JPS59170167A - Gold or silver ink for writing utensil - Google Patents

Abstract

PURPOSE:The titled ink, obtained by incorporating a metal powder pigement pretreated with methylhydrogenpolysiloxane and an amino-modified silicone oil on the surface thereof uniformly in an organic solvent, and having improved dispersibility of gold or silver dust pigment and further rust preventing and anticorrosive properties of the pigment. CONSTITUTION:An ink obtained by incorporating a metal powder pigment, gold or silver dust, pretreated with methylhydrogenpolysiloxane and an amino-modified silicone oil on the surface thereof uniformly in an organic solvent, e.g. n-heptane or ethyl cellosolve. EFFECT:The surface of the metal powder pigement protected with a film provides lustrous scripts.

Description

【発明の詳細な説明】 くイ）産業−１二の利用分野 本発明は筆記具用金銀インキに関し、更に詳しくは有機
溶剤に対する親和性及び分散性に１交れ、しかも金属粉
顔料表面を皮膜ににって保護し、金属粉顔料に対する防
錆及び防蝕特性を右する金銀インキに関づ−る。DETAILED DESCRIPTION OF THE INVENTION B) Industry-12 Field of Application The present invention relates to a gold and silver ink for writing instruments, and more specifically, it has good affinity for organic solvents and dispersibility, and also has the ability to form a film on the surface of metal powder pigments. This invention relates to gold and silver inks that are protected by metal powder pigments and have anti-rust and anti-corrosion properties against metal powder pigments.

（ロ）従来技術 従来一般に市販されている筆記具用インキは白色、有彩
色、金色、銀色等の各色が°あり、白色は無機顔料のチ
タン白（比重３．０〜４．０）を使用し、有彩色は白色
インキをベースとしてこれに油溶性染料を有機溶剤にと
かした液を混合してインキとしているかのが一般的であ
る。(B) Prior Art The inks for writing instruments that are generally commercially available come in various colors such as white, chromatic colors, gold, and silver.The white color uses an inorganic pigment, titanium white (specific gravity 3.0 to 4.0). Generally, chromatic colors are made by using white ink as a base and mixing it with a solution of an oil-soluble dye dissolved in an organic solvent.

また金銀インキは銅粉（比重７．０〜９．０）アルミ粉
（比重２．５〜３．０）を顔料どじでおり、いずれも比
重が大で、これをベヒクルにて分散し有機溶剤にて稀釈
して適度の粘度にしている。In addition, gold and silver ink uses copper powder (specific gravity 7.0 to 9.0) and aluminum powder (specific gravity 2.5 to 3.0) as pigments. Dilute to a suitable viscosity.

ところがこれらインキを充填する筆記具の先端は、合成
樹脂製で微細な隙間を設【プて構成されているため、少
なくともインキの粘度を５０ＣＰＳ（２５度ＣＢ型粘度
計にて測定）以下にする必要かある。However, the tip of the writing instrument used to fill these inks is made of synthetic resin with minute gaps, so the viscosity of the ink must be at least 50 CPS (measured with a 25 degree CB type viscometer) or less. There is.

しかしながら前述したにうに、金銀インキの顔料の比重
が大であるため、製造直後より金銀粉顔料の沈降が生じ
、経時と共にベヒクルと顔料との分離が激しくなる。However, as described above, since the specific gravity of the pigment in the gold and silver ink is high, the gold and silver powder pigment begins to settle immediately after production, and separation of the vehicle and the pigment becomes more severe as time passes.

このため筆記具のインキ容器にはスチールボールを入れ
、インキ中の顔料が沈降して色むらが生じた場合、筆記
具を振ることによりスチールボールが移動してインキが
撹拌されるようになっている。それでも顔料沈降の著し
い場合は、いくら娠つても沈降した顔料は容易に混溶せ
ず色むらは解消しないこともある。For this reason, a steel ball is placed in the ink container of the writing instrument, and if the pigment in the ink settles and uneven coloring occurs, shaking the writing instrument moves the steel ball and stirs the ink. However, if the pigment sedimentation is significant, the sedimented pigment may not be easily mixed and dissolved, and the color unevenness may not be resolved, no matter how long the pigment is precipitated.

その原因は、金属粉顔料の表面状態が非親油生の性質を
有し、ベヒクル及び有機溶剤との親和性が悪いために起
るものと考えられる。The reason for this is thought to be that the surface state of the metal powder pigment is non-oleophilic and has poor affinity with vehicles and organic solvents.

（ハ）′Ｒ明の目的（解決しようとする問題点）この発
明は上記従来の欠点を解消し、金銀粉顔料の分散性が良
好で、流通性及び描画性に優れ、しかも顔料の防錆、防
蝕特性を有し光沢のある悌記具用金銀インキの提供を目
的とする。(c) Purpose of 'R Ming (problems to be solved) This invention solves the above-mentioned conventional drawbacks, provides good dispersibility of gold and silver powder pigments, excellent distribution and drawability, and also prevents the pigment from rusting. The purpose of the present invention is to provide a gold and silver ink for use in writing instruments that has anti-corrosion properties and is glossy.

（ニ）問題点を解決づ−るための手段 本発明は、メチルハイドロジエンポリシロキ（ノン及び
アミン変性シリコンオイルにより、予め表面処理をほど
こした金銀粉顔料を用い、これを有機溶剤中に均一に混
溶したことを特徴とする。(d) Means for solving the problems The present invention uses gold and silver powder pigments that have been surface-treated in advance with methylhydrodiene polysiloxy (non- and amine-modified silicone oil), and uniformly immerses them in an organic solvent. It is characterized by being mixed with.

このように予め金銀粉顔料に前記表面処理をほどこせば
、顔料の表面状態は親水性より親油性に変化し、有機溶
剤やベヒクルに対する親和性は著しく向上し、経時振動
復元性、流通性、描画性及び分散性等良好になるととも
に、アミン変性シリコンオイルで防錆、防蝕して、筆跡
には金属光沢が栄えるという優れた結果が現われた。By subjecting gold and silver powder pigments to the above-mentioned surface treatment in advance, the surface state of the pigment changes from hydrophilic to lipophilic, and its affinity for organic solvents and vehicles is significantly improved, as well as its ability to recover from vibrations over time, flowability, etc. In addition to improved drawing and dispersibility, the amine-modified silicone oil provided excellent rust and corrosion protection, giving the handwriting a metallic luster.

これは表面処理剤であるハイドロジエンポリシロキサン
にて類別表面をコーテングカプセル化することにより、
有機溶剤やベヒクルとの親和性が保たれて顔料の沈降や
分離が防げ、表面処理剤の有する離型性がインキ中の顔
料同志及びベヒクル同志の凝集を防いでいるものと思わ
れ、また金属光沢が筆跡に栄える点については、アミン
変性シリコンオイルが金属表面に皮膜をつくって保護し
ているものと考えられる。This is achieved by coating and encapsulating the classified surface with hydrogen polysiloxane, a surface treatment agent.
It is thought that affinity with organic solvents and vehicles is maintained to prevent pigment sedimentation and separation, and the release properties of the surface treatment agent prevent pigments and vehicles from agglomerating together in the ink. The glossy appearance of the handwriting is thought to be due to the amine-modified silicone oil forming a protective film on the metal surface.

そして実験的に金属粉顔料を前述した表面処理をほどこ
し、この表面処理顔料を有機溶剤に分散させて金銀イン
キを作成し、表面処理をしていない従来の顔料を用いて
作成した金銀インキと全く同一条件にて比較試験したと
ころ、表面処理をＩＪだ顔料で作成したイン率は、表面
処理をしていない顔料で作成したインキに比べ、極めて
分散性が良好で、流通性及び描画性が良く、線描用ペン
先を用いた場合も極めて良好な描画性を示し、金属光沢
が元の顔料のままで鮮明であった。Then, we experimentally subjected the metal powder pigment to the surface treatment described above, and then dispersed this surface-treated pigment in an organic solvent to create gold and silver ink, which was completely different from the gold and silver ink created using conventional pigments without surface treatment. Comparative tests under the same conditions showed that the ink ratio created with pigments that were surface-treated with IJ had extremely good dispersibility, circulation, and drawing performance compared to inks created with pigments that were not surface-treated. Even when a line-drawing pen nib was used, extremely good drawing performance was exhibited, and the metallic luster remained clear as the original pigment.

ところが顔料表面未処理のインキは、線描用ペン先を用
いた場合、直ちに描画性が悪くなり、以後全く描画不能
で色調が黒く変色し、金属光沢は消えていた。またペン
の容器に充填した両者を同様に垂直に立てて放置し、経
時変化を１日目、５日目、１００日目５日問おきに振動
復元性、描画性、分散性の各点について比較試験を実施
したところ以下の如き結果となった。However, when the ink with untreated pigmented surface was used with a line-drawing pen nib, the drawing performance deteriorated immediately, and after that, no drawing was possible at all, the color tone turned black, and the metallic luster disappeared. In addition, both pens were filled in a pen container and left standing vertically, and the changes over time were measured on the 1st, 5th, and 100th days. When a comparative test was conducted, the following results were obtained.

（Ａ）表面処理を施していない金銀インキは、約１０日
位で沈降がひどく振動回数約１００回以上にて何とか分
散性が良好となる状態で描画性も余り良好とはいえず色
むらが目立ち、描画した場合の色調が黒味になり独特の
金属光沢が消失していた。(A) Gold and silver ink without surface treatment shows severe sedimentation after about 10 days, and after about 100 vibrations, the dispersibility becomes good, and the drawing performance is not very good, resulting in uneven color. It was noticeable, and when drawn, the color tone became blackish and the unique metallic luster was lost.

（Ｂ）表面処理を施した顔料を使用した金銀インキは、
３０日を経過した断点に於ても非常に振動撹拌による復
元１ヶが良好で、振動回数約５回〜１０回迄で完全に描
画が良好となり描画面の金属光沢が殆ど元の状態に近く
色の黒変も見られなかった。(B) Gold and silver ink using surface-treated pigments:
Even at the fracture point after 30 days, the restoration by vibration stirring was very good, and after about 5 to 10 vibrations, the drawing became completely good and the metallic luster on the drawing surface almost returned to its original state. No darkening of the color was observed.

実施例（１） 表面処理金粉 Ｎｏ　７０００金粉　　　　　１００．Ｏ１ｘｍ部（福
田金属箔粉工業株式会社製） メチルハイドロジエンポリシロキサン １．０重阻部 （信越化学工業株式会社製ＫＦ９９） アミノ変性シリコンオイル　　１．０重量部く信越化学
工業株式会社製商品名ＫＦ３９３）メチルクロロボルム （東亜合成化学工業株式会社製商品名スリーワーＲ） １００．０重量部 上記のものを゛均一に混合撹拌し約３０分〜１時間接取
出し風乾する。Example (1) Surface treatment gold powder No. 7000 gold powder 100. O1xm part (manufactured by Fukuda Metal Foil and Powder Industry Co., Ltd.) Methylhydrodiene polysiloxane 1.0 part by weight (KF99 manufactured by Shin-Etsu Chemical Co., Ltd.) Amino modified silicone oil 1.0 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) Product name KF393) Methyl chloroborum (manufactured by Toagosei Kagaku Kogyo Co., Ltd., trade name: 3WER R) 100.0 parts by weight The above ingredients were uniformly mixed and stirred, and then taken out and air-dried for about 30 minutes to 1 hour.

実施例（２） 表面処理銀粉 Ｎｏ　９００銀粉　　　　　１００．０重量部（福田金
属箔粉工業株式会社製） メチルハイドロジエンボリシロキザン １．０重量部 （信越化学工業株式会社製商品名ＫＦ９９）アミノ変性
シリコーンオイル （信越化学工業株式会社製商品名ＫＦ３８３）１．０重
用部 ジブチル錫ジアセテ−１−１，０重量部メチルク日ロホ
ルム　　　１００．０ｆｆｉｆｎ部（東亜合成化学工業
株式会社製商品名スリーワンＲ） 上記のものを均一になる様混合撹拌し約３０分〜１時間
接風乾する。Example (2) Surface treatment silver powder No. 900 silver powder 100.0 parts by weight (manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd.) 1.0 parts by weight of methylhydrodiene bolysiloxane (trade name KF99, manufactured by Shin-Etsu Chemical Co., Ltd.) Amino-modified Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF383) 1.0 parts dibutyltin diacetate-1-1,0 parts by weight Methylchloride 100.0 ffifn parts (trade name Three-One R, made by Toagosei Chemical Co., Ltd.) Above The mixture is mixed and stirred until it is uniform, and then air-dried for about 30 minutes to 1 hour.

筆記具用金銀インキの製造法 先に記した予め表面処理をせる金銀粉顔料を使用し流通
性、分散性、沈降性を改良せるインキの製造法を下記に
述べる。Method for producing gold and silver ink for writing instruments A method for producing an ink that uses the previously described gold and silver powder pigments that have been surface-treated to improve distribution, dispersibility, and sedimentation properties will be described below.

実施例（３） 筆記具用銀インキ Ｎ０９００ＳＡ（大東化成工業株式会社製　表面処理銀
粉） ２０．０重量部 ＢＧ−３０（日光ケミカル界面活性剤）１．０重（６）
部 ラスミン（共米社油脂工業製　防錆剤）ｉ、ｏ重量部 フタル酸ヂオクチル（大ハ化学工業株式会社製可塑剤） ３．０重量部 ノルマルへブタン　　　　　　　５．０重用部エチルセ
レソルブ　　　　　　　５．０重量部ビスペール１００
　５０％キシレン溶液２０．０重用部 （理化バーキュレス脂肪族炭化水素樹脂）パラロイドＡ
Ｆ６３　（ロムメイス社メタアクリル樹脂） ２０．０重量部 キシレン　　　　　　　　　　１５．０重量部インヘキ
サン　　　　　　　　１０．０重量部上記のものを混合
しホモミキサー（特殊機化工業株式会社製にて約１時間
分散ける後濾過し銀インキとした。Example (3) Silver ink for writing instruments N0900SA (surface-treated silver powder manufactured by Daito Kasei Kogyo Co., Ltd.) 20.0 parts by weight BG-30 (Nikko Chemical Surfactant) 1.0 parts by weight (6)
1 part Rasmin (corrosion inhibitor manufactured by Kyomaisha Yushi Kogyo Co., Ltd.) i, o parts by weight Dioctyl phthalate (plasticizer manufactured by Daiha Kagaku Kogyo Co., Ltd.) 3.0 parts by weight normal hebutane 5.0 parts by weight Ethyl ceresolve 5. 0 parts by weight Bisper 100
50% xylene solution 20.0 parts by weight (Rika Vercules aliphatic hydrocarbon resin) Paraloid A
F63 (methacrylic resin manufactured by Rommeis Co., Ltd.) 20.0 parts by weight It was filtered and made into silver ink.

実施例（４） 筆記具用金インキ Ｎｏ　７０００ＳＡ　（大東化成工業株式会社製　−面
処理金粉） ４０．０重量部 アミンＤ（理化バーキュレス社製　防錆剤）１．０重量
部 ターレン７２０．０（共栄社油脂工業株式会社製粘度調
接剤 １．０重足部 ダイヤナール５Ｒ−１０１５０％ギシロール授液　　　
　　　　　　　　　　　　　　　　　　４０．０重量部
（三菱レイヨン株式会社製メタアクリル樹脂）Ｄ、０．
Ｐ　（人ハ化学工業株式会社製可塑剤）２．０重用部 エトセル１０ＣＰＳ　　５０％キジロール溶液）５．０
重用部 （ダウケミカル社製エチルセルローズ）メチルイソブチ
ルケトン　　　　５．０７５ｍ部ブチルセロソルブ　　
　　　　　１．０重量部キシレン　　　　　　　　　　
　２．０重量部８Ｇ−３０（日光ケミカル界面活性剤）
屯　　　　　　　　　　　　　　　　　　１．０重量部
Ｎ−へブタン　　　　　　　　　２．０重用部上記のも
のを混合してホモミキサー（特殊機化工業株式会社製）
にて約１時間分散せる後濾過し金インキとした。Example (4) Gold ink No. 7000SA for writing instruments (manufactured by Daito Kasei Kogyo Co., Ltd. - surface treated gold powder) 40.0 parts by weight Amine D (rust preventive agent manufactured by Rika Vercules) 1.0 parts by weight Talene 720.0 (Kyoeisha Co., Ltd.) Viscosity regulator manufactured by Yushi Kogyo Co., Ltd. 1.0 heavy foot portion Dyanaru 5R-101 50% Gisirol infusion
40.0 parts by weight (methacrylic resin manufactured by Mitsubishi Rayon Co., Ltd.) D, 0.
P (Plasticizer manufactured by Jinha Kagaku Kogyo Co., Ltd.) 2.0 Heavy duty part Ethocel 10 CPS 50% Quijirol solution) 5.0
Heavy duty part (ethyl cellulose manufactured by Dow Chemical Company) Methyl isobutyl ketone 5.075 m parts Butyl cellosolve
1.0 parts by weight xylene
2.0 parts by weight 8G-30 (Nikko chemical surfactant)
Ton: 1.0 parts by weight N-hebutane 2.0 parts by weight Mix the above ingredients and mix with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)
After dispersing for about 1 hour, the mixture was filtered to obtain gold ink.

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Claims (1)

【特許請求の範囲】[Claims] １、メヂルハイドロジエンボリシロキザン及びアミン変
性シリコンオイルにて表面処理した金属粉顔料を、有機
溶剤中に均一に混合してなる筆記具用金銀インキ。1. Gold and silver ink for writing instruments, which is made by uniformly mixing metal powder pigments whose surface has been treated with methylhydrodiene polysiloxane and amine-modified silicone oil in an organic solvent.