JP6223908B2 - Extra lead holder pencil lead - Google Patents

Extra lead holder pencil lead Download PDF

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JP6223908B2
JP6223908B2 JP2014106872A JP2014106872A JP6223908B2 JP 6223908 B2 JP6223908 B2 JP 6223908B2 JP 2014106872 A JP2014106872 A JP 2014106872A JP 2014106872 A JP2014106872 A JP 2014106872A JP 6223908 B2 JP6223908 B2 JP 6223908B2
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lead
pencil lead
holder
carbon
extra
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JP2015221869A (en
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清水 修
修 清水
藤沢 清志
清志 藤沢
聡 坂西
聡 坂西
仁志 木野
仁志 木野
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Mitsubishi Pencil Co Ltd
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本発明は、高強度で折れ難く、かつ、任意に折ることができ、描線も安定して筆記することができ、また、カド書きで細かい文字も書くことができ、しかも、削る必要がないため削りカスもでない替芯式ホルダー鉛筆芯に関する。   The present invention is high-strength and difficult to break, can be folded arbitrarily, can stably draw a drawn line, can also write fine characters with a quadrature, and does not need to be scraped The present invention relates to a pencil lead holder that has no shaving residue.

従来の木軸鉛筆用の芯は、黒鉛などの体質材に、主に粘土などの結合材を加え、さらに必要に応じて所要の溶剤及び/または可塑剤を添加してこれらを混練し、この混練物を線状体に押出成形した後900〜1200℃の温度で焼成し、得られた焼結体の気孔中に油脂類等を含浸させて成形されている。   The core for a conventional wood spindle pencil is mainly made by adding a binder such as clay to an extender such as graphite, and further kneading these with a necessary solvent and / or plasticizer as required. The kneaded product is extruded into a linear body and then fired at a temperature of 900 to 1200 ° C., and the pores of the obtained sintered body are impregnated with fats and oils.

また、木軸鉛筆については、ナイフや削り器により削って使用する必要があり、削ることに伴い、削りカスが発生し、しかも、使用し続けることで木軸が短くなり持ちにくくなるなどの不満があった。更に、削り器を用いなくて済む紙巻軸やカット平型軸鉛筆(例えば、特許文献1参照)も提案されているが、削り器は不要になってもカスが出ること、使用し続けると長さが変わるこなどの課題があり、これらの課題については解決できていないのが現状である。   In addition, the wood axis pencil must be used by shaving with a knife or a sharpener, and the shavings are generated with the shaving, and the wood axis becomes shorter and harder to hold by continuing to use it. was there. In addition, a paper-wound shaft and a cut flat-shaft pencil (for example, see Patent Document 1) that do not require a sharpener have been proposed. The current situation is that these issues cannot be solved.

一方、従来の円断面芯を把持して使用するホルダー鉛筆は、文字を書く用途には適するが、芯先がすぐに丸くなることや、マークシートのように幅広い面を塗るには使い勝手が悪かった。加えて、これまでの鉛筆芯を矩形に成形して焼成した鉛筆芯(例えば、特許文献2参照)も知られているが、芯自体の強度が弱いことで、折れやすいものとなり、根本的な解決には至っていないのが現状である。   On the other hand, the conventional holder pencil that holds and uses a circular cross-section core is suitable for writing characters, but it is not easy to use when the core is rounded quickly or a wide surface such as a mark sheet is applied. . In addition, a pencil lead formed by baking a conventional pencil lead into a rectangular shape (see, for example, Patent Document 2) is also known. Currently, no solution has been reached.

実用新案登録第3032166号公報(実用新案登録請求の範囲、図1等)Utility Model Registration No. 3032166 (Utility Model Registration Request, FIG. 1 etc.) 実開昭61−78684号公報全文(考案の詳細な説明等)Full text of Shokai 61-78684 (detailed explanation of the invention, etc.)

本発明は、上記従来の課題等について、これを解消しようとするものであり、削る必要がなく、したがって削りカスが出ない、外観形状として短くなることがないので筆記具としての使い勝手も変わらなく、高強度で折れ難く、かつ、任意に折ることができ、描線も安定して筆記できて、カド書きで細かい文字も書くことができる替芯式ホルダー鉛筆芯を提供することを目的とする。   The present invention is intended to solve the above-mentioned conventional problems and the like, and it is not necessary to cut, therefore, no shaving residue is produced, and the appearance shape is not shortened, so the usability as a writing instrument is not changed, It is an object of the present invention to provide an extra lead holder pencil lead that can be folded with high strength, can be arbitrarily folded, can be drawn with stability, and can be used to write fine characters in a quad.

本発明者らは、上記従来技術の課題及び現状に鑑み、鋭意研究の結果、賦形性を有し焼成後高い炭素残査収率を示す組成物を焼成してなるアモルファス状炭素中に、少なくとも特定の体質材一種または二種以上を、均一かつ一方向に高度に配向制御させることなどにより、前記課題が効果的に解決し、上記目的の替芯式ホルダー鉛筆芯が得られることを見出し、本発明を完成するに至ったのである。   In view of the problems and current situation of the above-described conventional technology, the present inventors have intensively studied, and as a result, at least in amorphous carbon obtained by firing a composition having a formability and showing a high carbon residue yield after firing, One or two or more specific constitutional materials are found to solve the above-mentioned problem effectively by controlling the orientation highly uniformly in one direction, etc. The present invention has been completed.

すなわち、本発明は次の(1)〜(6)に存する。
(1) 賦形性を有し、焼成後高い炭素残査収率を示す組成物を焼成してなるアモルファス状炭素中に、炭素粉末、半金属窒化物、半金属酸化物及び粘土鉱物から選ばれる体質材の一種または二種以上を、均一かつ一方向に高度に配向制御させてなることを特徴とする替芯式ホルダー鉛筆芯。
(2) 炭素粉末が黒鉛、カーボンブラック、グラフェン、カーボンナノチューブから選ばれる少なくとも1種を用いることを特徴とする上記(1)記載の替芯式ホルダー鉛筆芯。
(3) 体質材が、窒化ホウ素、タルク、カオリン(カオリナイト、ハロイサイト)、シリカ、マイカ及び炭酸カルシウムから選ばれる少なくとも1種を用いることを特徴とする上記(1)又は(2)記載の替芯式ホルダー鉛筆芯。
(4) 断面の形状が四角形の矩形状であることを特徴とする上記(1)〜(3)の何れか一つに記載の替芯式ホルダー鉛筆芯。
(5) 鉛筆芯を把持し、任意に繰出して折ることができるホルダーを具備する上記(1)〜(4)の何れか一つに記載の替芯式ホルダー鉛筆芯。
(6) 表面にレーザー光を照射してカット用の傷をつけることを特徴とする上記(1)〜(5)の何れか一つに記載の替芯式ホルダー鉛筆芯。
That is, this invention exists in following (1)-(6).
(1) Selected from carbon powder, metalloid nitride, metalloid oxide, and clay mineral in amorphous carbon obtained by baking a composition having formability and high carbon residue yield after baking. An extra lead holder pencil lead characterized in that one or two or more types of extender materials are highly oriented uniformly and in one direction.
(2) The refill-type holder pencil lead according to (1), wherein the carbon powder is at least one selected from graphite, carbon black, graphene, and carbon nanotubes.
(3) The constitution described in (1) or (2) above, wherein the extender uses at least one selected from boron nitride, talc, kaolin (kaolinite, halloysite), silica, mica and calcium carbonate A lead-type holder pencil lead.
(4) The replaceable lead-type holder pencil lead according to any one of (1) to (3) above, wherein the cross-sectional shape is a rectangular rectangle.
(5) The replaceable lead-type holder pencil lead according to any one of the above (1) to (4), comprising a holder that holds a pencil lead and can be arbitrarily drawn and folded.
(6) The replacement-type holder pencil lead according to any one of (1) to (5) above, wherein the surface is irradiated with laser light to make a scratch for cutting.

本発明によれば、高強度で折れ難く、かつ、任意に折ることができ、描線も安定して筆記することができ、また、カド書きで細かい文字も書くことができ、しかも、削る必要がないため削りカスもでない替芯式ホルダー鉛筆芯が提供される。   According to the present invention, it is high-strength and difficult to break, and can be arbitrarily folded, the drawn line can be stably written, and fine characters can be written in quadruple writing. There is provided a replaceable lead holder pencil lead that is free of shavings.

(a)は本発明の替芯式ホルダー鉛筆芯の一例を示す平面図、(b)は本発明の替芯式ホルダー鉛筆芯を替芯式のホルダータイプの筆記具に適用した一例を示す斜視図である。(A) is a top view which shows an example of the extra lead-type holder pencil lead of this invention, (b) is a perspective view which shows an example which applied the extra lead-type holder pencil lead of this invention to the extra lead type holder type writing instrument. It is.

以下に、本発明の実施の形態を詳しく説明する。
本発明の替芯式ホルダー鉛筆芯は、賦形性を有し、焼成後高い炭素残査収率を示す組成物を焼成してなるアモルファス状炭素中に、炭素粉末、半金属窒化物、半金属酸化物及び粘土鉱物から選ばれる体質材の一種または二種以上を、均一かつ一方向に高度に配向制御させてなることを特徴とするものである。
Hereinafter, embodiments of the present invention will be described in detail.
The extra lead holder pencil lead of the present invention has a formability and a carbon powder, a semi-metal nitride, and a semi-metal in amorphous carbon formed by firing a composition having a high carbon residue yield after firing. It is characterized in that one or two or more constitutional materials selected from oxides and clay minerals are highly oriented uniformly and unidirectionally.

本発明において、上記構成となる替芯式ホルダー鉛筆芯は、例えば、賦形性を有し焼成後高い炭素残査収率を示す組成物と、カーボンブラック、黒鉛、カーボンブラック、グラフェン、カーボンナノチューブ等の炭素粉末と、窒化ホウ素、タルク、カオリン(カオリナイト、ハロイサイト)、シリカ、マイカ、炭酸カルシウム等の体質材一種または二種以上を混合し、成形段階でこれら体質材を均一かつ一方向に高度に配向させた後に焼成することにより得られるものである。   In the present invention, the refill-type holder pencil lead having the above configuration includes, for example, a composition having a formability and a high carbon residue yield after firing, carbon black, graphite, carbon black, graphene, carbon nanotube, etc. Carbon powder and boron nitride, talc, kaolin (kaolinite, halloysite), silica, mica, calcium carbonate, etc. are mixed in one or more types, and these materials are uniformly and unidirectionally advanced in the molding stage. It is obtained by firing after orientation.

本発明の賦形性を有し焼成後高い炭素残査収率を示す組成物としては、例えば、不活性ガス雰囲気中での焼成により5%以上の炭化収率を示す有機物質などを挙げることができる。
具体的には、カオリナイト、ハロイサイト、モンモリロナイト、ベントナイト等の粘土鉱物、ポリ塩化ビニル、ポリアクリロニトリル、ポリビニルアルコール、ポリ塩化ビニル−ポリ酢酸ビニル共重合体、ポリアミド、ポリイミド等の熱可塑性樹脂、フェノール樹脂、フラン樹脂、エポキシ樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂、リグニン、セルロース、トラガントガム、アラビアガム、糖類等の縮合多環芳香族を分子の基本構造内に持つ天然高分子物質、及び前記には含有されない、ナフタレンスルホン酸のホルマリン縮合物、コプナ樹脂等の縮合多環芳香族を分子の基本構造内に持つ合成高分子物質が挙げられる。
使用する組成物種とその使用量は、目的とする替芯式ホルダー鉛筆芯の形状等により適宜選択され、上述の成分の単独でも二種以上の混合体でも使用することができるが、特に、ポリ塩化ビニル樹脂、塩素化塩化ビニル樹脂を使用することが好ましく、炭素の持つ優れた特性を堅持するためにもその使用量は配合組成物全量中に、30質量部以上が好ましく、更に好ましくは、35〜60質量部が望ましい。
Examples of the composition having the formability of the present invention and exhibiting a high carbon residue yield after firing include organic substances that exhibit a carbonization yield of 5% or more by firing in an inert gas atmosphere. it can.
Specifically, clay minerals such as kaolinite, halloysite, montmorillonite, bentonite, etc., thermoplastic resins such as polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride-polyvinyl acetate copolymer, polyamide, polyimide, phenol resin , Thermosetting resins such as furan resins, epoxy resins and unsaturated polyester resins, natural polymeric substances having condensed polycyclic aromatics such as lignin, cellulose, tragacanth gum, gum arabic, and sugars in the basic structure of the molecule, and And synthetic polymer substances having a condensed polycyclic aromatic group in the basic structure of the molecule, such as a naphthalenesulfonic acid formalin condensate and a copna resin.
The type of composition to be used and the amount to be used are appropriately selected depending on the shape of the intended replacement core holder pencil lead, etc., and can be used alone or in combination of two or more of the above components. It is preferable to use a vinyl chloride resin or a chlorinated vinyl chloride resin, and the amount used thereof is preferably 30 parts by mass or more in the total amount of the blended composition in order to maintain the excellent characteristics of carbon, and more preferably, 35-60 mass parts is desirable.

本発明の炭素粉末としては、例えば、黒鉛、カーボンブラック、グラフェン、カーボンナノチューブなどが挙げられる。
また、本発明の半金属窒化物、半金属酸化物、粘土鉱物などの体質材としては、例えば、窒化ホウ素、窒化ケイ素、タルク、カオリン(カオリナイト、ハロイサイト)、シリカ、マイカ、炭酸カルシウムなどが挙げられる。
好ましくは、炭素粉末や、半金属窒化物、半金属酸化物、粘土鉱物などの体質材は、平均粒度(平均粒子径)が50μm以下、好ましくは、1〜10μmの粒子径のものを用いることが望ましい。この平均粒子径が50μm超の場合には、十分な強度が発現せず、また、平均粒子径が1μm未満の場合には体質材の配向が劣り、強度が発現しないばかりでなく硬度だけが硬くなる傾向を有するので好ましくない。
なお、本発明(後述する実施例等を含む)において、平均粒度(平均粒子径)は、レーザー回折・散乱式粒子径分布測定装置で測定した値をいう。
Examples of the carbon powder of the present invention include graphite, carbon black, graphene, and carbon nanotube.
Further, examples of the constitutional material such as semi-metal nitride, semi-metal oxide and clay mineral of the present invention include boron nitride, silicon nitride, talc, kaolin (kaolinite, halloysite), silica, mica, calcium carbonate and the like. Can be mentioned.
Preferably, an extender such as carbon powder, metalloid nitride, metalloid oxide, clay mineral, etc. should have an average particle size (average particle size) of 50 μm or less, preferably 1-10 μm. Is desirable. When the average particle diameter is more than 50 μm, sufficient strength is not expressed, and when the average particle diameter is less than 1 μm, the orientation of the extender is inferior, not only the strength is not expressed but also only the hardness is hard. This is not preferable.
In the present invention (including examples and the like to be described later), the average particle size (average particle size) refers to a value measured by a laser diffraction / scattering particle size distribution measuring apparatus.

用いる炭素粉末、半金属窒化物、半金属酸化物、粘土鉱物などの体質材種とその使用量は、目的とする替芯式ホルダー鉛筆芯の形状や芯の摩耗状態と被筆記面に形成される描線の状態、折るための加工のし易さ、替芯式ホルダー鉛筆芯としての使い勝手などにより適宜選択され、単独でも二種以上の混合体でも使用することができる。好ましくは、筆記描線の濃さなどから、特に黒鉛、窒化硼素を使用することが望ましく、炭素の持つ優れた特性を堅持するためにもその使用量は、配合組成物全量中に、70質量部以下が好ましく、更に好ましくは、40〜65質量部が望ましく、特に好ましくは、炭素粉末が10〜60質量部、その他の体質材が5〜55質量部とすることが望ましい。   The types of materials used, such as carbon powder, metalloid nitrides, metalloid oxides, and clay minerals, and the amount used are formed on the shape of the intended replacement lead pencil lead and the wear state of the lead and the writing surface. Depending on the state of the drawn lines, the ease of processing for folding, the ease of use as an extra lead-type holder pencil lead, and the like, it can be used alone or in combination of two or more. Preferably, it is desirable to use graphite and boron nitride in particular because of the darkness of the drawn lines, and the amount used is 70 parts by mass in the total amount of the blended composition in order to maintain the excellent characteristics of carbon. The following is preferable, more preferably 40 to 65 parts by mass, and particularly preferably 10 to 60 parts by mass of carbon powder and 5 to 55 parts by mass of other constitutional materials.

本発明では、上記賦形性を有し焼成後高い炭素残査収率を示す組成物と、カーボンブラック、黒鉛、カーボンブラック、グラフェン、カーボンナノチューブ等の炭素粉末と、窒化ホウ素、タルク、カオリン(カオリナイト、ハロイサイト)、シリカ、マイカ、炭酸カルシウム等の体質材一種または二種以上と、さらに必要に応じて、ジオクチルフタレート(DOP)、ジブチルフタレート(DBP)、リン酸トリクレジル(TCP)、アジピン酸ジオクチル(DOA)、ジアリルフタレート(DAP)、プロピレンカーボネート、アルコール類、ケトン類、エステル類などの所要の溶剤及び可塑剤の一種または二種以上を配合して、これらをヘンシェルミキサー、加圧ニーダー、2本ロールなどの混練機で混練して混練物を調整し、この混練物を押出成形等する際の成形段階で上記体質材を均一かつ一方向に高度に配向させた後に焼成することにより、得られるものである。
具体的には、上記混練物を、例えば、スクリュー型押出機などを用いて押出成形する際、押出ノズル直上の背面圧力を30MPa以上、好ましくは35MPa以上で、かつ溶融した混練物がノズルを通過する時のせん断速度を5×10(1/sec)以上、好ましくは7×10(1/sec)以上となるように押出条件を設定し、所定形状となるように成形、好ましくは、スクリュー式押出機の押出部分の先端形状が断面長方形状となる押出ノズルを装着し、断面が四角形の矩形状に成形を行ない、その後、従来と同様に、窒素ガスなどの不活性ガス雰囲気中で焼成し、得られた焼結体の気孔中に油脂類等を含浸させることにより本発明の替芯式ホルダー鉛筆芯を得ることができる。
In the present invention, the composition having the above-mentioned formability and showing a high carbon residue yield after firing, carbon powder such as carbon black, graphite, carbon black, graphene, carbon nanotubes, boron nitride, talc, kaolin (kaori) Knight, halloysite), silica, mica, calcium carbonate, etc., one or more, and if necessary, dioctyl phthalate (DOP), dibutyl phthalate (DBP), tricresyl phosphate (TCP), dioctyl adipate (DOA), diallyl phthalate (DAP), propylene carbonate, alcohols, ketones, esters and the like, and one or more of plasticizers are blended, and these are mixed into a Henschel mixer, pressure kneader, 2 The kneaded material is adjusted by kneading with a kneader such as a roll, and this kneading is performed. By firing after being highly oriented uniformly and in one direction the extender material in molding step during extrusion molding or the like, is obtained.
Specifically, when the kneaded product is extruded using, for example, a screw-type extruder, the back pressure immediately above the extrusion nozzle is 30 MPa or more, preferably 35 MPa or more, and the melted kneaded product passes through the nozzle. The extrusion conditions are set so that the shear rate at the time is 5 × 10 4 (1 / sec) or more, preferably 7 × 10 4 (1 / sec) or more, and molding is performed to a predetermined shape, Attach an extrusion nozzle that has a rectangular cross section at the tip of the extrusion part of the screw type extruder, and mold it into a rectangular shape with a rectangular cross section. Then, in the same manner as before, in an inert gas atmosphere such as nitrogen gas The extra lead holder pencil lead of the present invention can be obtained by firing and impregnating pores of the obtained sintered body with fats and oils.

なお、上記押出条件の制御は、使用する材料の選択、配合の調整などの他に、押出機のスクリュー形状、押出温度、押出速度、ノズル径などを好適に組み合わせることによって得られる。
溶融した混練物がノズルを通過する時のせん断速度は、流量Q(cm/sec)、ノズル半径R(cm)、円周率をπとしたとき次式により求められる。
せん断速度=4Q/πR(1/sec)
このようにして押出成形によって得られた線状体を焼成し、得られた焼結体の気孔中に油脂類等を含浸させることにより本発明の替芯式ホルダー鉛筆芯を得ることができる。
In addition, control of the said extrusion conditions is obtained by combining suitably the screw shape, extrusion temperature, extrusion speed, nozzle diameter, etc. of an extruder other than selection of the material to be used, adjustment of a mixing | blending, etc.
The shear rate when the melted kneaded material passes through the nozzle is obtained by the following equation when the flow rate Q (cm 3 / sec), the nozzle radius R (cm), and the circumferential ratio are π.
Shear rate = 4Q / πR 3 (1 / sec)
Thus, the linear body obtained by extrusion molding is fired, and the core of the obtained sintered body is impregnated with fats and oils to obtain the extra lead holder pencil core of the present invention.

本発明において、賦形性を有し、焼成後高い炭素残査収率を示す組成物を焼成してなるアモルファス状炭素中に、上述の体質材が、均一かつ一方向に高度に配向制御されているかの確認は、
X線回析による配向度(π)により確認できる。すなわち、配向度(π)は、芯体中のアモルファス状炭素結晶の押出軸方向に対する配向の程度を示すもので、この数値が1に近いほど、高度に配向制御されていることを意味する。
本発明(後述する実施例等を含む)において、X線回析は、芯の押出軸方向に対して垂直にX線を照射し、方位角2θを0〜90°スキャンし、(002)面の強度分布の最大値を示す方位角の位置を確認する(約26°近傍)。次に、この方位角の位置において芯をX線ビームの垂直面内において180°回転することにより、(002)面の強度分布をとり、強度最大値の1/2の点における半価幅(H)から下記式により配向度(π)が求められる。
配向度(π)=(180−H)/180 (1)
本発明では、配向度(π)が0.85以上のときに、上述の体質材が、均一かつ一方向に高度に配向制御されていることを意味する。より好ましくは、配向度(π)が0.90以上が望ましい。
本発明で得られる替芯式ホルダー鉛筆芯は、アモルファス状炭素中に、上記特性の体質材が、均一かつ一方向に高度に配向制御されており、その強度(曲げ強度)も強く、250〜450(MPa)の範囲となるものである。
In the present invention, in the amorphous carbon obtained by firing a composition having formability and showing a high carbon residue yield after firing, the above-mentioned extender is highly oriented uniformly and unidirectionally. To check if
This can be confirmed by the degree of orientation (π) by X-ray diffraction. That is, the degree of orientation (π) indicates the degree of orientation of the amorphous carbon crystal in the core in the direction of the extrusion axis, and the closer this value is to 1, the higher the orientation control.
In the present invention (including examples and the like to be described later), X-ray diffraction is performed by irradiating X-rays perpendicularly to the extrusion axis direction of the core, scanning an azimuth angle 2θ of 0 to 90 °, and (002) plane. The position of the azimuth angle indicating the maximum value of the intensity distribution is confirmed (around 26 °). Next, by rotating the core 180 ° in the vertical plane of the X-ray beam at the position of this azimuth angle, the intensity distribution of the (002) plane is taken, and the half-value width (1/2) at the point of 1/2 of the maximum intensity value ( The degree of orientation (π) is obtained from H) by the following formula.
Degree of orientation (π) = (180−H) / 180 (1)
In the present invention, when the degree of orientation (π) is 0.85 or more, it means that the above-mentioned extender material is highly uniformly controlled in one direction. More preferably, the degree of orientation (π) is 0.90 or more.
The replaceable lead-type holder pencil lead obtained in the present invention is characterized in that the extender having the above characteristics is uniformly and highly controlled in one direction in amorphous carbon, and its strength (bending strength) is also strong. It will be in the range of 450 (MPa).

本発明において、替芯式ホルダー鉛筆芯は、曲げ強度も強く上記範囲となるものであるので、従来では、断面四角形の矩形芯とした場合、厚みの薄い方向ではどうしても強度不足で折れやすいところであったが、本発明では、補強効果を発現できる上記平均粒度(平均粒子径)の高強度素材となる体質材を均一かつ一方向に高度に配向制御させることで、断面の形状が四角形の矩形状のホルダー鉛筆芯が得られるものとなる。
本発明において、断面の形状が四角形の矩形状その大きさとしては、用いる筆記具等により変動するものであるが、替芯式のホルダータイプの筆記具では、好ましくは、断面の高さ(厚さ)が0.2〜2mm、幅方向(幅)が3〜7mm、その長手方向の長さが1〜18cm程度に調整されることが望ましい。
また、替芯式ホルダー鉛筆芯では、上記曲げ強度を有し、折れ難く、新筆記面(新たな鋭角部)が露出できる構造、すなわち、任意に折ることができるように、表面にレーザー加工機によるレーザー光を照射して、所定間隔度(例えば、3〜10mmの間隔)に、カット用の傷、例えば、所定深さの溝(0.1〜1mm)を形成することが好ましい。
In the present invention, the replaceable lead type pencil lead has a high bending strength and falls within the above range. Conventionally, when a rectangular core with a square cross section is used, it is apt to be broken due to insufficient strength in the thin direction. However, in the present invention, the cross-sectional shape is a rectangular shape by controlling the orientation of the extender material, which is a high-strength material having the above average particle size (average particle size) capable of exhibiting a reinforcing effect, uniformly and in one direction. The holder pencil lead is obtained.
In the present invention, the shape of the cross-section is a rectangular rectangle, and the size thereof varies depending on the writing instrument to be used. However, in the replacement-type holder-type writing instrument, the height (thickness) of the cross section is preferable. Is preferably adjusted to 0.2 to 2 mm, the width direction (width) is 3 to 7 mm, and the length in the longitudinal direction is adjusted to about 1 to 18 cm.
In addition, the replaceable lead holder pencil lead has the above bending strength, is difficult to break, and has a structure in which a new writing surface (new acute angle part) can be exposed, that is, a laser processing machine on the surface so that it can be folded arbitrarily. It is preferable to form a flaw for cutting, for example, a groove (0.1 to 1 mm) having a predetermined depth at a predetermined interval (for example, an interval of 3 to 10 mm) by irradiating the laser beam.

図1(a)は、本発明の替芯式ホルダー鉛筆芯の一例を示す平面図であり、(b)は、本発明の替芯式ホルダー鉛筆芯を替芯式のホルダータイプの筆記具に適用した一例を示す斜視図である。
図1(a)の替芯式ホルダー鉛筆芯10は、幅5mm、厚さ1mm、長さ10cmであり、レーザー加工機で鉛筆芯表面に、長手方向と垂直に深さ0.3mmの溝11,11…を5mm間隔で形成したものである。
図1(b)の筆記具Aは、汎用の構造であり、軸筒1の内部には、図示しないが、コイルバネ等の弾性部材によって後方に付勢された芯タンク2が前後動可能に配置され、該芯タンク2の前方には、替芯式ホルダー鉛筆芯10の把持・解放を行うチャック3が取り付けられている。そして、そのチャック3の頭部3aは、前記軸筒1の前端に取り付けられた首部4から露出しており、チャック3が前後動する度に、その首部4の先端孔4aによって閉鎖、拡開が行われる。そして、ノック体5を押圧すると、芯タンク2を前進し、チャック3も前進し、そのチャック3の頭部3aが自らの弾性復元力によって拡開する。この拡開動作により、把持されていた替芯式ホルダー鉛筆芯10が解放されるため、替芯式ホルダー鉛筆芯10は自重で下降し、チャック3の頭部4から露出する。ここで、前記芯タンク2の前進動作を解除すると、その芯タンク2は、弾性部材によって後方に移動すると共に、チャック3も後方に向け移動する。この時、そのチャック3の頭部3aは、前記首部4の先端孔4aによって閉鎖せしめられ、再び、替芯式ホルダー鉛筆芯10を把持するものであり、所定の繰り出す操作により使用に供されるものである。
このタイプの筆記具Aでは、本発明の替芯式ホルダー鉛筆芯を用いることにより、筆記時は折れにくく、カド書きで細い描線、面書きで塗りやすい芯を実現可能となり、それ故芯表面に加工することも可能となり、鉛筆芯を把持し、任意に繰出して削らずに溝部11で折って、新筆記面(溝部11に沿って折ることで新たな鋭角部)を出すことも可能となると同時に削り器が不要で、削りカスや粉がでないなど機能を発現することができるものとなる。
FIG. 1A is a plan view showing an example of the extra lead holder pencil lead of the present invention, and FIG. 1B applies the extra lead holder pencil lead of the present invention to a replaceable holder type writing instrument. It is a perspective view showing an example.
1A has a width of 5 mm, a thickness of 1 mm, and a length of 10 cm. A groove 11 having a depth of 0.3 mm perpendicular to the longitudinal direction is formed on the surface of the pencil core by a laser processing machine. , 11... Are formed at intervals of 5 mm.
The writing instrument A shown in FIG. 1B has a general-purpose structure, and a core tank 2 urged rearward by an elastic member such as a coil spring is arranged in the shaft tube 1 so as to be movable back and forth, although not shown. In front of the lead tank 2, a chuck 3 for holding and releasing the replaceable lead type pencil lead 10 is attached. The head 3a of the chuck 3 is exposed from the neck 4 attached to the front end of the shaft tube 1, and is closed and expanded by the tip hole 4a of the neck 4 every time the chuck 3 moves back and forth. Is done. When the knock body 5 is pressed, the lead tank 2 is moved forward, the chuck 3 is also moved forward, and the head 3a of the chuck 3 is expanded by its own elastic restoring force. By this spreading operation, the gripping lead-type holder pencil lead 10 is released, so that the lead-type holder pencil lead 10 is lowered by its own weight and exposed from the head 4 of the chuck 3. Here, when the advance operation of the lead tank 2 is canceled, the lead tank 2 is moved backward by the elastic member, and the chuck 3 is also moved backward. At this time, the head portion 3a of the chuck 3 is closed by the tip hole 4a of the neck portion 4, and again grips the replacement lead type holder pencil lead 10 and is used by a predetermined feeding operation. Is.
In this type of writing instrument A, by using the extra lead holder pencil lead of the present invention, it becomes difficult to break at the time of writing, and it is possible to realize a thin drawn line by caddy writing, easy to apply by surface writing, and hence processing to the core surface At the same time, it becomes possible to grip the pencil lead, fold it at the groove 11 without arbitrarily drawing it out and cutting it, and to produce a new writing surface (a new acute angle part by folding along the groove 11). A shaving machine is unnecessary, and functions such as no shavings and powder can be exhibited.

本発明の替芯式ホルダー鉛筆芯は、上記実施形態に限定されるものではなく、本発明の技術思想の範囲内で、種々変更して実施することができる。例えば、ノック式でなくチャックで把持固定し、数回折っての使用後に、鉛筆芯を付け替え把持固定するなどであってもよいものである。   The extra lead holder pencil lead of the present invention is not limited to the above embodiment, and can be implemented with various modifications within the scope of the technical idea of the present invention. For example, instead of the knock type, it may be held and fixed with a chuck, and after use several times, the pencil lead may be replaced and held and fixed.

次に、実施例及び比較例により、本発明を更に具体的に説明するが、本願発明はこの実施例等によって何等限定されるものではない。   Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples and the like.

〔実施例1〜3及び比較例1〕
以下の実施例、比較例において、高速高圧での押し出しは、高樹脂圧力に耐えうるスクリュー式押出機を用いて行い、各実施例、比較例に記載の押し出し温度、背面圧力、せん断速度で行った。
また、配向度は、X線回析装置(リガク社製)を用いて、上述の条件で測定し、上記式にて算出し、曲げ強度はJIS S 6005:2013に準拠して測定した。
これらの結果を下記実施例1〜3及び比較例1中に記載した。
[Examples 1 to 3 and Comparative Example 1]
In the following Examples and Comparative Examples, extrusion at high speed and high pressure is performed using a screw type extruder that can withstand high resin pressure, and is performed at the extrusion temperature, back pressure, and shear rate described in each Example and Comparative Example. It was.
Further, the degree of orientation was measured under the above-mentioned conditions using an X-ray diffraction apparatus (manufactured by Rigaku Corporation), calculated according to the above formula, and the bending strength was measured according to JIS S 6005: 2013.
These results are described in Examples 1 to 3 and Comparative Example 1 below.

(実施例1)
配合組成物として、塩素化塩化ビニル樹脂45質量部を用い、これに天然黒鉛微粉末(平均粒度5μm)45質量部と窒化硼素(平均粒度6μm)10質量部に対し、可塑材としてジアリルフタレートモノマーを20質量部添加して、ヘンシェルミキサーで混合分散し、加圧ニーダー、二本ロールで混練した後、スクリュー式押出機にノズル先端の断面形状が長方形状の押出ノズルを装着し、押出温度を100℃に設定し、背面圧力を35MPa、せん断速度8×10(1/sec)が得られるようにスクリュー回転数で高速高圧で押し出しで、断面が矩形状に成形を行ない、その後、窒素ガス雰囲気中で焼成し、最後にアルファーオレフィンオリゴマー中に浸漬して、替芯式ホルダー鉛筆芯を得た。
Example 1
As a blended composition, 45 parts by mass of chlorinated vinyl chloride resin is used, and 45 parts by mass of natural graphite fine powder (average particle size 5 μm) and 10 parts by mass of boron nitride (average particle size 6 μm) are mixed with diallyl phthalate monomer as a plasticizer. 20 parts by mass, mixed and dispersed with a Henschel mixer, kneaded with a pressure kneader and two rolls, an extrusion nozzle having a rectangular cross section at the tip of the nozzle is attached to a screw type extruder, and the extrusion temperature is set. Set to 100 ° C., the back pressure is 35 MPa, the shear rate is 8 × 10 4 (1 / sec), extrusion is performed at a high speed and high pressure with a screw rotation speed, the cross section is formed into a rectangular shape, and then nitrogen gas It fired in atmosphere and was finally immersed in the alpha-olefin oligomer, and the extra lead-type holder pencil lead was obtained.

得られた替芯式ホルダー鉛筆芯は、幅5mm、厚さ1mm、長さ10cm、配向度0.91、曲げ強度が400MPaであった。
また、レーザー加工機(YAGレーザー、三菱電機社製、以下同様)で鉛筆芯表面に、長手方向と垂直に深さ0.3mmの溝を5mm間隔で形成した。
該鉛筆芯を図1に示すホルダーで把持することで、削る必要がなく、したがって削りカスが生じず、外観形状として短くなることが無いので筆記具としての使い勝手も変わらなく、高強度で折れ難く、且つ任意に折ることができ、描線も安定して使うことができ、カド書きで細かい文字も書くことが可能な替芯式ホルダー鉛筆芯を得ることができた。
The obtained replaceable core holder pencil lead had a width of 5 mm, a thickness of 1 mm, a length of 10 cm, an orientation degree of 0.91, and a bending strength of 400 MPa.
Further, grooves with a depth of 0.3 mm perpendicular to the longitudinal direction were formed on the surface of the pencil core with a laser processing machine (YAG laser, manufactured by Mitsubishi Electric Corporation, the same applies hereinafter) at intervals of 5 mm.
By gripping the pencil lead with the holder shown in FIG. 1, it is not necessary to sharpen, therefore no shaving residue is generated and the appearance shape is not shortened, so the usability as a writing instrument is not changed, and it is difficult to break with high strength. In addition, it was possible to obtain a replaceable lead type pencil lead that can be folded arbitrarily, the drawing line can be used stably, and fine characters can be written with a quad.

(実施例2)
配合組成物として、塩素化塩化ビニル樹脂45質量部を用い、これに天然黒鉛微粉末(平均粒度5μm)35質量部と窒化硼素(平均粒度6μm)20質量部に対し、可塑材としてジアリルフタレートモノマーを20質量部添加して、上記実施例1と同様に分散、混合し、高速高圧で押し出し〔(押出温度:100℃、背面圧力を30MPa、せん断速度7×10(1/sec)〕で押し出しで、断面が矩形状に成形を行ない、その後、窒素ガス雰囲気中で焼成し、最後にアルファーオレフィンオリゴマー中に浸漬して、替芯式ホルダー鉛筆芯を得た。
(Example 2)
As a blended composition, 45 parts by mass of a chlorinated vinyl chloride resin is used, and 35 parts by mass of natural graphite fine powder (average particle size 5 μm) and 20 parts by mass of boron nitride (average particle size 6 μm) are mixed with diallyl phthalate monomer as a plasticizer. 20 parts by mass, dispersed and mixed in the same manner as in Example 1 above, and extruded at high speed and high pressure [(extrusion temperature: 100 ° C., back pressure 30 MPa, shear rate 7 × 10 4 (1 / sec)]. By extrusion, the cross-section was formed into a rectangular shape, then fired in a nitrogen gas atmosphere, and finally immersed in an alpha-olefin oligomer to obtain an extra lead holder pencil lead.

得られた替芯式ホルダー鉛筆芯は、幅5mm、厚さ1mm、長さ18cm、配向度0.89、曲げ強度が380MPaであった。上記実施例1と同様にレーザー加工機で鉛筆芯表面に、長手方向と垂直に深さ0.3mmの溝を5mm間隔で形成した。
該鉛筆芯を図1のホルダーで把持することで、実施例1と同様に、削る必要がなく、したがって削りカスが生じず、外観形状として短くなることが無いので筆記具としての使い勝手も変わらなく、高強度で折れ難く、且つ任意に折ることができ描線も安定して使うことができ、カド書きで細かい文字も書くことが可能な替芯式ホルダー鉛筆芯を得ることができた。
The obtained replaceable core pencil lead had a width of 5 mm, a thickness of 1 mm, a length of 18 cm, an orientation degree of 0.89, and a bending strength of 380 MPa. In the same manner as in Example 1 above, grooves with a depth of 0.3 mm were formed at intervals of 5 mm perpendicular to the longitudinal direction on the surface of the pencil core with a laser processing machine.
By gripping the pencil lead with the holder of FIG. 1, it is not necessary to cut as in the first embodiment, and therefore no shaving residue is generated, and the appearance shape is not shortened, so the usability as a writing instrument is not changed, A high-strength, hard to break, and can be folded arbitrarily, the drawn line can be used stably, and a refill-type holder pencil lead capable of writing fine characters with a quadruple writing was obtained.

(実施例3)
配合組成物として、塩素化塩化ビニル樹脂45質量部を用い、これに天然黒鉛微粉末(平均粒度5μm)45質量部と窒化硼素(平均粒度6μm)10質量部に対し、可塑材としてジアリルフタレートモノマーを20質量部添加して、上記実施例1と同様に分散、混合し、高速高圧で押し出し〔(押出温度:100℃、背面圧力を50MPakg/cm2、せん断速度9×10(1/sec)〕で押し出しで、断面が矩形状に成形を行ない、その後、窒素ガス雰囲気中で焼成し、最後にアルファーオレフィンオリゴマー中に浸漬して、替芯式ホルダー鉛筆芯を得た。
(Example 3)
As a blended composition, 45 parts by mass of chlorinated vinyl chloride resin is used, and 45 parts by mass of natural graphite fine powder (average particle size 5 μm) and 10 parts by mass of boron nitride (average particle size 6 μm) are mixed with diallyl phthalate monomer as a plasticizer. 20 parts by mass, dispersed and mixed in the same manner as in Example 1, and extruded at a high speed and a high pressure [(extrusion temperature: 100 ° C., back pressure: 50 MPakg / cm 2 , shear rate: 9 × 10 4 (1 / sec )] To form a rectangular cross-section, then fired in a nitrogen gas atmosphere, and finally immersed in an alpha-olefin oligomer to obtain an extra lead holder pencil lead.

得られた替芯式ホルダー鉛筆芯は、幅7mm、厚さ0.7mm、長さ15cm、配向度0.93、曲げ強度が390MPaであった。実施例1と同様にレーザー加工機で鉛筆芯表面に、長手方向と垂直に深さ0.2mmの溝を7mm間隔で形成した。
該鉛筆芯を図1のホルダーで把持することで、実施例1と同様に、削る必要がなく、したがって削りカスが生じず、外観形状として短くなることが無いので筆記具としての使い勝手も変わらなく、高強度で折れ難く、且つ任意に折ることができ描線も安定して使うことができ、カド書きで細かい文字も書くことが可能な替芯式ホルダー鉛筆芯を得ることができた。
The obtained replaceable core holder pencil lead had a width of 7 mm, a thickness of 0.7 mm, a length of 15 cm, an orientation degree of 0.93, and a bending strength of 390 MPa. In the same manner as in Example 1, grooves with a depth of 0.2 mm were formed at intervals of 7 mm on the surface of the pencil core by a laser processing machine, perpendicular to the longitudinal direction.
By gripping the pencil lead with the holder of FIG. 1, it is not necessary to cut as in the first embodiment, and therefore no shaving residue is generated, and the appearance shape is not shortened, so the usability as a writing instrument is not changed, A high-strength, hard to break, and can be folded arbitrarily, the drawn line can be used stably, and a refill-type holder pencil lead capable of writing fine characters with a quadruple writing was obtained.

(比較例1)
配合組成物として、塩素化塩化ビニル樹脂45質量部を用い、これに天然黒鉛微粉末(平均粒度5μm)45質量部と窒化硼素(平均粒度6μm)10質量部に対し、可塑材としてジアリルフタレートモノマーを20質量部添加して、上記実施例1と同様に分散、混合し、背圧がかからず一般的な押出し圧力および速度で押し出し、断面が矩形状に成形を行ない、その後窒素ガス雰囲気中で焼成し、上記実施例1と同様にして替芯式ホルダー鉛筆芯を得た。
(Comparative Example 1)
As a blended composition, 45 parts by mass of chlorinated vinyl chloride resin is used, and 45 parts by mass of natural graphite fine powder (average particle size 5 μm) and 10 parts by mass of boron nitride (average particle size 6 μm) are mixed with diallyl phthalate monomer as a plasticizer. 20 parts by mass, dispersed and mixed in the same manner as in Example 1 above, extruding at a general extrusion pressure and speed without applying back pressure, forming a rectangular cross section, and then in a nitrogen gas atmosphere And a replacement core type pencil lead was obtained in the same manner as in Example 1 above.

得られた替芯式ホルダー鉛筆芯は、幅5mm、厚さ1mm、長さ10cm、配向度0.82、曲げ強度が240MPaであった。上記実施例1と同様にレーザー加工機で鉛筆芯表面に、長手方向と垂直に深さ0.3mmの溝を5mm間隔で形成した。
該鉛筆芯を図1のホルダーで把持したが、削る必要がなく、したがって削りカスが生じなかった。しかしながら、外観形状として短くなることが無いものの、配向度が低く、カド書きで細かい文字も書くことが可能な使い勝手を考慮すると、強度面等で課題が残る替芯式ホルダー鉛筆芯となった。
The resulting replaceable core pencil lead had a width of 5 mm, a thickness of 1 mm, a length of 10 cm, an orientation degree of 0.82, and a bending strength of 240 MPa. In the same manner as in Example 1 above, grooves with a depth of 0.3 mm were formed at intervals of 5 mm perpendicular to the longitudinal direction on the surface of the pencil core with a laser processing machine.
The pencil lead was gripped by the holder shown in FIG. 1, but it was not necessary to sharpen it. However, although the appearance is not shortened, the orientation degree is low, and considering the convenience of being able to write fine characters by writing, it has become a replaceable-type holder pencil lead that remains problematic in terms of strength and the like.

カド書きで細かい文字を好適に書くことができ、高強度で折れ難く、かつ、任意に折ることができ、描線も安定して筆記することができる替芯式ホルダー鉛筆芯に好適に用いることができる。   It is suitable for use with an extra lead holder pencil lead that can be used to write fine characters with quads, is strong and difficult to break, can be folded arbitrarily, and can be drawn with stability. it can.

10 替芯式ホルダー鉛筆芯         10 Extra lead holder pencil lead

Claims (5)

賦形性を有し、焼成後高い炭素残査収率を示す組成物を焼成してなるアモルファス状炭素中に、炭素粉末、半金属窒化物、半金属酸化物及び粘土鉱物から選ばれる体質材の一種または二種以上を、均一かつ一方向に高度に配向制御させてなる鉛筆芯と、該鉛筆芯を把持し、任意に繰出して折ることができるホルダーとを具備することを特徴とする替芯式ホルダー鉛筆芯。 In an amorphous carbon formed by firing a composition having a shapeability and showing a high carbon residue yield after firing, a constitutional material selected from carbon powder, metalloid nitride, metalloid oxide and clay mineral An extra lead comprising: a pencil lead in which one or two or more of them are uniformly and highly oriented in one direction, and a holder that holds the pencil lead and can be arbitrarily drawn out and folded. Formula holder pencil lead. 炭素粉末が黒鉛、カーボンブラック、グラフェン、カーボンナノチューブから選ばれる少なくとも1種を用いることを特徴とする請求項1記載の替芯式ホルダー鉛筆芯。   2. The replaceable core pencil lead according to claim 1, wherein the carbon powder is at least one selected from graphite, carbon black, graphene, and carbon nanotubes. 体質材が、窒化ホウ素、タルク、カオリン(カオリナイト、ハロイサイト)、シリカ、マイカ及び炭酸カルシウムから選ばれる少なくとも1種を用いることを特徴とする請求項1又は2記載の替芯式ホルダー鉛筆芯。   3. The extra lead holder pencil lead according to claim 1, wherein the extender is at least one selected from boron nitride, talc, kaolin (kaolinite, halloysite), silica, mica and calcium carbonate. 断面の形状が四角形の矩形状であることを特徴とする請求項1〜3の何れか一つに記載の替芯式ホルダー鉛筆芯。   The replaceable lead-type holder pencil lead according to any one of claims 1 to 3, wherein the cross-sectional shape is a rectangular rectangle. 表面にレーザー光を照射してカット用の傷をつけることを特徴とする請求項1〜の何れか一つに記載の替芯式ホルダー鉛筆芯。 The replaceable core pencil lead according to any one of claims 1 to 4 , wherein the surface is irradiated with a laser beam to make a cut flaw.
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JPS4973527U (en) * 1972-10-12 1974-06-26
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JP3205184B2 (en) * 1994-08-12 2001-09-04 三菱鉛筆株式会社 Fired pencil lead and method for producing the same
JP3032166U (en) * 1994-10-31 1996-12-17 有限会社マイディア Cut flat type pencil
JPH0976691A (en) * 1995-09-19 1997-03-25 Mitsubishi Pencil Co Ltd Baked pencil lead and its manufacture
JPH1088057A (en) * 1996-09-10 1998-04-07 Mitsubishi Pencil Co Ltd Fired pencil lead
JP2005343932A (en) * 2004-05-31 2005-12-15 Pentel Corp Pencil lead
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