JPH06145582A - Solid drawing material - Google Patents

Abstract

PURPOSE:To obtain a solid drawing material having a good affinity for paper and excellent in water resistance, drawing properties, and fixability by mixing starch into a solid drawing material formed using an alkali metal or ammonium salt of an aliph. carboxylic acid as a gelling agent. CONSTITUTION:Starch or a processed starch is mixed into a solid drawing material which contains a colorant and is formed using an alkali metal or ammonium salt of an 8-36C aliph. carboxylic acid as a gelling agent. Pref. the resulting drawing material contains 1-70wt.% colorant, 0.5-9wt.% starch or processed starch, and 0.1-3wt.% water-sol. resin. The obtd. material has an improved water resistance and a good affinity for paper and is excellent in drawing properties, feeling in drawing, and fixability. When the material contains a fluorescent pigment or dye as the colorant, it can be used as an underline marker.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid drawing material, which is particularly excellent in water resistance and writing quality and can be used as an underline marker when it contains a fluorescent colorant. It concerns materials.

[0002]

2. Description of the Related Art It is usual to add a gel-forming substance such as fatty acid alkali metal salt, polyvinylpyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose or the like in order to maintain the shape of a rod-shaped drawing material and increase its strength. However, when a picture or character drawn using a drawing material produced by adding such a gel-forming substance gets wet with water,
There is a problem that part or all of the material is dissolved and disappears, or that pictures and characters are blurred by bleeding in water. Conventionally, such problems have been abandoned as inevitable in the case of water-soluble drawing materials, but on the other hand, development of a technique for efficiently solving such problems has been desired. Although it is a lipophilic gelling agent or a hydrophilic gelling agent, when hot water-soluble polyvinyl alcohol or the like is used instead of the above gelling agent, the water resistance is improved, but the ease of writing is reduced. It has become clear from experiments conducted by the present inventors that various problems occur. Therefore, while maintaining the fixing power and colorability required as a drawing agent, excellent water resistance,
Moreover, it is desired to develop an excellent solid drawing material that does not reduce the writing property.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a solid drawing material excellent in water resistance and writing quality.

[0004]

The present invention is directed to carbon atoms of 8 to
It was made based on the finding that the above problems can be solved by adding starch or modified starch to a solid drawing material containing an alkali metal salt or ammonium salt of an aliphatic carboxylic acid having 36 as a gel-forming substance. That is,
The present invention is a solid drawing material containing an alkali metal salt or ammonium salt of an aliphatic carboxylic acid having 8 to 36 carbon atoms as a gel-forming substance, and containing a colorant, which contains starch or modified starch. A solid drawing material characterized by the above. Among these, in particular, 1 to
70% by weight (hereinafter abbreviated as%), 0.5 to 9% of starch or modified starch, or a mixture thereof and 0.1 to 3% of a water-soluble resin are preferable.
Those containing 1 to 20% of hydrophobic or hydrophilic silica are preferable.

The aliphatic carboxylic acid salts used in the present invention may be branched or unbranched and have 8 to 36 carbon atoms.
Alkali metal salt or ammonium salt of an aliphatic carboxylic acid, and an aliphatic carboxylic acid salt having 12 to 18 carbon atoms is particularly preferable. Examples of the aliphatic carboxylic acid constituting this aliphatic carboxylic acid salt include caprylic acid,
There may be mentioned pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid and melissic acid. Further, as the alkali metal salt of an aliphatic carboxylic acid, a lithium salt, a sodium salt and a potassium salt can be used,
Particularly preferred are sodium myristate, sodium palmitate, sodium stearate or a mixture thereof. The amount of the aliphatic carboxylic acid salt used is 5 to 30%, preferably 8 to 30% based on the total weight of the solid drawing material of the present invention.
20%. The reason for limiting the amount used is that if the amount of the aliphatic carboxylic acid salt is less than 5%, the solid drawing material is hard to solidify, which causes troubles in gel formation, and if it exceeds 30%. This is because the tendency of inhibiting the functions of the hydrophobic silica and the thixotropic agent occurs, which is not preferable from the viewpoint of coating property.

The colorant used in the present invention is not particularly limited, and known pigments or dyes can be used as necessary. For example, as the inorganic pigment, iron black, iron yellow, red iron oxide , Ultramarine, navy blue, alumina white, carbon black, aluminum powder, bronze powder, mica, etc., and organic pigments include naphthol green,
Nitroso or nitro pigments such as naphthol yellow, solsol red, lake kit C, brilliant carmine 6B, watching red, azo lake pigments such as Bordeaux 10B, insoluble azo pigments such as fast yellow, disazo yellow, pyrazolone orange, para red, lake red 4R and naphthol red , Condensed azo pigments such as chromophthal yellow, chromophthal red, peacock blue lake, alkali blue lake, rhodamine lake, methyl violet lake, malachite green lake and other dyed lake pigments, phthalocyanine blue, fast sky blue, phthalocyanine green Phthalocyanine pigments such as, anthrapyrimidine yellow, perinone orange, perylene red, thioindigo red, indanthro Sleng pigments such as blue, quinacridone red, quinacridone pigments such as quinacridone violet, dioxazine pigments such as dioxazine violet, is isoindolinone pigments and fluorescent pigments such as isoindolinone yellow and the like. Examples of white pigments include titanium oxide, zinc white, lead white, zinc sulfide, antimony oxide, alumina white, satin white, and barium sulfate, and titanium oxide is particularly preferable.

When the colorant is an inorganic pigment, the amount of the colorant used is 5 to 4 relative to the total weight of the solid drawing material of the present invention.
0% is preferable, more preferably 10 to 35%, and when the colorant is an organic pigment, 1 to 15% is preferable, and 2 to 10% is more preferable.

Examples of the starch used in the present invention include various known starches such as corn starch, potato starch, tapioca starch, wheat starch and the like, or a mixture of two or more thereof. Examples of the modified starch include oxidized starch, pregelatinized starch, esterified starch, etherified starch, crosslinked starch and grafted starch. Here, examples of esterified starch include acetate starch, phosphate starch, sulfate starch, nitrate starch, and xanthate starch, and examples of etherified starch include hydroxyalkyl starch, carboxymethyl starch, benzyl starch, and positive starch. Examples of the grafted starch include vinyl acetate graft starch and acrylic acid graft starch. These modified starches can also be used as a mixture with unmodified corn starch or the like. The modified starch can be easily obtained from, for example, Nitto Chemical Co., Ltd., Matsutani Chemical Industry Co., Ltd., etc. Of these starches and modified starches, those having a solubility at 90 ° C. (1 hour stirring) of 40% or more are preferable, and those of 98% or more are more preferable. The amount of starch or modified starch is preferably 0.5-9%, more preferably 1-4%.

In the present invention, hydrophobic or hydrophilic silica can be further contained. Among them, the hydrophobic silica is fine particles of high-purity silicon dioxide, the surface of which is hydrophobic in the solid drawing material of the present invention, and the surface of which has been previously treated to be hydrophobic. Not only that, but also those which have become hydrophobic during the preparation of the solid drawing material of the present invention. In addition, for hydrophobic silica whose surface has been subjected to hydrophobic treatment, Rhoseal MT-10 (Tokuyama Soda),
Nipsil SS hydrophobic silica (Nippon Silica Industry Co., Ltd.) and Aerosil R-972 hydrophobic silica (Nippon Aerosil Co., Ltd.) are commercially available. Further, as hydrophilic silica, Tokseal (Tokuyama Soda Co., Ltd.), Silicasil (Bayer), Harimic (Micron Co., Ltd.), Aerosil Elsil (Japan Aerosil Co., Ltd.), Nipseal (Nippon Silica Industry Co., Ltd.) , Syloid (Fuji Davison Chemical Co., Ltd.), Microsilica (Elchem), and the like. In the present invention, silica is contained in an amount of 1 to 20%, preferably 3 to 15% based on the total weight of the solid drawing material of the present invention. The silica used in the present invention has a particle size of 0.02 to 15 mμ and a specific surface area of 1 to 700.
Fine particles of m ² / g are preferred.

In the present invention, the use of silica improves the fluidity, viscosity and thixotropy of the solid drawing material of the present invention to improve the coating property on the image material and at the same time coat the coating surface with an aqueous ink. In this case, ink repelling, ink bleeding, ink floating and stains are prevented, and the color tone of the ink becomes clear. Also, when writing with an oil-based ink, particularly a ballpoint pen, on the coated surface, the ink coating easily dries and the ink paste becomes good.

In the present invention, it is preferable to use a water-soluble resin. Such a water-soluble resin generally has an average degree of polymerization of 100 to 3000, preferably 100 to 150.
0 natural resin or synthetic resin. 25 in the water
The solubility at 95 ° C is preferably 95% or more, more preferably 99% or more. The amount of the water-soluble resin used is 0.1 to 3%, preferably 0.5 to 3 based on the total weight of the solid drawing material of the present invention.
It is 2%, and by using a water-soluble resin in this range, the coated surface of the solid drawing material becomes strong, and it becomes difficult for the coated surface to be peeled off even if it is rubbed by something. The following can be mentioned as specific examples of the water-soluble resin. Examples thereof include natural polymers such as gum arabic and glue, semi-synthetic cellulose polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, and synthetic polymers such as polyvinylpyrrolidone, polyvinyl acetate and acrylic emulsion.

The water content of the solid drawing material is 20 to 60.
%, Preferably 25 to 55%. The reason why the water content is limited in this way is that if it is 20% or less, the coating property and the drawing property are deteriorated and the coated surface is roughened. Because it will collapse. It should be noted that the drying of the coated surface becomes slower as the water content increases, but the drying time can be shortened by using a highly volatile organic solvent together.

Further, in order to soften the coating film of the present invention and prevent the peeling of the drawing material, polyhydric alcohol, alcohol ether, ethanolamine and the like are added, if necessary, to the total weight of the solid drawing material of the present invention. Alternatively, 0 to 6% may be added. The amount of the polyhydric alcohol added is limited because if it exceeds 6%, the coating on the coated surface becomes too soft and repeated coating becomes difficult.

If desired, thixotropic agents such as organic bentonite and inorganic bentonite can be used. The amount of the thixotropic agent used is 0 to 5%, preferably 1 to 4%, based on the solid drawing material of the present invention.
Is. The reason for limiting the amount used in this way is that when the content of the thixotropic agent exceeds 5%, the viscosity increases, which causes problems in production. If necessary, a lubricant such as an aluminum metal stearate or an aliphatic metal salt such as zinc laurate can be added, and the amount thereof is 0.1 to the total weight of the solid drawing material of the present invention. 1%. The reason for adding this lubricant is to enhance the thixotropy of the solid drawing material of the present invention and improve the coating property.

The solid drawing material of the present invention can be produced, for example, by
First, in a predetermined amount of water, aliphatic carboxylate, starch and /
Alternatively, the modified starch and the water-soluble resin are heated to about 90 ° C. under reflux with stirring to be dissolved, and the coloring agent and silica previously dispersed in water are added and stirred, and then the solid drawing material is removed. It can be carried out by pouring into an extruding container, solidifying by cooling or extrusion molding, and inserting the resulting rod-shaped object into a closed container with a cap.

[0016]

According to the present invention, a solid drawing material having improved water resistance and excellent writing quality can be obtained. Further, the solid drawing material of the present invention has a good affinity with paper and is also excellent in drawing property and fixing property. Further, it is possible to provide a solid drawing material that can be used as an underline marker when it contains a fluorescent pigment or a fluorescent dye as a colorant.

[0017]

EXAMPLES The present invention will be described in more detail and specifically with reference to Examples. Reference Example Table-1 shows the solubility of various materials used in the examples of the present invention. Note that the 25 ° C soluble content (%) is 100 m for 1 g of the sample.
It is the measured value of the amount of dissolution when placed in 1 l of distilled water and allowed to stand at room temperature for 24 hours.
It is a measured value of the amount of dissolution when placed in 00 ml of distilled water and left at 90 ° C. for 1 hour.

[0018]

[Table 1] Table-1 Solubility of starches and water-soluble resins 25 ° C soluble content (%) 90 ° C soluble content (%) Starch (corn) 0.6 49 (potato) 0.1 or less 86.8 Modified starch (Piostarch 34) 3.0 99.5 (Cyprogum F) -500) 94.0 99.9 or higher (Starch CA-2) 0.1 or lower 19.4 (Rastergen FO) 0.1 or lower 99.3 (NSP-M) 0.1 or lower 98.4 (Z- 100) 4.5 74.3 Hydroxyethyl cellulose (NATROSOL 250GR) 99.9 or higher 99.9 or higher Polyvinyl alcohol (Gothenol NL-05) 5.3 99.9 or higher Polyvinylpyrrolidone (Rubiscor K-30) 99.9 or higher 99.9 or higher Carboxymethyl cellulose (serogen 5A) 99.9 or higher 99.9 or higher Methyl cellulose (Metroses 90SH-50) 99.9 or higher 99.9 or higher

Example 1 A solid drawing material No. 1 of the present invention was produced with the following composition. Parts by weight Water 40 Modified starch (Piostarch 34, Nitto Kagaku Co., Ltd.) 4 Polyvinylpyrrolidone 1 (Rubiscor K-30, BASF) Sodium stearate 22 (Efcochem B, Adeka Fine Chemicals) Monoethylene glycol ethyl ether 6 (Seafosol) MG, Nippon Shokubai Kagaku Co., Ltd. Silica (TK900, DEGGUSA) 7 CI Pigment Blue 2920 (Ultramarine Blue # 32 , Reckitt) In a container equipped with a stirrer and a thermometer, a predetermined amount of water, modified starch, polyvinylpyrrolidone, Monoethylene glycol ethyl ether and sodium stearate were added, and the mixture was heated to 90 ° C. under reflux with stirring. Then, a predetermined amount of silica and pigment mixed and dispersed in advance was added to this mixed solution, and the mixture was thoroughly stirred to give a solid state. Press the drawing material into the mold and cool it. It was inserted rod-like product in a closed propelling container. In this way, a solid drawing material (a cylinder having a length of 50 mm and a diameter of 8 mm) was formed. Modified starch blended with the above solid drawing material No. 1 (Piostarch 34, Nitto Kagaku Co., Ltd.)
Modified starch (Cyprogum F-500, Nitto Kagaku Co., Ltd.), modified starch (Starch CA-2, Nitto Kagaku Co., Ltd.), modified starch (Rastagen F0, Nitto Kagaku Co., Ltd.), Similar to Solid Drawing Material No. 1 except that modified starch (NSP-M, Nichiroku Kagaku Co., Ltd.), modified starch (Z-100, Nitto Kagaku Co., Ltd.), corn starch and potato starch were used. Solid drawing material No
28 was manufactured.

Example 2 A solid drawing material No. 9 of the present invention was produced by the following formulation. Parts by weight Water 45 Modified starch (Piostarch 34, Nitto Kagaku Co., Ltd.) 2 Sodium stearate 18 (Fcochem B, ADEKA FINE CHEMICAL) Methylcellulose 2 (Metroses 90SH-50, Shin-Etsu Chemical Co., Ltd.) Monoethylene glycol ethyl ether 4 (Seafosol MG, Nippon Shokubai Kagaku Co., Ltd.) Silica (TK900, DEGGUSA) 6 Yellow fluorescent pigment 23 (NKP-9635, Nippon Fluorescent Chemistry K, K) The present invention is manufactured by the same manufacturing method as in Example 1 except that the composition is different. The solid drawing material of Processed starch (Piostarch 34, Nitto Kagaku Co., Ltd.) blended with the above solid drawing material No. 9 was processed starch (Cyprogum F-5).
00, Nippon Starch Chemical Co., Ltd., modified starch (Starch CA)
-2, Nippon Starch Chemical Co., Ltd., modified starch (Rastergen F0, Nippon Starch Chemical Co., Ltd.), modified starch (NSP-M,
Nitto Kagaku Co., Ltd., modified starch (Z-100, Nitto Kagaku Co., Ltd.), solid drawing material in the same manner as solid drawing material No. 9 except that corn starch and potato starch were used instead.
No. 10-16 were manufactured.

Comparative Example The modified starch blended with the solid drawing material No. 1 of Example 1 (Piostarch 34, Nitto Kagaku Co., Ltd.) was mixed with hydroxyethyl cellulose (NATROSOL 250GR, AQUARO).
N), polyvinyl alcohol (Gothenol NL-05,
Nippon Synthetic Chemical Co., Ltd., polyvinylpyrrolidone (Rubiscor K-30, BASF), carboxymethyl cellulose (Serogen 5A, Daiichi Kogyo Co., Ltd.) and methyl cellulose (Metroses 90SH-50, Shin-Etsu Chemical Co., Ltd.) respectively Comparative solid drawing materials Nos. 1 to 5 were manufactured in the same manner as the solid drawing material No. 1 except that they were replaced. Similarly,
The modified starch blended with the solid drawing material No. 9 of Example 1 (Piostarch 34, Nitto Kagaku Co., Ltd.) was mixed with hydroxyethyl cellulose (NATROSOL 250GR, AQUARO).
N), Polyvinyl alcohol (Gohsenol NI-05,
Nippon Synthetic Chemical Co., Ltd., polyvinylpyrrolidone (Rubiscor K-30, BASF), carboxymethyl cellulose (Serogen 5A, Daiichi Kogyo Co., Ltd.) and methyl cellulose (Metroses 90SH-50, Shin-Etsu Chemical Co., Ltd.) respectively Comparative solid drawing materials Nos. 6 to 10 were produced in the same manner as the solid drawing material No. 1 except that they were replaced.

The water resistance and writing quality of the thus-produced solid drawing materials No. 1 to 16 of the present invention and the comparative solid drawing materials No. 1 to 10 were examined as follows. Water resistance test Writing on the paper specified in JIS P 3201 5 times in a spiral by hand, and after 1 minute, soak it in fresh water at room temperature for 1 hour, take it out, and check the state of the writing line. It was evaluated (JIS S-6037 6.6). ○ in the same paper as used in good △ slightly inferior × bad writing taste the water resistance test was evaluated actually the writability of when I wrote the characters and the like on the basis of the following criteria. ○ Smooth (writing resistance is small and constant) △ Slightly inferior (writing resistance is slightly large but constant) × Poor (writing resistance is large and non-uniform) The results are summarized in Table-2.

[0023]

[Table 2] Table-2 ──────────────────────────────────── Water resistance Comparison of writing taste Water resistance Writing ─────────────────────────────────── Inventive product No 1 ○ ○ Comparative product No 1 × ○ Inventive product No 2 ○ ○ Comparative product No 2 ○ × Inventive product No 3 ○ △ Comparative product No 3 × ○ Inventive product No 4 ○ ○ Comparative product No 4 × △ Inventive product No 5 ○ ○ Comparative product No 5 × ○ Inventive product No 6 ○ ○ Comparative product No 6 × ○ Inventive product No 7 ○ ○ Comparative product No 7 ○ × Inventive product No 8 ○ ○ Comparative product No 8 × ○ Inventive product No 9 ○ ○ Comparative product No 9 × △ Inventive product No 10 ○ ○ Comparative product No 10 × ○ Inventive product No 11 ○ △ Inventive product No 12 ○ ○ Inventive product No 13 ○ ○ Inventive product No 14 ○ ○ Inventive product No 15 ○ ○ Inventive product No 16 ○ ○

Claims (3)

[Claims] 1. A solid drawing material containing an alkali metal salt or an ammonium salt of an aliphatic carboxylic acid having 8 to 36 carbon atoms as a gel-forming substance and containing a colorant, which contains starch or modified starch. A solid drawing material characterized by: 2. A coloring agent of 1 to 70% by weight, starch or modified starch of 0.5 to 9% by weight, and a water-soluble resin of 0.1.
The solid drawing material according to claim 1, wherein the solid drawing material contains 3 to 3% by weight. 3. A fluorescent dye or fluorescent pigment is used as a coloring agent.
The solid drawing material according to claim 1 or 2, which contains -40% by weight.