JP3032365B2 - Correction fluid - Google Patents

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 correcting and concealing typographical errors or for correcting and concealing dirt on a paper surface. Liquid.

[0002]

2. Description of the Related Art Conventionally, correction fluids are broadly classified into three types: aqueous types, oily types, and aqueous and oily common types, which have different solvent compositions for the correction fluids, depending on the type of writing line requiring correction concealment. The aqueous type uses water as a main solvent and is intended for correcting and concealing writing lines of an oil-based writing instrument (Japanese Patent Publication No. 52-44646). The oil type is based on 1.1.1.1-trichloroethane as a main solvent. A representative chlorine-based solvent or the like has been used for the purpose of correcting and concealing a water-based writing instrument or the like (Japanese Patent Publication No. 61-65552).
issue). The correction fluid needs to be properly used depending on the type of writing line, but there is a water- and oil-based common type which has solved such a disadvantage (Japanese Patent Publication No. 1-5930).
No. 8). These correction liquids include naphthenic hydrocarbons represented by methylcyclohexane as main solvents and 1.1.
1-trichloroethane is used. As the concealing agent, titanium dioxide which is white and has a high concealing power, or zinc white, calcium carbonate or the like is used alone or in combination of two or more.As a coloring agent, an inorganic pigment such as carbon black or iron black, or a coloring agent is used. There is also a paper to which an organic pigment or the like is slightly added for colored paper.

[0003]

However, titanium dioxide, which is a concealing agent, has a higher specific gravity than solvents and resins, which are other essential components, and causes sedimentation and separation due to long-term storage. When a hard caking layer was formed with the concealing agent, the structure of the caking layer was hard to break even when stirring was performed at the time of 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 colorant, or an organic pigment or the like for colored paper, the difference in specific gravity between titanium dioxide and a colorant as a concealing agent, as described above, Due to the difference in surface polarity between the titanium dioxide particles and the color pigment particles, color separation occurs due to aggregation, sedimentation, etc., and even when agitated at the time of use, it is not completely homogenized, and the quality as a correction liquid cannot be maintained. Had the problem of saying.

[0004]

Means for Solving the Problems The present inventor has proposed that a montmorillonite clay mineral (smectite) is further added in an amount of 0.1 to 2 with respect to the total amount of a correction liquid comprising a solvent, a resin, a concealing agent, and a dispersant. By adding 0.0% by weight, it was found that sedimentation of the concealing agent during long-term storage was suppressed, and the formation of a hard caking layer due to the concealing agent that had settled out, and the occurrence of color separation and the like due to the use of a coloring agent, were suppressed. The present invention has been made. That is, the montmorillonite-based clay mineral used in the present invention is a group of typical minerals constituting clay, and is collectively called smectite, which includes montmorillonite, zauconite, nontronite, saponite, hectorite, etc., and also includes bentonite. It is included in this. These clay minerals are layered clay minerals having a structure and chemical composition similar to mica, and cations, such as alkylammonium salts and alkylbenzylammonium salts, which are compatible with the solvent used later, are selected and intercalated between the layers. Things can also be used. The addition amount is preferably 0.1 to 2.0% by weight based on the total amount of the correction liquid. If the content is less than 0.1% by weight, the expected thixotropy cannot be obtained, and it does not contribute to the effect of preventing sedimentation.
If the content is 2.0% by weight or more, the viscosity of the system becomes too high and the whole system becomes a gel state, and a smooth coating film cannot be obtained at the time of application. As the concealing agent used in the present invention, any of those conventionally used as concealing agents for correction fluids can be used, and one or more of titanium dioxide, zinc white, calcium carbonate and the like are mainly mixed and mixed. use. In particular, it is preferable to use an inorganic powder having a large refractive index such as titanium dioxide. As the dispersing agent, 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 ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxy Nonionic surfactants such as ethylene alkyl ether and polyoxyethylene alkyl phenyl ether; anionic surfactants such as alkyl sulfate, polyoxyethylene alkyl ether acetate and polyoxyethylene alkyl ether phosphate; alkyl ammonium salts; And cationic surfactants such as alkylbenzylammonium salts. Also, ICI's Solsperse 3000 or 9000 can be used. The organic solvent dissolves a resin described below, and includes, for example, an alcohol solvent having 3 to 5 carbon atoms, a ketone solvent such as methyl ethyl ketone, diethyl ketone, and methyl propyl ketone; an ester solvent such as ethyl acetate; .
Mixtures of chlorinated hydrocarbons such as 1-trichloroethane, aromatic or naphthenic hydrocarbon solvents such as toluene, cyclohexane, methylcyclohexane and ethylcyclohexane, n-hexane, n-pentane, n-octane, isooctane and paraffinic solvents ( For example, paraffin solvents such as Idemitsu Petrochemical Co., Ltd. (IP Solvent) may be used, or one or more of them may be used in combination. The resin is used for the purpose of imparting the above-mentioned concealing agent with the aging stability, forming the correction liquid coating film, and imparting the adhesion to the surface to be coated, and must be soluble in the solvent used. Specifically, there are acrylic resin, alkyd resin, petroleum resin, polyester resin and the like, and it is also possible to use one kind or a mixture of two or more kinds. In addition, in addition to the above components, a plasticizer for adjusting the hardness of the coating film and a flow improver or a leveling agent for improving the coating performance can be added in an appropriate amount.

[0005]

The basic crystal unit layer of the montmorillonite-based clay mineral in the present invention is formed by bonding an octahedral alumina layer with a tetrahedral silicate layer sandwiched from both sides, and the amount of isomorphous substitution of the silicate layer is small. Since the charge is as small as about 1/3 of the mica, the bond with the interlayer cation is weak. The thickness of the layer is less than 10 °, the spread is of the order of 0.1 μm, the specific surface area is as large as 800 m ² / g, and the charge of smectite spreads two-dimensionally on this large flat layer surface. There is a negative charge referred to as “” and a positive charge referred to as “PH dependent charge” appearing at the end face (cut surface) of the basic crystal unit layer. When the surrounding PH decreases, the end face becomes, for example, Al− (OH) + H ⁺ → Al ( Smectite swells due to the more positive charge, such as OH) ₂ ⁺ , where the negative charge on the flat layer surface and the positive charge on the end surface attract, while the solvent in the correction fluid system solvates the cations between the layers. However, it is presumed that a card house structure is formed with the solvent contained between the particles. When the card house structure develops over the entire system with an increase in the amount of addition, the system shows thixotropic properties,
In a stationary state such as long-term storage, it transitions to a gel state and suppresses sedimentation separation of concealing agent and color separation due to separation of colorant,
During use, if a mechanical stimulus such as agitation is applied which is greater than the bonding force between the end face and the layer face of the smectite, the card house structure is easily broken and rearranged into a sol state, and returns to a dispersion liquid in an initial production state. By utilizing these characteristics, the sedimentation force of the titanium dioxide particles having a large specific gravity cannot exceed the force for forming the card house structure, and sedimentation can be prevented as much as possible. Furthermore,
Since a large amount of solvent can be retained in the card house structure or between the smectite layers, even if the correction liquid is left standing for a long time, even if a slight amount of sedimentation layer is generated at the bottom, it can be controlled by a simple external force such as stirring. The retained solvent is easily released and diffuses into the resin in the sedimented layer to facilitate redispersion. Therefore, it is presumed that it is possible to prepare a correction solution having excellent temporal stability. Furthermore, the permanent charge of the flat layer surface of the smectite plate crystal, and the pH-dependent charge of the end surface, the smectite plate crystal is oriented according to the surface charge of the coloring agent,
It is presumed that it acts like a kind of zwitterionic surfactant and prevents the color separation phenomenon of the correction fluid.

[0006]

[Examples] The compounding tables of Examples and Comparative Examples are shown below. Example 1 Diamond BR-113 5% by weight (acrylic resin manufactured by Mitsubishi Rayon Co., Ltd.) Methylcyclohexane 36 {1.1.1-trichloroethane 2} Kronos KR-380 55 {(rutile type titanium manufactured by Titanium Industry Co., Ltd.) Homogenol L-18 1.5 (Dispersing agent manufactured by Kao Soap Co., Ltd.) SAN 0.5 (Synthetic smectite manufactured by Corp Chemical Co., Ltd.) Iron black 0.02 {Example 2 Dianal BR-113 5 weight % Methylcyclohexane 35 {1.1.1-Trichloroethane 2} Chronos KR-380 55 {Homogenol L-18 1.5} SWN 1.5 {Synthetic smectite manufactured by Corp Chemical Co.) Iron black 0.02} Example 3 Dianal BR-113 5% by weight IP Solvent 20〃 (Idemitsu Petrochemical Co., Ltd. Methylcyclohexane 15 toluene 2.5 chronos KR-380 55 homogenol L-18 1.5 SAN 1.0 iron black 0.02 Example 4 Dianal BR-113 5% by weight IP Solvent 20 メ チ ル Methylcyclohexane 15 ト ル エ ン Toluene 1.5 〃 Khronos KR-380 55 〃 Homogenol L-18 1.5 〃 SWN 2.0 鉄 Iron black 0.02 〃 Example 5 Diamond BR-113 5% by weight methylcyclohexane 36 {1.1.1-Trichloroethane 2} Kronos KR-380 55 {Homogenol L-18 1.5} SAN 0.5 {MA-100 0.02} (Carbon black manufactured by Mitsubishi Chemical Industry Co., Ltd.) 6 Dianal BR-113 5% by weight methylcyclohexane 35 1.1 1-trichloroethane 2 {Kronos KR-380 55} Homogenol L-18 1.5 {SWN 1.5} MA-100 0.02 {Comparative Example 1 Dianal BR-113 5% by weight methylcyclohexane 35} 1.1. 1-trichloroethane 2 〃 Kronos KR-380 55 〃 Homogenol L-18 1.5 〃 Iron black 0.02 比較 Comparative example 2 Dianal BR-113 5% by weight IP solvent 20 メ チ ル Methylcyclohexane 15 ト ル エ ン Toluene 3 ク ロ Kronos KR- 380 55.5 {Homogenol L-18 1.5} Iron black 0.02 {Comparative Example 3 Dianal BR-113 5% by weight methylcyclohexane 36} 1.1.1.1-Trichloroethane 2} Kronos KR-380 55.5 〃 Homogenol L-18 1.5 ＭＡ MA-100 .02 〃 the formulation of Examples and Comparative Examples using a ball mill to obtain a correction fluid for 24 hours for performing dispersion treatment. As described above, tests were performed on the stability over time and color separation of the correction liquids obtained in Examples 1 to 6 and Comparative Examples 1 to 3, and the test results are shown in Table 1.

[Table 1] * 1 Stability of the correction solution over time The correction solution was taken in a bottle with a stopper (25 ml), allowed to stand at room temperature for 3 months, and the state of the correction solution was observed. A: Almost no sedimentation product was observed. A: A sedimentation product was observed, but was easily redispersed. Δ: A sedimentation product was observed, and redispersion was somewhat difficult. X: A sedimentation product. * 2 Color separation of the correction solution Take the correction solution in a bottle with a stopper (25 ml), allow it to stand at room temperature for 3 months, and visually check the state of the correction solution. Observed. ：: Color separation is not observed △: Color separation is recognized X: Color separation is detected

[0007]

As described above, according to the present invention, the sedimentation of the concealing agent during long-term storage is suppressed, and the formation of a hard caking layer due to the sedimentation concealing agent and the like, and the occurrence of color separation due to the use of the coloring agent, etc., occur. It is possible to obtain a correction liquid having excellent temporal stability.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C09D 10/00 CA (STN) CAOLD (STN) REGISTRY (STN) WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. A correcting solution comprising a solvent, a resin, a concealing agent and a dispersing agent, wherein a montmorillonite clay mineral (smectite) is further added in an amount of 0.1 to 2.
Correction liquid characterized by adding 0% by weight