JP3407554B2 - Correction fluid - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a correction liquid, and more particularly, to a liquid having excellent concealing power required for concealment correction of characters and prints, and moreover It relates to a correction fluid with excellent properties. 2. Description of the Related Art Conventionally, a correction liquid for concealing and correcting handwritings of water-based inks and oil-based inks, printing marks of a typewriter or the like, and images copied by a dry copying machine has been used as a concealing material such as titanium oxide. , A solvent and a resin soluble in the solvent are known. Correction fluid, because it is used for the purpose of concealment correction, high concealment power is required,
In order to improve the hiding power, increasing the content of the hiding material, in addition to the above-described components, black pigments such as carbon black and iron black, and adding a colored pigment such as red iron oxide as a hiding power improver have been attempted. I have. [0003] However, when the content of the concealing material is increased, the leveling property of the coating film deteriorates,
Since irregularities are formed on the coating film, problems such as deterioration of the appearance of the concealed portion and the inability to obtain a clean handwriting when overwriting for correction are likely to occur. In addition, when the hiding power improving material is added, and when the hiding power improving material is stored for a long period of time, the hiding material and the hiding power improvement material are separated from each other, and color separation occurs. SUMMARY OF THE INVENTION An object of the present invention is to provide a correction liquid that does not reduce the leveling property of a coating film, does not cause a problem such as color separation even when stored for a long time, and has a high hiding power. SUMMARY OF THE INVENTION The present invention provides a correction liquid containing at least a concealing material, a solvent, a resin, and a titanium-based black pigment. Hereinafter, the present invention will be described. The concealing material is used to conceal handwriting, and uses titanium oxide. Various titanium oxides such as rutile type and anatase type can be used as the titanium oxide. Commercially available products include titone SR-1, R-650, R-3L,
R-310, A-110, A-150, R-5
N (manufactured by Sakai Chemical Industry Co., Ltd.), TYPEAK R-55
0, R-580, R-930, A-100, A
-220 (Ishihara Sangyo Co., Ltd.), Kronos KR-
310, KR-380, KR-480, KA-1
0, KA-20 and KA-30 (all manufactured by Titanium Industry Co., Ltd.) and Bayer RF
D-1, R-FD-2, R-FB-1, R-FB
-3, R-KB-3, R-CK-20 (both manufactured by Bayer AG, Germany), Taipaque R-630, R-CK
615, R-830 (all, manufactured by Ishihara Sangyo Co., Ltd.), Thai Pure R-900, R-901 (all, manufactured by DuPont
And organically treated titanium oxide (e.g., Japan Limited). These titanium oxides can be used alone or in combination of two or more, and the amount of use is preferably 20 to 50% by weight based on the total amount of the correction liquid. [0006] The solvent is a solvent for the resin to be described later and also forms the correction liquid of the present invention in a liquid state. In the aqueous correction liquid, water is used as a main solvent, but various water-soluble organic solvents can be used to adjust the drying property and the freeze resistance. Specific examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, alcohols such as normal propyl propyl alcohol, ethylene glycol, glycols such as propylene glycol, glycerin, polyhydric alcohols such as sorbitol,
Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, tertiary butyl cellosolve, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether. These water-soluble organic solvents can be used alone or in combination of two or more. An organic solvent is used in the oil-based correction fluid. Specifically, hydrocarbon solvents such as toluene, xylene, normal heptane, normal octane, cyclohexane, methylcyclohexane, and cyclopentane;
Halogenated hydrocarbon solvents such as 1,1-trichloroethane and tetrachloroethylene, ether solvents such as 1,4-dioxane, normal butyl ether and trioxane, ethyl methyl ketone, methyl-normal propyl ketone and the like And ester-based solvents such as propyl formate and ethyl acetate. These solvents can be used alone or in combination of two or more. In selecting the solvent, a solvent having a boiling point of 40 to 150 ° C. is preferable in consideration of the corrected drying time of the coating film. The amount used is 30 to 6 with respect to the total amount of the correction fluid.
0% by weight is preferred. If a paraffinic hydrocarbon such as normal heptane or normal octane or a naphthenic hydrocarbon such as cyclohexane or methylsilohexane is used in the oily correction liquid, the handwriting of the oily ink can be corrected. For the purpose of dispersing a pigment, forming a coating film, etc., a resin which can be dissolved or dispersed in a solvent to be used is used. In the case of an aqueous correction fluid, natural or semi-synthetic water-soluble polymers such as gum arabic, tragacanth gum, dextrin, processed starch, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, water-soluble acrylic resin, water-soluble styrene-acryl resin , A resin soluble in a solvent such as a synthetic water-soluble polymer such as a water-soluble styrene-maleic acid resin, and an acrylic resin, an alkyd resin, a vinyl resin, a polyester resin,
Resin which can be dispersed in a solvent such as a resin emulsion such as a styrene resin, a maleic acid resin and a urethane resin. These can be used alone or in combination of two or more, and the amount of use is 3 to 3 in solid content with respect to the total amount of the correction fluid.
20% by weight is preferred. For oil-based correction fluid, acrylic resin, alkyd resin, vinyl resin, polyester resin,
Resins soluble in solvents such as vinyl alkyl ether resins, styrene resins, styrene-butadiene-based elastomers, and rubber-based resins such as cyclized rubber. These can be used alone or in combination of two or more.
The solid content is preferably 5 to 20% by weight based on the total amount of the correction liquid. The titanium-based black pigment is used as a hiding power improving material. Specifically, titanium trioxide (Ti ₂ O ₃ ), titanium trioxide (Ti ₃ O ₅ ), titanium monoxide (TiO), titanium tetraoxide (Ti ₄ O ₇ ), nine such titanium oxide (Ti ₅ O ₉₎ and low-order titanium oxide, titanium nitride, include things like titanium sulfide,
These titanium pigments are blue-black to black black pigments. In addition, low-order titanium oxide generally means TinO2n-1.
Is obtained by stoichiometric mixing of titanium and titanium dioxide in a ratio of titanium and oxygen so as to have a ratio of titanium and oxygen, and firing at 600 ° C. or more in a nitrogen stream. Things. These can be used alone or in combination of two or more, and the amount of use is preferably 0.01 to 0.5% with respect to the total amount of the correction fluid. Commercially available products include black conductive titanium oxide M-1 (lower titanium oxide, titanium: oxygen = 1: 1.86), black conductive titanium oxide S
-1 (lower order titanium oxide, titanium: oxygen = 1: 1.67,
As described above, Tilack D (lower titanium oxide, manufactured by Ako Kasei Co., Ltd.) and titanium black (mainly composed of titanium monoxide, manufactured by Mitsubishi Materials Corporation) are listed. [0009] In addition to the above-described components, extender pigments such as silica and calcium carbonate which are conventionally used hiding power improvers may be used in combination. Furthermore, dispersing agents and anti-settling agents for the dispersion stability of concealing materials and pigments, thickeners for viscosity adjustment, plasticizers for adjusting the hardness of the coating film, and good coating performance A flow improver or a leveling agent can be appropriately added for smoothing. The correction liquid 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 the like. The correcting liquid of the present invention has improved hiding power because light is absorbed by the titanium-based black pigment contained in the coating film, and the specific gravity of the titanium-based black pigment is improved. Is almost the same as titanium oxide and has a similar chemical structure.
It is considered that there is no color separation due to sedimentation over time even when stored for a long time. Example 1 Kronos KR-380 (rutile type titanium oxide, manufactured by Titanium Co., Ltd.) 65 parts by weight Methylcyclohexane 120 parts by weight Acryloid B-66 (acrylic resin, manufactured by Rohm & Haas Co., USA) 12 parts by weight Black conductive titanium oxide M-1 (lower titanium oxide, titanium: oxygen = 1: 1.86, manufactured by Ishihara Sangyo Co., Ltd.) 0.1 part by weight Mizukasil P-801 (fine silica, Mizusawa Chemical) (Manufactured by Kogyo Co., Ltd.) 2 parts by weight Homogenol L-18 (surfactant, manufactured by Kao Corporation) 1.2 parts by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid. Example 2 Khronos KR-380 (described above) 70 parts by weight Xylene 100 parts by weight Acryloid B-66 (described above) 10 parts by weight Tilac D (lower titanium oxide, manufactured by Ako Kasei Co., Ltd.) 0.2 parts by weight Homogenol L-18 (described above) 1.5 parts by weight Each of the above components was prepared in the same manner as in Example 1 to obtain a correction liquid. Example 3 Khronos KR-380 (described above) 70 parts by weight Methylcyclohexane 70 parts by weight Ethylcyclohexane 30 parts by weight Acryloid B-67 (acrylic resin, manufactured by Rohm & Haas Co., USA) 10 parts by weight Titanium tripentaoxide 0.14 parts by weight Mizukasil P-801 (described above) 2 parts by weight Dioctyl adipate (plasticizer) 2.5 parts by weight Homogenol L-18 (described above) 1.3 parts by weight The above components were prepared in the same manner as in Example 1. A correction fluid was obtained. Example 4 Tytone R-5N (rutile type titanium oxide, manufactured by Sakai Chemical Industry Co., Ltd.) 43 parts by weight Water 29.6 parts by weight Movinyl 114 (vinyl acetate resin emulsion, manufactured by Hoechst Gosei Co., Ltd.) 15 parts by weight Part Black conductive titanium oxide M-1 (described above) 0.1 parts by weight Toksil U (amorphous silica, manufactured by Tokuyama Soda Co., Ltd.) 5.5 parts by weight Aerosil 200 (amorphous silica, manufactured by Nippon Aerosil Co., Ltd.) 2.1 parts by weight DISCOAT N-14 (anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 part by weight Proxel GXL (preservative, manufactured by Zeneca Corporation) 0.2 part by weight The components were made as in Example 1 to obtain a correction fluid. Example 5 Bayer R-FD-1 (rutile type organic treated titanium oxide, manufactured by Bayer AG, Germany) 40 parts by weight Water 19.4 parts by weight Ethanol 3.5 parts by weight SR-131 (acrylic resin, 26.5 parts by weight Tilac D (described above) 0.07 parts by weight P-820 (aluminum silicate, manufactured by Degussa, Germany) 15 parts by weight Discoat N-14 (described above) 1 part by weight Proxel GXL (described above) 0.2 part by weight Each of the above components was made in the same manner as in Example 1 to obtain a correction liquid. Example 6 Thai Pure R900 (rutile type titanium oxide, manufactured by DuPont Japan Limited) 40 parts by weight Water 22.9 parts by weight SR-131 (described above) 21.5 parts by weight Tilac D (described above) 0.1 Parts by weight P-820 (described above) 15 parts by weight Discoat N-14 (described above) 0.1 part by weight Proxel GXL (described above) 0.2 part by weight The above components were made in the same manner as in Example 1 to obtain a correction liquid. Was. Comparative Example 1 A correction liquid was obtained in the same manner as in Example 1 except that the black conductive titanium oxide was omitted. Comparative Example 2 A correction liquid was obtained in the same manner as in Example 2 except that iron black (Toda Color KN320, manufactured by Toda Kogyo KK) was used instead of Tilac D. Comparative Example 3 A correction liquid was obtained in the same manner as in Example 3 except that titanium pentaoxide was omitted. Comparative Example 4 A correction liquid was obtained in the same manner as in Example 4 except that the black conductive titanium oxide was omitted. Comparative Example 5 In Example 5, Tilac D was replaced with MA-100.
(Carbon black, manufactured by Mitsubishi Chemical Corporation) 0.01
A correction liquid was obtained in the same manner as in Example 5 except that the weight part was changed. Comparative Example 6 A correction liquid was obtained in the same manner as in Example 6, except that titanium pentaoxide was omitted. As described above, the correcting solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were subjected to a hiding power test and a stability test with time. Table 1 shows the results. Hiding power test: The above-mentioned correction liquid was applied to a gap of 50 μm.
JIS K5 using a film applicator
400 opacity test paper, dried,
The relaxation reflectance was measured using a color computer Model SM-4 (manufactured by Suga Test Instruments Co., Ltd.), and the hiding power was calculated from the following equation. HP = (B / W) × 100 HP: Hiding power (%) B: Relaxed reflectance of coating on black background (Y value) W: Relaxed reflectance of coating on white background (Y value) Stability test over time: The above correction solution was placed in a screw vial, allowed to stand at room temperature for one week, and visually checked for color separation. ：: Color separation ×: No color separation [Table 1] With respect to the correction liquids obtained in Examples 1 to 6 and Comparative Examples 1 to 6, the coating films prepared by the hiding power test were:
All had smooth surfaces, good appearance, and good overwritten handwriting. As described in detail above, the correction liquid of the present invention has a concealing power necessary for concealment correction of characters and prints and an excellent correction liquid free from color separation that occurs over time. It is.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08D 1/00-201/10 CA (STN)

Claims (1)

(57) [Claim 1] A correction fluid containing at least a concealing material, a solvent, a resin, and a titanium-based black pigment.