JP4241348B2 - Solid drawing material - Google Patents

Description

  The present invention relates to a solid drawing material such as a crayon, a pastel, a solid correction tool, a colored pencil lead, etc., which forms a drawing mark by attaching itself to a drawing object by rubbing against the drawing object and attaching a colorant to the drawing object.

  In general, solid drawing materials such as crayons, pastels, solid correction tools, and colored pencil cores are kneaded with a colorant, a binder, an extender, and a wear imparting material, and if necessary, a solvent such as water or methyl ethyl ketone (MEK). It is obtained by molding the addition.

  Solid drawing materials such as these are drawn by fixing solid materials colored by coloring materials on the drawing surface by self-wearing and separating when the solid drawing material itself is rubbed against the drawing surface such as paper. If it is formed so that it is relatively easy to wear, a highly colored drawing trace can be obtained. However, using a large amount of solids such as talc and mica and other coloring materials such as pigments for a binder such as resin to promote wear reduces the strength (breaking strength) of the molded product. There is a problem.

In order to obtain color development without impairing the strength (breaking strength) of the solid drawing material, Patent Document 1 discloses that the contact area between the porous silica and the resin acting as a binder using diatomaceous earth powder is reduced. A colored pencil lead that does not decrease the bending strength by being firmly bonded to the resin because the resin is easily included in the particles, A crayon is disclosed. Further, Patent Document 2 discloses a solid correction tool using a terpene resin and / or a terpene resin derivative as an adhesive material as means for improving the color developability by improving the concealability by overcoating.
JP-A-2-36281 JP-A-4-189199

When a porous roll disclosed in the above prior art is used in a dispersion process in which a resin or solvent component for obtaining a solid drawing material is contained, a silica or diatomaceous earth particle is crushed. The resulting finer particles tend to be pigmented and increase the resin's thickening properties. The resulting colored pencil lead, etc., becomes a core that is hard to wear, resulting in remarkable color development and writing. It will decline.
Furthermore, when an adhesive material is used for a solid correction tool or the like, since the drawing material itself is relatively soft due to the adhesive, wear due to rubbing with the paper surface is promoted, and a dark drawing trace can be obtained. On the other hand, the bending strength is weak. In addition, if there is not enough adhesive component, the effect of re-adhering the component that has fallen on the paper surface is weak, so that a solid correcting device with insufficient concealability by overcoating will result.

  An object of this invention is to provide the solid drawing material which has favorable color development property and concealment property, having practically sufficient intensity | strength.

  That is, the gist of the present invention is a solid drawing material containing at least particles in which flaky fine crystals of basic magnesium carbonate are aggregated in a tubular shape.

  The particles obtained by agglomerating the basic magnesium carbonate flaky fine crystals used in the present invention into a tubular shape have a high aspect ratio, so that they are oriented by roll dispersion and molding. A certain amount of bending strength is given to the product. At this time, the shearing force such as a roll is consumed for orienting the particles, and it is assumed that the tubular particles do not collapse. However, this tubular particle itself has a non-oriented aggregate structure in which flaky fine crystals of basic magnesium carbonate are entangled with each other, so that drawing shear force is consumed during solid drawing after molding. Since it is not broken, the surface of the tubular particle has fine voids, so that the effective contact area between the tubular particle and the other compound is relatively small. Since there will be a lot of space between the objects, other compounds are easily detached by the shearing force at the time of drawing, and although the bending strength is strong, the writing feeling is good and forms a highly colored drawing trace. be able to. In addition, the fact that the tubular particles have a large space in the apparent volume leads to high retention of the adhesive component, so that solid components such as extender materials and coloring materials are fixed on the paper surface, and this solid material is again solidified. In overcoating where the drawing material is applied to the drawing trace, re-adhesion is repeated with the porous material containing the adhesive material remaining on the drawing surface, so that the concealability is improved by increasing the thickness of the drawing trace. It is assumed that color developability is expressed.

Hereinafter, the present invention will be described in detail.
In the present invention, unlike the conventional plate-like basic magnesium carbonate having a low aspect ratio and granular aggregates in which they are entangled in space, the size of the short diameter with respect to the long diameter of the flaky fine crystal particles Aggregates in which plate-like particles having a very high aspect ratio are intertwined with each other in a submicron order form one tubular particle. The flaky fine crystals constituting the particles aggregated in a tubular shape preferably have a minor axis of 0.005 to 0.5 μm and a major axis of 0.1 to 10 μm. When the minor axis is smaller than 0.005 μm, the crystal thickness becomes too thin, the particle strength is lowered, and there is a possibility that it is easily broken and broken into fine particles. And if it exceeds 0.5 μm, the crystal becomes thick and can form a relatively strong tubular particle. However, it is difficult to self-disintegrate at the time of drawing, or it is difficult to obtain smooth wear, and color development is difficult. It will decline. If the longest diameter is smaller than 0.1 μm, the longest diameter of the shortest diameter is further reduced to 0.5 μm, so that the plate-like particles cannot be formed. The particles themselves become hard, and the particles themselves become hard, which inhibits the wear of the build material during drawing and reduces the color development.

  The tubular particles preferably have an outer diameter of 1 to 20 μm and a length of 5 to 200 μm. When the outer diameter of the tubular particles is smaller than 1 μm, the strength of the porous particles is difficult to obtain because the walls of the tubular particles become thin, and there is a possibility that they will be destroyed by dispersion with a hensil mixer or kneading with a roll. is there. When the outer diameter is larger than 20 μm, the shape of the porous body is almost spherical with respect to the length in the longitudinal direction, so that the orientation of the particles in the longitudinal direction depends on the shearing force during dispersion kneading and the pressure during molding. Since it becomes difficult to obtain, the strength of the solid drawing material is difficult to obtain. In addition, in the case where the length of the tubular particles is smaller than 5 μm, the shape of the porous body is almost spherical with respect to the length of the outer diameter, so that it is difficult to obtain the orientation of the particles, and the porous body is smaller. Therefore, there is a possibility that the thickening of the resin component or the like is increased to become hard and the color developability is lowered. Furthermore, when the length is larger than 200 μm, the orientation during molding tends to be too large, and the softness of the solid drawing material tends to be hard, which may cause problems in color development and writing quality. In order to obtain an appropriate orientation during molding, the ratio of the length / outer diameter of the tubular particles is optimally 2-50. Further, the inner diameter of the tubular porous body is preferably 0.5 to 5 μm. If the inner diameter is smaller than 0.5 μm, the cylindrical space becomes narrower, so the voids due to the interstices between the flaky microcrystals on the inner wall are dense and a relatively flat surface. It becomes difficult to encapsulate, and the tubular particles themselves become hard, so the color developability deteriorates. If the inner diameter is larger than 5 μm, the gaps between the particles formed by the entanglement of the flaky fine crystals widen and become rough, so that the voids become too wide and the structure becomes weak, so that the strength of the tubular particles is lost, and the resin component, etc. There is a possibility that the thickening will increase and the color will become harder.

And the specific surface area of these tubular particles by BET method is 70-200 m < ² > / g. And 70m ² / g less, since the tubular particle surface or an internal surface becomes dense and the strength is hardly broken high structure becomes smooth, easy coloring property after drawing is lowered, 200 meters ² / g larger than the tubular particle surface Since the gap between the gaps spreads and the resin component and the like are easily absorbed, the bonding with the extender and the coloring material is insufficient, and the strength of the solid drawing material is lowered.

  The Mohs hardness of the porous body is preferably 2 or more and 4 or less. If the Mohs hardness is less than 2, it becomes difficult to maintain the shape of the porous body, the resin component is strongly bonded to the build material and wear is reduced, and the color development is reduced. If the Mohs hardness is greater than 4, the structure used Depending on the material, these extender particles are scraped off and finely pulverized during dispersion kneading, making the particles of the entire material finer, making it difficult to wear during writing and lowering the color developability.

And in the pore distribution measured by the mercury intrusion method, the pore volume with a pore diameter of 0.01 to 100 μm is 5000 to 12000 mm ³ / g, and the pore volume with a pore diameter of 0.5 to 5 μm is 2250 to 10200 mm. It is good that it is ³ / g. If the pore volume with a pore diameter of 0.01 to 100 μm is smaller than 5000 mm ³ / g, the voids on the surface of the tubular particles are narrowly distributed and become dense, so that the tubular particles become strong and difficult to self-disintegrate with a load during writing. Therefore, the wear of the extender at the time of drawing is suppressed and the color developability is lowered. When the pore volume with a pore diameter of 0.01 to 100 μm is larger than 12000 mm ³ / g, the voids on the surface of the tubular particles are widely distributed and rough. As a result, the tubular particles are weakened and refined to increase the viscosity of the resin and reduce the color developability. Furthermore, if the pore volume with a pore diameter of 0.5 to 5 μm is smaller than 2250 mm ³ / g, the voids in the space of the tubular particles are narrowly distributed and the surface becomes almost flat, so that it is impossible to hold the adhesive component or the like. Therefore, it becomes difficult to express the concealability by recoating the solid drawing material again on the drawing trace, and when the pore volume with a pore diameter of 0.5 to 5 μm is larger than 10200 mm ³ / g, more resin components are absorbed. As a result, the bonding strength between the extender and the coloring material is lowered, and the strength of the solid drawing material is lowered.

  The manufacturing method of the porous body used by this invention can be used by a conventionally well-known method. For example, a first step of mixing a water-soluble magnesium salt and a water-soluble carbonate in an aqueous solution to obtain columnar particles of normal magnesium carbonate at 20 to 60 ° C., and 35 It can be obtained by drying such as alcohol washing and spray drying through a second step obtained by stirring and heating so that the pH is 7.5 to 11.5 at -80 ° C.

  The tubular porous body described above is provided as a development prototype name mug tube by Nippon Steel Mining Co., Ltd., and the average inner diameter of the caliber is 0.5 μm, 1.0 μm, and 5.0 μm. There are grades treated with alumina and various fatty acids.

  The amount of the porous particles used is not particularly limited, but is 2 to 30% by weight with respect to the total amount of the solid drawing material excluding the volatile solvent, and even more preferably 5 to 5 in view of the color developability and strength of the solid drawing material. 20% by weight is used. When the amount used is less than 2% by weight, practical strength can be obtained but no color developability is obtained. When it exceeds 30% by weight, color developability is obtained, but the strength is greatly reduced. There is a case.

The pressure-sensitive adhesive material used in the present invention is used for the purpose of obtaining high color development by improving the concealability by overcoating with a solid drawing material. For example, it is obtained by refining from the skin of pine or citrus fruits. Terpene resin, rosin resin obtained by refining raw pine crabs and pine roots, aliphatic (C ₅ ), aromatic (C ₉ ), copolymer (C ₅ / C ₉ ), fat Examples thereof include petroleum resins such as cyclic (hydrogenated), and coal-based resins such as coumarone-indene resin. Among these, in particular, when the adhesive is selected from terpene resins and / or terpene resin derivatives, rosin resins and / or rosin resin derivatives, when the colorant is used as a solid corrector which is a white pigment such as titanium oxide. This is a technique that improves the thickness of the coating film by overcoating at the time of correction, and it is possible to clearly erase the corrected characters and the like, and as a specific example, as a terpene resin, It is roughly divided into α-pinene, β-pinene, and dipentene (limonene) due to structural differences. The α-pinene type resin is YS Resin A Series (manufactured by Yashara Chemical Co., Ltd.), and the β-pinene type resin is YS Resin. PXN series (manufactured by Yasuhara Chemical Co., Ltd.) As terpene polymerization type resin (copolymer of α-, β-, dipentene), YS resin PX series, PF Series (above, manufactured by Yashara Chemical Co., Ltd.). As terpene resin derivatives, aromatic modified terpene resins YS Resin TO series, LP, (above, Yashara Chemical Co., Ltd.), hydrogenated terpene resins Clearon P series, M series, K series (above, Yashara Chemical) As a terpene phenol copolymer, YS Polystar 2000, T series, S series, Mighty Ace G series, YP-90LL (manufactured by Yasuhara Chemical Co., Ltd.) and the like can be mentioned. Furthermore, examples of the rosin resin include gum rosin, rosin alcohol, tall oil rosin, wood rosin and the like, and rosin resin derivatives include rosin glycerin ester as Harrier Star TF, NL, S, Harimac R80 (above, Harima Chemical Co., Ltd.). ), Ester gum 8L-JA, pentaline 2840 (above, manufactured by Eastman Chemical Co., Ltd.), water-added rosin ester, ester gum H, pine crystal KE-100 (above, Arakawa Chemical Industries, Ltd.), Licaroline HC, Licarodin HD, Licarodin F, Rikka Clear 90, Rikka Clear 100 (above, manufactured by Rika Finetech Co., Ltd.), Abitol E, Foralin 5020F (above, produced by Eastman Chemical Co., Ltd.), Rigarit R1010 as a hydrogenated petroleum resin (Eastman Chemical Co., Ltd.) It is.

  In addition to improving concealment with adhesives obtained from these terpene resins, rosin resins and their derivatives, adhesives that are particularly effective in imparting writing quality during correction and improving the strength and smoothness of the corrected coating surface As a selection condition, a solid adhesive material having a resin softening temperature of 90 ° C. or less, a liquid adhesive material having a resin viscosity (80 ° C.) of 40 to 100 mPa · s, etc., may be used alone or in combination. In order to express the effect of the present invention, it is more preferable. As described above, various adhesive materials such as petroleum resin and coumarone resin, which are conventionally known adhesive materials other than those described above, may be used in combination as long as the effects of the present invention are not hindered.

  Although the usage-amount of these adhesive materials is not specifically limited, It is 1 to 15 weight% with respect to the solid drawing material whole quantity except a volatile solvent part, More preferably, 4 to 8 weight% is used. When the amount used is less than 1% by weight, practical strength can be obtained, but color developability and concealment cannot be obtained, and when it exceeds 15% by weight, color developability is obtained, but the strength decreases. It may be big.

  Other materials for the solid drawing material include a resin as a binder, talc as an extender, calcium carbonate, various waxes for applying coloring materials, etc. on the paper surface, and wear imparting materials such as fats and oils such as stearic acid. Can be blended and used.

  The resin is not particularly limited, and specifically, polystyrene, polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polystyrene butadiene, polyvinyl chloride, polyvinyl acetate, polymethyl acrylate, polymethyl methacrylate, polyvinylidene chloride, Polytetrafluoroethylene, acrylic-styrene resin, acrylonitrile butadiene styrene resin, ethylene-tetrafluoroethylene copolymer, nitrocellulose, ethyl cellulose, methyl cellulose, cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, polypropylene glycol, polyacrylamide, poly Acrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl ether Maleic acid polymers, polyester polyol resins, polyester polyether resins, polyethylene terephthalate, polybutylene terephthalate, and the like. These may be used alone or in combination of two or more. In particular, nitrocellulose, polystyrene, ethylcellulose, methylcellulose, cellulose acetate, carboxymethylcellulose, hydroxyethylcellulose, and the like are separately listed as resins that can achieve the present invention.

  The body material is not particularly limited, and conventionally known body materials such as talc, mica, kaolin, clay, bentonite, various metal salts of Nε-lauroyl lysine, N-lauroyl-β-alanine, magnesium carbonate, magnesium sulfate, boron nitride As a fibrous material, potassium titanate whisker, calcium carbonate whisker, titanium dioxide whisker, magnesium sulfate whisker, calcium sulfate whisker, aluminum sulfate whisker, etc. can be used arbitrarily, and these can be used alone or in combination of two or more. It doesn't matter. In particular, as a constitution material capable of further achieving the present invention, talc, Nε-lauroyl lysine, various metal salts of N-lauroyl-β-alanine, basic magnesium sulfate whisker, titanium dioxide whisker, potassium titanate whisker, and the like. Raised.

  The colorant is not particularly limited, and various natural and synthetic dyes and various inorganic and organic pigments can be arbitrarily used. As dyes, Japanol Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black 200-L (19), Water Black # 7 (19), Kaya Set Black W9 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Deep Black (similar to 38), Direct Fast Black Conque (51) ), Kayara Spragley VGN (71), Kayak Direct Brilliant Yellow G (CI Direct Yellow (12), Direct Fast Yellow 5GL (26), Eisen Primula Yellow GCLH (44), Direct Fast Yellow R 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (Same 4), Direct Fast Scarlet 4BS (Same 23), Eisen Direct Durin BH (Same 31), Direct Scarlet B (Same 37), Kayak Direct Scarlet 3B (Same 39), Eisen Primula Vink Conk 2BLH (Same 75), Sumilite Red F3B (Same 80), Eisen Primula Red 4BH (Same 81), Kayaras Spralbin BL (Same 83) ), Cayalas Light Red F5G (225), Cayalas Light Red F5B (226), Cayalas Light Rose FR (227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), Be Zobliant Sky Blue 8GS (41), Sumilite Splash Blue BRR Conch (71), Dibogen Turquoise Blue S (86), Water Blue # 3 (86), Kayara Star Coyze Blue GL (86), Direct dyes such as Daiwa Blue 215H (same 87), Kayalas Spral Blue FFRL (same 108), Kayalas Spral Blue FF2GL (same 106), Kayalas Splatter Coyze Blue FBL (same 199) and Acid Blue Black 10B (CI Acid Black 1), Nigrosine (2), Water Black R455 (2), Water Black R510 (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26) ), Kayanol Milling Black BR Conch (Same as 31), Mitsui Nylon Black GL (Same as 52), Eisen Opal Black WH Extra Conk (Same as 52), Sumilan Black WA (Same as 52), Launyl Black BG Extra Conk (Same as 107), Kayanol Milling Black TLB ( 109), Suminoll Milling Black B (109), Kayanol Milling Black TLR (110), Eisen Opal Black New Conque (119), Water Black 187-L (154), Acid Yellow # 10 (C) . I. Acid Yellow 1), Kayaku Acid Brilliant Flavin FF (7: 1), Kayasil Yellow CG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Water Yellow # 1 (same as above) 23), Daiwadar torazine (same as 25), Kyakuto torazine (same as 23), Suminol Fast Yellow R (same as 25), Diacid Light Yellow 2GP (same as 29), Suminol Milling Yellow 0 (same as 38), Suminoll Milling Yellow MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol N5G (110), Sumino Lumilling Yellow 4G 200% (same as 141), Kayanol Yellow NG (same 135), Kayanol Milling Yellow 5GW (same 127), Kayanol Milling Yellow 6GW (same 142), Sumitomo Fast Scarlet A (CI Acid Red) 8), Kayak Silk Scarlet (same 9), Solar Rubin Extra (same 14), Daiwa New Coxin (same 18), Water Scarlet (same 18), Daiwa Red 102 (same 18), Eisenbonso RH (same as above) 26), Daiwa Red No. 2 (same as 27), Suminol Leveling Brilliant Red S3B (same as 35), Kayasil Rubinol 3GS (same as 37), Eisen Erythrosine (same as 51), Kayaqua acid Rhodamine FB (same as 52), Daiwa Red No. 106 (52), Suminol Levelingle Nord 3GP (57), diacid alizarin rubinol F3G 200% (82), alizarin rubinol 5G (83), iseneosin GH (87), water red # 2 (87), Daiwa red 103WB (87) ), Water Pink # 2 (92), Eisen Acid Phloxin PB (92), Daiwa Red No. 104 (92), Rose Bengal (94), Kayanol Milling Scarlet FGW (111), Kayanol Milling Rubin 3BW (129), Suminol Milling Brilliant Red 3BN Conch (131), Suminol Milling Brilliant Red BS (138), Eisen Opal Pink BH (186), Suminol Milling Brilliant Red B Conch (249), Kayak acid yellowtail Ant Red 3BL (254), Kayaku Acid Brilliant Red BL (265), Kyanol Milling Red GW (276), Mitsui Acid Violet 6BN (17), Water Violet # 1 (49), Ink Violet L10 ( 49), Sumitomo Patent Pure Blue VX (C.I. I. Acid Blue 1), Water Blue # 106 (same 1), Patent Blue AF (same 7), Water Blue # 9 (same 9), Daiwa Blue 1 (same 9), Ink Blue L20 (same 9), Supranol Blue B (same 15), Water Blue # 116 (same 15), Orient Surble Blue OBX (same 22), Suminol Leveling Blue 4GL (same 23), Mitsui Nylon Fast Blue G (same 25), Kayasil Blue AGG (same as above) 40), Kayasil Blue BR (41), Mitsui Alizarin Saphirol SE (43), Suminol Leveling Sky Blue R Extraconk (62), Mitsui Nylon Fast Sky Blue R (78), Sumitomo Brilliant Indocyanine 6Bh / e (83), Sandlancyanine N-6B 350% 90), Water Blue # 105 (90), Orient Soluble Blue OBB (93), Spranol Cyanine 7BF (100), Sumitomo Brilliant Blue 5G (103), Acid Blue (103), Asilane Brilliant Blue FFR (same as 104), Kyanol Milling Ultra Sky SE (same as 112), Kyanol Milling Cyanine 5R (same as 113), Eisen opal cyanine 2GLH (same as 158), Daiwa Guinea Green B (C.I. Acid Green 3 ), Acid Brilliant Milling Green (same 9), Daiwa Green # 70 (same 16), Cyanol Cyanine Green G (same 25), Suminol Milling Green G (same 27), Water Orange # 17 (C.I. Acid Orange 56) Food, Water Yellow # 2 (CI Food Yellow 3), Food Yellow 5 (CI Food Yellow 3), Food Red 3 (CI Food Red 14), Food Blue 2 No. (CI Acid Blue 74), food dyes such as Green No. 2 for Food (CI Acid Green 5), Malachite Green (C.I. 42000), Victoria Blue FB (C.I. 44045) And basic dyes such as methyl violet FN (C.I. 42535), rhodamine F4G (C.I. 45160) and rhodamine 6GCP (C.I. 45160).

  Special Black 6, S170, S610, 5, 4, 4A, 550, 35, 250, 100, Printex 150T, U, V, 140U, 140V, 95 90, 85, 80, 75, 55, 45, P, XE2, L6, L, 300, 30, 30, 35, 25, 200, A, G (above, manufactured by Degussa Japan Co., Ltd.), # 2400B, # 2350, # 2300, # 2200B, # 1000, # 950, # 850, # MCF88, MA600, MA100, MA7, MA11, # 50 # 52, # 45, # 44, # 33, # 32, # 30, CF9, # 20B, # 4000B (manufactured by Mitsubishi Kasei Co., Ltd.), MONARCH 1300, 1100, 100 , 900, 880, 800, 700, MOGUL L, REGAL 400R, 660R, 500R, 330R, 300R, 99R, ELFTEX 8, 12, BLACK PERALS 2000 (above, United States, Cabot Co Ltd.), Raven7000, 5750, 5250, 5000, 3500, 2000, 1500, 1255, 1250, 1200, 1170, 1060, 1040, 1035, 1020, 1000, 890H, 890, 850, 790, 780, 760, 500, 450, 430, 420, 410, 22, 22, 16, 825 Oil Beads, H20 , C, Conductex 975, 900, SC (above Carbon black, such as Colombian Carbon Japan Co., Ltd.), KA-10, 10P, 15, 20, 30, 35, 60, 80, 90, KR-310, 380, 460, 480 (above, manufactured by Titanium Industry Co., Ltd.), P25 (made by Nippon Aerosil Co., Ltd.), etc., BS-605, 607 (above, made by Toyo Aluminum Co., Ltd.), bronze powder P -555, P-777 (above, manufactured by Nakajima Metal Foil Industry Co., Ltd.), Bronze Powder 3L5, 3L7 (above, manufactured by Fukuda Metal Foil Industry Co., Ltd.), black iron oxide, Inorganic pigments such as yellow iron oxide, red iron oxide, ultramarine, bitumen, cobalt blue, chrome green, chromium oxide, Hansa Yellow-10G, 5G, 3G, 4, GR, A, Benzidine Yellow, Permanen Yellow NCCG, Tartrazine Lake, Quinoline Yellow, Sudan 1, Permanent Orange, Indanthrene Brilliant Orange GN, Permanent Brown FG, Para Brown, Fire Red, Brilliant Carmine 6B, Bordeaux 5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Examples thereof include organic pigments such as alkali blue lake, phthalocyanine blue, indigo, acid green lake, and phthalocyanine green. In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfate, calcium sulfide, strontium sulfide, calcium tungstate and the like can be used.

  In the present invention, in addition to the above, natural wax groups such as carnauba wax, beeswax, and wax, polyethylene wax, montan wax, paraffin wax, zinc stearyl ketone, microcrystalline wax and other synthetic wax groups, stearic acid, Wear imparting materials such as various metal salts of stearic acid such as aluminum stearate, magnesium stearate, calcium stearate, and plasticizers such as diallyl phthalate, dimethyl phthalate, butyl phthalyl butyl glycolate, and propylene carbonate as required Can be used.

  In the present invention, when the above materials are molded as a solid drawing material, these materials are arbitrarily blended, and depending on the properties of the binder used, polar solvents such as water, MEK, alcohol, etc., and nonpolar solvents such as toluene are arbitrarily selected. While being used, it is molded after stirring, pulverizing, and kneading with a hensil mixer, ball mill, three-roll mill or the like. A method of cooling and molding a crayon, a pass, and the like after being put in a mold while heating and melting can be employed. Furthermore, in the case of a colored pencil lead or the like, a material with a little solvent remaining is loaded into a cylinder for a vertical extruder, the material in the cylinder is extruded by a hydraulic piston, and a dryer is used for the organic solvent contained. A method of forming by using an existing method such as forced drying using the method can be adopted.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited only to an Example.

(Example 1)
Nitrocellulose (binding material) 18 parts by weight Nε-lauroyllysine (extrinsic material) 30 parts by weight Magtube (particles in which flaky fine crystals of basic magnesium carbonate are aggregated in a tubular shape, outer diameter 3.5 μm, length 20 μm, inner diameter 1 μm, manufactured by Nippon Steel Mining Co., Ltd.) 10 parts by weight Stearic acid (abrasion imparting material) 13 parts by weight Propylene carbonate (plasticizer) 3 parts by weight Phthalocyanine blue (colorant) 20 parts by weight Titanium oxide (colorant) 6 parts by weight Methyl ethyl ketone (solvent) 100 parts by weight

  In order to remove the residual solvent completely after dispersing with the Hensyl mixer, kneading with a three roll and further dispersing, forming with a vertical extruder while adjusting the methyl ethyl ketone content as a solvent. It was dried at 0 ° C. for 8 hours to obtain a blue colored pencil lead having a nominal diameter of 2.

(Example 2)
The same operation as in Example 1 was performed except that 20 parts by weight of phthalocyanine blue in Example 1 was changed to 15 parts by weight, and 5 parts by weight was replaced with YS resin PX800 (terpene polymerization resin, softening temperature 85 ° C.). A colored pencil lead was obtained.

(Examples 3 to 11)
The same operation as in Example 1 was performed except that the amount of the magtube used in Example 1 was changed to 1, 2, 5, 10, 22, 25, 38, 40, and 45 parts by weight. Obtained.

(Examples 12 to 20)
The same operation as in Example 2 was performed except that the amount of the magtube used in Example 2 was changed to 1, 2, 5, 10, 22, 25, 38, 40, and 45 parts by weight, and a blue colored pencil lead was respectively used. Obtained.

(Examples 21 and 22)
In Examples 1 and 2, a white colored pencil lead was obtained in the same manner as in Examples 1 and 2 except that phthalocyanine blue was changed to titanium oxide.

(Comparative Examples 1 and 2)
In Examples 1 and 2, a blue colored pencil lead was obtained in the same manner as in Examples 1 and 2 except that the magtube was changed to diatomaceous earth.

(Comparative Examples 3 and 4)
In Examples 21 and 22, a white colored pencil lead was obtained in the same manner as in Examples 21 and 22 except that the mug tube in each example was changed to diatomaceous earth.

  The bending strength (unit: MPa) and the density (unit: D) as a color-changing property of the colored pencil cores obtained in Examples 1 to 20 and Comparative Examples 1 and 2 described in JIS S 6005 Measured based on. Black paper was used as the test paper in the density measurement of Examples 21 and 22 and Comparative Examples 3 and 4, and the density measurement value for black paper was obtained by dividing the drawing line area density by the drawn line area density. Measurement was performed based on 6005. The measured density value (unit: D) for the obtained black paper means that the lower the value, the better the white color developability.

Method of measuring the number of times of overcoating The character of 10 points “Declaration” with a word processor, 20 characters in a line, 20 sheets of paper output by a word processor and further copied by a dry copy machine at a fixed position density. The average number of overcoats until disappeared was determined by a monitor survey of 10 subjects. The smaller the average number of times, the better the concealability.

Claims (4)

A solid drawing material containing at least particles in which flaky fine crystals of basic magnesium carbonate are aggregated in a tubular shape. 2. The solid drawing material according to claim 1, wherein the flaky fine crystal has a minor axis of 0.005 μm to 0.5 μm and a major axis of 0.1 μm to 10 μm. Particles obtained by agglomerating the flaky fine crystals of basic magnesium carbonate into a tubular shape have an outer diameter of 1 μm to 20 μm, a length of 5 μm to 200 μm, a length / outer diameter ratio of 2 to 50, and an inner diameter of 0.5 μm to 5 μm, BET specific surface area of 70 m ² / g to 200 m ² / g, Mohs hardness of 2 to 4 in pore distribution measured by mercury porosimetry, 0.01 μm above 100μm volume of pores is not more than 5000 mm ³ / g or more 12000 mm ³ / g, according to claim 1 or less of the pore volume pore diameter 0.5μm or 5μm is not more than 2250 mm ³ / g or more 10200mm ³ / g Or the solid drawing material of Claim 2. The solid drawing material according to any one of claims 1 to 3, further comprising an adhesive material.