JP4270603B2 - Non-firing colored pencil lead - Google Patents

Description

【００２７】
表１に示した実施例１、２、比較例１〜３の試験結果は、本発明の実施例の非焼成色鉛筆芯が特定の粘度のジメチルシリコーンオイルを使用することにより、同一の芯体から消しゴムが消去できる色芯と消去できない従来の色芯をつくり分け、かつ、芯全体を見ても色ムラのない芯であることを示している。これに対し、比較例１、２でも消去可能な色芯と消去できない色芯をつくり分けることはできたが、含浸浴を汚染し、色ムラがあった。具体的にはやや耐油性が低いジスアゾイエローＡＡＡが含浸浴中に溶出し、浴が黄色に着色した。また、芯は先端部分、外周部分のジスアゾイエローＡＡＡが溶出したため、中心部に比べて青味が強く、色ムラができた。なお、比較例３は、従来の消しゴムで消去できない色芯の配合例の１つである。
【００２８】
【発明の効果】
本発明は叙上の通りであり、撥水撥油性物質を添加することにより、強度が大きくて描画時に摩耗可能な非焼成色鉛筆芯多孔体をつくり、該多孔体に特定の粘度のジメチルシリコーンオイルを含浸することにより、バラツキが少ない高品質の非焼成色鉛筆芯であり、粘度が異なるジメチルシリコーンオイルの選択によって、消しゴムで消去できない従来の非焼成色鉛筆芯と消しゴムで容易に消去できる非焼成色鉛筆芯のいずれも得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention mainly relates to a wood pencil pencil and a pencil pencil for mechanical pencils. By selecting and impregnating the same porous body with dimethyl silicone oil having different kinematic viscosities, conventional non-baking that cannot be easily erased with an eraser. The present invention provides a method for producing a non-fired colored pencil lead and a non-fired colored pencil lead capable of producing both a colored pencil lead and an unfired colored pencil lead that can be easily erased with an eraser.
[0002]
[Prior art]
The conventional non-fired colored pencil core is dissolved and swollen with a solvent such as water or a plasticizer as necessary, and kneaded and extruded with waxes, extenders, colorants, etc. Later, it is manufactured by a wet method in which the solvent or plasticizer is dried and removed.
[0003]
However, since the drying temperature must be set below the melting point of the wax to prevent the wax from bleeding in the drying process, there is a problem that it takes an enormous amount of drying time. In addition, in the case of a core manufactured by a dry method that does not use a solvent or a plasticizer and omits the drying step, it is a fact that a product approaching the quality of a wet method core is not commercially available.
Conventional wet-type pencil pencils, in terms of strength and writing quality, are worn during drawing by partially inhibiting the adhesion of build materials and colorants with binders, thereby improving lubricity and colorability. It is expressed.
[0004]
However, kneading and molding waxes together with compounding compositions such as extenders, colorants, binders, etc. has a great effect on smooth writing feeling and excellent colorability, but the reduction in strength is also great. A colored pencil lead satisfying the balance of is not obtained.
In addition, non-fired colored pencil cores with excellent erasability are commercially available, but most of them are formulated from binders and waxes, which are nonpolar organic substances, as the main components and removed from paper fibers. , And softening to improve colorability and drawing with low writing pressure, making it difficult to enter the core composition between paper fibers at the time of drawing, thereby expressing erasability .
[0005]
However, it is difficult to enter the core composition between paper fibers at the time of drawing to express erasability, but the coloring agent is strong due to the wax between the paper fibers at the time of drawing. The core composition once fixed to the paper and fixed between the fibers of the paper cannot be completely removed by the adsorption force of the eraser, and its erasability is not satisfactory in practice. In order to remove the drawn line by the adsorption power of the eraser, it is possible to use oils or waxes that are liquid at room temperature for all the waxes. However, in the conventional wet process, drying oils or waxes to heat at 50-60 ° C. during the like can not dry while maintaining the core shape by bleeding, without subjected to practical use.
[0006]
As a method for solving these problems, the present inventor comprises a water-repellent / oil-repellent substance and / or an extender coated with a water- and oil-repellent substance, or an uncoated extender, a pigment, a binder, and the like. As a result of drying and removing the solvent, plasticizer, etc. after kneading and extruding with a compounded composition and, if necessary, a solvent or a plasticizer, open pores resulting from the water- and oil-repellent substance being difficult to wet By forming and forming a non-fired colored pencil core porous body that can be worn at the time of drawing, and impregnating the porous body with oils or waxes, etc., and impregnating with solid oils or waxes that are solid at room temperature A non-fired colored pencil lead that cannot be erased with a conventional eraser can be obtained, and a non-fired colored pencil lead that can be easily erased with an eraser can be obtained by impregnating liquid oils or waxes at room temperature. It discloses a door. (Patent No. 2641810, JP-A-5-331406, JP-A-7-126568).
[0007]
However, in this method, some of the pigments (soluble azo pigments, dyed lake dyes) are easily dissolved in fats and oils and waxes, and the pigments elute at the time of impregnation, so that the hue at the tip and center of the core May be different or may contaminate the impregnation bath of fats and oils.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to solve the disadvantages of the conventional method for producing a non-fired colored pencil lead, which has exceptionally excellent bending strength, mechanical strength such as tip strength, and smooth writing, and has uneven color. An object of the present invention is to provide a non-fired colored pencil lead having no surface.
In addition, select a specific viscosity oil that does not dissolve even with specific pigments (soluble azo pigments, etc.) It is to make it possible to make them separately.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor, as a result of a water- and oil-repellent substance and / or a constitution material or pigment coated with a water- and oil-repellent substance, kneaded together with the blended composition and solvent, extruded, After molding, the solvent and the like are removed by drying to form open pores caused by the water- and oil-repellent material being difficult to wet, and the porous body is impregnated with dimethyl silicone oil having a specific viscosity. We found what could be done and completed the present invention.
[0010]
That is, the non-fired colored pencil lead of the present invention comprises a water- and oil-repellent substance and / or a composition or a pigment coated with a water- and oil-repellent substance, a composition comprising an uncoated body material, a pigment, a binder, and the like, and After kneading and extruding with a solvent or plasticizer as necessary, the solvent, plasticizer, etc. are dried and removed to form open pores resulting from the water and oil repellent material being difficult to wet, and drawing Sometimes a wearable non-fired colored pencil core porous body having a kinematic viscosity at 25 ° C. of 0.05 to 30.00 cm ² / sec. It is selected from the dimethyl silicone oil that is impregnated and is impregnated.
DETAILED DESCRIPTION OF THE INVENTION
The contents of the present invention will be described in detail below. The dimethyl silicone oil impregnated in the core of the present invention has a kinematic viscosity at 25 ° C. of 0.05 to 30.00 cm ² / sec. The range can be selected . 0.05 cm ² / sec. If it is less than 0, the volatility is high, the temporal stability is very low, and if long-term stability is required, 0.20 cm ² / sec. The above is preferable. In addition, 30.00 cm ² / sec. If it exceeds 1, it depends on the pore diameter of the core, but it becomes difficult to uniformly impregnate the silicone oil up to the center of the core. Needless to say, these several types of silicone oils with different viscosities can also be mixed and used. In addition, in order to make it easy to erase with a eraser like a fired black lead, the kinematic viscosity at 25 ° C. is 0.05 to 1.00 cm ² / sec. When a wax-type color core that cannot be erased by a conventional eraser is selected, that is, when fixing properties are required for the core, the kinematic viscosity at 25 ° C. is 2.00 to 30.00 cm ² / sec. . Of dimethyl silicone oil, and more preferably a kinematic viscosity at 25 ° C. of 5.00 to 30.00 cm ² / sec. Choose from dimethyl silicone oil.
[0012]
As a method for impregnating with dimethyl silicone oil, a non-fired colored pencil lead porous body is immersed in the oil and heated as necessary to fill the pores. Of course, the pressure can be reduced or increased for the purpose of promoting the impregnation.
[0013]
The water- and oil-repellent substances used in the present invention may be blended as powders according to their properties, or may be blended with other constitutional materials and / or pigments. Should be selected.
[0014]
As the water and oil repellent substance used as powder, fluororesin powder such as graphite fluoride, carbon fluoride, PTFE (polytetrafluoroethylene), boron nitride, etc. can be used alone or in combination, but the strength is high. In order to form a porous body with a moderate amount of wear and a large amount of impregnated oil, the use of (CF) _n type fluorinated graphite is preferred because it has the lowest surface energy and excellent lubricity. Considering the production of a light colored pencil, it is preferable to use boron nitride having high whiteness and excellent lubricity.
Their blending amount is not generally determined by the surface energy of the water- and oil-repellent substance, but considering the hardness of the core resulting from the impregnation rate of dimethylsilicone oil, handwriting property and mechanical strength, it is 2 to 2 of the total blended composition amount. Addition and blending of 20% by weight are preferred.
[0015]
When the binder used is water-soluble and water is used as a solvent, N-long chain acyl basic amino acids such as N-lauroyl-L-lysine and / or N-lauroyl asparagine, which is a powder water repellent substance Higher fatty acid esters of N-long chain acyl acidic amino acids such as acid β lauryl ester and N-stearyl aspartic acid β stearyl ester can also be used. In this case, the blending amount of the higher fatty acid ester of N-long chain acyl basic amino acid and N-long chain acyl acidic amino acid is preferably 3 to 40% by weight of the total blended composition amount.
Of course, the above-mentioned water- and oil-repellent substances can be mixed and used simultaneously.
[0016]
Examples of the pigment used in the present invention include organic pigments having low oil resistance such as disazo yellow AAA and pyrazolone orange, and other known organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, carbon black, iron black All known inorganic pigments such as petals, bitumen, and titanium dioxide can be used. In addition, although final color etc. can be used for dyeing pigments, since a part is eluted in dimethyl silicone oil, care is required.
[0017]
As the binder used in the present invention, all known constitutional materials such as calcium carbonate, kaolin, talc, precipitated barium sulfate, talc, mica and potassium titanate whisker can be used.
Examples of the binder used in the present invention include cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, and cellulose nitrate, pullulan, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, tragacanth gum, and gum arabic. , Guar gum, dammar gum, locust bean gum, etc., which can be used either individually or mixed regardless of natural, but considering the drying time, it is a water-soluble resin or a thermoplastic resin that dissolves and swells in a low-boiling solvent. Among them, it is preferable to select a material having high bending strength and rigidity in consideration of writing quality and strength.
[0018]
The non-fired colored pencil lead of the present invention configured as described above has the following action. A substance excellent in water repellency and oil repellency has a large contact angle with respect to an organic polymer substance as a binder, a solvent such as water, a plasticizer, and the like, and is difficult to wet. Therefore, a molded product obtained by kneading, extruding with other compounding compositions, and a solvent, and further removing the solvent by drying forms gaps (open pores) due to the difficulty of wetting of the water and oil repellent material, A non-fired colored pencil lead porous body is obtained. This open pore can be impregnated with oil or the like. When impregnating this non-fired colored pencil lead porous body with dimethyl silicone oil, the pigment does not elute at the time of impregnation, the hue at the tip and center of the lead is uniform and non-uniform, and the oil impregnation bath is pigmented. Will not be contaminated. Furthermore, by changing the viscosity of the dimethyl silicone oil, various colored pencil cores having different colorability, slippage, erasability, strength, hardness and the like can be obtained from one kind of non-fired colored pencil core porous body. That is, the kinematic viscosity at 25 ° C. is 2.00 to 30.00 cm ² / sec. Is impregnated with a conventional non-fired colored pencil lead that cannot be erased with an eraser, and has a kinematic viscosity at 25 ° C. of 0.05 to 1.00 cm ² / sec. By impregnating with dimethyl silicone oil, a non-fired colored pencil lead that can be easily erased with an eraser is obtained.
[0019]
【Example】
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the examples.
[0020]
(Example 1)
Carboxymethyl cellulose 6% by weight
Talc 71% by weight
Titanium dioxide 10% by weight
Disazo Yellow AAA 4% by weight
Phthalocyanine blue 4% by weight
Graphite fluoride 5% by weight
After adding water corresponding to the same weight to the above blended composition, mixing and dispersing them with a kneader, adjusting the moisture while kneading with two rolls, pelletizing this kneaded product and using a single screw extruder After extrusion molding, the moisture was removed by drying at 120 ° C. for 3 hours to obtain a non-fired green pencil core porous body having a diameter of 3.0 mm. This porous body was impregnated with dimethyl silicone oil (kinematic viscosity at 25 ° C . : 0.30 cm ² / sec. ) At 120 ° C. to obtain a non-fired green pencil lead having a diameter of 3.0 mm. The results are shown in Table 1.
[0021]
(Example 2)
A non-fired green pencil lead porous body similar to that of Example 1 was impregnated with dimethyl silicone oil (kinematic viscosity at 25 ° C . : 10.00 cm ² / sec. ) At 120 ° C. to obtain a non-fired green pencil lead having a diameter of 3.0 mm . Obtained. The results are shown in Table 1.
[0022]
(Comparative Example 1)
A non-fired green pencil lead porous body similar to that in Example 1 was impregnated with liquid paraffin at 120 ° C. to obtain a non-fired green pencil lead having a diameter of 3.0 mm. The results are shown in Table 1.
[0023]
(Comparative Example 2)
Stearic acid 20% by weight
Microcrystalline wax 15% by weight
65% synthetic wax
A non-fired green pencil lead porous body similar to that of Example 1 was impregnated with a melt composed of the above composition at 120 ° C. to obtain a non-fired green pencil lead having a diameter of 3.0 mm. The results are shown in Table 1.
[0024]
(Comparative Example 3)
Carboxymethyl cellulose 7% by weight
Talc 55% by weight
Titanium dioxide 10% by weight
Disazo Yellow AAA 4% by weight
Phthalocyanine blue 4% by weight
Stearic acid 4% by weight
Microcrystalline wax 3% by weight
Synthetic wax 13% by weight
After adding water corresponding to the same weight to the above blended composition, mixing and dispersing them with a kneader, adjusting the moisture while kneading with two rolls, pelletizing this kneaded product and using a single screw extruder After extrusion molding, it was dried at 50 ° C. for 60 hours to remove moisture, and a non-fired green pencil lead having a diameter of 3.0 mm was obtained. The results are shown in Table 1.
[0025]
About the non-baked colored pencil lead of Examples 1 and 2 and Comparative Examples 1 to 3, the eraser erase rate, the contamination of the impregnation bath, and the color unevenness of the lead were measured and confirmed.
(1) Eraser Erase Rate The eraser erase rate was determined from the following formula.
Eraser erasure rate (%) = [{(drawing line density) − (drawing line density)} / (drawing line density)] × 100
(2) Contamination of impregnation bath It was visually confirmed whether the impregnation bath after impregnation of the non-fired colored pencil core was contaminated by elution of the pigment.
(3) Color unevenness of the core The difference in hue between the tip of the core and the middle was confirmed, and the hue of the outer peripheral portion and the central portion was visually confirmed by dividing the core vertically.
[0026]
[Table 1]

[0027]
The test results of Examples 1 and 2 and Comparative Examples 1 to 3 shown in Table 1 show that the non-fired colored pencil lead of the example of the present invention was obtained from the same core by using dimethyl silicone oil having a specific viscosity. The eraser has a color core that can be erased and a conventional color core that cannot be erased. On the other hand, in Comparative Examples 1 and 2, it was possible to create a color core that could be erased and a color core that could not be erased, but the impregnation bath was contaminated and there was color unevenness. Specifically, disazo yellow AAA, which has slightly low oil resistance, eluted into the impregnation bath, and the bath was colored yellow. Further, since the disazo yellow AAA at the tip portion and the outer peripheral portion of the core was eluted, the bluish color was strong compared to the center portion, and color unevenness was formed. Comparative Example 3 is one example of a color core that cannot be erased with a conventional eraser.
[0028]
【The invention's effect】
The present invention is as described above, and by adding a water- and oil-repellent substance, a non-fired colored pencil core porous body that has high strength and can be worn at the time of drawing is produced, and a dimethyl silicone oil having a specific viscosity is provided in the porous body. It is a high quality non-firing colored pencil lead that has less variation by impregnating with a conventional non-firing colored pencil lead that cannot be erased with an eraser by selecting a dimethyl silicone oil with a different viscosity and can be easily erased with an eraser Any of these can be obtained.

Claims (3)

In the process of producing a non-fired colored pencil lead, no waxes are added and blended at the time of blending, and the water- and oil-repellent substance and / or a constitution material or pigment coated with a water- and oil-repellent substance is added and blended. After forming open pores due to the fact that the water / oil repellent material is difficult to wet to form a non-fired colored pencil core porous body, the porous body has a kinematic viscosity at 25 ° C. of 0.05 to 1.00 cm ² / sec. . A method for producing an eraser erasable non-fired colored pencil lead impregnated with dimethyl silicone oil in the range of In the process of producing a non-fired colored pencil lead, no waxes are added and blended at the time of blending, and the water- and oil-repellent substance and / or a constitution material or pigment coated with a water- and oil-repellent substance is added and blended. After forming open pores due to the fact that the water / oil repellent material is difficult to wet to form a non-fired colored pencil core porous body, the porous body has a kinematic viscosity at 25 ° C. of 2.00 to 30.00 cm ² / sec. . A non-erasable erasable non-fired colored pencil lead produced by impregnating dimethyl silicone oil in the range of In the process of producing a non-fired colored pencil lead, no waxes are added and blended at the time of blending, and the water- and oil-repellent substance and / or a constitution material or pigment coated with a water- and oil-repellent substance is added and blended. After forming open pores due to the fact that the water / oil repellent material is difficult to wet to form a non-fired colored pencil core porous body, the porous body has a kinematic viscosity at 25 ° C. of 2.00 to 30.00 cm ² / sec. . A non-erasable non-fired colored pencil lead impregnated with dimethyl silicone oil in the range of