JP4919652B2 - Solid drawing material and method for producing the same - Google Patents

Description

  The present invention relates to a solid drawing material such as a solid drawing material for mechanical pencils and a solid drawing material for wooden shafts, which is mainly used for writing instruments.

  In general, important characteristics required for a solid drawing material are good writing feeling, good color development of drawn lines, and high mechanical strength.

  As a conventional solid drawing material, for example, in which a fibrous material is used as a reinforcing material when a binder and graphite are used as main materials and a pencil core is manufactured by heat treatment at high temperature after kneading and extrusion molding. A method for producing a solid drawing material characterized in that graphite whiskers are used as the fibrous material (see, for example, Patent Document 1), and an extender and a binder as main materials, and a solvent and / or plastic as necessary. Vapor phase growth that is a solid drawing material kneaded with an agent and fired at a high temperature after extrusion, and having a diameter of 0.01 to 0.15 μm and a fiber length / fiber diameter of 50 to 10,000 as part of the extender A fired solid drawing material containing fibers in an amount of 1 to 60% by weight of the entire solid drawing material (for example, see Patent Document 2) is known.

  In addition, extrudates that are composed of an extender such as graphite and carbon black and a binder such as clay, natural polymer, pitch, and asphalt and kneaded with a solvent and / or plasticizer as required. In a method for producing a pencil core that is molded and fired at high temperature, a fired pencil that uses carbon nanotubes (fine tube-like graphite) having a diameter of 1 to 50 nm and a length of 0.5 to 50 μm as at least a part of the extender. A core manufacturing method (see Patent Document 3 by the present applicant) is known.

  However, the techniques described in Patent Documents 1 and 2 use graphite whisker as a reinforcing material and vapor-grown fibers having specific physical properties as part of a constitution material, and have bending strength, concentration, and writing performance. Although there is a good balance, there is a problem in that even if the fibrous materials having the above characteristics are used, the compression strength, writing quality, and drawn line density cannot be further improved. Further, in the techniques described in Patent Documents 1 and 2, since the extender is large, the orientation of the original carbon of the pencil core is broken, the compressive strength is weak, and the contained material is large, so the writing feeling is good. However, further improvement was necessary to improve the writing property.

  In addition, the technique described in Patent Document 3 is blended with carbon nanotubes as a modifier, and the main purpose is to provide strength as a composite material, further improving the compressive strength and improving the solidity of the present invention. The effective pore volume and surface area that can be impregnated with oil in the drawing material are increased, the writing is smooth, the color development and drawing density are sufficient, the amount of wear is small, the erasability is good, and the drawing is done manually. The technical idea is different from that of providing a solid drawing material that is not easily soiled even when rubbed.

Usually, solid drawing materials such as mechanical pencil lead and pencil lead have fine pores after firing, and these pores are impregnated with a frictional wear adjusting agent such as lubricating oil, so The balance of darkness is adjusted. However, during normal manufacturing, pores (claude cells) that are not open systems are formed in the core. Such pores were not impregnated with oil, and the more Claude cells, the more fragile the core was. Therefore, in the conventional solid drawing material, since the closed cell is included, the effective pore volume that can be impregnated with oil is small, and the oil impregnation in the solid drawing material is also achieved by the techniques of Patent Documents 1 to 3 described above. There is a problem in that the effective effective pore volume and surface area cannot be increased.
Japanese Patent Laid-Open No. 62-129370 (Claims, Examples, etc.) JP 2002-105377 A (Claims, Examples, etc.) JP-A-8-325504 (Claims, Examples, etc.)

  The present invention is to solve this problem in view of the above-mentioned problems of the prior art, and further improves the compressive strength and increases the effective pore volume and surface area capable of oil impregnation in the solid drawing material, To provide a solid drawing material that has a smooth writing quality, has sufficient color developability and drawing line density, has a small amount of wear, has good erasability, and is resistant to contamination even when the drawing line is rubbed by hand, and a method for producing the same Objective.

  As a result of intensive studies to solve the above-described conventional problems and the like, the present inventor can obtain the above-described solid drawing material and a method for producing the same by including a nanomaterial in at least the solid drawing material. The inventors have found out that the present invention has been completed.

That is, this invention exists in following (1)-( 10 ).
(1) A nanomaterial having a particle size of 0.7 to 100 nm selected from the following group A that is 0.01 to 5% by weight based on the total amount of the solid drawing material , and graphite that is not coated with the nanomaterial. solid drawing, characterized in that formed by filling at least a solid drawing material compounding compositions containing form a firing treatment was formed by solid drawing material core, the lubricant in the pores of said solid painting material core Wood.
Group A: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphorous oxide ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multiple composition composite nanoparticles as Pt-Au multiple composition composite nanoparticles (2) the lubricant, the (1 using a lubricant is a particle size selected from the following group B containing nanomaterials 0.7~100nm ) Solid drawing material according to.
Group B: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphate ceramics, carbide ceramics, silicate ceramics and borides ceramics (except for silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles (3) A solid drawing material core is formed by firing the blended composition for solid drawing material, and the solid drawing material core is formed in the pores of the solid drawing material core. Filled with a lubricant containing a nanomaterial having a particle size of 0.7 to 100 nm selected from the following group C Characteristic solid drawing material.
Group C: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphate ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles (4) When a lubricant containing the nanomaterial is used, 0.01-5 wt% of the nanomaterial is lubricated with respect to the total amount of the solid drawing material The solid drawing material according to (2) or (3), which is contained in the agent.
(5) The solid drawing according to any one of (1) to (4), wherein the solid drawing material is a calcined pencil lead for mechanical pencils containing at least graphite and / or carbon black and amorphous carbon in the nanomaterial. Wood.
( 6 ) The solid drawing material according to any one of (1) to ( 5 ), wherein the nanomaterial is obtained by any one of a gas phase synthesis method, a liquid phase synthesis method, and a mechanical pulverization method. .
(7) surface in the amorphous carbon particles of the nano-material, the at least one of carbon graphite and diamond are coated (1) to a solid painting material according to any one of (6).
( 8 ) The solid drawing material according to any one of (1) to ( 7 ), wherein the solid drawing material is a fired pencil lead containing at least a coloring material, an extender, and a ceramic binder.
( 9 ) (a) graphite or graphite and carbon black, (b) thermoplastic synthetic resin, (c) an organic solvent capable of dissolving the thermoplastic synthetic resin, and (d) a particle size selected from the following group D is 0.00. 7-10 nm nanomaterials are kneaded, molded, dried and fired in a non-oxidizing atmosphere to obtain a solid drawing material core, and the pores of the solid drawing material core are filled with a lubricant. A method for producing a solid drawing material.
Group D: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphorous oxide ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles ( 10 ) (a) Graphite or graphite and carbon black, (b) thermoplastic synthetic resin, (c) organic solvent capable of dissolving the thermoplastic synthetic resin A solid drawing material core body is formed by kneading, molding, drying and firing in a non-oxidizing atmosphere. Method for producing a solid drawing material characterized by a particle size selected from the following group E in the pores of said solid drawing material core is filled with a lubricant containing nanomaterials 0.7～100Nm.
Group E: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphorous oxide ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles

  According to the present invention, by incorporating a nanomaterial in the solid drawing agent, the compressive strength is further improved, and the effective pore volume and surface area that can be impregnated with oil in the solid drawing material are increased, and the writing quality is smooth. Thus, there are provided a solid drawing material having a sufficient color developability and drawing line density, a small amount of wear, good erasability, and difficult to get dirty even if the drawing line is rubbed by hand, and a method for producing the same.

Hereinafter, embodiments of the present invention will be described in detail.
Solid drawing material of the present invention, as a first invention, to form a solid drawing material substrate made by sintering process the solid drawing material compounding composition containing at least nanomaterials, pores of said solid painting material core a lubricant are those characterized by comprising filled within, also, as a second invention, to form a solid drawing material substrate made by sintering process the solid drawing material compounding composition, said solid It is characterized by filling the pores of the drawing material core with a lubricant containing a nanomaterial.
Hereinafter, the term “present invention” refers to both the first invention and the second invention.

In the present invention, the nanomaterial to be used is not particularly limited as long as it is generally classified as a nanomaterial, and any of them can be used.
As the nanomaterial that can be used, various ceramic materials can be used. For example, metal oxide ceramics such as silicon, titanium, zirconium, aluminum, and cerium, nitride ceramics, phosphorous oxide ceramics, and carbide ceramics. Any of silicate ceramics and boride ceramics (excluding silicon oxide ceramics) can be used, but these may be used alone, but two or more may be used in combination. Yes, it is appropriately selected depending on the shape of the target molded body and the molding method.

As the nanomaterial can be used, as other than the ceramic material, for example, metal nanoparticles include any carbon particles child diamond nanoparticles child.
The metal nanoparticles can be used, it is possible to use various metal nanoparticles, such as silver (Ag) nanoparticles, platinum (Pt) nanoparticles, gold (Au) nanoparticles child of any single composition nanoparticles, Fe-Pd, Fe-Pt , Pt-Pd, Pt-a u of which multiple composition composite nanoparticles, amorphous carbon, graphite, either can be used for coating nanoparticles coated such as a diamond and ceramic materials These can be used alone or in admixture of two or more, and are appropriately selected depending on the shape of the target molded product and the molding method.

Also, as the diamond nanoparticles can be used, the diamond nanoparticles was produced by the explosion method, EACVD method include those made of diamond nanoparticles produced by a vapor phase synthesis method and a liquid phase growth method, specifically the nano Tech Systems Inc. CD (Cluster diamond), CDS ( Cluster diamond Slurry), GCD (Graphite Cluster diamond), GCDS (graphite Cluster diamond slurry), Ru can be used JETRO Co. population or diamond.

In the present invention, the particle size of the nanomaterial is such that the pores (closed cells) and the pores (closed cells) in the solid drawing are connected at the time of production, thereby further forming open pores (open cells). In the case of nanomaterials made of ceramic materials, metal nanoparticles, diamond nanoparticles, and carbon nanoparticles, preferably 0.7-100 nm, more preferably 1-20 nm, and particularly preferably 3-15 nm. Yes.

When the particle size of nanomaterials, metal nanoparticles, diamond nanoparticles, carbon particles, etc. made of the above ceramic materials is less than 1 nm, monodispersion as particles is difficult and easily aggregates, and the reactivity becomes unstable and unstable. or, on the other hand, if it exceeds 100 nm, collapsed structure as a pencil lead strength is lowered, it has an unwanted.

  In the present invention, the nanomaterial is preferably produced by any one of a gas phase synthesis method, a liquid phase synthesis method, and a mechanical pulverization method from the viewpoint of production efficiency, lot variation, and material stability. Is desirable.

The gas phase synthesis method is a method for producing nanomaterials by an instantaneous gas phase synthesis method (Flash Creation Method; FCM), a gas aggregation method (Gleiter), laser ablation, or the like.
The liquid phase synthesis method is to produce nanomaterials by electroplating method, liquid quenching method or the like.
The mechanical pulverization method is a method for producing nanomaterials by a high strain processing method, a powder metallurgical method, a rotational flow method, or the like.
These synthesis methods can be appropriately selected and used depending on the type of nanomaterial and the embodiment of the solid drawing material.

The content of these nanomaterials is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, particularly preferably 0.1 to the total amount of the solid drawing material composition. We then desirable to 2wt%.
When the content of the nanomaterial is less than 0.01% by weight, the effective pore volume hardly changes, and the difference from the non-added pencil lead does not appear. On the other hand, if the content of the nanomaterial exceeds 5% by weight, the effective pore volume increases, but the structure of the pencil core collapses and the strength decreases, which is not preferable.

As described above, the solid drawing material of the present invention contains a nanomaterial as a blended composition, but other components are appropriately adjusted according to the type of the solid drawing material, such as a constitution material, a lubricant, and a binder component. It can be selected and used.
For example, in the solid drawing material calcined pencil leads for mechanical pencils, in addition nanomaterials, graphite and / or rather is preferable that at least carbon black and amorphous carbon, in a further, the firing pencil core, a colorant structure It is preferable to contain at least a material and a ceramic binder. Further, in a mechanical pencil baked pencil leads, as other components, alpha-olefin oligomers, fatty acid esters, spindle oil, waxes, Ki out using boron nitride, talc, silicone oil, silica fine particles, a metal soap, the baked adult pencil leads, as other components, and silicone oil, lard, acrylic resins, epoxy resins, celluloid and other thermoplastic resins.

Examples of the graphite used in the present invention include natural graphite, artificial graphite, quiche graphite, expanded graphite, expanded graphite, and the like. As the carbon black, oil furnace black, gas furnace black, channel black, thermal black, acetylene black, Examples of the ceramic binder include crystalline or amorphous SiO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , ZrO, MgO, boron nitride, B ₂ O ₃ , and AlN. These may be used alone or in combination of two or more.

  Moreover, as an extender material used by this invention, if it is used for the conventional solid drawing material, it will not specifically limit, All can be used. For example, depending on the color of a white based material such as boron nitride, kaolin, talc, mica, calcium carbonate, and the hue of a solid drawing material, a colored based material can be used, and naturally several kinds of mixtures can be used. Particularly preferred are boron nitride, kaolin and talc because of their physical properties and shape.

As the coloring material used in the present invention, any material can be used as long as it is classified into generally used ink compositions for writing instruments, for example, aqueous pigment ink, aqueous dye ink, oil pigment ink. Oil-based dye inks can be used, but are not limited thereto.
Examples of the pigment include titanium oxide, iron black, carbon black, bitumen, ultramarine blue, blue No. 1, petal, yellow iron oxide, chromium oxide, chromium hydroxide, zinc oxide, zirconium oxide, cobalt oxide, fish scale foil, oxy Bismuth chloride, Titanium mica, Blue No. 2, Blue No. 404, Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, DPP Red, Yellow No. 4, Yellow No. 5, Green And pigments such as No. 3 can be used, and these can be used alone or in admixture of two or more.

As the lubricant used in the present invention, any lubricant can be used as long as it is generally classified as a lubricant, and any lubricant or grease can be used.
Examples of the lubricating oil include mineral oils such as engine oils, α-olefin oligomers, synthetic oils such as silicone oils and ester oils, and vegetable oils such as castor oils. Examples of greases include calcium soap greases and lithium. Examples include soaps such as soap grease, and non-soaps such as Benton grease and silica gel grease, but are not necessarily limited thereto.

  The binder component used in the present invention is not particularly limited as long as it is used in conventional solid drawing materials, and any of them can be used. For example, celluloses such as carboxymethyl cellulose, polyvinyls such as polyvinylpyronidone, polyethers such as polyoxyethylene, acrylic acids such as polyacrylic acid, inorganic polymers such as tetraethyl orthosilicate (TEOS) condensate, montmorillonite And clay, ceramic glass and the like. These can be used alone or in admixture of two or more.

Examples of the thermoplastic synthetic resin used in the present invention include polyvinyl alcohol, polyvinyl chloride, polychlorinated vinyl chloride, polyamide, polyethylene, polypropylene, polyether ether ketone, and the like.
The organic solvent to be used is preferably one that can dissolve the thermoplastic synthetic resin, specifically, dioctyl phthalate, dibutyl phthalate, tricresyl phosphate, dioctyl adipate, diallyl isophthalate, propylene carbonate, alcohols, ketones, Esters can be used.

This solid drawing material of the first invention, in addition to the nano-material, the solid drawing grades, for example, baked pencil leads for mechanical pencils, each component used in baked formation pencil lead (extender material, colorant such as pigment, surfactant lubricating active agents, perfumes, thermoplastic resin, an organic solvent, etc.) kneading, molding, drying and non-oxidizing by firing treatment in an atmosphere to obtain a solid drawing material core, the pores of said solid painting material core It can be manufactured by filling the agent.
In the first aspect of the present invention, for example, in the production of a baked pencil lead for a mechanical pencil, the solid drawing material is preferably (a) graphite or graphite and carbon black in total from 30 to 30 in terms of strength, concentration and writing quality. 60 wt%, (b) 30-60 wt% thermoplastic synthetic resin, (c) 10-30 wt% organic solvent capable of dissolving the thermoplastic synthetic resin, and (d) 0.01-5 wt nanomaterial. % With a Henschel mixer, kneaded with a pressure kneader and two rolls, molded with an extruder, dried in an electric furnace at 110 to 250 ° C., and then in a non-oxidizing atmosphere (nitrogen gas The solid drawing material core is obtained by baking at 800 to 1400 ° C. for 20 to 40 hours in an atmosphere or under an inert gas atmosphere, and α-olefin oligomer, silicone oil, ester oil is contained in the pores of the solid drawing material core. Synthetic oils such as Le, vegetable oils such as castor oil, it is desired to produce by filling the like impregnated with a lubricant such as grease.

In the second invention, the solid drawing material compound formulations mentioned above, for example, baked pencil leads for mechanical pencils, each component used in baked formation pencil lead (extender material, colorant such as pigment, surfactant, perfume, heat thermoplastic resins, such as an organic solvent) kneading, molding, drying and non-oxidizing made by firing treatment in an atmosphere solid drawing material core is formed, containing the nanomaterial in the pores of said solid painting material core It can be manufactured by filling a lubricant.
When the lubricant containing the nanomaterial is used, the content of the nanomaterial is preferably 0.01 to 5% by weight, more preferably 0.1 to 3%, based on the total amount of the solid drawing material to be produced. It is desirable that the nanomaterial is filled in the pores of the solid drawing material core by being contained in the lubricant so as to be 0.1% by weight, particularly preferably 0.1 to 2% by weight.
If the content of the nanomaterial is less than 0.01% by weight, the effect of the present invention cannot be exhibited. On the other hand, even if the content of the nanomaterial exceeds 5% by weight, the effect of the present invention can be exhibited. However, there is a manufacturing disadvantage that it is difficult to fill the core.

  In the second aspect of the present invention, for example, in the production of a baked pencil lead for a mechanical pencil, the solid drawing material is preferably (a) graphite or graphite and carbon black in total from 30 to 30 in terms of strength, concentration and writing quality. 60% by weight, (b) 30-60% by weight of a thermoplastic synthetic resin, and (c) 10-30% by weight of an organic solvent capable of dissolving the thermoplastic synthetic resin are dispersed and mixed with a Henschel mixer, and a pressure kneader , Kneaded with two rolls, molded with an extruder, dried in an electric furnace at 110-250 ° C., and then 800-1400 in a non-oxidizing atmosphere (nitrogen gas atmosphere, inert gas atmosphere) A solid drawing material core is obtained by firing at 20 ° C. for 20 to 40 hours, and a lubricant (dispersion) containing the nanomaterial in the pores of the solid drawing material core, for example, the above-described nanomaterial is contained. Shamed α-Olephy Oligomers, silicone oils, synthetic oils such as ester oils, vegetable oils such as castor oil, it is desired to produce by filling with a lubricant such as grease impregnation or the like. The mixing ratio of nanomaterial: lubricant is preferably 1: 1000 to 1: 2 from the viewpoint of characteristics as a lubricant.

In the first invention, as described above, nanomaterials in solid drawing blend composition, preferably, those having a particle size and content was allowed at least containing nanomaterials the specific range by firing treatment to Rukoto Thus, a solid drawing material core body in which the pore shape during solid drawing is changed is obtained. Specifically, in the conventional manufacturing, etc., since there are pores (closed cells, independent pores) in the solid drawing material, the effective pore volume and surface area that can be impregnated with oil cannot be increased. In the present situation, the intended solid drawing material cannot be obtained. On the other hand, in the solid drawing material of the present invention, the inclusion of nanomaterials connects the pores (closed cells) and the pores (closed cells) in the solid drawing material to form open pores (open cell, continuous). Since the effective pore volume and surface area that can be impregnated with oil in the solid drawing material can be increased, the amount of lubricant that can be impregnated with oil increases. This greatly improves the lubrication of the core of the solid drawing material, so there is no excessive wear, so the amount of wear is reduced, and the smooth drawing line is irregularly reflected when nanomaterials such as nanoparticles enter the core. In the case of containing graphite, the friction between the paper and the carbon particles and the carbon particles is reduced, and the erasability is improved. Furthermore, since a nanomaterial can be contained without interfering with the orientation of carbon, a constitutional effect is added and the compressive strength is also improved. Furthermore, since the wear amount of the core is small, the amount of carbon on the drawn line is small, and the hand is difficult to get dirty.

In the second invention, filling the lubricant to form a solid drawing material substrate made by sintering process the solid drawing material compound formulations, containing nanomaterials in the pores of said solid painting material core Therefore, the effective pore area does not increase because it is not added during the firing of the first invention. However, since the nanomaterial contained in the lubricant acts as a suspension, the lubrication of the core is significantly better than when no nanomaterial is added. For this reason, since there is no excessive wear, the amount of wear is reduced, and by filling the pores in the core with nanomaterials such as nanoparticles, smooth drawn lines cause irregular reflection and become dark colors, In the case of containing graphite, the friction between paper and carbon particles and carbon particles is reduced, and the erasability is improved. Furthermore, since a nanomaterial can be contained without interfering with the orientation of carbon, the effect as a filler is added and the compressive strength is also improved. Furthermore, since the wear amount of the core is small, the amount of carbon on the drawn line is small, and the hand is difficult to get dirty.

The solid drawing material of the present invention configured as described above is not limited to the above embodiment, and can be implemented with various modifications within the scope of the technical idea of the present invention. For example, the first invention is obtained core, i.e., to form a solid drawing material substrate made by sintering process the solid drawing material compounding composition containing at least nanomaterials, the said solid painting material core The pores may be filled with a lubricant containing nanomaterials. In this case, since the nanomaterial in the solid drawing material core and the nanomaterial in the lubricant are completely independent, the same or different nanomaterials may be used in different contents. The preferred content of nanomaterials in this case, up to that 10% by weight and Do in the solid drawing material in.

  Next, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1
Natural scaly graphite (average particle size 7 μm) 47 parts by weight Ceria nanoparticles (cerium oxide nanoparticles, average particle size 10 nm) 3 parts by weight Polyvinyl chloride 50 parts by weight Sodium stearate 1 part by weight Dioctyl phthalate 20 parts by weight After mixing and dispersing, kneading with a pressure kneader and two rolls and extrusion molding into a linear body, heat treatment in air to remove the remaining plasticizer and solidification (drying), in a nitrogen gas atmosphere Baking at 1000 ° C. and finally dipping in an α-olefin oligomer (Lion Corporation, Lipoloop 20) and soaking in oil gave a mechanical pencil lead HB having a diameter of 0.570 mm.

(Example 2)
In Example 1, a mechanical pencil lead HB having a diameter of 0.570 mm was obtained in the same manner as in Example 1 except that 47 parts by weight of graphite was changed to 48 parts by weight and 3 parts by weight of ceria nanoparticles were changed to 2 parts by weight. It was.

(Example 3)
In Example 1, a mechanical pencil lead HB having a diameter of 0.570 mm was obtained in the same manner as in Example 1 except that 47 parts by weight of graphite and 45 parts by weight of ceria nanoparticles were changed to 5 parts by weight. It was.

Example 4
In Example 1 above, for mechanical pencils having a diameter of 0.570 mm, as in Example 1, except that 47 parts by weight of graphite was changed to 49.9 parts by weight and 3 parts by weight of ceria nanoparticles were changed to 0.1 parts by weight. A wick HB was obtained.

(Example 5)
In Example 1, a mechanical pencil lead HB having a diameter of 0.570 mm was obtained in the same manner as in Example 1 except that 47 parts by weight of graphite and 40 parts by weight of ceria nanoparticles were changed to 10 parts by weight. It was.

(Example 6)
Example 1 For mechanical pencils having a diameter of 0.570 mm, as in Example 1, except that 47 parts by weight of graphite was changed to 49.995 parts by weight and 3 parts by weight of ceria nanoparticles were changed to 0.005 parts by weight. A wick HB was obtained.

(Example 7)
In Example 1 above, for mechanical pencils having a diameter of 0.570 mm, as in Example 1, except that 47 parts by weight of graphite was changed to 49.99 parts by weight and 3 parts by weight of ceria nanoparticles were changed to 0.01 parts by weight. A wick HB was obtained.

(Example 8)
In Example 1, a mechanical pencil lead HB having a diameter of 0.570 mm was obtained in the same manner as in Example 1 except that 47 parts by weight of graphite was changed to 49 parts by weight and 3 parts by weight of ceria nanoparticles were changed to 1 part by weight. It was.

(Delete)

(Example 9 )
In Example 1, the diameter was 0 as in Example 1, except that 47 parts by weight of graphite and 49 parts by weight of ceria nanoparticles were changed to 1 part by weight of silver nanoparticles (average particle size: 8 nm). A 570 mm mechanical pencil lead HB was obtained.

(Example 10 )
In Example 1, the diameter was 0 as in Example 1, except that 47 parts by weight of graphite and 49 parts by weight of ceria nanoparticles were changed to 1 part by weight of diamond nanoparticles (average particle size: 5 nm). A 570 mm mechanical pencil lead HB was obtained.

(Delete)

(Example 11 )
In Example 1, except that 47 parts by weight of graphite was changed to 49 parts by weight, and 3 parts by weight of ceria nanoparticles were changed to 1 part by weight of diamond nanoparticles coated with graphite (average particle size: 15 nm). Similarly, a mechanical pencil lead HB having a diameter of 0.570 mm was obtained.

(Delete)

(Delete)

(Example 12 )
In Example 1, except that 47 parts by weight of graphite and 50 parts by weight of ceria nanoparticles were deleted, the same composition as in Example 1 was obtained, and after mixing, kneading, molding, drying and firing, α-olefin A mechanical pencil lead having a diameter of 0.570 mm, in which 1 part by weight of silver nanoparticles is mixed with the total weight, immersed in a liquid in which silver nanoparticles (average particle size: 8 nm) are dispersed in an oligomer. HB was obtained.

(Example 13 )
In Example 1, except that 47 parts by weight of graphite was changed to 49 parts by weight and 3 parts by weight of ceria nanoparticles were changed to 1 part by weight of silver nanoparticles (average particle size: 8 nm), the same composition as in Example 1 was mixed. , After kneading, molding, drying and firing, dipping in oil in which silver nanoparticles (average particle size: 8 nm) are dispersed in an α-olefin oligomer, soaking in oil, 2 parts by weight of silver nanoparticles are mixed with the total weight A mechanical pencil lead HB having a diameter of 0.570 mm was obtained.

(Example 14 )
Boron nitride (average particle size 6 μm) 39 parts by weight Vinyl chloride resin 43 parts by weight Dioctyl phthalate 16 parts by weight Oleic acid amide 1 part by weight Ceria nanoparticles (cerium oxide nanoparticles, average particle size 10 nm) 1 part by weight Henschel mixer After kneading with a pressure kneader and two rolls, set the extrusion temperature to 100 ° C. with a screw type extruder, extrude into a thin line, and remove the remaining plastic material from these, After heat treatment at 180 ° C. for 10 hours in air, the temperature was raised to 1000 ° C. in a nitrogen atmosphere, followed by firing at 1000 ° C. for 1 hour. Next, it heat-fired at 700 degreeC in air | atmosphere, carbonized material was removed, and the white core material was obtained. 100 g of this core was immersed in a container containing 150 g of a perhydropolysilazane xylene solution (20% by weight) and then fired in nitrogen gas at 1200 ° C. for 1 hour to obtain a white fired core having a diameter of 0.57 mm. Further, the white core was immersed in red air and left at 70 ° C. for 24 hours. The surface of the fired core body filled with this ink was washed to obtain a red fired pencil core having a diameter of 0.570 mm.

(Comparative Example 1)
In Example 1, the mechanical pencil core HB having a diameter of 0.570 mm was prepared in the same manner as in Example 1 except that 0.5 parts by weight of ceria nanoparticles were replaced with graphite and the amount of graphite used was 50 parts by weight. Obtained.

(Comparative Example 2)
A mechanical pencil lead HB having a diameter of 0.570 mm was obtained in the same manner as in Example 1 except that the ceria nanoparticles (average particle size 10 nm) were changed to ceria particles (average particle size 1 μm) in Example 1. .

(Comparative Example 3)
In Example 14 , a mechanical pencil lead HB having a diameter of 0.570 mm was obtained in the same manner as in Example 14 except that 39 parts by weight of boron nitride and 40 parts by weight of ceriana particles were omitted.

(Comparative Example 4)
In Example 1, except that 47 parts by weight of graphite was changed to 49 parts by weight, and 3 parts by weight of ceria nanoparticles were changed to 1 part by weight of graphite whiskers (“Glass Car” manufactured by Nikkiso Co., Ltd., diameter 500 nm, length 20 μm). In the same manner as in Example 1, a mechanical pencil lead HB having a diameter of 0.570 mm was obtained.

(Comparative Example 5)
Example 1 In the same manner as in Example 1 except that 47 parts by weight of graphite and 49 parts by weight of ceria nanoparticles were changed to 1 part by weight of vapor grown carbon fiber (diameter 100 nm, length 1000 μm). A mechanical pencil lead HB having a diameter of 0.570 mm was obtained.

About each solid drawing material (mechanical pencil lead HB, red pencil lead) obtained in Examples 1 to 14 and Comparative Examples 1 to 5, the liquid content, the compressive strength (N), and the amount of wear were determined by the following methods. (Mm), concentration, erasure rate (%), specific surface area (m ² / g), effective pore volume index, writing feeling by sensory evaluation, and evaluation of stain resistance.
These results are shown in Table 1 below.

(Measurement method of liquid content)
The liquid content of the α-olefin oligomer when impregnated with the α-olefin oligomer, or the liquid content of the α-olefin oligomer when the α-olefin oligomer impregnated with the nanomaterial is impregnated, is the weight before impregnation and after the impregnation. The weight was calculated from the weight.
(Measurement method of compressive strength)
The core was measured with Tensilon (ORIENTEC RTC-1150A) by compression test at 2 mm × ∞ from the side (n = 100).

(Test method for wear test)
The wear length of the core when writing at a writing angle of 75 °, a load of 300 gf, and a writing distance of 5 m was measured (n = 10).
(Measurement method of concentration)
It is the value which measured the drawn line written by the abrasion test with the densitometer (sakura DENSI TOMETER PDA65) (n = 10x4 places).
(Erasing rate measurement method)
The stroke erasure rate after the stroke drawn by the abrasion test was reciprocated 5 times with an eraser (EP-105E) was determined (n = 10).

(Measurement method of specific surface area and pore volume)
It measured with the mercury porosimeter (Pore Master GT type | mold made by QUANTACHROM) (n = 10).
(Effective pore volume index calculation method)
The effective pore volume index is calculated by dividing the porosity (cc%) calculated from the pore volume (effective pore volume) measured with a mercury porosimeter by the actual porosity calculated from the ratio of the material density to the solid drawing material density. Indicated. This value indicates that the effective pore volume is improved by the present invention compared to the comparative example (n = 10).

[Evaluation method of writing feeling, resistance to dirt on hands (difficulty in dirt)]
Written feeling and resistance to stains on the hands (hardness of stains) were evaluated by the following evaluation criteria (average value) with a monitor of 10 people in the shape of a pencil incorporated in a wooden shaft.
Evaluation criteria:
A: Very better than Comparative Example 1.
○: Better than Comparative Example 1.
○ ′: Same as Comparative Example 1.
Δ: worse than Comparative Example 1.
X: Very worse than Comparative Example 1.
-: Comparative Example 1 is a reference (control).
The evaluation of Example 14 was performed using Comparative Example 3 as an evaluation standard instead of Comparative Example 1.

As is clear from the results of Table 1 above, the solid drawing materials of 1 to 14 within the scope of the present invention are superior in compressive strength as compared with Comparative Examples 1 to 5 outside the scope of the present invention, and in the solid drawing material. As a result, the oil content is high. As a result, it has a sufficient color developability and a drawn line density, is less worn, has good erasability, has a good writing feeling (writing quality), and is hardly stained. In particular, when ceria nanoparticles are compared with Comparative Example 1, the effective pore volume of Example 8 (0.01 parts by weight) to Example 5 (10 parts by weight) is large, and as a result, the liquid content is high. Especially Example 4 (0.1 weight part)-Example 1 (3 weight part) are favorable, and Example 2 (2 weight part) is still more favorable.
On the other hand, when ceria particles (1 μm) having a large particle size are used as in Comparative Example 2, the liquid content increases, but the strength decreases, which is not suitable. Moreover, it turned out that intensity | strength falls similarly even if it uses a carbon fiber with a large diameter like the comparative example 4. FIG. Furthermore, the comparative example 5 is the composition of the literature 2 illustrated by the prior art. Although the bending strength seems to be strong, the compressive strength which is important in practical use is small. Further, it was found that the items of writing feeling and stain resistance by sensory evaluation were less effective than the examples.

On the other hand, since Example 12 is different from Comparative Example 1 only in the part where silver nanoparticles are dispersed in the α-olefin oligomer to be immersed in oil, the specific surface area and the effective pore volume index are the same. Since the specific gravity of the liquid component increases due to the effect of the nanoparticles, the liquid content calculated by weight increases. Moreover, since the nano-particle which is a solid is filled in the pore part, the compressive strength is also improved. In addition, changes in the amount of wear, concentration, and erasure rate have appeared due to optical properties such as lubricity and absorption and scattering of the nanoparticles. In Example 13 , a solid drawing material core is formed by baking a blending composition for a solid drawing material containing at least a nanomaterial, and the nanomaterial is contained in the pores of the solid drawing material core. The lubricant is further filled. In this case, the compressive strength is further improved, the effective pore volume in the solid drawing material is large, and as a result, the oil content is further increased. As a result, the coloring property and the drawing line density are further sufficient, the wear is small, the erasability is good, the writing feeling (writing quality) is good, and the stain is difficult.
Furthermore, also in Example 14 showing the baked colored pencil lead, the increase in the effective pore volume increases the liquid content of the ink, resulting in better color development (density), resulting in improved writing feeling. Yes.

Claims (10)

A blending composition for solid drawing material comprising at least a nanomaterial having a particle size of 0.7 to 100 nm selected from the following group A, which is 0.01 to 5% by weight based on the total amount of the solid drawing material , and graphite. baking treatment was solid drawing material core formed comprising a solid drawing material, characterized in that formed by filling the lubricant in the pores of said solid drawing material core.
Group A: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphorous oxide ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube, fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles Wherein as the lubricant, solid drawing material according to claim 1, wherein the use of lubricants is a particle size selected from the following group B containing nanomaterials 0.7～100Nm.
Group B: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphate ceramics, carbide ceramics, silicate ceramics and borides ceramics (except for silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles A solid drawing material core body is formed by baking the blending composition for solid drawing material, and a nanomaterial having a particle size of 0.7 to 100 nm selected from the following group C in the pores of the solid drawing material core body A solid drawing material comprising a lubricant contained therein.
Group C: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphate ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles When using the lubricant containing the said nanomaterial, the solid drawing material of Claim 2 or 3 which contains 0.01-5 weight% of nanomaterial in a lubricant with respect to solid drawing material whole quantity. The solid drawing material according to any one of claims 1 to 4, wherein the solid drawing material is a calcined pencil lead for mechanical pencils containing at least graphite and / or carbon black and amorphous carbon in the nanomaterial. The solid drawing material according to any one of claims 1 to 5 , wherein the nanomaterial is obtained by any one of a gas phase synthesis method, a liquid phase synthesis method, and a mechanical pulverization method. Surface amorphous carbon particles of the nano-material, graphite and solid painting material according to any one of claims 1 to 6 in which at least one carbon of the diamond is coated. The solid drawing material according to any one of claims 1 to 7 , wherein the solid drawing material is a fired pencil lead containing at least a coloring material, an extender, and a ceramic binder. (A) graphite or graphite and carbon black, (b) thermoplastic synthetic resin, (c) an organic solvent capable of dissolving the thermoplastic synthetic resin, and (d) a particle size selected from the following group D is 0.7 to 100 nm. kneading the nanomaterials, molding, drying and non-oxidative and fired in an atmosphere to obtain a solid drawing material core, solid drawing material characterized by filling the lubricant in the pores of said solid painting material core Manufacturing method.
Group D: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphorous oxide ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles (A) Graphite or graphite and carbon black, (b) a thermoplastic synthetic resin, (c) an organic solvent capable of dissolving the thermoplastic synthetic resin is kneaded, molded, dried and fired in a non-oxidizing atmosphere. A solid drawing material comprising: forming a core and filling a lubricant containing a nanomaterial having a particle size of 0.7 to 100 nm selected from the following group E into pores of the solid drawing material: Production method.
Group E: silicon, titanium, zirconium, aluminum, cerium oxide ceramics, nitride ceramics, phosphorous oxide ceramics, carbide ceramics, silicate ceramics and borides ceramics (excluding silicon oxide ceramics), diamond nanoparticles , Carbon nanoparticles (excluding carbon black, carbon nanotube and fullerene), silver nanoparticles, platinum nanoparticles, gold nanoparticles, Fe-Pd multi-composite composite nanoparticles, Fe-Pt multi-composite composite nanoparticles, Pd- Pt multi-composite composite nanoparticles, Pt-Au multi-composite composite nanoparticles