JP4352914B2 - Pencil lead - Google Patents

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JP4352914B2
JP4352914B2 JP2004022469A JP2004022469A JP4352914B2 JP 4352914 B2 JP4352914 B2 JP 4352914B2 JP 2004022469 A JP2004022469 A JP 2004022469A JP 2004022469 A JP2004022469 A JP 2004022469A JP 4352914 B2 JP4352914 B2 JP 4352914B2
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kinematic viscosity
polybutene
pencil lead
impregnated
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JP2005213391A (en
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出口勝男
潤 吉森
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Pentel Co Ltd
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Description

本発明は、木軸鉛筆の芯、シャープペンシル用の芯(以下まとめて鉛筆芯と表現する)に関するもので、着色剤としての黒鉛や、着色剤を結合する成分、熱処理によって炭化する気孔形成成分を含有し、混練成形後に焼成されて得られる鉛筆芯に関する。   TECHNICAL FIELD The present invention relates to a wood pencil lead, a mechanical pencil lead (hereinafter collectively referred to as a pencil lead), graphite as a colorant, a component that binds the colorant, and a pore-forming component that is carbonized by heat treatment. And a pencil lead obtained by firing after kneading and molding.

鉛筆芯は粘土、各種合成樹脂などを結合材として使用し、体質材や必要に応じて使用される着色剤、気孔形成剤、可塑剤、溶剤などと共にニーダー、ヘンシェルミキサー、3本ロールなどで均一分散させ、押し出し成形後、800℃〜1200℃で高温焼成して得られる。焼成芯体の気孔中に種々物質を種々目的で含浸している。含浸成分の一例としては、流動パラフィン、シリコーン油やスピンドル油(特許文献1参照)、アルファ−オレフィンオリゴマー(特許文献2参照)等が知られている。その他、パラフィンワックス、カルナバワックス、マイクロクリスタリン等のワックス類も知られている。
これらの含浸成分は、加圧、減圧などや加熱した油状物中に焼成芯体を浸漬した後、余剰の油状物を表面より除去して鉛筆芯の気孔に含浸させている。
特開昭55−025368号公報 特開昭63−135469号公報
The pencil core uses clay, various synthetic resins, etc. as a binder, and it is uniform with a kneader, Henschel mixer, three rolls, etc. together with a constitution material and coloring agents, pore forming agents, plasticizers, solvents, etc. It is obtained by dispersing and extruding, followed by high-temperature firing at 800 ° C to 1200 ° C. The pores of the fired core are impregnated with various substances for various purposes. As examples of impregnation components, liquid paraffin, silicone oil, spindle oil (see Patent Document 1), alpha-olefin oligomer (see Patent Document 2), and the like are known. In addition, waxes such as paraffin wax, carnauba wax, and microcrystalline are known.
These impregnating components are obtained by immersing the fired core in pressurized, decompressed, or heated oil, and then removing excess oil from the surface to impregnate the pores of the pencil core.
Japanese Patent Laid-Open No. 55-025368 JP-A-63-135469

含浸成分により、濃い筆跡の効果が期待できる。しかし、濃い筆跡は手などによる擦過によって筆記線の黒鉛が手に付着するとか、紙に広がったりする汚れが目立つ様になってくる。濃い筆跡と汚れ難さ(定着性)は逆の傾向にある。濃い筆跡と汚れ難さは(定着性)両立する傾向ではない。即ち、濃い筆跡をもたらす含浸成分はよごれ易いという一般的傾向にある。この逆相関関係を破り、濃い筆跡と汚れ難い(高い定着性)鉛筆芯を提供することが本発明の目的である。
含浸成分にはいくつかの条件ある。例えば、含浸させる時は液状であること。即ち、少なくとも焼成芯体の気孔に含浸させる際には、容易に含浸できるだけの粘度である必要がある。そして、経時的に安定であるとともに安全であること。更に、空気中の湿度の影響を品質に与えないように非吸湿性であることなどである。これらの条件を満足した上に濃度向上・定着性向上への寄与が大きなものが好ましい訳であるが、現在汎用されている流動パラフィン、シリコーン油、スピンドル油、アルファ−オレフィンオリゴマー、ワックス類とも濃い筆跡と定着性の両立は満足できていないものである。それゆえ、上記の条件を満足しつつ、濃い筆跡と定着性とを両立する鉛筆芯が得られれば、実用的効果は絶大なものとなる。
Due to the impregnating component, the effect of dark handwriting can be expected. However, the dark handwriting becomes noticeable when the writing line graphite adheres to the hand by rubbing with a hand or the like, or the stain spreads on the paper. Dark handwriting and stain resistance (fixability) tend to be reversed. Dark handwriting and stain resistance do not tend to be compatible. That is, there is a general tendency that impregnated components that produce dark handwriting tend to be dirty. It is an object of the present invention to break this inverse correlation and provide a dark handwriting and a highly resistant (high fixability) pencil lead.
There are several conditions for the impregnation component. For example, it must be liquid when impregnated. That is, at least when the pores of the fired core are impregnated, the viscosity needs to be easily impregnated. And it must be stable and safe over time. Furthermore, it is non-hygroscopic so as not to affect the quality of humidity in the air. It is preferable to satisfy these conditions and contribute greatly to improving density and fixability. However, currently used liquid paraffin, silicone oil, spindle oil, alpha-olefin oligomer, and waxes are also strong. The balance between handwriting and fixability is not satisfactory. Therefore, if a pencil lead that satisfies both the above-described conditions and achieves both a strong handwriting and a fixing property can be obtained, the practical effect becomes enormous.

本発明は、焼成させた芯体が有する気孔中に含浸された成分がポリブテンを含み、且つ動粘度が、25℃で3,000mm2/sec以上160,000mm2/sec以下、100℃で27mm2/sec以上1,300mm2/sec以下である鉛筆芯を要旨とする。 In the present invention, the component impregnated in the pores of the fired core contains polybutene, and the kinematic viscosity is 3,000 mm2 / sec to 160,000 mm2 / sec at 25 ° C and 27 at 100 ° C. The gist of the pencil lead is from mm2 / sec to 1,300 mm2 / sec.

ポリブテンを含む、動粘度25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下の含浸成分を含浸させた鉛筆芯は、体質材(黒鉛、窒化硼素、タルク等)の表面に、ポリブテンが濡れ、膜を形成し、主に黒鉛に起因する強い反射光を抑えることができる。筆跡を形成する成分中の反射光が少なくなるので筆跡が濃く黒く見えることとなる。また、このような含浸成分は粘性のある液体であり、黒鉛同士の結合を助け、筆記時紙に定着していない黒鉛の剥離(手で擦ったときの汚れ)が抑えられ高い定着性が得られ、筆跡を手などで擦っても汚れにくくなるものである。
尚、動粘度の測定はJIS K 2283に準じて測定できる。
Impregnation component containing polybutene having a kinematic viscosity of 25 to 3,000 to 160,000 mm2 / sec (c · S · t) and 100 ° C to 27 to 1,300 mm2 / sec (c · S · t) The pencil core impregnated with polybutene wets the surface of an extender (graphite, boron nitride, talc, etc.), forms a film, and can suppress strong reflected light mainly due to graphite. Since the reflected light in the components forming the handwriting is reduced, the handwriting looks dark and black. In addition, such impregnating components are viscous liquids that help bond graphite together and suppress the exfoliation of graphite that is not fixed on the paper at the time of writing (dirt when rubbed by hand), resulting in high fixability. Even if the handwriting is rubbed with a hand or the like, it becomes difficult to get dirty.
The kinematic viscosity can be measured according to JIS K 2283.

以下、詳述する。
本発明に係わる焼成芯体は、従来用いられている構成材料及び製造方法を限定なく用いることができる。具体的には、粘土やポリ塩化ビニル、ポリ塩素化ポリエチレン、フラン樹脂、ポリビニルアルコール、スチロール樹脂、アクリル樹脂、尿素樹脂、メラミン樹脂、ポリエステル樹脂などの合成樹脂を結合材として使用し、黒鉛、窒化硼素、タルクなどの体質材や必要に応じて使用される有機顔料や無機顔料などの着色材、ポリメチルメタクリレート(PMMA)などの気孔形成剤、フタル酸ジオクチル(DOP)、フタル酸ジブチル(DBP)などの可塑剤、水、アルコール、ケトン、エステル、芳香族炭化水素などの溶剤と共にニーダー、ヘンシェルミキサー、3本ロールなどで均一分散させた後、高温焼成し、これに含浸成分を含浸させて得られる。
Details will be described below.
For the fired core according to the present invention, conventionally used constituent materials and manufacturing methods can be used without limitation. Specifically, synthetic resin such as clay, polyvinyl chloride, polychlorinated polyethylene, furan resin, polyvinyl alcohol, styrene resin, acrylic resin, urea resin, melamine resin, polyester resin is used as a binder, graphite, nitriding Constitutional materials such as boron and talc, coloring materials such as organic pigments and inorganic pigments used as necessary, pore forming agents such as polymethyl methacrylate (PMMA), dioctyl phthalate (DOP), dibutyl phthalate (DBP) Obtained by uniformly dispersing with a kneader, Henschel mixer, 3 rolls, etc. together with a plasticizer such as water, alcohol, ketone, ester, aromatic hydrocarbon, etc. It is done.

本発明で使用する、ポリブテンを含む含浸成分の動粘度は、25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下である必要がある。動粘度が25℃で3,000mm2/sec(c・S・t)以下であると、濃度向上に効果があるが、定着性向上には効果がみられない。動粘度が25℃で160,000mm2/sec(c・S・t)以上を超えても定着性のいっそうの向上がみられず、急激に濃度低下現象が明確になる。
動粘度が25℃で3,000以上160,000mm2/sec(c・S・t)以下の含浸成分は、粘性液体であるため芯体に含浸しにくい傾向がある。よって、加熱することによって動粘度を下げ芯体に含浸させる必要がある。含浸温度は通常100℃前後で実施される。芯体に含浸させるには、動粘度100℃で27以上1,300mm2/sec(c・S・t)以下である必要がある。動粘度100℃で1,300mm2/sec(c・S・t)以上あると加熱しても粘性が高いため芯体中の気孔に入り難くなる。
濃度と定着性とも向上させるには動粘度が25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下である必要がある。この範囲で油状物が含浸されると濃度向上と定着性向上の相乗効果が出ることが分かった。
The kinematic viscosity of the impregnated component containing polybutene used in the present invention is 3,000 to 160,000 mm2 / sec (c · S · t) at 25 ° C., 27 to 1,300 mm 2 / sec at 100 ° C. ( c · S · t) or less. When the kinematic viscosity is 3,000 mm2 / sec (c · S · t) or less at 25 ° C., the density is improved, but the effect of improving the fixability is not observed. Even if the kinematic viscosity exceeds 160,000 mm2 / sec (c · S · t) at 25 ° C., no further improvement in fixability is observed, and the phenomenon of density reduction is sharply clarified.
An impregnation component having a kinematic viscosity of 3,000 or more and 160,000 mm2 / sec (c · S · t) at 25 ° C. is a viscous liquid and thus tends to be difficult to impregnate the core. Therefore, it is necessary to lower the kinematic viscosity and impregnate the core body by heating. The impregnation temperature is usually about 100 ° C. In order to impregnate the core body, it is necessary that the kinematic viscosity is 100 ° C. and is 27 or more and 1,300 mm 2 / sec (c · S · t) or less. When the kinematic viscosity is 1,300 mm2 / sec (c · S · t) or more at 100 ° C., it is difficult to enter pores in the core body because of high viscosity even when heated.
In order to improve both density and fixability, the kinematic viscosity is 3,000 to 160,000 mm2 / sec (c · S · t) at 25 ° C, and 27 to 1,300 mm2 / sec (c · S · t at 100 ° C). t) Must be less than or equal to It was found that when the oily material was impregnated within this range, a synergistic effect of improving the concentration and fixing property was obtained.

ポリブテンを含み、且つ動粘度が25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下の含浸成分は、例えば次の方法で作製できる。
動粘度が25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下のポリブテンを単独または混合して使用してもよいし、従来から動粘度の小さい含浸油である流動パラフィン、シリコーン油、スピンドル油、アルファ−オレフィンオリゴマー等を希釈油として使用し動粘度を調整してもよい。ちなみに、上記従来含浸油の動粘度は25℃で200mm2/sec(c・S・t)以下、100℃で40mm2/sec(c・S・t)以下である。
動粘度が25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下の範囲の代表的なポリブテンはHV−35、HV−50、HV−100、HV−300:新日本石油化学(株)製、35H,100H、300H、35R、100R、300R:出光石油化学(株)製等がある。
また動粘度が25℃で3,000以上160,000mm2/sec(c・S・t)以下、100℃で27以上1,300mm2/sec(c・S・t)以下の範囲外であっても、例えばポリブテンHV−3000(動粘度が25℃で1,000,000mm2/sec(c・S・t)、100℃で5,700mm2/sec(c・S・t)を動粘度が小さい従来含浸油として使用されている流動パラフィン、スピンドル油、シリコーン油、アルファ−オレフィンオリゴマー等で希釈して動粘度調整してもよいし、動粘度の小さいポリブテン(例、ポリブテンLV−7:動粘度が25℃で40mm2/sec(c・S・t)、100℃で3.6mm2/sec(c・S・t)で希釈して動粘度を調整してもよい。
これらが本発明における含浸成分として好適に使用できるものである。
It contains polybutene and has a kinematic viscosity of 3,000 to 160,000 mm2 / sec (c · S · t) at 25 ° C., 27 to 1,300 mm2 / sec (c · S · t) at 100 ° C. The impregnation component can be produced, for example, by the following method.
Kinematic viscosity of 3,000 at 25 ℃ 160,000 mm2 / sec (c · S · t) or less, either alone or mixed with more than 27 1,300 mm2 / sec (c · S · t) following polybutene 100 ° C. Alternatively, the kinematic viscosity may be adjusted by using liquid paraffin, silicone oil, spindle oil, alpha-olefin oligomer, etc., which are conventionally impregnated oils with low kinematic viscosity, as diluent oil. Incidentally, the kinematic viscosity of the conventional impregnating oil is 200 mm 2 / sec (c · S · t) or less at 25 ° C. and 40 mm 2 / sec (c · S · t) or less at 100 ° C.
Typical kinematic viscosity ranges from 3,000 to 160,000 mm2 / sec (c · S · t) at 25 ° C, and 27 to 1,300 mm2 / sec (c · S · t) at 100 ° C. Polybutene includes HV-35, HV-50, HV-100, HV-300: manufactured by Shin Nippon Petrochemical Co., Ltd., 35H, 100H, 300H, 35R, 100R, 300R: manufactured by Idemitsu Petrochemical Co., Ltd.
The kinematic viscosity is outside the range of 3,000 to 160,000 mm2 / sec (c · S · t) at 25 ° C, 27 to 1,300 mm2 / sec (c · S · t) at 100 ° C. However, for example, polybutene HV-3000 (kinematic viscosity is 1,000,000 mm2 / sec (c · S · t) at 25 ° C, and 5,700 mm2 / sec (c · S · t) at 100 ° C is low. The kinematic viscosity may be adjusted by dilution with liquid paraffin, spindle oil, silicone oil, alpha-olefin oligomer or the like conventionally used as impregnation oil, or polybutene having a low kinematic viscosity (eg, polybutene LV-7: kinematic viscosity) May be diluted at 25 ° C. at 40 mm 2 / sec (c · S · t) and at 100 ° C. at 3.6 mm 2 / sec (c · S · t) to adjust the kinematic viscosity.
These can be suitably used as impregnation components in the present invention.

このような含浸成分を焼成芯体に含浸させる方法としては、一般的な含浸方法と同様に含浸油を100℃前後に保ち、動粘度を下げた含浸成分に芯体を浸漬し含浸を行う。尚、含浸させる焼成芯体の組成材料及び焼成条件は任意で良い。含浸後は適宜、遠心分離機などで焼成芯体表面の余分量の含浸成分を除去して鉛筆芯とすれば良い。   As a method for impregnating the fired core with such an impregnating component, impregnation is performed by immersing the core in an impregnating component having a reduced kinematic viscosity while maintaining the impregnating oil at around 100 ° C., as in the general impregnation method. The composition material and firing conditions of the fired core to be impregnated may be arbitrary. After the impregnation, an excessive amount of impregnated components on the surface of the fired core body may be appropriately removed with a centrifuge to form a pencil lead.

以下、実施例に基き本発明を説明するが、本発明は実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example.

(実施例1)
塩化ビニル樹脂 30重量部
黒鉛 35重量部
タルク 15重量部
カーボンブラック 2重量部
ジオクチルフタレート 10重量部
ステアリン酸 2重量部
メチルエチルケトン 30重量部
上記配合を配合物として、ニーダー及び3本ロールにより十分に混練後、細線状に押し出し成形し、空気中で300℃まで加熱し、更に、不活性雰囲気で800℃に加熱し、呼び直径0.7mmの焼成芯体を得た。これを100℃に加熱したポリブテン(HV−300:動粘度25℃で160,000mm2/sec(c・S・t)、100℃で590mm2/sec(c・S・t))に16時間浸漬後、表面上の余なポリブテンを除去して鉛筆芯を得た。
Example 1
30 parts by weight of vinyl chloride resin 35 parts by weight of graphite 35 parts by weight of talc 15 parts by weight of carbon black 2 parts by weight 10 parts by weight of dioctyl phthalate 2 parts by weight of stearic acid 30 parts by weight Methyl ethyl ketone 30 parts by weight Extruded into a thin line, heated to 300 ° C. in air, and further heated to 800 ° C. in an inert atmosphere to obtain a fired core having a nominal diameter of 0.7 mm. After being immersed in polybutene heated to 100 ° C. (HV-300: 160,000 mm 2 / sec (c · S · t) at 25 ° C., 590 mm 2 / sec (c · S · t) at 100 ° C.) for 16 hours The excess polybutene on the surface was removed to obtain a pencil lead.

(実施例2)
実施例1においてポリブテン(LV−300)の代わりに混合ポリブテン(LV−50とHV−300重量比50:50、動粘度25℃で3,000mm2/sec(c・S・t)、100℃で27mm2/sec(c・S・t))を使用した以外実施例1と同様にして鉛筆芯を得た。
(Example 2)
In Example 1, instead of polybutene (LV-300), mixed polybutene (LV-50 and HV-300 weight ratio 50:50, kinematic viscosity at 25 ° C., 3,000 mm 2 / sec (c · S · t), at 100 ° C. A pencil lead was obtained in the same manner as in Example 1 except that 27 mm2 / sec (c · S · t) was used.

(実施例3)
実施例1においてポリブテン(LV−300)の代わりにポリブテン(HV−1900:動粘度25℃で650,000mm2/sec(c・S・t)、100℃で3,800mm2/sec(c・S・t))と流動パラフィン(ダフニーオイルCP 68N、出光石油化学(株)製:動粘度25℃で140mm2/sec(c・S・t)、100℃で9mm2/sec(c・S・t)とを重量比で60:40の割合で混合したもの(動粘度25℃で10,000mm2/sec(c・S・t)、100℃で100mm2/sec(c・S・t)を使用した以外は実施例1と同様にして鉛筆芯を得た。
(Example 3)
In Example 1, instead of polybutene (LV-300), polybutene (HV-1900: kinematic viscosity at 25 ° C., 650,000 mm 2 / sec (c · S · t), at 100 ° C., 3,800 mm 2 / sec (c · S · t)) and liquid paraffin (Daffney Oil CP 68N, manufactured by Idemitsu Petrochemical Co., Ltd.): kinematic viscosity at 25 ° C. and 140 mm 2 / sec (c · S · t), 100 ° C. and 9 mm 2 / sec (c · S · t) In a ratio of 60:40 by weight ratio (except for using a kinematic viscosity of 10,000 mm2 / sec (c · S · t) at 25 ° C and 100 mm2 / sec (c · S · t) at 100 ° C) A pencil lead was obtained in the same manner as in Example 1.

(実施例4)
実施例1においてポリブテン(LV−300)の代わりにポリブテン(HV−1900:動粘度25℃で650,000mm2/sec(c・S・t)、100℃で3,800mm2/sec(c・S・t)とポリブテン(LV−10:動粘度25℃で40mm2/sec(c・S・t)、100℃で3.6mm2/sec(c・S・t))とを重量比で90:10の割合で混合したもの(動粘度25℃で100,000mm2/sec(c・S・t)、100℃で1,300mm2/sec(c・S・t))を使用した以外実施例1と同様にして鉛筆芯を得た。
Example 4
In Example 1, instead of polybutene (LV-300), polybutene (HV-1900: kinematic viscosity at 25 ° C., 650,000 mm 2 / sec (c · S · t), at 100 ° C., 3,800 mm 2 / sec (c · S · t) and polybutene (LV-10: kinematic viscosity at 25 ° C. 40 mm 2 / sec (c · S · t), 100 ° C. 3.6 mm 2 / sec (c · S · t)) at a weight ratio of 90:10 The same as in Example 1 except that a mixture of kinematic viscosity (100,000 mm 2 / sec (c · S · t) at 25 ° C., 1,300 mm 2 / sec (c · S · t) at 100 ° C.) was used. I got a pencil lead.

(比較例1)
実施例1においてポリブテン(LV−300)の代わりに流動パラフィン(ダフニーオイルCP 68N、出光石油化学(株)製:動粘度25℃で140mm2/sec(c・S・t)、100℃で9mm2/sec(c・S・t))を用いた以外すべて実施例1と同様にして鉛筆芯を得た。
(Comparative Example 1)
In Example 1, instead of polybutene (LV-300), liquid paraffin (Dafney Oil CP 68N, manufactured by Idemitsu Petrochemical Co., Ltd.): kinematic viscosity: 140 mm 2 / sec (c · S · t) at 25 ° C., 9 mm 2/100 ° C. A pencil lead was obtained in the same manner as in Example 1 except that sec (c · S · t) was used.

(比較例2)
実施例1においてポリブテン(LV−300)の代わりにポリブテン(LV−10:動粘度25℃で40mm2/sec(c・S・t)、100℃で3.6mm2/sec(c・S・t))を用いた以外すべて実施例1と同様にして鉛筆芯を得た。
(Comparative Example 2)
In Example 1, instead of polybutene (LV-300), polybutene (LV-10: kinematic viscosity at 25 ° C. at 40 mm 2 / sec (c · S · t), at 100 ° C. at 3.6 mm 2 / sec (c · S · t) ) Was used in the same manner as in Example 1 to obtain a pencil lead.

(比較例3)
実施例1においてポリブテン(LV−300)の代わりにポリブテン(HV−1900:動粘度25℃で650,000mm2/sec(c・S・t)、100℃で3,800mm2/sec(c・S・t))を用いた以外すべて実施例1と同様にして鉛筆芯を得た。
(Comparative Example 3)
In Example 1, instead of polybutene (LV-300), polybutene (HV-1900: kinematic viscosity at 25 ° C., 650,000 mm 2 / sec (c · S · t), at 100 ° C., 3,800 mm 2 / sec (c · S · A pencil lead was obtained in the same manner as in Example 1 except that t)) was used.

上記各例により得られた鉛筆芯の筆跡濃度と定着性を測定した。結果を表1に示す。 The handwriting density and fixability of the pencil lead obtained in the above examples were measured. The results are shown in Table 1.

Figure 0004352914

以上より、本発明の鉛筆芯は、濃い筆跡濃度と高い定着性とを両立しえるものである。
Figure 0004352914

As described above, the pencil lead of the present invention can achieve both high handwriting density and high fixability.

Claims (1)

焼成させた芯体が有する気孔中に含浸された成分がポリブテンを含み、且つ動粘度が、25℃で3,000mm2/sec以上160,000mm2/sec以下、100℃で27mm2/sec以上1,300mm2/sec以下である鉛筆芯。 The component impregnated in the pores of the fired core contains polybutene, and the kinematic viscosity is 3,000 mm2 / sec to 160,000 mm2 / sec at 25 ° C, and 27 mm2 / sec at 100 ° C. A pencil lead of 1,300 mm2 / sec or less.
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