenol L -18 (Kao Corporation, dispersant) 1.2 parts by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid for recycled paper.

Example 2 Titanics JR701 (manufactured by Teica Co., Ltd., alumina-silica-zinc-treated titanium oxide) 70.0 parts by weight Bayferox 420 (manufactured by Bayer Co., Ltd., yellow iron oxide) 2.6 parts by weight Part Black conductive titanium oxide M-1 (Ishihara Sangyo Co., Ltd., lower titanium oxide) 0.5 part by weight Methylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd.) 79.0 parts by weight Acryloid B-67 (described above) 13 0.0 parts by weight Mizukasil P-80 (described above) 9.0 parts by weight Homogenol L-18 (described above) 1.0 part by weight The above components were made in the same manner as in Example 1 to obtain a modified liquid for recycled paper.

Example 3 Thaitone R-7E (manufactured by Sakai Chemical Industry Co., Ltd., alumina-silica treated titanium oxide) 72.0 parts by weight YP-100N (Tone Sangyo Co., Ltd., yellow iron oxide) 0.9 weight Part: Tilack D (manufactured by Ako Kasei Co., Ltd., low titanium oxide) 0.2 parts by weight Water: 79.0 parts by weight Movinyl 114 (manufactured by Hoechst Gosei Co., Ltd., vinyl acetate resin emulsion) 26.7 parts by weight DISCOAT N -14 (manufactured by Daiichi Kogyo Co., Ltd., anionic surfactant) 0.2 parts by weight Proxel GXL (manufactured by Zeneca Co., Ltd., preservative) 0.3 parts by weight The above components were prepared in the same manner as in Example 1. A correction solution for recycled paper was obtained.

Example 4 Titatone R-650 (alumina-silica-zinc treated titanium oxide, manufactured by Sakai Chemical Industry Co., Ltd.) 36.0 parts by weight Titanics JR-800 (alumina-silica-zinc manufactured by Teica Co., Ltd.) Treated titanium oxide) 40.0 parts by weight Talox HY-100 (manufactured by Titanium Co., Ltd., yellow iron oxide) 1.8 parts by weight Black conductive titanium oxide M-1 (described above) 0.7 parts by weight Water 52.0 Parts by weight Ethanol 10.0 parts by weight SR-131 (acrylic resin, manufactured by Ryo Kagaku Kogyo Co., Ltd.) 45.0 parts by weight Discoat N-14 (described above) 0.2 parts by weight Proxel GXL (described above) 0.3 Parts by weight The above components were prepared in the same manner as in Example 1 to obtain a correction liquid for recycled paper.

Example 5 Titanics JR-805 (alumina-silica-treated titanium oxide, manufactured by Teica Corp.) 65.0 parts by weight Bayferox 910 (manufactured by Bayer Corp., yellow iron oxide) 11.0 parts by weight Tilac D (described above) 3.3 parts by weight Water 55.0 parts by weight Ethanol 5.0 parts by weight SR-131 (described above) 43.0 parts by weight Discoat N-14 0.3 parts by weight Proxel GXL 0.4 parts by weight

Comparative Example 1 A recycled paper was prepared in the same manner as in Example 1 except that Kronos KR-380 was replaced by Titanics JR-301 (manufactured by Teica Co., Ltd., alumina-treated titanium oxide). A correction fluid was obtained.

Comparative Example 2 In Example 2, the biferrox 420 was replaced by pigm
A correction liquid for recycled paper was obtained in the same manner as in Example 1 except that ent yellow 154 (a benzimidazolone-based yellow pigment manufactured by Dainippon Ink and Chemicals, Inc.) was used.

Comparative Example 3 In Example 3, Tilac D was replaced with MA-100.
(Mitsubishi Kasei Kogyo Co., Ltd., carbon black) was used in the same manner as in Example 1 to obtain a correction liquid for recycled paper.

The correction liquids obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were tested for the uniformity of the color tone of the dried coating film. Table 1 shows the results.

[0028]

[Table 1]

* 1 State of dried coating film: The above-mentioned correction liquid for recycled paper has a clearance of 0.1 on opacity measurement paper (JIS K5400).
It was applied with a 52 mm applicator, and the color unevenness of the dried coating film was visually evaluated.

[0030]

As described in detail above, the correction liquid for recycled paper of the present invention has a sufficient concealing property,
When applied to light yellow-based recycled paper, a dried coating film having a color tone that is inconspicuous is formed, and the color tone of the dried coating film becomes uniform, so that the coating film has practically excellent quality.

Claims (2)

[Claims] 1. A correction liquid containing at least a concealing material, a coloring material, a solvent, and a binder soluble in the solvent, wherein the concealing material contains at least titanium oxide whose surface is treated with alumina-silica. And a coloring agent containing at least yellow iron oxide and low-order titanium oxide. 2. The amount of titanium oxide whose surface is treated with alumina-silica is 30 to 70% by weight with respect to the total amount of the correction liquid, and the amount of yellow iron oxide used is 0.00
2. The correction liquid for recycled paper according to claim 1, wherein the correction liquid is 1 to 5% by weight, and the amount of the lower titanium oxide used is 0.01 to 5% by weight based on the total amount of the correction liquid.