JP2003253185A - Solid drawing material - Google Patents

Abstract

(57) [Problem] To provide a solid drawing material having good color developability while having practical strength. SOLUTION: Calcium carbonate having an amino group present on the particle surface is used at least in an amount of 2 to 30% by weight based on the total amount of the solid drawing material, and if necessary, conventionally known talc, kaolin, magnesium carbonate, magnesium sulfate, A constitutional material selected from fibrous materials, a binder selected from clay, synthetic resin, and the like, a dye, an inorganic pigment, an organic pigment, a metal powder pigment,
A solid drawing material using at least a coloring material selected from inorganic fluorescent pigments and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crayon, a pastel, a solid correction tool, a colored pencil lead, and the like. The present invention relates to a solid drawing material that wears and attaches a coloring material to a drawing object to form a drawing trace.

[0002]

2. Description of the Related Art Generally, solid drawing materials such as crayons, pastels, solid correction tools, and colored pencil leads are coloring materials such as organic pigments and inorganic pigments, and binders such as clay, organic bentonite, carboxymethyl cellulose, and polyethylene resin. And body materials such as talc, mica, calcium carbonate, and if necessary carnauba wax, polyethylene wax,
It is obtained by kneading fats and oils and a wear-promoting material such as stearic acid, and optionally adding water and a solvent such as methyl ethyl ketone (MEK).

[0003]

It is extremely difficult to improve both the strength and the color developability of the above-mentioned solid drawing materials that have been conventionally used, and it has practically sufficient strength and good color developability. There is a problem in that a solid drawing material exhibiting the above can not be obtained.

The reason for this is as follows. When the amount of the colorant used is increased and the amount of the binder and the extender used is reduced, the strength is improved, but the color developability is decreased. This is because the solid drawing material is less likely to wear due to the filling effect of the coloring material. On the contrary, when the amount of the colorant used is reduced and the amount of the binder and the extender used is increased, the strength is improved.
The color developability decreases. This is because the amount of coloring material used is small. In addition, if both the amount of the coloring material and the amount of the extender used are increased and the amount of the binder used is decreased, the color developability is improved,
It cannot hold the strength to withstand drawing operations and breaks. This is because the amount of binder used is small. That is, it is difficult to improve both the color developability and strength of the solid drawing material by changing the compounding ratio of the conventionally known coloring material, binder and extender.

[0005]

That is, according to the present invention, in a solid drawing material using at least an extender, a binder and a coloring agent, at least calcium carbonate having an amino group on the particle surface is used as the extender. The subject is a solid drawing material that is characterized in that.

The present invention will be described in detail below. The calcium carbonate having an amino group on the surface of the particles used in the present invention is used as an extender, and the amino group of the cationic polymer compound having an amino group and the anion (carbonate ion) on the calcium carbonate surface are It is a particle bonded by hydrogen bonding. The calcium carbonate having an amino group on the surface of the particles used in the present invention can be produced by a conventionally known production method. Specifically, limestone is dry-milled with a mill such as a roll mill. Cationic polymer hydrochloride is added to the obtained coarse powder of limestone, and while being reacted, water-based pulverization is performed by a wet media type ultrafine pulverizer.

The calcium carbonate having an amino group on the surface of the particles, which is obtained by the above-mentioned production method, is marketed by Phimatec Co., Ltd. under the trade name AFF series,
There are grades with a particle size of ˜1.8 μm. Specifically, AFF-95 (average particle diameter 1.8 μm), AFF
Examples include -95 (average particle size 1.0 μm) and AFF-100 (average particle size 0.8 μm).

The amount of calcium carbonate having an amino group present on the surface of these particles is preferably 2 to 30% by weight, more preferably 5 to 20% by weight, based on the total amount of the solid drawing material excluding the volatile solvent content. When the amount used is less than 2% by weight, practical strength may be obtained but color development may not be obtained, and when it exceeds 30% by weight, practical strength may be obtained but color development is not obtained. There are cases. Furthermore,
It is also possible to use one obtained by treating the surface of calcium carbonate having an amino group on the particle surface with a fatty acid, and specifically, AFF-95 SuperO (average particle diameter 1.8 μm).
m, oleic acid treatment), AFF-95 SuperO
(Average particle size 1.0 μm, oleic acid treatment), AFF-
100 SuperO (average particle size 0.8 μm, treated with oleic acid) (above, manufactured by Phimatech Co., Ltd.). Those treated with these fatty acids have a characteristic that writing characteristics such as drawing operability are improved. The calcium carbonate having an amino group on the surface of the particles may be used in combination with a fatty acid untreated product and a treated product.

As the extender, calcium carbonate having an amino group on the particle surface may be used alone, and if necessary, conventionally known talc, mica, kaolin, clay, bentonite, Nε. -Lauroyl lysine, various metal salts of N-lauroyl-β-alanine, magnesium carbonate, magnesium sulfate, boron nitride and potassium titanate whiskers as fibrous substances, calcium carbonate whiskers, titanium dioxide whiskers, magnesium sulfate whiskers, calcium sulfate whiskers, Aluminum sulfate whiskers and the like may be used together.

The resin as the binder used in the present invention is specifically nitrocellulose, 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, polyacrylic acid,
Examples thereof include polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ether, maleic acid polymer, polyester polyol resin, polyester polyether resin, polyethylene terephthalate and polybutylene terephthalate. These may be used alone or in combination of two or more.

The colorant used in the present invention is not particularly limited, and various natural and synthetic dyes and various inorganic and organic pigments can be arbitrarily used. As the dye, Japanol Fast Black D Conc (C.I.
Direct Black 17), Water Black 100
L (same 19), water black 200-L (same 1)
9), Water Black # 7 (19), Kayaset Black W9 (19), Direct Fast Black B (22), Direct Fast Black AB (3)
2), Direct Deep Black EX (38 same), Direct Deep Black (38 similar product), Direct Fast Black Conc (51 same), Kayaras Supra Ray VGN (71 same), Kayak Direct Brilliant Yellow G (CI) Direct Yellow (12 same), Direct Fast Yellow 5GL (26 same), Eisen Primula Yellow GCLH (44 same), Direct Fast Yellow R (50 same), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (4), Direct Fast Scarlet 4BS (23), Eisen Direct Durin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (3)
9), Eisen Primula Binconk 2BLH (7
5), Sumilite Red F3B (80), Eisen Primula Red 4BH (81), Kayaras Sprarubin BL (83), Kayaras Light Red F5G (22)
5), Kayaras Light Red F5B (same 226), Kayaras Light Rose FR (same 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (same 15), Benzo Brilliant Sky Blue 8GS (41 same), Sumilite Supra Blue BRR Conch (71 same), Dibogen Turquoise Blue S (86 same), Water Blue # 3 (86 same), Kayala Star Coise Blue GL (86 same), Daiwa Blue 215H ( Same as 87), Kayaras Sprawl Blue FFRL
(Same as 108), Kayaras Sproll Blue FF2GL (Same as 106), Kayaras Spractor Coise Blue FBL
(Ibid. 199), etc. and acid blue black 1
0B (CI Acid Black 1), Nigrosine (2), Water Black R455 (2), Water Black R510 (2), Suminol Milling Black 8BX (24), Kayanol Milling Black V
LG (26), Kyanol Milling Black BR Conc (31), Mitsui Nylon Black GL (5)
2), Eisen Opal Black WH Extra Conc (52), Sumilan Black WA (52), Raunyl Black BG Extra Conc (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (same) 109), Kayanor Milling Black TLR (110 same), Eisen Opal Black New Conc (119 same), Water Black 18
7-L (154), Acid Yellow # 10 (C.I.
I. Acid Yellow 1), Kayaku Acid Brilliant Flavin FF (7: 1), Kayasil Yellow CG (1)
7), Xylene Light Yellow 2G 140% (17),
Suminol Leveling Yellow NR (19 same), Water Yellow # 1 (23 same), Daiwa Dadrazine (2 same)
5), Kayactorazine (23), Suminol Fast Yellow R (25), Diacid Light Yellow 2
GP (29), Suminol Milling Yellow 0 (3)
8), Suminol Milling Yellow MR (42), Water Yellow # 6 (42), Kayanor Yellow NF
G (49), Suminol Milling Yellow 3G (7)
2), Suminol Fast Yellow G (same as 61), Suminol Milling Yellow G (same as 78), Kayanol Yellow N
5G (110 same), Suminol Milling Yellow 4G20
0% (141 same), Kayanor Yellow NG (13 same)
5), Kayanor Milling Yellow 5GW (127),
Kaya Knoll Milling Yellow 6GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Koksin (18), Water Scarlet (18), Daiwa Red No. 102 (18), Aizen Bonso RH (2)
6), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS (37), Eisen Erythrosin (5)
1), Kayaqua Acid Rhodamine FB (52), Daiwa Red No. 106 (52), Suminol Leveling Rubinol 3GP (57), Diacid Alizarin Rubinol F3G 200% (82), Alizarin Rubinol 5G (82). 83), Aizeneocin GH (87 same), Water Red # 2 (87 same), Daiwa Red 103WB
(Same as 87), Water Pink # 2 (Same as 92), Aizen Acid Phloxine PB (Same as 92), Daiwa Red 104
No. (92), Rose Bengal (94), Kyanol Milling Scarlet FGW (111), Kyanol Milling Rubin 3BW (129), Suminol Milling Brilliant Red 3BN Conc (131), Suminol Milling Brilliant Red BS (same 138),
Eisen Opal Pink BH (same 186), Suminol Milling Brilliant Red B Conc (same 249), Kayak Acid Brilliant Red 3BL (same 254),
Kayaqua Acid Brilliant Red BL (265),
Kayanol Milling Red GW (same as 276), Mitsui Acid Violet 6BN (same as 17), Water Violet # 1 (same as 49), Ink Violet L10
(Id. 49), Sumitomo Patent Pure Blue VX (C.
I. Acid Blue 1), Water Blue # 106
(Same 1), Patent Blue AF (Same 7), Water Blue # 9 (Same 9), Daiwa Blue No. 1 (Same 9), Ink Blue L20 (Same 9), Splanol Blue B (Same 1).
5), Water Blue # 116 (15), Orient Sulblue Blue OBX (22), Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (4)
0), Kayacil Blue BR (41), Mitsui Alizarin Sapphirole SE (43), Suminol Leveling Sky Blue R Extraconc (62), Mitsui Nylon Fast Sky Blue R (78), Sumitomo Brilliant Indocyanine 6Bh / e (same as 83), Sandlancyanin N-6B 350% (same as 90), Water Blue # 105 (same as 90), Orient Solble Blue OBB (same as 93), Splanol cyanine 7BF (same as 100), Sumitomobrilliant Blue 5G (Ibid 10
3), Acid Blue (103), Asilane Brilliant Blue FFR (104), Kyanol Milling Ultra Sky SE (112), Kyanol Milling Cyanine 5R (113), Aizen Opal Cyanine 2
GLH (158), Daiwa Guinea Green B (C.
I. Acid Green 3), Acid Brilliant Milling Green (9), Daiwa Green # 70 (1)
6), Kayanol Cyanine Green G (same as 25), Suminol Milling Green G (same as 27), Water Orange # 17 (C.I. Acid Orange 56), and other acid dyes such as Water Yellow # 2 (C.I. Food Yellow 3), Food Yellow No. 5 (CI Food Yellow 3), Food Red No. 3 (CI Food Red 14), Food Blue No. 2 (CI Acid Blue 74), Food green 2
No. (CI Acid Green 5) and other food dyes, Malachite Green (CI 42000), Victoria Blue FB (CI 44045), Methyl Violet FN (CI 42535), Rhodamine F4G ( C.
I. 45160), Rhodamine 6GCP (C.I.45
And basic dyes such as 160).

As the pigment, Special Black
6, S170, S610, S5, S4, S4A, S550, S35, S250, S100, Printex
150T, U, V, 140U, 140V, 95, 90, 85, 80, 75, 55, 4
5, same P, same XE2, same L6, same L, same 300, same 3
0, the same 3, the same 35, the same 25, the same 200, the same A, the same G (above, manufactured by Degussa Japan KK), # 2400B, # 2.
350, # 2300, # 2200B, # 1000, # 9
50, # 850, # MCF88, MA600, MA10
0, MA7, MA11, # 50, # 52, # 45, # 4
4, # 33, # 32, # 30, CF9, # 20B, # 4
000B (above, Mitsubishi Kasei Co., Ltd.), MONARCH
1300, 1100, 1000, 900, 8
80, 800, 700, MOGUL L, REGA
L 400R, 660R, 500R, 330R,
300R, 99R, ELFTEX 8, 12 and B
LACK PERALS 2000 (above, manufactured by Cabot Co. LTD in the United States), Raven 7000, 57
50, 5250, 5000, 3500, 200
0, same 1500, same 1255, same 1250, same 120
0, 1170, 1060, 1040, 103
5, 1020, 1000, 890H, 890,
850, 790, 780, 760, 500,
Same 450, same 430, same 420, same 410, same 22, 22, same 16, same 14, same 825 Oil Beads, same H2
Carbon blacks such as 0, C, Conductex 975, 900, SC (above, Columbian Carbon Japan Co., Ltd.), KA-10, 10P, 1
5, the same 20, the same 30, the same 35, the same 60, the same 80, the same 9
0, KR-310, 380, 460, 480 (above, manufactured by Titanium Industry Co., Ltd.), P25 (manufactured by Nippon Aerosil Co., Ltd.) and the like, BS-605, 607.
(Above, manufactured by Toyo Aluminum Co., Ltd.), bronze powder P-
555 and P-777 (Nakajima Metal Foil Industry Co., Ltd.)
Powder), bronze powder 3L5, 3L7 (manufactured by Fukuda Metal Foil Industry Co., Ltd.), black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, dark blue, cobalt blue, chrome green. , Inorganic pigments such as chromium oxide, Hansa Yellow-10G, 5G, 3G, 4 and GR,
Same A, Benzidine Yellow, Permanent Yellow NCC
G, Tartrazine Lake, Quinoline Yellow, Sudan 1, Permanent Orange, Induslen Brilliant Orange GN, Permanent Brown FG, Para Brown, Fire Red, Brilliant Carmine 6B, Bordeaux 5B, Thioindigo Red, Fast Violet B, Dioxane Violet, Alkali Organic pigments such as blue lake, phthalocyanine blue, indigo, acid green lake, phthalocyanine green and the like can be mentioned. In addition to these, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, cadmium zinc sulfate, calcium sulfide, strontium sulfide, and calcium tungstate can be cited.

In the present invention, natural waxes such as carnauba wax, beeswax, and wood wax, polyethylene wax, montan wax, paraffin wax, zinc stearyl ketone, other than the above-mentioned essential components may be added, if necessary.
Synthetic wax group such as microcrystalline wax,
Abrasive agents such as various metal salts of stearic acid such as stearic acid, aluminum stearate, magnesium stearate and calcium stearate, and plasticizers such as diallyl phthalate, dimethyl phthalate, butylphthalyl butyl glycolate and propylene carbonate. Etc. can be used.

In the present invention, the solid drawing material is prepared by arbitrarily blending the above-mentioned blending materials, and depending on the characteristics of the binder used, a polar solvent such as water, methyl ethyl ketone (MEK) or alcohol, or a non-polar solvent such as toluene. While optionally using, it is molded after stirring, crushing, and kneading with a Hensyl mixer, a ball mill, a three-roll mill or the like by a disperser. A method in which a crayon, a pass, and the like are put into a mold while being heated and melted, and then cooled and molded can be adopted. Furthermore, in the case of a colored pencil lead, etc., a material with a slight amount of solvent remaining is loaded into a cylinder for a vertical extruder, and the material inside the cylinder is extruded with a hydraulic piston, and a dryer is used for the organic solvent contained. An existing method such as forced drying can be used to perform molding.

[0015]

The calcium carbonate having an amino group on the surface of the particles used in the present invention is positively charged by the action of the amino group on the surface. On the other hand, the fibers of the paper, which is the material to be drawn, are negatively charged. Therefore, calcium carbonate having an amino group on the particle surface is electrically attracted to and adheres to the paper fibers. Therefore, it is possible to uniformly adhere to the paper surface, and since the coating film of the drawing material according to the present invention is formed so that the paper surface is not exposed, the adverse effect of the paper surface on the color developability is suppressed and the color developability is improved. Further, calcium carbonate having an amino group on the surface of the particles does not cause aggregation because the amino groups on the surface are uniformly treated. Therefore, the particle size distribution is narrowed and the maximum particle size can be controlled. Therefore, the dispersibility of the coloring agent and the calcium carbonate, which triggers coloring on the paper surface, is improved, and the coloring property is also improved.
Incidentally, calcium carbonate having an amino group on the particle surface is treated with a fatty acid, and a compounding amount that does not impair the effect of the amino group is used, and the lubricating effect of the fatty acid can further improve the color developability. I think it was done.

[0016]

EXAMPLES The present invention will be described below based on examples.
The invention is not limited to the examples. <Example 1> Nitrocellulose (binder) 18 parts by weight N [epsilon] -lauroyl lysine (extendant) 20 parts by weight AFF-95 (calcium carbonate having an amino group on the particle surface, manufactured by Phimatech Co., Ltd., particle diameter 1 0.0 μm) 20 parts by weight Stearic acid (wear property imparting material) 13 parts by weight Propylene carbonate (plastic material) 3 parts by weight Phthalocyanine blue- (coloring material) 26 parts by weight MEK (solvent) 100 parts by weight After dispersing with a Hensil mixer, kneading and further dispersing with a triple roll, molding with a vertical extruder while adjusting the solvent content, and then drying at 80 ° C. for 8 hours to completely remove the residual solvent content. A blue pencil lead having a nominal diameter of 2 was obtained.

Example 2 Nitrocellulose (binder) 18 parts by weight Nε-lauroyl lysine (extendant) 20 parts by weight AFF-95 SuperO (calcium carbonate surface-treated with amino groups having amino groups present on the particle surface) , Manufactured by Phimatech Co., Ltd. 20 parts by weight Stearic acid (wear property imparting material) 13 parts by weight Propylene carbonate (plastic material) 3 parts by weight Phthalocyanine bleu (coloring material) 26 parts by weight MEK (solvent) 100 parts by weight Is blended, dispersed with a Hensil mixer, kneaded with a three-roll mill and further dispersed, and molded with a vertical extruder while adjusting the solvent content, and at 80 ° C. at 80 ° C. to completely remove the residual solvent content. After drying for an hour, a blue pencil lead having a nominal diameter of 2 was obtained.

<Example 3> Nitrocellulose (binder) 18 parts by weight Nε-lauroyl lysine (extendant) 20 parts by weight AFF-100 (calcium carbonate having an amino group on the particle surface, manufactured by Phimatech Co., Ltd., Particle size 0.8 μm) 10 parts by weight AFF-95 SuperO (calcium carbonate having an amino group present on the particle surface and further surface-treated with oleic acid, manufactured by Phimatech Co., Ltd.) 10 parts by weight stearic acid (wearing material) 13 parts by weight Propylene carbonate (plastic material) 3 parts by weight Phthalocyanine bleu (coloring material) 26 parts by weight MEK (solvent) 100 parts by weight The above materials are blended and dispersed in a Hensyl mixer, followed by kneading and further mixing with a three-roll mill. After adjusting the solvent content and molding with a vertical extruder, dry at 80 ° C for 8 hours to completely remove the residual solvent content. To give a blue color pencil leads of nominal diameter 2.

<Examples 4 to 10> AF in Example 1
The nominal diameter was the same as in Example 1 except that the amount of F-95 (calcium carbonate having an amino group on the particle surface) changed to 1, 2, 5, 10, 25, 38, 40 parts by weight. A blue pencil lead of 2 was obtained.

<Comparative Example 1> In Example 1, the AFF-
95 (calcium carbonate with an amino group on the particle surface)
In the same manner as in Example 1 except that the previously known Nanox # 30 (heavy calcium carbonate, particle size 1.1 μm, manufactured by Maruo Calcium Co., Ltd.) was used. I got a core.

<Comparative Example 2> In Example 1, the amount of Nε-lauroyl lysine (extendant) used was 10 parts by weight, and AF was used.
F-95 (calcium carbonate having an amino group on the particle surface) was changed to Nanox # 30 (heavy calcium carbonate, particle size 1.1 μm, manufactured by Maruo Calcium Co., Ltd.), and the amount used was 1 part by weight, phthalocyanine. A blue colored pencil lead having a nominal diameter of 2 was obtained in the same manner as in Example 1 except that the amount of the blue (coloring material) used was changed to 54 parts by weight.

<Comparative Example 3> In Example 1, the AFF-
95 (calcium carbonate with an amino group on the particle surface)
Nanox # 30 (heavy calcium carbonate, particle size 1.1
μm, manufactured by Maruo Calcium Co., Ltd., and used at 4
A blue colored pencil lead having a nominal diameter of 2 was obtained in the same manner as in Example 1 except that 0 parts by weight and the amount of phthalocyanine blue (coloring material) used were changed to 6 parts by weight.

The above Examples 1 to 10 and Comparative Examples 1 to 3
The strength (using bending strength (unit: MPa) as a substitute characteristic) and the color developability (using concentration (unit: D) as a substitute characteristic) of the colored pencil lead obtained in accordance with JIS S 60
It was measured based on 05. The results are shown in Table 1.

[0024]

[Table 1]

[0025]

INDUSTRIAL APPLICABILITY As described above, by using calcium carbonate having an amino group on the particle surface, it is possible to obtain a solid drawing material having practically sufficient strength and improved color development. .

Claims (2)

[Claims] 1. A solid drawing material using at least an extender, a binder and a coloring material, wherein at least calcium carbonate having an amino group on the particle surface is used as the extender. 2. The solid drawing material according to claim 1, wherein the calcium carbonate having an amino group on the surface of the particles has a surface further treated with a fatty acid.