JP7067324B2 - Solid drawing material - Google Patents

Description

The present invention relates to a solid drawing material which is a mixed molded product containing at least a shaping material and a coloring component and which forms a drawing mark by self-wearing due to rubbing.

Conventionally, crayon, which is a solid drawing material, is known to be molded from oils such as pigments, waxes and a small amount of mineral oil, and those containing a large amount of soft waxes can form thick and dark drawing marks. On the other hand, it gets caught on the paper and feels heavy to draw, and because it is soft, it is easy to break when a strong force is applied. In some cases, unintended parts of the surface to be drawn, such as paper, may be soiled, or dust may adhere to the desk, clothes, or room. On the other hand, those containing a large amount of hard wax are hard to break, have a light drawing comfort, and have less residue, but the drawing marks tend to be thinner. , Drawing resistance, drawing density, and axis strength were in conflict with each other. Generally, in educational settings such as infants and children, non-absorbent surfaces (smooth surfaces) such as plastic and glass surfaces are not limited to paper, regardless of whether the shape is a thin shaft that is easy to draw lines or a thick shaft that is easy to paint. ), Which is a solid drawing material that can draw thick and dark drawing marks on various supports with a soft drawing feeling, but is highly versatile and does not stain the picture, desk, or room due to the residue of the drawing material. Is requested.

In an attempt to solve such a problem, in Patent Document 1 (Japanese Patent Laid-Open No. 56-047463), a solid drawing material containing isoparaffin polyethylene having a softening point of 60 ° C. to 100 ° C. suppresses the generation of residue. The fact is disclosed.

Further, Patent Document 2 (Japanese Unexamined Patent Publication No. 01-144474) contains a phthalate ester that is solid at room temperature and has a regular molecular structure and is easy to delaminate, so that the drawing marks are coated without lowering the concentration. A solid drawing material that can reduce the amount of residue is disclosed.

Further, Patent Document 3 (Japanese Unexamined Patent Publication No. 04-033970) discloses a solid drawing material which imparts plasticity by tristearate sorbitan acid to improve delamination of wax.

Japanese Unexamined Patent Publication No. 56-047463 Japanese Unexamined Patent Publication No. 01-144474 Japanese Unexamined Patent Publication No. 04-033970

It is said that the solid drawing material described in Patent Document 1 preferably contains 20% by weight or more of isoparaffin polyethylene having a softening point of 60 ° C. to 100 ° C. in order to suppress the generation of residue. The material as a whole is hard and hard to wear, and it is hard to generate residue and break, but it is a little sticky, so it is not a big problem when writing on paper, but it is drawn when writing on a non-absorbent surface. It was very comfortable.

The solid drawing materials described in Patent Documents 2 and 3 are compounds in which phthalates and sorbitan acid tristearate are extremely polar (highly hydrophilic) as compared with waxes, so that the amount of residue is reduced. However, it was not possible to draw on the non-absorbent surface, and even if it was possible to draw, the drawing comfort was heavy. In addition, since highly polar compounds have the property of easily precipitating on the surface due to humidity or temperature changes, powdery (white) precipitates are likely to be generated on the surface of the main body of the solid drawing material, and the appearance tends to be poor. There was a problem that it was difficult to put it into practical use.

The present invention is a mixed molded product containing a coloring component and at least wax A, wax B, wax C, and wax D as excipients, and is a solid drawing material that forms drawing marks by self-wearing due to rubbing. In
The wax A is at least one wax selected from microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax having a needle penetration of 20 or more and 40 or less at 25 ° C., and the content thereof is a solid drawing material. 5% by weight or more and 25% by weight or less with respect to the total amount,
The wax B is at least one wax selected from microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax having a needle penetration of 0.1 or more and less than 15 at 25 ° C., and the content thereof is solid. 1% by weight or more and 20% by weight or less with respect to the total amount of drawing material,
The wax C is a ketone wax having a melting point of 70 ° C. or higher and 95 ° C. or lower, and the content thereof is 20% by weight or more and 35% by weight or less with respect to the total amount of the solid drawing material.
The wax D is a paraffin wax, and the first gist is a solid drawing material whose content is more than 0% by weight and 7% by weight or less with respect to the total amount of the solid drawing material, and the content of the wax A is solid. The content of the wax B is 2% by weight or more and 10% by weight or less with respect to the total amount of the solid drawing material, and the content of the wax C is solid. The second gist is a solid drawing material having a wax D content of 2% by weight or more and 5% by weight or less with respect to the total amount of the solid drawing material, which is 23% by weight or more and 33% by weight or less with respect to the total amount of the drawing material. do.

In the solid drawing material of the present invention, as a shaping material, a soft wax A having a needle penetration of 20 or more and 40 or less at 25 ° C. is 5% by weight or more and 25% by weight or less based on the total amount of the solid drawing material, and a needle at 25 ° C. By using a hard wax B having a filling degree of 0.1 or more and less than 15 in combination with 1% by weight or more and 20% by weight or less with respect to the total amount of the solid drawing material, the drawing material becomes a base having appropriate wear resistance and adhesiveness. .. In this state, drawing on a non-absorbent surface having less unevenness on the surface than the paper surface is due to the adhesiveness of wax A and wax B, so that the writing comfort is heavy and the strength is insufficient. If there is too much wax A, there will be a lot of residue and the strength will be weak, and if there is too much wax B, it will be hard and the drawing density will be low. It is possible to obtain a drawing material that can leave a dark drawing mark with a light drawing comfort by simultaneously imparting breakage strength and wear resistance due to the difference between the two. In addition, the density on the non-absorbent surface and the drawing comfort can be improved at the same time.

The content of the wax A is 7% by weight or more and 15% by weight or less with respect to the total amount of the solid drawing material, and the content of the wax B is 2% by weight or more and 10% by weight or less with respect to the total amount of the solid drawing material. The content of the wax C is 23% by weight or more and 33% by weight or less with respect to the total amount of the solid drawing material, and the content of the wax D is more than 2% by weight and less than 5% by weight with respect to the total amount of the solid drawing material. It is preferable to have a solid drawing material which has a good balance between fixing to the paper surface due to the adhesiveness of the wax and abrasion resistance, and has very little residue and is light in writing comfort.

Hereinafter, embodiments of the present invention will be described in detail.

Pigments can be mainly used as the coloring component, and conventionally known titanium dioxide, titanium black, zinc oxide, carbon black, iron black, aniline black, Hansaello-10G, 5G, 3G, R, G, and benzidine are used. Yellow G, Benzidine Yellow 5G, Benzidine Yellow 8G, Permanent Yellow NCG, Quinacridone Yellow, Permanent Orange 2G, Induslen Brilliant Orange GK, Balkan Orange, Pyrazoline Orange TMP, Permanent Brown FG, Para Brown, Permanent Red 4R, Fire Red, Brilliant Carmin BS, Pyrazolon Red, Bordeaux 5B, Thio Indigo Red, Nafsol Carmin HR, Nafsol Red F5RK, Nafsol Red F3RK-70, Permanent Red FGR, Permanent Carmin FB, Permanent Red 2B, Brilliant Carmin 6B, Watching Red, Permanent Red FRLL, Carmine Lake, Carmine FBB, Fast Violet B, Methyl Violet Lake, Induslen Violet, Induslen Blue, Acid Green Lake, Dichloroquinacridone Red, Kinacridone Magenta, Dichloroquinacridone Magenta, Kinacridone Violet, Kinacridone Orange, Quinacridone Maroon, Indigo, Dioxazine Violet, Perylene Red, Perylene Vermillion, Perylene Maroon, Perylene Carlet, Perylene Brown, Perylene Violet, Perylene Black, Perinon Orange, Perinon Red, Isoindrinone Yellow G, Isoindrinon Yellow R , Isoindolinon Yellow 6G, Isoindolinon Orange, Isoindrin Yellow R, Isoindrin Yellow G, Isoindrin Orange, Isoindrin Red, DPP Red, DPP Orange, DPP Scarlet, DPP Rubin, Alkaline Blue, Copper Phtalianin Blue, Copper Phthalocyanin green, first sky blue, petal pattern, navy blue, ultramarine blue, Victoria blue lake, marcarite green lake, pigment green B, viridian, iron oxide, iron hydroxide, shenner, amber, aluminum powder, bronze powder, lake pigment, etc. Organic pigments, inorganic pigments and metal powder pigments, colored processed powders and fluorescent pigments that combine dyes and pigments with resin powder, phosphorescent pigments, natural It can be appropriately selected from those in which the surface of mica is coated with a metal oxide, pearl pigments in which the surface of synthetic mica is coated with a metal oxide, and the like. At this time, these pigments may be washed with water and then dried, pH-adjusted with a pH adjuster such as an alkaline agent, or the surface of the pigment may be treated with a surfactant or the like, and may be used alone or in combination of two or more. You may use it. It is also possible to use a dye together.

The amount of these coloring components used is preferably 3% by weight or more and 40% by weight or less with respect to the total amount of the solid drawing material.

Examples of the wax A that can be used include microcrystalline wax, Fisher Tropsch wax, polyethylene wax (low molecular weight polyethylene), and polypropylene wax (low molecular weight polypropylene) having a needle penetration of 20 or more and 40 or less at 25 ° C., and Hi-Mic. -1045 (melting point 72 ° C, needle insertion degree 37, manufactured by Nippon Seiho Co., Ltd.), Hi-Mic-1070 (melting point 80 ° C, needle insertion degree 20, manufactured by Nippon Seiho Co., Ltd.), high wax 110P (polyethylene) Wax, melting point 109 ° C., needle insertion degree 25, manufactured by Mitsui Kagaku Co., Ltd., etc. are applicable, and the amount used is 5% by weight or more and 25% by weight or less, preferably 7% by weight, based on the total amount of solid drawing material. It is 15% by weight or less. Further, those having a melting point of 60 ° C. or higher and 130 ° C. or lower are preferable.

Examples of wax B that can be used include microcrystalline wax, Fisher Tropsch wax, polyethylene wax (low molecular weight polyethylene), and polypropylene wax (low molecular weight polypropylene) having a needle penetration at 25 ° C. of 0.1 or more and less than 15. -Mic-2095 (microcrystalline wax, melting point 101 ° C, needle insertion degree 8, manufactured by Nippon Seiho Co., Ltd.), Hi-Mic-1090 (microcrystalline wax, melting point 88 ° C, needle insertion degree 6, Nippon Seiho () (Made by Co., Ltd.), Hi-Mic-1080 (microcrystalline wax, melting point 84 ° C, needle insertion degree 12, manufactured by Nippon Seiko Co., Ltd.), FT115 (Fisher Tropschwax, melting point 113 ° C, needle insertion degree 1, Japan) Seikan Co., Ltd.), SX105 (Fisher-Tropsch wax, melting point 102 ° C, needle insertion degree 1, Nippon Seiko Co., Ltd.), FT-0165 (Fisher-Tropsch wax, melting point 73 ° C, needle insertion degree 5) , Nippon Seiko Co., Ltd.), FT-0070 (Fisher-Tropsch wax, melting point 72 ° C, needle insertion degree 11, manufactured by Nippon Seiko Co., Ltd.), Sazole wax H1 (Fisher-tropsh wax, melting point 112 ° C) , Needle insertion degree 1, manufactured by Sazole Co., Ltd.), Sazole wax C80 (Fisher tropush wax, melting point 88 ° C., needle insertion degree 4-9, manufactured by Sazole Co., Ltd.), Sunwax 171-P (low molecular weight polyolefin) , Needle insertion degree 5, manufactured by Sanyo Kasei Kogyo Co., Ltd.), Sunwax 151-P (low molecular weight polyethylene, needle insertion degree 4, manufactured by Sanyo Kasei Kogyo Co., Ltd.), Sunwax 131-P (low molecular weight polyolefin, needle) Quantity 4, Sanyo Kasei Kogyo Co., Ltd.), Sunwax 161-P (low molecular weight polyethylene, needle insertion degree 2, Sanyo Kasei Kogyo Co., Ltd.), Sunwax E-310 (low molecular weight polyolefin, needle insertion degree) 5. Sanyo Kasei Kogyo Co., Ltd.), Sunwax E-330 (low molecular weight polyethylene, needle penetration 4, Sanyo Kasei Kogyo Co., Ltd.), Sunwax E-250P (low molecular weight polyethylene, needle penetration 5, Sanyo Kasei Kogyo Co., Ltd.), Neowax (polyethylene wax, melting point 110 ° C, needle insertion degree 5, Yasuhara Chemical Co., Ltd.), high wax HP10A (polyethylene wax, melting point 116 ° C, needle insertion degree 2, Mitsui Chemicals Co., Ltd. ( (Co., Ltd.), High Wax 210P (polyethylene wax, melting point 114 ° C, needle insertion degree 4, manufactured by Mitsui Kagaku Co., Ltd.), High Wax 210MP (polyethylene wax, melting point 11) 2 ° C, needle entry 3, Mitsui Chemicals Co., Ltd.), High Wax 4202E (polyethylene wax, melting point 100 ° C, needle entry 5, Mitsui Chemicals Co., Ltd.), High Wax NL100 (polyethylene wax, melting point 103 ° C) , Needle insertion degree 3, manufactured by Mitsui Chemicals Co., Ltd.), High wax NP056 (polyethylene wax, melting point 124 ° C, needle insertion degree 2, manufactured by Mitsui Chemicals Co., Ltd.), etc. are applicable, and the amount used is the total amount of solid drawing material. It is 1% by weight or more and 20% by weight or less, preferably 2% by weight or more and 10% by weight or less. Further, those having a melting point of 60 ° C. or higher and 130 ° C. or lower are preferable.

The detailed reason is unknown when the difference in needle penetration between wax A and wax B is 15 or more, but a well-balanced balance between disintegration when the drawing material is worn and coating film formation is obtained, and a light and smooth drawing comfort is obtained. It is also possible to use one kind or a mixture of two or more kinds of waxes as long as they are within the range of needle penetration.

The wax C that can be used is a ketone wax having a melting point of 70 ° C. or higher and 95 ° C. or lower, and examples thereof include diheptadecylketone, dipentadecylketone, diundecylketone, and ditridecylketone. It can also be mixed and used. As the ketone wax, a reagent or Kao Wax T-1 (manufactured by Kao Corporation) can be used as a commercially available product.

The amount used is 20% by weight or more and 35% by weight or less, and more preferably 23% by weight or more and 33% by weight or less with respect to the total amount of the solid drawing material in order to give the solid drawing material an appropriate wear resistance. Ketone wax is relatively hard but has high crystallinity, and since it becomes fine and brittle crystals at room temperature, it becomes a starting point of disintegration at the time of drawing, and when used in combination with wax A, wax B, and wax D, it imparts abrasion resistance to the solid drawing material. As a result, it is possible to obtain a dark drawing density while maintaining a strong breaking strength. Also, the drawing comfort on the non-absorbent surface is light. If the amount used is less than 20% by weight, the wear points are reduced and it becomes difficult to wear, and it is necessary to increase the amount of soft wax in order to maintain the drawing density, which makes drawing comfort on both the paper surface and the non-absorbent surface heavy. .. When the amount used is more than 35% by weight, the drawing marks finely worn due to the brittleness of the wax cannot be sufficiently fixed by other waxes, and the drawing performance on the paper surface or the smooth surface is deteriorated.

The wax D that can be used is paraffin wax, and the amount used thereof is more than 0% by weight and less than 7% by weight with respect to the entire solid drawing material. Further, it is more preferable that the melting point is 45 ° C. or higher and 70 ° C. or lower. Paraffin wax is mainly composed of a linear saturated hydrocarbon compound and has strong non-polarity, so that the waxes do not easily stick to each other and have very high blocking resistance. In addition, although it is a hard wax, the crystals are large, so if it is blended together with wax A, wax B, and wax C in a range of more than 0% by weight and less than 7% by weight, the disintegration of wax C from the disintegration point becomes large. The amount of wear can be increased without reducing the strength, and the appropriate adhesiveness of wax A and wax B allows them to be efficiently fixed as drawing marks on the drawing surface without forming scraps, so even with a light force, the plastic can be used. It is possible to obtain a high-density drawing mark on a non-absorbent surface such as glass or glass. When the amount used is 2% by weight or more and 5% by weight or less, the adhesiveness and blocking resistance of wax A and wax B are well-balanced, and the amount of residue is very small, which is particularly preferable.
If it is not added at all, it will be hard and will only disintegrate finely even if force is applied, so it will be a drawing material with a low drawing density on the paper surface, and the non-absorbent surface drawing performance of plastic and glass will also deteriorate, but if the amount used exceeds 7% by weight. Due to the high blocking resistance of the overcoated drawing marks and the underlying coating film, it is not possible to form a thick integral coating film by fixing in an overlapping state, and the part drawn from above is a large amount of coating residue. Will be.

In addition to the above essential wax components, animals and plants conventionally used in solid drawing materials such as beef fat hardening oil, sunflower hardening oil, fish fat hardening oil, carnauba wax, beeswax, wood wax, montan wax, and petrolatum. Natural waxes such as waxes and petroleum waxes and synthetic waxes can also be used as a shaping material, and the amount of the excipient as a whole is preferably 30% by weight or more and 90% by weight or less.

In addition to the dispersion of pigments, oil can be added to adjust the drawing comfort. This oil can be appropriately selected and used from animal oil, vegetable oil, mineral oil and the like. For example, beef oil, pig oil, whale oil, rice bran oil, corn oil, avocado oil, macadamia nut oil, jojoba oil, olive oil, castor oil, sesame oil, soybean oil, peanut oil, coconut oil, sunflower oil, cottonseed oil. , Benibana oil, flaxseed oil, white oil, spindle oil, machine oil, engine oil, gear oil, turbine oil, cylinder oil and the like, and may be used alone or in combination of one or more of these. In particular, from the viewpoint of pigment dispersibility, it is preferable to select cow oil, spindle oil, machine oil, white oil and other mineral oils. If the amount of oil used is too small, the dispersion of the pigment will be insufficient and the drawing comfort will be poor, and if it is large, the quality will easily deteriorate over time such as bleeding. It is preferably about 30% by weight, and the amount used is particularly preferably 1% by weight or more and 15% by weight or less in order to obtain a drawing mark having a light writing comfort on a non-absorbent surface and a high density.

Further, as the filler, calcium carbonate, talc, clay, silica, barium sulfate and the like can be used. In particular, talc is preferable from the viewpoint of fluidity at the time of melting of the molding, and the amount used is preferably 10% by weight or more and 30% by weight or less. Further, sorbitan fatty acid ester, phthalate ester, oil-modified isophthalic acid resin and the like can be used as a lubricant, a shape-removing agent and a surfactant, and sorbitan fatty acid ester and oil-modified isophthalic acid resin are particularly preferable.

In the solid drawing material of the present invention, each of the above components is mixed at room temperature or by heating and stirring, and if necessary, kneaded with a kneader such as a kneader, a roll mill, a dissolver, a Henschel mixer, etc., and this is poured into a mold in a molten state, or It can be obtained by cooling and solidifying after injection, press-fitting or extruding.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples.

<Example 1> Blue crayon dipentadecylketone (ketone wax, melting point 85 degrees, manufactured by Tokyo Chemical Industry Co., Ltd.)
30 parts by weight Hi-Mic-1070 (microcrystalline wax, melting point 80 ° C, needle insertion degree 20, manufactured by Nippon Seiko Co., Ltd.) 13 parts by weight Hi-Mic-2095 (microcrystalline wax, melting point 101 ° C, needle insertion degree) 8. Nippon Seiko Co., Ltd.) 9 parts by weight paraffin wax-130 (paraffin wax, melting point 56 ° C, manufactured by Nippon Seiko Co., Ltd.)
4 parts by weight Super Oil N46 (mineral oil, manufactured by Shin Nippon Oil Co., Ltd.) 5 parts by weight Synseledin P-120 (oil-modified isophthalic acid resin, manufactured by Toshin Oil & Fat Co., Ltd.) 3 parts by weight KRONOS titanium oxide KA-10 ( CI PIGMENT WHITE 6, manufactured by Titanium Kogyo Co., Ltd. 4 parts by weight ultramarine # 05 (CI PIGMENT BLUE 29, HOLLIDAY PIGME)
NTS, UK) 4 parts by weight Cylinder Blue 5029 (CI PIGMENT BLUE 15: 1, manufactured by Dainichi Seika Kogyo Co., Ltd.) 3 parts by weight Talk 25 parts by weight Heat and dissolve the above ingredients and knead with a disper for 30 minutes. After mixing and pouring into a mold, the cylinder was cooled to obtain a blue crayon having a substantially truncated cone shape with a curved tip while gradually reducing the diameter of one end of a cylinder having a diameter of 11 mm toward the tip at a ridge angle of 28.0 degrees.

<Example 2> Red crayon wax T-1 (ketone wax, melting point 80 degrees, manufactured by Kao Co., Ltd.) 27 parts by weight Hi-Mic-1045 (microcrystalline wax, melting point 72 ° C, needle insertion degree 37, Nihonsei 12 parts by weight Hi-Mic-1090 (microcrystalline wax, melting point 88 ° C, needle insertion degree 6, manufactured by Nippon Seiko Co., Ltd.) 2 parts by weight neowax (polyethylene wax, melting point 110 ° C, needle) 5 parts by weight, manufactured by Yasuhara Chemical Co., Ltd. 5 parts by weight Paraffin wax-130 (mentioned above) 2 parts by weight Beef fat hardening oil 13 parts by weight Super oil N46 (mentioned above) 7 parts by weight Yellow Vaseline 7 parts by weight Seika First Red 1531 (C.I. I. PIGMENT RED 48: 3, manufactured by Dainichi Seika Kogyo Co., Ltd. 5 parts by weight Talk 20 parts by weight The above components are heated and melted, kneaded with a disper for 30 minutes, poured into a mold, cooled, and cooled. A red crayon was obtained by forming the same shape as above.

<Example 3> Yellow crayon dipentadecyl ketone (described above) 26 parts by weight Hi-Mic-1045 (described above) 10 parts by weight Hi-Mic-1070 (described above) 3 parts by weight Hi-Mic-2095 (described above) 1 part by weight Sazole wax H1 (Fischer-Tropsch wax, melting point 112 ° C, needle insertion degree 1,
Sazole Co., Ltd.) 5 parts by weight paraffin wax-140 (paraffin wax, melting point 61 ° C, manufactured by Nippon Seiro Co., Ltd.)
3 parts by weight hydrogenated beef tallow 14 parts by weight Super oil N46 (mentioned above) 8 parts by weight yellow petrolatum 6 parts by weight Hansa Yellow 10GM (CI PIGMENT YELLOW 3, Mikuni Color Co., Ltd.)
Manufactured by 4 parts by weight talc 20 parts by weight The above components were heated and dissolved, kneaded with a disper for 30 minutes, poured into a mold, and then cooled to form a yellow crayon in the same shape as in Example 1.

<Example 4> Pale orange crayon oil wax T-1 (described above) 20 parts by weight Hi-Mic-1070 (described above) 10 parts by weight Hi-Mic-1090 (described above) 2 parts by weight neowax (described above) 5 parts by weight Paraffin wax-130 (mentioned above) 7 parts by weight beef fat hardening oil 11 parts by weight Daphney oil KP-15 (manufactured by Idemitsu Kosan Co., Ltd.) 10 parts by weight TITANIX JR-800 (titanium oxide, manufactured by Teika Co., Ltd.) 13 parts by weight PV Fast Orange GRL (CI PIGMENT ORANGE 43)
, Clariant, Switzerland) 1 part by weight talc 21 parts by weight Heat and dissolve the above ingredients, knead with a disper for 30 minutes, pour into a mold, cool, and form into the same shape as in Example 1 and have a pale orange color. I got a crayon.

<Example 5> Red crayon oil wax T-1 (described above) 32 parts by weight Hi-Mic-1045 (described above) 23 parts by weight Hi-Mic-2095 (described above) 1 part by weight paraffin wax-130 (described above) 3 parts by weight Hardened beef oil 2 parts by weight Super oil N46 (mentioned above) 7 parts by weight Yellow petrolatum 7 parts by weight Seika First Red 1531 (mentioned above) 5 parts by weight Talk 20 parts by weight Heat and dissolve the above ingredients, knead with a disper for 30 minutes, and mold. After pouring, it was cooled and formed into the same shape as in Example 1 to obtain a red crayon.

<Comparative Example 1> Red Crayon Kao Wax T-1 (described above) 37 parts by weight Hi-Mic-1045 (described above) 7 parts by weight Hi-Mic-1090 (described above) 3 parts by weight Paraffin wax-130 (described above) 1 part by weight Hardened beef oil 13 parts by weight Super oil (mentioned above) 7 parts by weight Yellow petrolatum 7 parts by weight Seika First Red 1531 (mentioned above) 5 parts by weight Talk 20 parts by weight Heat and dissolve the above ingredients, knead with a disper for 30 minutes, and pour into a mold. After that, it was cooled and formed into the same shape as in Example 1 to obtain a red crayon.

<Comparative Example 2> Red crayon dipentadecylketone (described above) 15 parts by weight Hi-Mic-1045 (described above) 12 parts by weight Hi-Mic-2095 (described above) 3 parts by weight paraffin wax-140 (described above) 7 parts by weight beef fat Hardened oil 24 parts by weight Super oil (mentioned above) 7 parts by weight Yellow petrolatum 7 parts by weight Seika First Red 1531 (mentioned above) 5 parts by weight Talk 20 parts by weight The above ingredients were heated and melted, kneaded with a disper for 30 minutes, and poured into a mold. After that, it was cooled and formed into the same shape as in Example 1 to obtain a red crayon.

<Comparative Example 3> Red Crayon Kao Wax T-1 (described above) 21 parts by weight Hi-Mic-1070 (described above) 27 parts by weight Hi-Mic-2095 (described above) 2 parts by weight Paraffin wax-130 (described above) 1 part by weight Hardened beef oil 10 parts by weight Super oil (mentioned above) 7 parts by weight Yellow petrolatum 7 parts by weight Seika First Red 1531 (mentioned above) 5 parts by weight Talk 20 parts by weight Heat and dissolve the above ingredients, knead with a disper for 30 minutes, and pour into a mold. After that, it was cooled and formed into the same shape as in Example 1 to obtain a red crayon.

<Comparative Example 4> Red Crayon Dipentadecylketone (described above) 30 parts by weight Hi-Mic-1070 (described above) 1 part by weight Hi-Mic-2095 (described above) 10 parts by weight neowax (described above) 10 parts by weight paraffin wax- 130 (mentioned above) 4 parts by weight super oil (mentioned above) 7 parts by weight yellow petrolatum 7 parts by weight Seika First Red 1531 (mentioned above) 5 parts by weight talc 26 parts by weight Heat and dissolve the above ingredients, knead with a disper for 30 minutes, and mold. After pouring, it was cooled and formed into the same shape as in Example 1 to obtain a red crayon.

<Comparative Example 5> Blue Crayon Kao Wax T-1 (mentioned above) 25 parts by weight Hi-Mic-1045 (mentioned above) 18 parts by weight Hi-Mic-1090 (mentioned above) 5 parts by weight Paraffin wax-130 (mentioned above) 8 parts by weight Hardened beef oil 5 parts by weight Super oil N46 (mineral oil, manufactured by Shin Nippon Petroleum Co., Ltd.) 5 parts by weight Synseledin P-120 (oil-modified isophthalic acid resin, manufactured by Toshin Oil & Fat Co., Ltd.) 3 parts by weight KRONOS titanium oxide KA -10 (CI PIGMENT WHITE 6, manufactured by Titanium Kogyo Co., Ltd.) 4 parts by weight ultramarine # 05 (CI PIGMENT BLUE 29, HOLLIDAY PIGME)
NTS, UK) 4 parts by weight Cyanine Blue 5029 (CI PIGMENT BLUE 15: 1, manufactured by Dainichi Seika Kogyo Co., Ltd.) 3 parts by weight Talk 20 parts by weight Heat and dissolve the above ingredients and knead with a disper for 30 minutes. After mixing and pouring into a mold, the mixture was cooled and formed into the same shape as in Example 1 to obtain a blue crayon.

<Comparative Example 6> Blue Crayon Kaohwax T-1 (described above) 25 parts by weight Hi-Mic-1045 (described above) 18 parts by weight Hi-Mic-1090 (described above) 5 parts by weight hydrogenated beef oil 13 parts by weight Super oil N46 ( Mineral oil, manufactured by Shin Nippon Petroleum Co., Ltd.) 5 parts by weight Synseledin P-120 (oil-modified isophthalic acid resin, manufactured by Toshin Oil & Fat Co., Ltd.) 3 parts by weight KRONOS Titanium oxide KA-10 (CI PIGMENT WHITE 6) , Titanium Kogyo Co., Ltd.) 4 parts by weight ultramarine # 05 (CI PIGMENT BLUE 29, HOLLIDAY PIGME)
NTS, UK) 4 parts by weight Cyanine Blue 5029 (CI PIGMENT BLUE 15: 1, manufactured by Dainichi Seika Kogyo Co., Ltd.) 3 parts by weight Talk 20 parts by weight Heat and dissolve the above ingredients and knead with a disper for 30 minutes. After mixing and pouring into a mold, the mixture was cooled and formed into the same shape as in Example 1 to obtain a blue crayon.

<Comparative Example 7> Yellow Crayon Dipentadecylketone (mentioned above) 26 parts by weight Hi-Mic-1045 13 parts by weight Hi-Mic-2095 0.5 parts by weight Paraffin wax-140 (mentioned above) 7 parts by weight Hardened beef oil 15. 5 parts by weight Super Oil N46 (mentioned above) 8 parts by weight Yellow Vaseline 6 parts by weight Hansa Yellow 10GM (CI PIGMENT YELLOW 3, Mikuni Color Co., Ltd.)
Manufactured by 4 parts by weight talc 20 parts by weight The above components were heated and dissolved, kneaded with a disper for 30 minutes, poured into a mold, and then cooled to form a yellow crayon in the same shape as in Example 1.

<Comparative Example 8> Yellow Crayon Dipentadecylketone (mentioned above) 20 parts by weight Hi-Mic-1045 13 parts by weight Hi-Mic-2095 15 parts by weight Neowax (mentioned above) 7 parts by weight Paraffin wax-140 (mentioned above) 1 weight Part Beef Fat Hardened Oil 6 parts by weight Super Oil N46 (mentioned above) 8 parts by weight Yellow Vaseline 6 parts by weight Hansa Yellow 10GM (CI PIGMENT YELLOW 3, Mikuni Color Co., Ltd.)
4 parts by weight talc 19 parts by weight The above components were heated and dissolved, kneaded with a disper for 30 minutes, poured into a mold, cooled, and formed into the same shape as in Example 1 to obtain a yellow crayon.

<Comparative Example 9> Red Crayon Weissen 0252C (isoparaffin polyethylene, softening point 75 ° C, manufactured by Nippon Seiro Co., Ltd.) 36 parts by weight paraffin wax-155 (paraffin wax, melting point 69 ° C, manufactured by Nippon Seiro Co., Ltd.)
20 parts by weight Fish oil Hydrogenated oil 4 parts by weight Daphne oil KP-15 (mentioned above) 13 parts by weight Seika First Red 1531 (mentioned above) 8 parts by weight Tarku 19 parts by weight Heat and dissolve the above ingredients, knead with a disper for 30 minutes, and mold. After pouring, it was cooled and formed into the same shape as in Example 1 to obtain a red crayon.

<Comparative Example 10> Black Crayon Beef Fat Hardened Oil 40 parts by weight Phthalate dihexadecyl ester (phthalate ester, melting point 43 degrees) 50 parts by weight Carbon MA100 (carbon black, manufactured by Mitsubishi Chemical Corporation) 10 parts by weight It was melted by heating, kneaded with a disper for 30 minutes, poured into a mold, and then cooled to form a shape similar to that of Example 1 to obtain a black crayon.

<Comparative Example 11> Blue Crayon Paraffin Wax-130 (mentioned above) 35 parts by weight Carnauba Wax 25 parts by weight Sorbitanoic acid tristearate (sorbitan fatty acid ester) 30 parts by weight Cyanine Blue 5029 (mentioned above) 10 parts by weight Heat-dissolve the above components Then, the mixture was kneaded with a disper for 30 minutes, poured into a mold, cooled, and formed into the same shape as in Example 1 to obtain a blue crayon.

The following tests were performed using the crayon obtained in each Example and Comparative Example as a test sample. Method of measuring the weight of scraps The test sample is drawn 100 times on a 10 cm straight line on drawing paper (basis weight 73.3 to 210 g / cubic meter, whiteness of 75% or more). The drawing conditions are a drawing load of 1 kg, a drawing direction for advancing the test sample (crayon) on the paper surface, and an angle formed by the axis of the cylindrical rod-shaped crayon (hereinafter referred to as a drawing angle) of 60 degrees. Collect all the debris scattered on the paper and weigh it. The difference in the weight of the shaft before and after drawing is used as the amount of wear of the shaft, and the residue is calculated by the following formula.
Waste (%) = (Weight (g) / Wear amount (g) of waste on paper) x 100
If the amount of residue is 10% or less, the residue is not a concern and is good.

Drawing resistance measurement method When a test sample was drawn using TRIBO-MASTER (TYPE: TL201SA) manufactured by Trinity Lab Co., Ltd. under the conditions of a drawing load of 300 g, a drawing angle of 70 °, and a drawing speed of 4 cm / sec. , The resistance value (unit: gf) applied in the drawing direction was measured. Each time the test sample is measured, the test sample is rotated 120 ° to change the ground contact surface of the test sample with respect to the paper surface (the part that is not worn is grounded each time). Shows the average value. The larger the value, the greater the resistance required for drawing and the worse the writing quality (feels heavier). If the resistance value is different by 20 gf or more, the feeling of drawing is different, and if the resistance value is 150 gf or less, the feeling of drawing is light.

Breaking strength measuring method The breaking strength of the test sample was measured by JIS S 6026 using FUDOH RHEO METER (NRM-2010J) manufactured by Leotech Co., Ltd. The practical breakage strength is 1200 gf or more.

Non-absorbent surface drawing property A test sample is drawn back and forth on Alfan PK-002 40 μm (OPP film, manufactured by Oji F-Tex Co., Ltd.) with a drawing load of 500 g, and the drawing comfort is confirmed.
◎: Dark drawing is possible and drawing comfort is light ○: Dark drawing is possible but drawing comfort is heavy △: Drawing is possible but light ×: Cannot be drawn

Drawing density A test sample is drawn back and forth on drawing paper with a drawing load of 500 g, and the same color and density of Pentel Co., Ltd. Zuko Crayon (PTCG1-16) are compared.
○: Equivalent to or darker than zukou crayon ×: thinner than zukou crayon

As shown in Table 1, in Examples 1 to 5, good results were obtained in all of scraping, drawing resistance, breakage strength, non-absorbent surface drawing property, and density. Further, Examples 1 to 3 are particularly good with little residue.

On the other hand, in Comparative Example 1, since the amount of the ketone wax added to the wax C is too large, the drawing density is considerably low and the non-absorbent surface drawing property is also deteriorated. In Comparative Example 2, since the amount of the ketone wax added to the wax C is too small, the drawing resistance is large and the amount of residue is increased. In Comparative Example 3, since the amount of wax A is too large, the breaking strength is weak. In Comparative Example 4, since the amount of wax A is too small, a large amount of residue is generated, the drawing density is low, the non-absorbent surface drawing property is lowered, and the drawing resistance is high. In Comparative Example 5, since the amount of the paraffin wax added to the wax D is too large, the amount of residue is very large. In Comparative Example 6, since the paraffin wax of Wax D is not contained at all, the non-absorbent surface drawing property and the drawing density are poor. In Comparative Example 7, since the amount of wax B is too small, the breaking strength is weak. In Comparative Example 8, since the amount of wax B is too large, the drawing density and drawing resistance are poor. Since Comparative Example 9 contains a large amount of hard isoparaffin-based polyethylene, there is little residue, but drawing on a non-absorbent surface is heavy. In Comparative Example 10, since only beef tallow hydrogenated oil having insufficient wear resistance and fixing power is used as the shaping material, the non-absorbent surface drawing property and the drawing density are deteriorated. In Comparative Example 11, since a large amount of paraffin wax is added, the non-absorbent surface drawing property is good, but the abrasion property and the fixing property are insufficient, so that the drawing density is poor.

Claims (2)

In a solid drawing material which is a mixed molded product containing a coloring component and at least wax A, wax B, wax C, and wax D as excipients and which forms drawing marks by self-wearing due to rubbing.
The wax A is at least one wax selected from microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax having a needle penetration of 20 or more and 40 or less at 25 ° C., and the content thereof is a solid drawing material. 5% by weight or more and 25% by weight or less with respect to the total amount,
The wax B is at least one wax selected from microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax having a needle penetration of 0.1 or more and less than 15 at 25 ° C., and the content thereof is solid. 1% by weight or more and 20% by weight or less with respect to the total amount of drawing material,
The wax C is a ketone wax having a melting point of 70 ° C. or higher and 95 ° C. or lower, and the content thereof is 20% by weight or more and 35% by weight or less with respect to the total amount of the solid drawing material.
The wax D is a paraffin wax, and the content thereof is more than 0% by weight and 7% by weight or less with respect to the total amount of the solid drawing material. The content of the wax A is 7% by weight or more and 15% by weight or less with respect to the total amount of the solid drawing material, and the content of the wax B is 2% by weight or more and 10% by weight or less with respect to the total amount of the solid drawing material. A claim that the content of the wax C is 23% by weight or more and 33% by weight or less with respect to the total amount of the solid drawing material, and the content of the wax D is 2% by weight or more and 5% by weight or less with respect to the total amount of the solid drawing material. Item 1. The solid drawing material according to Item 1.