JP4620363B2 - Contents visible writing instrument member and writing instrument - Google Patents

Contents visible writing instrument member and writing instrument Download PDF

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JP4620363B2
JP4620363B2 JP2004040433A JP2004040433A JP4620363B2 JP 4620363 B2 JP4620363 B2 JP 4620363B2 JP 2004040433 A JP2004040433 A JP 2004040433A JP 2004040433 A JP2004040433 A JP 2004040433A JP 4620363 B2 JP4620363 B2 JP 4620363B2
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writing instrument
ink
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visible
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JP2005231084A (en
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隆雄 小山
清和 桜井
佐々木　　洋
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Hitachi Ltd
Mitsubishi Pencil Co Ltd
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Mitsubishi Pencil Co Ltd
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本発明は、筆記具用インキ、塗布液、修正液などの内容物がインキ収容容器、インキ収容管、塗布液容器、塗布液収容管等の樹脂製の筆記具用部材に接触し、その内容物を外部から確実に視認することができる内容物可視型筆記具用部材及びその筆記具用部材を備えた筆記具に関する。   In the present invention, the contents such as the ink for the writing instrument, the coating liquid, and the correction liquid come into contact with the resin-made writing instrument member such as the ink storage container, the ink storage pipe, the coating liquid container, and the coating liquid storage pipe. The present invention relates to a member for a content visible type writing instrument that can be surely visually recognized from the outside, and a writing instrument including the member for the writing instrument.

従来、筆記具用インキなどの内容物と接触する筆記具用部材としては、例えば、ボールペンにおけるインキ収容管（リフィール）、コレクター構造を備えた直液式筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材、バルブ機構を有する筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材などの各種構造のものが知られている。
これらの筆記具用部材は、その先端にボールペン型チップや繊維芯からなるペン芯などのペン先を取り付けることなどにより筆記具として使用に供されるものである。 Conventionally, as a member for a writing instrument that comes into contact with contents such as ink for a writing instrument, for example, an ink storage tube (refill) in a ballpoint pen, a shaft body that directly stores ink in a direct liquid writing instrument having a collector structure (an ink storage container) ) And an ink tank member serving as a shaft (ink container) for directly storing ink in a writing instrument having a valve mechanism are known.
These writing instrument members are used as a writing instrument by attaching a pen tip such as a ballpoint pen tip or a pen core made of a fiber core to the tip of the member.

これらの筆記具は、そのインキ残量が外から確認できるように、インキ収容容器やインキ収容管などの筆記具用部材を透明又は半透明の視認性を有する材質、一般に、コスト、汎用性、成形性等の点からポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）などの熱可塑性樹脂で形成している。   These writing instruments are made of transparent or semi-transparent material for writing instruments such as ink storage containers and ink storage tubes so that the remaining amount of ink can be confirmed from the outside, generally cost, versatility, and moldability. In view of the above, it is formed of a thermoplastic resin such as polypropylene (PP), polyethylene (PE), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT).

このような筆記具にあっては、インキなどの内容物がインキ収容容器やインキ収容管などの筆記具用部材の内側表面部（内壁面部）に付着してインキの残量の確認が困難となる問題があった。
このような問題に対して、例えば、特定物性のシリコーンオイルが塗布されているボールペン用インキ収容管（特許文献１参照）や、透明又は半透明の熱可塑性樹脂で形成されたインキ収容室の内面にエポキシ系樹脂とパーフルオロアルキル基を有する（メタ）アクリル酸系熱硬化性樹脂とによりなるインキ反発面を形成したことを特徴とする筆記具用インキ収容室（特許文献２参照）などが知られている。 In such a writing instrument, it is difficult to check the remaining amount of ink because the contents such as ink adhere to the inner surface part (inner wall surface part) of the member for the writing instrument such as the ink container or the ink container. was there.
For such problems, for example, an ink storage tube for a ballpoint pen (see Patent Document 1) coated with silicone oil having specific physical properties, or an inner surface of an ink storage chamber formed of a transparent or translucent thermoplastic resin. Ink storage chambers for writing instruments (refer to Patent Document 2) and the like, in which an ink-repellent surface comprising an epoxy resin and a (meth) acrylic acid-based thermosetting resin having a perfluoroalkyl group are formed, are known. ing.

しかしながら、上記各文献に記載される筆記具用インキ収容管などは、処理しないものよりもインキ残量の視認性等は良好であるが、上記シリコーンオイルによる塗布や、エポキシ系樹脂とパーフルオロアルキル基を有する（メタ）アクリル酸系熱硬化性樹脂とによりなるインキ反発面は、未だインキ収容管の部材表面との密着性が不充分であるため、そのインキ残量等の確認が経時的に劣化するという課題があり、また、近年、優れた筆記性能、塗布性能を有する低表面張力のインキ、塗布液、修正液などが開発されており、このような低表面張力のインキや塗布液等に対してはインキ残量等の確認が未だ不十分であるという課題もあり、更に、近年の消費者ニーズ等はその品質の要求が高く、インキや塗布液等の内容物を外部から確実に視認することができる高品質の内容物可視（視認）型筆記具用部材及びその筆記具用部材を備えた筆記具が切望されているのが現状である。
特公昭６１−４０１９６号公報（特許請求の範囲、実施例等） 特開平７−８１２９０号公報（特許請求の範囲、実施例等） However, the ink storage tube for writing instruments described in each of the above documents has better visibility of the remaining amount of ink than the untreated one, but the application with the silicone oil, the epoxy resin and the perfluoroalkyl group, etc. The ink repellent surface made of (meth) acrylic acid-based thermosetting resin with a sufficient amount of ink still has insufficient adhesion to the surface of the ink containing tube. In recent years, low surface tension inks, coating liquids and correction liquids with excellent writing performance and coating performance have been developed, and such low surface tension inks and coating liquids have been developed. On the other hand, there is a problem that confirmation of the remaining amount of ink is still inadequate, and in addition, there is a high demand for quality in recent consumer needs, etc., and contents such as ink and coating liquid are reliably externally supplied. The writing tool having a high quality of the contents visible (visible) type writing instrument member and a writing instrument member which can be sure have been required at present.
Japanese Patent Publication No. 61-40196 (Claims, Examples, etc.) JP-A-7-81290 (Claims, Examples, etc.)

本発明は、上記従来技術の課題及び現状等に鑑み、これを解消しようとするものであり、インキや塗布液等の内容物を外部から確実に視認することができると共に、その視認性は経時的にも良好となる内容物可視（視認）型筆記具用部材及びその筆記具用部材を備えた筆記具を提供することを目的とする。   The present invention intends to solve this problem in view of the above-mentioned problems and the present situation of the prior art, and the contents such as ink and coating liquid can be surely visually recognized from the outside, and the visibility is improved over time. It aims at providing the writing instrument provided with the member for visible (visual recognition) type writing instruments and the writing instrument member which become the contents favorable also.

本発明者らは、上記従来の課題等を解決するために、鋭意検討した結果、筆記具用インキ、塗布液、修正液などの内容物を収容（接触）するインキ収容容器、インキ収容管、塗布液容器、塗布液収容管等の樹脂製の筆記具用部材の少なくとも内側表面部に、特定の処理を施すことにより、上記目的の内容物可視型筆記具用部材及び筆記具が得られることを見い出し、本発明を完成するに至ったのである。   As a result of intensive studies to solve the above-described conventional problems, the present inventors have found that an ink storage container, an ink storage tube, and a coating that contain (contact) contents such as writing instrument ink, coating liquid, and correction liquid. It has been found that the above-mentioned contents-visible type writing instrument member and writing instrument can be obtained by performing a specific treatment on at least the inner surface portion of a resin writing instrument member such as a liquid container and a coating liquid storage tube. The invention has been completed.

すなわち、本発明は、次の（１）〜（１３）に存する。
（１） 内容物が接触する樹脂製の筆記具用部材の少なくとも内側表面部は、撥水撥油処理されていることを特徴とする内容物可視型筆記具用部材。
（２） 筆記具用部材の少なくとも内側表面部は、活性化処理された後に、撥水撥油処理されている上記（１）記載の内容物可視型筆記具用部材。
（３） 筆記具用部材の少なくとも内側表面部は、活性化処理された後に、ＳｉＯ2の薄膜が形成され、該ＳｉＯ2薄膜に撥水撥油処理されている上記（２）記載の内容物可視型筆記具用部材。
（４） 活性化処理が、オゾン処理、空気プラズマ処理、酸素プラズマ処理、コロナ処理、紫外線照射処理、高圧放電処理及び酸処理から選ばれる一種又は二種以上を複合化させて処理する上記（２）又は（３）に記載の内容物可視型筆記具用部材。
（５） 撥水撥油処理が、シリコーン処理及びフッ素処理から選ばれる少なくとも１種である上記（１）〜（４）の何れか一つに記載の内容物可視型筆記具用部材。
（６） 撥水撥油処理が、少なくとも２回行われる上記（１）〜（５）の何れか一つに記載の内容物可視型筆記具用部材。
（７） 活性化処理が、空気プラズマ処理であり、撥水撥油処理が、シリコーン処理である上記（２）又は（５）に記載の内容物可視型筆記具用部材。
（８） 活性化処理が、酸素プラズマ処理であり、撥水撥油処理が、シリコーン処理である上記（２）又は（５）に記載の内容物可視型筆記具用部材。
（９） 筆記具用部材に、ポリオレフィン系熱可塑性樹脂を用いてなる上記（１）〜（８）の何れか一つに記載の内容物可視型筆記具用部材。
（１０） ポリオレフィン系熱可塑性樹脂がポリプロピレンである上記（９）に記載の内容物可視型筆記具用部材。
（１１） 内容物には、水又は極性有機溶媒を含む上記（１）〜（１０）の何れか一つに記載の内容物可視型筆記具用部材。
（１２） 内容物可視型筆記具用部材がインキ収容容器、インキ収容管、塗布液容器、塗布液収容管の何れか一つである上記（１）〜（１１）の何れか一つに記載の内容物可視型筆記具用部材。
（１３） 上記（１）〜（１２）の何れか一つに記載の内容物可視型筆記具用部材を備えたことを特徴とする筆記具。 That is, the present invention resides in the following (1) to (13).
(1) A content-visible writing instrument member, wherein at least an inner surface portion of a resin-made writing instrument member in contact with the contents is subjected to water / oil repellent treatment.
(2) The content visible type writing instrument member according to the above (1), wherein at least the inner surface portion of the writing instrument member is subjected to an activation treatment and then a water and oil repellent treatment.
(3) The content visible according to (2) above, wherein at least the inner surface portion of the writing instrument member is activated, and then a SiO 2 thin film is formed, and the SiO 2 thin film is subjected to water / oil repellent treatment. Member for mold writing instruments.
(4) The above (2), wherein the activation treatment is performed by combining one or more selected from ozone treatment, air plasma treatment, oxygen plasma treatment, corona treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, and acid treatment. ) Or a member for visible writing instrument according to (3).
(5) The content visible writing instrument member according to any one of (1) to (4), wherein the water / oil repellent treatment is at least one selected from silicone treatment and fluorine treatment.
(6) The content visible writing instrument member according to any one of (1) to (5), wherein the water / oil repellent treatment is performed at least twice.
(7) The member for visible content writing instrument according to the above (2) or (5), wherein the activation treatment is an air plasma treatment and the water / oil repellent treatment is a silicone treatment.
(8) The member for visible content writing instrument according to the above (2) or (5), wherein the activation treatment is an oxygen plasma treatment, and the water / oil repellent treatment is a silicone treatment.
(9) The content-visible writing instrument member according to any one of (1) to (8), wherein a polyolefin-based thermoplastic resin is used for the writing instrument member.
(10) The member for visible content writing instrument according to (9), wherein the polyolefin-based thermoplastic resin is polypropylene.
(11) The content visible writing instrument member according to any one of (1) to (10), wherein the content contains water or a polar organic solvent.
(12) The content visible type writing instrument member according to any one of (1) to (11) above, wherein the member is any one of an ink container, an ink container, a coating liquid container, and a coating liquid container. Contents visible writing instrument.
(13) A writing instrument comprising the content-visible writing instrument member according to any one of (1) to (12).

本発明によれば、筆記具用インキ、塗布液、修正液などの内容物が接触する樹脂製の筆記具用部材の少なくとも内側表面部を活性化処理された後に、ＳｉＯ 2 の薄膜を形成し、該ＳｉＯ 2 薄膜に撥水撥油処理して単分子膜が形成されているので、筆記具用部材の表面との密着性が向上し、インキ残量等の確認が確実に、しかも、その視認性（クリアドレイン性）は経時的に優れると共に、低表面張力のインキ等に対してもインキ残量等の確認が確実となる高品質の内容物可視型筆記具用部材及びその筆記具用部材を備えた筆記具が提供される。 According to the present invention, after at least the inner surface portion of the resin writing tool member to which the contents such as the writing tool ink, the coating liquid, and the correction liquid come into contact is activated, a thin film of SiO 2 is formed, Since the SiO 2 thin film is formed with a water and oil repellent treatment and a monomolecular film is formed, the adhesion to the surface of the writing instrument member is improved, and the remaining amount of ink is reliably confirmed and its visibility ( Clear drainability) is superior over time, and a high-quality contents visible-type writing instrument member capable of confirming the remaining amount of ink even for low surface tension ink, etc., and a writing instrument provided with the writing instrument member but Ru is provided.

以下に、本発明の実施形態を詳しく説明する。
本発明の内容物可視型筆記具用部材は、内容物が接触する樹脂製の筆記具用部材の少なくとも内側表面部が撥水撥油処理されてい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 content visible type writing instrument member of the present invention is characterized in that at least the inner surface portion of the resin writing instrument member in contact with the contents is subjected to water / oil repellent treatment.

本発明の筆記具用部材の構造としては、筆記具用インキ、塗布液、修正液、液状化粧料などの内容物が接触することとなるインキ収容容器、インキ収容管、塗布液容器、塗布液収容管などが挙げられる。例えば、図１におけるボールペンにおけるインキ収容管（リフィール、図示符号１１）、図２におけるコレクター構造を備えた直液式筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材（図示符号２１）、図３におけるバルブ機構を有する筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材（図示符号３１）などが挙げられ、筆記具用インキ、塗布液、修正液などの内容物が接触し、その内容物を外から視認できる透明又は半透明の樹脂製の筆記具用部材であれば、その構造、製法等は特に限定されものではない。   As the structure of the writing instrument member of the present invention, the ink storage container, the ink storage pipe, the coating liquid container, and the coating liquid storage pipe that are in contact with the contents such as the writing instrument ink, the coating liquid, the correction liquid, and the liquid cosmetics. Etc. For example, an ink tank member (illustration 11) serving as a shaft (ink container) for directly storing ink in the ink storage tube (refill, reference numeral 11) in the ballpoint pen in FIG. 1 and the direct liquid writing instrument having the collector structure in FIG. 21), an ink tank member (reference numeral 31) serving as a shaft body (ink container) for directly storing ink in the writing instrument having the valve mechanism in FIG. 3, ink for writing instrument, coating liquid, correction liquid, etc. The structure, manufacturing method, etc. are not particularly limited as long as the contents are in contact with each other and the contents are transparent or translucent resin writing instrument members that can be visually recognized from the outside.

本発明において、筆記具用部材の材質（樹脂）としては、例えば、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、環状ポリオレフィン、ポリメチルペンテンなどのポリオレフィン系樹脂、ポリカーボネート（ＰＣ）、ポリスチレン、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）やポリブチレンテレフタレート（ＰＢＴ）、ポリアミド、並びに、フッ素樹脂、フッ化ビニリデンなどのフッ素プラスチックなどの透明又は半透明の視認性を有し、かつ、内容物に対して耐性を有する熱可塑性樹脂が挙げられ、好ましくは、耐溶剤性、経済性、生産性等からポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、環状ポリオレフィン、ポリメチルペンテンなどから選ばれるポリオレフィン系熱可塑性樹脂、更に好ましくは、ポリプロピレン（ＰＰ）が望ましい。   In the present invention, the material (resin) of the writing instrument member is, for example, a polyolefin resin such as polypropylene (PP), polyethylene (PE), cyclic polyolefin, polymethylpentene, polycarbonate (PC), polystyrene, polyethylene terephthalate (PET). ), Transparent or translucent visibility such as polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyamide, and fluoroplastics such as fluororesin and vinylidene fluoride, and the contents A thermoplastic resin having resistance, preferably a polyolefin-based thermoplastic resin selected from polypropylene (PP), polyethylene (PE), cyclic polyolefin, polymethylpentene, etc. in view of solvent resistance, economy, productivity, etc. Even better Details, polypropylene (PP) is preferable.

本発明では、筆記具用インキ、塗布液、修正液、液状化粧料などの内容物が接触するインキ収容容器、インキ収容管、塗布液容器、塗布液収容管などの樹脂製筆記具用部材の少なくとも内側表面部には、撥水撥油処理がされていることが必要である。
本発明において、撥水撥油処理としては、例えば、シリコーン処理及び／又はフッ素処理が挙げられる。 In the present invention, at least the inside of a member for a resin writing instrument such as an ink storage container, an ink storage tube, a coating liquid container, a coating liquid storage tube, etc. with which the contents such as ink for writing instruments, coating liquid, correction liquid, and liquid cosmetics come into contact. The surface portion needs to be subjected to water / oil repellent treatment.
In the present invention, examples of the water / oil repellent treatment include silicone treatment and / or fluorine treatment.

本発明に用いる他のシリコーン処理としては、例えば、ジメチルシリコーンを有するシリコーンワニスの硬化物からなるシリコーン処理、上記シリコーンワニスの硬化機構が、縮合型、付加型、ＵＶ型の何れかであるもの、更に、上記シリコーンワニスにはシリカ微粒子が含有してなるもの、または、アクリル系樹脂とジメチルシリコーンとがグラフトしてなる処理が挙げられる。   Examples of the other silicone treatment used in the present invention include, for example, a silicone treatment comprising a cured product of a silicone varnish having dimethyl silicone, and the curing mechanism of the silicone varnish is any of a condensation type, an addition type, and a UV type, Furthermore, the silicone varnish includes a silica fine particle-containing treatment or a treatment obtained by grafting an acrylic resin and dimethyl silicone.

上記シリコーンワニスの硬化物による処理としては、例えば、付加型、ＵＶ型、縮合型が挙げられ、付加型は硬化時の副生成物がなく、深部まで硬化する点で優れ、また、ＵＶ型は硬化性及び取り扱い性に優れている。上記縮合型には、脱アルコール型、脱オキシウム型、脱酢酸型、脱アミン型、脱アミド型、脱アミノキシ型、脱アセトン型、脱水素型、脱水型などがあり、また、これらは一液型又はニ液型で硬化するものである。これらのシリコーンワニスの硬化物による処理においては、好ましくは、筆記具用部材の材質、用いるインキ種等により最も好適となる付加型、ＵＶ型、縮合型から選択してシリコーンワニスの硬化物からなる処理面を構成することができ、特に、作業性、使用性、コスト、密着性に優れる点から縮合型が好ましく、更に好ましくはエタノール系インキに対してもシリコーンワニスの硬化物中で最も優れる点から、一液型の脱オキシウム型が特に望ましい。   Examples of the treatment with the cured product of the silicone varnish include an addition type, a UV type, and a condensation type. The addition type is excellent in that it has no by-products at the time of curing and cures to a deep portion. Excellent curability and handleability. The above condensation types include dealcohol, deoxime, deacetate, deamine, deamid, deaminoxy, deacetone, dehydrogenate, and dehydrated types. It cures in a mold or a two-part type. In the treatment with a cured product of these silicone varnishes, a treatment comprising a cured product of a silicone varnish, preferably selected from an addition type, a UV type, and a condensation type, which is most suitable depending on the material of the writing instrument member, the type of ink used, etc. In particular, the condensation type is preferable from the viewpoint of excellent workability, usability, cost, and adhesion, and more preferably from the most excellent cured silicone varnish for ethanol-based inks. A one-pack type deoxyxium type is particularly desirable.

また、上記シリコーンワニスにシリカ微粒子が含有してなる処理は、シリコーンワニス硬化物単独からなるものに較べ、更にその硬度、強度を向上させるものである。このシリカ等を充填することにより硬度、強度を向上させることができる。シリカ中にあるシラノール基とシリコーンワニスが加水分解した後のシラノール基と脱水縮合反応によりシロキサン結合して化学的に強固に結合して硬度、強度を向上させることができるものとなる。シリカの含有量はシリコーンワニス中のシリコーンに対して、重量で１〜１００％、好ましくは、５〜５０％とすることが望ましく、また、シリカは非晶質シリカが望ましい。   Moreover, the process which silica fine particles contain in the said silicone varnish improves the hardness and intensity | strength further compared with what consists of a silicone varnish hardened | cured material alone. By filling the silica or the like, the hardness and strength can be improved. Silanol groups in the silica and the silanol groups after the silicone varnish are hydrolyzed and siloxane bonds by a dehydration condensation reaction and chemically bonded to improve hardness and strength. The content of silica is 1 to 100% by weight, preferably 5 to 50%, based on the silicone in the silicone varnish, and the silica is preferably amorphous silica.

本発明に用いるフッ素処理としては、パーフルオロアルキル基を有するフッ素樹脂によるフッ素処理、パーフルオロポリエーテル基、或いはパーフルオロアルキル基を有するシランカップリング処理などが挙げられる。   Examples of the fluorine treatment used in the present invention include fluorine treatment with a fluororesin having a perfluoroalkyl group, silane coupling treatment having a perfluoropolyether group, or a perfluoroalkyl group.

本発明に用いるフッ素処理としては、例えば、下記構造式（Ｉ）の含フッ素化合物（結合残基が両末端型）による処理、

Figure 0004620363
下記構造式（ＩＩ）の含フッ素化合物（結合残基が片末端型）による処理
Figure 0004620363
 下記構造式（ＩＩＩ）の含フッ素化合物（結合残基が片末端型）による処理
Figure 0004620363
 などが挙げられる。
これらのフッ素処理は、末端の結合残基であるアルコキシシラン基が表面の水酸基等と化学結合することにより形成する単分子膜によって撥水撥油性が発揮される。
上記に示す以外のシリコーン処理又はフッ素処理に用いる材料としては、例えば、Ｘ−３１−６０８−Ｔ（脱オキシウム型：シリコーン２０ｗｔ％に対して非晶質シリカ粒子を５ｗｔ％含有、信越化学工業社製）、ＩＮＴ−３０４ＶＣ（フッ素樹脂の２ｗｔ％溶液、溶剤：ＣＦ3ＣＦ2ＣＨＦＣＨＦＣＦ3、ＮＩマテリアル社製）、ＳＧ−２０４（ポリシロキサングラフトポリマー、日本触媒社製）、Ｎｏ．３０９（フッ素樹脂の１５ｗｔ％溶液、溶剤：イソへキサン／アセトン混合溶媒、ＩＮＴスクリーン社製）、ＪＳ−０２５（ポリシロキサングラフトアクリル樹脂、日本ペイント社製）、ＩＮＴ−３０４ＶＢ（フッ素樹脂の４ｗｔ％溶液、溶剤：ＣＦ3ＣＦ2ＣＨＦＣＨＦＣＦ3、ＩＮＴスクリーン社製）、テフロン（登録商標）ＡＦ１６００（パーフルオロフッ素樹脂、三井・デュポンフロロケミカル社製）、サイトップＣＴＬ１１０Ａ（パーフルオロフッ素樹脂、末端カルボキシル基、旭硝子社製）、同ＣＴＬ１１０Ｓ（パーフルオロフッ素樹脂、末端−ＣＦ3基、旭硝子社製）等を用いることができる。 As the fluorine treatment used in the present invention, for example, treatment with a fluorine-containing compound of the following structural formula (I) (bonded residues are both terminal types),
Figure 0004620363
 Treatment with a fluorine-containing compound of the following structural formula (II) (bonding residue is one-end type)
Figure 0004620363
 Treatment with a fluorine-containing compound of the following structural formula (III) (bonding residue is one terminal type)
Figure 0004620363
 Etc.
These fluorine treatments exhibit water and oil repellency by a monomolecular film formed by chemically bonding an alkoxysilane group as a terminal bonding residue with a hydroxyl group on the surface.
Examples of materials used for silicone treatment or fluorine treatment other than those described above include, for example, X-31-608-T (deoxynium type: containing 5 wt% of amorphous silica particles relative to 20 wt% of silicone, Shin-Etsu Chemical Co., Ltd. Ltd.), INT-304VC (2wt% solution of fluorine resin, solvent: CF 3 CF 2 CHFCHFCF 3, NI material Co.), SG-204 (polysiloxane graft polymer, manufactured by Nippon Shokubai Co.), No. 309 (15 wt% solution of fluororesin, solvent: isohexane / acetone mixed solvent, manufactured by INT Screen), JS-025 (polysiloxane graft acrylic resin, manufactured by Nippon Paint), INT-304VB (4 wt% of fluororesin) Solution, solvent: CF 3 CF 2 CHFCHFCF 3 (manufactured by INT Screen), Teflon (registered trademark) AF1600 (perfluoro fluororesin, Mitsui / DuPont Fluorochemical), Cytop CTL110A (perfluoro fluororesin, terminal carboxyl group) Asahi Glass Co., Ltd.), CTL110S (perfluoro fluororesin, terminal-CF 3 group, manufactured by Asahi Glass Co., Ltd.) and the like can be used.

本発明において、筆記具用部材の少なくとも内側表面部（内壁面）に上記シリコーン処理やフッ素処理による撥水撥油処理する方法としては、例えば、図４に示すシリコーン化合物、上記パーフルオロアルキル基を有するフッ素樹脂、上記ジメチルシリコーンを有するシリコーンワニス（付加型、ＵＶ型、縮合型）又はシリカ微粒子を含有するもの、上記グラフト樹脂等をそのまま塗布、または適宜、パーフルオロ溶媒（住友３Ｍ社製のフロリナートＰＦ−５０８０、フロリナートＨＦＥ−７２００）、ＭＣＨ（メチルシクロヘキサン、以下同様）、ＩＰＡ／トルエンの混合液溶媒、ｎ−ＰＡなどの溶媒に溶解して筆記具用部材の少なくとも内側表面部（内壁面）に塗布することにより、または、これらの筆記具用部材を前記各樹脂液中等に浸漬処理することにより、筆記具用部材の少なくともインキ等の内容物と接触する内側表面部（内壁面）に上記各シリコーン処理、各フッ素処理からなる撥水撥油面を形成することができる。
これらの撥水撥油処理は、透明又は半透明であるので、内容物であるインキ残量等の視認を損なうことがないものである。 In the present invention, at least the inner surface portion (inner wall surface) of the writing instrument member may have, for example, the silicone compound and the perfluoroalkyl group shown in FIG. A fluororesin, a silicone varnish containing dimethyl silicone (addition type, UV type, condensation type) or silica fine particles, the above graft resin or the like is applied as it is, or a perfluoro solvent (Fluorinert PF manufactured by Sumitomo 3M Co., Ltd.) -5080, Fluorinert HFE-7200), MCH (methylcyclohexane, the same applies hereinafter), IPA / toluene mixed solvent, n-PA, etc. and dissolved on at least the inner surface (inner wall surface) of the writing instrument member. Or by writing these writing instrument members in the resin liquids, etc. By soaked processing, it may form at least the inner surface portion in contact with contents, such as ink (inner wall surface) to each siliconized, water- and oil-repellent surface made of the fluorine treatment of the writing instrument member.
Since these water and oil repellent treatments are transparent or translucent, the visual recognition of the remaining amount of ink or the like as the contents is not impaired.

好ましい、撥水撥油処理としては、上記図４（ａ）及び（ｂ）に示す構造のシリコーン化合物によるシリコーン処理（面）とするものが望ましい。
このシリコーン処理（撥水撥油処理）により、インキ残量等の確認等が確実に、しかもその視認性（クリアドレイン性）は経時的に優れると共に、後述する低表面張力のインキ等に対してもインキ残量等の確認が確実となるものであるが、これらの効果を更に発揮せしめるために、撥水撥油処理を少なくとも２回行うことが好ましく、例えば、上記各種の同じ又は異なるシリコーン処理を少なくとも２回、上記各種の同じ又は異なるフッ素処理を少なくとも２回、または、上記シリコーン処理と、上記フッ素処理とを夫々少なくとも１回行うことにより実施することができる。
なお、上記撥水撥油処理をする前に、筆記具用部材の内壁面等の油分を除去して撥水撥油処をより確実に行うために、ｎ−ヘキサン、アセトン等の溶剤で筆記具用部材の少なくとも内壁面を洗浄することが好ましい。 As a preferable water / oil repellent treatment, a silicone treatment (surface) with a silicone compound having the structure shown in FIGS. 4 (a) and 4 (b) is desirable.
This silicone treatment (water and oil repellency treatment) ensures confirmation of the remaining amount of ink, etc., and its visibility (clear drain property) is superior over time, and it can be used for low surface tension inks described later. However, in order to further demonstrate these effects, it is preferable to perform the water / oil repellent treatment at least twice, for example, the same or different silicone treatments described above. Can be carried out by performing at least twice the same or different fluorine treatments at least twice, or at least once each of the silicone treatment and the fluorine treatment.
In addition, before removing the water and oil repellent treatment, in order to remove the oil on the inner wall surface of the writing instrument member and perform the water and oil repellent treatment more reliably, a solvent such as n-hexane or acetone is used. It is preferable to clean at least the inner wall surface of the member.

本発明では、筆記具用部材の内側表面部（内壁面）に、上記の強固な撥水撥油面を更に密着せしめる点から、好ましくは、筆記具用部材の内側表面部（内壁面）を活性化処理により、親水基を持たない表面部では親水基を持つ表面部とし、また、親水基を持つ表面部では更に親水基をより多く持つ表面部とした後に、上記撥水撥油処理することが望ましく、更に好ましくは、撥水撥油面を更に密着せしめる点から、活性化処理により上記親水基を持つ又はより多く持つ表面部とした後に、ＳｉＯ2の薄膜を形成した後、該ＳｉＯ2薄膜に上記撥水撥油処理を施すことが特に望ましい。
本発明に用いることができる活性化処理としては、例えば、オゾン処理、空気や酸素等によるプラズマ処理、コロナ処理、紫外線照射処理、高圧放電処理及び酸処理から選ばれる少なくとも一種の（一種又はニ種以上を複合化させた）活性化処理が挙げられる。 In the present invention, the inner surface portion (inner wall surface) of the writing instrument member is preferably activated from the viewpoint that the above-mentioned strong water / oil repellent surface is further adhered to the inner surface portion (inner wall surface) of the writing instrument member. By the treatment, the surface portion having no hydrophilic group is changed to a surface portion having a hydrophilic group, and the surface portion having a hydrophilic group is further changed to a surface portion having more hydrophilic groups, and then the water and oil repellent treatment can be performed. Desirably, more preferably, from the viewpoint of further adhering the water- and oil-repellent surfaces, the SiO 2 thin film is formed after forming the SiO 2 thin film after forming the surface part having the hydrophilic group or having more by an activation treatment. It is particularly desirable to perform the above water / oil repellent treatment.
Examples of the activation treatment that can be used in the present invention include at least one selected from ozone treatment, plasma treatment with air or oxygen, corona treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, and acid treatment (one kind or two kinds). An activation treatment in which the above is combined) may be mentioned.

オゾン処理としては、筆記具用部材の内側表面部をオゾン分子と接触させて、ヒドロキシペルオキシ基や水酸基やカルボニル基等の官能基（親水基）を導入することを目的とし、筆記具用部材をオゾンに暴露することにより行われる。暴露方法としては、オゾンが存在する雰囲気に所定時間保持する方法、オゾン気流中に所定時間暴露する方法等が挙げられるが、特に限定されない。
プラズマ処理としては、筆記具用部材を空気、酸素、窒素、二酸化炭素、アルゴン、ネオンなどを含む容器内におき、グロー放電により生じるプラズマに晒すことにより行われ、筆記具用部材の内側表面部に酸素、窒素などを含むカルボン酸基、カルボニル基、アミノ基などの官能基（親水基）を導入することを目的とし、プラズマ発生の放電形式は、直流放電、低周波放電、ラジオ波放電、マイクロ波放電などがあるが特に限定されない。好ましくは、酸素原子を含む親水性官能基を導入する点から、空気プラズマ処理、酸素プラズマ処理である。 The purpose of ozone treatment is to introduce functional groups (hydrophilic groups) such as hydroxyperoxy groups, hydroxyl groups, and carbonyl groups by bringing the inner surface of the writing instrument members into contact with ozone molecules. It is done by exposure. Examples of the exposure method include, but are not particularly limited to, a method of holding in an atmosphere in which ozone is present for a predetermined time, a method of exposing to an ozone stream for a predetermined time, and the like.
The plasma treatment is performed by placing the writing instrument member in a container containing air, oxygen, nitrogen, carbon dioxide, argon, neon, etc., and exposing it to plasma generated by glow discharge. In order to introduce functional groups (hydrophilic groups) such as carboxylic acid groups, carbonyl groups, amino groups such as nitrogen, etc., the plasma generation discharge type is DC discharge, low frequency discharge, radio frequency discharge, microwave There are discharges, but there is no particular limitation. Air plasma treatment and oxygen plasma treatment are preferred from the viewpoint of introducing a hydrophilic functional group containing oxygen atoms.

コロナ処理としては、コロナ放電が生じる電界内に筆記具用部材を通過等させることにより、筆記具用部材の内側表面部を活性化処理することができる。
紫外線照射処理としては、筆記具用部材の内側表面部に紫外線を照射する方法で、筆記具用部材の内側表面部に紫外線が照射されると、筆記具用部材の内側表面部領域の二重結合等の化学構造に紫外線が吸収され、吸収されたエネルギーにより化学結合が切断され、生じたラジカルに空気中の酸素が結合することによって得られるカルボニル基、カルボキシル基などを導入することを目的とし、紫外線を照射する光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプ等を用いることができるが特に限定されない。 As the corona treatment, the inner surface portion of the writing instrument member can be activated by passing the writing instrument member through an electric field in which corona discharge occurs.
As the ultraviolet irradiation treatment, when the inner surface portion of the writing instrument member is irradiated with ultraviolet rays by the method of irradiating the inner surface portion of the writing instrument member with ultraviolet rays, the double bond of the inner surface portion region of the writing instrument member, etc. Ultraviolet rays are absorbed into the chemical structure, the chemical bond is broken by the absorbed energy, and the purpose is to introduce carbonyl groups, carboxyl groups, etc. obtained by bonding oxygen in the air to the generated radicals. As a light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used, but is not particularly limited.

高圧放電処理としては、筆記具用部材を多数設けた電極間に数十万ボルトの高電圧を加え、空気中で放電させて処理する方法で、放電によって空気中の酸素と筆記具用部材の表面が活性化され、表面に酸素が取り込まれ、極性基を導入することにより筆記具用部材の表面を活性化処理することができる。
酸処理としては、筆記具用部材をクロム混酸液、次亜塩素酸ソーダ／塩酸／水系、塩素酸塩−硫酸系、硫酸などに直接浸漬させることにより行うことができる。
これらの活性化処理の中でも、酸素原子を含む親水性官能基を導入する点から、好ましくは、空気プラズマ処理、酸素プラズマ処理で活性化処理をすることが望ましい。 The high-pressure discharge treatment is a method in which a high voltage of several hundred thousand volts is applied between electrodes provided with a large number of writing instrument members and the discharge is performed in the air. The discharge causes oxygen in the air and the surface of the writing instrument member to be discharged. It is activated, oxygen is taken into the surface, and the surface of the writing instrument member can be activated by introducing a polar group.
The acid treatment can be performed by directly immersing the writing instrument member in a chromium mixed acid solution, sodium hypochlorite / hydrochloric acid / water system, chlorate-sulfuric acid system, sulfuric acid, or the like.
Among these activation treatments, the activation treatment is preferably performed by air plasma treatment or oxygen plasma treatment from the viewpoint of introducing a hydrophilic functional group containing oxygen atoms.

また、上記筆記具用部材の少なくとも内側表面部を活性化処理された後に、ＳｉＯ2の薄膜を形成する方法としては、例えば、筆記具用部材の少なくとも内側表面部にシリカゾル溶液を塗布、熱硬化させることによりＳｉＯ2の薄膜を形成することができる。
このＳｉＯ2の薄膜形成用のシリカゾル溶液としては、例えば、アルコキシシラン重合物を含有するシリカゾル溶液、アルコキシシラン重合物とコロイダルシリカとを含有シリカゾル溶液などが挙げられる。
ＳｉＯ2の薄膜は、用いるシリカゾル溶液濃度、塗布量及び回数、筆記具用部材の材質などによりその膜厚が変動することとなる。また、撥水撥油面を更に強固に筆記具用部材の内側表面部に密着せしめる点から、活性化処理された後に、ＳｉＯ2の薄膜を形成することが特に好ましい。 In addition, as a method of forming a thin film of SiO 2 after at least the inner surface portion of the writing instrument member is activated, for example, a silica sol solution is applied to at least the inner surface portion of the writing instrument member and thermally cured. Thus, a thin film of SiO 2 can be formed.
Examples of the silica sol solution for forming a thin film of SiO 2 include a silica sol solution containing an alkoxysilane polymer and a silica sol solution containing an alkoxysilane polymer and colloidal silica.
The film thickness of the SiO 2 thin film varies depending on the concentration of silica sol solution used, the coating amount and the number of times, the material of the writing instrument member, and the like. In addition, it is particularly preferable to form a thin film of SiO 2 after the activation treatment from the viewpoint that the water / oil repellent surface is more firmly adhered to the inner surface portion of the writing instrument member.

本発明において、筆記具用部材の少なくとも内側表面部に撥水撥油処理により形成されるシリコーン処理及びフッ素処理の少なくとも１種等による撥水撥油処理の厚み（処理厚）は、単分子膜であり、ナノオーダー（ｎｍレベル）であるため、その処理厚を測定することは困難性を有し、筆記具用部材の少なくとも内側表面部が目的の撥水撥油効果が発揮できる処理面となるものであればよいものである。なお、目的の撥水撥油効果が発揮できる処理面とするためには、塗布回数、塗布液濃度等を変えることにより調整することができる。   In the present invention, the thickness (treatment thickness) of the water / oil repellent treatment by at least one of the silicone treatment and the fluorine treatment formed by water / oil repellent treatment on at least the inner surface of the writing instrument member is a monomolecular film. Yes, because it is nano-order (nm level), it is difficult to measure the treatment thickness, and at least the inner surface of the writing instrument member becomes a treated surface that can exhibit the desired water and oil repellent effect If it is good. In order to obtain a treated surface capable of exhibiting the desired water / oil repellent effect, it can be adjusted by changing the number of times of coating, the concentration of the coating solution, and the like.

図５は、筆記具用部材の少なくとも内側表面部をプラズマ処理等の活性化処理した後に、シリカゾル溶液を塗布、熱硬化させることによりＳｉＯ2の薄膜を形成し、該ＳｉＯ2薄膜に図４（ａ）及び（ｂ）に示すシリコーン処理（撥水撥油処理）を示す模式図であり、この形態では、筆記具用部材の少なくとも内側表面部上にＳｉＯ2の薄膜、該ＳｉＯ2薄膜上にシリコーン処理（撥水撥油処理）面が形成されるものとなる。 5, at least the inner surface portion of the writing instrument member after activation treatment such as plasma treatment, coating a silica sol solution, by thermally curing to form a SiO 2 thin film, FIG. 4 to the SiO 2 thin film (a ) and (a schematic diagram showing a siliconized (water- and oil-repellent processing) shown in b), in this embodiment, a thin film of SiO 2 on at least an inner surface portion of the writing instrument member, silicone treatment to the SiO 2 thin film A (water / oil repellent treatment) surface is formed.

本発明において、筆記具用部材の少なくとも内側表面部に接触する内容物としては、例えば、筆記具用インキ、塗布液、修正液、化粧液、液状染毛剤などが挙げられる。
内容物が筆記具用インキであれば、用途、目的に応じ、ボールペン用、加圧ボールペン用、サインペン用、マーキングペン用、アンダーライン用などの水性又は油性の液状インキ、ゲル状インキなどの筆記具用インキに好適に調製することができる。
また、内容物の表面張力は、特に限定されないが、本発明では、優れた筆記性能、塗布性能を有する３０ｍＮ／ｍ（２５℃）以下の低表面張力のインキ、塗布液、修正液などであっても、インキ残量等の確認を確実に発揮することができる。 In the present invention, examples of the contents in contact with at least the inner surface portion of the writing instrument member include writing instrument ink, coating liquid, correction liquid, cosmetic liquid, and liquid hair dye.
If the content is ink for writing instruments, depending on the application and purpose, it is used for writing pens such as water-based or oil-based liquid inks such as for ballpoint pens, pressurized ballpoint pens, sign pens, marking pens, underlines, etc. It can be suitably prepared for ink.
Further, the surface tension of the contents is not particularly limited, but in the present invention, it is an ink, a coating liquid, a correction liquid, etc. having a low surface tension of 30 mN / m (25 ° C.) or less having excellent writing performance and coating performance. However, the confirmation of the ink remaining amount can be surely exhibited.

本発明の筆記具は、上述の如く、１）内容物が接触する樹脂製の筆記具用部材（インキ収容容器、インキ収容管、塗布液容器、塗布液収容管等）の少なくとも内側表面部に、撥水撥油処理された撥水撥油面が形成されたもの、若しくは、２）上記筆記具用部材の少なくとも内側表面部は、活性化処理された後に、撥水撥油処理された撥水撥油面が形成されたもの、または、３）上記筆記具用部材の少なくとも内側表面部は、活性化処理された後に、ＳｉＯ2の薄膜が形成され、該ＳｉＯ2薄膜に撥水撥油処理された撥水撥油面が形成されたものから構成される内容物可視（視認）型筆記具用部材を備えたことを特徴とするものであり、例えば、上記内容物可視（視認）型筆記具用部材の先端にペン先（ボールペン型チップ、ペン芯、塗布体等）を取り付けることなどにより作製することができる。 As described above, the writing instrument of the present invention is repellent on at least the inner surface of a resin writing instrument member (an ink container, an ink container tube, a coating liquid container, a coating liquid container tube, etc.) in contact with the contents. A water / oil / oil repellent surface that has been subjected to a water / oil repellent treatment, or 2) a water / oil / oil repellent that has been subjected to a water / oil / oil repellent treatment after at least the inner surface portion of the writing instrument member has been activated. 3) At least the inner surface of the writing instrument member is activated, and then a SiO 2 thin film is formed, and the SiO 2 thin film is subjected to water / oil repellent treatment. It is characterized by comprising a content visible (viewing) type writing instrument member comprising a water / oil repellent surface, for example, the tip of the content visible (visible) type writing instrument. Pen tip (ballpoint tip, pen core, coated body, etc.) It can be produced by attaching.

次に、本発明の内容物可視型筆記具用部材及びそれを備えた筆記具の具体的な実施形態を図１〜図３により更に詳しく説明する。
図１（ａ）及び（ｂ）は、本発明の筆記具用部材をボールペンのインキ収容管（リフィール）に適用したもの、及びそのインキ収容管を備えた筆記具（ボールペン）を示す縦断面図である。
このインキ収容管１１の少なくとも内側表面部には、上記１）〜３）の何れか手段で撥水撥油処理された撥水撥油面が形成されたものであり、本実施形態ではインキ収容管１１がポリプロピレン製であり、その少なくとも内側表面（内壁面）部は、空気プラズマ処理された後に、ＳｉＯ2の薄膜が形成され、該ＳｉＯ2薄膜に図４（ａ）に示す化合物を用いて撥水撥油処理された撥水撥油面が形成されたものである。
このインキ収容管１１の先端にはペン先となるボールペン型チップ１０を具備したインキ収容部材となっている。なお、１２はインキ収容管１１に充填されているボールペン用インキ、１３はペン先部とインキ収容管との継ぎ手部材であり、１４はインキ追従体である。
この筆記具部材となるインキ収容管１１等は、図１（ｂ）に示すように、ボールペン用軸体１５に装着してボールペンＡとして用いられる。なお、１６は尾栓である。 Next, specific embodiments of the content-visible writing instrument member and the writing instrument including the same according to the present invention will be described in more detail with reference to FIGS.
1 (a) and 1 (b) are longitudinal sectional views showing a writing instrument member according to the present invention applied to an ink storage tube (refill) of a ballpoint pen and a writing instrument (ball pen) provided with the ink storage tube. .
At least the inner surface portion of the ink storage tube 11 is formed with a water / oil repellent surface that has been subjected to water / oil repellent treatment by any one of the means 1) to 3). tube 11 is made of polypropylene, the at least inner surface (inner wall surface) portion, after being air plasma treatment, the SiO 2 thin film is formed, using the compounds shown in FIGS. 4 (a) to the SiO 2 thin film A water / oil repellent surface subjected to water / oil repellent treatment is formed.
At the tip of the ink containing tube 11 is an ink containing member provided with a ballpoint pen tip 10 as a pen tip. In addition, 12 is the ink for ball-point pens with which the ink storage tube 11 is filled, 13 is a joint member of a pen point part and an ink storage tube, 14 is an ink follower.
As shown in FIG. 1B, the ink storage tube 11 or the like serving as a writing instrument member is attached to a ballpoint pen shaft 15 and used as a ballpoint pen A. Reference numeral 16 denotes a tail plug.

図２は、本発明の筆記具部材をコレクター構造を備えた直液式筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材に適用したもの、及びその軸体を備えた直液式の筆記具を示す縦断面図である。
本実施形態の筆記具用部材２１は、インキ２０を中綿等に吸蔵させないで直接貯溜する軸体となるインキタンク部材となるものである。
このインキタンク部材２１の少なくとも内側表面部には、上記１）〜３）の何れか手段で撥水撥油処理された撥水撥油面が形成されたものであり、本実施形態ではインキタンク部材２１がポリプロピレン製であり、その少なくとも内側表面（内壁面）部は、酸素プラズマ処理された後に、ＳｉＯ2の薄膜が形成され、該ＳｉＯ2薄膜に図４（ｂ）に示す化合物を用いて撥水撥油処理された撥水撥油面が形成されたものである。
このインキタンク部材２１の前部には、インキタンク部材２１内の空気が温度上昇等によって膨張した場合にインキタンク部材２１から押し出されるインキ２０をペン先や空気孔からボタ落ちさせないために一時的に保溜するインキ保溜体（コレクター部材）２２が内蔵され、コレクター部材２２の先端部には繊維芯からなるペン先２３が設けられた構成となっている。
また、図２中の２５はホルダー部材であり、２６はインキタンク部１１の後部に固着される後部軸体であり、２７はキャップである。
この筆記具用部材（インキタンク部材）２１を備えた直液式筆記具Ｂにおいて、インキタンク部材２１からペン先２３へのインキ導出は、コレクター部材２２の中心孔に付設されたインキ流路２２ａを設けた中継芯２４を介してインキタンク部材２１からインキ２０をペン先２３に導出することにより行われる。なお、中継芯２４を介在させることなく、ペン先２３の後部をインキタンク部剤２１内に直接配置してインキの導出を行ってもよい。 FIG. 2 shows a case in which the writing instrument member of the present invention is applied to an ink tank member serving as a shaft body (ink storage container) for directly storing ink in a direct liquid type writing instrument having a collector structure, and a straight body including the shaft body. It is a longitudinal cross-sectional view which shows a liquid type writing instrument.
The writing instrument member 21 of the present embodiment is an ink tank member serving as a shaft body that directly stores the ink 20 without occluding the ink 20 in the batting or the like.
At least an inner surface portion of the ink tank member 21 is formed with a water / oil repellent surface which has been subjected to water / oil repellent treatment by any of the means 1) to 3). In this embodiment, the ink tank member 21 is is made of polypropylene, the at least inner surface (inner wall surface) portion, after being oxygen plasma treatment, the SiO 2 thin film is formed, using the compound shown in FIG. 4 (b) to the SiO 2 thin film A water / oil repellent surface subjected to water / oil repellent treatment is formed.
In front of the ink tank member 21, the ink 20 pushed out from the ink tank member 21 when the air in the ink tank member 21 expands due to a temperature rise or the like is temporarily prevented from dropping from the pen tip or the air hole. An ink reservoir (collector member) 22 that is retained in the container is incorporated, and a tip end of the collector member 22 is provided with a pen tip 23 made of a fiber core.
2 is a holder member, 26 is a rear shaft fixed to the rear part of the ink tank 11, and 27 is a cap.
In the direct liquid writing instrument B provided with the writing instrument member (ink tank member) 21, the ink flow from the ink tank member 21 to the pen tip 23 is provided with an ink flow path 22 a attached to the central hole of the collector member 22. The ink 20 is led out from the ink tank member 21 to the pen tip 23 through the relay core 24. Note that the ink may be led out by arranging the rear portion of the pen tip 23 directly in the ink tank member 21 without interposing the relay core 24.

図３は、本発明の筆記具用部材を、撹拌ボールを内蔵したバルブ機構部を有するバルブ式筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材に適用したもの、及びそのインキタンク部材を備えたバルブ式の筆記具を示す縦断面図である。
本実施形態の筆記具用部材３１は、インキ３０を中綿等に吸蔵させないで直接貯溜する軸体となるインキタンク部材となるものである。
このインキタンク部材３１の少なくとも内側表面部には、上記１）〜３）の何れか手段で撥水撥油処理された撥水撥油面が形成されたものであり、本実施形態ではインキタンク部材３１がポリプロピレン製であり、その少なくとも内側表面（内壁面）部は、酸素プラズマ処理された後に、ＳｉＯ2の薄膜が形成され、該ＳｉＯ2薄膜に図４（ａ）に示す化合物を用いて撥水撥油処理された撥水撥油面が形成されたものである。
このインキタンク部材３１を備えた筆記具は、インクタンク部３１内にバルブ機構部３２が取り付けられて繊維芯からなるペン先３３へインキが供給される構成となっている。
また、図３中の３４はホルダー部材であり、３５はバルブ機構部３２とホルダー部材３４間に介在し、ペン先３３の後部を保持する保持部材であり、３６はキャップであり、３７は撹拌ボールである。
また、本実施形態のバルブ式筆記具Ｃは、中継芯を介さないでインキをペン先へ供給するものであるが、中継芯を設け、インキタンク部材３１からバルブ機構部３２、中継芯を介在して繊維芯からなるペン先３３へインキを供給する構成にしてもよい。 FIG. 3 shows a case in which the writing instrument member of the present invention is applied to an ink tank member serving as a shaft body (ink container) for directly storing ink in a valve-type writing instrument having a valve mechanism having a built-in stirring ball. It is a longitudinal cross-sectional view which shows the valve-type writing instrument provided with the ink tank member.
The writing instrument member 31 according to the present embodiment is an ink tank member that serves as a shaft body that directly stores the ink 30 without causing the filling 30 or the like to occlude.
At least an inner surface portion of the ink tank member 31 is provided with a water / oil repellent surface that has been subjected to water / oil repellent treatment by any of the means 1) to 3). In this embodiment, the ink tank member 31 is made of polypropylene, the at least inner surface (inner wall surface) portion, after being oxygen plasma treatment, the SiO 2 thin film is formed, using the compounds shown in FIGS. 4 (a) to the SiO 2 thin film A water / oil repellent surface subjected to water / oil repellent treatment is formed.
The writing instrument provided with the ink tank member 31 is configured such that a valve mechanism 32 is attached in the ink tank portion 31 and ink is supplied to a pen tip 33 made of a fiber core.
3, 34 is a holder member, 35 is a holding member that is interposed between the valve mechanism portion 32 and the holder member 34 and holds the rear portion of the pen tip 33, 36 is a cap, and 37 is a stirring member. It is a ball.
Further, the valve-type writing instrument C of the present embodiment supplies ink to the pen tip without using a relay core, but a relay core is provided, and the valve mechanism 32 and the relay core are interposed from the ink tank member 31. In this case, the ink may be supplied to the nib 33 made of a fiber core.

本発明の筆記具用部材及びその筆記具用部材を備えた筆記具は、上記実施形態に限定されるものでなく、本発明の要旨を変更しない範囲で種々の形態に変更できることはいうまでもない。
本発明の筆記具用部材は、筆記具用インキ、塗布液、修正液、液状化粧料などの内容物が接触するインキ収容容器、インキ収容管、塗布液容器、塗布液収容管等の樹脂製の筆記具用部材の少なくとも内側表面部に、撥水撥油処理がされていること、または、樹脂製の筆記具部材の少なくとも内側表面部を活性化処理された後に、撥水撥油処理がされていること、並びに、活性化処理された後に、ＳｉＯ2の薄膜を形成し、該ＳｉＯ2薄膜に撥水撥油処理がされていることを要旨とするので、本発明の各種筆記具用部材を筆記具に用いた場合には、上記筆記具用部材以外の構造は特に限定されるものではなく、ペン先としてボールペン型チップ、繊維芯等からなるペン芯、塗布体等を取り付けることなどにより、その筆記具用部材を備えたボールペン、サインペン、マーキングペン、筆ペン、直液式筆記具、バルブ式筆記具、修正液塗布具、液状化粧料塗布具等の各種筆記具の構造が適用されるものである。 It goes without saying that the writing instrument member of the present invention and the writing instrument including the writing instrument member are not limited to the above embodiment, and can be changed to various forms without departing from the scope of the present invention.
The writing instrument member of the present invention is a writing instrument made of resin, such as an ink container, an ink container, a coating liquid container, a coating liquid container, and the like, which are in contact with contents such as ink for writing instruments, coating liquid, correction liquid, and liquid cosmetics. At least the inner surface part of the member for use is subjected to water / oil repellent treatment, or at least the inner surface part of the resin writing instrument member is subjected to activation treatment and then subjected to water / oil repellent treatment. In addition, since the SiO 2 thin film is formed after the activation treatment and the SiO 2 thin film is subjected to water and oil repellency treatment, the various writing instrument members of the present invention are used for the writing instrument. In such a case, the structure other than the writing instrument member is not particularly limited, and the writing instrument member is attached by attaching a ballpoint pen tip, a pen core made of a fiber core or the like as a pen tip, an application body, or the like. Ball with Various writing instrument structures such as a pen, a sign pen, a marking pen, a brush pen, a direct liquid writing instrument, a valve writing instrument, a correction liquid applicator, and a liquid cosmetic applicator are applied.

このように構成される本発明では、筆記具用インキ、塗布液、修正液、液状化粧料などの内容物が接触するインキ収容容器、インキ収容管、塗布液容器、塗布液収容管等の樹脂製の筆記具用部材の少なくとも内側表面部に、撥水撥油処理がされているので、インキ残量等の確認が確実に、しかもその視認性（クリアドレイン性）は経時的に優れると共に、低表面張力のインキ等に対してもインキ残量等の確認が確実となる高品質の内容物可視型筆記具用部材及びその筆記具用部材を備えたボールペン、サインペン、マーキングペン、筆ペン、直液式筆記具、バルブ式筆記具、塗布具等の筆記具が提供されることとなる。
また、樹脂製の筆記具用部材の少なくとも内側表面部を活性化処理された後に、撥水撥油処理してなるもの、並びに、活性化処理された後に、ＳｉＯ2の薄膜を形成し、該ＳｉＯ2薄膜に撥水撥油処理してなるものは、筆記具用部材の表面との密着性が向上して、そのインキ残量等の確認等が更に確実に、しかもその視認性（クリアドレイン性）は経時的にも更に優れ、かつ、低表面張力のインキ等に対してもインキ残量等の確認が更に確実となる高品質の内容物可視型筆記具用部材及びその筆記具用部材を備えた各種の筆記具が提供されることとなる。 In the present invention configured as described above, it is made of resin such as an ink storage container, an ink storage tube, a coating liquid container, a coating liquid storage tube, etc. with which contents such as ink for writing instruments, coating liquid, correction liquid, and liquid cosmetics come into contact. Since the water repellent and oil repellent treatment is applied to at least the inner surface of the writing instrument member, the remaining amount of ink is surely confirmed, and its visibility (clear drainability) is excellent over time and low surface. High-quality contents that can confirm the remaining amount of ink even for tension ink, etc. Visible writing instrument members and ballpoint pens, sign pens, marking pens, writing pens, direct liquid writing instruments equipped with the writing instrument members Writing instruments such as valve-type writing instruments and applicators will be provided.
Further, at least the inner surface portion of the resin writing instrument member is activated and then subjected to water and oil repellency treatment, and after the activation treatment, a thin film of SiO 2 is formed, and the SiO 2 is made by water-repellent oil repellent into 2 thin film, improved adhesion to the surface of the writing instrument member, the confirmation of the ink remaining amount or the like is more reliably, yet their visibility (clear drain resistance) Is a material with high quality contents that can be used to confirm the remaining amount of ink even for low surface tension inks, etc. Will be provided.

次に、実施例及び比較例により本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。   EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example etc.

〔実施例１〜１７及び比較例１〜２〕
（実施例１）
ポリプロピレン製の円筒状のインキ収容軸（内径１０ｍｍ、外径１２ｍｍ、長さ６０ｍｍ、実施例２以下も同様）の油分を除くため、ｎ−ヘキサンでインキ収容軸内面を洗浄し、その後ｎ−ヘキサンを室温下で揮発させた。
次いで、インキ収容軸をＳＵＳ製試験管立てに立てた後、プラズマアッシャーのチャンバーに入れ、高周波発生器の出力１００Ｗ、照射時間３分間の酸素プラズマ処理を４回行った。このプラズマ処理後のインキ収容軸に下記組成のシリカゾル溶液Ｎｏ．１をピペット状充填機で充填後、速やかに液を引き抜き、更に、インキ収容軸の開放部を下向きにして余分なシリカゾル溶液をスポンジ状の吸収体で吸収除去した。
シリカゾル溶液Ｎｏ．１組成：
６ｗｔ％アルコキシシラン重合物溶液 １
エタノール ７ [Examples 1-17 and Comparative Examples 1-2]
Example 1
In order to remove the oil content of the cylindrical ink containing shaft made of polypropylene (inner diameter 10 mm, outer diameter 12 mm, length 60 mm, the same as in Example 2 and below), the inner surface of the ink containing shaft was washed with n-hexane, and then n-hexane. Was volatilized at room temperature.
Next, after placing the ink containing shaft in a SUS test tube stand, it was put into a plasma asher chamber, and oxygen plasma treatment was performed 4 times with an output of 100 W from a high frequency generator and an irradiation time of 3 minutes. The silica sol solution No. having the following composition was placed on the ink containing shaft after the plasma treatment. After filling 1 with a pipette-like filling machine, the liquid was quickly drawn out, and the excess silica sol solution was absorbed and removed with a sponge-like absorber with the open part of the ink containing shaft facing downward.
Silica sol solution no. 1 composition:
6 wt% alkoxysilane polymer solution 1
Ethanol 7

次に、上記シリカゾル溶液で処理したインキ収容軸を室内温が１２０℃の恒温槽に入れて１時間熱処理を行った後、恒温槽を停止させ、室内温が６０℃以下になったら、インキ収容軸を恒温槽から取り出し、室温下（２５℃、以下同様）まで自然冷却させ、内面にＳｉＯ2の薄膜が形成されたインキ収容軸を得た。
上記で得られたインキ収容軸に下記の調製法により得た撥水撥油処理剤Ａを充填して、そのまま１時間ほど放置した。放置中は、溶剤の揮発を抑制するためにアルミ箔などで蓋をした。
撥水撥油処理剤Ａの調製：
図４に示す構造のＦ（結合残基が両末端）を３Ｍ社製フロリナートＰＦ−５０８０に溶解し、０．２ｗｔ％の撥水処理剤を調製する。 Next, the ink containing shaft treated with the silica sol solution was put into a thermostat having a room temperature of 120 ° C. and subjected to heat treatment for 1 hour, and then the thermostat was stopped. The shaft was taken out from the thermostat and allowed to cool naturally to room temperature (25 ° C., the same applies hereinafter) to obtain an ink containing shaft having an SiO 2 thin film formed on the inner surface.
The ink containing shaft obtained above was filled with the water / oil repellent agent A obtained by the following preparation method and left as it was for about 1 hour. During standing, it was covered with aluminum foil to suppress the volatilization of the solvent.
Preparation of water and oil repellent treatment agent A:
F having a structure shown in FIG. 4 (both residues at both ends) is dissolved in 3M Fluorinert PF-5080 to prepare a 0.2 wt% water repellent treatment agent.

上記１時間放置後、撥水撥油処理剤を排出し、インキ収容軸の開放部を下向きにして余分な撥水撥油処理剤をスポンジ状の吸収体で吸収除去した。
次いで、室内温が１２０℃の恒温槽に入れて１５分間熱処理を行った後、恒温槽を停止させ、室温下まで自然冷却させて内壁面が撥水撥油処理されたインキ収容管となるインキ収容軸を得た。 After standing for 1 hour, the water / oil repellent treatment agent was discharged, and the excess water / oil repellent treatment agent was absorbed and removed with a sponge-like absorber with the open portion of the ink containing shaft facing downward.
Next, after heat treatment for 15 minutes in a thermostatic chamber having a room temperature of 120 ° C., the thermostatic chamber is stopped, and the ink is used as an ink containing tube whose inner wall surface is water- and oil-repellent treated by being naturally cooled to room temperature. A storage shaft was obtained.

（実施例２）
上記実施例１において、シリカゾル溶液Ｎｏ．１を下記Ｎｏ．２に代えた以外は実施例１と同様にして内壁面が撥水撥油処理されたインキ収容軸を得た。
シリカゾル溶液Ｎｏ．２組成：
６ｗｔ％アルコキシシラン重合物溶液 １
３０ｗｔ％コロイダルシリカ溶液 ２
エタノール １５ (Example 2)
In Example 1 above, the silica sol solution No. No. 1 below. An ink containing shaft having an inner wall surface subjected to water / oil repellent treatment was obtained in the same manner as in Example 1 except that it was replaced with 2.
Silica sol solution no. 2 composition:
6 wt% alkoxysilane polymer solution 1
30 wt% colloidal silica solution 2
Ethanol 15

（実施例３）
上記実施例１において、撥水撥油処理剤Ａを下記の調製法により得た撥水撥油処理剤Ｂに代えた以外は実施例１と同様にして内壁面が撥水撥油処理されたインキ収容軸を得た。
撥水撥油処理剤Ｂの調製：
図４に示す構造のＤ（結合残基が片末端）を３Ｍ社製フロリナートＰＦ−５０８０に溶解し、０．２ｗｔ％の撥水処理剤を調製した。 (Example 3)
In Example 1 above, the inner wall surface was subjected to water / oil repellent treatment in the same manner as in Example 1 except that the water / oil repellent agent A was replaced with the water / oil repellent agent B obtained by the following preparation method. An ink receiving shaft was obtained.
Preparation of water / oil repellent treatment agent B:
D having the structure shown in FIG. 4 (the binding residue is at one end) was dissolved in 3M Fluorinert PF-5080 to prepare a 0.2 wt% water repellent treatment agent.

（実施例４）
上記実施例１において、シリカゾル溶液Ｎｏ．１を上記（実施例２の）シリカゾル溶液Ｎｏ．２に代えると共に、撥水撥油処理剤Ａを上記（実施例３）の調製法により得た撥水撥油処理剤Ｂに代えた以外は、実施例１と同様にして内壁面が撥水撥油処理されたインキ収容軸を得た。 Example 4
In Example 1 above, the silica sol solution No. No. 1 is the silica sol solution no. 2 and the inner wall surface is water repellent in the same manner as in Example 1 except that the water and oil repellent agent A is replaced with the water and oil repellent agent B obtained by the preparation method of Example 3 above. An oil receiving shaft subjected to oil repellent treatment was obtained.

（実施例５）
ポリプロピレン製のインキ収容軸の油分を除くため、ｎ−ヘキサンでインキ収容軸内面を洗浄し、その後ｎ−ヘキサンを室温下で揮発させた。
次いで、インキ収容軸をＳＵＳ製試験管立てに立てた後、プラズマアッシャーのチャンバーに入れ、高周波発生器の出力１００Ｗ、照射時間３分間の酸素プラズマ処理を４回行った。このプラズマ処理後のインキ収容軸に実施例１で用いたシリカゾル溶液Ｎｏ．１をピペット状充填機で充填後、速やかに液を引き抜き、更に、インキ収容軸の開放部を下向きにして余分なシリカゾル溶液をスポンジ状の吸収体で吸収除去した。
次に、上記シリカゾル溶液で処理したインキ収容軸を室内温が１２０℃の恒温槽に入れて１時間熱処理を行った後、恒温槽を停止させ、室内温が６０℃以下になったら、インキ収容軸を恒温槽から取り出し、室温下まで自然冷却させ、ＳｉＯ2の薄膜が形成されたインキ収容軸を得た。
次いで、撥水撥油処理剤となるサイトップＣＬＴ１０７Ｍ（旭硝子社製）を上記で得られたインキ収容軸に充填して、その後速やかに吸引して余分な撥水撥油処理剤を除き、更に、インキ収容軸の開放部を下向きにして余分な撥水撥油処理剤をスポンジ状の吸収体で吸収除去した。
その後、室内温が１２０℃の恒温槽に入れて１５分間熱処理を行った後、恒温槽を停止させ、室温まで自然冷却させて内壁面に撥水撥油処理されたインキ収容軸を得た。
次に、図４に示した構造のＦ（結合残基が両末端）を３Ｍ社製フロリナートＨＦＥ−７２００に溶解し、０．２ｗｔ％の撥水撥油処理剤を得た。
得られた撥水撥油処理剤を上記で得られたインキ収容軸に充填して、その後速やかに吸引して余分な撥水撥油処理剤を除き、更に、インキ収容軸の開放部を下向きにして余分な撥水撥油処理剤をスポンジ状の吸収体で吸収除去した。
次いで、室内温が１２０℃の恒温槽に入れて１５分間熱処理を行った後、恒温槽を停止させ、室温まで自然冷却させて内壁面が撥水撥油処理されたインキ収容軸を得た。 (Example 5)
In order to remove the oil content of the polypropylene ink storage shaft, the inner surface of the ink storage shaft was washed with n-hexane, and then n-hexane was volatilized at room temperature.
Next, after placing the ink containing shaft in a SUS test tube stand, it was put into a plasma asher chamber, and oxygen plasma treatment was performed 4 times with an output of 100 W from a high frequency generator and an irradiation time of 3 minutes. The silica sol solution No. 1 used in Example 1 was applied to the ink receiving shaft after the plasma treatment. After filling 1 with a pipette-like filling machine, the liquid was quickly drawn out, and the excess silica sol solution was absorbed and removed with a sponge-like absorber with the open part of the ink containing shaft facing downward.
Next, the ink containing shaft treated with the silica sol solution was put into a thermostat having a room temperature of 120 ° C. and subjected to heat treatment for 1 hour, and then the thermostat was stopped. The shaft was taken out of the thermostatic chamber and allowed to cool naturally to room temperature to obtain an ink containing shaft on which a thin film of SiO 2 was formed.
Next, Cytop CLT107M (Asahi Glass Co., Ltd.), which is a water / oil repellent treatment agent, is filled into the ink containing shaft obtained above, and then quickly sucked to remove excess water / oil repellent treatment agent, The excess water and oil repellent treatment agent was absorbed and removed with a sponge-like absorber with the open part of the ink containing shaft facing downward.
Thereafter, the chamber was placed in a thermostat having a room temperature of 120 ° C. and subjected to heat treatment for 15 minutes, and then the thermostat was stopped and allowed to cool naturally to room temperature to obtain an ink containing shaft that had been subjected to water / oil repellent treatment on the inner wall surface.
Next, F having the structure shown in FIG. 4 (bonding residues at both ends) was dissolved in 3M Fluorinert HFE-7200 to obtain 0.2 wt% of a water / oil repellent treatment agent.
Fill the ink containing shaft obtained above with the obtained water / oil repellent treatment agent, and then quickly suck it to remove the excess water / oil repellent treatment agent. Then, excess water and oil repellent treatment agent was absorbed and removed with a sponge-like absorber.
Next, after heat treatment was performed for 15 minutes in a thermostatic chamber having a room temperature of 120 ° C., the thermostatic bath was stopped and naturally cooled to room temperature to obtain an ink containing shaft whose inner wall surface was subjected to water / oil repellent treatment.

（実施例６）
上記実施例５において、シリカゾル溶液Ｎｏ．１を実施例２で用いたシリカゾル溶液Ｎｏ．２に代えた以外は実施例５と同様にして内壁面が撥水撥油処理されたインキ収容軸を得た。 (Example 6)
In Example 5, the silica sol solution No. No. 1 in the silica sol solution No. 1 used in Example 2. An ink receiving shaft having an inner wall surface subjected to water / oil repellent treatment was obtained in the same manner as in Example 5 except that it was replaced with 2.

（実施例７）
上記実施例５において、撥水撥油処理剤〔図４に示す構造のＦ（結合残基が両末端）を３Ｍ社製フロリナートＨＦＥ−７２００に溶解し、０．２ｗｔ％の撥水撥油処理剤〕を下記の調製法により得た撥水撥油処理剤に代えた以外は、実施例５と同様にして内壁面が撥水撥油処理されたインキ収容軸を得た。
撥水処理剤の調製：
図４に示した構造のＤ（結合残基が片末端）を３Ｍ社製フロリナートＨＦＥ−７２００に溶解し、０．２ｗｔ％の撥水処理剤を調製した。 (Example 7)
In Example 5 above, the water / oil repellent treatment agent [F having the structure shown in FIG. 4 (bonded residues at both ends) was dissolved in 3M Fluorinert HFE-7200, and 0.2 wt% water / oil repellent treatment was performed. The ink containing shaft whose inner wall surface was subjected to water / oil repellent treatment was obtained in the same manner as in Example 5 except that the agent was replaced with the water / oil repellent agent obtained by the following preparation method.
Preparation of water repellent treatment:
D having the structure shown in FIG. 4 (bonding residue at one end) was dissolved in 3M Fluorinert HFE-7200 to prepare a 0.2 wt% water repellent treatment agent.

（実施例８）
上記実施例５において、シリカゾル溶液Ｎｏ．１を実施例２で用いたシリカゾル溶液Ｎｏ．２に代えると共に、撥水撥油処理剤〔図４に示す構造のＦ（結合残基が両末端）を３Ｍ社製フロリナートＨＦＥ−７２００に溶解し、０．２ｗｔ％の撥水撥油処理剤〕を上記実施例６の調製法により得た撥水撥油処理剤に代えた以外は実施例５と同様にして内壁面が撥水撥油処理されたインキ収容軸を得た。 (Example 8)
In Example 5, the silica sol solution No. No. 1 in the silica sol solution No. 1 used in Example 2. 2 and a water / oil repellent treatment agent [F having a structure shown in FIG. 4 (bonding residues at both ends) is dissolved in 3M Fluorinert HFE-7200, and 0.2 wt% of the water / oil repellent treatment agent ] Was obtained in the same manner as in Example 5 except that the water- and oil-repellent treatment agent obtained by the preparation method of Example 6 was used to obtain an ink containing shaft whose inner wall surface was subjected to water- and oil-repellency treatment.

（実施例９）
ポロプロピレン製のインキ収容軸の油分を除くため、ｎ−ヘキサンでインキ収容軸内面を洗浄し、その後、ｎ−ヘキサンを室温下で揮発させ、脱脂処理したインキ収容軸を得た。
次いで、フッ素系撥水撥油処理剤ＩＮＴ３０４−ＶＣ（フッ素樹脂の２ｗｔ％溶液、溶剤：ＣＦ3ＣＦ2ＣＨＦＣＨＦＣＦ3、ＮＩマテリアル社製）を上記で得られたインキ収容軸に充填して、その後速やかに吸引して余分な撥水撥油処理剤を除き、更に、インキ収容軸の開放部を下向きにして余分な撥水撥油処理剤をスポンジ状の吸収体で吸収除去した。
次に、室内温が８０℃の恒温槽に入れて６０分間熱処理を行った後、恒温槽を停止させ、室温下まで自然冷却させて内壁面に撥水撥油処理されたインキ収容軸を得た。 Example 9
In order to remove the oil content of the polypropylene containing ink containing shaft, the inner surface of the ink containing shaft was washed with n-hexane, and then the n-hexane was volatilized at room temperature to obtain a degreased ink containing shaft.
Next, a fluorine-based water and oil repellent treatment agent INT304-VC (2 wt% solution of fluororesin, solvent: CF 3 CF 2 CHFCHFCF 3 , manufactured by NI Materials) is filled in the ink containing shaft obtained above, and then The excess water- and oil-repellent agent was removed immediately by suction, and the excess water- and oil-repellent agent was absorbed and removed with a sponge-like absorber with the open portion of the ink containing shaft facing downward.
Next, after heat treatment for 60 minutes in a thermostatic chamber having an indoor temperature of 80 ° C., the thermostatic chamber is stopped and naturally cooled to room temperature to obtain an ink containing shaft that has been subjected to water / oil repellent treatment on the inner wall surface. It was.

（実施例１０）
ポリプロピレン製のインキ収容軸の油分を除くため、ｎ−ヘキサンでインキ収容軸内面を洗浄し、その後、ｎ−へキサンを室温下で揮発させ、脱脂処理したインキ収容軸を得た。
次いで、上記で得られたインキ収容軸に対してオゾン処理（三菱オゾナイザＯＳ―ＩＮ、三菱電機社製）をオゾン濃度２０ｇ／ｍ3で６０分間行った。
次に、上記実施例９のフッ素系撥水撥油処理剤ＩＮＴ３０４−ＶＣ（ＮＩマテリアル社製）を先に得られたインキ収容軸に充填して、その後速やかに吸引して余分な撥水剤を除き、更に、インキ収容軸の開放部を下向きにして余分な撥水処理剤をスポンジ状の吸収体で吸収除去した。
次いで、室内温が８０℃の恒温槽に入れて６０分間熱処理を行った後、恒温槽を停止させ、室温まで自然冷却させて内壁面に撥水撥油処理面が形成されたインキ収容軸を得た。 (Example 10)
In order to remove the oil content of the polypropylene ink containing shaft, the inner surface of the ink containing shaft was washed with n-hexane, and then n-hexane was volatilized at room temperature to obtain a degreased ink containing shaft.
Next, ozone treatment (Mitsubishi Ozonizer OS-IN, manufactured by Mitsubishi Electric Corporation) was applied to the ink containing shaft obtained above for 60 minutes at an ozone concentration of 20 g / m 3 .
Next, the fluorine-based water- and oil-repellent treating agent INT304-VC (manufactured by NI Material) of Example 9 was filled in the previously obtained ink containing shaft, and then quickly sucked to remove excess water-repellent agent. The excess water repellent was absorbed and removed with a sponge-like absorber with the open part of the ink containing shaft facing downward.
Next, after performing heat treatment for 60 minutes in a thermostatic chamber having an indoor temperature of 80 ° C., the thermostatic chamber was stopped, and the ink containing shaft having a water- and oil-repellent treatment surface formed on the inner wall surface by being naturally cooled to room temperature. Obtained.

（実施例１１）
上記実施例１０において、フッ素系撥水撥油処理剤ＩＮＴ３０４−ＶＣに代え、シリコーン系撥水撥油処理剤Ｘ−３１−６０８−Ｔ（脱オキシウム型：シリコーン２０ｗｔ％に対して非晶質シリカ粒子を５ｗｔ％含有、信越化学工業社製）をメチルシクロへキサンで固形分濃度３％に希釈調整したものを用いた以外は、実施例１０と同様にしてインキ収容軸を得た。 (Example 11)
In Example 10 above, instead of the fluorine-based water / oil repellent agent INT304-VC, a silicone-based water / oil repellent agent X-31-608-T (deoxynium type: amorphous silica with respect to 20 wt% silicone) An ink containing shaft was obtained in the same manner as in Example 10 except that 5 wt% of the particles (manufactured by Shin-Etsu Chemical Co., Ltd.) were used and diluted with methylcyclohexane to a solid content concentration of 3%.

（実施例１２）
ポリプロピレン製のインキ収容軸の油分を除くため、ｎ−ヘキサンでインキ収容軸内面を洗浄し、その後ｎ−ヘキサンを室温下で揮発させた。
次いで、インキ収容軸をＳＵＳ製試験管立てに立てた後、プラズマアッシャーのチャンバーに入れ、高周波発生器の出力１００Ｗ、照射時間３分間の酸素プラズマ処理を４回行った。
このプラズマ処理後のインキ収容軸に上述のシリカゾル溶液Ｎｏ．１をピペット状充填機で充填後、速やかに液を引き抜き、更に、インキ収容軸の開放部を下向きにして余分なシリカゾル溶液をスポンジ状の吸収体で吸収除去した。
次に、上記シリカゾル溶液で処理したインキ収容軸を室内温が１２０℃の恒温槽に入れて１時間熱処理を行った後、恒温槽を停止させ、室内温が６０℃以下になったら、インキ収容軸を恒温槽から取り出し、室温下まで自然冷却させ、ＳｉＯ2の薄膜が形成されたインキ収容軸を得た。
上記で得られたインキ収容軸に下記の調製法により得たシリコーン系撥水撥油処理剤を充填して、その後速やかに吸引して余分な撥水撥油処理剤を除き、更に、インキ収容軸の開放部を下向きにして余分な撥水撥油処理剤をスポンジ状の吸収体で吸収除去した。
シリコーン系撥水撥油処理剤の調製：
シリコーン系撥水撥油処理剤Ｘ−３１−６０８−Ｔ（脱オキシウム型：シリコーン２０ｗｔ％に対して非晶質シリカ粒子を５ｗｔ％含有、信越化学工業社製）をイソヘキサンに溶解して２．５ｗｔ％濃度の撥水撥油処理剤。
次いで、室内温が８０℃の恒温槽に入れて1２時間熱処理を行った後、恒温槽を停止させ、室温まで自然冷却させて内壁面に撥水撥油処理面が形成されたインキ収容軸を得た。 (Example 12)
In order to remove the oil content of the polypropylene ink storage shaft, the inner surface of the ink storage shaft was washed with n-hexane, and then n-hexane was volatilized at room temperature.
Next, after placing the ink containing shaft in a SUS test tube stand, it was put into a plasma asher chamber, and oxygen plasma treatment was performed 4 times with an output of 100 W from a high frequency generator and an irradiation time of 3 minutes.
The above-described silica sol solution No. is attached to the ink receiving shaft after the plasma treatment. After filling 1 with a pipette-like filling machine, the liquid was quickly drawn out, and the excess silica sol solution was absorbed and removed with a sponge-like absorber with the open part of the ink containing shaft facing downward.
Next, the ink containing shaft treated with the silica sol solution was put into a thermostat having a room temperature of 120 ° C. and subjected to heat treatment for 1 hour, and then the thermostat was stopped. The shaft was taken out of the thermostatic chamber and allowed to cool naturally to room temperature to obtain an ink containing shaft on which a thin film of SiO 2 was formed.
The ink containing shaft obtained above is filled with the silicone-based water / oil repellent agent obtained by the following preparation method, and then quickly sucked to remove the excess water / oil repellent agent, and further contains the ink. Excess water and oil repellent treatment agent was absorbed and removed with a sponge-like absorbent body with the shaft open part facing down.
Preparation of silicone water and oil repellent treatment agent:
1. Silicone water and oil repellent treatment agent X-31-608-T (deoxynium type: containing 5 wt% of amorphous silica particles with respect to 20 wt% of silicone, manufactured by Shin-Etsu Chemical Co., Ltd.) is dissolved in isohexane. 5 wt% concentration water / oil repellent treatment agent.
Next, after heat treatment for 12 hours in a thermostatic chamber having an indoor temperature of 80 ° C., the thermostatic chamber was stopped, and the ink containing shaft having a water- and oil-repellent treatment surface formed on the inner wall surface by being naturally cooled to room temperature. Obtained.

（実施例１３）
上記実施例１２において、シリカゾル溶液Ｎｏ．１を実施例２で用いたシリカゾル溶液Ｎｏ．２に代えた以外は実施例１２と同様にして内壁面が撥水撥油処理処理されたインキ収容軸を得た。 (Example 13)
In Example 12, the silica sol solution No. No. 1 in the silica sol solution No. 1 used in Example 2. An ink receiving shaft was obtained in the same manner as in Example 12 except that the inner wall surface was treated with a water / oil repellent treatment, except that the number was changed to 2.

（実施例１４）
上記実施例１２において、シリコーン系撥水撥油処理剤に代え、上記実施例９のフッ素系撥水撥油処理剤ＩＮＴ３０４−ＶＣ（ＮＩマテリアル社製）を用いた点、この撥水撥油処理後のインキ軸を室内温が８０℃の恒温槽に入れて６０分間熱処理を行った後、恒温槽を停止させ、室温下まで自然冷却させて内壁面に撥水撥油処理されたインキ収容軸を得る点以外は、上記実施例１２と同様にした。 (Example 14)
In Example 12, in place of the silicone-based water- and oil-repellent agent, the fluorine-based water- and oil-repellent agent INT304-VC (manufactured by NI Materials) of Example 9 was used. After the ink shaft was placed in a thermostatic chamber with a room temperature of 80 ° C. and heat-treated for 60 minutes, the thermostatic chamber was stopped and allowed to cool naturally to room temperature, and the inner wall surface was subjected to water and oil repellent treatment. Except for the point obtained, the same procedure as in Example 12 was performed.

（実施例１５）
上記実施例１２において、シリカゾル溶液Ｎｏ．１を実施例２で用いたシリカゾル溶液Ｎｏ．２に代えた点、また、シリコーン系撥水撥油処理剤に代え、上記実施例９と同様のフッ素系撥水剤ＩＮＴ３０４−ＶＣ（ＮＩマテリアル社製）を用いた点、この撥水処理後のインキ軸を室内温が８０℃の恒温槽に入れて６０分間熱処理を行った後、恒温槽を停止させ、室温下まで自然冷却させて内壁面に撥水撥油されたインキ収容軸を得る点以外は、上記実施例１２と同様にした。 (Example 15)
In Example 12, the silica sol solution No. No. 1 in the silica sol solution No. 1 used in Example 2. 2 and the point that the same fluorine-based water repellent INT304-VC (manufactured by NI Materials) as in Example 9 was used in place of the silicone-based water and oil repellent treatment agent. The ink shaft was placed in a thermostat with a room temperature of 80 ° C. and heat-treated for 60 minutes, and then the thermostat was stopped and allowed to cool naturally to room temperature to obtain an ink containing shaft that was water and oil repellent on the inner wall surface. Except for this point, the procedure was the same as in Example 12.

（実施例１６）
ポロプロピレン製のインキ収容軸の油分を除くためｎ−ヘキサンでインキ収容軸内面を洗浄し、その後ｎ−ヘキサンを室温下で揮発させた。
このインキ収容軸をＳＵＳ製試験管立てに立てた後、プラズマアッシャーのチャンバーに入れ、高周波発生器の出力１００Ｗ、照射時間３分間の酸素プラズマ処理を４回行った。
上記シリカゾル溶液Ｎｏ．１をピペット状充填機で充填後、速やかに液を引き抜き、更にインキ収容軸の開放部を下向きにして余分なシリカゾル溶液をスポンジ状の吸収体で吸収除去した。
次いで、室温が１２０℃の恒温槽に入れて１時間熱処理を行った後、恒温槽を停止させ、室温が６０℃以下になったら、インキ収容軸を恒温槽から取り出し室温まで自然冷却させＳｉＯ2の薄膜が形成されたインキ収容軸を得た。
次に、フッ素系撥水撥油処理剤サイトップＣＬＴ１０７Ｍ（旭硝子社製）を先に得られたインキ収容軸に充填して、その後速やかに吸引して余分な撥水剤を除き、更にインキ収容軸の開放部を下向きにして余分な撥水処理剤をスポンジ状の吸収体で吸収除去した。
次いで、室内温が１２０℃の恒温槽に入れて１５分間熱処理を行った後、恒温槽を停止させ、室温まで自然冷却させて内壁面に撥水撥油処理されたものを得た。
次に、実施例９と同様のフッ素系撥水撥油処理剤ＩＮＴ３０４−ＶＣ（ＮＩマテリアル社製）を用いて先に得られたインキ収容軸に充填して、その後速やかに吸引して余分な撥水剤を除き、更にインキ収容軸の開放部を下向きにして余分な撥水処理剤をスポンジ状の吸収体で吸収除去した。
次いで、室内温が８０℃の恒温槽に入れて６０分間熱処理を行った後、恒温槽を停止させ、室温まで自然冷却させて内壁面に撥水撥油処理されたインキ収容軸を得た。 (Example 16)
In order to remove the oil content of the polypropylene containing ink containing shaft, the inner surface of the ink containing shaft was washed with n-hexane, and then n-hexane was volatilized at room temperature.
The ink containing shaft was set up in a SUS test tube stand and then placed in a plasma asher chamber, and an oxygen plasma treatment was performed four times with a high frequency generator output of 100 W and an irradiation time of 3 minutes.
The silica sol solution No. After filling 1 with a pipette-like filling machine, the liquid was quickly drawn out, and the excess silica sol solution was absorbed and removed with a sponge-like absorber with the open part of the ink containing shaft facing downward.
Then, the room temperature was carried out for 1 hour heat treatment placed in a thermostat at 120 ° C., a water-bath was stopped, when room temperature becomes 60 ° C. or less, SiO 2 was naturally cooled to room temperature was taken out of the ink accommodating shaft from a constant temperature bath An ink receiving shaft on which a thin film was formed was obtained.
Next, fluorinated water and oil repellent treatment agent Cytop CLT107M (Asahi Glass Co., Ltd.) is filled into the ink containing shaft obtained earlier, and then quickly sucked to remove excess water repellent and further contain ink. The excess water-repellent agent was absorbed and removed with a sponge-like absorber with the shaft open part facing down.
Subsequently, after heat-treating for 15 minutes in a thermostatic chamber having a room temperature of 120 ° C., the thermostatic bath was stopped, and naturally cooled to room temperature to obtain a water- and oil-repellent-treated inner wall surface.
Next, the ink containing shaft previously obtained was filled using the same fluorine-based water and oil repellent treating agent INT304-VC (manufactured by NI Material Co., Ltd.) as in Example 9, and then quickly sucked to remove excess. The water-repellent agent was removed, and the excess water-repellent agent was absorbed and removed with a sponge-like absorber with the open portion of the ink containing shaft facing downward.
Next, after heat treatment was performed for 60 minutes in a thermostatic chamber having an indoor temperature of 80 ° C., the thermostatic bath was stopped and naturally cooled to room temperature to obtain an ink containing shaft that was subjected to water / oil repellent treatment on the inner wall surface.

（実施例１７）
上記実施例１６において、シリカゾル溶液Ｎｏ．１を実施例２で用いたシリカゾル溶液Ｎｏ．２に代えた点以外は、上記実施例１６と同様してインキ収容軸を得た。 (Example 17)
In Example 16 above, the silica sol solution No. No. 1 in the silica sol solution No. 1 used in Example 2. An ink receiving shaft was obtained in the same manner as in Example 16 except that the point was changed to 2.

（比較例１）
撥水撥油処理、活性化処理が共にされていないポリプロピレン製の円筒状のインキ収容軸（内径１０ｍｍ、外径１２ｍｍ、長さ６０ｍｍ）を用いた。 (Comparative Example 1)
A polypropylene cylindrical ink containing shaft (inner diameter 10 mm, outer diameter 12 mm, length 60 mm) that was not subjected to both water and oil repellent treatment and activation treatment was used.

（比較例２）
撥水撥油処理しないで、活性化処理（酸素プラズマ処理）のみを施したポリプロピレン製の円筒状のインキ収容軸（内径１０ｍｍ、外径１２ｍｍ、長さ６０ｍｍ）を用いた。 (Comparative Example 2)
A cylindrical ink containing shaft (inner diameter: 10 mm, outer diameter: 12 mm, length: 60 mm) made of polypropylene and subjected only to activation treatment (oxygen plasma treatment) without using water / oil repellent treatment was used.

上記実施例１〜１７及び比較例１〜２で得られた各インキ収容軸（管）について、先端にペン先となる繊維束体又は樹脂粒子焼結体等からなる多孔質なペン芯やボールペンチップを取り付けて、下記評価方法により、インキ収容管のインキのハジキ性、残量確認性の評価を行った。
これらの評価結果を下記表１に示す。 About each ink accommodation axis | shaft (tube | pipe) obtained in the said Examples 1-17 and Comparative Examples 1-2, the porous pen core and ball-point pen which consist of the fiber bundle body used as a pen point or a resin particle sintered body at the front-end | tip. The chip was attached, and the evaluation of the repellency of the ink in the ink storage tube and the remaining amount confirmation was performed by the following evaluation method.
The evaluation results are shown in Table 1 below.

（インキのハジキ性、残量確認性の評価方法）
下記組成のインキＡ（表面張力２２ｍＮ／ｍ）、インキＢ（表面張力２５ｍＮ／ｍ）を充填して、製造直後及び５０℃にて１ケ月経過後のインキ収容管を使用して、下記評価方法によりインキのハジキ性、残量確認性を評価した。 (Evaluation method for ink repelling and remaining amount confirmation)
Ink A (surface tension 22 mN / m) and ink B (surface tension 25 mN / m) of the following composition were filled, and the following evaluation method was performed using an ink containing tube immediately after production and after 1 month at 50 ° C. Was used to evaluate the repelling property and remaining amount confirmation property of the ink.

インキＡの配合組成（配合単位：重量％）
エチルアルコール ７２．５
イソプロピルアルコール ７．５
ポリビニルブチラール ５．０
カーボンブラック ４．０
ステアリルアルコール １１．０ Formulation composition of ink A (compounding unit: wt%)
Ethyl alcohol 72.5
Isopropyl alcohol 7.5
Polyvinyl butyral 5.0
Carbon black 4.0
Stearyl alcohol 11.0

インキＢの配合組成（配合単位：重量％）
水（精製水） ７１．７０
カーボンブラックＭＡ−１００（三菱化学社製） １５．００
ジョンクリル６２（分散剤、ジョンソン社製） １０．００
アミノメチルプロパノール ０．１０
バイオデン−１８（防腐剤、大和化学工業社製） ０．２０
パラキシレングルコール ２．８５
４，４´−ビス（ヒドロキシメチル）ジベンジルエーテル ０．１５ Composition composition of ink B (compounding unit: wt%)
Water (purified water) 71.70
Carbon black MA-100 (Mitsubishi Chemical Corporation) 15.00
Jonkrill 62 (dispersant, manufactured by Johnson) 10.00
Aminomethylpropanol 0.10
Bioden-18 (preservative, manufactured by Daiwa Chemical Industry Co., Ltd.) 0.20
Paraxylene glycol 2.85
4,4'-bis (hydroxymethyl) dibenzyl ether 0.15

（インキのハジキ性の評価方法）
図２及び３のインキタンク軸内にインキＡ又はＢを半分量充填して軸をペン先下向きからペン先上向きにひっくり返したときのインキのインキタンク軸内壁面からのハジキ性を目視にて観察し下記評価基準で評価した。
評価基準：
◎：インキを完全にはじく。
○：インキが内壁面に僅かにインキが残る。
△：インキが内壁面に半分以上残る。
×：インキが内壁の全面に残る。 (Evaluation method of ink repellent properties)
When the ink tank shaft shown in FIGS. 2 and 3 is filled with half of the ink A or B and the shaft is turned over from the pen tip downward to the pen tip upward, the repellency of the ink from the inner wall surface of the ink tank shaft is visually observed. Observed and evaluated according to the following evaluation criteria.
Evaluation criteria:
A: The ink is completely repelled.
○: Ink slightly remains on the inner wall surface.
Δ: More than half of the ink remains on the inner wall surface.
X: Ink remains on the entire inner wall.

（残量確認性の評価方法）
図１のインキタンク軸内にインキＡ又はＢを充填し、筆記してインキを消費させて、インキタンク軸の残量確認（視認）性を目視にて観察し下記評価基準で評価した。
評価基準：
◎：インキを完全にハジキ、残量の確認が良好。
○：残量の確認ができるが、壁面に僅かにインキが残る。
△：残量の確認ができるが、壁面にインキが残る。
×：残量の確認ができない。 (Evaluation method for remaining capacity confirmation)
The ink tank shaft in FIG. 1 was filled with ink A or B, written and consumed, and the remaining amount confirmation (visibility) of the ink tank shaft was visually observed and evaluated according to the following evaluation criteria.
Evaluation criteria:
A: The ink is completely repelled and the remaining amount is confirmed.
○: The remaining amount can be confirmed, but a little ink remains on the wall surface.
Δ: The remaining amount can be confirmed, but ink remains on the wall surface.
×: The remaining amount cannot be confirmed.

Figure 0004620363
Figure 0004620363

上記表１の結果から明らかなように、本発明範囲となる実施例１〜１７は、本発明の範囲外となる比較例１〜２に較べて、インキのハジキ性、残量確認性に優れていることが判明した。
特に、実施例１〜８及び１２〜１７の活性化処理された後に、ＳｉＯ2の薄膜を形成し、該ＳｉＯ2薄膜に撥水撥油処理された筆記具用部材は、軸基材との密着性を向上させるため、更にインキのハジキ性、残量確認性に優れていることが判明した。 As is clear from the results of Table 1 above, Examples 1 to 17 within the scope of the present invention are superior in ink repellency and remaining amount confirmation as compared with Comparative Examples 1 and 2 that are outside the scope of the present invention. Turned out to be.
In particular, after the activation treatment of Examples 1 to 8 and 12 to 17, the SiO 2 thin film was formed, and the SiO 2 thin film was subjected to water and oil repellency treatment. In order to improve the properties, it has been found that the ink has excellent repellent properties and remaining amount confirmation properties.

（ａ）及び（ｂ）は、本発明の筆記具用部材をボールペン用インキ収容管に適用した一例、及びそのインキ収容管を備えた筆記具（ボールペン）の縦断面図である。(A) And (b) is the longitudinal cross-sectional view of an example which applied the member for writing instruments of this invention to the ink accommodating tube for ball-point pens, and the writing instrument (ball pen) provided with the ink accommodating tube. 本発明の筆記具部材をコレクター構造を備えた直液式筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材に適用したもの、及びその軸体を備えた直液式の筆記具を示す縦断面図である。The writing instrument member of the present invention applied to an ink tank member serving as a shaft body (ink container) for directly storing ink in a direct liquid writing instrument having a collector structure, and a direct liquid writing instrument including the shaft body FIG. 本発明の筆記具用部材を、撹拌ボールを内蔵したバルブ機構部を有するバルブ式筆記具におけるインキを直接貯溜する軸体（インキ収容容器）となるインキタンク部材に適用したもの、及びそのインキタンク部材を備えたバルブ式の筆記具を示す縦断面図である。The writing instrument member of the present invention is applied to an ink tank member that serves as a shaft body (ink container) for directly storing ink in a valve-type writing instrument having a valve mechanism having a built-in stirring ball, and the ink tank member It is a longitudinal cross-sectional view which shows the valve-type writing instrument provided. （ａ）と（b）は、本発明に用いるシリコーン処理に用いる各シリコーン化合物を説明する説明図である。(A) And (b) is explanatory drawing explaining each silicone compound used for the silicone process used for this invention. 筆記具用部材の少なくとも内側表面部をプラズマ処理等の活性化処理した後に、シリカゾル溶液を塗布、熱硬化させることによりＳｉＯ2の薄膜を形成し、該ＳｉＯ2薄膜に図４（ａ）及び（ｂ）に示すシリコーン処理（撥水撥油処理）を示す模式図である。At least the inner surface portion of the writing instrument member after activation treatment such as plasma treatment, coating a silica sol solution, by thermally curing to form a SiO 2 thin film, FIG. 4 to the SiO 2 thin film (a) and (b It is a schematic diagram which shows the silicone treatment (water / oil repellent treatment) shown in FIG.

符号の説明Explanation of symbols

１０ ペン先（ボールペン型チップ）
１１ 筆記具用部材（インキ収容管）
Ａ 筆記具（ボールペン） 10 Pen tip (ballpoint tip)
11 Materials for writing instruments (ink storage tube)
A Writing instrument (ballpoint pen)

Claims (11)

２５℃における表面張力が３０ｍＮ／ｍ以下のインキが接触する有底筒状の樹脂製の筆記具用部材の少なくとも内側表面部は、活性化処理された後に、アルコキシシラン基を持つＳｉＯ 2 の薄膜が形成され、該ＳｉＯ 2 薄膜に、パーフルオロポリエーテル基、又はパーフルオロアルキル基を有するシランカップリング処理、並びに、パーフルオロアルキル基を有するフッ素樹脂によるフッ素処理から選ばれる少なくとも１種による撥水撥油処理がされ、単分子膜が形成されていることを特徴とする内容物可視型筆記具用部材。 At least the inner surface portion of the bottomed cylindrical resin writing instrument member in contact with ink having a surface tension at 25 ° C. of 30 mN / m or less is subjected to an activation treatment, and then an SiO 2 thin film having an alkoxysilane group is formed. The SiO 2 thin film thus formed is subjected to water repellency by at least one selected from a silane coupling treatment having a perfluoropolyether group or a perfluoroalkyl group and a fluorine treatment with a fluororesin having a perfluoroalkyl group. A member for visible contents writing instrument, which is treated with oil to form a monomolecular film . 前記２５℃における表面張力が３０ｍＮ／ｍ以下のインキが接触する有底筒状の樹脂製の筆記具用部材に、更に撹拌ボールが内蔵される請求項１に記載の内容物可視型筆記具用部材。   The content-visible writing instrument member according to claim 1, wherein a stirring ball is further incorporated in the bottomed cylindrical resin writing instrument member that comes into contact with ink having a surface tension at 25 ° C. of 30 mN / m or less. ２５℃における表面張力が３０ｍＮ／ｍ以下のインキが接触する筒状の樹脂製の筆記具用部材であって、更に追従体を内蔵し、少なくとも内側表面部は、活性化処理された後に、アルコキシシラン基を持つＳｉＯ 2 の薄膜が形成され、該ＳｉＯ 2 薄膜に、パーフルオロポリエーテル基、又はパーフルオロアルキル基を有するシランカップリング処理、並びに、パーフルオロアルキル基を有するフッ素樹脂によるフッ素処理から選ばれる少なくとも１種による撥水撥油処理がされ、単分子膜が形成されていることを特徴とする内容物可視型筆記具用部材。 This is a cylindrical resin writing instrument member that comes into contact with ink having a surface tension at 25 ° C. of 30 mN / m or less, and further has a built-in follower, and at least the inner surface portion is activated, and then alkoxysilane. A SiO 2 thin film having a group is formed, and the SiO 2 thin film is selected from a silane coupling treatment having a perfluoropolyether group or a perfluoroalkyl group, and a fluorine treatment with a fluororesin having a perfluoroalkyl group. A member for visible content writing instrument, wherein a monomolecular film is formed by water and oil repellent treatment with at least one of the above . 活性化処理が、オゾン処理、空気プラズマ処理、酸素プラズマ処理、コロナ処理、紫外線照射処理、高圧放電処理及び酸処理から選ばれる一種又は二種以上を複合化させて処理する請求項１〜３の何れか一つに記載の内容物可視型筆記具用部材。 The activation treatment is performed by combining one or more selected from ozone treatment, air plasma treatment, oxygen plasma treatment, corona treatment, ultraviolet irradiation treatment, high-pressure discharge treatment, and acid treatment . The member for visible contents type writing instruments as described in any one . 撥水撥油処理が、少なくとも２回行われる請求項１〜４の何れか一つに記載の内容物可視型筆記具用部材。 The member for a content visible type writing instrument according to any one of claims 1 to 4 , wherein the water / oil repellent treatment is performed at least twice. 活性化処理が、空気プラズマ処理であり、撥水撥油処理が、シリコーン処理である請求項４に記載の内容物可視型筆記具用部材。 The member for visible contents writing instrument according to claim 4 , wherein the activation treatment is an air plasma treatment, and the water and oil repellent treatment is a silicone treatment. 活性化処理が、酸素プラズマ処理であり、撥水撥油処理が、シリコーン処理である請求項４に記載の内容物可視型筆記具用部材。 The member for visible contents writing instrument according to claim 4 , wherein the activation treatment is an oxygen plasma treatment, and the water and oil repellent treatment is a silicone treatment. 筆記具用部材に、ポリオレフィン系熱可塑性樹脂を用いてなる請求項１〜７の何れか一つに記載の内容物可視型筆記具用部材。 The content visible type writing instrument member according to any one of claims 1 to 7 , wherein a polyolefin thermoplastic resin is used for the writing instrument member. ポリオレフィン系熱可塑性樹脂がポリプロピレンである請求項８に記載の内容物可視型筆記具用部材。 The member for visible content writing instruments according to claim 8 , wherein the polyolefin-based thermoplastic resin is polypropylene. 内容物には、水又は極性有機溶媒を含む請求項１〜９の何れか一つに記載の内容物可視型筆記具用部材。 The content-visible writing instrument member according to any one of claims 1 to 9 , wherein the content contains water or a polar organic solvent. 請求項１〜１０の何れか一つに記載の内容物可視型筆記具用部材を備えたことを特徴とする筆記具。 A writing instrument comprising the member for a content visible writing instrument according to any one of claims 1 to 10 .
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