JPS627771A - White coating type erasing solution - Google Patents

Abstract

PURPOSE:The titled erasing solution having improved fluidity, opacifying properties, high drying rate and improved rewriting properties, comprising specific ground limestone, a volatile solvent and a binder as essential components. CONSTITUTION:(A) ground limestone having 1.0-1.5mu average particle diameter based on specific surface area, >=20mu maximum particle diameter by Hoover mullter test method and 1.0-2.0m<2>/g specific surface area by air permeation method is blended with (B) a volatile solvent(e.g., 1,1,1-trichloroethane) and (C) a binder(preferably acrylic ester methacrylic ester copolymer as main components. A blending ratio of each component to an erasing solution is preferably 40-70wt% component A, 30-60wt% component B and 5-20wt% component C.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a correction fluid that covers and conceals typographical errors by coating and enables correct printing and writing on this coating film, and particularly relates to a correction fluid that has excellent coating film performance. This invention relates to a white coat type oil-based correction fluid.

[Conventional technology]

Traditionally, type printing, ballpoint pen handwriting, water-based ink handwriting,
Water-based or oil-based correction fluids in which pigments are dispersed in water or low-boiling point solvents containing binders have been used as concealment correction fluids for toner copies, etc.; When correcting ink handwriting, it was troublesome to have to select and use different water-based correction fluids.

Therefore, a correction fluid that can be used for both oil-based ink and water-based ink has been developed by using a solvent that is poorly soluble in oil-based ink as a correction fluid solvent.

In such correction fluids, fine titanium oxide powder has conventionally been used as a pigment to improve hiding properties, but since this fine titanium oxide powder has a small specific surface area,
A problem arose in that the coating film became glossy and the drying properties during rewriting were significantly deteriorated.

Therefore, one method to improve this problem is to add a small amount of finely powdered silica (approximately 10%) to reduce the gloss of the coating film and improve dryness during rewriting. It has been done.

[Problem that the invention seeks to solve]

However, when just adding fine powdered silica,
This fine powdered silica has a high oil absorption value due to its excessive specific surface area, resulting in poor fluidity, resulting in variations in coating thickness when used as a correction fluid, and the disadvantages of poor appearance of the repaired area. .

Therefore, it is an object of the present invention to provide a correction fluid that has excellent fluidity, quickly dries a coating film, has good hiding properties, has low gloss, and has excellent rewriting properties.

[Means for solving problems]

The present inventor has conducted extensive research in order to eliminate the above-mentioned drawbacks and to provide a correction fluid that can achieve the above-mentioned objectives.
In a correction fluid containing a volatile solvent and a binder as essential components, the pigment has an average particle diameter of 1.0 to 1.5 microns based on the specific surface area and a maximum particle diameter of 20 microns or less according to the Huber-Maller test method. When using a pigment whose main component is heavy calcium carbonate and whose specific surface area is within the range of 1°0 to 2.0 m2/g measured by the air permeation method, the above-mentioned disadvantages can be eliminated and the above-mentioned objectives can be achieved. The inventors discovered a new fact that it is possible to provide a correction fluid that can be used as a correction fluid, and completed the present invention.

To explain the present invention in detail, the reason why calcium carbonate is limited to heavy calcium carbonate with a predetermined particle size range and a predetermined specific surface area range is that compared to the case where finely powdered silica is simply added, the reason is that This is because an excellent correction fluid can be obtained. That is, if the average diameter of the particles is 1.0'-
If the maximum particle size is 1.5 microns and 20 microns or less, the smoothness of the coating film can be improved, but if it is larger than this range, the rewriting properties of the coating film will deteriorate. Also, the specific surface area is 1. When the specific surface area is smaller than Om''/g, the oil absorption value and water absorption value are low, which may cause problems with ink absorption during rewriting, and when the specific surface area is larger than the above specific surface area, the ink will evaporate when trying to satisfy the concealment property. It is necessary to limit the amount of solvent,
If this happens, the fluidity will decrease, which is not practical. Regarding paint film gloss, the smaller the particle diameter is than 1.0 micron and the smaller the specific surface area is less than 1.0 m2/g, the more the paint film gloss increases.

On the other hand, ultrafine calcium carbonate has a small average particle size,
Since the specific surface area is also large, the gloss of the paint film can be reduced, but as mentioned above, because the specific surface area is large, the drying properties, fluidity, smoothness and hiding properties of the paint film are inferior, and the main component of the pigment in the correction fluid is It is unsuitable for use as a

Titanium oxide can be used as a pigment other than the above-mentioned heavy calcium carbonate used in the present invention, and it is preferable to select 50 to 85 parts by weight based on 100 parts by weight of the above-mentioned heavy calcium carbonate. As mentioned above, the present invention does not require the use of finely powdered silica, which is harmful to the quality of the coating film. Finely powdered silica can be used, provided that the amount is limited to 15 parts by weight or less.

If the proportion of the pigment whose main component is heavy calcium carbonate is reduced more than necessary, the hiding power will decrease, and if the proportion of the pigment to the total amount of correction fluid is increased more than necessary, the hiding power will improve, but it will not be corrected. Application characteristics as a liquid,
In particular, fluidity and smoothness are reduced. Therefore, (the blending ratio of pigment to 1 positive liquid is 40 to 70% by weight).

Next, the volatile solvent to be blended in the correction fluid of the present invention is preferably one whose main component is a halogen hydrocarbon that is hardly soluble in oil-based ink, and considering the adjustment of the drying time of the coating film,
Those having a boiling point of 70 to 150°C are preferable. Specifically, in a halogenated hydrocarbon solvent, for example, 1.1.1. ) Lichloroethane, 1.1.2-) Chlorine-based products such as reflorethane, trichlorethylene, tetrachlorethylene, perchlorethylene, 1,2-dichloropropane, etc., product name, Guiflon S2-T (Daikin Industries, Ltd.) ) can be selected from one or more fluorine-based compounds such as.

Examples of solvents other than the halogenated hydrocarbon solvent used in the present invention include normal heptane, normal octane, ligroin, petroleum benzene,
It can be selected from one or more of petroleum spirit, naphtha, cyclohexane, methylcyclohexane, toluene, xylene, etc., and if flammability, odor, etc. are taken into consideration, 5 to 5 parts by weight of the halogenated hydrocarbon solvent may be selected.
Preferably, the amount is selected to be 15 parts by weight.

If the proportion of the volatile solvent mainly composed of the halogenated hydrocarbon solvent is reduced more than necessary in the total amount of correction fluid, the application properties of the correction fluid will deteriorate, and if the proportion of the volatile solvent in the total amount of correction fluid is increased more than necessary. Concealability is reduced. Therefore, the blending ratio of the volatile solvent to the correction fluid is 30 to 60% by weight.

Next, as the binder, acrylic resin, alkyd resin, vinyl resin, polyester resin, petroleum resin, etc. are used. All of these have the property of increasing the effect of binding the pigment to the coated surface, but in consideration of film performance, it is desirable to use an acrylic ester/methacrylic ester copolymer. This binder forms a coating film and adheres the coating film to the paper surface by selecting a combination that is soluble in the volatile solvent. However, if the ratio of binder to pigment is reduced more than necessary, cracks may occur in the film (and if the ratio is increased more than necessary, a satisfactory surface gloss or matte surface or good rewriting properties cannot be obtained, making it difficult to rewrite). Therefore, the weight ratio of binder to pigment is approximately 5:100 to 20:100.
It is.

The correction fluid of the present invention is prepared by uniformly mixing and dispersing the pigment mainly composed of heavy calcium carbonate in a solution consisting of these volatile solvents and binders at a predetermined ratio. , a dispersant such as a nonionic surfactant may be added as necessary.

〔Effect of the invention 〕

As described above, since the correction fluid of the present invention contains a pigment whose main component is heavy calcium carbonate in a specific range, it has excellent fluidity, the coating film dries quickly, and has good hiding properties and gloss. It has the remarkable effect of being easy to rewrite.

〔Example 〕

Next, the present invention will be explained in detail with reference to examples.Example 1 SatoJL2S= (Pigment) Heavy calcium carbonate (Note 1) 30 Titanium oxide (Note 2) 15 (Binder) Acrylic acid ester/meth 3 Acrylic Acid ester copolymer (volatile solvent) Perchlorethylene 51.5 (dispersant) Homogenol L-95 (Note 3) 0.5 total
100.0 Example 2 Weight % (R material) Heavy calcium carbonate (Note 1) 25.2 Titanium oxide (Note 2) 19.2 Fine silica powder (Note 4) 3.6 (Binder) Acrylic ester Meth 4-acrylic ester copolymer (volatile solvent) 1.1.1. l-lichloroethane 40 Toluene 7.5 (dispersant) Homogenol L-95 (Note 3) 0.5 total
100.0 Example 3 Weight % (Pigment) Heavy calcium carbonate (Note 1) 23.8 Titanium oxide (Note 2) 19.0 Fine silica powder (Note 4) 2.4 (Binder) Acrylic ester meth 3,8 acrylic ester copolymer (volatile solvent) 1.1.1. Trichloroethane 10.5
Trichlorethylene 39.3 (dispersant) Homogenol L-95 (Note 3) 1.2 total
100.0 Comparative Example 1 Weight Solvent) 1. 1.1. Trichloroethane 40 Toluene 7.5 (dispersant) Homogenol L-95 (Note 3) 0.5 total
100.0 Comparative Example 2 Riichi (pigment) Ultrafine calcium carbonate (Note 5) 23.8 Titanium oxide (Note 2) 19.0 Fine silica powder (Note 4) 2.4 (Binder) Acrylic ester Meta 3.8 Acrylic acid ester copolymer (volatile solvent) 1.1.1. ) Lichloroethane 10.5
Trichlorethylene 39.3 (dispersant) Homogenol L-95 (Note 3) 1.2 total
ioo,.

Here, (Note 1), (Note 2), (Note 3), (Note 4) and (Note 5) mean the following.

(Note 1); Product name, Super #1500 (Maruo Calcium Co., Ltd.) Average particle diameter 1.5 microns (calculated from specific surface area), maximum particle diameter 20 microns (Huber Maller test method), specific surface area 1.5 m" / g (Air permeation method) (Note 2): Product name, Tybake CR-50 (Ishihara Sangyo Co., Ltd.) Average particle size 0.275 microns (calculated from specific surface area), maximum particle size 0.35 microns (Hoover Maller test method) ), specific surface area 10.5m2/g (air permeation method) (Note 3): Nonionic surfactant (Kao Soap Company) (Note 4)
:Product name, Jilton R-2C (Mizusawa Chemical Industry Co., Ltd.) Average particle diameter 0.0275 microns (calculated from specific surface area),
Maximum particle diameter 0.035 microns (Huber Maller test method), specific surface area 150 m''/g (air permeation method) (Note 5): Product name, Homocal D (Shiraishi Kogyo Co., Ltd.) Average particle diameter 0.07 microns (electron microscopy) (according to the photograph), specific surface area 16.5 m2/g (BET method) Among the components of the above examples and comparative examples, the pigment was dispersed in a solution consisting of a binder, a volatile solvent, and a dispersant using a homogenizer. It was a white correction fluid.

Next, the performance of the correction fluid on each side is shown in the table below.

A fluidity test was conducted by dropping the correction fluid on each side onto a glass plate tilted at 60 degrees and measuring the flow distance. The correction fluid of the example showed good fluidity, but The correction liquid of Comparative Example 1, which did not use calcium carbonate, had less than half the fluidity, and the correction liquid of Comparative Example 2, which used ultrafine calcium carbonate instead of heavy calcium carbonate, also had poor fluidity. In addition, water-based ballpoint pen [trademark, PILOTH
i-Tecpoint (Pilot Mannen Pensha)] and oil-based ballpoint pen [trade name, Pilot BP-3 (Pilot Mannen Pensha)] were coated with the correction liquid of each example to a thickness of 20 microns, - times of Upon application, a smooth white coating film with good hiding properties could be formed, the coating film dried quickly, rewriting could be performed without any problem, and the coating film had little gloss, which was satisfactory. On the other hand, the correction fluid of the comparative example which did not contain heavy calcium carbonate had insufficient hiding power or poor coating film smoothness after one application.

table Here, ◯ and △ mean the following.

○: Good △: Handwriting looks thin

Claims (1)

[Claims] (1) In a correction fluid containing a pigment, a volatile solvent, and a binder as essential components, the pigment has an average particle diameter of 1.0 to 1.5 microns based on the specific surface area and a maximum particle diameter of 1.0 to 1.5 microns based on the Huber-Maller test method. A white coat-type correction fluid made using a pigment whose main component is heavy calcium carbonate, which has a specific surface area of 20 microns or less as measured by an air permeation method and a specific surface area in the range of 1.0 to 2.0 m^2/g.