JP2009144050A - Correction fluid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a correction fluid, a coated film obtained from which does not separate even when written using an ultrafine ballpoint pen of a ball size of ≤0.5 mm. <P>SOLUTION: This correction fluid comprises at least titanium oxide, a hydrocarbon solvent and a resin soluble in the solvent, wherein a sample is provided by forming a dry coated film of thickness of ≥30 μm and ≤50 μm on a surface of a test paper as a substrate by use of the correction liquid, when the sample is bent to 180° along a cylinder of diameter of 0.5 mm, an angle at which a crack is observed on the surface of the coated film is ≥90°. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a correction liquid that conceals and erases typographical errors and the like, and particularly relates to a correction liquid that is excellent in re-writing property when applied thickly.

Conventionally, a correction liquid comprising at least a concealing material such as titanium oxide, a hydrocarbon solvent such as methylcyclohexane, and a resin such as acrylic soluble in the solvent is known (see Patent Document 1).
In addition, the correction liquid may be concealed and corrected for typographical errors and rewritten on the coating film, and preferably has a high fixability.
Japanese Unexamined Patent Publication No. 57-024765

  In recent years, ball-point pens that can be used to write thin characters have become ultra-thin, and the balls used therein are extremely small with a diameter of 0.5 mm or less, and even ball pens with a diameter of 0.25 mm or less have been released. In addition, when the ball has a small diameter, the load applied per unit area of the ball is much larger than that of a conventional ballpoint pen using a ball having a large diameter. Therefore, there has been a problem that the coating film is broken when the correction liquid coating film is written with this ultra-fine ballpoint pen.

  As an improvement measure, the present invention comprises at least a dry coating film having a thickness of 30 μm or more and 50 μm or less on a test paper surface as a substrate, comprising at least a titanium oxide, a hydrocarbon solvent, and a resin soluble in the solvent. A correction liquid having an angle of 90 ° or more on the surface of the coating film when the sample is bent to 180 ° along a cylinder having a diameter of 0.5 mm is used as a gist.

  When a dry coating film having a thickness of 30 μm or more and 50 μm or less is formed as a specimen and bent to 180 ° along a cylinder having a diameter of 0.5 mm, the correction liquid having an angle of 90 ° or more on the surface of the coating film is It can be said that it is difficult for the coating film to break by simply denting the pen tip and the coating film in contact with the pen pressure, and it can be said that the coating film is strong against writing with an extra fine ballpoint pen. In addition, the correction liquid whose angle is 90 ° or more uses a high molecular weight resin in the blending composition, uses a resin having a glass transition point of 50 ° C. or less, and has a large blending ratio of solids such as a resin. It can be obtained by adding a plasticizer to impart flexibility, or by combining particles having protrusions extending from the center of the tetrahedron in the direction of the four apexes.

  Titanium oxide is a white pigment having the highest hiding power in consideration of the most white color on the paper surface and covering the ground as a correction liquid. Specific examples of products include TITON SR-1 (specific gravity 4.1), R-650 (specific gravity 4.1), R-62N (specific gravity 3.9), and R-42 (specific gravity 4.1). R-7E (specific gravity 3.9), R-21 (specific gravity 4.0) (above, manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-310 (specific gravity 4.2), KR-380 ( Specific gravity 4.2), 480 (specific gravity 4.2) (made by Titanium Industry Co., Ltd.), Taipure R-900 (specific gravity 4.0), R-902 (specific gravity 4.0), R- 960 (specific gravity 3.9), R-931 (specific gravity 3.6) (manufactured by DuPont Japan Limited), TITANIX JR-301 (specific gravity 4.1), JR-805 (specific gravity 3.9) JR-603 (specific gravity 4.0), JR800 (specific gravity 3.9), JR-403 (specific gravity 4.0), JR 701 (specific gravity 4.1) (above, manufactured by Teika Co., Ltd.). The amount of titanium oxide added is preferably 30 to 60% by weight based on the total amount of ink.

The hydrocarbon solvent is preferably a solvent having a boiling point of 40 to 150 ° C. in consideration of the drying property of the coating film. In particular,
Normal pentane (boiling point 36.0 ° C), cyclopentane (boiling point 49.2 ° C), methylcyclopentane (boiling point 71.8 ° C) normal hexane (boiling point 68.7 ° C), isohexane (boiling point 62 ° C), normal heptane ( In addition to aliphatic hydrocarbon solvents such as normal octane (boiling point 98.4 ° C), cyclohexane (boiling point 80.0 ° C), methylcyclohexane (boiling point 100.9 ° C), ethylcyclohexane (boiling point 132 ° C), Exol DSP 100 / 140 (initial boiling point 102 ° C., dry point 138 ° C.) (Exxon Chemical Co., Ltd.) and other hydrocarbon hydrocarbon solvent mixtures. These can be used alone or in combination. The amount of solvent used is preferably 30 to 60% by weight based on the total amount of ink.

The resin that is soluble in the hydrocarbon solvent causes pigment dispersion and correction liquid fixing on the paper surface. Alkyd resins, thermoplastic elastomers, and the like can be used, but acrylic resins are preferred in consideration of pigment dispersibility, fixability on paper, and the like.
Hereinafter, the acrylic resin will be described. Usable monomers are methyl acrylate, ethyl acrylate, isopropyl acrylate, normal butyl acrylate, 2-ethylhexyl acrylate as acrylate ester, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl as methacrylic acid ester. Examples include methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. As cationic monomers, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (Meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-di-tert-butylaminoethyl (meth) acrylate, N, N-dicyclohexylaminoethyl (meth) acrylate, N, N dimethylamino Examples include ethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. In addition to these monomers, vinyl acetate, styrene, vinyl toluene, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, hydroxypropyl acrylate, acrylamide, N- A copolymerizable vinyl monomer such as methylolacrylamide, diacetoneacrylamide, or glycidylmethacrylate can also be contained.

  In consideration of the adhesion of the coating film to paper, the glass transition point of the resin soluble in the hydrocarbon solvent is preferably −70 ° C. to 50 ° C. The glass transition point is the temperature at which the polymer substance changes from glassy to rubbery. The glass transition point is calculated by the following equation (1) from the glass transition temperature of the homopolymer of the resin monomer and the weight fraction.

  Further, particles having a shape in which protrusions extend from the center of the tetrahedron toward the four apexes, specifically, Panatetra WZ-0501, WZ-0511, WZ-0531, WZ made of zinc oxide with tetrapot whiskers. -05E1 and WZ-05F1 (manufactured by Amtec Co., Ltd.), and needle-like particles of potassium titanate or calcium carbonate can be added to impart strength to the coating film. In addition, plate-like particles such as mica and talc, and massive particles such as silica and calcium carbonate can be used. The addition amount is preferably 3 to 15% by weight.

  For pigment dispersion stability, nonionic surfactants such as alkyl sulfate ester salts, alkyl phosphate salts, polycarboxylic acid polymers, polyethylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene fatty acid esters, etc. A dispersant such as an ionic surfactant, a quaternary ammonium salt, or an alkylamine salt can be added.

  The ink is obtained by dispersing and mixing the above components using a stirring and dispersing machine such as a ball mill, an attritor, a sand grinder, and an impeller.

Example of resin production (manufacturing conditions)
A 500 ml reaction vessel equipped with a stirrer, a nitrogen gas inlet, a thermometer, and a reflux condenser was charged with the substances shown in Table 1 below, and polymerized while stirring at 80 ° C. for 7 hours in a nitrogen gas stream. A polymer component (acrylic resin) having consistency was obtained. Table 1 also shows the solid content, weight average molecular weight, and glass transition temperature of the obtained resin solution.

Example 1
TITANIX JR701 (titanium oxide, manufactured by Teika Co., Ltd.) 40.0 parts by weight Resin 1 23.2 parts by weight Methylcyclohexane 35.8 parts by weight Disperbyk-108 (surfactant, manufactured by BYK-Chemie (Germany))
1.0 part by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 2
TITANIX JR701 (previously described) 40.0 parts by weight Resin 2 23.4 parts by weight Methylcyclohexane 35.6 parts by weight Disperbyk-180 (surfactant, BYK-CHEMIE (Germany))
1.0 part by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 3
TITANIX JR701 (previously described) 35.0 parts by weight Resin 3 23.2 parts by weight Methylcyclohexane 39.0 parts by weight Disperbyk-180 (previously described) 1.0 part by weight Each of the above components was dispersed in a ball mill for 24 hours, Obtained.

Example 4
TITANIX JR701 (previously described) 40.0 parts by weight Resin 4 24.0 parts by weight Methylcyclohexane 35.0 parts by weight Disperbyk-180 (previously described) 1.0 part by weight Each of the above components was dispersed in a ball mill for 24 hours, Obtained.

Example 5
TITANIX JR701 (previously described) 40.0 parts by weight Resin 5 20.0 parts by weight Methylcyclohexane 36.0 parts by weight MAR-N (plasticizer, manufactured by Daihachi Chemical Co., Ltd.) 3.0 parts by weight Disperbyk-180 (previously described) 1.0 part by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 6
TITANIX JR701 (previously described) 35.0 parts by weight Resin 6 20.0 parts by weight Methylcyclohexane 36.0 parts by weight Panatetra WZ-0501 (particle plasticizer having a shape in which protrusions extend from the center of the tetrahedron toward the four apexes, ) Manufactured by Amtec) 8.0 parts by weight BYK405 (surfactant, manufactured by BYK-CHEMIE (Germany)) 1.0 part by weight Each of the above components was dispersed by a ball mill for 24 hours to obtain a correction liquid.

Example 7
TITANIX JR800 (titanium oxide, manufactured by Teika Co., Ltd.) 35.0 parts by weight Resin 6 18.8 parts by weight Methylcyclohexane 34.2 parts by weight Panatetra WZ-0501 (previously described) 5.0 parts by weight Wiscal A (needle calcium carbonate (Manufactured by Maruo Calcium Co., Ltd.) 5.0 parts by weight BYK405 (described above) 1.0 part by weight Disperbyk-108 (described above) 1.0 part by weight Each of the above components was dispersed in a ball mill for 24 hours to obtain a correction liquid. .

Example 8
TITANIX JR800 (previously described) 30.0 parts by weight Resin 6 20.0 parts by weight Methylcyclohexane 33.0 parts by weight Panatetra WZ-0501 (previously described) 15.0 parts by weight BYK405 (previously described) 1.0 part by weight Disperbyk-108 (previously described) ) 1.0 part by weight The above components were dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 9
TITANIX JR800 (previously described) 35.0 parts by weight Resin 6 20.0 parts by weight Methylcyclohexane 33.0 parts by weight Panatetra WZ-0501 (previously described) 2.0 parts by weight Whiscal A (previously described) 8.0 parts by weight Disperbyk-180 ( 1.0 part by weight Disperbyk-108 (described above) 1.0 part by weight Each of the above components was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Comparative Example 1
TITANIX JR701 (described above) 45.0 parts by weight Resin 1 15.0 parts by weight Methylcyclohexane 39.0 parts by weight BYK-108 (surfactant, manufactured by BYK-CHEMIE (Germany)) 1.0 part by weight Dispersion treatment was carried out with a ball mill for 24 hours to obtain a correction liquid.

Comparative Example 2
TITANIX JR701 (previously described) 40.0 parts by weight Resin 5 20.0 parts by weight Methylcyclohexane 39.0 parts by weight Disperbyk-180 (previously described) 1.0 part by weight Each of the above components is dispersed in a ball mill for 24 hours, Obtained.

Comparative Example 3
TITANIX JR800 (previously described) 46.0 parts by weight Resin 6 20.0 parts by weight Methylcyclohexane 33.0 parts by weight Disperbyk-180 (previously described) 1.0 part by weight Each of the above components is dispersed in a ball mill for 24 hours, Obtained.

Test paper preparation method PPC paper CR-KPA4-W (manufactured by Crown Co., Ltd.), 100 parts of curable silicone resin KS-779H (manufactured by Shin-Etsu Chemical Co., Ltd.), curing agent CAT-PL-8 (Shin-Etsu Chemical Co., Ltd.) Co., Ltd.) 1 part, a release agent composed of 2200 parts of methyl ethyl ketone (MEK) / toluene mixed solvent system was applied so that the coating amount was 0.1 g / mm ^2, and allowed to stand at room temperature for 24 hours. Got.

Test piece preparation method When the coating film applied on the test paper is folded to 180 ° along a cylinder with a diameter of 0.5 mm, the test piece for measuring the angle at which the coating surface cracks is as follows. To make.
About 2 milliliters of the correction fluids of the examples and comparative examples were placed at a position of about 20 mm from the longitudinal end on the above-mentioned test paper surface with a width of 85 mm and a length of 115 mm, and this was applied to an applicator (a stainless steel cylinder with a diameter of 20 mm and a length of 50 mm). However, the center axis of the cylinder is arranged horizontally with respect to the coating surface, and the coating is applied so that the column surface and the coating surface are stretched to the opposite side in the longitudinal direction. The correction liquid applied on the test paper surface is allowed to stand at about 25 ° C. for 24 hours or longer to form a dry coating film. In addition, the dry state of a dry coating film confirms the state which 95% or more of the added solvent evaporated in weight conversion.

Coating thickness measurement Separately from the test piece, the thickness of the dried coating film prepared with the same method was measured with a thickness gauge using a thickness gauge, and the difference from the thickness of the test paper measured with the thickness gauge. The film thickness was 30 mm or more and 50 mm or less.

Break angle measurement Using a cylindrical mandrel bending tester of JISK5600-5-1, the mandrel part was remodeled into a cylindrical shape (material: stainless steel) with a diameter of 0.5 mm, and the coating surface was opposite to the mandrel part, 90 ° The bending break angle was measured at 15 seconds.

Ballpoint Pen Coating Film Peeling Test Pen correction fluid XZL61-W containers filled with the correction fluids obtained in Examples and Comparative Examples were used to produce a coating film having a thickness of 50 to 100 μm on fine paper. Water-based gel ink pen pens rich BG202-A (ball diameter 0.25 mm), BG203-A (ball diameter 0.3 mm), BG204-A (ball diameter 0.4 mm) 6 mm vertically at a writing load of 300 g. 6 lines were drawn, and the area where the coating film peeled off in 100 square millimeters was measured. .

Claims (1)

A dry coating film having a thickness of 30 μm or more and 50 μm or less is formed on a test paper surface serving as a base material, comprising at least a titanium oxide, a hydrocarbon solvent, and a resin soluble in the solvent. A correction fluid in which the angle at which cracks occur on the coating film surface is 90 ° or more when bent to 180 ° along a 5 mm cylinder.