JP6257449B2 - Firing solid drawing material - Google Patents
Firing solid drawing material Download PDFInfo
- Publication number
- JP6257449B2 JP6257449B2 JP2014114136A JP2014114136A JP6257449B2 JP 6257449 B2 JP6257449 B2 JP 6257449B2 JP 2014114136 A JP2014114136 A JP 2014114136A JP 2014114136 A JP2014114136 A JP 2014114136A JP 6257449 B2 JP6257449 B2 JP 6257449B2
- Authority
- JP
- Japan
- Prior art keywords
- drawing material
- fired
- solid drawing
- dye
- resin
- 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.)
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- 239000007787 solid Substances 0.000 title claims description 97
- 238000010304 firing Methods 0.000 title description 5
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 45
- 229910052582 BN Inorganic materials 0.000 claims description 25
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
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- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- RJZLMBIYRSBCDQ-UHFFFAOYSA-N 6-amino-5-[[2-[ethyl(phenyl)sulfamoyl]phenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonic acid Chemical compound CCN(C1=CC=CC=C1)S(=O)(=O)C1=CC=CC=C1N=NC1=C(N)C=CC2=C1C(O)=CC(=C2)S(O)(=O)=O RJZLMBIYRSBCDQ-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、強度、耐光性を損なわず、裏うつりのしない、色相、消しゴム消去性に優れた蛍光などのアンダーライン用途等に好適な焼成固形描画材に関する。 The present invention relates to a calcined solid drawing material suitable for underline applications such as fluorescence, which does not impair strength and light resistance, does not suffer from back-faced, and has excellent hue and eraser erasability.
従来の「消しゴムで消去可能な焼成色鉛筆芯」としては、例えば、白色又は淡色の多孔質の芯体を製造後に、その気孔内に染料インクを充填して製造するものが主であった（例えば、特許文献１参照）。
しかしながら、この色鉛筆芯の芯体強度は、白色又は淡色の多孔質の芯体の強度に依存したものとなり、また、染料の耐候性、色相等も何ら強化されることはないなどの課題があるのが現状であった。
As the conventional “fired colored pencil core erasable with an eraser”, for example, a white or light-colored porous core body is manufactured, and a dye ink is filled in the pores after manufacturing the core (for example, , See Patent Document 1).
However, the core strength of the colored pencil lead depends on the strength of the white or light-colored porous core, and there is a problem that the weather resistance, hue, etc. of the dye are not enhanced at all. Was the current situation.
一方、蛍光固形描画材としては、例えば、蛍光顔料、ワックス類、常温で固体である脂肪酸及びガードナー値４以下の粘着付与樹脂からなる蛍光固形筆記材（例えば、特許文献２参照）などが知られている。
しかしながら、この種の蛍光固形筆記材は、非焼成のものであり、強度が脆弱となるなどの課題があるのが現状であった。
On the other hand, as a fluorescent solid drawing material, for example, a fluorescent solid writing material (for example, see Patent Document 2) made of a fluorescent pigment, a wax, a fatty acid that is solid at room temperature, and a tackifier resin having a Gardner value of 4 or less is known. ing.
However, this type of fluorescent solid writing material is unfired and has a problem such as weakness in strength.
本発明は、上記した従来技術の課題、現状等に鑑み、これらを解消しようとするものであり、強度、耐光性を損なわず、裏うつりのしない、色相、消しゴム消去性に優れた蛍光などのアンダーライン用途等に好適な焼成固形描画材を提供することを目的とする。 The present invention is intended to solve the above-described problems of the prior art, the current situation, and the like, and does not impair the strength and light resistance, and does not cause back lining, such as fluorescence excellent in hue and eraser erasability. It aims at providing the baking solid drawing material suitable for underline use etc.
本発明者らは、上記従来の課題等に鑑み、鋭意検討した結果、固形描画材芯体の気孔内に染料を内包した樹脂などを含浸させることによって、上記目的の焼成固形描画材が得られることを見出し、本発明を完成するに至ったものである。 As a result of intensive studies in view of the above-described conventional problems, the present inventors can obtain the above-mentioned fired solid drawing material by impregnating a resin containing a dye in the pores of the solid drawing material core. As a result, the present invention has been completed.
すなわち、本発明は、次の（１）〜（６）に存する。
（１） 固形描画材芯体の気孔内に染料を溶解した下記Ａ群の有機溶剤に可溶な樹脂又は該有機溶剤に可溶な下記Ｂ群の染料を内包した樹脂を充填し、該有機溶剤を実質的に含まず、かつ、下記Ｃ群から選ばれる潤滑油を充填したことを特徴とする焼成固形描画材。
Ａ群：イソプロピルアルコール、エタノール、メトシキメチルブタノール、ベンジルアルコール、トルエン、キシレン、アセトン、メチルエチルケトン、酢酸エチル、エチルセロソルブ、フェニルセロソルブ、ベンジルアルコール
Ｂ群：染着樹脂、ドープ染料
Ｃ群：パラフィンオイル、α−オレフィンオイル、脂肪酸エステル、エステルオイル、合成油、ヒマシオイル、グリース
（２） 前記染料を溶解又は内包した樹脂が、厚さ1μｍ以下の皮膜状であることを特徴とする上記（１）に記載の焼成固形描画材。
（３） 上記（１）又は（２）に記載の固形描画材芯体が、少なくとも窒化ホウ素とセラミック結合材を配合して焼成された焼成セラミック芯体であることを特徴とする焼成固形描画材。
（４） 上記（１）〜（３）の何れか一つに記載の固形描画材芯体が、断面四角形の矩形状であることを特徴とする焼成固形描画材。
（５） 上記（１）〜（４）の何れか一つに記載の焼成固形描画材をホルダーで把持し、任意の長さで適宜繰り出して使用することを特徴とする焼成固形描画材。
（６） 焼成固形描画材芯に用いる成分を混練、成型、乾燥及び非酸化性雰囲気下で焼成処理及び／又は大気下での焼成処理して固形描画材芯体を得、該焼成固形描画材芯体の気孔内に染料を溶解した下記Ａ群の有機溶剤に可溶な樹脂又は該有機溶剤に可溶な下記Ｂ群の染料を内包した樹脂を充填し、該有機溶剤を実質的に含まず、かつ、下記Ｃ群から選ばれる潤滑油を充填したことを特徴とする焼成固形描画材の製造方法。
Ａ群：イソプロピルアルコール、エタノール、メトシキメチルブタノール、ベンジルアルコール、トルエン、キシレン、アセトン、メチルエチルケトン、酢酸エチル、エチルセロソルブ、フェニルセロソルブ、ベンジルアルコール
Ｂ群：染着樹脂、ドープ染料
Ｃ群：パラフィンオイル、α−オレフィンオイル、脂肪酸エステル、エステルオイル、合成油、ヒマシオイル、グリース
That is, this invention exists in following (1)-( 6 ).
(1) A solid drawing material core is filled with a resin soluble in an organic solvent of the following group A in which a dye is dissolved or a resin encapsulating a dye of the following group B soluble in the organic solvent, and the organic A fired solid drawing material characterized by being substantially free from a solvent and filled with a lubricating oil selected from the following group C.
Group A: isopropyl alcohol, ethanol, methoxymethylbutanol, benzyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, ethyl cellosolve, phenyl cellosolve, benzyl alcohol
Group B: Dyeing resin, dope dye
Group C: Paraffin oil, α-olefin oil, fatty acid ester, ester oil, synthetic oil, castor oil, grease (2) The resin in which the dye is dissolved or encapsulated is a film having a thickness of 1 μm or less. The fired solid drawing material according to (1) above.
(3) A fired solid drawing material, wherein the solid drawing material core according to (1) or (2) is a fired ceramic core that is fired by blending at least boron nitride and a ceramic binder. .
(4) A fired solid drawing material, wherein the solid drawing material core according to any one of the above (1) to ( 3 ) has a rectangular shape with a square cross section.
(5) A fired solid drawing material, wherein the fired solid drawing material according to any one of the above (1) to ( 4 ) is held by a holder and appropriately drawn out at an arbitrary length.
(6) The components used for the fired solid drawing material core are kneaded, molded, dried and fired in a non-oxidizing atmosphere and / or fired in the atmosphere to obtain a solid drawing material core, and the fired solid drawing material Filled with a resin soluble in the organic solvent of the following group A in which the dye is dissolved in the pores of the core or a resin encapsulating the dye of the following group B soluble in the organic solvent, and substantially containing the organic solvent And a method for producing a calcined solid drawing material, which is filled with a lubricating oil selected from Group C below.
Group A: isopropyl alcohol, ethanol, methoxymethylbutanol, benzyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, ethyl cellosolve, phenyl cellosolve, benzyl alcohol
Group B: Dyeing resin, dope dye
Group C: paraffin oil, α-olefin oil, fatty acid ester, ester oil, synthetic oil, castor oil, grease
本発明によれば、強度、耐光性を損なわず、裏うつりのしない、色相、消しゴム消去性に優れた蛍光などのアンダーライン用途等に好適な焼成固形描画材が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the baking solid drawing material suitable for underline uses etc. which do not impair intensity | strength and light resistance, and do not carry out a back surface, the hue, and the fluorescence excellent in the eraser erase property etc. is provided.
以下に、本発明の実施の形態を詳しく説明する。
本発明の焼成固形描画材は、固形描画材芯体の気孔内に染料を溶解又は内包した樹脂を充填し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 fired solid drawing material of the present invention is characterized in that a resin in which a dye is dissolved or encapsulated is filled in pores of a solid drawing material core.
本発明の焼成固形描画材は、焼成固形描画材芯体に染料を溶解又は内包した樹脂を充填してなるものであれば、その製法等は特に限定されず、例えば、少なくとも、体質材、熱可塑性合成樹脂などのバインダー成分、有機溶剤などの各成分を適宜選択した焼成固形描画材用配合組成物を用いて焼成処理して多孔質体の焼成固形描画材芯体を得、該焼成固形描画材芯体の気孔内に染料を溶解又は内包した樹脂を充填することにより得ることができる。 The baking solid drawing material of the present invention is not particularly limited as long as the baking solid drawing material is formed by filling a resin in which a dye is dissolved or encapsulated in a baking solid drawing material core. A sintered solid drawing material core of a porous body is obtained by firing treatment using a blended composition for a fired solid drawing material in which a binder component such as a plastic synthetic resin and each component such as an organic solvent are appropriately selected. It can be obtained by filling the pores of the core material with a resin in which a dye is dissolved or encapsulated.
用いることができる体質材としては、従来の焼成固形描画材芯体に使用されているものであれば、特に限定されるものではなく、いずれも使用することができる。例えば、窒化ホウ素、カオリン（カオリナイト、ハロイサイト）、タルク、マイカ、炭酸カルシウム等の白色系体質材や有色系の体質材も使用することができ、当然これら数種類の混合物も使用できる。特に、好ましくは、その物性、形状から窒化ホウ素、カオリン、タルクが挙げられる。 The extender that can be used is not particularly limited as long as it is used in a conventional fired solid drawing material core, and any of them can be used. For example, a white type material such as boron nitride, kaolin (kaolinite, halloysite), talc, mica, calcium carbonate, or a colored type material can be used, and naturally, a mixture of these several types can also be used. Particularly preferred are boron nitride, kaolin and talc because of their physical properties and shape.
また、用いることができるバインダー成分としては、従来の焼成固形描画材芯体に使用されているものであれば、特に限定されるものではなく、いずれも使用することができる。例えば、カルボキシルメチルセルロース等のセルロース類、ポリビニルピロニドン等のポリビニル類、ポリオキシエチレン等のポリエーテル類、ポリアクリル酸等のアクリル酸類、テトラエチルオルソシリケート（ＴＥＯＳ）縮合体等の無機高分子、モンモリロナイト、ベントナイト等の粘土、セラミックガラス等が挙げられる。これらは、単独で、又は２種以上混合して用いることができる。 Moreover, as a binder component which can be used, if it is used for the conventional baking solid drawing-material core, it will not specifically limit, All can be used. For example, celluloses such as carboxymethyl cellulose, polyvinyls such as polyvinylpyronidone, polyethers such as polyoxyethylene, acrylic acids such as polyacrylic acid, inorganic polymers such as tetraethyl orthosilicate (TEOS) condensate, montmorillonite And clay such as bentonite, ceramic glass and the like. These can be used alone or in admixture of two or more.
また、用いる熱可塑性合成樹脂としては、例えば、ポリビニルアルコール、ポリ塩化ビニル、ポリ塩素化塩化ビニル、ポリアミド、ポリエチレン、ポリプロピレン、ポリエーテルエーテルケトンなどを挙げられる。
用いる有機溶剤は、上記熱可塑性合成樹脂を溶解し得るものが好ましく、具体的には、ジオクチルフタレート（ＤＯＰ）、ジブチルフタレート（ＤＢＰ）、トリクレジルホスフェート、ジオクチルアジペート、ジアリルイソフタレート、プロピレンカーボネート、アルコール類、ケトン類、エステル類などを用いることができる。
Examples of the thermoplastic synthetic resin to be used include polyvinyl alcohol, polyvinyl chloride, polychlorinated vinyl chloride, polyamide, polyethylene, polypropylene, and polyether ether ketone.
The organic solvent to be used is preferably one that can dissolve the thermoplastic synthetic resin. Specifically, dioctyl phthalate (DOP), dibutyl phthalate (DBP), tricresyl phosphate, dioctyl adipate, diallyl isophthalate, propylene carbonate, Alcohols, ketones, esters and the like can be used.
具体的な焼成固形描画材芯体としては、例えば、少なくとも窒化ホウ素とセラミック結合材を配合して焼成した焼成セラミック芯体、少なくとも黒鉛を配合して焼成した焼成芯体、少なくとも窒化ホウ素と層状ケイ酸塩鉱物を配合して焼成した焼成芯体、少なくともタルクと層状ケイ酸塩鉱物を配合して焼成した焼成芯体などが挙げられる。 Specific examples of the fired solid drawing material core include, for example, a fired ceramic core that is fired by mixing at least boron nitride and a ceramic binder, a fired core that is fired by mixing at least graphite, and at least boron nitride and a layered silica. Examples thereof include a fired core body that is fired by blending a silicate mineral and a fired core body that is fired by blending at least talc and a layered silicate mineral.
セラミック結合材としては、例えば、窒化ケイ素、酸化ケイ素、酸化ホウ素、酸化アルミニウム、層状ケイ酸塩鉱物およびその焼成物などが挙げられ、黒鉛としては、例えば、天然黒鉛、人造黒鉛、キッシュ黒鉛、膨張黒鉛、膨張化黒鉛などが挙げられる。 Examples of the ceramic binder include silicon nitride, silicon oxide, boron oxide, aluminum oxide, layered silicate mineral, and fired products thereof. Examples of graphite include natural graphite, artificial graphite, quiche graphite, and expanded. Examples thereof include graphite and expanded graphite.
本発明の焼成固形描画材において、上記体質材、熱可塑性合成樹脂などのバインダー成分、有機溶剤、水などの各成分を配合、具体的には、用いる材料種により、例えば、シャープペンシル用焼成固形描画材芯、シャープペンシル用以外の焼成固形描画材芯に用いる各成分（体質材、バインダー成分、熱可塑性樹脂、有機溶剤など）を混練、成型、乾燥及び非酸化性雰囲気下で焼成処理、及び／又は大気下での焼成処理して、各多孔質の焼成固形描画材芯体を得、該焼成固形描画材芯体の気孔内に染料を溶解又は内包した樹脂をアルコールなどを用いて含浸させ、好ましくは、更に潤滑油を充填することにより製造することができる。 In the fired solid drawing material of the present invention, the above-mentioned build material, a binder component such as a thermoplastic synthetic resin, an organic solvent, water, and other components are blended. Specifically, depending on the material used, for example, a fired solid for mechanical pencils Kneading, molding, drying, and baking in a non-oxidizing atmosphere for each component (external material, binder component, thermoplastic resin, organic solvent, etc.) used for the drawing material core and the solid baking material core other than for mechanical pencils, and By firing in the atmosphere to obtain each porous fired solid drawing material core, and impregnating a resin in which the dye is dissolved or encapsulated in the pores of the fired solid drawing material core with alcohol or the like Preferably, it can be produced by further filling with a lubricating oil.
用いることができる染料としては、消去性、耐水性の点から、油溶性染料、ジメチルジステアリルアンモニウム塩のカチオン及び酸性染料とで構成される造塩染料、蛍光色素などが挙げられる。
油溶性染料としては、例えば、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｙｅｌｌｏｗ ２、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｙｅｌｌｏｗ ６、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ４９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌａｃｋ ２２等、これらの市販品が挙げられ、また、酸性染料としては、例えば、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ １、Ｃ．Ｉ．Ａｃｉｄ Ｙｅｌｌｏｗ３、Ｃ．Ｉ．Ａｃｉｄ Ｏｒａｎｇｅ １０、Ｃ．Ｉ．Ａｃｉｄ Ｏｒａｎｇｅ ２８、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ５１、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ５７、Ｃ．Ｉ．Ａｃｉｄ Ｖｉｏｌｅｔ ７、Ｃ．Ｉ．Ａｃｉｄ Ｂｌｕｅ ２２、Ｃ．Ｉ．Ａｃｉｄ Ｇｒｅｅｎ ４０、Ｃ．Ｉ．Ａｃｉｄ Ｂｒｏｗｎ ４５、Ｃ．Ｉ．Ａｃｉｄ Ｂｌａｃｋ ５１等、これらの市販品が挙げられる。
蛍光色素としては、例えば、Ｃ．Ｉ．ベーシックレッド１、Ｃ．Ｉ．ベーシックイエロー１、Ｃ．Ｉ．ベーシックイエロー４０、Ｃ．Ｉ．ベーシックバイオレット１１等の蛍光染料が挙げられる。また、これらの蛍光染料を合成樹脂に溶解させ、微粉体とした蛍光顔料も使用することができる。このような蛍光顔料としては、シンロイヒカラーＳＢ−１５（イエロー、シンロイヒ社製）、エポカラーＦＰ−１１２（ピンク）等のエポカラーＦＰシリーズ（日本触媒社製）、ＮＫＷ−２１００Ｅシリーズ、ＮＫＷ−６２００Ｅシリーズ（日本蛍光社製）、Ｒｙｕｄｙｅ−ＬＵＭＩＮＯＵＳシリーズ（大日本インキ社製）等を使用することができる。
Examples of the dye that can be used include oil-soluble dyes, salt-forming dyes composed of a cation and an acid dye of dimethyl distearyl ammonium salt, and fluorescent dyes from the viewpoint of erasability and water resistance.
Examples of the oil-soluble dye include C.I. I. Solvent Yellow 2, C.I. I. Solvent Yellow 6, C.I. I. Solvent Red 25, C.I. I. Solvent Red 49, C.I. I. Solvent Violet 8, C.I. I. Solvent Blue 25, C.I. I. These commercially available products such as Solvent Black 22 and the like are mentioned, and examples of the acid dye include C.I. I. Acid Yellow 1, C.I. I. Acid Yellow3, C.I. I. Acid Orange 10, C.I. I. Acid Orange 28, C.I. I. Acid Red 51, C.I. I. Acid Red 57, C.I. I. Acid Violet 7, C.I. I. Acid Blue 22, C.I. I. Acid Green 40, C.I. I. Acid Brown 45, C.I. I. These commercial products, such as Acid Black 51, are mentioned.
Examples of fluorescent dyes include C.I. I.
用いる染料を溶解した樹脂は、アルコールなどに可溶かつ溶液粘度が低く、用いる染料との親和性が高い樹脂であることが必要であり、例えば、各種変性フェノール樹脂、ケトン樹脂、マレイン酸樹脂、アルデヒド樹脂などが挙げられる。
また、染料を内包した樹脂は、樹脂分子中に染料を内包したものであり、例えば、染着樹脂、ドープ染料が挙げられる。
上記染料を溶解した樹脂、及び染料を内包した樹脂の樹脂種としては、例えば、ブチラール樹脂、各種変性フェノール樹脂、ケトン樹脂、マレイン酸樹脂、アルデヒド樹脂、エチルセルロースなどのアルキルセルロース、アクリル樹脂、スルホン酸樹脂など、水に不溶である樹脂が挙げられ、これらは有機溶剤に可溶である。
有機溶剤としては、例えば、イソプロピルアルコール（ＩＰＡ）、エタノール、メトシキメチルブタノール、ベンジルアルコール、トルエン、キシレン、アセトン、メチルエチルケトン、酢酸エチル、エチルセロソルブ、フェニルセロソルブ、ベンジルアルコールなどが挙げられる。
染料を溶解した樹脂としては、具体的には、樹脂着色用染料を樹脂に練りこむ方法や、有機溶剤に染料と樹脂を所定の割合、具体的には、質量比で染料：樹脂が１０：１〜１：２、好ましくは、３：１〜１：１で溶かしてそのまま使用する方法や、乾燥させて使用する方法などが挙げられる。
また、染料を内包した樹脂としては、具体的には、樹脂の重合過程で染料を添加する方法や、樹脂分子に染料を化学結合させる方法などが挙げられ、これらの場合、染料と樹脂を割合は、質量比で染料：樹脂が５：１〜１：３、好ましくは、３：１〜１：１であることが望ましい。
更に好ましくは、前記染料を溶解又は内包した樹脂は、厚さ1μｍ以下の皮膜状であるものが望ましい。この厚さ1μｍ以下の皮膜状は、1μｍ以下の多孔体鉛筆芯に含浸させることや、有機溶剤中の濃度などを適正にすることにより行うことができる。
The resin in which the dye to be used is dissolved must be a resin that is soluble in alcohol and has a low solution viscosity and high affinity with the dye to be used. For example, various modified phenol resins, ketone resins, maleic acid resins, Examples include aldehyde resins.
The resin encapsulating the dye is one in which the dye is encapsulated in the resin molecule, and examples thereof include a dyeing resin and a dope dye.
Examples of the resin type of the resin in which the dye is dissolved and the resin including the dye include butyral resins, various modified phenol resins, ketone resins, maleic acid resins, aldehyde resins, ethyl cellulose and other alkyl celluloses, acrylic resins, sulfonic acids Resins that are insoluble in water, such as resins, can be mentioned, and these are soluble in organic solvents.
Examples of the organic solvent include isopropyl alcohol (IPA), ethanol, methoxymethylbutanol, benzyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, ethyl cellosolve, phenyl cellosolve, and benzyl alcohol.
Specifically, the resin in which the dye is dissolved is a method of kneading a resin coloring dye into the resin, or a predetermined ratio of the dye and the resin in the organic solvent, specifically, the dye: resin in a mass ratio of 10: Examples include a method of dissolving 1 to 1: 2, preferably 3 to 1: 1 and using it as it is, or a method of using it after drying.
Specific examples of the resin containing the dye include a method of adding a dye during the resin polymerization process and a method of chemically bonding the dye to the resin molecule. In these cases, the ratio of the dye to the resin is used. Is 5: 1 to 1: 3, preferably 3: 1 to 1: 1 by weight ratio of dye: resin.
More preferably, the resin in which the dye is dissolved or encapsulated is a film having a thickness of 1 μm or less. The film having a thickness of 1 μm or less can be formed by impregnating a porous pencil lead having a thickness of 1 μm or less, or by adjusting the concentration in the organic solvent.
用いる潤滑油としては、例えば、パラフィンオイル、α−オレフィンオイル、脂肪酸エステル、アルキレングリコールエーテルなどのエステルオイル、シリコーンオイルなどの合成油、ヒマシオイル等の植物油、グリース等を挙げることできる。 Examples of the lubricating oil to be used include paraffin oil, α-olefin oil, fatty acid ester, ester oil such as alkylene glycol ether, synthetic oil such as silicone oil, vegetable oil such as castor oil, grease, and the like.
本発明において、シャープペンシル用の焼成固形描画材の製造では、例えば、（ａ）窒化ホウ素などの体質材合計で４０〜７０質量％と、（ｂ）ベントナイトなどのバインダー成分２０〜５０質量％と、（ｃ）水や有機溶剤１０〜３０質量％をヘンシェルミキサーで分散混合し、加圧ニーダー、二本ロールで混練し、押出成型機により成型した後、電気炉で１１０〜２５０℃で乾燥し、次いで、非酸化性雰囲気下（窒素ガス雰囲気下、不活性ガス雰囲気下）で８００〜１４００℃、２０〜４０時間で焼成して固形描画材芯体を得、該焼成固形描画材芯体の気孔内に上記油溶性染料、造塩染料、蛍光染料などの染料を溶解又は内包した樹脂をアルコールに溶解して含浸させ、乾燥させ、好ましくは、更に潤滑油を充填することにより製造することができる。
得られる焼成固形描画材において、染料を溶解又は内包した樹脂の含有量は、成形種、溶剤種、染料種により変動するものであるが、色相、耐光性及び強度のバランスを高度に両立させる点から、好ましくは、焼成固形描画材全量に対して、３〜５０質量％、更に好ましくは、５〜３０質量％が望ましい。
In the present invention, in the production of a calcined solid drawing material for a mechanical pencil, for example, (a) 40 to 70% by mass in total of an extender material such as boron nitride, and (b) 20 to 50% by mass of a binder component such as bentonite (C) 10-30% by mass of water or an organic solvent is dispersed and mixed with a Henschel mixer, kneaded with a pressure kneader and two rolls, molded with an extruder, and then dried at 110 to 250 ° C. in an electric furnace. Subsequently, the solid drawing material core is obtained by firing at 800 to 1400 ° C. for 20 to 40 hours in a non-oxidizing atmosphere (in a nitrogen gas atmosphere and an inert gas atmosphere). A resin in which pores are dissolved or encapsulated in the above-mentioned oil-soluble dye, salt-forming dye, fluorescent dye or the like is dissolved in alcohol, dried, and preferably filled with lubricating oil. Can.
In the obtained baked solid drawing material, the content of the resin in which the dye is dissolved or encapsulated varies depending on the molding type, the solvent type, and the dye type, but highly balances the hue, light resistance and strength. Therefore, preferably 3 to 50% by mass, more preferably 5 to 30% by mass, based on the total amount of the calcined solid drawing material.
本発明の焼成固形描画材は、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、上記染料を溶解又は内包した樹脂を充填させる方法として、ワックスに溶解して含浸させる方法を用いたり、熱をかけて含浸させる方法を用いる方法等であってもよいものである。 The fired solid drawing material of the present invention is not limited to the above-described embodiment, and can be implemented with various modifications within the scope of the technical idea of the present invention. For example, as a method of filling a resin in which the above dye is dissolved or encapsulated, a method of dissolving and impregnating in a wax may be used, or a method of using a method of impregnation by applying heat may be used.
本発明の焼成固形描画材は、固形描画材種（シャープペンシル用、木軸用、ホルダー用等）により、各種形状、大きさに成形することができ、例えば、円柱状、断面四角形の矩形状などの任意の形状としたりすることができ、矩形状としたものでは、図１に示す替え芯式のホルダータイプの筆記具Ａにより使用に供することができる。
本発明において、断面の形状が四角形の矩形状の大きさとしては、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０．２〜５ｍｍ、幅方向（幅）が３〜１０ｍｍ、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。
この筆記具Ａは、汎用の構造であり、図１に示すように、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、焼成固形描画芯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、把持されていた焼成固形描画１０が解放されるため、焼成固形描画材芯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、焼成固形描画材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、固形描画材が蛍光色材タイプの固形描画材芯を用いることにより、アンダーラインマーカーなどとして使用することができる。
The fired solid drawing material of the present invention can be formed into various shapes and sizes depending on the type of solid drawing material (for mechanical pencils, wooden shafts, holders, etc.). In the case of a rectangular shape, it can be used for use by the rewriting type holder-type writing instrument A shown in FIG.
In the present invention, the size of the cross-sectional shape of the quadrangular rectangular shape varies depending on the writing instrument to be used. However, in the holder type writing instrument of a replacement core type, the height (thickness) of the cross section is preferable. Is preferably adjusted to 0.2 to 5 mm, the width direction (width) is 3 to 10 mm, and the length in the longitudinal direction is adjusted to about 1 to 18 cm.
The writing instrument A has a general-purpose structure. As shown in FIG. 1, a core tank 2 urged rearward by an elastic member such as a coil spring is movable back and forth inside the
In this type of writing instrument A, the solid drawing material can be used as an underline marker or the like by using a solid drawing material core of a fluorescent color material type.
このように構成される本発明の焼成固形描画材が、何故、色相、耐光性及び強度に優れた消しゴムで消去可能な焼成固形描画材となるかは以下の作用機構により発揮できるものである。
すなわち、焼成処理に得られる固形描画材芯体の多孔質体骨格を樹脂で強化させると共に、強化材料が着色剤となっていることと、着色剤が固体であり、結果として焼成固形描画材芯の材料が消去性の良い材料のみで構成されることとなるので、これらにより、色相、耐光性及び強度に優れた消しゴムで消去可能な焼成固形描画材芯となるものである。
本発明では、固形描画材芯体の気孔内に蛍光染料を溶解又は内包した樹脂を充填してなる焼成固形描画材では、上記効果等と共に、裏うつりもなく、アンダーライン用の焼成固形描画材として利用可能であるので、塗布した箇所を目立たせるためには、染料を蛍光とすれば、下地の隠ぺいをせず、かつ、塗布部分のハイライトを行うことのできる固形描画材とすることができる。
The reason why the fired solid drawing material of the present invention configured as described above becomes a fired solid drawing material erasable with an eraser excellent in hue, light resistance and strength can be exhibited by the following mechanism.
That is, the porous skeleton of the solid drawing material core obtained in the firing treatment is reinforced with resin, and the reinforcing material is a colorant, and the colorant is solid, and as a result, the fired solid drawing material core Since these materials are composed only of materials having good erasability, these form a baked solid drawing material core that can be erased with an eraser excellent in hue, light resistance and strength.
In the present invention, the fired solid drawing material in which the pores of the solid drawing material core are filled with a resin in which a fluorescent dye is dissolved or encapsulated is filled with the above-described effects and the like, and there is no back-slip, and the fired solid drawing material for underline In order to make the coated part stand out, if the dye is made fluorescent, it is possible to make a solid drawing material that does not conceal the base and can highlight the coated part. it can.
次に、実施例及び比較例により、本発明を更に詳述するが、本発明は下記実施例等により制限されるものではない。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in full detail, this invention is not restrict | limited by the following Example etc.
（実施例１）
配合組成物：
塩化ビニル樹脂 ４０質量％
フタル酸ジオクチル（ＤＯＰ） １０質量％
窒化ホウ素 ５０質量％
上記配合組成物を混練し、この混練物を押出機にて断面四角形の矩形状に押出成形し、不活性ガス雰囲気１０００℃で５時間加熱し、窒化ホウ素とバインダー炭素の焼成芯体を作製した。この焼成芯体を大気雰囲気７００℃で１２時間加熱し、窒化ホウ素のみの焼成芯体を作成した。ここにシリケート４０（コルコート社製）を含浸し、乾燥した後、不活性雰囲気１０００℃で５時間加熱して矩形状白色焼成芯体を得た。
この矩形状白色焼成芯体に、下記配合組成物を含浸し、８０℃で１２時間乾燥した。
配合組成物：
スピロンレッドＣ−ＰＨ（保土ヶ谷化学製） ２０質量％
ブチラール樹脂：エスレックＢＬ−１（積水化学製） ２０質量％
イソプロピロピルアルコール（以下「ＩＰＡ」という） ６０質量％
この乾燥で得られた細孔にα−オレフィンオイル（モービル石油社製：スペクトラシン４）を１００℃で６時間含浸し、幅５ｍｍ、厚さ０．８ｍｍ、長さ１２０ｍｍの矩形状の赤色焼成固形描画材を得た。
本実施例は、焼成固形描画材芯体の気孔内に染料を溶解した樹脂が充填された形態である。すなわち、上記乾燥によりＩＰＡは揮発しており、スピロンレッドＣ−ＰＨはブチラール樹脂に溶解し、安定した状態となっている。
該焼成固形描画材を把持することができるホルダー、すなわち、図１に示す筆記具で把持して任意の長さで、繰り出して使用することができた。
Example 1
Formulation composition:
40% by mass of vinyl chloride resin
Dioctyl phthalate (DOP) 10% by mass
Boron nitride 50% by mass
The above blended composition was kneaded, and this kneaded product was extruded into a rectangular shape with a square cross section with an extruder and heated at 1000 ° C. for 5 hours in an inert gas atmosphere to prepare a sintered core of boron nitride and binder carbon. . This fired core was heated at 700 ° C. in the atmosphere for 12 hours to prepare a fired core made of only boron nitride. This was impregnated with silicate 40 (manufactured by Colcoat Co.), dried, and then heated in an inert atmosphere at 1000 ° C. for 5 hours to obtain a rectangular white fired core.
This rectangular white fired core was impregnated with the following composition and dried at 80 ° C. for 12 hours.
Formulation composition:
Spiron Red C-PH (Hodogaya Chemical) 20% by mass
Butyral resin: SREC BL-1 (manufactured by Sekisui Chemical) 20% by mass
60% by mass of isopropyl alcohol (hereinafter referred to as “IPA”)
The pores obtained by this drying were impregnated with α-olefin oil (manufactured by Mobil Oil Co., Ltd .: Spectracin 4) at 100 ° C. for 6 hours, and were fired in a rectangular red shape having a width of 5 mm, a thickness of 0.8 mm and a length of 120 mm. A solid drawing material was obtained.
In this embodiment, a resin in which a dye is dissolved is filled in the pores of the fired solid drawing material core. That is, IPA is volatilized by the above drying, and spiron red C-PH is dissolved in butyral resin and is in a stable state.
The holder that can hold the fired solid drawing material, that is, the writing tool shown in FIG. 1, can be drawn out and used in an arbitrary length.
（実施例２）
配合組成物：
スメクタイト ４０質量％
蒸留水 １０質量％
窒化ホウ素 ５０質量％
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、不活性雰囲気１２００℃で５時間加熱し、窒化ホウ素とスメクタイトの焼成芯体を作製した。
この焼成芯体に、下記配合組成物を含浸し、８０℃で１２時間乾燥した。
配合組成物：インクＡ
スピロンレッドＣ−ＧＨ（保土ヶ谷化学社製） ２０質量％
ブチラール樹脂：エスレックＢＬ−１（積水化学社製） ２０質量％
ＩＰＡ ６０質量％
この乾燥で得られた細孔にα−オレフィンオイル（モービル石油社製：スペクトラシン４）を６０℃で６時間含浸し、幅８ｍｍ、厚さ１ｍｍ、長さ１００ｍｍの矩形状の赤色焼成固形描画材を得た。
本実施例は、焼成固形描画材芯体の気孔内に染料を溶解した樹脂が充填された形態である。すなわち、上記インクＡを乾燥させた時点でスピロンレッドＣ−ＧＨはブチラール樹脂に溶解し、安定した状態となっている。
該焼成固形描画材を把持することができるホルダー、すなわち、図１に示す筆記具で把持して任意の長さで、繰り出して使用することができた。
(Example 2)
Formulation composition:
Smectite 40% by mass
10% by weight of distilled water
Boron nitride 50% by mass
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and heated at 1200 ° C. for 5 hours in an inert atmosphere to prepare a sintered core body of boron nitride and smectite.
This fired core was impregnated with the following composition and dried at 80 ° C. for 12 hours.
Formulation composition: Ink A
Spiron Red C-GH (Hodogaya Chemical Co., Ltd.) 20% by mass
Butyral resin: ESREC BL-1 (manufactured by Sekisui Chemical Co., Ltd.) 20% by mass
IPA 60% by mass
The pores obtained by this drying were impregnated with α-olefin oil (manufactured by Mobil Sekiyu Co., Ltd .: Spectracin 4) at 60 ° C. for 6 hours, and a rectangular red fired solid drawing having a width of 8 mm, a thickness of 1 mm and a length of 100 mm. The material was obtained.
In this embodiment, a resin in which a dye is dissolved is filled in the pores of the fired solid drawing material core. That is, when the ink A is dried, the spirone red C-GH is dissolved in the butyral resin and is in a stable state.
The holder that can hold the fired solid drawing material, that is, the writing tool shown in FIG. 1, can be drawn out and used in an arbitrary length.
（実施例３）
配合組成物：
塩化ビニル樹脂 ４５質量％
フタル酸ジオクチル（ＤＯＰ） １０質量％
窒化ホウ素 ４５質量％
上記配合組成物を混練し、この混練物を押出機にて断面四角形の矩形状に押出成形し、不活性ガス雰囲気１０００℃で５時間加熱し、窒化ホウ素とバインダー炭素の焼成芯体を作製した。この焼成芯体を大気雰囲気７００℃で１２時間加熱し、窒化ホウ素のみの焼成芯体を作成した。ここにシリケート４０（コルコート社製）を含浸し、乾燥した後、不活性雰囲気１０００℃で５時間加熱して矩形状白色焼成芯体を得た。
この矩形状白色焼成芯体に、下記配合組成物を含浸し、８０℃で１２時間乾燥した。
配合組成物：
ＤＤＰレッド（染料内包型樹脂） ２０質量％
ＩＰＡ ６０質量％
この乾燥で得られた細孔にα−オレフィンオイル（モービル石油社製：スペクトラシン４）を６０℃で６時間含浸し、幅５ｍｍ、厚さ０．８ｍｍ、長さ１２０ｍｍの矩形状の赤色焼成固形描画材を得た。
本実施例は、焼成固形描画材芯体の気孔内に染料を内包した樹脂が充填された形態である。すなわち、上記乾燥によりＩＰＡは揮発しており、染料内包型樹脂のＤＤＰレッドが気孔内に安定した状態で保持された状態となっている。
該焼成固形描画材を把持することができるホルダー、すなわち、図１に示す筆記具で把持して任意の長さで、繰り出して使用することができた。
(Example 3)
Formulation composition:
45% by mass of vinyl chloride resin
Dioctyl phthalate (DOP) 10% by mass
Boron nitride 45% by mass
The above blended composition was kneaded, and this kneaded product was extruded into a rectangular shape with a square cross section with an extruder and heated at 1000 ° C. for 5 hours in an inert gas atmosphere to prepare a sintered core of boron nitride and binder carbon. . This fired core was heated at 700 ° C. in the atmosphere for 12 hours to prepare a fired core made of only boron nitride. This was impregnated with silicate 40 (manufactured by Colcoat Co.), dried, and then heated in an inert atmosphere at 1000 ° C. for 5 hours to obtain a rectangular white fired core.
This rectangular white fired core was impregnated with the following composition and dried at 80 ° C. for 12 hours.
Formulation composition:
DDP Red (dye-containing resin) 20% by mass
IPA 60% by mass
The pores obtained by this drying were impregnated with α-olefin oil (manufactured by Mobil Sekiyu Co., Ltd .: Spectracin 4) at 60 ° C. for 6 hours, and were fired in a rectangular red shape having a width of 5 mm, a thickness of 0.8 mm and a length of 120 mm. A solid drawing material was obtained.
In this embodiment, a resin containing a dye is filled in the pores of the fired solid drawing material core. That is, the IPA is volatilized by the drying, and the DDP red, which is a dye-containing resin, is held in a stable state in the pores.
The holder that can hold the fired solid drawing material, that is, the writing tool shown in FIG. 1, can be drawn out and used in an arbitrary length.
（実施例４）
配合組成物：
塩化ビニル樹脂 ４０質量％
フタル酸ジオクチル（ＤＯＰ） １０質量％
窒化ホウ素 ５０質量％
上記配合組成物を混練し、この混練物を押出機にて断面四角形の矩形状に押出成形し、不活性ガス雰囲気１０００℃で５時間加熱し、窒化ホウ素とバインダー炭素の焼成芯体を作製した。この焼成芯体を大気雰囲気７００℃で１２時間加熱し、窒化ホウ素のみの焼成芯体を作成した。ここにシリケート４０（コルコート社製）を含浸し、乾燥した後、不活性雰囲気１０００℃で５時間加熱して矩形状白色焼成芯体を得た。
この矩形状白色焼成芯体に、下記配合組成物を含浸し、８０℃で１２時間乾燥した。
配合組成物（インクＡ）：
Ｓ．Ｂ．Ｎオレンジ７０１（保土ヶ谷化学社製） ２０質量％
ブチラール樹脂：エスレックＢＬ−１（積水化学社製） ２０質量％
ＩＰＡ ６０質量％
この乾燥で得られた細孔にα−オレフィンオイル（モービル石油社製：スペクトラシン４）を６０℃で６時間含浸し、幅５ｍｍ、厚さ３ｍｍ、長さ１００ｍｍの矩形状の橙色焼成固形描画材を得た。
本実施例は、焼成固形描画材芯体の気孔内に染料を溶解した樹脂が充填された形態である。すなわち、上記インクＡを乾燥させた時点でＳ．Ｂ．Ｎオレンジ７０１はブチラール樹脂に溶解し、安定した状態となっている。
該焼成固形描画材を把持することができるホルダー、すなわち、図１に示す筆記具で把持して任意の長さで、繰り出して使用することができた。
Example 4
Formulation composition:
40% by mass of vinyl chloride resin
Dioctyl phthalate (DOP) 10% by mass
Boron nitride 50% by mass
The above blended composition was kneaded, and this kneaded product was extruded into a rectangular shape with a square cross section with an extruder and heated at 1000 ° C. for 5 hours in an inert gas atmosphere to prepare a sintered core of boron nitride and binder carbon. . This fired core was heated at 700 ° C. in the atmosphere for 12 hours to prepare a fired core made of only boron nitride. This was impregnated with silicate 40 (manufactured by Colcoat Co.), dried, and then heated in an inert atmosphere at 1000 ° C. for 5 hours to obtain a rectangular white fired core.
This rectangular white fired core was impregnated with the following composition and dried at 80 ° C. for 12 hours.
Formulation composition (ink A):
S. B. N Orange 701 (Hodogaya Chemical Co., Ltd.) 20% by mass
Butyral resin: ESREC BL-1 (manufactured by Sekisui Chemical Co., Ltd.) 20% by mass
IPA 60% by mass
The pores obtained by this drying were impregnated with α-olefin oil (manufactured by Mobil Sekiyu Co., Ltd .: Spectracin 4) at 60 ° C. for 6 hours to produce a rectangular orange baked solid drawing having a width of 5 mm, a thickness of 3 mm and a length of 100 mm. The material was obtained.
In this embodiment, a resin in which a dye is dissolved is filled in the pores of the fired solid drawing material core. That is, when the ink A is dried, S.I. B. N orange 701 is dissolved in butyral resin and is in a stable state.
The holder that can hold the fired solid drawing material, that is, the writing tool shown in FIG. 1, can be drawn out and used in an arbitrary length.
（実施例５）
配合組成物：
塩化ビニル樹脂 ４０質量％
フタル酸ジオクチル（ＤＯＰ） １０質量％
窒化ホウ素 ５０質量％
上記配合組成物を混練し、この混練物を押出機にて断面四角形の矩形状に押出成形し、不活性ガス雰囲気１０００℃で５時間加熱し、窒化ホウ素とバインダー炭素の焼成芯体を作製した。この焼成芯体を大気雰囲気７００℃で１２時間加熱し、窒化ホウ素のみの焼成芯体を作成した。ここにシリケート４０（コルコート社製）を含浸し、乾燥した後、不活性雰囲気１０００℃で５時間加熱して矩形状白色焼成芯体を得た。
この矩形状白色焼成芯体に、下記配合組成物を含浸し、８０℃で１２時間乾燥した。
配合組成物（インクＢ）：
シンロイヒカラーＳＢ−１５ ２０質量％
ブチラール樹脂：エスレックＢＬ−１（積水化学社製） ２０質量％
ＩＰＡ ６０質量％
この乾燥で得られた細孔にα−オレフィンオイル（モービル石油社製：スペクトラシン４）を６０℃で６時間含浸し、幅８ｍｍ、厚さ１ｍｍ、長さ１００ｍｍの矩形状の蛍光黄色焼成固形描画材を得た。
本実施例は、焼成固形描画材芯体の気孔内に蛍光色素を溶解した樹脂が充填された形態である。すなわち、上記インクＢを乾燥させた時点で蛍光色素であるシンロイヒカラーＳＢ−１５はブチラール樹脂内に分散し内包されて、安定した状態となっている。
該焼成固形描画材を把持することができるホルダー、すなわち、図１に示す筆記具で把持して任意の長さで、繰り出して使用することができた。また、裏うつりもなく、塗布した箇所、特にアンダーライン用途に好適な焼成固形描画材となった。
(Example 5)
Formulation composition:
40% by mass of vinyl chloride resin
Dioctyl phthalate (DOP) 10% by mass
Boron nitride 50% by mass
The above blended composition was kneaded, and this kneaded product was extruded into a rectangular shape with a square cross section with an extruder and heated at 1000 ° C. for 5 hours in an inert gas atmosphere to prepare a sintered core of boron nitride and binder carbon. . This fired core was heated at 700 ° C. in the atmosphere for 12 hours to prepare a fired core made of only boron nitride. This was impregnated with silicate 40 (manufactured by Colcoat Co.), dried, and then heated in an inert atmosphere at 1000 ° C. for 5 hours to obtain a rectangular white fired core.
This rectangular white fired core was impregnated with the following composition and dried at 80 ° C. for 12 hours.
Formulation composition (ink B):
Sinroich color SB-15 20% by mass
Butyral resin: ESREC BL-1 (manufactured by Sekisui Chemical Co., Ltd.) 20% by mass
IPA 60% by mass
The pores obtained by this drying were impregnated with α-olefin oil (manufactured by Mobil Oil Co., Ltd .: Spectracin 4) at 60 ° C. for 6 hours, and were rectangular fluorescent yellow fired solids having a width of 8 mm, a thickness of 1 mm and a length of 100 mm. A drawing material was obtained.
In this embodiment, a resin in which a fluorescent dye is dissolved is filled in the pores of the fired solid drawing material core. That is, when the ink B is dried, the Sinlohi color SB-15, which is a fluorescent dye, is dispersed and included in the butyral resin and is in a stable state.
The holder that can hold the fired solid drawing material, that is, the writing tool shown in FIG. 1, can be drawn out and used in an arbitrary length. Moreover, it became a baked solid drawing material suitable for the applied part, especially an underline use, without a back slip.
（実施例６）
配合組成物：
塩化ビニル樹脂 ４０質量％
フタル酸ジオクチル（ＤＯＰ） １０質量％
窒化ホウ素 ５０質量％
上記配合組成物を混練し、この混練物を押出機にて断面四角形の矩形状に押出成形し、不活性ガス雰囲気１０００℃で５時間加熱し、窒化ホウ素とバインダー炭素の焼成芯体を作製した。この焼成芯体を大気雰囲気７００℃で１２時間加熱し、窒化ホウ素のみの焼成芯体を作成した。ここにシリケート４０（コルコート社製）を含浸し、乾燥した後、不活性雰囲気１０００℃で５時間加熱して矩形状白色焼成芯体を得た。
この矩形状白色焼成芯体に、下記配合組成物を含浸し、８０℃で１２時間乾燥した。
配合組成物（インクＣ）：
エポカラーＦＰ−１１２ ２０質量％
ブチラール樹脂：エスレックＢＬ−１（積水化学社製） ２０質量％
ＩＰＡ ６０質量％
この乾燥で得られた細孔にα−オレフィンオイル（モービル石油社製：スペクトラシン４）を６０℃で６時間含浸し、幅８ｍｍ、厚さ１ｍｍ、長さ１００ｍｍの矩形状の蛍光桃色焼成固形描画材を得た。
本実施例は、焼成固形描画材芯体の気孔内に蛍光色素を溶解した樹脂が充填された形態である。すなわち、上記インクＣを乾燥させた時点で蛍光色素であるエポカラーＦＰ−１１２はブチラール樹脂内に分散し内包されて、安定した状態となっている。
該焼成固形描画材を把持することができるホルダー、すなわち、図１に示す筆記具で把持して任意の長さで、繰り出して使用することができた。また、裏うつりもなく、塗布した箇所、特にアンダーライン用途に好適な焼成固形描画材となった。
(Example 6)
Formulation composition:
40% by mass of vinyl chloride resin
Dioctyl phthalate (DOP) 10% by mass
Boron nitride 50% by mass
The above blended composition was kneaded, and this kneaded product was extruded into a rectangular shape with a square cross section with an extruder and heated at 1000 ° C. for 5 hours in an inert gas atmosphere to prepare a sintered core of boron nitride and binder carbon. . This fired core was heated at 700 ° C. in the atmosphere for 12 hours to prepare a fired core made of only boron nitride. This was impregnated with silicate 40 (manufactured by Colcoat Co.), dried, and then heated in an inert atmosphere at 1000 ° C. for 5 hours to obtain a rectangular white fired core.
This rectangular white fired core was impregnated with the following composition and dried at 80 ° C. for 12 hours.
Formulation composition (ink C):
Epocolor FP-112 20% by mass
Butyral resin: ESREC BL-1 (manufactured by Sekisui Chemical Co., Ltd.) 20% by mass
IPA 60% by mass
The pores obtained by this drying were impregnated with α-olefin oil (manufactured by Mobil Sekiyu Co., Ltd .: Spectracin 4) at 60 ° C. for 6 hours to form a rectangular fluorescent pink baked solid having a width of 8 mm, a thickness of 1 mm and a length of 100 mm. A drawing material was obtained.
In this embodiment, a resin in which a fluorescent dye is dissolved is filled in the pores of the fired solid drawing material core. That is, when the ink C is dried, the Epochal FP-112, which is a fluorescent dye, is dispersed and included in the butyral resin, and is in a stable state.
The holder that can hold the fired solid drawing material, that is, the writing tool shown in FIG. 1, can be drawn out and used in an arbitrary length. Moreover, it became a baked solid drawing material suitable for the applied part, especially an underline use, without a back slip.
（比較例１）
配合組成物：
窒化ホウ素 ４０質量％
カオリン ３５質量％
ポリビニルアルコール １８質量％
ポリエチレングリコール ７質量％
上記配合組成物と同重量との水とをへンシェルミキサーで混合分散し、２本ロールで混練し、水分調整した後、細線状に押出成形し、これから残留する水を除去すべく、空気中で１０５℃にて１５時間熱処理して、しかる後アルゴンガス中にて１１００℃まで昇温して１１００℃で１ 時間焼成した。さらに、酸化雰囲気で７００℃で加熱焼成し、炭素化物を除去して白色の焼成芯体を得た。
次に、
スピロンレッドＣ−ＧＨ（保土谷化学工業社製） ２５質量％
エチルアルコール ２５質量％
オレイルアルコール ５０質量％
からなる赤色溶液に上記焼成芯体を浸し、常温で２４時間放置した。溶液から芯体を取り出した後、８０℃で５時間乾操してエチルアルコールを除去して幅５ｍｍ、厚さ０．８ｍｍ、長さ１２０ｍｍの矩形状の赤色焼成固形描画材とした。ここではスピロンレッドＣ−ＧＨはオレイルアルコール中に溶解した状態であって、樹脂に溶解された状態とはなっていない。
(Comparative Example 1)
Formulation composition:
Boron nitride 40% by mass
Kaolin 35% by mass
Polyvinyl alcohol 18% by mass
Polyethylene glycol 7% by mass
The above blended composition and water of the same weight are mixed and dispersed with a Henschel mixer, kneaded with two rolls, adjusted for moisture, extruded into a thin line, and then air is removed to remove the remaining water. Then, it was heat-treated at 105 ° C. for 15 hours, and then heated to 1100 ° C. in an argon gas and baked at 1100 ° C. for 1 hour. Furthermore, it was heated and fired at 700 ° C. in an oxidizing atmosphere to remove the carbonized product, and a white fired core was obtained.
next,
Spiron Red C-GH (Hodogaya Chemical Co., Ltd.) 25% by mass
Ethyl alcohol 25% by mass
Oleyl alcohol 50% by mass
The fired core was dipped in a red solution consisting of and left at room temperature for 24 hours. After the core was taken out of the solution, it was dried at 80 ° C. for 5 hours to remove ethyl alcohol to obtain a rectangular red fired solid drawing material having a width of 5 mm, a thickness of 0.8 mm and a length of 120 mm. Here, Spiron Red C-GH is in a state dissolved in oleyl alcohol and not in a resin.
上記実施例１〜６において、染料を内包した樹脂の、厚さが1μｍ以下の皮膜状であることの確認は、下記方法で測定した。
また、上記で得られた各色のシャープペンシル芯について、下記試験方法により、曲げ強度、描線の発色、耐光性、消去性について評価した。
これらの結果を下記表１に示す。
In the said Examples 1-6, confirmation of the film-form whose thickness of the resin which included the dye was 1 micrometer or less was measured with the following method.
The mechanical pencil cores of the respective colors obtained above were evaluated for bending strength, color development of drawn lines, light resistance, and erasability by the following test methods.
These results are shown in Table 1 below.
（樹脂皮膜の厚みの測定方法）
得られた芯をレーザーカットし、断面を電子顕微鏡（Ｓ−４８００、日立ハイテク社製）にて測定した。
(Measurement method of resin film thickness)
The obtained core was laser cut, and the cross section was measured with an electron microscope (S-4800, manufactured by Hitachi High-Tech).
〔試験方法〕
（曲げ強度の評価方法）
ＪＩＳ−Ｓ−６００５−２００７に準拠して曲げ強度を測定した（ｎ＝１００）。
〔Test method〕
(Bending strength evaluation method)
The bending strength was measured according to JIS-S-6005-2007 (n = 100).
（描線の発色の評価方法）
JＩＳ Ｓ ６００５：２００７に規定されている画線機を用いた濃度測定方法と同様に分光測色計を用いて測定したL*ab値における彩度（ａ2＋ｂ2）1/2で示す（ｎ＝１００）。
(Evaluation method for coloration of drawn lines)
The saturation (a 2 + b 2 ) 1/2 of the L * ab value measured using a spectrocolorimeter in the same manner as the density measuring method using the drawing machine defined in JIS S 6005: 2007 ( n = 100).
（耐光性の評価方法）
上記画線した描線に、ＪＩＳ Ｌ ０８４１：２００４に準拠して露光した際の色差ΔＥ*ａｂ＝［（ΔＬ*）2＋（Δａ*）2＋（Δｂ*）2］1/2を測定した（ｎ＝１００）。
(Light resistance evaluation method)
A color difference ΔE * ab = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1/2 was measured when the drawn line was exposed in accordance with JIS L 0841: 2004. (N = 100).
（消去性の評価方法）
ＪＩＳ Ｓ ６０５０−２００８に開示されているプラスチック字消しの消し能力（消字率）試験に準拠し、Ｅ（消字率：＝消去率）＝（１−Ｍ／Ｃ）×１００〔Ｍ：摩消部の濃度、Ｃ：着色部の濃度〕により、消去率（５往復）を測定した（ｎ＝１００）。
(Evaluation method for erasability)
In accordance with the erasing ability (erasing rate) test of plastic erasing disclosed in JIS S 6050-2008, E (erasing rate: = erasing rate) = (1-M / C) × 100 [M: Erasing rate (5 reciprocations) was measured (concentration of erased part, C: density of colored part) (n = 100).
上記表１の結果をみると、本発明範囲となる実施例１〜６は、本発明の範囲外となる比較例１に較べ、曲げ強度、描線の発色、耐光性、消しゴム消去性について優れていることが判明した。
また、実施例５〜６の固形描画材を図１に示す替え芯式のホルダータイプの筆記具で筆記（マーク）したところ、裏うつりもなく、好適なアンダーラインマーカーなどとして使用することができ、消しゴム消去性にも優れていることが判明した。
Looking at the results of Table 1 above, Examples 1 to 6, which are within the scope of the present invention, are superior in bending strength, color development of the drawn lines, light resistance, and eraser erasability compared to Comparative Example 1 that is outside the scope of the present invention. Turned out to be.
Moreover, when the solid drawing material of Examples 5 to 6 was written (marked) with a rewriting type holder-type writing instrument shown in FIG. 1, there was no backside movement and it could be used as a suitable underline marker, It was found that the eraser was excellent in erasability.
ホルダータイプの固形マーキング、アンダーラインに好適に用いることができる。 It can be suitably used for holder-type solid marking and underline.
Claims (6)
Ａ群：イソプロピルアルコール、エタノール、メトシキメチルブタノール、ベンジルアルコール、トルエン、キシレン、アセトン、メチルエチルケトン、酢酸エチル、エチルセロソルブ、フェニルセロソルブ、ベンジルアルコール
Ｂ群：染着樹脂、ドープ染料
Ｃ群：パラフィンオイル、α−オレフィンオイル、脂肪酸エステル、エステルオイル、合成油、ヒマシオイル、グリース Filled with a resin soluble in the organic solvent of the following group A in which the dye is dissolved in the pores of the solid drawing material core or a resin encapsulating the dye of the following group B soluble in the organic solvent, A fired solid drawing material characterized in that it is not contained and filled with a lubricating oil selected from the following group C.
Group A: isopropyl alcohol, ethanol, methoxymethylbutanol, benzyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, ethyl cellosolve, phenyl cellosolve, benzyl alcohol
Group B: Dyeing resin, dope dye
Group C: paraffin oil, α-olefin oil, fatty acid ester, ester oil, synthetic oil, castor oil, grease
Ａ群：イソプロピルアルコール、エタノール、メトシキメチルブタノール、ベンジルアルコール、トルエン、キシレン、アセトン、メチルエチルケトン、酢酸エチル、エチルセロソルブ、フェニルセロソルブ、ベンジルアルコールGroup A: isopropyl alcohol, ethanol, methoxymethylbutanol, benzyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, ethyl acetate, ethyl cellosolve, phenyl cellosolve, benzyl alcohol
Ｂ群：染着樹脂、ドープ染料Group B: Dyeing resin, dope dye
Ｃ群：パラフィンオイル、α−オレフィンオイル、脂肪酸エステル、エステルオイル、合成油、ヒマシオイル、グリースGroup C: paraffin oil, α-olefin oil, fatty acid ester, ester oil, synthetic oil, castor oil, grease
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| EP3461869B1 (en) * | 2017-09-29 | 2020-04-22 | Faber- Castell AG | Coloured lead or coloured chalk, pencil with a coloured lead and method for producing a coloured lead or coloured chalk |
| JP7034684B2 (en) * | 2017-11-30 | 2022-03-14 | 株式会社パイロットコーポレーション | Fired colored pencil lead |
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| JPS5424748Y2 (en) * | 1974-09-06 | 1979-08-21 | ||
| JPS585951B2 (en) * | 1974-11-29 | 1983-02-02 | パイロツトインキ カブシキガイシヤ | Tashiyoku Enshinyou Ink |
| JPS5423615A (en) * | 1977-07-22 | 1979-02-22 | Furointo Sangiyou Kk | Colored glass beads and method of making same |
| JPH0630991B2 (en) * | 1984-06-14 | 1994-04-27 | パイロツトプレシジヨン株式会社 | Discolored core |
| JPH0734024A (en) * | 1993-07-20 | 1995-02-03 | Pilot Precision Co Ltd | Color pencil lead |
| JP2006057083A (en) * | 2004-07-20 | 2006-03-02 | Sakura Color Prod Corp | Crayon |
| JP4806921B2 (en) * | 2004-10-29 | 2011-11-02 | ぺんてる株式会社 | Pencil lead |
| JP2010126686A (en) * | 2008-11-28 | 2010-06-10 | Pentel Corp | Fired lead for pencil |
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