JPH07173417A - Liquid eraser - Google Patents

Abstract

PURPOSE:To long prevent the settling of a hiding material and to improve the aging stability of liquid eraser by compounding a solvent, a resin, the hiding material, a dispersant, and fluorophlogopite. CONSTITUTION:0.1-10.0wt.% fluorophlogopite is added to a liquid eraser which comprises an inorg. powder having a high refractive index as the hiding material, an org. solvent, a resin sol. in the solvent, and a nonionic, anionic, or cationic surfactant as the dispersant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a correction liquid for concealing typographical errors and for concealing stains on the surface of paper. In particular, there is little sedimentation of the concealing agent during long-term storage, coloration, etc. Regarding liquid.

[0002]

2. Description of the Related Art Conventionally, correction fluids are roughly classified into three types, that is, an aqueous type, an oily type, or an aqueous common oil type having different solvent compositions of the correction fluids, depending on the type of the writing line that requires the correction concealment. The water-based type uses water as the main solvent and is intended for the correction and concealment of writing lines of oil-based writing instruments (for example, Japanese Examined Patent Publication No. 52-44246), while the oil-based type uses 1.1.1-trichloroethane as the main solvent. A typical chlorinated solvent or the like has been used and used properly for the purpose of concealing the correction of water-based writing instruments and the like (for example, Japanese Patent Publication No. 61-36).
552). The correction fluid is complicated because it needs to be used properly depending on the type of writing line, but there is a water-based oil-based common type that solves such a drawback (for example, Japanese Patent Publication No.
-59308). These correction solutions use naphthenic hydrocarbons represented by methylcyclohexane and 1.1.1-trichloroethane as main solvents. Further, as the hiding agent, white and highly hiding power titanium dioxide alone, or zinc white, calcium carbonate or the like is used alone or in combination of two or more, and carbon black is used as a colorant.
Some pigments include inorganic pigments such as iron black and some organic pigments for colored paper.

[0003]

However, since titanium dioxide, which is the above-mentioned masking agent, has a larger specific gravity than the other essential components, solvent and resin, it causes sedimentation and separation due to long-term storage, and the resin at the bottom of the container. When a hard caking layer in which the hiding agent was entangled was formed, the structure of the caking layer was not easily broken even when agitated during use, and it was difficult to return to the dispersion liquid at the initial stage of production. Further, in a system using an inorganic pigment such as carbon black or iron black as a coloring agent, or an organic pigment for coloring paper, due to the difference in specific gravity between titanium dioxide as a masking agent and the coloring agent, Due to the difference in surface polarity between the titanium dioxide particles and the color pigment particles, color separation occurs due to aggregation, sedimentation separation, etc., and even if stirring is performed during use, they are not completely homogenized,
There was a problem that the quality as a correction fluid could not be maintained.

[0004]

DISCLOSURE OF THE INVENTION The inventor of the present invention has proposed a correction solution comprising a solvent, a resin, a masking agent, and a dispersant, and further contains fluorophlogopite in an amount of 0.1 to 10.0 based on the total amount of the correction solution.
By adding parts by weight, it is found that the sedimentation of the masking agent during long-term storage is suppressed, and the formation of a hard caking layer due to the masking agent that has settled or the occurrence of color separation due to the use of a coloring agent is less likely to occur. It came to offer.

That is, the fluorophlogopite mica in the present invention is a synthetic product obtained by melting and cooling a formulation containing a fluorine compound under normal pressure to crystallize, and is a plate-like silicate crystal. In fluorophlogopite (KMg ₃ AlSi ₃ O ₁₀ F ₂ ), K is Na or C.
Those substituted with a, Sr, Ba, etc. can also be synthesized. Particularly, those substituted with Na have weak bonding between silicate layers and are physicochemically unique such as swelling and dispersing in water to form a sol or gel. Show the property. Preferably, like bentonite, cations, such as alkylammonium salts, are present between the layers.
It is also possible to form a sol or a gel in a familiar organic solvent by using an organic complex in which an alkylbenzylammonium salt, particularly a surfactant having an alkyl group of C ₁₂ or more is intercalated. . The amount used is preferably 0.1 to 10.0 parts by weight with respect to the total amount of the correction fluid. If the amount is less than 0.1 parts by weight, the expected thixotropy cannot be obtained, which is not useful for the effect of preventing sedimentation. If it is 10.0 parts by weight or more, the viscosity of the system becomes too thick and the whole system becomes a gel state, and a smooth coating film cannot be obtained at the time of application.

With respect to the masking agent used in the present invention, any of those conventionally used as a masking agent for a correction fluid can be used, and mainly one or two kinds of titanium dioxide, zinc white, calcium carbonate and the like can be used. Mix and use the above. In particular, it is preferable to use an inorganic powder having a large refractive index such as titanium dioxide.

As the dispersant, various nonionic, anionic and cationic surfactants can be used. For example, sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxy Nonionic surfactants such as ethylene alkyl ether and polyoxyethylene alkylphenyl ether, alkyl sulfates, anionic surfactants such as polyoxyethylene alkyl ether acetate and polyoxyethylene alkyl ether phosphate, alkyl ammonium salts, Examples thereof include cationic surfactants such as alkylbenzyl ammonium salts. Further, ICI's Solspers 3000 or 9000 can also be used.

The organic solvent is a solvent which dissolves the resin described later, and includes, for example, alcohol solvents having 3 to 5 carbon atoms, ketone solvents such as methyl ethyl ketone, diethyl ketone and methyl propyl ketone, acetic acid esters such as ethyl acetate, 1 1.1.1. A mixture of chlorinated hydrocarbons such as trichloroethane, aromatic or naphthenic hydrocarbon solvents such as toluene, cyclohexane, methylcyclohexane, ethylcyclohexane, n-hexane, n-pentane, n-octane, isooctane and paraffinic solvents (eg, Idemitsu Petrochemical Co., Ltd. IP solvent)
And the like, and it is also possible to use one kind or a mixture of two or more kinds.

The resin is used for imparting dispersion stability of the above-mentioned masking agent, forming a correction fluid coating film, and imparting adhesion to the surface to be coated, and it must be soluble in the solvent used. . Specifically, there are acrylic resins, alkyd resins, petroleum resins, polyester resins and the like, and it is possible to use one kind or a mixture of two or more kinds. In addition to the above components, an appropriate amount of a plasticizer for adjusting the hardness of the coating film and a flow improver or a leveling agent for improving the coating performance may be added.

[0010]

The basic crystal unit layer of fluorophlogopite in the present invention is formed by bonding the alumina octahedron layer with the silicic acid tetrahedron layer sandwiched from both sides, and the layer thickness is on the order of 10Å and the specific surface area is Although it is roughly 9 m ² / g, those having Na between the layers have a property of adsorbing moisture in the air and swelling to be finely cleaved. It is presumed that the system exhibits thixotropic properties due to the interaction between the dispersed particles in the same manner as bentonite with the amount of colloidal dispersion (sol state) added in the correction solution solvent. Na between layers is an exchangeable cation, and its effective capacity is 7 MB
It is as large as 0-80 milligram equivalent / 100 g, and preferably, an organic material which is well compatible with the organic solvent used between the layers, particularly an intercalated surfactant having a C ₁₂ or more alkyl group, is added in a small amount. It is recommended that the above effects be exhibited more efficiently. As a result,
When it is left standing for a long period of time, it will transition to a gel state, suppressing the segregation of the masking agent and the color separation due to the separation of the coloring agent,
When a mechanical stimulus such as stirring is applied at the time of use, it is easily transformed into a sol state and returns to the dispersion liquid in the initial production state.

[0011]

[Examples] The formulation tables of Examples and Comparative Examples are shown below. [Production of Fluorine Mica Organic Complex] Aqueous Solution of Cationic Surfactant (Distearyldimethylammonium Chloride) 5
00 ml is heated to 40 ° C. above the Kraft point, 50 g of Na-fluorine mica is added with stirring, and the dispersion is stirred for 3 h so that the reaction proceeds sufficiently. After the reaction, after thoroughly washing with distilled water to remove the by-product NaCl,
It was obtained by drying for 24 h at room temperature under vacuum. Example 1 10 parts by weight of DIALAL BR-113 (acrylic resin manufactured by Mitsubishi Rayon Co., Ltd.) 1.1.1-Trichloroethane 60 〃 Chronos KR-380 100 〃 (rutile type titanium manufactured by Titanium Industry Co., Ltd.) SWANOL-3475 1.0 〃 (Nikko Chemicals Co., Ltd. activator) ME-100 0.1 〃 (Corp Chemical Co., Ltd. synthetic Na-fluorine mica) Iron black 0.05 〃 Example 2 Diinal BR-113 10 weight Part 1.1-Trichloroethane 60 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 ME-100 10 〃 Iron black 0.05 〃 Example 3 Dialnal BR-113 10 parts by weight 1.1.1 -Trichloroethane 60〃 Chronos KR-380 100〃 SWANOL-3475 1.0〃 Or-ME- 100 0.1 〃 (fluorine mica organic complex) Iron black 0.05 〃 Example 4 Dianal BR-113 10 parts by weight 1.1.1-trichloroethane 60 〃 Kronos KR-380 100 〃 SWANOL-3475 1.0 〃 Or-ME-100 10 〃 Iron black 0.05 〃 Example 5 Dianal BR-113 10 parts by weight Methylcyclohexane 50 〃 1.1.1-Trichloroethane 10 〃 Kronos KR-380 100 〃 SWANOL-3475 1.0 〃 Or-ME-100 0.1 〃 Iron black 0.05 〃 Example 6 Dianal BR-113 10 parts by weight Methylcyclohexane 50 〃 1.1.1-Trichloroethane 10 〃 Kronos KR-380 100 〃 SWANOL-3475 1 0.0 〃 Or-ME-100 0.1 〃 Iron black 0.0 〃 Comparative Example 1 Dianal BR-113 10 parts by weight 1.1.1-Trichloroethane 60 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 Iron black 0.05 〃 Comparative Example 2 Dialnal BR-113 10 parts by weight Parts Methylcyclohexane 50 〃 1.1.1-trichloroethane 10 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 Iron black 0.05 〃 Comparative example 3 Dialnal BR-113 10 parts by weight 1.1.1- Trichloroethane 60 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 ME-100 0.05 〃 Iron black 0.05 〃 Dispersion treatment was carried out for 24 hours by using a ball mill to mix the formulations of Examples and Comparative Examples. Got The correction liquids obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were tested for dispersion stability and color separation, and the test results are shown in Table 1.

[0012]

[Table 1] * 1 Dispersion stability of the correction solution The correction solution was placed in a bottle (25 ml) with a stopper and allowed to stand at room temperature for 3 months, and then the state of the correction solution was observed. ⊚: Almost no sedimentation product was observed ○: Sedimentation product was recognized, but was easily redispersed Δ: Sedimentation product was recognized, and redispersion was slightly difficult ×: Sedimentation product , Which is very difficult to redisperse. * 2 Color-separation property of correction fluid Put the correction fluid in a sealed bottle (25 ml) and let it stand at room temperature for 3 months, then visually check the state of the correction fluid. I observed. ◯: No color separation was observed Δ: Some color separation was recognized ×: Color separation was recognized

[0013]

As described above, according to the present invention, sedimentation of the masking agent during long-term storage is suppressed, and a hard caking layer is not easily generated by the masking agent left unattended and color separation due to the use of a colorant is less likely to occur. It is possible to obtain a correction liquid having excellent stability over time.

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[Procedure amendment]

[Submission date] February 25, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

DISCLOSURE OF THE INVENTION The inventor of the present invention has proposed a correction solution comprising a solvent, a resin, a masking agent, and a dispersant, and 0.05 to 6.0 of fluorophlogopite based on the total amount of the correction solution.
It was found that the addition of wt% suppresses sedimentation of the masking agent during long-term storage, and that it is difficult to generate a hard caking layer due to the precipitated masking agent or the like and color separation due to the use of a coloring agent. It came to offer.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

That is, the fluorophlogopite mica in the present invention is a synthetic product obtained by melting and cooling a formulation containing a fluorine compound under normal pressure to crystallize, and is a plate-like silicate crystal. In the fluorophlogopite (KMg ₃ AlSi ₃ O ₁₀ F ₂ ), K is Na,
Those substituted with Ca, Sr, Ba, etc. can also be synthesized. Particularly, those substituted with Na have a weak bond between silicate layers and are physicochemically unique, such as swelling or dispersing in water to form a sol or gel. Show the property. Like bentonite,
By using an organic complex in which a cation such as an alkylammonium salt or an alkylbenzylammonium salt, particularly a surfactant having an alkyl group of C ₁₂ or more, is intercalated between the layers, the sol in a familiar organic solvent is used. It is also possible to form a gel. The amount used is preferably 0.05 to 6.0% by weight with respect to the total amount of the correction fluid. If it is less than 0.05 % by weight, the expected thixotropy cannot be obtained, and it is not useful for the effect of preventing sedimentation. 6.0
If the content is more than 10% by weight, the viscosity will be too high and the whole system will be in a gel state.
A smooth coating film cannot be obtained during application.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

[Examples] The formulation tables of Examples and Comparative Examples are shown below. [Production of Fluorine Mica Organic Complex] Aqueous Solution of Cationic Surfactant (Distearyldimethylammonium Chloride) 5
00 ml is heated to 40 ° C. above the Kraft point, 50 g of Na-fluorine mica is added with stirring, and the dispersion is stirred for 3 h so that the reaction proceeds sufficiently. After the reaction, after thoroughly washing with distilled water to remove the by-product NaCl,
It was obtained by drying for 24 h at room temperature under vacuum. Example 1 10 parts by weight of DIALAL BR-113 (acrylic resin manufactured by Mitsubishi Rayon Co., Ltd.) 1.1.1-Trichloroethane 60 〃 Chronos KR-380 100 〃 (rutile type titanium manufactured by Titanium Industry Co., Ltd.) SWANOL-3475 1.0 〃 (Nikko Chemicals Co., Ltd. activator) ME-100 0.1 〃 (Corp Chemical Co., Ltd. synthetic Na-fluorine mica) Iron black 0.05 〃 Example 2 Diinal BR-113 10 weight Part 1.1-Trichloroethane 60 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 ME-100 10 〃 Iron black 0.05 〃 Example 3 Dialnal BR-113 10 parts by weight 1.1.1 -Trichloroethane 60〃 Chronos KR-380 100〃 SWANOL-3475 1.0〃 Or-ME- 100 0.1 〃 (fluorine mica organic complex) Iron black 0.05 〃 Example 4 Dianal BR-113 10 parts by weight 1.1.1-trichloroethane 60 〃 Kronos KR-380 100 〃 SWANOL-3475 1.0 〃 Or-ME-100 10 〃 Iron black 0.05 〃 Example 5 Dianal BR-113 10 parts by weight Methylcyclohexane 50 〃 1.1.1-Trichloroethane 10 〃 Kronos KR-380 100 〃 SWANOL-3475 1.0 〃 Or-ME-100 0.1 〃 Iron black 0.05 〃 Example 6 Dianal BR-113 10 parts by weight Methylcyclohexane 50 〃 1.1.1-Trichloroethane 10 〃 Kronos KR-380 100 〃 SWANOL-3475 1 0.0 〃 Or-ME-100 10 〃 Iron black 0.05 Comparative Example 1 Dianal BR-113 10 parts by weight 1.1.1-Trichloroethane 60 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 Iron black 0.05 〃 Comparative Example 2 Dialnal BR-113 10 parts by weight Methylcyclohexane 50 〃 1.1.1-Trichloroethane 10 〃 Chronos KR-380 100 〃 SWANOL-3475 1.0 〃 Iron black 0.05 〃 Comparative Example 3 Dialnal BR-113 10 parts by weight 1.1.1-Trichloroethane 60〃 chronos KR-380 100〃 SWANOL-3475 1.0〃 ME-100 0.05〃 iron black 0.05〃 Dispersion treatment was carried out for 24 hours by using a ball mill for the compounding of the examples and comparative examples, and the correction solution was prepared. Obtained. The correction liquids obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were tested for dispersion stability and color separation, and the test results are shown in Table 1.

Claims (1)

[Claims] 1. A correction liquid comprising a solvent, a resin, a masking agent and a dispersant, further comprising 0.1 to 10.0 parts by weight of fluorophlogopite added to the total amount of the correction liquid. liquid.