JPH0144218B2

JPH0144218B2 -

Info

Publication number: JPH0144218B2
Application number: JP58190146A
Authority: JP
Inventors: Masahiro Ootsuka
Original assignee: Orient Chemical Industries Ltd
Current assignee: Orient Chemical Industries Ltd
Priority date: 1983-10-11
Filing date: 1983-10-11
Publication date: 1989-09-26
Also published as: JPS6081268A

Description

【発明の詳細な説明】本発明は、着色オイル組成物に関するものであ
り、その主な目的は、石油製品の着色、或は石油
系溶剤を用いたところの、筆記具用・印刷用およ
び記録用として好適な黒色オイル組成物を提供す
るにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a colored oil composition, and its main purpose is to color petroleum products, or to use petroleum solvents for writing instruments, printing, and recording. The object of the present invention is to provide a black oil composition suitable as a black oil composition.

現在市販されている油性インキ製品は、大部分
キシレンを主溶剤とし、着色剤としては一般の油
溶性染料を用いているが、この様な油性インキを
用いた文具や事務用記録機を使用する場合、キシ
レンの甚しい不快臭や、その毒性が問題となる。 Most oil-based ink products currently on the market use xylene as the main solvent and general oil-soluble dyes as colorants, but stationery and office recorders that use such oil-based inks are not used. In this case, the extremely unpleasant odor of xylene and its toxicity become a problem.

近時キシレンに代る溶剤として脂肪族炭化水素
または脂環式炭化水素系溶剤等の石油系溶剤が提
案され、また、石油系溶剤可溶の油溶性染料も提
案されているが、これらの溶剤と油溶性染料との
組合せにおいても、溶解濃度の不足およびコスト
高という欠点があり、満足すべきものでない。 Recently, petroleum solvents such as aliphatic hydrocarbon or alicyclic hydrocarbon solvents have been proposed as solvents to replace xylene, and oil-soluble dyes that are soluble in petroleum solvents have also been proposed. The combination of oil-soluble dyes and oil-soluble dyes is also unsatisfactory because of the disadvantages of insufficient dissolved concentration and high cost.

特に今迄、積年の懸案となつてきたことは、黒
色染料には石油系溶剤に十分溶解するものがな
く、極性の第２溶剤の併用が必要であるというこ
とである。例えば、特公昭52−43408号公報では、
黒色染料として、C.I.ソルベントブラツク３
のジヘプチル誘導体が例示されている（実施例
３）が、該染料も前記した欠点を有しており、更
に溶解性を上げるべく長鎖アルキルアニリンを用
いると、そのジアゾ化にはニトロシル硫酸によら
ねばならないという不利益を生ずる。 In particular, a problem that has been a concern for many years is that there are no black dyes that are sufficiently soluble in petroleum-based solvents, and that it is necessary to use a polar second solvent in combination. For example, in Japanese Patent Publication No. 52-43408,
CI Solvent Black 3 as a black dye
(Example 3), but this dye also has the drawbacks mentioned above, and when a long-chain alkylaniline is used to further increase the solubility, its diazotization requires nitrosyl sulfate. This results in the disadvantage of having to do so.

本発明者は、如上の問題点を根本的に解決すべ
く種々検討した結果、一般式〔式中、Ｒは、ＨまたはCH₃、R₁，R₂は、Ｈ，
C₄〜C₁₈のアルキル基、アルケニル基またはアル
キル置換基があつてもよいベンジル基（但し、同
時にＨでない）を示す。〕で表わされる新規な黒色ジスアゾ染料が、脂肪族
炭化水素および脂環式炭化水素等の石油系溶剤並
びにハロゲン化炭化水素に極めて良好な溶解性を
有することを見出し、本発明を完成した。 As a result of various studies to fundamentally solve the above-mentioned problems, the inventor found that the general formula [In the formula, R is H or CH ₃ , R ₁ and R ₂ are H,
Indicates a _C4 to _C18 alkyl group, an alkenyl group, or a benzyl group which may have an alkyl substituent (but not H at the same time). ] The present invention was completed based on the discovery that a novel black disazo dye represented by the following has extremely good solubility in petroleum solvents such as aliphatic hydrocarbons and alicyclic hydrocarbons, as well as halogenated hydrocarbons.

本発明に係る着色オイル組成物は、一般式
（）の黒色染料を、石油系溶剤および／または
ハロゲン化炭化水素並びに必要に応じて樹脂及び
添加物等と混合して、調製される。 The colored oil composition according to the present invention is prepared by mixing the black dye of the general formula () with a petroleum solvent and/or a halogenated hydrocarbon, and if necessary, a resin and additives.

本発明に用いられる石油系溶剤としては、目的
に応じて各沸点範囲の脂肪族炭化水素系溶剤また
は／および脂環式化合物系溶剤が用いられる。脂
肪族炭化水素系溶剤としては、ヘキサン、リグロ
イン、ミネラルスピリツト、精製ゴム揮発油、軽
油等が用いられ、脂環式化合物系溶剤としては、
シクロヘキサン、メチルシクロヘキサン、ジメチ
ルシクロヘキサン、エチルシクロヘキサン、プロ
ピルシクロヘキサン、ブチルシクロヘキサン等が
用いられる。 As the petroleum solvent used in the present invention, aliphatic hydrocarbon solvents and/or alicyclic compound solvents having various boiling point ranges are used depending on the purpose. As aliphatic hydrocarbon solvents, hexane, ligroin, mineral spirits, refined rubber volatile oil, light oil, etc. are used, and as alicyclic compound solvents,
Cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, propylcyclohexane, butylcyclohexane, etc. are used.

本発明に用いられるハロゲン化炭化水素として
は、１，１，１―トリクロルエタン、１，１，２
―トリクロルエタン、１，１，１，２―テトラク
ロルエタン、塩化ヘキシル、クロルベンゼン等が
挙げられる。 The halogenated hydrocarbons used in the present invention include 1,1,1-trichloroethane, 1,1,2
-trichloroethane, 1,1,1,2-tetrachloroethane, hexyl chloride, chlorobenzene and the like.

本発明に用いられる樹脂としては、石油樹脂、
キシレン樹脂、スチレン系樹脂、クマロン樹脂な
ど前記溶剤に可溶の樹脂が用いられる。なお、添
加物としては、磁性体微粒子、微分散顔料、各種
界面活性剤、ワツクス等が用いられる。 The resin used in the present invention includes petroleum resin,
Resins that are soluble in the above solvents are used, such as xylene resins, styrene resins, and coumaron resins. In addition, as additives, magnetic fine particles, finely dispersed pigments, various surfactants, wax, etc. are used.

本発明における着色剤は、所望の色調に従つて
適宜の濃度に調製すればよいが、市販の石油系溶
剤可溶性染料による補色も可能である。参考例
（一般式（）において、Ｒ＝Ｈ、R₁，R₂＝ｎ―
C₁₂H₂₅とした本発明黒色ジスアゾ染料の合成）４―フエニルアゾ―１―ナフチルアミン24.7g
（0.1モル）を濃塩酸25g含む水に分散し、５℃以
下となし、亜硝酸ソーダ7gを含む水溶液を加え
ジアゾ化した。 The colorant used in the present invention may be adjusted to an appropriate concentration according to the desired color tone, but a complementary color using a commercially available petroleum solvent-soluble dye is also possible. Reference example (in general formula (), R=H, R ₁ , R ₂ = n-
Synthesis of black disazo dye of the present invention with C ₁₂ H ₂₅ ) 24.7 g of 4-phenylazo-1-naphthylamine
(0.1 mol) was dispersed in water containing 25 g of concentrated hydrochloric acid, the temperature was kept below 5°C, and an aqueous solution containing 7 g of sodium nitrite was added to diazotize.

他方、１，８―ジアミノナフタレン15.8g（0.1
モル）をキシレン100mlにとかし、無水炭酸カリ
20g、トリエチルアミン5g加え、よくかきまぜな
がら80℃でラウリルブロマイド50g（0.2モル）を
60分かかつて滴下し、次いで120℃に昇温し、ジ
アミノナフタレンのなくなるまで反応した（３時
間かかつた）。冷却後氷水60mlを加え、５〜８℃
で上記ジアゾ化液を加えカツプリングした。 On the other hand, 15.8g (0.1
mol) in 100 ml of xylene and anhydrous potassium carbonate.
Add 20 g of triethylamine and 5 g of triethylamine, and add 50 g (0.2 mol) of lauryl bromide at 80℃ while stirring well.
The mixture was added dropwise for 60 minutes, then the temperature was raised to 120°C, and the reaction was carried out until the diamino-naphthalene disappeared (it took 3 hours). After cooling, add 60ml of ice water and bring to 5-8℃.
Then, the above diazotization solution was added and coupled.

１時間後PH11〜12となし、静置して、黒色染料
のキシレン溶液を分取した。キシレン溶液を水洗
し、ついでキシレンを回収して、室温で液状の黒
色染料を64g得た。 After 1 hour, the pH was adjusted to 11 to 12, and the solution was left to stand, and a xylene solution of the black dye was collected. The xylene solution was washed with water, and then the xylene was recovered to obtain 64 g of a black dye that was liquid at room temperature.

得られたものは、C.I.ソルベント・ブラツク３
に比し赤味の黒色染料であつた。 The result is CI Solvent Black 3
It was a black dye with a reddish tinge.

実施例１本発明に係る黒色染料（一般式（）におい
て、Ｒ＝Ｈ、R₁，R₂＝ｎ―C₁₂H₂₅）10部アイソ
パ―Ｅ（エクソン化学社製）90部如上の配合物を混合溶解したのち、孔径1μの
テフロンフイルターで加圧過して、ジエツト印
刷方式用黒色記録液を得た。得られたものは、経
時安定性に優れ、吐出ノズルに目詰りを起さず、
記録紙に記録された画像は濃度が高く鮮明であつ
た。Example 1 Black dye according to the present invention (in the general formula (), R = H, R ₁ , R ₂ = n-C ₁₂ H ₂₅ ) 10 parts Isopar-E (manufactured by Exxon Chemical Co., Ltd.) 90 parts The above formulation After mixing and dissolving the mixture, the mixture was pressurized and filtered through a Teflon filter with a pore size of 1 μm to obtain a black recording liquid for jet printing. The obtained product has excellent stability over time, does not cause clogging of the discharge nozzle,
The image recorded on the recording paper was high in density and clear.

実施例２本発明に係る黒色染料（一般式（）におい
て、（Ｒ＝ｐ―CH₃，R₁，R₂＝ｎ―C₈H₁₇） 10部ネオポリマー140（日本石油社製） 10部アイソパーＧ（エクソン化学社製） 40部メチルシクロヘキサン 40部如上の配合物を混合溶解したのち、孔径1μの
テフロンフイルターで加圧過して、ジエツト印
刷方式用黒色記録液を得た。得られたものは、経
時安定性に優れ、ガラス、プラスチツク或いは金
属などへの印字に適した記録液である。Example 2 Black dye according to the present invention (in the general formula (), (R=p-CH ₃ , R ₁ , R ₂ =n-C ₈ H ₁₇ ) 10 parts Neopolymer 140 (manufactured by Nippon Oil Co., Ltd.) 10 parts Isopar G (manufactured by Exxon Chemical Co., Ltd.) 40 parts Methylcyclohexane 40 parts After mixing and dissolving the above formulations, the mixture was pressurized and filtered through a Teflon filter with a pore size of 1 μm to obtain a black recording liquid for jet printing. This recording liquid has excellent stability over time and is suitable for printing on glass, plastic, metal, etc.

実施例３本発明に係る黒色染料（一般式（）におい
て、Ｒ＝Ｈ、R₁，R₂＝ｎ―C₁₂H₂₅） 30部 IPソルベント1620（出光石油化学社製） 70部如上の配合物を混合溶解して、濃厚黒色オイル
組成物を得た。Example 3 Black dye according to the present invention (in the general formula (), R = H, R ₁ , R ₂ = n-C ₁₂ H ₂₅ ) 30 parts IP Solvent 1620 (manufactured by Idemitsu Petrochemical Co., Ltd.) 70 parts The above formulation The components were mixed and dissolved to obtain a rich black oil composition.

得られたものは、石油製品の着色、漁網の染色
等に有用であつた。 The obtained product was useful for coloring petroleum products, fishing nets, etc.

実施例４本発明に係る黒色染料（一般式（）におい
て、（Ｒ＝Ｈ、R₁，R₂＝CH₂・C₆H₅） 15部ネオポリマー120（日本石油社製） 12部エチルシクロヘキサン 73部以上の配合物を混合溶解し、これを過して黒
色のフエルトペン用インキを得た。得られたもの
は、経時安定性に優れ、マーカー容器にセツトし
筆記テストを行なつたところ、濃度の高い鮮明な
筆跡を得た。Example 4 Black dye according to the present invention (in the general formula (), (R=H, R ₁ , R ₂ = CH ₂・C ₆ H ₅ ) 15 parts Neopolymer 120 (manufactured by Nippon Oil Co., Ltd.) 12 parts ethylcyclohexane More than 73 parts of the formulation were mixed and dissolved to obtain a black ink for felt pens.The obtained ink had excellent stability over time, and was tested in a writing test by setting it in a marker container. , a clear handwriting with high density was obtained.

実施例５本発明に係る黒色染料（一般式（）におい
て、（Ｒ＝CH₃、R₁，R₂＝ｎ―C₈H₁₇）４部 TiO₂ミル 80部メチルシクロヘキサン 15部ワツクス１部如上の配合物を混合溶解して、灰色ペイントマ
ーカー用インキを得た。Example 5 Black dye according to the present invention (in the general formula (), (R=CH ₃ , R ₁ , R ₂ =n-C ₈ H ₁₇ ) 4 parts TiO ₂ mil 80 parts Methylcyclohexane 15 parts Wax 1 part A gray paint marker ink was obtained by mixing and dissolving the following formulations.

なおTiO₂ミルは次の様にして調製した。 Note that the TiO ₂ mill was prepared as follows.

TiO₂ 34部ネオポリマー120 10部トクシノール102（徳島製油社製） 10部メチルシクロヘキサン 25部分散剤１部如上の配合物をボールミル中で24時間分散処理
した。TiO ₂ 34 parts Neopolymer 120 10 parts Toxinol 102 (manufactured by Tokushima Oil Co., Ltd.) 10 parts Methylcyclohexane 25 parts Dispersion 1 part The above formulation was dispersed in a ball mill for 24 hours.

実施例６本発明に係る黒色染料（一般式（）におい
て、（Ｒ＝ｏ―CH₃、R₁，R₂＝ｎ―C₁₂H₂₅）５部ハイレジンQPA（東邦石油樹脂社製） 20部アルペースト240（東洋アルミ社製） 10部アイソパーＥ（エクソン化学社製） 65部如上の配合物を混合溶解して、ふち取りマーカ
ー用インキを得た。Example 6 Black dye according to the present invention (in general formula (), (R=o-CH ₃ , R ₁ , R ₂ =n-C ₁₂ H ₂₅ ) 5 parts Hi-Resin QPA (manufactured by Toho Oil Resin Co., Ltd.) 20 parts Alpaste 240 (manufactured by Toyo Aluminum Co., Ltd.) 10 parts Isopar E (manufactured by Exxon Chemical Co., Ltd.) 65 parts The above formulations were mixed and dissolved to obtain an ink for edge-marking markers.

得られた組成物をマーカー容器にセツトし、筆
記テストを行なつたところ、鮮明な黒色のふち取
り筆跡を得た。 When the obtained composition was placed in a marker container and a writing test was conducted, clear black bordered handwriting was obtained.

実施例７実施例２のメチルシクロヘキサン40部を１，
１，１―トリクロルエタン40部に代えたほかは実
施例２と同様にして、ジエツト印刷方式用黒色記
録液を得た。得られたものは、経時安定性に優
れ、吐出ノズルに目詰りを起こさず、ガラス、プ
ラスチツク或は金属などへの印字に適した記録液
であつた。Example 7 40 parts of methylcyclohexane from Example 2 was added to 1,
A black recording liquid for jet printing was obtained in the same manner as in Example 2 except that 40 parts of 1,1-trichloroethane was used. The obtained recording liquid had excellent stability over time, did not cause clogging of the discharge nozzle, and was suitable for printing on glass, plastic, metal, etc.

Claims

[Claims] 1. General formula [Wherein, R is H or CH ₃ , R ₁ and R ₂ are H,
Indicates a _C4 to _C18 alkyl group, an alkenyl group, or a benzyl group optionally having an alkyl substituent (but not H at the same time)] The black disazo dye represented by It is dissolved in
Colored oil composition.