JP2007321057A - Correction fluid and applicator using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a correction fluid slightly thickening with time and to provide an applicator using the same. <P>SOLUTION: The correction fluid comprises a non-polar organic solvent, titanium oxide and a resin prepared by carrying out polymerization using one or two or more kinds selected from acrylic acid, methacrylic acid, an acrylic ester, a methacrylic ester and a derivative thereof and soluble in the non-polar organic solvent. The solubility parameter of the non-polar organic solvent is ≥8.2 to <8.5. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a correction liquid containing at least an organic solvent as a liquid medium, titanium oxide as a concealing material, and a resin, and an applicator using the correction liquid.

In general, the correction liquid is a composition containing a solvent, a resin, a masking material, etc., and water is used as a solvent, and a water-soluble acrylic resin (ammonium salt, amine salt, sodium salt, etc.), (meth) acrylic ester resin Emulsions, styrene-butadiene copolymer resin emulsions, ethylene-vinyl acetate resin emulsions, etc., which are called aqueous correction fluids mainly used to hide oily handwriting that is difficult to dissolve in water, Using a non-polar organic solvent, and using a resin polymerized with one or more selected from acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid and derivatives thereof, either oily or aqueous It is known that it is called a dual-use correction liquid that hides the ink handwriting.
Resins polymerized using one or more selected from acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, and derivatives thereof used in this dual-use correction liquid, The film-forming property is better than that of the resin, and it is often used as a resin suitable for a correction liquid that needs to be written on the surface of the coating film.

Titanium oxide, which has a high concealing effect, is often used as the concealing material. However, since titanium oxide is a substance with a high specific gravity, titanium oxide settles when left standing for a long time, and the resin solution is mainly used in the applicator. It will be divided into two layers of a separation liquid as a component and a sediment mainly composed of titanium oxide. In such a state where the layers are separated, the supernatant with less concealment material is discharged or the titanium oxide sedimentation layer becomes clogged and cannot be applied, so a metal ball as a stirring member in the applicator, etc. In use, the applicator was shaken to re-stir the correction solution.
As the operation of shaking such an applicator is unnecessary, a correction liquid and a high-pressure gas are sealed in the applicator, the inside of the applicator is pressurized during use by a so-called pump mechanism, or a bag containing the correction liquid is placed. An applicator that supports liquid discharge by a method such as pressing with a spring, a so-called pressure applicator, has been developed, and a high-viscosity correction liquid that suppresses settling of titanium oxide is forcibly discharged and applied by pressure. Things are also known.
However, the high-viscosity correction solution used for the pressure applicator can increase the viscosity of the resin solution with a so-called thickener or the like, or can suppress the precipitation of titanium oxide to some extent by increasing the amount of titanium oxide, Thickeners tend to increase in viscosity over time. When the amount of titanium oxide is increased, the distance between titanium oxide particles is shortened, and aggregation of titanium oxide particles is promoted. Tend to thicken. When such a correction liquid having a large viscosity with time is left for a long period of time, there is a problem that the ink discharge amount is reduced, the handwriting is rubbed and the concealability is impaired.

Patent Document 1 discloses N-lauroyl-glutamic acid-α, γ-di-n-butyramide and a fatty acid or an alcohol derivative of fatty acid, and / or N-lauroyl-L-glutamic acid di (cholesteryl behenyl octyl) as a gelling agent. Dodecyl), N-lauroyl-L-glutamic acid (cholesteryl octyldodecyl), N-lauroyl-L-glutamic acid di (phytosteryl 2-octyldodecyl) It is disclosed that there is little thickening.
Patent Document 2 contains 30 to 60% by weight of a white pigment having a particle surface coated with an organic polysiloxane, 25 to 60% by weight of an organic solvent, and 3 to 20% by weight of a binder soluble in the solvent. It is disclosed that by using a correction liquid characterized by the above, aggregation of the pigment is suppressed and the dispersion state is stabilized.
Patent Document 3 discloses a highly concealable liquid composition comprising at least a concealing agent, a cyclopentane organic solvent, and an acrylic resin.
JP 2004-143292 A JP 63-256666 A Japanese Patent No. 2921011

However, even when the gelling agent disclosed in the above-mentioned Patent Document 1 is used, the action of the gelling agent gradually progresses over time. At present, solution components that cannot be captured by the network structure are separated or sufficient results are not obtained.
Further, when the surface treatment is applied to the white pigment as described in Patent Document 2, the effect of the resin used is poor and the effect of dispersion by the resin is lacking. Thus, aggregation could not be prevented.
In addition, cyclopentane described in Patent Document 3 has little thickening with time and does not rub the handwriting. However, as described above, the solvent tends to volatilize through the coating destination and the container during storage of the applicator, so-called processing is performed. When high-pressure gas was sealed like a pressure correction liquid, there was a problem that volatilization was further promoted.

That is, the present invention was polymerized using a nonpolar organic solvent, titanium oxide, acrylic acid, methacrylic acid, an ester of acrylic acid, an ester of methacrylic acid, and one or more selected from these derivatives. The non-polar organic solvent comprises a resin soluble in the non-polar organic solvent, and the non-polar organic solvent includes at least the following groups A, B, and C, and the solubility parameter of the solvent calculated from these solvents: The gist is a correction fluid having a value of 8.0 or more and less than 8.4.
Group A: Organic solvent C that is a nonpolar organic solvent and has a solubility parameter of less than 7.6 Group B: Organic solvent C that is a nonpolar organic solvent and has a solubility parameter of 7.7 or more and 7.9 or less: Organic solvent that is a non-polar organic solvent and has a solubility parameter of 8.40 or more

The non-polar organic solvent of Group C is a solvent having a boiling point exceeding 130 ° C except for toluene designated as a deleterious substance. Therefore, in order to obtain good drying properties, it is necessary to use a low boiling point solvent of 70 ° C or lower. is there. Therefore, a non-polar solvent of Group A containing a low boiling point solvent at 70 ° C. or lower is used in combination.
Here, it is possible to set the solubility parameter to 8.0 or more and less than 8.4 by using a non-polar organic solvent of group A and a non-polar organic solvent of group C. Problems remain when used. In other words, it is impossible to avoid the minute gaps at the application destination of the correction tool, the volatilization of the minute solvent permeating from the material of the application tool, and when a high-pressure gas is sealed like a so-called pressure application tool, The volatilization of the solvent is further promoted. This volatilization shortens the distance of the titanium oxide particles and increases the viscosity, and the solubility parameter may change during storage.
Since the non-polar organic solvent of group B has a boiling point of 70 ° C. or higher and the solubility parameter is intermediate between the groups A and C, a non-polar organic solvent of 70 ° C. or higher is used in combination with group A. Compared to the case, even when the solvent composition changes during storage as an applicator, the change in solubility can be reduced.
As the titanium oxide used in the present invention, silica-treated titanium oxide is preferable. This is because the polar group portion of the resin and silica have a good affinity, and the adsorptivity of the resin is stronger than other titanium oxides. Therefore, when adjusting the solubility of the resin, it is possible to cover a decrease in the adsorptivity of the resin with respect to titanium oxide, and to further reduce the viscosity increase with time.

The nonpolar organic solvent of the correction fluid is a group A having a solubility parameter of less than 7.6, a group B having a solubility parameter of 7.7 to 7.9, and a group C having a solubility parameter of 8.4 or more. It is a mixed solvent consisting of As the non-polar organic solvent of Group A, 2,2,5-trimethylhexane (solubility parameter δ: 6.5), 4-methylheptane (δ: 7.4), 2-methylheptane (δ: 7.3) ), 3-methylheptane (δ: 7.4), 2,2-dimethylhexane (δ: 7.1), 2,3-dimethylhexane (δ: 7.3), 2,4-dimethylhexane (δ 7.2), 2,5-dimethylhexane (δ: 7.2), 3,3-dimethylhexane (δ: 7.2), 3,4-dimethylhexane (δ: 7.4), 3- Ethylhexane (δ: 7.5), 2,2,3-trimethylpentane (δ: 7.2), 2,2,4-trimethylpentane (δ: 6.9), 2,3,3-trimethylpentane (Δ: 7.3), 2,3,4-trimethylpentane (δ: 7.3), 2-methyl-3-ethylpe Tan (δ: 7.2), 3-methyl-3-ethylpentane (δ: 7.2), 2,2,5-trimethylhexane (δ: 6, 5), 2,3-dimethylheptane (δ: 7.3), 2-methyloctane (δ: 7.5), hexane (δ: 7.3), 2-methylpentane (δ: 7.0), 3-methylpentane (δ: 7.1), 2,2-dimethylbutane (δ: 6.7), 2,3-dimethylbutane (δ: 7.0), heptane (δ: 7.5), 2-methylhexane (δ: 7.2), 3 -Methylhexane (δ: 7.3), 2,2-dimethylhexane (δ: 6.9), 2,3-dimethylpentane (δ: 7.2), 2,4-dimethylpentane (δ: 7. 0), 3,3-dimethylpentane (δ: 7.1), 3-ethylpentane (δ: 7.2), 2,2,3-trimethylbutane (δ: 6. The non-polar organic solvent of group B includes decane (δ: 7.7), nonane (δ: 7.7), methylcyclopentane (δ: 7.9), methylcyclohexane (δ: 7). 9), and the non-polar organic solvent of group C, ethylcyclohexane (δ: 8.4), o-xylene (δ: 8.9), m-xylene (δ: 8.9), p-xylene ( δ: 8.8) and the like.
The amount used is preferably 30 to 95% by weight based on the total amount of the correction fluid.

The solubility parameter δ is a value indicating the solubility of the solvent and the binder and the solubility of the solvent and the handwriting. The following three methods are generally known as methods for obtaining the solubility parameter δ.
(1) A method in which a solubility parameter is related to a physical property of an article and defined using a quantitative expression. The calculation formula is shown in the following formula 1.
(2) A method of calculating from the chemical structure.
(3) A method in which the dissolving power of an article having an unknown solubility parameter δ is systematically compared with the dissolving power of an article having a known solubility parameter δ.
As the solubility parameter δ of the nonpolar organic solvent of the present invention, a value obtained by the method (1) among the above three methods is adopted. This is because the value obtained by the method (1) in the nonpolar organic solvent accurately represents the actual solubility as compared with other methods.

  Three or more non-polar organic solvents can be used in combination, but the solubility parameter in this case is calculated by proportionally calculating the solubility parameter of the solvent to be used in combination with the mixing ratio and rounding up to the first decimal place. To do.

  Resin soluble in the non-polar organic solvent polymerized by using one or more selected from acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid and derivatives thereof, dispersion and correction of pigments This will fix the liquid on the paper surface. For example, usable acrylic monomers include methyl acrylate (solubility parameter δ: 9.7), ethyl acrylate (solubility parameter δ: 9.2), and normal butyl acrylate (solubility parameter δ: 8.7) and methacrylic acid esters include methyl methacrylate (solubility parameter δ: 9.3), ethyl methacrylate (solubility parameter δ: 9.0), n-butyl methacrylate (solubility parameter δ: 8.7). ), 2-ethylhexyl methacrylate (solubility parameter δ: 8.3), lauryl methacrylate (solubility parameter δ: 8.3), stearyl methacrylate (solubility parameter δ: 8.3), and the like. In addition to these monomers, a copolymerizable monomer such as styrene (solubility parameter δ: 9.4) can also be contained. In consideration of fixing property and coating property, the amount used is preferably 1 to 20% by weight based on the whole correction liquid.

  Articles having a solubility parameter δ of the solubility parameter of a resin polymerized using one or more selected from acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid and derivatives thereof Is determined by a systematic comparison of the dissolving power of an article having an unknown solubility parameter δ with the dissolving power of. That is, 40% by weight of acrylic acid, methacrylic acid, an ester of acrylic acid, an ester of methacrylic acid, and a resin polymerized using one or more selected from these derivatives are added to the nonpolar organic solvent group under certain conditions. The solubility parameter of the solvent that is stirred and dissolves in the shortest time is taken as the solubility parameter of the resin.

  As pigments used in the correction fluid, TITONESR-1, 650, R62N, R3L, R7E (above, manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-310, KR-380, 480 (above, Titanium Industry Co., Ltd.), Taipure R-900, R-602, R-960, R-931 (above, manufactured by DuPont Japan, Limited), TITANIX JR301, JR805, JR602, JR701, Examples thereof include titanium oxide such as JR800 (manufactured by Teika Co., Ltd.). The amount used is preferably 30 to 80% by weight based on the whole correction liquid.

  In addition to the above components, extender pigments such as silica and calcium carbonate may be used in combination in order 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.

In addition, when it is necessary to make the applicator into a refill form or to improve the ink use-up property, a backflow preventer can be used. The backflow preventer moves following the movement of the correction liquid interface accompanying the consumption of the correction liquid. The backflow prevention body is made of a material that does not easily change its shape due to the correction liquid. There are a solid backflow prevention body and a liquid backflow prevention body as the backflow prevention body, and they are selected depending on the shape of the applicator and the required function. The solid backflow preventer can physically scrape off the correction liquid adhering to the inner wall of the container when the correction liquid interface moves as the correction liquid is consumed. . On the other hand, the liquid backflow preventive body has a feature of following even when the cross-sectional shape and diameter of the container are partially different, or even when the inner wall is uneven. As the material of the solid movable stopper, vulcanized rubber such as nitrile rubber, hydrogenated nitrile rubber, and fluorine rubber, polyester-based, nitrile-based, polyamide-based, and fluorine-based thermoplastic elastomers are used. For the base material of the liquid backflow prevention body, a solvent that is not compatible with the correction liquid or is difficult to be compatible with the correction liquid is used. Specifically, in addition to water, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, glycerin monoacetate, diethylene glycol, tetraethylene glycol, trimethylolethane, trimethylolpropane, 1,3-butanediol, , 4-butanediol, 1,4-butenediol, polypropylene glycol, polyethylene glycol and the like can be used. These can be used alone or in combination.
When using a pressurizing applicator, a correction fluid and high-pressure gas are sealed in the applicator, or a pump mechanism is disposed at the rear end. In addition, if the above-described backflow preventer is disposed at the interface between the correction liquid and the high-pressure gas, the ink use-up property can be improved. Since the backflow prevention body in this case requires a function of suppressing the permeation of gas, a solid and liquid backflow prevention body are used in combination as necessary.

In addition, when the backflow prevention body changes its physical properties due to drying and moisture absorption, it is necessary to use a backflow prevention body having a function of blocking outside air. In this case, a solvent that does not dissolve the backflow preventer used together is used. Specifically, mobile SHF21 (α kinematic viscosity at 40 ° C .: 0.52 m ² / s), 41 (kinematic viscosity at 40 ° C .: 1.75 m ² / s), 61 (at 40 ° C.) Kinematic viscosity 2.88 m ² / s), 82 (kinematic viscosity at 40 ° C. 4.76 m ² / s), 401 (kinematic viscosity at 40 ° C. 42 m ² / s), 1003 (at 40 ° C.) Kinematic viscosity 137.4 m ² / s) (manufactured by Mobil Chemical Products International Inc.), polybutene LV-7 (kinematic viscosity 1.1 m ² / s at 40 ° C.), LV-10 (kinematic at 40 ° C. Viscosity 1.9 m ² / s), LV-25 (kinematic viscosity at 40 ° C. 5.24 m ² / s), LV-50 (kinematic viscosity at 40 ° C. 11 m ² / s), LV-100 (at 40 ° C. kinematic viscosity of 20.5m ² / s), kinematic viscosity at HV-15 (40 ℃ Kinematic viscosity at 65.5m ² / s), kinematic viscosity 230 m ² / s at HV-35 (40 ℃), kinematic viscosity 345m ² / s at HV-50 (40 ℃), HV-100 (40 ℃ 950 m ² / s), HV-300 (kinematic viscosity at 40 ° C. 2600 m ² / s), HV-1900 (kinematic viscosity at 40 ° C. 16000 m ² / s), HV-3000 (kinematic viscosity at 40 ° C. 32000 m ² / S) (manufactured by Nippon Oil Co., Ltd.), Lucant HC-10 made of ethylene-α-olefin (kinematic viscosity at 40 ° C. 6 m ² / s), HC-20 (kinematic viscosity at 40 ° C. 15.5 m) ² / s), a kinematic viscosity ^38m 2 / s at HC-40 (40 ℃), kinematic viscosity 130m ² / s at HC-100 (40 ℃), kinematic viscosity at ^{HC-150 (40 ℃ 220m 2} / s), HC-600 (kinematic viscosity at 40 ° C. 985) m ² / s), HC-2000 (kinematic viscosity at 40 ° C. 3750 m ² / s) (Mitsui Petrochemical Co., Ltd.), liquid paraffin, silicon oil, etc., low polarity non-volatile or hardly volatile These solvents can be used, and these can be used alone or in combination.

  When a low-polarity solvent is used as the base material of the backflow preventive body as a viscosity modifier for the backflow preventive body composition, Aerosil R972, R974, 200 (made by Nippon Aerosil Co., Ltd.), fatty acid, Disparone A670-20M and 6900-20X (made by Enomoto Kasei Co., Ltd.) made of amide can be used. When a highly polar solvent is used for the base material, guar gum, hydroxypropylated guar gum, carboxymethyl Hydroxypropylated guar gum, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, welan gum, rhamzan gum, gellan gum, alginic acid, sodium alginate, ammonium alginate, potassium alginate, propylene glycol alginate Water-soluble polysaccharides such as tellurium, locust bean gum, tamarind gum, gum arabic, tragacanth gum, caraya gum, carrageenan, succinoglucan, polyacrylic acid, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, N-vinylacetamide co-crosslinked product, etc. These synthetic polymers, viscosity minerals such as smectite, and the like can be added, and these can be used alone or in admixture of two or more.

  In addition, a surfactant can be used in the backflow preventive composition using a high-polar solvent as a base material in order to further improve the usability of the ink, and it can be used as a nonionic, anionic, or cationic ion. Surfactants such as fluorine-based and fluorine-based surfactants can be used. Specific examples of nonionic surfactants include polyoxyethylene such as polyoxyethylene monostearate (5 to 15, added number of moles of oxyethylene, hereinafter the same) glyceryl, polyoxyethylene monooleate (5 to 15), etc. Glycerin fatty acid ester, hexaglyceryl monolaurate, hexaglyceryl monomyristate, hexaglyceryl monostearate, monooleic acid, decaglyceryl monolaurate, decaglyceryl monomyristate, decaglyceryl monostearate, decaglyceryl monooleate, monolinol Polyglycerin fatty acid ester such as decaglyceryl acid, decaglyceryl monoisostearate, decaglyceryl diisostearate, decaglyceryl trioleate, monococonut oil fatty acid polyoxyethylene (20 Polyoxyethylene such as sorbitan, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (2) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan monoisostearate Sorbitan fatty acid ester, polyoxyethylene monolaurate (6) sorbite, polyoxyethylene sorbite ester such as polyoxyethylene tetrastearate (30-60) sorbit, polyoxyethylene (20-60) castor oil, polyoxyethylene (20-100) Polyoxyethylene castor oil / hardened castor oil such as hydrogenated castor oil, polyoxyethylene (5-30) phytosterol, polyoxyethylene (25) phytostanol, poly Polyoxyethylene sterols such as xylethylene (30) cholestanol, hydrogenated sterols polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene (4 -25) Lauryl ether, polyoxyethylene (2-40) cetyl ether, polyoxyethylene (2-20) stearyl ether, polyoxyethylene (10-50) oleyl ether, polyoxyethylene (10-30) behenyl ether, etc. Polyoxyethylene alkyl ether, polyoxyethylene (7-20) nonylphenyl ether, polyoxyethylene (10-30) octylphenyl ether Polyoxyethylene alkyl phenyl ethers such as ether, polyoxyethylene (5-15) stearylamine, polyoxyethylene (5-15) oleylamine, polyoxyethylene (8) stearylpropylenediamine, polyoxyethylene (4-15) stearin Acid amide, polyoxyethylene alkylamine / fatty acid amide such as polyoxyethylene (5) oleic acid amide, polyoxyethylene lanolin, polyoxyethylene (5-40) lanolin alcohol, N-propyl-N- (2-hydroxyethyl) ) Perfluorooctanesulfonamide, polyoxyethylene higher fatty acid alcohol ether, acetylene glycol (Surfinol 465, 485, manufactured by Shin-Etsu Chemical Co., Ltd.), polyoxyethylene (3-20) -N-propyl Fluorine-based surfactants such as Le perfluorooctane sulfonamides. Specific examples of anionic surfactants include sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, hydrogenated coconut oil fatty acid sodium glyceryl sulfate, etc. Polyoxyethylene such as sodium oxyethylene (2-4) lauryl ether sulfate, polyoxyethylene (2-4) lauryl ether sulfate triethanolamine, polyoxyethylene (2) ammonium lauryl ether sulfate, polyoxyethylene nonylphenyl ether sodium sulfate Alkyl ether sulfate, cocoyl sarcosine sodium, lauroyl sarcosine sodium, lauroyl sarcosine potassium, myristoyl sarcosine sodium, N-acyl amino acid salts such as sodium lumitoyl sarcosine, sodium lauroylmethylalanine, alkyl ether carboxylates such as sodium polyoxyethylene (3-6) tridecyl ether acetate, alkyl phosphates such as sodium lauryl phosphate, etc. N-acyl taurine salts such as polyoxyethylene alkyl ether salts, sodium N-cocoylmethyl taurate, sodium N-lauroylmethyl taurine, sodium N-myristoylmethyl taurine, N-palmitoylmethyl taurine sodium, sodium N-stearolylmethyl taurine Sulfonates such as dioctyl sodium sulfosuccinate, sodium lauryl sulfoacetate, sodium tetradecene sulfonate, lauryltrimethylammonium chloride, cetyl chloride Methylammonium, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyltrimethylammonium chloride, alkylammonium salts, alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, perfluorooctanesulfonic acid, potassium perfluorooctanesulfonate, perfluorooctanesulfone Lithium acid, ammonium perfluorooctanesulfonate, N-propyl-N-perfluorooctylsulfonylglycine potassium salt, bis (2- (N-propylperfluorooctylsulfonylamino) ethyl) ammonium phosphate, perfluorocaprylic acid, ammonium perfluorooctanoate Fluorine surfactant such as sodium naphthalene sulfonate And sodium dialkylsulfosuccinate, sodium alkyldiphenyl ether disulfonate, potassium alkyl phosphate, and the like. Specific examples of cationic surfactants include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, alkyl ammonium salts such as distearyl dimethyl ammonium chloride, N- (3- (perfluorooctane) And fluorinated surfactants such as sulfonamido) propyl) -N, N, N, -trimethylammonium iodide. Specific examples of amphoteric surfactants include betaine-type amphoteric surfactants such as lauryl betaine, stearyl betaine, coconut oil fatty acid aminopropyldimethylaminoacetic acid betaine, and N-coconut oil fatty acid acyl-N-carboxylmethyl-N-hydroxyethyl. Examples include imidazoline-type amphoteric surfactants such as ethylenediamine sodium and N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine / sodium lauryl sulfate.

  In addition, when water is used as the base material, an appropriate amount of an antiseptic and fungicide such as sodium dehydroacetate, 1,2-benzothiazolin-3-one or sodium benzoate should be added to prevent mold formation in the backflow preventive composition. Can do. In addition, in the case of easily evaporating materials such as water, in order to suppress evaporation, non-volatile and / or hardly soluble non-volatile and / or hardly volatile organic solvents in this base material, or those whose viscosity is adjusted, rubber A molded article such as a synthetic rubber, elastomer, or plastic having elasticity can be used as an anti-drying body at the interface of the backflow prevention body composition. In the case where the anti-drying body is a liquid composition, polybutene, α-olefin, ethylene α-olefin, liquid paraffin, etc. can be used as the organic solvent, and these can be used alone or in combination of two or more. , Aerosil R972, R974 (manufactured by Nippon Aerosil Co., Ltd.), etc., hydrogenated castor oil-based ones such as Disparon 305 (manufactured by Enomoto Kasei Co., Ltd.) Cellulose-based materials, metal soaps, bentonites and the like can be used alone or in admixture of two or more. Moreover, the anti-drying body by a solid molding and the anti-drying body by a liquid composition can also be used together.

1, 2, and 3 are applicators that contain correction fluid.
The correction liquid 1 is accommodated in a free state inside a shaft 2 serving as a coating liquid storage section, and a front shaft 3 is connected to the tip of the shaft 2. Further, a ball holder 5 on which a ball 4 is rotatably held is connected to the tip of the front shaft 3. The ball 4 is urged forward by a coil spring 6 and functions as a valve that controls the discharge of the correction liquid 1 by liquid-tightly contacting the inner edge of the ball holder 5. Backflow prevention bodies 8 and 9 that move following the movement of the interface of the correction fluid 1 accompanying the consumption of the correction fluid 1 are arranged behind the interface of the correction fluid 1 in the shaft 2. Here, 8 represents a solid backflow prevention body, 9 represents a liquid backflow prevention body, FIG. 1 shows an example using only a solid backflow prevention body, and FIGS. 2 and 3 show examples using both a solid backflow prevention body and a liquid backflow prevention body. It is. The rear end opening of the shaft 2 is sealed with a tail plug 8, and the space between the tail plug 10 and the backflow preventer 8 or 9 is filled with compressed nitrogen 7. The pressure by the compressed nitrogen 7 supports the discharge by pushing the correction liquid 1 from behind via the backflow preventer 8 or 9.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited only to an Example.

An example of a combination of raw materials in the production of acrylic resin is shown in Table 1.

Production conditions The materials shown in Table 1 above were charged into a 500 ml reaction vessel equipped with a stirrer, nitrogen gas inlet, thermometer, and reflux condenser, and polymerized while stirring at 80 ° C. for 7 hours in a nitrogen gas stream. A polymer component having a viscosity was obtained.

Example 1
Kronos KR-380 (manufactured by Titanium Industry Co., Ltd., alumina-silica treated titanium oxide)
50.0 parts by weight Resin 1 26.0 parts by weight Methylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd., solvent) 12.2 parts by weight cyclopentane (manufactured by Maruzen Petrochemical Co., Ltd., solvent) 2.1 parts by weight 2- Methylpentane (reagent, solvent) 2.1 parts by weight ethylcyclohexane (manufactured by Maruzen Petrochemical Co., Ltd., solvent) 4.6 parts by weight Homogenol L-18 (Kao Corporation, dispersant) 1.2 parts by weight Solvent, Put the dispersant in the same container, stir with an impeller mixer, disperse the preliminary dispersion with titanium oxide and resin added for 24 hours with a ball mill, and add the following solvent while stirring the dispersion with an impeller mixer. Correction fluid 1 was obtained.
Methylcyclohexane (as described above) 1.4 parts by weight Cyclopentane (as described above) 0.2 parts by weight 2-Methylpentane (as described above) 0.2 parts by weight

Solid backflow preventer 1
A black nitrile rubber having a hardness of 64 ° (Duroe hardness type A) was injection molded into a bottomed cylindrical shape as shown in FIG. 1 to obtain a solid backflow prevention body.

  After the correction liquid 1 was allowed to stand at room temperature for 7 days after dispersion, the correction liquid 1 and the solid backflow prevention body 1 were arranged as shown in FIG.

Example 2
TITON R62N (manufactured by Sakai Chemical Industry Co., Ltd., alumina-silica treated titanium oxide)
50.0 parts by weight Resin 2 26.0 parts by weight Methylcyclohexane (previously described) 11.7 parts by weight cyclopentane (previously described) 2.1 parts by weight ethylcyclohexane (previously described) 6.8 parts by weight homogenol L-18 (previously described) 1 .2 parts by weight Put a solvent and a dispersant in the same container, stir with an impeller mixer, disperse the preliminary dispersion with titanium oxide and resin for 24 hours with a ball mill, and stir the dispersion with an impeller mixer. Correction fluid 2 was obtained by adding the following solvent.
Methylcyclohexane (described above) 1.3 parts by weight Cyclopentane (described above) 0.2 parts by weight 2-Methylpentane (described above) 0.7 parts by weight

  After the correction liquid 2 was allowed to stand at room temperature for 7 days after dispersion, the correction liquid 2 and the solid backflow preventer 1 were arranged as shown in FIG.

Example 3
TITONE R62N (previously described) 50.0 parts by weight Resin 3 30.0 parts by weight cyclopentane (previously described) 5.0 parts by weight ethylcyclohexane (previously described) 13.8 parts by weight homogenol L-18 (previously described) 1.2 parts by weight above The components were dispersed in a ball mill for 24 hours to obtain Correction Solution 3.

Liquid backflow preventer 1
Glycerin 97.0 parts by weight NORVEMER EC-1 (manufactured by Noveon) 3.0 parts by weight The above components were stirred for 1 minute and then allowed to stand at 50 ° C. for 24 hours to obtain a liquid backflow preventer 1.

  After the correction liquid 3 was allowed to stand at room temperature for 10 days after dispersion, the correction liquid 3, the solid backflow prevention body 1 and the liquid backflow prevention body 1 were arranged as shown in FIG.

Example 4
TITANIX JR301 (manufactured by Teika Co., Ltd., alumina-treated titanium oxide)
50.0 parts by weight Resin 2 20.0 parts by weight Methylcyclohexane (previously described) 4.3 parts by weight ethylcyclohexane (previously described) 24.5 parts by weight Homogenol L-18 (previously described) 1.2 parts by weight Correction liquid 4 was obtained by dispersion treatment for 24 hours.

  After the correction liquid 4 was allowed to stand at room temperature for 10 days after dispersion, the correction liquid 4, the solid backflow prevention body 1 and the liquid backflow prevention body 1 were arranged as shown in FIG.

(Comparative Example 1)
In Example 2, a correction liquid was obtained in the same manner as in Example 1 except that ethylcyclohexane was changed to methylcyclohexane.

(Comparative Example 2)
A correction fluid was obtained in the same manner as in Example 2 except that ethylcyclohexane was changed to octane (reagent) in Example 2.

(Comparative Example 3)
A correction fluid was obtained in the same manner as in Example 3 except that ethylcyclohexane was changed to heptane (reagent) in Example 3.

  About the correction liquid obtained by the above Examples 1-4 and Comparative Examples 1-3, the confirmation test was done about the viscosity increase in a storage state.

Viscosity over time The viscosity of the correction fluid on the day after the trial production and the viscosity after one month at room temperature using a CVO (Rheometer manufactured by Bohlin Instruments Co.) is 0.05 (1 / sec). And measured by the difference in viscosity.

The longitudinal cross-sectional view which shows an example. The longitudinal cross-sectional view which shows an example. The longitudinal cross-sectional view which shows an example.

Explanation of symbols

1 correction fluid 2 shaft 3 front shaft 4 ball 5 ball holder 6 coil spring 8 backflow prevention body 9 backflow prevention body 10 tail plug

Claims (5)

A nonpolar organic solvent, titanium oxide, and acrylic acid, methacrylic acid, an ester of acrylic acid, an ester of methacrylic acid and a derivative thereof, polymerized using one or more kinds, the nonpolar organic solvent The non-polar organic solvent comprises at least the following group A, group B, and group C, and the solubility parameter value of the solvent calculated from these solvents is 8.0 or more. Correction fluid that is less than 8.4.
Group A: Organic solvent C that is a nonpolar organic solvent and has a solubility parameter of less than 7.6 Group B: Organic solvent C that is a nonpolar organic solvent and has a solubility parameter of 7.7 or more and 7.9 or less: Organic solvent that is a non-polar organic solvent and has a solubility parameter of 8.40 or more The correction liquid according to claim 1, wherein a difference in solubility parameter between the nonpolar organic solvent and the resin is 0.4 or more and 2.0 or less. The correction liquid according to claim 1 or 2, wherein the titanium oxide is silica-treated. The nonpolar organic solvent of Group A is 2-methylpentane, the nonpolar organic solvent of Group B is methylcyclohexane, and the nonpolar organic solvent of Group C is ethylcyclohexane. The correction fluid according to claim 3. An applicator, which is a mechanism that incorporates the correction liquid according to any one of claims 1 to 4 and that assists liquid discharge by pressurization.

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