JP2007291377A - Retouching fluid and coating tool using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a retouching fluid starting an agitator body to move from a settled state of titanium oxide after the lapse of time in a stationary state with a small number of times of shaking, redispersing the titanium oxide with a small number times of shaking after starting the agitator body to move and returning the titanium oxide to the original uniform dispersed state. <P>SOLUTION: The retouching fluid comprises the titanium oxide, a nonpolar volatile organic solvent and a resin soluble in the nonpolar volatile organic solvent. In the retouching fluid, the complex modulus of elasticity at 1 Hz frequency under a shear stress within the range of &ge;0.1 to &le;1.0 Pa is &ge;0.1 to &le;10 Pa. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention conceals handwriting and printed characters and images by forming a coating film with a concealing power on the handwriting and printed characters and images formed on the paper surface, and corrects them on the coating film. This correction liquid can be rewritten and relates to a correction liquid containing at least titanium oxide as a masking agent.

In general, by forming a white paint film that does not transmit visible light on the handwriting or printed characters and images formed on the paper, the handwriting and the print are concealed, and the correction can be rewritten on the paint film. As a liquid, a liquid in which titanium oxide, which is a white pigment having a high concealing effect, is dispersed in a liquid medium is known.
Titanium oxide, which imparts concealability to the correction fluid, is known to settle because it has a higher specific gravity than the liquid medium, making it difficult to maintain a uniform dispersion state. In order to use titanium oxide dispersed in a liquid medium, a stirrer such as a metal sphere is accommodated in the container together with ink, and the container is shaken before use to move the stirrer. There is known a method of stirring and using titanium oxide again in a uniform dispersion state.
In addition, a method for adjusting the fluid physical properties of the correction liquid to prevent the titanium oxide from settling is also known. For example, Patent Document 1 discloses a correction fluid having a viscosity at a shear rate of 20 ° C. and 1.9 sec ⁻¹ of 1000 mPa · s or more, and Patent Document 2 discloses a correction fluid having a viscosity of 100 cps or more. Each listed
JP 2000-177295 A JP 2000-319442 A

In the above-mentioned patent document, the correction liquid is made to have a high viscosity to suppress the fluidity and the titanium oxide is prevented from settling. However, since the liquid is high in viscosity, even after the settling, the container is shaken uniformly. It was hard to return.
An object of the present invention is to provide a correction liquid that easily returns from a state in which titanium oxide has settled to a dispersed state.

  That is, the present invention contains at least titanium oxide, a nonpolar volatile organic solvent, and a resin that is soluble in the nonpolar volatile organic solvent, and has an amplitude of 0.1 Pa to 1.0 Pa in shear stress ( The gist is a correction fluid having a complex elastic modulus with respect to 25 ° C. and a frequency of 1 Hz of 0.1 Pa or more and 10 Pa or less.

Since the titanium oxide particles and the resin or dispersant form an aggregate, resistance is generated when the distance between the titanium oxide particles is about to change, and the magnitude of the resistance is detected as a complex elastic modulus. Can do. That is, the particles of titanium oxide are aggregated and settled by using a correction liquid having a complex elastic modulus of 0.1 Pa to 10 Pa with respect to a shear stress (25 ° C., frequency 1 Hz) having an amplitude of 0.1 Pa to 1.0 Pa. It is presumed that, in addition to resistance, the titanium oxide particles are easily separated and redispersed even in a settled state.
For example, if the complex elastic modulus is too large, the resistance for separating the titanium oxide particles also increases, so it is considered that redispersion is difficult. If the complex elastic modulus is too small, the steric hindrance does not work and the strong bonds are formed. It is thought that it becomes easy to form a particle aggregate.

  In addition, according to the Fourier law, which is a general law of substance movement, a shearing force, which is a resistance force, is applied to the correction fluid flowing through a gap having an appropriate width and length, so that the complex elastic modulus is 0.1 Pa. In the correction liquid of 10 Pa or less, the maximum inscribed circle diameter is 0.025 mm or more and 0.075 mm or less and the length is 0.5 mm or more and 1.0 mm or less as a liquid passage for discharging the correction liquid from the application destination. After passing through a certain shear passage, the titanium oxide agglomerates that could not be broken by re-dispersion with a stirrer are broken by shear, and the re-dispersion assisting effect is exerted. It is assumed that it will be obtained.

  The complex elastic modulus of fluid such as correction fluid, ink, paint, etc. is a value obtained by dividing the amplitude of strain with respect to the amplitude of shear stress given as a sine wave to the sample by the amplitude of the shear stress. Measure the amplitude of strain (25 ° C) when the shear stress is applied with a sine wave with a frequency of 1 Hz and the amplitude changed from 0.1 to 1.0 Pa, and divide by the amplitude of the corresponding shear stress. It is a value calculated by

The resistance of the three-dimensional structure of the resin and dispersant to deformation is considered to be one of the causes of the complex elastic modulus of the correction fluid, so the molecular structure of the resin and dispersant present between the titanium oxide particles, and the titanium oxide The complex elastic modulus of the correction fluid can be adjusted to an appropriate size by adjusting the way in which the particles are bonded to the resin or dispersant. Specifically, for example, it is considered that the complex elastic modulus tends to be smaller when a material having a side chain is used rather than a linear molecular structure. In addition, even when the resin or dispersant bonded to the titanium oxide particles is long, or when the resin or dispersant is intertwined, the three-dimensional structure of the resin or dispersant is easily deformed, so the complex elastic modulus becomes small. It is thought that it shows a tendency. When the molecular structure of the resin or dispersant is rigid against deformation, the complex elastic modulus tends to increase.
The form and strength of the bond between the titanium oxide and the resin or dispersant is considered to be one of the causes of the complex elastic modulus of the correction fluid. Physical adsorption is the main form of bonding between titanium oxide and resin or dispersant. As a factor that contributes to physical adsorption, there is a strong adsorption point on the surface of titanium oxide particles as a factor that affects the bond with the resin and dispersant on the titanium oxide side. This is due to the polarization part of the surface of the titanium oxide particles due to lattice defects of the crystals in the titanium particles. From the resin and dispersant side, there are polarization and double triple bonds due to polar groups in the molecule. In addition, there is a chemical bond between the titanium oxide particles and the resin by a silane coupling agent or the like. If the bond between the titanium oxide and the resin or dispersant is weak, it will be in the same state as when the force through the resin or dispersant does not work, and the complex elastic modulus will be reduced.

Titanium oxide is a pigment that provides concealability to the coating film. Titanium oxide has anatase type, rutile type and brookite type depending on the crystal form, but only anatase type and rutile type are used in industry. Since the rutile type (refractive index 2.71) has a higher refractive index than the anatase type (refractive index 2.52), the rutile type has a higher concealing effect, and the coated base is concealed. The rutile form is suitable for use, but either can be used. In addition, when the particle size of the primary particles of titanium oxide is one-half of the wavelength of light, the light scattering is the highest and the concealing property is most easily exhibited. The particle size of the titanium oxide in the coating film is visible light About 0.2 μm or more and 0.5 μm or less, which is about a half of the wavelength of 380 nm to 780 nm, is desirable.
Titanium oxide is commercially available in which the surface of the particles is untreated and the surface is titanium oxide, or in which the surface is treated with inorganic metal hydrous oxide and the surface is covered with inorganic hydrous oxide fine particles. Yes. Examples of the inorganic metal hydrous oxide covering the surface of titanium oxide include alumina, silica, titania, zirconia, tin oxide, antimony oxide, and zinc oxide. Further, in order to easily wet volatile hydrocarbons, these untreated or inorganic metal hydrous oxide-treated titanium oxides are combined with coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents, silicone oils, It is also known to use a surface treated with a fluorine-based oil or the like to make the surface hydrophobic or lipophilic. Oxidation surface-treated with organic chemicals such as polyols such as pentaerythritol and trimethylolpropane, alkanolamines such as triethanolamine and organic acid salts of trimethylolamine, silicon resins and silicon chemicals such as alkylchlorosilane Titanium pigments are also commercially available.
Specific examples of titanium oxide products include TITON SR-1 (specific gravity 4.1, alumina treatment), R-650 (specific gravity 4.1, zinc oxide / silica / alumina treatment), and R-62N (specific gravity 3). .9, silica / alumina treatment), R-42 (specific gravity 4.1, alumina treatment), R-7E (specific gravity 3.9, silica / alumina treatment), R-21 (specific gravity 4.0, silica)・ Alumina treatment (above, manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-310 (specific gravity 4.2, untreated, titanium oxide amount 98% or more), KR-380 (specific gravity 4.2, alumina / silica) Treatment), KR-380N (specific gravity 4.2, alumina / silica / zinc oxide treatment), KR-480 (specific gravity 4.2, alumina / silica treatment) (above, manufactured by Titanium Industry Co., Ltd.), Taipure R -900 (specific gravity 4.0, alumina treatment R-902 (specific gravity 4.0, alumina / silica treatment), R-960 (specific gravity 3.9, silica / alumina treatment), R-931 (specific gravity 3.6, alumina / silica treatment) ( DuPont Co., Ltd.), TITANIX JR-301 (specific gravity 4.1, alumina treatment), JR-805 (specific gravity 3.9, alumina / silica treatment), JR-603 (specific gravity 4.0, alumina)・ Zinc oxide treatment), JR-800 (specific gravity 3.9, alumina / silica treatment), JR-403 (specific gravity 4.0, alumina / silica treatment), JR-701 (specific gravity 4.1, alumina / silica)・ Zinc oxide treatment (above, manufactured by Teika Co., Ltd.), Type R-830 (specific gravity 4.2, alumina / silica / zinc oxide treatment), R-780 (specific gravity 4.0, alumina / silica treatment), R-780-2 ( Specific gravity 3.8, alumina / silica treatment) (above, manufactured by Ishihara Sangyo Co., Ltd.).
The amount of titanium oxide added is preferably 30% by weight or more and 60% by weight or less based on the total amount of ink.

In addition, in order to adjust the color tone of the correction coating film and gloss, black pigments such as carbon black, iron oxide, silica, alumina, calcium carbonate, mica, aluminum silicate, extender pigments, coloring pigments for coloring, Unnecessary resin particles can be used in combination with the nonpolar volatile organic solvent. The amount used is preferably 0.01% by weight or more and 20% by weight or less with respect to titanium oxide.
Moreover, in order to make it easy to dry the handwriting of rewriting with water-based ink, or to make drying of a coating film quick, it is preferable that the pigment volume concentration in a dry coating film shall be 70 volume% or more.

  As a specific example of a nonpolar volatile organic solvent that serves as a dispersion medium for titanium oxide, paraffinic hydrocarbons include normal pentane (specific gravity 0.621 (20 ° C., boiling point 36.0 ° C.), normal hexane (specific gravity 0.659 ( 20 ° C), boiling point 68.7 ° C), normal heptane (specific gravity 0.684 (25 ° C), boiling point 98.4 ° C), normal octane (specific gravity 0.703 (25 ° C), boiling point 125.6 ° C), isopentane 2-methylbutane (specific gravity 0.620 (20 ° C.), boiling point 27.8 ° C.), 2,2-dimethylpropane (specific gravity 0.591 (20 ° C.), boiling point 9.4 ° C.), isohexane as 2-hexane Methyl pentane (specific gravity 0.653 (20 ° C), boiling point 60.2 ° C), 3-methylpentane (specific gravity 0.664 (20 ° C), boiling point 63.2 ° C), 2,2-dimethylbutane (specific gravity 0. 649 ( 0 ° C.), boiling point 49.7 ° C.), 2,3-dimethylbutane (specific gravity 0.657 (20 ° C.), boiling point 58.0 ° C.), 2-methylhexane (specific gravity 0.679 (25 ° C.) as isoheptane, Boiling point 90.0 ° C), 3-methylhexane (specific gravity 0.687 (25 ° C), boiling point 91.8 ° C), 2,3-dimethylpentane (specific gravity 0.695 (25 ° C), boiling point 89.7 ° C) 2,4-dimethylpentane (specific gravity 0.673 (25 ° C.), boiling point 80.5 ° C.), 3,3-dimethylpentane (specific gravity 0.693 (25 ° C.), boiling point 86.0 ° C.), 3-ethyl Pentane (specific gravity 0.698 (25 ° C), boiling point 93.4 ° C), 2,2,3-trimethylbutane (specific gravity 0.690 (25 ° C), boiling point 80.0 ° C), 4-methylheptane as isooctane (Specific gravity 0.705 (20.0 ° C), Boiling point 11 0.7 ° C), 2-methylheptane (specific gravity 0.702 (16.0 ° C), boiling point 117.6 ° C), 3-methylheptane (specific gravity 0.706 (20.0 ° C), boiling point 118.9 ° C) ), 2,2-dimethylhexane (specific gravity 0.695 (20 ° C), boiling point 108.8 ° C), 2,3-dimethylhexane (specific gravity 0.712 (20 ° C), boiling point 115.6 ° C), 2, 4-dimethylhexane (specific gravity 0.700 (20 ° C), boiling point 109.4 ° C), 2,5-dimethylhexane (specific gravity 0.693 (20 ° C), boiling point 109.1 ° C), 3,3-dimethylhexane (Specific gravity 0.710 (20 ° C), boiling point 111.9 ° C), 3,4-dimethylhexane (specific gravity 0.719 (20 ° C), boiling point 117.7 ° C), 3-ethylhexane (specific gravity 0.718 ( 16.0 ° C), boiling point 118.5 ° C), 2,3,3-to Limethylpentane (specific gravity 0.712 (25 ° C), boiling point 109.8 ° C), 2,2,4-trimethylpentane (specific gravity 0.687 (25 ° C), boiling point 99.2 ° C), 2,3,3 -Trimethylpentane (specific gravity 0.726 (20 ° C), boiling point 114.7 ° C), 2,3,4-trimethylpentane (specific gravity 0.719 (20 ° C), boiling point 113.4 ° C), 2-methyl-3 -Ethylpentane (specific gravity 0.719 (20 ° C), boiling point 115.6 ° C), 3-methyl-3-ethylpentane (specific gravity 0.727 (20 ° C), boiling point 118.2 ° C), etc. are known. . Naphthenic hydrocarbons are cyclopentane (specific gravity 0.741 (25 ° C), boiling point 49.2 ° C), cyclohexane (specific gravity 0.779 (20 ° C), boiling point 80.7 ° C), methylcyclohexane (specific gravity 0.771 ( 25 ° C), boiling point 100.9 ° C), ethylcyclohexane (specific gravity 0.792 (15 ° C), boiling point 132 ° C), methylcyclopentane (specific gravity 0.744 (25 ° C), boiling point 71.8 ° C), etc. It has been. Moreover, aliphatic hydrocarbon type mixed solvents such as Exol DSP 100/140 (initial boiling point 102 ° C., dry point 138 ° C.) (manufactured by Exxon Chemical Co., Ltd.) are also included. These can be used alone or in combination, and the amount used is preferably 30 to 60% by weight based on the total amount of the ink. The nonpolar volatile organic solvent preferably has a boiling point of 40 ° C. to 150 ° C. in consideration of the drying property of the coating film.

Resin soluble in the non-polar volatile organic solvent brings about dispersion of pigment and fixability of the modified coating film on the paper surface, etc., such as alkyd resin, thermoplastic elastomer, ethylene / vinyl acetate copolymer, Acrylic resins can be preferably used. As an example, alkyd resins such as Teslac 2158-100 (manufactured by Hitachi Chemical Polymer Co., Ltd.) and phthalkid DX615 (50% by weight xylene solution, manufactured by Hitachi Chemical Co., Ltd.), Califlex TR-1107, (Clayton polymer) ), Tuffprene A, Asaprene T-431 (above, Asahi Kasei Chemicals Corporation) and other thermoplastic elastomers, Smitate RB-11 (Sumitomo Chemical Co., Ltd.), Evaflex 150 (Mitsui / DuPont Poly) And ethylene / vinyl acetate copolymer such as Chemical Co.).
The acrylic resin is a copolymer having at least an acrylic ester and / or a methacrylic ester as a monomer, and also includes those copolymerized using other monomers. As acrylic acid ester and methacrylic acid ester, methyl acrylate, ethyl acrylate, isopropyl acrylate, normal butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert- Examples thereof include butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. Particularly, the cationic monomer includes N, N-dimethylaminoethyl acrylate. , N, N-di Tylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl acrylate, N , N-diethylaminopropyl methacrylate, N, N-dibutylaminoethyl acrylate, N, N-dibutylaminoethyl methacrylate, N, N-dipropylaminoethyl acrylate, N, N-dipropylaminoethyl methacrylate, N, N- Diisopropylaminoethyl acrylate, N, N-diisopropylaminoethyl methacrylate, N, N-di-tert-butylaminoethyl acrylate, N, N-di-tert-butylaminoethyl Methacrylate, N, N-dicyclohexylaminoethyl acrylate, N, N-dicyclohexylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl methacrylamide, N, N-diethylaminoethyl acrylamide, N, N -Diethylaminoethyl methacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminopropyl acrylamide, N, N-diethylaminopropyl methacrylamide and the like.
As monomers other than acrylic acid ester and methacrylic acid ester, vinyl acetate, styrene, vinyl toluene, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, hydroxy acrylate A monomer copolymerizable with acrylic acid esters and methacrylic acid esters such as propyl, acrylamide, N-methylol acrylamide, diacetone acrylamide, and glycidyl methacrylate can also be contained. An acrylic resin can be obtained by a polymerization reaction using these monomers as raw materials. Commercially available acrylic resins include Paraloid B-44, B-50, B-60, B-66, B-67, B-72 (above, manufactured by Rohm and Haas, UK) , Dianal BR-50, BR-60, BR-75, BR-85 (manufactured by Mitsubishi Rayon Co., Ltd.) and the like.

In order to improve the adhesion of the dried coating film to the paper by the correction liquid, the coating film may be deformed in accordance with deformation such as folding of the paper. In order to impart deformability to the coating film, a method of using a resin having a low glass transition point or a method of adding a plasticizer or the like can be used.
The glass transition point is the temperature at which the polymer substance changes from glassy to rubbery. The glass transition point is calculated from the glass transition temperature and the weight fraction of the homopolymer of the resin monomer. By using a resin having a glass transition point of −70 ° C. to 50 ° C., a correction liquid for forming a coating film corresponding to the deformability can be obtained.
Plasticizers include phthalate esters such as di-normal octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate and diisodecyl phthalate, tri-2-ethylhexyl trimellitic acid, tetra-2 pyromellitic acid -Aromatic carboxylic acid esters such as ethylhexyl, aliphatic dibasic acid esters such as di-2-ethylhexyl adipate and diisodecyl adipate, fatty acid monoesters such as methyl ricinoleate and methoxyethyl acetyl ricinoleate.
You may use together using resin with a low glass transition point, and adding a plasticizer.

  Nonionic surfactants such as alkyl sulfates, alkyl phosphates, polycarboxylates, polyethylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene fatty acid esters, etc. for pigment dispersion stability A dispersant such as a surfactant, a quaternary ammonium salt, and an alkylamine salt can be added.

  The correction liquid of the present invention can be produced by a known method. For example, the correction liquid can be obtained by dispersing the compound using a dispersing machine such as a ball mill, a planetary ball mill, an attritor, a sand grinder, or a bead mill. .

  The applicator that stores such correction liquid has a liquid chamber that stores and stores the correction liquid, and an application unit that discharges the correction liquid and applies it to the paper surface. Since the correction liquid contains a volatile organic solvent, the liquid chamber is blocked from the outside air when not in use to prevent the volatile organic solvent from volatilizing and reducing the amount of the correction liquid. There is a need. In addition, since it is preferable that the correction liquid in the liquid chamber does not come into contact with the outside air even during use, the liquid chamber and the application part are connected by a relatively narrow liquid flow path, and only the correction liquid consumed in use is used. A structure in which the liquid chamber is supplied to the application unit and is not directly opened to the outside air is preferable.

The applicator is a brush that can occlude and hold the correction fluid, an elastic porous material such as a sponge, or a spatula that does not occlude the fluid but can be spread. Various shapes can be used to spread on. It is desirable that the material to be rubbed against the paper is a material resistant to wear. Moreover, even if it does not dissolve in a non-polar volatile organic solvent and swells, it must have very little swelling. Materials suitable for these conditions include engineer plastics such as polyoxymethylene and polybutylene terephthalate in addition to metals such as stainless steel.
The discharge port for the correction fluid preferably includes a valve that opens only when the liquid is discharged in order to avoid communication between the inside and the outside air other than when the liquid is discharged. From the closed state in which the valve body is in circumferential contact with the annular valve seat, the projecting portion of the valve body is brought into contact with the paper surface, the valve body is retracted, and a gap is formed between the valve seat and the valve seat. Can be used to pour out correction fluid. As the valve body, a ball pen type can be used by using a spherical body that is urged forward by a resilient member such as a coil spring. Moreover, you may use together the cap which coat | covers an application part. As the cap mounting method, press-fitting, screw tightening, or the like can be used.

  It is preferable to form a shear passage having a maximum inscribed circle diameter of 0.025 mm to 0.075 mm and a length of 0.5 mm to 1.0 mm as a path for such correction fluid. For example, when the application part is provided with a valve body that is arranged so that it can move back and forth inside the cylindrical member, the largest inscribed circle that can be drawn among the inscribed circles that contact the inner wall of the cylindrical member and the outer wall of the valve body. By forming a portion having a circular diameter of 0.025 mm or more and 0.075 mm or less over a length in the longitudinal direction of 0.5 mm or more and 1.0 mm or less, a shear passage can be formed. Even if it does not make it the clearance gap between several components, you may form a part with a diameter of 0.025 mm or more and 0.075 mm or less over 0.5 mm or more and 1.0 mm or less as a simple tubular part.

For correction fluids that are relatively high in viscosity and difficult to flow, a means for forcibly discharging the correction fluid can be used, and the liquid chamber is formed of a thin molded product or soft material that can be deformed by human power. It is good also as a squeeze bottle which can press and increase the internal pressure and adjust the discharge amount, fill the back part of the liquid in the liquid chamber with a compressed gas, or have a piston-cylinder structure pushed by an elastic member or a compressed gas.
For squeeze bottles, polyamide (nylon 6, 11, 12, 66, 610, 612, 6t, 6i, 9t, m5t, etc.), polyacrylonitrile, polyether nitrile containers It can be. Nylon 6 can be said to be most suitable considering the ease of deformation with a finger or the like and the non-permeability of a nonpolar volatile organic solvent. Furthermore, it is also possible to use a molded article having a laminated structure composed of a plurality of products composed of a soft plastic layer such as polyethylene and a layer selected from polyamide, polyacrylonitrile, polyethernitrile, aluminum and the like.

  In order to disperse the correction liquid stored in the liquid chamber, a stirring member may be disposed in the liquid chamber together with the correction liquid. As the stirring member, a spherical body or a rod body made of a metal having a high specific gravity or a resin containing metal powder can be preferably employed. When it is made of metal, in order to avoid corrosion due to a minute amount of moisture in the correction liquid, it is desirable that it is made of stainless steel or made of steel subjected to rust prevention treatment such as chromate treatment.

Acrylic resin solution 1
Propyl methacrylate (monomer) 42 parts by weight Butyl methacrylate (monomer) 30 parts by weight Stearyl methacrylate (monomer) 10 parts by weight N, N-diethylaminoethyl methacrylate (monomer) 3 parts by weight Methyl methacrylate (monomer) 10 parts by weight Butyl acrylate (monomer) 5 parts by weight methylcyclohexane (polymerization solvent) 150 parts by weight azobisisobutylnitrile (polymerization initiator) 0.8 part by weight The above materials are placed in a 500 ml reaction vessel equipped with a stirrer, nitrogen gas inlet, thermometer and reflux condenser. The mixture was stirred and polymerized at 90 ° C. for 7 hours in a nitrogen gas stream to obtain a colorless and transparent acrylic resin solution 1 (resin content: 40% by weight).

Acrylic resin solution 2
Propyl methacrylate (monomer) 40 parts by weight Butyl methacrylate (monomer) 24 parts by weight Cyclohexyl methacrylate (monomer) 20 parts by weight N, N-dimethylaminoethyl acrylate (monomer) 8 parts by weight Butyl acrylate (monomer) 5 parts by weight Styrene (monomer) 3 parts by weight methylcyclohexane (polymerization solvent) 50 parts by weight ethylcyclohexane (polymerization solvent) 50 parts by weight azobisisobutylnitrile (polymerization initiator) 0.7 parts by weight Stirrer, nitrogen gas inlet, thermometer, reflux condenser Was stirred and polymerized at 95 ° C. for 6 hours in a nitrogen gas stream to obtain a colorless and transparent acrylic resin solution 2 (resin content: 50% by weight).

Acrylic resin solution 3
Butyl methacrylate (monomer) 62 parts by weight Cyclohexyl methacrylate (monomer) 20 parts by weight N, N-diethylaminoethyl methacrylate (monomer) 18 parts by weight Methylcyclohexane (polymerization solvent) 100 parts by weight Azobisisobutylnitrile (polymerization initiator) 0.7 Part by weight The above materials are placed in a 500 ml reaction vessel equipped with a stirrer, nitrogen gas inlet, thermometer and reflux condenser, and polymerized by stirring at 100 ° C. for 6 hours in a nitrogen gas stream. An acrylic resin solution 3 having a resin content (resin content: 50% by weight) was obtained.

Example 1
Acrylic resin solution 1 (resin content 40% by weight) 16.5 parts by weight Kronos KR-380N (alumina / silica / zinc oxide-treated titanium oxide, specific gravity 4.2, manufactured by Titanium Industry Co., Ltd.) 44.5 parts by weight P-801 (fine silica, manufactured by Mizusawa Chemical Co., Ltd.) 2.7 parts by weight antigel (dispersant, manufactured by BERND SCHWEGMANN, Germany)
1.2 parts by weight Prophane 2012E (fatty acid alkylolamide type nonionic surfactant, manufactured by Sanyo Chemical Industries, Ltd.) 0.4 parts by weight methylcyclohexane 34.7 parts by weight Methylcyclohexane was placed in a stainless steel container equipped with a stirrer. The acrylic resin solution 1 was added while stirring with a propeller-type stirrer (TORNADO PM-202, manufactured by ASONE Co., Ltd.) and stirred for about 10 minutes. While stirring, chronos KR-380N and Mizukasil P-801 were added in small amounts in order of each powder so as not to harden. Further, antigel and profan 2012E were added, and the agitator was changed to a slit-passing homogenizer (ULTRA-TURRAX T50, shaft generator G45G used, manufactured by IKA, Germany) and mixed for about 30 minutes. The obtained mixture was used in a bead mill (DYNO-MILL Typ KDL, disk peripheral speed 15 m / s, flow rate 0.0010 to 0.0013 m3 / hr, using 1 mm diameter zirconia beads, manufactured by WA Bachofen, Switzerland). Then, dispersion was performed while cooling so that the liquid temperature did not exceed 45 ° C., and the correction liquid of Example 1 was obtained.

Example 2
Acrylic resin solution 2 (resin content 50% by weight) 11.0 parts by weight TITANIX JR-701 (alumina / silica / zinc oxide-treated titanium oxide, specific gravity 4
. 1, manufactured by Teika Co., Ltd.) 44.0 parts by weight aluminum silicate 3.3 parts by weight homogenol L-18 (special polycarboxylic acid type polymer surfactant, manufactured by Kao Corporation)
1.5 parts by weight MAR-N (methylacetyl ricinoleate, plasticizer, manufactured by Daihachi Chemical Industry Co., Ltd.)
0.6 parts by weight methylcyclohexane 20.0 parts by weight cyclopentane 19.6 parts by weight All the above materials are placed in a magnetic ball mill pot (outer diameter of about 12 cm) using a magnetic ball (diameter of about 10 mm). The correction liquid of Example 2 was obtained by dispersing for 24 hours at 40 rpm.

Example 3
Acrylic resin solution 3 (resin content 50% by weight) 15.6 parts by weight Taipure R-900 (alumina-treated titanium oxide, specific gravity 4.0, manufactured by DuPont)
41.9 parts by weight Aluminum silicate 2.5 parts by weight Prophan 2012E (described above) 0.4 parts by weight Anti-Terra-206 (alkylolamine salt of unsaturated fatty acid, dispersant, manufactured by BYK Chemie, Germany) 0 parts by weight Methylcyclohexane 33.6 parts by weight Cyclopentane 5.0 parts by weight Methylcyclohexane was put in a stainless steel container, and the resin solution 1 was added while stirring with a propeller-type stirrer (TORNADO PM-202, manufactured by ASONE Co., Ltd.). After stirring for about 5 minutes, TYPURE R-900 and aluminum silicate were added in this order while continuing stirring so that each powder would not harden, and then all the remaining materials were added and further stirred for 10 minutes. The obtained mixture was put into an alumina planetary ball mill pot (using an alumina ball having a diameter of about 3 mm) and dispersed in a planetary ball mill (planetary mill pulverisete 5, FRITSCH, Germany) at a rotation speed of 250 rpm for 45 minutes. The correction fluid of Example 3 was obtained.

Example 4
Acrylic resin solution 1 (resin content 40% by weight) 16.5 parts by weight Paraloid B-66 (previously described) 0.5 parts by weight Kronos KR-380N (previously described) 42.0 parts by weight Mizukacil P-801 (previously described) 2.0 Part by weight Antigel (previously described) 0.5 part by weight Homogenol L-18 (previously described) 1.0 part by weight MAR-N (previously described) 0.4 part by weight methylcyclohexane 37.1 part by weight Methylcyclohexane was placed in a stainless steel container and propeller. While stirring with a mold stirrer (TORNADO PM-202, manufactured by ASONE Co., Ltd.), Paraloid B-66 was added, and stirring was performed until Paraloid B-66 was completely dissolved. After Paraloid B-66 is dissolved, add Antigel, Homogenol L-18, MAR-N, and Acrylic Resin Solution 1 in this order, and after stirring for about 10 minutes, while stirring, Chronos KR-380N and Mizukacil P-801, respectively. Was added little by little and stirred so as not to harden the powder. Further, the agitator was changed to a slit-passing type homogenizer (ULTRA-TURRAX T50, shaft generator G45G used, manufactured by IKA, Germany) and mixed for about 30 minutes. While cooling the resulting mixture so that the liquid temperature does not exceed 45 ° C., a bead mill (DYNO-MILL Typ KDL, disk peripheral speed 15 m / s, using 1 mm diameter zirconia beads, manufactured by WA Bachofen, Switzerland) The correction liquid of Example 4 was obtained.

Example 5
Acrylic resin solution 1 (resin content 40% by weight) 16.5 parts by weight Kronos KR-380N (previously described) 22.5 parts by weight TITANIX JR-701 (previously described) 20.5 parts by weight Mizukacil P-801 (previously described) 3.5 Part by weight Antigel (previously described) 1.0 part by weight Prophane 2012E (previously described) 0.5 part by weight methylcyclohexane 21.0 part by weight cyclopentane 9.5 parts by weight Kyowasol C-600M (2-methylpentane and 3-methyl A mixture of isohexane having a total of 95% or more of pentane and 5% or less of normal hexane, specific gravity of 0.66, boiling point of 62 ° C., manufactured by Kyowa Hakko Chemical Co., Ltd.) 5.0 parts by weight All of the above is put into an alumina planetary ball mill pot (using an alumina ball having a diameter of about 3 mm), and a planetary ball mill (planetary m ll Pulverisette 5, FRITSCH Co., dispersed in 45 minutes at a rotation speed 250rpm to obtain a correction fluid of Example 5 in Germany).

Example 6
Acrylic resin solution 2 (resin content: 50% by weight) 14.0 parts by weight TITANIX JR-701 (described above) 43.0 parts by weight Aluminum silicate 1.5 parts by weight Antigel (described above) 1.2 parts by weight Anti-Terra-206 ( 0.3 parts by weight tri-2-ethylhexyl trimellitate (plasticizer) 0.3 parts by weight methylcyclohexane 31.7 parts by weight Kyowasol C-600M 8.0 parts by weight All the above materials were made of alumina. It was put in a planetary ball mill pot (using an alumina ball having a diameter of about 3 mm) and dispersed in a planetary ball mill (planetary mill pulverisete 5, FRITSCH, Germany) at a rotation speed of 250 rpm for 45 minutes to obtain a correction solution of Example 6. .

Example 7
Acrylic resin solution 2 (resin content 50% by weight) 13.6 parts by weight Paraloid B-67 (described above) 1.0 part by weight TITANIX JR-701 (described above) 22.0 parts by weight Taipure R-900 (described above) 22.0 Parts by weight aluminum silicate 2.0 parts by weight antigel (previously described) 1.2 parts by weight homogenol L-18 (previously described) 0.3 parts by weight MAR-N (previously described) 0.5 parts by weight methylcyclohexane 32.9 parts by weight Kyowasol C-600M 4.5 parts by weight Methylcyclohexane is put into a stainless steel container, and paraloid B-67 is added while stirring with a propeller type stirrer (TORNADO PM-202, manufactured by ASONE Co., Ltd.). Stir until dissolved. After paraloid B-67 is dissolved, Kyowazol C-600M, Antigel, Homogenol L-18, MAR-N, and Acrylic Resin Solution 2 are added in this order. After stirring for about 10 minutes, TITANIX JR-701, In order of Taipure R-900 and aluminum silicate, a small amount was added and stirred so that each powder did not harden. Next, the agitator was changed to a slit-passing type homogenizer (ULTRA-TURRAX T50, shaft generator G45G used, manufactured by IKA, Germany) and mixed for about 30 minutes. The obtained mixture was dispersed and carried out in a bead mill (DYNO-MILL Typ KDL, using 1 mm diameter zirconia beads, manufactured by WA Bachofen, Switzerland) while cooling so that the liquid temperature did not exceed 45 ° C. The correction fluid of Example 7 was obtained.

Example 8
Acrylic resin solution 3 (resin content 50% by weight) 14.5 parts by weight Kronos KR-380N (previously described) 41.0 parts by weight Taipure R-900 (previously described) 4.0 parts by weight Mizukacil P-801 (previously described) 0.5 Part by weight Antigel (previously described) 1.5 parts by weight Anti-Terra-206 (previously described) 0.2 parts by weight Methylcyclohexane 32.8 parts by weight Kyowasol C-600M 5.5 parts by weight All the above materials are planets made of alumina. The solution was placed in a ball mill pot (using an alumina ball having a diameter of about 3 mm) and dispersed for 45 minutes at a rotational speed of 250 rpm in a planetary ball mill (planetary mill pulveritette 5, manufactured by FRITSCH, Germany) to obtain a correction solution of Example 8.

Example 9
Acrylic resin solution 1 (resin content 40% by weight) 7.5 parts by weight Acrylic resin solution 2 (resin content 50% by weight) 7.0 parts by weight Kronos KR-380N (described above) 40.0 parts by weight Aluminum silicate 1.5% by weight Part antigel (previously described) 1.0 part by weight Profan 2012E (previously described) 0.5 part by weight Anti-Terra-206 (previously described) 0.2 part by weight tri-2-ethylhexyl trimellitate (plasticizer) 0.5 part by weight Methylcyclohexane 31.8 parts by weight Cyclopentane 10.0 parts by weight Methylcyclohexane and cyclopentane are placed in a stainless steel container and stirred with a propeller-type stirrer (TORNADO PM-202, manufactured by ASONE Co., Ltd.). Fan 2012E, Anti-Terra-206, tri-2-ethylhexyl trimellitate, Acrylic resin solution 1 was added in the order of the acrylic resin solution 2, after stirring for about 10 minutes, subsequently stirring, Kronos KR-380 N, in order of aluminum silicate was added and stirred in portions so that these powders are not solidify. The stirrer was changed to a slit-passing type homogenizer (ULTRA-TURRAX T50, shaft generator G45G used, manufactured by IKA, Germany) and mixed for about 30 minutes. While cooling the resulting mixture so that the liquid temperature does not exceed 45 ° C., a bead mill (DYNO-MILL Typ KDL, disk peripheral speed 15 m / s, flow rate 0.0010 to 0.0013 m 3 / hr (or 1.0 × 10-3 to 1.3 × 10 −3 m 3 / hr), using zirconia beads having a diameter of 1 mm, manufactured by WA Bachofen, Switzerland), a correction solution of Example 9 was obtained.

Example 10
Acrylic resin solution 2 (resin content: 50% by weight) 4.0 parts by weight Acrylic resin solution 3 (resin content: 50% by weight) 8.0 parts by weight TITANIX JR-701 (described above) 3.0 parts by weight Taipure R-900 (described above) 37.0 parts by weight Aluminum silicate 2.5 parts by weight Antigel (previously described) 1.0 part by weight Anti-Terra-206 (previously described) 0.5 parts by weight Tri-2-ethylhexyl trimellitate (plasticizer) 0.4 Parts by weight methylcyclohexane 23.6 parts by weight cyclopentane 10.0 parts by weight Kyowasol C-600M 10.0 parts by weight All the above materials are put in a pot for an alumina planetary ball mill (using an alumina ball having a diameter of about 3 mm). In a planetary mill (planetary mill pulverisete 5, manufactured by FRITSCH, Germany) The correction liquid of Example 10 was obtained by dispersing at a rotation number of 250 rpm for 45 minutes.

Comparative Example 1
Paraloid B-66 (acrylic resin, manufactured by Rohm and Haas, UK)
4.0 parts by weight Kronos KR-380N (previously described) 42.0 parts by weight antigel (previously described) 0.5 parts by weight methylcyclohexane 53.5 parts by weight All the above materials were made of magnetic balls (diameter of about 10 mm). The solution was placed in a magnetic ball mill pot (outer diameter of about 12 cm) and dispersed at a rotational speed of 40 rpm for 24 hours to obtain a correction liquid of Comparative Example 1.

Comparative Example 2
Acrylic resin solution 1 (resin content 40% by weight) 16.5 parts by weight Kronos KR-380N (previously described) 44.5 parts by weight Mizukacil P-801 (previously described) 2.7 parts by weight Antigel (previously described) 1.2 parts by weight Pro Fan 2012E (described above) 1.2 parts by weight Methylcyclohexane 33.9 parts by weight Methylcyclohexane is placed in a stainless steel container, and the acrylic resin solution 1 is stirred with a propeller type stirrer (TORNADO PM-202, manufactured by ASONE Co., Ltd.). In addition, after stirring for about 10 minutes, with continued stirring, a small amount was added and stirred in the order of Kronos KR-380N and Mizukacil P-801 in order to prevent the powders from solidifying. Further, antigel and profan 2012E were added, and the agitator was changed to a slit-passing homogenizer (ULTRA-TURRAX T50, shaft generator G45G used, manufactured by IKA, Germany) and mixed for about 30 minutes. While cooling the resulting mixture so that the liquid temperature does not exceed 45 ° C., a bead mill (DYNO-MILL Typ KDL, disk peripheral speed 15 m / s, using 1 mm diameter zirconia beads, manufactured by WA Bachofen, Switzerland) ) To obtain a correction fluid of Comparative Example 2.

Comparative Example 3
Paraloid B-67 (acrylic resin, manufactured by Rohm and Haas, UK)
7.0 parts by weight TITANIX JR-701 (previously described) 43.0 parts by weight aluminum silicate 3.0 parts by weight homogenol L-18 (previously described) 1.0 part by weight Anti-Terra-206 (previously described) 1.0 part by weight methyl Cyclohexane 30.0 parts by weight Cyclopentane 15.0 parts by weight All the above materials are put in a magnetic ball mill pot (outer diameter: about 12 cm) using magnetic balls (diameter: about 10 mm) and rotated at a rotational speed of 40 rpm for 24 hours. Dispersed to obtain a correction liquid of Comparative Example 3.

Applicator Structure As the applicator that accommodates such a correction liquid, for example, the tip valve type applicator shown in FIG. 1 can be suitably used.
The applicator of this example mainly includes a container main body 1 that contains correction fluid, a front shaft 2 that is screwed into an opening of the container main body 1, an application unit 3 that protrudes from the tip of the front shaft 2, and an application The cap 4 covers and seals the portion 3.
The container body 1 contains a correction body (not shown) and a stirring body 5 which is a metal cylindrical body. If the applicator is gripped and shaken, the mass is much larger than that of the correction liquid. The body moves by the inertia of the swing, and the correction liquid is stirred. A screw thread serving as an inner screw for screwing with the front shaft 2 is formed on the outer wall on the opening side of the container body 1, and a small diameter portion on which the cap 4 can be fitted is formed on the outer side of the bottom portion serving as the rear end. Is formed.
The front shaft 2 has a portion joined to the container body 1 as a double cylindrical portion, and forms a screw thread as an external screw on the inner wall of the outer tube 2a. Further, the rear end of the inner cylindrical portion 2 b extends inside the container main body 1, and a gap 6 is formed between the inner cylindrical portion 2 b and the inner wall of the container main body 1. Even if a coarse solid matter is generated due to some aggregation of the pigment, it accumulates in the gap 6 and the solid matter is difficult to enter the coating destination side by the wall of the inner cylindrical portion 2b, thereby obstructing the flow of the liquid. It has become difficult.
Although the application part 3 is press-fitted into the tip of the front shaft 2, as shown in FIG. 2 which is an enlarged view of the I part in FIG. 1, the application part 3 includes an outer cylinder 3a, a valve body 3b, and a valve body 3b. The valve seat 3d is formed of a coil spring 7 that is biased forward, and on the inner wall of the small diameter portion formed by caulking the tip of the outer cylinder 3a. ing.
As shown in FIG. 3 which is a cross-sectional view taken along the line II-II ′ of FIG. 2, the range portion of the large diameter portion 3c of the valve body 3b in the gap between the outer cylinder 3a and the valve body 3b is maximized. The inscribed circle diameter (α) is 0.025 mm or more and 0.075 mm or less, and the length (β: the length in the longitudinal direction of the maximum diameter portion of the large diameter portion 3c) is 0.5 mm or more and 1 mm or less. .
At the time of use, the tip pressing portion 3c of the application destination 3 is pressed against the paper surface or the like, the valve body 3b is moved backward, a gap is formed between the outer cylinder 3a and the valve body 3b, and the correction liquid is discharged. .

  A test applicator was created in the same shape as that shown in FIG. The container body 1 has a bottomed cylindrical body having a total length of about 90 mm, an outer diameter of about 10 mm, and a wall thickness of about 0.5 mm by blow molding with nylon 6, and the front shaft 2 is made of polybutylene terephthalate. It was set as the injection molded product, and the stainless steel outer cylinder 3a, the valve body 3b, and the coil spring 7 were installed in combination. As the stirring body 5, a cylindrical stainless steel stirring body (about 3 g) having a diameter of about 4 mm and a length of about 28 mm was used.

  By adjusting the size of the large-diameter portion 3c in the valve body 3b of the application portion for testing, a test in which the maximum inscribed circle diameter (α) and the length in the longitudinal direction (β) of the maximum diameter portion of the large-diameter portion 3c are different. An applicator was prepared (see Table 1).

  Tables 2 and 3 show the results of the complex elastic modulus of the correction fluids of Examples 1 to 10 and Comparative Examples 1 to 3, the applicator used for the test, the number of swings until the stirrer starts to move, the concealability, and the redispersibility. I write.

Measurement of complex elastic modulus The correction liquid is stirred for about 1 minute at a rotational speed of 3000 rpm to 6000 rpm with a stirrer (TKHOMODYPER Model 2.5, manufactured by Primix Co., Ltd.) of an edge turbine type rotor blade, and is in a uniform state. I made it. This correction fluid was applied to a stress-controlled rheometer, VISCOANALYSER VAR100 (Relogica, Sweden) using a cone-shaped geometry (diameter 40 mm, gap angle 4 °) from a shear stress of 0.1 Pa at a frequency of 1 Hz. It was measured at intervals of 8 equal logarithms up to 1.0 Pa (25 ° C.). In order to prevent the correction fluid from drying during the measurement, the measurement was performed with a dedicated windshield cover.
The results are shown in (Table 2).

Stirring body movement start test Each test sample is stored in a stationary state at 50 ° C. for 3 months with the applicator containing the correction solution facing upward.
Thereafter, the test sample is freely dropped from a position of 20 cm in height in a glass tube having an inner diameter of 15 mm in a direction in which the coating portion faces downward, and is made to collide with a cedar board having a thickness of 2 cm. Immediately after that, the application part was directed upward and the sense of movement of the stirrer was confirmed, and it was measured how many times the stirrer could be confirmed to have moved when dropped.
The results are shown in (Table 3).

Concealment evaluation 1
In the stirrer movement start test, after the stirrer started to move, it was dropped twice more, then the ink was taken out of the container, and the opacity measurement paper (corresponding to JIS K5400-1990 and JIS K5600-1999, Nippon Paint Inspection) (Applied by Taiyou Kikai Co., Ltd.) with a gap of 50 μm and a width of 30 mm and a 20 mm diameter round blade applicator, left at room temperature for 10 minutes, and after drying, the white and black parts of the paper for measuring the concealment rate The luminous reflectance (Y value) of the coating film of the color difference meter (SM color computer (using TM type 2 optical path glare prevention optical system, light source C-2 ° (C light 2 ° field of view)), condensing lens φ12 mm, It was measured with a data base φ12 mm), S & M COLOR COMPUTER MODEL SM-5-IS-2B, manufactured by Suga Test Instruments Co., Ltd.). By dividing the measured luminous reflectance (Y value) of the black portion by the luminous reflectance (Y value) of the white portion, the concealment rate was obtained as a percentage.
The results are shown in (Table 3).

Concealment evaluation 2
In the stirrer moving start test, after the stirrer started moving again, it was dropped two more times, and then using a test applicator, a cover rate measurement paper (corresponding to JIS K5400-1990 and JIS K5600-1999, Foundation) Painted a 15 mm x 15 mm square on the Japan Paint Inspection Association, made by Taiyu Kikai Co., Ltd., left at room temperature for 10 minutes, and after drying, the coating of the white part and black part of the paper for measuring the concealment rate Luminous reflectance (Y value) is measured using a color difference meter (SM color computer (using TM type 2 optical path anti-glare optical system, light source C-2 ° (C light 2 ° field of view)), condensing lens φ12mm, data base φ12mm ), S & M COLOUR COMPUTER MODEL SM-5-IS-2B, manufactured by Suga Test Instruments Co., Ltd.). By dividing the measured luminous reflectance (Y value) of the black portion by the luminous reflectance (Y value) of the white portion, the concealment rate was obtained as a percentage.
The results are shown in (Table 3).

Coating film observation The coating film obtained in the concealability evaluation 2 was observed by observing the coating film surface with a scanning electron microscope (SCANNING MICROSCOPE JSM-5310LV, manufactured by JEOL Ltd.) at a magnification of 1000 times. The grain size was visually determined.
The results are shown in (Table 3).

From these results, the following matters can be understood.
In Example 1, since the complex elastic modulus is a correction liquid having a complex elastic modulus of greater than 0.35 Pa and less than 0.42 Pa, the stirrer starts to move in a single drop in the stirrer movement start test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of Example 1 by filling an applicator, the result in the applicator 1 having a portion corresponding to a shear passage as a liquid passage is obtained. The concealment rate is 3% higher than the result in the applicator 2, and the size of the particles observed by coating film observation is small.

In Example 2, since the complex elastic modulus is a correction liquid having a complex elastic modulus greater than 6.8 Pa and less than 9.3 Pa, the stirrer starts to move in a single drop in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of Example 2 by filling an applicator, the result in the applicator 3 having a portion corresponding to a shear passage as a liquid passage is obtained. The concealment rate is 3% higher than the result in the applicator 4, and the size of the particles observed by coating film observation is small.

In Example 3, since the complex elastic modulus is a correction liquid having a complex elastic modulus greater than 3.1 Pa and less than 5.2 Pa, the stirrer started to move by two drops in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of Example 3 by filling an applicator, the result in the applicator 5 having a portion corresponding to a shear passage as a liquid passage is obtained. It can be said that the concealment rate was 3% higher than the result of the applicator 12, and only very fine particles were observed in the coating film observation, confirming that the dispersion state was good.

In Example 4, since the complex elastic modulus is a correction liquid having a complex elastic modulus of greater than 0.22 Pa and less than 0.26 Pa, the stirrer starts to move in a single drop in the stirrer movement start test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealability evaluation 2 and the coating film observation using the correction liquid of Example 4 filled in the applicator, the result in the applicator 9 having a portion corresponding to the shear passage as the liquid passage is obtained. It can be said that the concealment rate was 2% higher than the result of the concealability evaluation 1, only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Example 5, since the complex elastic modulus is a correction liquid having a complex elastic modulus greater than 7.5 Pa and less than 8.3 Pa, the stirrer started to move in two drops in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of Example 5 by filling an applicator, the result in the applicator 10 having a portion corresponding to a shear passage as a liquid passage is obtained. It can be said that the concealment rate was 3% higher than the result of the concealability evaluation 1, and only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Example 6, since the complex elastic modulus is a correction liquid having a complex elastic modulus of greater than 2.1 Pa and less than 3.0 Pa, the stirrer starts to move in a single drop in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of Example 6 by filling an applicator, the result in the applicator 11 having a portion corresponding to a shear passage as a liquid passage is obtained. It can be said that the concealment rate was 2% higher than the result of the concealability evaluation 1, only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Example 7, since the complex elastic modulus is a correction liquid having a complex elastic modulus greater than 0.90 Pa and less than 1.6 Pa, the stirrer starts to move in one drop in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of Example 7 by filling an applicator, the result in the applicator 3 having a portion corresponding to a shear passage as a liquid passage is obtained. It can be said that the concealment rate was 2% higher than the result of the concealability evaluation 1, only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Example 8, since the complex elastic modulus is a correction liquid having a complex elastic modulus of greater than 0.80 Pa and less than 0.85 Pa, the stirrer starts to move in a single drop in the stirrer movement start test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and the coating film observation using the correction liquid of Example 8 filled in the applicator, the result in the applicator 5 having a portion corresponding to the shear passage as the liquid passage is obtained. It can be said that the concealment rate was 2% higher than the result of the concealability evaluation 1, only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Example 9, since the complex elastic modulus is a correction liquid having a complex elastic modulus of greater than 1.2 Pa and less than 1.5 Pa, the stirrer started to move in a single drop in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealability evaluation 2 and the coating film observation using the correction liquid of Example 9 filled in the applicator, the result in the applicator 10 having a portion corresponding to the shear passage as the liquid passage is obtained. It can be said that the concealment rate was 2% higher than the result of the concealability evaluation 1, only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Example 10, since the complex elastic modulus is a correction liquid having a complex elastic modulus greater than 0.11 Pa and less than 0.14 Pa, the stirrer started to move in two drops in the stirrer start-up test. In the concealment evaluation 1, the concealment rate is 90% or more, and it can be said that the correction liquid has sufficient concealment.
Moreover, in the concealment evaluation 2 and coating film observation using the correction liquid of Example 10 filled in the applicator, the result in the applicator 11 having a portion corresponding to the shear passage as the liquid passage is obtained. It can be said that the concealment rate was 2% higher than the result of the concealability evaluation 1, only very fine particles were observed in the coating film observation, and it was confirmed that the dispersion state was good.

In Comparative Example 1, since the complex elastic modulus is a correction liquid having a complex elastic modulus of greater than 0.074 Pa and less than 0.096 Pa, eight drops are required for the stirrer to start moving in the stirrer movement start test. In the concealment evaluation 1, the concealment rate is less than 80%, and it can be said that the correction liquid cannot sufficiently conceal the base.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of the comparative example 1 by filling an applicator, the result in the applicator 6 which does not have a part corresponding to a shear passage as a liquid passage is obtained. The concealment rate is 3% lower than the result of the concealment evaluation 1. In observation of the coating film, only very fine particles were observed, and it can be said that it was confirmed to be in a good dispersion state.

In Comparative Example 2, the complex elastic modulus is a correction liquid greater than 24 Pa and less than 30 Pa, and exceeds 10 Pa. Therefore, 26 times are required for the stirrer to start moving in the stirrer movement start test. In the concealment evaluation 1, the concealment rate is less than 90%, and it can be said that the correction liquid cannot sufficiently conceal the base.
Moreover, in the concealability evaluation 2 and coating film observation which used the correction liquid of the comparative example 2 by filling an applicator, the result in the applicator 7 which does not have a portion corresponding to a shear passage as a liquid passage is obtained. It can be said that very coarse grains were observed in the coating film observation, and the dispersion state was confirmed to be the same as the result of the hiding property evaluation 1.

In Comparative Example 3, since the complex elastic modulus is a correction liquid larger than 5.1 Pa and less than 60 Pa and exceeds 10 Pa, 54 drops are required for the stirring body to start moving in the stirring body movement start test. In the concealment evaluation 1, the concealment rate is less than 90%, and it can be said that the correction liquid cannot sufficiently conceal the base.
Moreover, in the concealment evaluation 2 and coating film observation which used the correction liquid of the comparative example 3 by filling an applicator, the result in the applicator 8 which does not have a part corresponding to a shear passage as a liquid passage is obtained. It can be said that very coarse grains were observed in the coating film observation, and the dispersion state was confirmed to be the same as the result of the hiding property evaluation 1. Similarly, in the concealability evaluation 2 and the coating film observation using the correction liquid of Comparative Example 3 filled in the applicator, the result in the applicator 5 having a portion corresponding to the shear path as the liquid path is As with the results of the concealment evaluation 1, extremely coarse particles are observed in the coating film observation, and in the correction liquid whose complex elastic modulus is not in the range of 0.1 Pa or more and 10 Pa or less, the liquid passage is used as a shear passage. It can be said that even if the applicator has a corresponding part, it was confirmed that the dispersion state was poor.

The longitudinal cross-sectional view which shows an example of an applicator. The I section enlarged view of FIG. II-II 'line cross section arrow directional view of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container main body 2 Front shaft 2a Outer cylinder 2b Inner cylinder part 3 Application | coating part 3a Outer cylinder 3b Valve body 3c Large part 3d Valve seat 4 Cap 5 Stirrer 6 Crevice 7 Coil spring

Claims (2)

Contains at least titanium oxide, a non-polar volatile organic solvent, and a resin soluble in the non-polar volatile organic solvent, and has an amplitude of 0.1 Pa to 1.0 Pa in shear stress (25 ° C., frequency 1 Hz) Correction fluid having a complex elastic modulus of 0.1 Pa to 10 Pa. The maximum inscribed circle diameter that can be drawn in the cross-sectional space of the liquid passage for discharging the correction fluid of claim 1 from the application destination is 0.025 mm to 0.075 mm and the length is 0.5 mm to 1.0 mm. The applicator for storing the correction fluid according to claim 1, which has a shear passage.