JPH07122040B2 - Solid corrector composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition which is applied to a correction agent, in particular a solid-state composition, for obscuring and erasing characters and lines written on a paper surface by coating.

[0002]

2. Description of the Related Art Titanium oxide is used in a solvent of higher volatility than before for the purpose of correcting characters, lines, symbols, etc. written on the surface of paper by various writing instrument inks, printing, printer printing of OA equipment, type printing, copying, etc. A paint-type correction liquid containing a white pigment as described above dispersedly contained in a high concentration is widely used. However, in such a correction solution, the pigment is liable to settle and separate during storage, and it is necessary to shake the container before use to re-disperse it with a stirring ball in the container, and gradually increase the viscosity by volatilizing the solvent. As a result, the coating property is deteriorated and the hands and the surroundings are easily soiled during use.

Therefore, recently, a solid correction agent has been actively researched as an alternative to the above-mentioned correction liquid. This solid correction agent is generally a thixotropic gel-like composition containing a binder and a white pigment and a dispersion medium such as water solidified into a rod-like shape. The coating film is adapted to cover and erase the corrected portion. Conventionally, an acrylic resin having a glass transition point of 10 ° C. or lower is used as the binder, a polyacrylic acid-based thickener, a fatty acid soap as a gelling agent, and N-methyl-2-pyrrolidone as a viscosity reducing agent. (Japanese Patent Application Laid-Open No. 3-780), carboxymethylcellulose or the like is used as the binder, and an alkali metal salt or ammonium salt of an aliphatic carboxylic acid is used as a gelling agent, and a gel is formed from organic or inorganic salts. A composition using a toughening agent (JP-A-3-126774) is known.

[0004]

By the way, in recent years, those using water-based ink as marking pens, ballpoint pens, etc. have appeared, and there is no health problem due to organic solvents like conventional oil-based writing instruments. Demand tends to increase. However, the conventional solid corrector composition is inferior in applicability to water-based inks, and when applied on the handwriting of a water-based writing instrument, the elution of ink may cause the correction coating film to be colored and smeared. When a correction character or the like was written on the film with an aqueous writing instrument, there was a problem that the color of the undercoating film was highlighted in the handwriting and became whitish, or bleeding occurred and the handwriting was unclear.

Further, the solid correction agent is generally used in the form of a rod shaft filled in a lipstick type extruding container or the like, but from the viewpoint of practicality, it does not collapse or break during application, and is smooth and smooth. It is necessary to form a uniform coating film and to be able to completely cover up and erase the corrected portion with a thin film thickness of one coating, and the coating film surface becomes smooth so that correction characters can be easily written, and It is also required that the coating film dry quickly in order to quickly perform rewriting and the next correction. However, at present, we have not realized anything that can satisfy all these requirements,
Further quality improvement is required to replace the existing correction fluid.

In view of the above situation, the present invention is capable of beautifully hiding and erasing without causing coloring on any of the writing surfaces of water-based and oil-based inks, and is also effective for writing correction characters and the like on the corrected coating film. Provided is a solid correction agent composition which can be used with any of the oil-based writing instruments without any trouble, is excellent in various properties such as formability, coating property, hiding property, and drying property, and has a long life, and is extremely highly practical. Is intended.

[0007]

To achieve SUMMARY OF to the above objects, a solid modifier composition according to claim 1 of the present invention, the following as essential components (a) ~ (e); (a) molecule Has a cationic functional group, and an anionic group
Cationic water-soluble resin having the property of becoming water-insoluble by reacting with a compound having (b) a gel-forming agent (b) having a multi-layer structure and retaining a liquid phase component between layers
And a moisturizing agent composed of solid particles having (d) a white pigment , and (e) a water- lower alcohol solvent .

A second aspect of the present invention adopts a constitution in which the moisturizing agent as the component (f) in the solid correcting composition of the first aspect is a swelling synthetic mica.

[0009]

Detailed constitution and action of the invention The solid correcting composition of the present invention is thixotropic, and normally maintains the required molding shape as a solid in the form of a hydrogel, but when it is applied to the paper surface at the time of correction. The contact portion is fluidized by the stress of pressing and rubbing and is applied on the paper surface, and the portion to be corrected is concealed and erased by the formed coating film. At this time,
Since the solid correction agent is an aqueous composition, if the characters etc. of the correction portion on the paper surface are written in oil-based ink, there is naturally no risk of elution of the ink. Good hiding and erasing can be done without coloring the film, and when writing (rewriting) correction characters etc. on the surface of the corrected coating film, not only oil-based writing tools but also water-based writing tools can stain the coating film. You can write beautifully and clearly without any blurring or blurring.

Further, in the solid modifier composition of the present invention,
Since it contains the moisturizing agent as the component (c), it does not easily deteriorate with time due to drying in a solid state and has a long life.
Since the solvent of the component (e) is a water-lower alcohol system, the coating film can be dried quickly, so that correction characters can be written quickly.

The above-mentioned applicability to water-based inks mainly depends on the cationic water-soluble resin of the component (a) contained as a film forming agent in the composition. That is, the cationic water-soluble resin in the solid modifier is included in the molecule.
A such as acid dyes or direct dyes sulfone group or carboxyl group of the cationic functional group is used in an aqueous ink
Since it reacts with the nonionic group to become water-insoluble, even if the water-based ink on the writing surface elutes to some extent in the initial stage of coating, the contact area with this ink will be converted into a water-resistant layer, and thus the ink on the surface of the coating film Discharging is prevented, and even when writing with a water-based writing instrument on the modified coating film, the coating film on the handwriting part is likewise converted to a water-resistant layer. No penetrating into the inside, and sharp and beautiful handwriting can be obtained.

Further, the cationic water-soluble resin has an effect of improving the dispersion of solid particles such as white pigment during the preparation of the solid correction agent, which makes the composition of the entire correction agent uniform and the coating property at the time of correction is good. A smooth and corrected coating film can be obtained, and rewriting on the surface of the coating film can be smoothly and easily performed.

Such a cationic water-soluble resin has a cationic functional group in the molecule and an anionic group.
It has the property of becoming insoluble in water by reacting with the compound
There is no particular limitation as long as it is a polyamine, and part of the side chain is 1
Typical examples include tertiary amine-, quaternary-ammonium-, or pyridinium-containing poly (meth) acrylic acid ester chlorides and acetates, such as cationic acrylic resin and cationic acrylic styrene. Commercially available resins such as resin and cationic acrylic / silicone resin can be preferably used. The amount used is about 1 to 20% by weight of the whole solid modifier composition, particularly preferably 5%.
It is preferable that the content is in the range of 15 to 15% by weight, and if it is too small, a good correction film cannot be formed, and the formability and strength as a solid correction agent are insufficient. Cause decline.

The gel-forming agent as the component (b) functions as an excipient responsible for solidifying the composition, and specific examples thereof include fatty acid soap, particularly preferably lauric acid, myristic acid, palmitic acid and stearin. 12 carbon atoms such as acid
Examples thereof include alkali metal salts and ammonium salts of about 18 aliphatic carboxylic acids. And, this blending amount is in the range of 5 to 30% by weight, and more preferably in the range of 10 to 20% by weight in the solid modifier composition, and when it is too small, it cannot exert a sufficient effect, and when it is too much, it is solid. The strength as a correction agent decreases.

The moisturizing agent as the component (c) contains a liquid phase component between the layers.
It consists of solid particles with a multi-layered structure that retains
Yes, the (e) component water-lower alcohol solvent is placed between the layers.
By incorporating it , it has a function of stabilizing the solid correction agent in a wet state . As such a moisturizer, the above-mentioned multilayer structure is used.
Although various natural minerals and synthetic products having structures can be used , swelling synthetic mica is recommended as a particularly suitable one. That is, this swelling synthetic mica is an artificial mineral generally known as dimonite, is extremely homogeneous in composition and structure, exhibits almost perfect cleavage that easily delaminates up to a thickness of μm, and its interlayer Has the property of efficiently taking in and coordinating the molecules of the liquid phase component in the composition, and exhibits high liquid retention because the taken-in liquid molecules are difficult to volatilize at room temperature. It has a high affinity for Japanese resins and is highly dispersed in the composition, forming a stable three-dimensional network structure containing a liquid phase component together with the resin component during gelation of the composition, and thus a solid correction agent. Suppresses performance deterioration over time. Further, this swelling synthetic mica functions as a thixotropic agent, accelerates this solidification when the composition is solidified by gelling, and fluidizes the correction agent due to the pressure sliding during application on the paper surface. To provide good coatability.

However, such swelling synthetic mica is classified into the intercalation method and the melting method, and commercially available products of the intercalation method are ME-100H and ME-100H manufactured by Corp Chemical. -100
Examples of commercially available products of the melting method such as M and ME-100S include DMA-350 manufactured by Topy Industries, Ltd. In addition, since the quality of natural mica varies widely depending on the production area and harvest lot, and its cleavage is incomplete due to the fact that it is not homogeneous in composition and is affected by impurities, etc., its performance and reliability as a moisturizer and thixotropic agent are low. It has been found to be significantly inferior to the swelling synthetic mica.

The suitable size of the swellable synthetic mica to be used is preferably an average particle size of about 1 to 100 μm. If it is too large, the dispersibility and thixotropy in the composition will be insufficient, and as a solid correction agent. This leads to a decrease in coating property. Further, the blending amount thereof is in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 2% by weight, in the solid modifier composition,
If the amount is too small, the effect cannot be sufficiently exerted. On the contrary, if the amount is too large, the viscosity of the correction agent composition before solidification becomes large, which makes it difficult to handle and makes it difficult to produce a solid correction agent.

As the white pigment of the component (d), titanium oxide is preferable from the viewpoint of hiding power, but a small amount of other white pigment may be used together with this titanium oxide, if necessary. The amount of this white pigment compounded is 4 in the solid modifier composition.
The amount is preferably in the range of 0 to 60% by weight, and when the amount is too small, sufficient hiding property cannot be imparted, and conversely, when the amount is too large, the coatability is deteriorated.

The water-lower alcohol solvent as the component (e) is preferably added in an amount of 15 to 30% by weight in the composition. If the amount is too small, the coatability deteriorates. This causes a decrease in the shape retention strength as a correction agent and the drying speed of the coating film. Although the lower alcohol has an effect of accelerating the drying of the coating film, if it is too much, the change with time of the coating film due to volatilization after solidification of the coating film becomes large, so that the weight ratio is 0.5 / water / water. It is preferable to use it in the range of 3 to 3, or 20% by weight or less in the composition alone. The lower alcohol may be any one having a high volatility of about 1 to 4 carbon atoms, but ethanol is most preferable.

The solid modifier composition of the present invention contains the above-mentioned components (a) to (e) as a basic composition, and together with them, if necessary, a film-forming agent other than the cationic water-soluble resin and an alignment agent. You may mix | blend various additives, such as an accelerator, a spreading auxiliary agent, a coloring agent, a viscosity modifier, and a preservative.

The orientation accelerator is a component that aids the orientation of the pigment particles and facilitates solidification when the composition is gelled and solidified, and aluminum hydroxide or the like is preferably used.
The spreadability aid is a component that improves the elongation when the solid correction agent is applied to the paper surface, and metal soaps of straight chain fatty acids such as zinc stearate and aluminum stearate are preferably used. The blending amount of such an orientation accelerator and a spreading aid is preferably in the range of about 0.1 to 5% by weight in the solid modifier composition.

As film-forming agents other than the cationic water-soluble resin, pullulan, etherified starch, chitosan, sodium alginate, locust bean gum, guar gum, methyl cellulose, water-soluble polysaccharides such as carboxymethyl cellulose, water-soluble acrylic resin, polyvinyl Natural and synthetic water-soluble resins such as alcohol and polyvinylpyrrolidone, as well as water-insoluble resins such as acrylic acid resins, methacrylic acid resins, acrylic copolymers, vinyl acetate resins, vinyl acetate copolymers, natural rubber and polyurethane resins. An example is a resin emulsion. However, if the amount of these film-forming agents used is too large, the above-mentioned characteristics based on the cationic water-soluble resin will be impaired, so it is preferable to set it to 20% by weight or less based on the cationic water-soluble resin.

In order to produce a solid modifier, first, a fatty acid and an alkaline aqueous solution such as NaOH are reacted at about 70 to 80 ° C. to form a fatty acid soap as a gel-forming agent, which contains a cationic water-soluble resin. The resin component, the lower alcohol, and water are mixed while stirring, and further, while maintaining the above temperature, solid particles such as a moisturizer and a white pigment and, if necessary, an orientation promoter, a spreading aid, and a colorant are added. The mixture may be stirred to form a dispersion liquid, and the dispersion liquid may be poured into a suitable mold container such as a lipstick-type extrusion container, cooled, and solidified. As described above, the reaction between the fatty acid and the alkali is carried out first in order to prevent the activity of the cationic water-soluble resin, that is, the reactivity with the dye component of the water-based ink, from being weakened by the alkali component. It is undesirable to use too much alkali with respect to fatty acids, eg NaO.
In H, it is preferable to set it to about 1.5 mol per 1 mol of fatty acid. If the above-mentioned lipstick-type extrusion container is used, it can be used as it is as an applicator for the solid correction agent without removing the solidified product.

[0024]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. In the following, "parts" means "parts by weight".

Example 4 2.0 parts of myristic acid and 5.0 parts of palmitic acid were added to an aqueous solution of caustic soda prepared by dissolving 2.9 parts of NaOH in 3.0 parts of water.
Parts and 5.0 parts of stearic acid were added and reacted at 70 to 80 ° C. to produce metal soap, which was used as a gel former solution. Next, 10.0 parts of a cationic water-soluble resin described below is dissolved in a mixed solvent of 9.0 parts of ethanol and 10.0 parts of water, and the obtained resin solution and the gel forming agent solution are mixed, While stirring this mixture under heating at 75 to 80 ° C .; titanium oxide (Tiawhite TCR-10, rutile type, manufactured by Tochem Brod., Ltd.) 50.0 parts Swelling synthetic mica (manufactured by Topy Industries, Ltd.) DMA-350) 9.0 parts Aluminum hydroxide (orientation promoter) 2.0 parts Zinc stearate (spreadability aid) 1.5 parts Lanolin (lanolin FE-1 manufactured by Yoshikawa Oil Co., Ltd.) 0.5 parts The mixture was added and mixed, and the obtained slurry was poured into a lipstick-type extrusion container and allowed to cool to prepare a solid correction agent. The cationic water-soluble resin used in each example is as follows.

Example 1 ... Acrybase LZ-536 (cationic methylmethacrylate-dimethylaminoacrylate copolymer) manufactured by Fujikura Chemical Co., Ltd. Example 2 ... Acrybase LZ-54 manufactured by Fujikura Chemical Co., Ltd.
7 (same as above) Example 3 ... Watersol made by Dainippon Ink and Chemicals (cationic acrylic / styrene resin) Example 4 ... Made by Kanebo (cationic acrylic / silicone resin)

Example 5 Solid correction was carried out in the same manner as in Example 1 except that the amount of the cationic water-soluble resin (Acrybase LZ-536 manufactured by Fujikura Kasei Co., Ltd.) in Example 1 was changed to 8.0 parts. An agent was prepared.

Example 6 The amount of the cationic water-soluble resin (Acrybase LZ-536 manufactured by Fujikura Kasei Co., Ltd.) used in Example 1 was adjusted to 12.0.
A solid correction agent was produced in the same manner as in Example 1 except that the parts were changed.

Example 7 A solid correction agent was prepared in the same manner as in Example 1 except that the amount of palmitic acid and the amount of stearic acid used in the gel forming agent were changed to 7.0 parts and 3.0 parts, respectively.

Example 8 A solid correction agent was prepared in the same manner as in Example 1 except that the amount of palmitic acid used in the gel forming agent was changed to 3.0 parts and that of stearic acid was changed to 7.0 parts.

Example 9 ME-10 manufactured by Coop Chemical Co. as a swelling synthetic mica
A solid correction agent was prepared in the same manner as in Example 1 except that 1.2 parts of 0 was used.

Example 10 Example 1 except that 1.5 parts of aluminum stearate was used instead of zinc stearate as a spreading aid.
A solid correction agent was prepared in the same manner as in.

Comparative Example 1 Instead of the cationic water-soluble resin, partially saponified polyvinyl alcohol (DENKA POVAL B-17 manufactured by Denki Kagaku Kogyo Co., Ltd.)
Solid correction agents were prepared in the same manner as in Examples 1 to 4 except that 10.0 parts were used.

Comparative Example 2 A solid correction agent was prepared in the same manner as in Examples 1 to 4, except that 10.0 parts of carboxymethyl cellulose (CMC Daicel manufactured by Daicel) was used instead of the cationic water-soluble resin.

Comparative Example 3 Example 1 was repeated except that 7.0 parts of pullulan (Pullulan PF20 manufactured by Hayashibara Co., Ltd.) was used instead of the cationic water-soluble resin.
A solid correction agent was prepared in the same manner as described above.

Comparative Example 4 In place of the cationic water-soluble resin, an acrylic resin emulsion (Movinyl 952 manufactured by Hoechst Gosei Co., Ltd.) 10.0
Same as Examples 1 to 4 except that parts were used,
The composition did not solidify and a solid modifier could not be made.

Comparative Example 5 Examples 1 to 4 except that no swelling synthetic mica was used.
A solid modifier composition was prepared in the same manner as in.

Comparative Example 6 A solid correction agent was prepared in the same manner as in Examples 1 to 4 except that ethanol was not used during the preparation of the resin solution and the amount of water used was changed to 19.0 parts.

With respect to the solid correctors prepared in the above Examples and Comparative Examples, the stains on the coating film when it was applied to the surface of the paper to erase the handwriting by the oil-based and water-based writing instruments, the oil-based on the coating surface after drying and the water-based writing instruments The rewriting property, the modeling property as a solid correction agent, the coating property (spreadability and adherence) on the paper surface, and the drying property of the coating film were examined, and evaluated in the following four stages. The results are shown in Table 2. In addition, in the test of coating film stain and rewriting ability, as an oil-based writing tool, Magic ink # 900 (black) manufactured by Teranishi Chemical Industry Co., Ltd., and an aqueous writing tool manufactured by Zebra Company B
e-Pen 0.5 (black) was used. (-) In Comparative Example 4 in the table indicates that measurement is impossible.

[Coating film stain] A: No coloring occurred. Δ ... Slightly colored. O: Very slight coloring was observed. X: remarkable coloring occurred.

[Rewriting ability] ⊚: Corrected characters with deep color were obtained. ○: The color was slightly faded, but the letters were corrected. Δ: The color faded and became whitish, resulting in unclear corrected characters. X: The outline was blurred due to bleeding, and the corrected characters were difficult to read.

[Modeling property] ⊚: Even if the tip of the molded product is strongly pressed against the paper surface, it does not collapse or break. ◯: No breakage or breakage of the molded product under normal application conditions. Δ: The molded product collapses or breaks with a slight pressure. X: A solid molded product cannot be obtained.

[Coatability ... Spreadability, adherence] ⊚: extremely good. △… Slightly inferior. ○: Good. ×: defective.

[Drying property] ⊙: very fast △… Slightly slow. ○ ... fast. × ... Very slow.

[0045]

[Table 1]

[0046]

According to the invention of claim 1, regardless of whether the repaired portion is a water-based or oil-based ink writing surface, it can be beautifully hidden and erased without causing coloring, and the object to be corrected is not restricted, and Both water-based and oil-based writing instruments can be used for writing correction characters and the like on the modified coating film without any trouble, and it can be applied very smoothly to the paper surface and can be applied very smoothly. It is possible to provide a solid correction agent composition having a very high practicability, in which the coating film is quickly dried, and correction characters and the like can be rapidly written, and the solid correction agent has excellent moldability and has a long life. .

According to the second aspect of the present invention, there is an advantage that the above solid correction composition can be provided with a particularly long-term change and a long life.

Claims (2)

[Claims] 1. The following (a) to (e) as essential components; (a) Anionic group having a cationic functional group in the molecule.
Water- soluble resin having a property of becoming water-insoluble by reacting with a compound having (b) a gel-forming agent, (c) having a multi-layer structure, and retaining a liquid phase component between the layers.
A solid modifier composition comprising a moisturizing agent composed of solid particles having properties , (d) a white pigment, and (e) a water-lower alcohol solvent. 2. The solid modifier composition according to claim 1, wherein the moisturizing agent as the component (c) is a swelling synthetic mica.