JP2002254895A - Sintering-type solid correction utensil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid correction utensil which shows a hiding power by a small wet-on-wet coating frequency and also rewriting properties on a corrective coast as a solid correction utensil which is stable over time. SOLUTION: This solid correction utensil contains at least an extender material, a clay and/or a silicon compound and an inorganic powder with a refractive index of 2.0 or more, the initial hiding power of handwriting being 60% or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel sintered type solid corrector.

[0002]

2. Description of the Related Art Conventionally, a solid corrector uses a concealing agent such as titanium oxide and an emulsion of polyethylene, rosin, a polyhydric alcohol resin, etc. (JP-B-56-341).
No. 93), those using a concealing material such as titanium oxide and a 5- to 7-valent sugar alcohol, an aromatic aldehyde, a naphthenic solvent (JP-A-58-162677), resins,
What consists of a mixture of wax and titanium white
And a rod-shaped crayon-type solid corrector using a water-soluble resin and a concealing material such as titanium oxide to form a film having good water dispersibility (Japanese Patent Publication No. 8-119356). Gazette) has been proposed.
These are all non-fired solid correctors.

On the other hand, as a general sintering type solid drawing material, a synthetic resin as a forming aid and boron nitride as a body material are kneaded together with clay and formed into a fine wire shape, which is then formed in a non-oxidizing atmosphere. After obtaining a black skeleton with carbonized synthetic resin, heat treatment is again performed in an oxidizing atmosphere to sinter the clay and simultaneously scatter the carbide to obtain a whitened core. Further, there is a type in which a lubricating liquid such as an olefin oligomer or oleic acid is impregnated into pores formed by scattering of carbides to express writing taste and coloring.

[0004]

[Problems to be Solved by the Invention] Japanese Patent Publication No. Hei 8-01935
The solid correction tool described in Japanese Patent Publication No. 6 has good workability,
It can also be used to modify PC copies and fax manuscripts,
Because the coating is water-soluble, rewriting with water-based ink
The coating film dissolves and cannot be written well. Tokiko 56-34
The solid correction device described in the 193 publication needs to maintain a large water content, and when correcting a typographical error in a solid form, the solid has poor strength and easily breaks, making it impossible to perform a good correction. The solid fixation device described in JP-A-62-169873 uses an organic solvent and wax,
Solvents are easily scattered and solidified from solids, and there is a chronological problem that the correction agent cannot be applied without being properly applied to the correction surface, and with wax, the overcoating and hiding are incomplete. Above, the coating surface is weak and cannot be rewritten. There is a problem. Furthermore, all of these conventional solid correction devices are of the raw core type, and by using titanium oxide as a coloring agent, have the effect of concealing the base, but because the strength of the coating film at the time of correction writing is soft, There is a problem that writing cannot be performed because the pen tip of the writing instrument is buried.

On the other hand, the writing line of the sintered core is white,
The written handwriting cannot hide the underlying characters and the like. This is due to the fact that the refractive index of boron nitride is less than 2.0 and the lubricating property of the liquid impregnated in the pores of the sintered core is re-applied on the white line written first. In this case, the fixability at the time of re-application is poor, and the coating film cannot be thickened.

Conventional sintered cores have the property that the writing lines can be erased with an eraser by impregnating oil having a lubricating effect such as oleic acid into the pores of the core previously dyed with a dye or the like and abrading the oil. are doing. Therefore, it is naturally possible to impregnate the pores with wax if the eraser erasability is not required. However, the obtained writing line, like the writing line of a conventional solid correction tool, cannot be thickened because the slip property of the wax component on the writing line deteriorates the fixation at the time of re-application, and the writing film cannot be thickened. Even when the pen is rewritten on the surface with a water-based or oil-based pen, the ball at the tip of the nib slips and the phenomenon that writing cannot be performed remains.

According to the present invention, the pen nibs are buried in the paint film and the paint film is deformed and peels off or slips even when rewriting and rewriting. As a result of research with a focus on solid correction tools that do not
As a means of increasing the white hiding power of the conventional sintering type solid drawing agent, reforming the surface of the base material and reviewing the selection of the material, and impregnating the pores of these sintered cores with adhesive resin It was possible to provide an unprecedented solid correction tool.

[0008]

That is, the present invention is based on a completely novel technical idea, and includes at least a body material, a clay and / or a silicon compound, and an inorganic powder having a refractive index of 2.0 or more. The gist of the present invention is a sintered solid correction tool having an initial concealment ratio of 60% or more.

The details will be described below. The clay and silicon compound used in the present invention are used as a binder. As the clay, a material such as kaolin, clay, bentonite, etc., which forms a skeleton by sintering by heat treatment can be used. As the silicon compound, silicon nitride powder, silicon fluoride, silicon oxide and the like can be used. Furthermore, a silicon-containing polymer such as a silicon resin can also be used. The polymer forms a skeleton of a silicon compound such as silicon oxide or silicon nitride by heat treatment in air or a nitrogen atmosphere. These clays and silicon compounds may be used alone or in combination.

As the constitutional material used in the present invention, any material can be used as long as it is used for a conventionally known sintered type solid drawing material. Examples include mica, talc, boron nitride, silica, alumina, calcium carbonate and the like.

The above-mentioned body material is a particle that is fixed on the paper surface during writing and is the largest particle among the particles that wear out, and it can be assumed that the refractive index is improved by providing the particles with a concealing property. . Therefore, in order to impart the concealing property to the body material particles, if the body material is reviewed from the viewpoint that titanium oxide is previously coated on the surface of the body material, the flaky plate-shaped crystal particles have good cleavage properties themselves. Such mica, talc and boron nitride are particularly good. As mica, Beniungmo, Shiroumo, So-downmo, Sericite, Vanajinmo, Illite, Kinmo, Kuromo, Tetsumo,
Chinwaldunmo and the like. As talc or boron nitride, those having a low particle surface lubricity and a large particle diameter are preferred. The preferred particle size of mica, talc, and boron nitride is preferably an average particle size of about 2 to 70 μm. These extenders may be used alone or in combination.

As the extender, those whose surface is treated with microtitanium are particularly preferably used. this is,
This is because the surface of the body material is whitened by forming the micro titanium coating layer on the body material. As a method of forming a microtitanium coating layer on the surface of the extender pigment, a dry method by a hybridization system in which microtitanium particles are forcibly beaten to the surface of the extender material, or a method of attaching colloidal titanium hydroxide to the surface of the extender material, A method in which the surface of the body material is further coated in a dispersion medium of microtitanium and then fired in air to form a microtitanium coating layer can be exemplified, but the method is not particularly limited. What is necessary is just to form a microtitanium coating layer on the surface of the body material in the final sintered core, and the amount of microtitanium coated on the surface of the body material is preferably 5 to 50% by weight based on the weight of the body material. .

The reason why the body material on which the microtitanium coating layer is formed is whitened is as follows. The base material with the micro-titanium coating layer formed thereon causes interference between the reflected light of the base constituent material and the reflected light of the micro-titanium surface, causing diffused reflection. This is because the angle of light is significantly different from that of a conventional body material not treated with microtitanium. By the way, when a material with a microtitanium coating layer formed on the surface of a cleavable material such as talc, mica, and boron nitride is used as a constitutional material, the handwriting by the solid correction tool is counteracted by the writing load after it is fixed on the paper surface. The particle surface of the receiving pigment is peeled off one by one, and a new particle surface appears.At this time, the coated microtitanium forms new irregularities on the peeled particle surface, and fixes the particles during subsequent recoating. make it easier. As described above, the body material on which the microtitanium coating layer is formed can achieve high concealment by a synergistic effect of the optical characteristics of the microtitanium existing on the body material surface and the wear mechanism.

The inorganic powder having a refractive index of 2.0 or more is used for improving the concealment of writing lines, and includes rutile type titanium oxide (specific gravity: 2.76) and anatase type titanium oxide ( Specific gravity: 2.52), lead titanate (specific gravity: 2.7)
0), zircon oxide (specific gravity: 2.40), zinc sulfide (specific gravity: 2.40), antimony oxide (specific gravity: 2.19),
Zinc flower (specific gravity: 2.00), zinc oxide (specific gravity: 2.0)
2), lead white (specific gravity: 2.02) and the like, and the amount of use is preferably 5 to 10% by weight with respect to the total amount of the solid correction tool in consideration of not hindering the orientation effect of the body material. When the amount is less than 5% by weight, the concealing property cannot be improved, and when the amount is more than 10% by weight, the orientation effect of the body material is hindered and the strength is reduced.

The sintered solid correction tool of the present invention is required to have a first hand concealment ratio of 60% or more. Here, the writing initial hand concealment ratio indicates the concealment ratio when writing is performed once on the surface to be written. It is a value obtained by measuring the reflectance (Y value) and the reflectance (Y value) of black high-quality paper and calculating by the following formula. Initial writing concealment rate (%) = Y value of writing surface / Y value of black paper × 100
A conventionally known non-sintering type solid correction tool is different from a liquid correction liquid in that a portion to be corrected is not concealed by a single writing, but is written a plurality of times and is repeatedly applied to the solid correction tool. The thickness of the coating film is increased to hide the base. In contrast, the conventional sintered solid core is
Even if it was attempted to write over and overcoat a plurality of times, the thickness of the coating film did not increase, so that it could not be used as a correction tool.
However, in the case of sintering a composition containing a constitutional material, a clay and / or a silicon compound, and an inorganic powder having a refractive index of 2.0 or more, the initial writing concealment rate of this composition is 60%.
What has been adjusted as described above, becomes a coating film having a practical concealing property by writing over and applying multiple times,
It can be used as a sintered solid correction tool.

Various methods can be used for adjusting the concealment rate at the beginning of writing of the sintered solid correction tool of the present invention to 60% or more. For example, using a body material having a microtitanium coating layer formed thereon, the contact between the binder and the body material is made point contact, and the amount of wear during writing by smoothing the collapse of the body material from the core is increased. And how to do it.

The manufacture of the sintered type solid corrector according to the present invention comprises:
Conventionally known methods for manufacturing a sintered core can be employed. An example of the manufacturing method is as follows.
A composition containing at least the above essential components is sufficiently kneaded with a Hensyl mixer, a pressure kneader, a roll, or the like, then formed into a fine wire shape using an extruder or the like, and then fired in an inert atmosphere. The synthetic resin used as the profile is carbonized to obtain a black first fired core made of a carbide binder. Incidentally, the fired core body at this time has fine pores volatilized when the plasticizer or the synthetic resin is carbonized. Further, a firing treatment is performed in an oxygen atmosphere in order to volatilize the carbide binder in the black first firing core and sinter clay such as kaolin. As a result, pores communicating with the pores generated during the first fired core are generated by the volatilization of the carbide binder, and the second fired core in which the core itself has changed from black to a white sintered core can be obtained. it can. Also,
In order to improve the bending strength of the white sintered core, the xylene solution containing perhydropolysilazane is impregnated into the pores of the first and second fired cores and then heat-treated in an ammonia atmosphere. There is also a method of obtaining a white sintered core that forms a stronger silicon nitride skeleton by repeating a cycle of generating a silicon skeleton several times.

Various materials other than the above-mentioned materials can be used for the sintered solid corrector of the present invention. When impregnating the pores formed when forming the sintered core with an adhesive substance, the sintered core melted and impregnated with conventional waxes and the like,
The writing line is more firmly fixed on the paper. Next, when writing on the first writing line and then again on the writing line, since the wear particles are further laminated from the stickiness of the adhesive substance, the coating film becomes thicker each time rewriting, resulting in concealment. improves. And since the coating film formed by lamination with these adhesive substances is hard, it can be written without re-writing the pen tip at the time of rewriting. Examples of the adhesive substance include polyisobutylene resin, polyisobutadiene resin, polyisoprene resin, terpene resin, and ketone resin, which can be used alone or in combination. In order to impregnate the pores with such a substance exhibiting tackiness, the tacky substance is dissolved in an organic solvent which is soluble and relatively volatile with each resin, or the viscosity is increased by heating the tacky substance itself. A method of infiltrating into the pores of the sintered core body by lowering it or the like can be adopted.

Further, there may be mentioned aluminum hydroxide which acts as a binder after heat treatment, and various fibrous materials for the purpose of improving the orientation during molding. For example, there are potassium titanate fiber, aluminum borate fiber, calcium sulfate fiber, silicon nitride fiber, titanium oxide fiber and the like.

Further, conventionally known various resins are used as a shaping material for forming the clay and / or silicon compound and various body materials into a fine wire shape. For example, thermoplastic resins such as vinyl chloride resin and polyvinyl alcohol, thermosetting resins such as phenol resin, furan resin and epoxy resin, natural polymer substances such as lignin, cellulose, carboxymethyl cellulose, petroleum asphalt, coal tar pitch, and naphtha decomposition And pitches such as carbonized pitch such as pitch.

Further, plasticizers such as metal soap, dioctyl phthalate, dibutyl phthalate, tricresyl phosphate, dioctyl adipate, propylene carbonate, water, alcohols and ketones or organic solvents are used as plasticizers for plasticizing these synthetic resins. Use alone or in combination.

[0022]

The sintering type solid corrector of the present invention contains an inorganic powder having a refractive index of 2.0 or more, so that the concealing rate of the powder itself is high, the initial concealment rate is 60% or more, Since the coating can be applied, practically satisfactory hiding properties are imparted to the coating film.

[0023]

The present invention will be described below with reference to examples.
The present invention is not limited only to the examples. <Example 1> Brown moth (building agent) 50 parts by weight Titanium oxide (inorganic powder) 8 parts by weight Vinyl chloride resin (organic excipient) 20 parts by weight Dioctyl phthalate (plasticizer) 21 parts by weight Zinc stearate (lubricant) 1 100 parts by weight Methyl ethyl ketone (solvent) 100 parts by weight The above mixture was mixed and dispersed with a Hensyl mixer, heated and kneaded with a roll, and then extruded to remove these residual solvent and plasticizer in air. Heat treatment was performed at 200 ° C. Then, the mixture was treated at 1100 ° C. in a nitrogen atmosphere to obtain a calcined core in which the resin component was carbonized. It was further treated in air at 1100 ° C. to obtain a white sintered core having a diameter of 2 mm. This white sintered core was placed in a MEK solution of polyisopolybutylene resin for 24 hours.
After allowing to stand for a period of time, a sintered solid corrector having pores filled with a polyisobutylene resin was obtained.

Example 2 50 parts by weight of microtitanium-coated brown moth (building agent) 8 parts by weight of titanium oxide (inorganic powder) 20 parts by weight of vinyl chloride resin (organic excipient) 21 parts by weight of dioctyl phthalate (plasticizer) 21 parts by weight of stearin 1 part by weight of zinc oxide (lubricant) 100 parts by weight of methyl ethyl ketone (solvent) 100 parts by weight of the above composition was mixed and dispersed by a Hensyl mixer, heated and kneaded with a roll, extruded, and the remaining solvent and plasticizer were removed. It was heat-treated at 200 ° C. in air to remove it. Then, it was treated at 1100 ° C. in a nitrogen atmosphere to obtain a fired core in which the resin component was carbonized. It was further treated in air at 1100 ° C. to obtain a white sintered core having a diameter of 2 mm. This white sintered core was placed in a MEK solution of polyisopolybutylene resin.
After allowing to stand for 4 hours, a sintered solid corrector having pores filled with a polyisobutylene resin was obtained. In addition, the microtitanium-coated sirumbo was obtained by the following method. 1) 100 g of the brown moth is placed in a colloidal solution in which 10 g of titanium hydroxide is dispersed, and the titanium hydroxide is adhered to the surface of the brown moth. After drying, powder (a) is obtained. 2) Next, (a) was placed in a solution in which 1% of nitrocellulose was dissolved in 100 cc of methyl ethyl ketone to obtain (a) in which a nitrocellulose coating was formed on the surface. 3) Next, (a) is put into a solution in which 10 g of microtitanium is dispersed to obtain (c) with microtitanium adhered on the titanium hydroxide. 4) Next, (c) is placed in an air atmosphere at 1000 to 1400 ° C.
To obtain a coated brown mound covered with about 10% of microtitanium.

<Example 3> White moth (building agent) 50 parts by weight Titanium oxide (inorganic powder) 8 parts by weight Vinyl chloride resin (organic excipient) 20 parts by weight Dioctyl phthalate (plasticizer) 21 parts by weight Zinc stearate ( Lubricant) 1 part by weight Methyl ethyl ketone (solvent) 100 parts by weight The above components were mixed and dispersed with a Hensyl mixer, heated and kneaded with a roll, and then extruded to remove these residual solvent and plasticizer. Heat treatment was performed at 200 ° C. in air. Then, it was treated at 1100 ° C. in a nitrogen atmosphere to obtain a fired core in which the resin component was carbonized. Further treatment in air at 1100 ° C. gave a sintered solid corrector having a diameter of 2 mm.

<Example 4> Microtitanium-coated brown moth (the same constitutional agent as used in Example 2) 50 parts by weight Titanium oxide (inorganic powder) 8 parts by weight Vinyl chloride resin (organic excipient) 20 parts by weight Dioctyl phthalate (plasticizer) 21 parts by weight Zinc stearate (lubricant) 1 part by weight Methyl ethyl ketone (solvent) 100 parts by weight The above ingredients are mixed and dispersed by a Hensyl mixer, heated and kneaded by a roll, and extruded. Heat treatment was performed at 200 ° C. in air to remove these residual solvents and plasticizers. Then, it was treated at 1100 ° C. in a nitrogen atmosphere to obtain a fired core in which the resin component was carbonized. Further treatment in air at 1100 ° C. gave a sintered solid corrector having a diameter of 2 mm.

<Example 5> 50% by weight of brown moth (building agent) 8 parts by weight of titanium oxide (inorganic powder) 20 parts by weight of vinyl chloride resin (organic excipient) 21 parts by weight of dioctyl phthalate (plasticizer) 21 parts by weight of zinc stearate ( Lubricant) 1 part by weight Methyl ethyl ketone (solvent) 100 parts by weight The above components were mixed and dispersed with a Hensyl mixer, heated and kneaded with a roll, and then extruded to remove these residual solvent and plasticizer. Heat treatment was performed at 200 ° C. in air. Then, it was treated at 1100 ° C. in a nitrogen atmosphere to obtain a fired core in which the resin component was carbonized. It was further treated in air at 1100 ° C. to obtain a white sintered core having a diameter of 2 mm. While the paraffin wax which melted this white sintered core was dissolved, 2
It was left still for 4 hours to obtain a sintered solid corrector in which the pores of the sintered core were filled with paraffin wax.

<Embodiments 6 and 7> The same as in Embodiment 2 except that in place of the microtitanium-coated brown moth, talc and boron nitride were used, each of which was treated with a microtitanium-coated body material. The operation was performed to obtain a sintered solid correction tool.

<Examples 8 to 12> All of Example 1 was repeated except that the polyisobutylene resin of the impregnated dispersion was replaced with an isobutadiene resin, an isoprene resin, a polybutene resin, a terpene resin, and a ketone resin. The same operation as described above was performed to obtain a sintered solid correction tool.

<Comparative Example 1> White moth (building agent) 58 parts by weight Vinyl chloride resin (organic excipient) 20 parts by weight Dioctyl phthalate (plasticizer) 21 parts by weight Zinc stearate (lubricant) 1 part by weight Methyl ethyl ketone (solvent) 100 parts by weight The above composition was mixed and dispersed by a Hensyl mixer, heated and kneaded with a roll, extruded, and heat-treated at 200 ° C. in air to remove these residual solvent and plasticizer. Then, it was treated at 1100 ° C. in a nitrogen atmosphere to obtain a fired core in which the resin component was carbonized. It was further treated in air at 1100 ° C. to obtain a white sintered core having a diameter of 2 mm. While the paraffin wax which melted this white sintered core was dissolved, 2
It was left still for 4 hours to obtain a sintered solid corrector in which the pores of the sintered core were filled with paraffin wax.

Using the sintering-type solid correction tools obtained in the above Examples and Comparative Examples, the initial writing concealment ratio was measured. The measuring method was carried out using a record streaker used in the density measurement of JIS S6005, but in the measurement of the concealment rate of the writing line, the writing line was not written like the coated surface. And must be obtained in such a way that they are not overcoated. Therefore, we focused on the need to accurately reproduce the whiteness at which people started writing as much as possible.

Specifically, the cross-sectional diameter of the tip is 0.5 mm
Holder with a sintered solid correction tool that has been machined to
, And about 3 mm from the holder-tip. Then, writing is started from an arbitrary position on black paper (black high-quality paper), and the measurement is terminated once when the tip width of the spiral writing is about 1 cm. At this time, the pitch of the line width is 1 mm, the writing load is 300 g, and the writing angle is 75 °. Next, the tip of the same sample was cut out in the same manner as above, and the same sample was loaded into the holder in the same manner as above, and drawing was started from a position inside the writing start position, and the tip width was similarly 1 cm. Finish writing at the place. The handwriting on the black paper at this time has a gap between the tip widths at the beginning of writing, but it depends on the hardness of the sintered core, but after 2/3 of the tip width, the pitch interval where the writing lines do not overlap each other Can be written with
It is possible to reproduce the coated surface with a line that is close to the initial writing condition corrected with a solid correction tool and enlarged. The first-hand writing concealment ratio is calculated from the ratio of the reflectance of the black paper as the base written in this way to the writing surface reflectance. In the reflectance measurement, the Y value was used, and CM-3700d manufactured by Minolta was used as a measuring instrument. Initial writing concealment rate (%) = Y value of coated surface / Y value of black paper × 1
00

Concealment: As an evaluation from the beginning of writing to the completion of overcoating and complete concealment of the background, a 10-point "gi" is created by a word processor, output by a printer, and the paper is dried by a dry copying machine. Using the samples obtained in each of the examples, the number of times the characters were erased by visual judgment was monitored using 10 samples, and the average of three times was calculated. .

With respect to the rewriting property of the corrected part, a 10-monitor monitoring using a water-based ballpoint pen (K105, manufactured by Pentel Co., Ltd.) was performed on the painted portion of the painted paper piece obtained from the above-described concealing test. And evaluated according to the criteria described below. ：: Can be re-written △: Can be re-written, but part of the writing line is blurred ×: Cannot be re-written

The results are shown in Table 1.

[Table 1]

[0036]

As described above, according to the present invention, the number of times of concealing the base as the sintered solid correction tool is significantly reduced.
It is possible to obtain a sintering-type solid correction tool with good rewriting on the coating film surface.

Claims (5)

[Claims] 1. A composition comprising at least a body material, a clay and / or a silicon compound, and an inorganic powder having a refractive index of 2.0 or more,
A sintered solid correction tool with a first hand concealment ratio of 60% or more. 2. The sintered solid correction tool according to claim 1, wherein the pores are impregnated with an adhesive substance. 3. The adhesive substance according to claim 2, wherein the adhesive substance is at least one selected from polyisobutylene resin, polyisobutadiene resin, polyisoprene resin, polybutene resin, terpene resin, and ketone resin. The sintering type solid correction tool according to the above. 4. The sintered solid correction tool according to claim 1, wherein the body material has a surface treated with microtitanium. 5. The sintered solid correction tool according to claim 1, wherein the body material is one or a combination of boron nitride, talc, and mica.