JP2001192601A - Solid drawing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solid drawing material having practical strength and also having color developability with clear handwriting. SOLUTION: This solid drawing material is characterized by containing a secondary amide-type long-chain acylamino acid salt represented by the general formula (1) shown below. (RCONH(CH2)mCOO)nM (1), wherein RCO is a 8-36C long chain acyl; m is 1 or 2; n is a 1-3 integer; and M is a univalent, divalent or trivalent metal.

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 colored pencil lead, and the like, which are obtained by kneading and molding a colorant with a binder, a body material, etc., and which are worn by being rubbed against a drawing object. The present invention relates to a solid drawing material that forms a drawing mark by attaching a coloring agent to a drawing target.

[0002]

2. Description of the Related Art Generally, solid drawing materials such as crayon, pastel, and colored pencil lead include coloring agents such as organic pigments and inorganic pigments, binders such as clay, organic bentonite, carboxymethyl cellulose, and polyethylene resin, talc, and mica. , Calcium carbonate and the like, and carnauba wax, polyethylene wax and oils and fats, and if necessary, molded by using a solvent such as water and methyl ethyl ketone (MEK).

[0003] Such a solid drawing material is self-wearing and forms a trace of application, so that in order to obtain a good writing quality, the wearability is promoted. When it becomes easy to perform, the strength (bending strength) as a molded article becomes weak. For example, it is known that if you try to improve the writing taste with a colored pencil lead, you can use a low-melting wax or oil to make it soft and easy to wear itself, but the writing taste and coloring of the resulting colored pencil lead are known. Even if the property is improved, it tends to break in terms of strength. On the other hand, if a resin or a wax having a high melting point is used to make it difficult to bend, the adhesion to the paper surface is reduced and the color developability is reduced, in addition to the fact that the resin and the wax are hardly worn. In Japanese Patent Publication No. 5-58467, an Nω-long-chain acyl basic amino acid is proposed as having both the above-mentioned writing taste and the difficulty in breaking. Specific examples of Nω-long-chain acyl basic amino acids include Nε-lauroyllysine and Nε-palmitoyllysine. However, these basic amino acids are highly reactive substances due to the amino groups in the molecule, and a lubricant component such as a binder or a wax used in a solid drawing material reacts and loses cleavage of particles. As a result, the solid drawing material has a structure that is hard and hard to wear, resulting in poor writing taste and poor coloring of coating marks.

[0004]

Accordingly, an object of the present invention is to provide a solid drawing material having both practical strength and vivid coloration of handwriting.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a solid drawing material containing a secondary amide type long-chain acylamino acid salt represented by the following general formula (1): Was found to be excellent in strength and coloring of handwriting, and completed the present invention. That is, the gist of the present invention is a solid drawing material characterized by containing a secondary amide type long-chain acylamino acid salt represented by the following general formula (1).

[0006]

Embedded image (RCONH (CH ₂ ) mCOO) nM (1) (where RCO is a long-chain acyl group having 8 to 36 carbon atoms, m is 1 or 2, n is an integer of 1 to 3, M is 1
Represents a divalent, divalent or trivalent metal)

Hereinafter, the present invention will be described in detail. The method for producing the secondary amide-type long-chain acylamino acid salt represented by the general formula (1) used in the present invention is not particularly limited,
Usually, it is produced by condensing an acid halide of a saturated and / or unsaturated long-chain fatty acid with an amino acid in the presence or absence of a base, and isolated as a desired metal salt.

The long-chain fatty acids constituting the secondary amide-type long-chain acylamino acid salt represented by the general formula (1) used in the present invention include octanoic acid, decanoic acid, undecanoic acid,
Lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid,
A saturated and / or unsaturated fatty acid having 8 to 36 carbon atoms represented by nanodecanoic acid, oleic acid, linoleic acid and the like is used.

The amino acids constituting the secondary amide type long chain acyl amino acid salt represented by the general formula (1) used in the present invention include β-alanine and γ-aminobutyric acid.

The secondary amide type long-chain acylamino acid salt represented by the general formula (1) used in the present invention includes alkali metal salts such as lithium salt, sodium salt and potassium salt, magnesium salt, calcium salt and barium. Alkaline earth metal salts such as salts, and other aluminum salts and zinc salts. Among them, calcium salts and aluminum salts are preferable because they have the property of producing white plate-like crystals having high wettability.

Specific examples of the secondary amide type long chain acyl amino acid salt represented by the general formula (1) used in the present invention include octanoyl-β-alanine lithium salt, octanoyl-β-alanine sodium salt, octanoyl- β-
Alanine potassium salt, octanoyl-β-alanine calcium salt, octanoyl-β-alanine magnesium salt, octanoyl-β-alanine barium salt, octanoyl-β-alanine aluminum salt, octanoyl-β
-Zinc alanine, lithium octanoyl-γ-aminobutyrate, sodium octanoyl-γ-aminobutyrate,
Octanoyl-γ-aminobutyric acid potassium salt, octanoyl-γ-aminobutyric acid calcium salt, octanoyl-γ-
Magnesium aminobutyrate, barium octanoyl-γ-aminobutyrate, aluminum octanoyl-γ-aminobutyrate, zinc octanoyl-γ-aminobutyrate, sodium decanoyl-β-alanine, decanoyl-β-
Alanine potassium salt, decanoyl-β-alanine lithium salt, decanoyl-β-alanine calcium salt, decanoyl-β-alanine magnesium salt, decanoyl-β-
Alanine barium salt, decanoyl-β-alanine aluminum salt, decanoyl-β-alanine zinc salt, decanoyl-γ-aminobutyric acid sodium salt, decanoyl-γ-aminobutyric acid potassium salt, decanoyl-γ-aminobutyric acid lithium salt, decanoyl-γ -Calcium aminobutyrate, magnesium decanoyl-γ-aminobutyrate, barium decanoyl-γ-aminobutyrate, aluminum decanoyl-γ-aminobutyrate, zinc decanoyl-γ-aminobutyrate, sodium lauroyl-β-alanine, Lauroyl-β-alanine potassium salt, lauroyl-β-alanine lithium salt, lauroyl-β-alanine calcium salt, lauroyl-β-alanine magnesium salt, lauroyl-β-alanine barium salt, lauroyl-β-alanine aluminum salt, lauroyl -Β-alanine aluminum salt, lauroyl-β-alanine zinc salt, lauroyl-γ-aminobutyric acid sodium salt, lauroyl-γ-aminobutyric acid potassium salt, lauroyl-γ-aminobutyric acid lithium salt, lauroyl-γ-aminobutyric acid calcium salt , Magnesium lauroyl-γ-aminobutyrate, barium lauroyl-γ-aminobutyrate, aluminum lauroyl-γ-aminobutyrate, aluminum lauroyl-γ-aminobutyrate, zinc lauroyl-γ-aminobutyrate, myristoyl-β- Alanine sodium salt, myristoyl-
β-alanine potassium salt, myristoyl-β-alanine lithium salt, myristoyl-β-alanine calcium salt, myristoyl-β-alanine magnesium salt, myristoyl-β-alanine barium salt, myristoyl-β
-Alanine aluminum salt, myristoyl-β-alanine n salt, myristoyl-γ-aminobutyric acid Na salt, myristoyl-γ-aminobutyric acid K zinc salt, myristoyl-γ-
Lithium aminobutyrate, myristoyl-γ-aminobutyric acid calcium salt, myristoyl-γ-aminobutyric acid magnesium salt, myristoyl-γ-aminobutyric acid barium salt, myristoyl-γ-aminobutyric acid aluminum salt, myristoyl-γ-aminobutyric acid zinc salt, Palmitoyl-β-alanine sodium salt, palmitoyl-β-alanine potassium salt, palmitoyl-β-alanine lithium salt, palmitoyl-β-alanine calcium salt, palmitoyl-β
-Alanine magnesium salt, palmitoyl-β-alanine barium salt, palmitoyl-β-alanine aluminum salt, palmitoyl-β-alanine zinc salt, palmitoyl-γ-aminobutyric acid sodium salt, palmitoyl-γ-
Potassium aminobutyrate, lithium palmitoyl-γ-aminobutyrate, calcium salt of palmitoyl-γ-aminobutyrate, magnesium salt of palmitoyl-γ-aminobutyrate, barium palmitoyl-γ-aminobutyrate, aluminum salt of palmitoyl-γ-aminobutyrate, Palmitoyl-γ-
Zinc aminobutyrate, sodium stearoyl-β-alanine, potassium stearoyl-β-alanine, lithium stearoyl-β-alanine, stearoyl-β
-Alanine calcium salt, stearoyl-β-alanine magnesium salt, stearoyl-β-alanine barium salt, stearoyl-β-alanine aluminum salt, stearoyl-β-alanine zinc salt, stearoyl-γ-aminobutyric acid sodium salt, stearoyl-γ- Potassium aminobutyrate, lithium stearoyl-γ-aminobutyrate, calcium stearoyl-γ-aminobutyrate, magnesium stearoyl-γ-aminobutyrate, barium stearoyl-γ-aminobutyrate, aluminum stearoyl-γ-aminobutyrate, And stearoyl-γ-aminobutyric acid zinc salt. These may be used alone or as a mixture of two or more.

The amount of the secondary amide-type long-chain acylamino acid salt represented by the general formula (1) used in the present invention is not particularly limited, but is preferably 2 to 50 with respect to the total amount excluding the volatile solvent.
%, More preferably 5 to 40% by weight.
When the amount used is less than 2% by weight, practical strength is obtained but no color developability is obtained, and when it exceeds 50% by weight, the color developability is obtained but the strength is greatly reduced. There are cases.

The material of the solid drawing material used in the present invention includes, in addition to the secondary amide type long-chain acylamino acid salt represented by the general formula (1), a binder such as a resin for shaping, Various waxes and fats and oils such as stearic acid for applying a coloring agent or the like with structuring agents such as talc or mica can be blended.

The binder used in the present invention is not particularly limited, and specific examples thereof include nitrified cotton, polystyrene, polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polystyrene butadiene, polyvinyl chloride, and polyvinyl acetate. , Polymethyl acrylate, polymethyl methacrylate, polyvinylidene chloride,
Polytetrafluoroethylene, AS resin, ABS resin,
Ethylene-tetrafluoroethylene copolymer, nitrocellulose, ethylcellulose, methylcellulose, cellulose acetate, carboxymethylcellulose, hydroxyethylcellulose, polyethylene glycol, polypropylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl ether, maleic acid polymerization Products, 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.

The extender used in the present invention is not particularly limited, and talc, calcium carbonate, mica, kaolin clay, boron nitride, graphite fluoride, potassium titanate whisker, calcium carbonate whisker, titanium dioxide whisker, magnesium sulfate Whiskers, calcium sulfate whiskers, aluminum sulfate whiskers, and the like. 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, Japananol Fast Black D Conc (C.I.
Direct Black 17), Water Black 100
L (19), Water Black 200-L (1)
9), Water Black # 7 (19), Kaya Set Black W9 (19), Direct Fast Black B (22), Direct Fast Black AB (3)
2), Direct Deep Black EX (38), Direct Deep Black (38 similar products), Direct Fast Black Conch (51), Kayalas Sprague VGN (71), Kayak Direct Brilliant Yellow G (CI) Direct Yellow), Direct Fast Yellow 5GL (26), Eizen Primula Yellow GCLH (44), Direct Fast Yellow R
(50), 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 (3)
7), kayak direct scarlet 3B (39),
Aizen Primula Bin Conch 2BLH (75), Sumilight Red F3B (80), Aizen Primula Red 4BH (81), Kayalas Sprulbin BL (8)
3), Kayasu Light Red F5G (225), Kayasu Light Red F5B (226), Kayasu Light Rose FR (227), Direct Sky Blue 6B
(CI Direct Blue 1), Direct Sky Blue 5B (15), Benzo Brilliant Sky Blue 8GS (41), Sumilite Supra Blue BRR Conch (71), Dibogen Turquoise Blue S (8)
6), Water Blue # 3 (86), Kayara Star Koizu Blue GL (86), Daiwa Blue 215H
(Id. 87), Kayalas Spral Blue FFRL (Id. 10)
8), Kayarus Spral Blue FF2GL (10
6), Kayara Splatter Coizu Blue FBL (1st)
99) etc. 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 V
LG (26), Kayanol Milling Black BR Conc (31), Mitsui Nylon Black GL (5)
2), Eisen Opal Black WH Extra Conch (52), Sumilan Black WA (52), Ranyl Black BG Extra Conc (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (52) 109), Kayanol Milling Black TLR (110), Eisen Opal Black New Conc (119), Water Black 187
-L (154), Acid Yellow # 10 (CI.
Acid Yellow 1), Kayak Acid Brilliant Flavin FF (7: 1), Kayasil Yellow CG (1)
7), xylene light yellow 2G140% (17),
Suminol Leveling Yellow NR (19), Water Yellow # 1 (23), Daiwadladrazine (2)
5) Kayaktor Trazine (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), Kayanol Yellow NF
G (49), Suminol Milling Yellow 3G (7
2), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol Yellow N
5G (110), Suminol milling yellow 4G20
0% (141), Kayanol Yellow NG (13
5), Kayanol milling yellow 5GW (127),
Kayanol 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 102 (18), Aizen Bon Saw RH (2)
6), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS (37), Aizen Erythrosin (5)
1), kayak acid rhodamine FB (52), Daiwa Red No. 106 (52), Suminol leveling rubinol 3GP (57), diacid alizarin rubinol F3G 200% (82), alizarin rubinol 5G (52) 83), Aizenosine GH (87), Water Red # 2 (87), Daiwa Red 103WB
(87), Water Pink # 2 (92), Eisen Acid Phloxine PB (92), Daiwa Red 104
No. (No. 92), Rose Bengal (No. 94), Kayanol milling scarlet FGW (No. 111), Kayanol milling rubin 3BW (No. 129), Sumino milling brilliant red 3BN conch (No. 131), Sumino milling brilliant red BS (138),
Eisen Opal Pink BH (186), Suminol Milling Brilliant Red B Conc (249), Kayak Acid Brilliant Red 3BL (254),
Kayaku Acid Brilliant Red BL (265),
Kayanol Milling Red GW (276), Mitsui Acid Violet 6BN (17), Water Violet # 1 (49), Ink Violet L10
(Ibid. 49), Sumitomo Patent Pure Blue VX (C.I.
I. Acid Blue 1), Water Blue $ 106
(1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue No. 1 (9), Ink Blue L20 (9), Spranol Blue B (1)
5), Water Blue # 116 (15), Orientable Blue OBX (22), Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (4)
0), Kayasil Blue BR (41), Mitsui Ali Zyrin Safirol SE (43), Suminol Leveling Sky Blue R Extra Conch (62), Mitsui Nylon Fast Sky Blue R (78), Sumitomobrilliant Indocyanine 6Bh / E (83), Sandran cyanine N-6B 350% (90), Water Blue # 105 (90), Orient Soluble Blue OBB (93), Spranol Cyanine 7BF
(100), Sumitomo Brilliant Blue 5G (1)
03), Acid Blue (103), Asilane Brilliant Blue FFR (104), Kayanol Milling Ultrasky SE (112), Kayanol Milling Cyanine 5R (113), Eisen Opal Cyanine 2GLH (158), Daiwa Guinea Green B (C.I.
I. Acid Green 3), Acid Brilliant Milling Green (9), Daiwa Green # 70 (1)
6), Kayanol Cyanine Green G (25), Suminol Milling Green G (27), acid dyes such as Water Orange # 17 (CI Acid Orange 56), and Water Yellow # 2 (CI) Food Yellow 3), Food Yellow No. 5 (CI Food Yellow 3),
Food dyes such as Food Red No. 3 (CI Food Red 14), Food Blue 2 (CI Acid Blue 74), Food Green 2 (CI Acid Green 5), and the like,
Malachite Green (CI.42000), Victoria Blue FB (CI.44045), Methyl Violet FN (CI.42535), Rhodamine F4G
(CI. 45160), rhodamine 6GCP (C.I.
I. 45160) and the like.

As the pigment, Special Blac is used.
k6, same S170, same S610, same 5, same 4, same 4A,
550, 35, 250, 100, Printe
x150T, U, V, 140U, 140V, 95, 90, 85, 80, 75, 55, 4
5, P, XE2, L6, L, 300, 3
0, 3, 35, 25, 200, A, G (all made 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 (Mitsubishi Chemical Corporation), MONARCH
1300, 1100, 1000, 900, 8
80, 800, 700, MOGUL L, REGA
L 400R, 660R, 500R, 330R,
Same 300R, Same 99R, ELFTEX 8, Same 12, B
LACK PEARLS2000 (manufactured by Cabot Co. Ltd., USA), Raven 7000, 575
0, 5250, 5000, 3500, 200
0, 1500, 1255, 1250, 120
0, 1170, 1060, 1040, 103
5, 1020, 1000, 890H, 890,
850, 790, 780, 760, 500,
450, 430, 420, 410, 22, 16, 16, 825 Oil Beads, H2
Carbon blacks such as 0, C, Conductex 975, 900, and SC (all manufactured by Colombian Carbon Japan Co., Ltd.), KA-10, 10P, 1
5, 20, 30, 35, 60, 80, 9
Titanium oxides such as KR-310, 380, 460, and 480 (all manufactured by Titanium Industry Co., Ltd.) and P25 (manufactured by Nippon Aerosil Co., Ltd.), BS-605, and 607
(These are manufactured by Toyo Aluminum Co., Ltd.), Bronze Powder P-
555, P-777 (above, Nakajima Metal Foil Industry Co., Ltd.)
Metal powder pigments such as Bronze Powder 3L5 and 3L7 (all manufactured by Fukuda Metal Foil Industry Co., Ltd.), black iron oxide, yellow iron oxide, red iron oxide, ultramarine, navy blue, cobalt blue, chrome green , Inorganic pigments such as chromium oxide, Hansa Yellow-10G, 5G, 3G, 4 and GR,
A, Benzidine Yellow, Permanent Yellow NCC
G, tartrazine lake, quinoline yellow, Sudern 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, and Phthalocyanine Green. In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfate, calcium sulfide, strontium sulfide, and calcium tungstate may be used.

In the present invention, in addition to the above, natural waxes such as carnauba wax, beeswax and wood wax, synthetic waxes such as polyethylene wax, montan wax, paraffin wax, zinc stearyl ketone and microcrystalline wax; Various metal salts of stearic acid such as stearic acid, aluminum stearate, magnesium stearate, calcium stearate, and, if necessary, plasticizers such as diallyl phthalate, dimethyl phthalate, butyl phthalyl butyl glycolate, and propylene carbonate. Can be used.

In the present invention, when the above materials are molded as a solid drawing material, these blending materials are optionally blended, and depending on the characteristics of the binder used, a polar solvent such as water or alcohol, or a non-polar solvent such as toluene. While using a solvent arbitrarily, kneading is performed by stirring, pulverizing, dispersing equipment such as a Hensyl mixer, a ball mill, a roll mill, and the like. In the case of a core, the material with a small amount of solvent remaining is loaded into a cylinder for a vertical extruder, the material in the cylinder is extruded with a hydraulic piston, and the solvent contained is forcibly dried using a dryer. Existing methods can be adopted.

In addition, as long as the effect of the long-chain acylaminosulfonate used in the present invention is not hindered,
N-long chain acyl amino acids such as Nε-lauroyl lysine and N-lauroyl aspartic acid β-stearyl ester and their esters may be used in combination.

[0021]

Hereinafter, the present invention will be described based on examples.
The present invention is not limited only to the embodiments. Production Example (Synthesis of N-lauroyl-β-alanine calcium) N-lauroyl-β-alanine (hereinafter abbreviated as LBA) 4
5.7 g was suspended in 280 g of water, and the temperature was raised to 60 ° C., and a 30% aqueous solution of sodium hydroxide was added dropwise to form an LBA-Na salt and completely dissolved. PH of the solution is 9 ~
After adjusting to 9.5, an equivalent amount or more of an aqueous solution of calcium chloride was charged dropwise. A white precipitate was formed with the dropwise addition. After completion of the dropwise addition, the mixture was aged for 2 hours, filtered, washed and dried to obtain LBA-Ca.
50 g of white crystals of the salt were obtained.

<Example 1> Nitrocellulose (resin) 15 parts by weight N-lauroyl-β-alanine calcium 30 parts by weight Stearic acid 3 parts by weight Montan wax 10 parts by weight Propylene carbonate (plasticizer) 3 parts by weight Phthalocyanine blue (colored) 39 parts by weight MEK (solvent) 100 parts by weight After mixing the above materials, dispersing with a Hensyl mixer, kneading and further dispersing with three rolls, adjusting the solvent content, forming with a vertical extruder, and remaining. After drying at 80 ° C. for 8 hours to completely remove the solvent, a blue colored pencil lead having a diameter of about 1.3 mm was obtained.

<Examples 2 to 10> N-lauroyl-β-
The amount of alanine calcium used was 1, 2, 4, 15, 4
The same operation as in Example 1 was performed except that the weight was changed to 5, 50, 65, 70, and 75 parts by weight to obtain a blue colored pencil lead.

Comparative Example 1 A blue colored pencil lead was obtained in the same manner as in Example 1 except that N-lauroyl-β-alanine calcium was changed to Nε-lauroyl lysine.

The bending strength (unit: MPa) and the density (unit: D) as a substitute property of the color developing properties of the color pencil cores obtained in the above Examples and Comparative Examples were measured based on JIS S6005. Table 1 shows the results.

[0026]

[Table 1]

[0027]

As described above, the use of the secondary amide-type long-chain acylamino acid salt of the present invention makes it possible to obtain a solid drawing material with reduced strength and improved color developability.

Claims (2)

[Claims] 1. A solid drawing material comprising a secondary amide type long-chain acylamino acid salt represented by the following general formula (1). Embedded image (RCONH (CH ₂ ) mCOO) nM (1) (where RCO is a long-chain acyl group having 8 to 36 carbon atoms, m is 1 or 2, n is an integer of 1 to 3, M is 1
Represents a divalent, divalent or trivalent metal) 2. The solid drawing material according to claim 1, wherein the solid drawing material is a non-fired pencil lead.