JP2000119582A - Production of fired lead of color pencil - Google Patents
Production of fired lead of color pencilInfo
- Publication number
- JP2000119582A JP2000119582A JP10298180A JP29818098A JP2000119582A JP 2000119582 A JP2000119582 A JP 2000119582A JP 10298180 A JP10298180 A JP 10298180A JP 29818098 A JP29818098 A JP 29818098A JP 2000119582 A JP2000119582 A JP 2000119582A
- Authority
- JP
- Japan
- Prior art keywords
- fired
- core
- atmosphere
- fired lead
- lead body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、十分な発色性、描
線濃度をもちながら、経時安定性、機械的強度、即ち、
曲げ強度、引張強度、衝撃強度等に優れた、焼成芯体に
インクを含浸した焼成色鉛筆芯の製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a method for producing color inks, which has sufficient color developing properties and drawing density, while maintaining stability over time and mechanical strength.
The present invention relates to a method for producing a baked colored pencil lead obtained by impregnating a baked lead body with ink and having excellent bending strength, tensile strength, impact strength and the like.
【０００２】[0002]
【従来の技術】従来の焼成色鉛筆芯は、結合材として一
種及び／又は二種以上の粘土等が用いられ、これに窒化
硼素等の体質材、更に必要に応じて耐熱性の顔料、反応
促進材を添加、配合した配合組成物を混練し、この混練
物を押出成形した後、熱処理を経て多孔質焼成芯体と
し、この芯体の気孔中に染料および顔料から成るインク
等を充填させて色鉛筆芯としていた。この時、色鉛筆芯
の重要特性としては、機械的強度が強く、発色性が良
く、筆記描線の濃度が濃いものが要求されている。2. Description of the Related Art A conventional baked color pencil lead uses one or / and two or more kinds of clays as a binder, a body material such as boron nitride, a heat-resistant pigment if necessary, and a reaction accelerator. The kneaded mixture was kneaded with the added composition, and the kneaded product was extruded, and then subjected to a heat treatment to form a porous fired core, and the pores of the core were filled with an ink or the like comprising a dye and a pigment. I had a colored pencil lead. At this time, as the important characteristics of the color pencil lead, those having high mechanical strength, good coloring properties, and high density of writing lines are required.
【０００３】ところが、従来の焼成色鉛筆芯は機械的強
度が充分でなく、濃度および発色性においても充分なも
のが得られていないのが現状である。そこで、上記の要
求を達成するためには、充分な機械的強度を保持しつ
つ、気孔率を増加させることにより芯体に充填されるイ
ンク量を多くする必要がある。また、従来結合材として
用いられている粘土等による焼成芯体は、窒化硼素等の
体質材と粘土等の結合材の焼結力が弱く、粘土等自身の
強度も低いため、得られる焼成色鉛筆芯は実用強度に達
していないのが現状である。更に、粘土は不純物を含ん
でいるため、得られる焼成芯体は一般に有色となり、描
線の発色性に悪影響を与えることとなる。特に、淡色系
の描線のくすんだ色の原因となっている。[0003] However, at present, conventional baked color pencil cores do not have sufficient mechanical strength and do not have sufficient density and coloring properties. Therefore, in order to achieve the above requirements, it is necessary to increase the porosity while maintaining sufficient mechanical strength to increase the amount of ink to be filled in the core. In addition, the fired core made of clay or the like, which has been conventionally used as a binder, has a weak sintering force between the body material such as boron nitride and the binder such as clay, and the strength of the clay or the like itself is low. At present, the core has not reached practical strength. Further, since the clay contains impurities, the fired core obtained is generally colored, which has an adverse effect on the coloring of the drawn lines. In particular, it causes the dull color of the light-colored lines.
【０００４】本発明者らは、上記の課題等を解決する方
法として、少なくとも体質材からなる第２焼成芯体の気
孔内にペルヒドロポリシラザン含有液を充填させ、窒素
雰囲気等の不活性雰囲気中又はアンモニアガス雰囲気中
で熱処理することにより、結合材として窒化珪素を生成
させ、芯体の気孔中にインクを充填させてなる焼成色鉛
筆芯及びその製造方法を提案している（特開平８−４８
９３１号）。この製造方法等は、十分な発色性、描線濃
度をもちながら、機械的強度等に優れた焼成色鉛筆芯が
得られるものである。しかしながら、上記製造方法で
は、焼成後の芯体が空気中の水分で吸湿劣化する場合が
あり、この吸湿劣化した芯体では所期の曲げ強度等が得
られないという若干の課題を有している。As a method for solving the above-mentioned problems, the present inventors fill at least the pores of a second fired core made of a constitutional material with a perhydropolysilazane-containing liquid, and apply the perhydropolysilazane-containing liquid in an inert atmosphere such as a nitrogen atmosphere. Alternatively, there has been proposed a fired colored pencil lead obtained by forming silicon nitride as a binder by heat treatment in an ammonia gas atmosphere, and filling the pores of the lead with ink (Japanese Patent Laid-Open No. 8-48).
No. 931). This production method and the like can provide a fired colored pencil lead excellent in mechanical strength and the like while having sufficient coloring properties and drawing line density. However, in the above manufacturing method, there is a case where the core after firing may be deteriorated by moisture absorption in the air due to moisture in the air. I have.
【０００５】この課題を解決する方法として、さらに本
発明者らはペルヒドロポリシラザン充填後の熱処理を１
２００〜１４００℃とした製造方法を提案している（特
願平１０−２６９７４４号）。しかし、上記のように熱
処理温度を１０００℃以上に設定すると、芯体の気孔内
に残った微量の有機溶剤などの炭素化により芯が黒ず
み、彩度の高い色の芯を得にくいという点に若干の課題
がある。As a method for solving this problem, the present inventors further carried out a heat treatment after filling perhydropolysilazane for 1 hour.
A production method at 200 to 1400 ° C. has been proposed (Japanese Patent Application No. 10-269744). However, when the heat treatment temperature is set to 1000 ° C. or higher as described above, the core is darkened due to carbonization of a trace amount of organic solvent remaining in the pores of the core, and it is difficult to obtain a core with high color saturation. There are some challenges.
【０００６】また、本発明者らは、彩度の高い焼成鉛筆
芯として、少なくとも体質材からなる第２焼成芯体の気
孔内にポリシラザン類含有液を充填させ、大気中で熱処
理することにより、結合材として酸化珪素を生成させ、
芯体の気孔中にインクを充填させてなる焼成色鉛筆芯及
びその製造方法を提案している（特願平１０−１９０３
９５号、同１０−１９０３９６号）。しかし、結合材を
酸化珪素とした場合、窒化珪素と同程度の強度とする
と、生成する気孔量が小さく硬く、書き味、着色力の点
で窒化珪素芯に及ばないという点に若干の課題がある。Further, the present inventors have proposed that a polysilazane-containing liquid is filled into pores of at least a second fired core made of a constitutional material as a fired pencil lead having high chroma, and heat-treated in the air. Producing silicon oxide as a binder,
A fired colored pencil lead in which ink is filled in pores of a lead body and a method for producing the same have been proposed (Japanese Patent Application No. 10-1903).
No. 95, No. 10-190396). However, when silicon oxide is used as the binder, if the strength is about the same as that of silicon nitride, there is a slight problem in that the amount of generated pores is small and hard, and the writing quality and coloring power are not as good as the silicon nitride core. is there.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、上記
従来技術の課題を解決すると共に、上記発明者らの先行
技術を更に改良することであり、格段に優れた機械的強
度、鮮やかで優れた発色性及び滑らかな書き味を有する
焼成色鉛筆芯の製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to further improve the prior art of the present inventors. An object of the present invention is to provide a method for producing a baked color pencil lead having excellent color developability and smooth writing taste.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために鋭意研究を行った結果、第２焼成芯体
の気孔内にペルヒドロポリシラザン含有液を充填させ、
焼成して窒化珪素を生成させた後、特定の雰囲気、か
つ、特定の温度で焼成することによって解決し得ること
を見い出し、本発明を完成するに至ったのである。すな
わち、本発明の焼成色鉛筆芯の製造方法は、少なくとも
体質材と有機質の賦形材を含む配合組成物を混練、押出
成形、非酸化性雰囲気で焼成することにより、該有機質
の賦形材が炭素化された炭素をバインダーとする第１焼
成芯体を形成し、該第１焼成芯体を酸化雰囲気中で加熱
して炭素のバインダーを酸化除去して第２焼成芯体を形
成し、該第２焼成芯体の気孔内にペルヒドロポリシラザ
ン含有液を充填させ、窒素雰囲気等の不活性雰囲気中又
はアンモニアガス雰囲気中にて１０００℃以上で焼成し
て窒化珪素を生成させた後、酸化雰囲気中にて６００℃
以上で焼成して第３焼成芯体を得、更に該第３焼成芯体
の気孔内にインクを充填させることを特徴とする。な
お、本発明で規定する「窒素雰囲気等の不活性雰囲気
中」とは、窒素ガス雰囲気中、または、アルゴンガス雰
囲気中等の不活性ガス雰囲気中をいう。Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, filled the pores of the second fired core with a perhydropolysilazane-containing liquid,
After firing to produce silicon nitride, it was found that the problem could be solved by firing in a specific atmosphere and at a specific temperature, and the present invention was completed. That is, the method for producing a fired color pencil lead of the present invention comprises kneading a compounded composition containing at least a body material and an organic excipient, extruding, and firing in a non-oxidizing atmosphere, whereby the organic excipient is obtained. Forming a first fired core using carbonized carbon as a binder, heating the first fired core in an oxidizing atmosphere to oxidize and remove the carbon binder to form a second fired core, After the perhydropolysilazane-containing liquid is filled in the pores of the second fired core, and fired at 1000 ° C. or higher in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere, silicon nitride is generated. 600 ° C in
The third fired core is obtained by firing as described above, and the pores of the third fired core are filled with ink. The “in an inert atmosphere such as a nitrogen atmosphere” defined in the present invention refers to a nitrogen gas atmosphere or an inert gas atmosphere such as an argon gas atmosphere.
【０００９】[0009]
【発明の実施の形態】以下に、本発明の実施形態を詳し
く説明する。本発明の焼成色鉛筆芯の製造方法は、ま
ず、少なくとも体質材と有機質の賦形材を含む配合組成
物を混練、押出成形、非酸化性雰囲気で焼成することに
より、該有機質の賦形材が炭素化された炭素をバインダ
ーとする第１焼成芯体を得、該第１焼成芯体を酸化雰囲
気中で加熱して炭素のバインダーを酸化除去して第２焼
成芯体を得、次いで、該第２焼成芯体の気孔内にペルヒ
ドロポリシラザン含有液を充填させ、窒素雰囲気等の不
活性雰囲気中又はアンモニアガス雰囲気中にて１０００
℃以上で焼成して窒化珪素を生成させた後、酸化雰囲気
中にて６００℃以上で焼成して第３焼成芯体を得、更に
該第３焼成芯体の気孔内にインクを充填させることを特
徴とする。Embodiments of the present invention will be described below in detail. The method for producing a fired colored pencil lead of the present invention comprises first kneading a compounded composition containing at least a body material and an organic excipient, extruding, and firing in a non-oxidizing atmosphere, whereby the organic excipient is obtained. A first calcined core using carbonized carbon as a binder is obtained, and the first calcined core is heated in an oxidizing atmosphere to oxidize and remove the carbon binder to obtain a second calcined core. The perhydropolysilazane-containing liquid is filled in the pores of the second calcined core, and the perforated polysilazane-containing liquid is charged in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere.
Baking at a temperature of at least 600 ° C. to produce silicon nitride, and then baking at a temperature of at least 600 ° C. in an oxidizing atmosphere to obtain a third fired core, and further filling the pores of the third fired core with ink. It is characterized by.
【００１０】本発明において、第１焼成芯体は、少なく
とも体質材と有機質の賦形材を含む配合組成物より得ら
れる。第１焼成芯体に用いる体質材として、まず留意す
ることは耐熱温度である。本発明の場合、窒素雰囲気等
の不活性雰囲気中又はアンモニアガス雰囲気中にて１０
００℃以上で焼成する工程があるため、前記温度で劣
化、変質、焼結等を起こさない体質材を選択する必要が
ある。従って、本発明において使用できる具体的な体質
材としては、窒化硼素、アルミナ、ジルコニア等が挙げ
られるが、その物性、形状から窒化硼素が特に好まし
い。In the present invention, the first fired core is obtained from a compound composition containing at least a filler and an organic excipient. The first thing to keep in mind as the constitutional material used for the first fired core is the heat-resistant temperature. In the case of the present invention, in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere,
Since there is a step of firing at 00 ° C. or higher, it is necessary to select a constitutional material that does not cause deterioration, alteration, sintering, or the like at the above temperature. Accordingly, specific examples of the constitutional material that can be used in the present invention include boron nitride, alumina, and zirconia. Boron nitride is particularly preferred in view of its physical properties and shape.
【００１１】また、第１焼成芯体に用いる有機質の賦形
材としては、例えば、ポリ塩化ビニル樹脂、塩素化ポリ
塩化ビニル樹脂、ポリビニルアルコールなどの熱可塑性
樹脂、フラン樹脂、フェノール樹脂、エポキシ樹脂など
の熱硬化性樹脂、リグニン、セルロース、トラガントガ
ムなどの天然高分子物質、石油アスファルト、コールタ
ールピッチ、ナフサ分解ピッチ、合成樹脂の乾留ピッチ
などのピッチ類等いずれも使用可能で、当然これら数種
類の混合物も使用できる。更に、高せん断力を加えて行
う混練時の特性向上及び押出成形の特性向上の目的で、
水、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）、プロピレンカーボナー
ト、アルコール類、ケトン類、エステル類など有機質の
賦形材の可塑剤又は溶剤の一種又は二種以上を、必要に
応じて上記配合組成物に添加しても良い。The organic excipient used for the first fired core includes, for example, thermoplastic resins such as polyvinyl chloride resin, chlorinated polyvinyl chloride resin, polyvinyl alcohol, furan resin, phenol resin, and epoxy resin. Thermosetting resins such as lignin, cellulose, natural polymer materials such as tragacanth gum, petroleum asphalt, coal tar pitch, naphtha cracking pitch, pitches such as synthetic resin pitch, etc. Mixtures can also be used. Furthermore, for the purpose of improving the characteristics at the time of kneading performed by applying a high shear force and improving the characteristics of extrusion molding,
Plasticizers for organic excipients such as water, dioctyl phthalate (DOP), dibutyl phthalate (DBP), tricresyl phosphate (TCP), dioctyl adipate (DOA), propylene carbonate, alcohols, ketones and esters One or two or more solvents may be added to the above composition as needed.
【００１２】これら配合組成物をヘンシェルミキサー、
加圧ニーダー、二本ロール等で十分混練した後、押出成
形機により細線状等に押出成形し、次いで、窒素雰囲気
中又はアルゴンガスなどの不活性ガス中等の非酸化性雰
囲気中で焼成することにより、有機質の賦形材が炭素化
された炭素をバインダーとする第１焼成芯体が得られ
る。[0012] These blended compositions are used in a Henschel mixer,
After sufficiently kneading with a pressure kneader, two rolls, etc., extrude into a fine wire shape using an extruder, and then fire in a non-oxidizing atmosphere such as a nitrogen atmosphere or an inert gas such as an argon gas. As a result, a first fired core using the carbonized carbon as the organic excipient is obtained.
【００１３】本発明において、第２焼成芯体は、上記で
得られた第１焼成芯体を酸化雰囲気中で加熱することに
より、炭素のバインダーを酸化除去して得られる。な
お、第１焼成芯体にペルヒドロポリシラザン含有液を含
浸せしめ、窒素雰囲気等の不活性雰囲気中又はアンモニ
アガス雰囲気中での熱処理により窒化珪素を生成させた
焼成芯体を得た後に、酸化雰囲気中で加熱し、第１焼成
芯体の炭素のバインダーを酸化除去することにより、ペ
ルヒドロポリシラザン含有液の含浸前の焼成芯体の強度
を満足できる範囲内で強めてもよい。In the present invention, the second fired core is obtained by heating the first fired core obtained above in an oxidizing atmosphere to oxidize and remove the carbon binder. The first fired core is impregnated with a liquid containing perhydropolysilazane, and a fired core in which silicon nitride is generated by heat treatment in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere is obtained. The strength of the fired core body before impregnation with the perhydropolysilazane-containing liquid may be increased within a range that can be satisfied by heating in the medium to oxidize and remove the carbon binder of the first fired core body.
【００１４】本発明において、ペルヒドロポリシラザン
含有液を充填させ、窒素雰囲気等の不活性雰囲気中又は
アンモニアガス雰囲気中での熱処理により高強度の焼成
芯体を得るのに有用な芯体は、気孔が微細で充分に存在
し、かつ、均一に分散していて、体質材が高配向してい
る芯体となることが必要である。これによりペルヒドロ
ポリシラザン含有液は、芯体中に微細で均一に分散して
含浸され、窒化珪素が芯体中に微細で均一に分散して生
成するものとなる。In the present invention, a core useful for obtaining a high-strength fired core by filling with a perhydropolysilazane-containing liquid and performing heat treatment in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere is a pore. It is necessary that the core material is fine and sufficiently present, uniformly dispersed, and the core material is highly oriented. As a result, the perhydropolysilazane-containing liquid is finely and uniformly dispersed and impregnated in the core, and silicon nitride is finely and uniformly dispersed in the core to be generated.
【００１５】第２焼成芯体に充填させるペルヒドロポリ
シラザン含有液は、セラミックス前駆体ポリマーであ
り、ペルヒドロポリシラザンを有機溶剤で溶解したもの
であり、該ペルヒドロポリシラザン含有液が第２焼成芯
体に含浸可能なものであれば、使用する有機溶剤は特に
限定されず、いずれも使用可能である。使用できる有機
溶剤としては、例えば、ベンゼン、トルエン、キシレ
ン、エーテル、ＴＨＦ、塩化メチレン、四塩化炭素等、
芳香族炭化水素系等の有機溶剤が挙げられる。The perhydropolysilazane-containing liquid to be filled in the second fired core is a ceramic precursor polymer, and is obtained by dissolving perhydropolysilazane in an organic solvent. The organic solvent to be used is not particularly limited as long as the organic solvent can be impregnated, and any of them can be used. Examples of usable organic solvents include, for example, benzene, toluene, xylene, ether, THF, methylene chloride, carbon tetrachloride, and the like.
Organic solvents such as aromatic hydrocarbons are exemplified.
【００１６】本発明において、ペルヒドロポリシラザン
は、主鎖に〔−Ｓｉ−Ｎ−〕構造を有し、側鎖に水素の
みが結合しているものである。そのため、窒素雰囲気等
の不活性雰囲気中又はアンモニアガス雰囲気中での熱分
解で消去するのは水素のみであり、非常に高い収率で窒
化珪素が得られるものである。また、メチル基等の有機
成分を含まないため、炭素を含まない無色透明で高純度
の窒化珪素が得られる。In the present invention, perhydropolysilazane has a [-Si-N-] structure in the main chain, and has only hydrogen bonded to a side chain. Therefore, only hydrogen is erased by thermal decomposition in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere, and silicon nitride can be obtained with a very high yield. Further, since it does not contain an organic component such as a methyl group, colorless, transparent and high-purity silicon nitride containing no carbon can be obtained.
【００１７】更に、窒化珪素が他の焼結法より低い６０
０℃という低温度で得られるものであるが、薄膜等と異
なり、鉛筆芯の場合、芯径にもより一概できるものでは
ないが、６００℃程度の温度域では経時的に安定な芯体
が得にくく、１０００℃以上で焼成する必要があり、好
ましくは、１２００〜１４００℃、さらに書き味等も考
慮すると１２００〜１３００℃で焼成することが望まし
い。以上より、本発明の焼成色鉛筆芯における第２焼成
芯体にペルヒドロポリシラザン含有液を含浸したものの
焼成温度としては、１２００〜１３００℃が好適であ
る。Furthermore, silicon nitride has a lower 60% than other sintering methods.
Although it can be obtained at a low temperature of 0 ° C., unlike a thin film, in the case of a pencil lead, the core diameter cannot be generally determined, but a stable core over time in a temperature range of about 600 ° C. It is difficult to obtain, and it is necessary to bake at 1000 ° C. or higher, preferably 1200 to 1400 ° C., and more preferably 1200 to 1300 ° C. in consideration of writing taste and the like. As described above, the firing temperature of the fired colored pencil lead of the present invention obtained by impregnating the second fired core body with the perhydropolysilazane-containing liquid is preferably 1200 to 1300 ° C.
【００１８】第２焼成芯体にペルヒドロポリシラザン含
有液を充填させる方法としては、第２焼成芯体をペルヒ
ドロポリシラザン含有液中に浸漬し、必要に応じて加
熱、減圧、加圧等の条件下で含浸させることにより行う
ことができる。As a method for filling the second fired core with the perhydropolysilazane-containing liquid, the second fired core is immersed in the perhydropolysilazane-containing liquid, and if necessary, heated, depressurized, pressurized or the like. This can be done by impregnating underneath.
【００１９】本発明において、上記ペルヒドロポリシラ
ザン含有液を充填せしめた第２焼成芯体を窒素雰囲気等
の不活性雰囲気中又はアンモニアガス雰囲気中にて１０
００℃以上で焼成することにより、芯体中に非晶質の窒
化珪素を生成させた焼成芯体が得られることとなる。更
に、高強度の焼成芯体を得るために、必要に応じてペル
ヒドロポリシラザン含有液の含浸、焼成工程を繰り返し
行ってもよい。なお、繰り返し含浸、焼成の場合、時
間、エネルギー節減のため、最終焼成のみ１０００℃以
上で行い、それより前の焼成を６００℃程度で行っても
目的の高強度等となる色鉛筆芯が得られる。また、第２
焼成芯体を容器に入れ、求める強度に対して必要十分な
量のペルヒドロポリシラザン含有液をこの容器に注入
し、芯体を含有液に浸漬したまま１０００℃以上で焼成
すれば、ペルヒドロポリシラザンの充填、焼成工程を１
回で終了させることが可能である。In the present invention, the second fired core filled with the above-mentioned perhydropolysilazane-containing liquid is treated in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere.
By firing at 00 ° C. or higher, a fired core in which amorphous silicon nitride is formed in the core can be obtained. Furthermore, in order to obtain a high-strength calcined core, the impregnation with the perhydropolysilazane-containing liquid and the calcining step may be repeated as necessary. In the case of repeated impregnation and baking, in order to save time and energy, only the final baking is performed at 1000 ° C. or more, and even if the previous baking is performed at about 600 ° C., a color pencil lead having the desired high strength or the like can be obtained. . Also, the second
The fired core is placed in a container, a necessary and sufficient amount of a perhydropolysilazane-containing liquid for the required strength is poured into the container, and the core is immersed in the liquid and fired at 1000 ° C. or more to obtain perhydropolysilazane. Filling and firing process
It is possible to end in times.
【００２０】本発明において、上記により得られた焼成
芯体は、ペルヒドロポリシラザン含有液の有機溶剤等が
気孔内に微量に残って炭素化し、やや灰色を帯びること
があるため、さらに酸化雰囲気中にて６００℃以上で焼
成し、残留炭素を除去して白色の第３焼成芯体を得るこ
とが必要である。残留炭素を除去するには、少なくとも
６００℃は必要であり、また除去効率を向上させるに
は、より高い温度とする必要があるが、その際、体質材
の劣化温度を考慮する必要がある。上記で好ましい体質
材として例示した窒化硼素の場合では、９００℃を越え
ると酸化して酸化硼素となり、潤滑性が失われるため、
好ましくは、７００℃〜９００℃が望ましい。また、酸
化雰囲気としては、通常の空気でも良いが、除去効率を
向上させるため酸素を混合させてもよく、１００％の酸
素を用いることも可能である。ただし、窒化珪素、窒化
硼素等は水分を含んだ状態で高温下で加熱すると酸化さ
れやすいため、十分に乾燥した雰囲気とすることが肝要
である。In the present invention, the fired core obtained above may be carbonized due to trace amounts of the organic solvent and the like in the perhydropolysilazane-containing liquid remaining in the pores, and may become slightly gray. At 600 ° C. or higher to remove the residual carbon and obtain a white third fired core. At least 600 ° C. is required to remove the residual carbon, and a higher temperature is required to improve the removal efficiency. At that time, it is necessary to consider the deterioration temperature of the body material. In the case of boron nitride exemplified above as a preferred constitutional material, when it exceeds 900 ° C., it oxidizes to boron oxide and loses lubricity.
Preferably, 700 ° C to 900 ° C is desirable. As the oxidizing atmosphere, ordinary air may be used, but oxygen may be mixed for improving the removal efficiency, and 100% oxygen may be used. However, since silicon nitride, boron nitride, and the like are easily oxidized when heated at a high temperature in a state of containing water, it is important to provide a sufficiently dry atmosphere.
【００２１】本発明において、焼成色鉛筆芯は、上記で
得た第３焼成芯体の気孔内に、インクを充填させること
により得られる。第３焼成芯体に含浸させるインクとし
ては、従来公知の色鉛筆芯用のものであればいずれも使
用することができる。例えば、染料、顔料等の着色剤
を、動植物油、合成油、アルコール類、炭化水素油、水
等に溶解、分散させ、あるいは必要に応じて樹脂、界面
活性剤等を更に添加し製造された一般的に用いられてい
る印刷用インク、スタンプインク、ボールペンインク、
水性筆記用インク等が用いられる。また、第３焼成芯体
にインクを含浸させる方法としては、第３焼成芯体をイ
ンク中に浸漬し、加熱、減圧、加圧等の条件下で気孔内
に充填させる。さらに、繰り返し含浸を行ってもよい。In the present invention, a fired pencil lead is obtained by filling the pores of the third fired core obtained above with ink. As the ink to be impregnated into the third fired core, any conventionally known ink for a colored pencil can be used. For example, dyes, coloring agents such as pigments, animal and vegetable oils, synthetic oils, alcohols, hydrocarbon oils, dissolved and dispersed in water, etc., or, if necessary, a resin, further manufactured by adding a surfactant and the like. Commonly used printing ink, stamp ink, ballpoint pen ink,
An aqueous writing ink or the like is used. As a method for impregnating the third fired core with the ink, the third fired core is immersed in the ink and filled in the pores under conditions such as heating, decompression, and pressurization. Further, repeated impregnation may be performed.
【００２２】このように構成される焼成色鉛筆芯の製造
方法では、下記の作用等を有することとなる。ペルヒド
ロポリシラザンを充填させた第２焼成芯体を窒素雰囲気
等の不活性雰囲気中又はアンモニアガス雰囲気中にて焼
成しても気孔が微細なため、ペルヒドロポリシラザン含
有液の有機溶剤が微量残ることは避け難く、その結果炭
素化し、得られる芯体はやや灰色を帯びるものであった
が、本発明ではペルヒドロポリシラザンを充填させた第
２焼成芯体を窒素雰囲気等の不活性雰囲気中又はアンモ
ニアガス雰囲気中にて１０００℃以上で焼成して窒化珪
素を生成させた後、酸化雰囲気中にて６００℃以上で焼
成して残留炭素を除去することにより、白色の第３焼成
芯体が得られ、この芯体にインクを充填させた芯の描線
は彩度が高く鮮やかなものとなる。The method for producing a fired pencil lead having the above-described structure has the following functions. Even if the second fired core filled with perhydropolysilazane is fired in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere, the pores are fine, so that a trace amount of the organic solvent in the perhydropolysilazane-containing liquid remains. Is difficult to avoid, resulting in carbonization, and the resulting core is slightly grayish. However, in the present invention, the second fired core filled with perhydropolysilazane is treated in an inert atmosphere such as a nitrogen atmosphere or in an ammonia atmosphere. After firing at 1000 ° C. or higher in a gas atmosphere to generate silicon nitride, firing at 600 ° C. or higher in an oxidizing atmosphere to remove residual carbon, a white third fired core is obtained. The drawn line of the core filled with ink in the core has a high saturation and is vivid.
【００２３】[0023]
【実施例】次に、本発明を実施例により、更に具体的に
説明するが、本発明はこの実施例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, but the present invention is not limited to these examples.
【００２４】 （実施例１） 窒化硼素 ４１．３重量％ 塩化ビニル樹脂 ４１．３重量％ ジオクチルフタレート（ＤＯＰ） １６．５重量％ ステアリン酸亜鉛 ０．９重量％ 上記配合組成物を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、細線状に押出成
形し、これから残留する可塑剤を除去すべく空気中で１
８０℃にて加熱処理して、しかるのち窒素雰囲気中にて
１０００℃まで昇温させた後、１０００℃にて焼成して
第１焼成芯体を得た。Example 1 Boron nitride 41.3% by weight Vinyl chloride resin 41.3% by weight Dioctyl phthalate (DOP) 16.5% by weight Zinc stearate 0.9% by weight The above composition was mixed with a Henschel mixer. After dispersing and kneading with a pressure kneader and two rolls, the mixture is extruded into a fine wire and then removed in air to remove the residual plasticizer.
A heat treatment was performed at 80 ° C., and then the temperature was raised to 1000 ° C. in a nitrogen atmosphere, followed by firing at 1000 ° C. to obtain a first fired core.
【００２５】次いで、この第１焼成芯体を大気中、約７
００℃で加熱焼成して残留している炭素化した樹脂分を
除去し、白色の第２焼成芯体を得た。この第２焼成芯体
に、ペルヒドロポリシラザン含有液を室温下で１日含浸
後、窒素雰囲気中で６００℃まで昇温させて、６００℃
にて焼成して焼成芯体を得た。次に、もう一度、この焼
成芯体にペルヒドロポリシラザン含有液を含浸し、窒素
雰囲気中で１２５０℃まで昇温して、１２５０℃にて焼
成した後、７００℃まで降温し、大気中で７００℃にて
焼成して、直径０．５７ｍｍの白色の第３焼成芯体を得
た。次に、桃色インクに上記第３焼成芯体を浸し、７０
℃で２４時間放置した。この桃色インクが充填された第
３焼成芯体表面をアルコールで洗浄し、直径０．５７ｍ
ｍの桃色の焼成色鉛筆芯を得た。Next, the first fired core is placed in the atmosphere for about 7 hours.
The remaining carbonized resin was removed by heating and baking at 00 ° C. to obtain a white second baking core. After impregnating the second fired core body with the perhydropolysilazane-containing liquid at room temperature for one day, the temperature was raised to 600 ° C. in a nitrogen atmosphere, and 600 ° C.
To obtain a fired core. Next, once more, the fired core body is impregnated with a perhydropolysilazane-containing liquid, heated to 1250 ° C. in a nitrogen atmosphere, fired at 1250 ° C., cooled to 700 ° C., and then heated to 700 ° C. in air. To obtain a white third fired core having a diameter of 0.57 mm. Next, the third fired core body is immersed in pink ink,
Left at 24 ° C. for 24 hours. The surface of the third fired core body filled with the pink ink was washed with alcohol, and the diameter was 0.57 m.
m of a baked colored pencil lead was obtained.
【００２６】（比較例１）実施例１と同様の第２焼成芯
体を得た後、実施例１と同条件下で、ペルヒドロポリシ
ラザン含有液の含浸、窒素雰囲気中での焼成を２度繰り
返し、窒素雰囲気中で室温まで降温させ、直径０．５７
ｍｍのやや灰味の白色の第３焼成芯体を得た。さらに、
実施例１と同様に桃色インクに上記第３焼成芯体を浸す
ことなどにより染色し、直径０．５７ｍｍの桃色の焼成
色鉛筆芯を得た。(Comparative Example 1) After obtaining a second fired core similar to that of Example 1, impregnation with a perhydropolysilazane-containing liquid and firing in a nitrogen atmosphere were performed twice under the same conditions as in Example 1. Repeatedly cooling down to room temperature in a nitrogen atmosphere,
A slightly ashy white third calcined core having a thickness of 2 mm was obtained. further,
The third fired core was soaked in pink ink in the same manner as in Example 1 to obtain a fired pink pencil lead having a diameter of 0.57 mm.
【００２７】（比較例２）実施例１と同様の第２焼成芯
体を得た後、これに、ペルヒドロポリシラザン含有液を
室温下で１日含浸後、大気中で６００℃まで昇温させ
て、６００℃にて焼成して焼成芯体を得た。次に、もう
一度、ペルヒドロポリシラザン含有液の含浸し、大気中
で１２５０℃まで昇温し、１２５０℃にて焼成して、直
径０．５７ｍｍの白色の第３焼成芯体を得た。次に、桃
色インクに上記第３焼成芯体を浸し、７０℃で２４時間
放置した。この桃色インクが充填された第３焼成芯体表
面をアルコールで洗浄し、直径０．５７ｍｍの桃色の焼
成色鉛筆芯を得た。(Comparative Example 2) A second fired core similar to that of Example 1 was obtained, impregnated with a perhydropolysilazane-containing solution at room temperature for one day, and then heated to 600 ° C in air. And fired at 600 ° C. to obtain a fired core. Next, the liquid was again impregnated with a perhydropolysilazane-containing liquid, heated to 1250 ° C. in the air, and fired at 1250 ° C. to obtain a white third fired core having a diameter of 0.57 mm. Next, the third fired core was immersed in pink ink and left at 70 ° C. for 24 hours. The surface of the third fired core filled with the pink ink was washed with alcohol to obtain a fired pink pencil lead having a diameter of 0.57 mm.
【００２８】上記実施例１及び比較例１、２で得られた
焼成色鉛筆芯について、ＪＩＳ−Ｓ−６００５−１９８
９に準拠して曲げ強度平均値（ＭＰａ）、並びに、濃度
（Ｖ）、彩度（Ｃ）及び官能評価による書き味について
評価した。これらの結果を下記表１に示す。The baked colored pencil cores obtained in Example 1 and Comparative Examples 1 and 2 were subjected to JIS-S-6005-198.
The average bending strength (MPa), the density (V), the saturation (C) and the writing taste by the sensory evaluation were evaluated in accordance with No. 9. The results are shown in Table 1 below.
【００２９】[0029]
【表１】 [Table 1]
【００３０】上記表１の結果から明らかなように、本発
明範囲の実施例１の焼成色鉛筆芯は、本発明の範囲外と
なる比較例１及び２に較べて、彩度、濃度とも同等以上
で、着色性に優れ、曲げ強度が強く、また、書き味に優
れている焼成色鉛筆芯が得られることが判明した。As is evident from the results in Table 1, the baked color pencil lead of Example 1 in the scope of the present invention has the same saturation and density as those of Comparative Examples 1 and 2 which are out of the scope of the present invention. It was found that a baked color pencil lead having excellent coloring properties, high bending strength, and excellent writing taste was obtained.
【００３１】[0031]
【発明の効果】本発明によれば、少なくとも体質材と炭
素のバインダーからなる第１焼成芯体を酸化雰囲気中で
加熱して炭素のバインダーを酸化除去して形成した第２
焼成芯体の気孔内に、ペルヒドロポリシラザン含有液を
充填し、１０００℃以上で焼成して窒化珪素を生成させ
た後、酸化雰囲気で加熱して残留炭素を除去することに
より、機械的強度に優れ、実用上折れ難く、きわめて鮮
やかで優れた発色性と良好な書き味を有する焼成色鉛筆
芯の製造方法が提供される。According to the present invention, the second fired core formed by heating the first fired core made of at least the body material and the carbon binder in an oxidizing atmosphere to oxidize and remove the carbon binder is formed.
The pores of the fired core body are filled with a perhydropolysilazane-containing liquid and fired at 1000 ° C. or higher to generate silicon nitride, and then heated in an oxidizing atmosphere to remove residual carbon, thereby increasing mechanical strength. Provided is a method for producing a fired colored pencil lead which is excellent, hardly broken in practical use, extremely vivid and has excellent color developability and good writing taste.
Claims (1)
む配合組成物を混練、押出成形、非酸化性雰囲気で焼成
することにより、該有機質の賦形材が炭素化された炭素
をバインダーとする第１焼成芯体を形成し、該第１焼成
芯体を酸化雰囲気中で加熱して炭素のバインダーを酸化
除去して第２焼成芯体を形成し、該第２焼成芯体の気孔
内にペルヒドロポリシラザン含有液を充填させ、窒素雰
囲気等の不活性雰囲気中又はアンモニアガス雰囲気中に
て１０００℃以上で焼成して窒化珪素を生成させた後、
酸化雰囲気中にて６００℃以上で焼成して第３焼成芯体
を得、更に該第３焼成芯体の気孔内にインクを充填させ
ることを特徴とする焼成色鉛筆芯の製造方法。1. A kneading composition comprising at least a body material and an organic excipient, kneading, extruding, and firing in a non-oxidizing atmosphere to convert the carbonized carbon of the organic excipient into a binder. A first fired core to be formed, and heating the first fired core in an oxidizing atmosphere to oxidize and remove the carbon binder to form a second fired core; Is filled with a perhydropolysilazane-containing liquid, and fired at 1000 ° C. or more in an inert atmosphere such as a nitrogen atmosphere or an ammonia gas atmosphere to generate silicon nitride.
A method for producing a fired pencil lead, comprising firing at 600 ° C. or higher in an oxidizing atmosphere to obtain a third fired core, and further filling ink into pores of the third fired core.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10298180A JP2000119582A (en) | 1998-10-20 | 1998-10-20 | Production of fired lead of color pencil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10298180A JP2000119582A (en) | 1998-10-20 | 1998-10-20 | Production of fired lead of color pencil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000119582A true JP2000119582A (en) | 2000-04-25 |
Family
ID=17856260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10298180A Withdrawn JP2000119582A (en) | 1998-10-20 | 1998-10-20 | Production of fired lead of color pencil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000119582A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299677B1 (en) * | 1996-06-25 | 2001-10-09 | Borden Chemical, Inc. | Binders for cores and molds |
| US6709501B2 (en) | 2001-05-25 | 2004-03-23 | Mitsubishi Pencil Kabushiki Kaisha | Baked color pencil lead and process for producing the same |
-
1998
- 1998-10-20 JP JP10298180A patent/JP2000119582A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299677B1 (en) * | 1996-06-25 | 2001-10-09 | Borden Chemical, Inc. | Binders for cores and molds |
| US6709501B2 (en) | 2001-05-25 | 2004-03-23 | Mitsubishi Pencil Kabushiki Kaisha | Baked color pencil lead and process for producing the same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20060110 |