JP2004083692A - Oily marker ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oily marker ink including a highly safe solvent as an ink solvent and affording nonrepellent and highly adhesive holograph even if written on the surface of a material of poor wettability such as a kraft tape for packing use. <P>SOLUTION: The oily marker ink comprises a poly(N-acylalkyleneimine)-modified silicone, a colorant and a solvent and optionally, a film-forming resin. <P>COPYRIGHT: (C)2004,JPO

Description

【００１３】
（式中、Ｒ^１は水素原子、炭素数１〜２２のアルキル基、炭素数６〜２２のアリール基、又は炭素数７〜２２のアリールアルキル基若しくはアルキルアリール基を示し、ｎは２又は３の数を示す。）
で表される繰り返し単位（以下、繰り返し単位（１）という）からなるポリ（Ｎ−アシルアルキレンイミン）セグメント（以下セグメント（Ｂ）という）を有するものが好ましく、特にセグメント（Ａ）の末端又は側鎖のケイ素原子の少なくとも１個に、ヘテロ原子を含むアルキレン基を介して、セグメント（Ｂ）が結合したオルガノポリシロキサンが好ましい。
【００１４】
ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンにおいて、セグメント（Ａ）とセグメント（Ｂ）との重量比（（Ａ）／（Ｂ））は、筆跡のはじきを抑制し、密着性を向上させる観点から、好ましくは５／９５〜９９／１であり、更に好ましくは２０／８０〜９６／４、より好ましくは４０／６０〜９６／４である。
【００１５】
また、ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンの重量平均分子量は、筆跡のはじきを抑制し、密着性を向上させる観点から、１０，０００〜５，０００，０００が好ましく、１０，０００〜１，０００，０００がより好ましく、５０，０００〜５００，０００が特に好ましい。尚、この重量平均分子量は、クロロホルムを展開溶媒としたＧＰＣ（ゲル浸透型液体クロマトグラフィー）から求めた、ポリスチレン換算重量平均分子量である。
【００１６】
セグメント（Ａ）を形成するオルガノポリシロキサンとしては、例えば一般式（２）
【００１７】
【化３】

【００１８】
（式中、Ｒは炭素数１〜２２のアルキル基、フェニル基、又はヘテロ原子を含むアルキル基を示し、複数個のＲは同一でも異なっていても良いが、少なくとも１個はヘテロ原子を含むアルキル基である。ｍは１００〜５０００の数を示す。）
で表される化合物が挙げられる。
【００１９】
一般式（２）において、Ｒで示される炭素数１〜２２のアルキル基としては、炭素数１〜３のアルキル基が好ましく、メチル基が更に好ましい。また、ヘテロ原子を含むアルキル基としては、窒素原子、酸素原子及び／又はイオウ原子を好ましくは１〜３個含む炭素数２〜２０のアルキル基が挙げられ、以下に示す基が好ましい。
【００２０】
【化４】

【００２１】
ヘテロ原子を含むアルキル基は、オルガノポリシロキサンの末端又は側鎖のケイ素原子の少なくとも１個にあればよく、オルガノポリシロキサン中のヘテロ原子を含むアルキル基の数は１〜３００が好ましく、１〜１００が更に好ましい。
【００２２】
セグメント（Ａ）を形成するオルガノポリシロキサンの重量平均分子量は、１，０００〜１，０００，０００が好ましく、１，０００〜５００，０００が更に好ましい。重量平均分子量の測定方法は、前記と同じである。
【００２３】
セグメント（Ｂ）において、繰り返し単位（１）中のＲ^１は、アルキル基としては、炭素数１〜１２のアルキル基が好ましく、炭素数１〜３のアルキル基が更に好ましい。炭素数１〜３のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基等が例示される。アリール基としてはフェニル基、ナフチル基等が、アリールアルキル基としては、アルキル基の炭素数が１〜２０のフェニルアルキル基、ナフチルアルキル基等が、アルキルアリール基としては、アルキル基の炭素数が１〜２０のアルキルフェニル基、アルキルナフチル基等が挙げられる。またｎは２又は３を示す。
【００２４】
セグメント（Ｂ）中の繰り返し単位（１）の重合度は特に制限はないが、例えば１〜５００が好ましく、６〜１００が更に好ましい。
【００２５】
セグメント（Ａ）とセグメント（Ｂ）との結合において、介在するヘテロ原子を含むアルキレン基として、窒素原子、酸素原子及び／又はイオウ原子を好ましくは１〜３個含む炭素数２〜２０のアルキレン基が挙げられる。具体的には、アルキレン鎖の炭素−炭素間及び／又は末端に、▲１▼第２級アミン又は第３級アミン、▲２▼第２級アミン又は第３級アミンにＨ^＋が付加して得られるアンモニウム塩、▲３▼第４級アンモニウム塩、▲４▼酸素原子及び／又は▲５▼イオウ原子を含む炭素数２〜２０のアルキレン基が挙げられる。これらのうち、下記の構造が、好ましく挙げられる。
【００２６】
【化５】

【００２７】
（式中、Ｘ⁻はアンモニウム塩の対イオンを示す。）
上記におけるＸ⁻の具体例としては、塩素、ヨウ素、臭素等のハロゲンイオン、メトサルフェート、エトサルフェート、メトフォスフェート、エトフォスフェート等の有機アニオンが挙げられる。
【００２８】
本発明で用いられるポリ（Ｎ−アシルアルキレンイミン）変性シリコーンは、例えば、環状イミノエーテルの開環重合物であるポリ（Ｎ−アシルアルキレンイミン）とセグメント（Ａ）を形成するオルガノポリシロキサンとを反応させる、特開平７−１３３３５２号公報段落番号３４〜４２記載の方法により得ることができる。これらは、単一化合物あるいは混合物であっても良い。
【００２９】
［着色剤］
本発明に用いられる着色剤としては、酸性染料、塩基性染料、顔料等が挙げられる。
【００３０】
染料としては、油溶性染料が好ましく、さらには後述する溶剤に可溶であるものが好ましい。染料の例としては、バリファストブラック３８１０，３８２０，３８３０，３８４０（以上、オリエント化学工業（株）製）、スピロンブラックＧＭＨスペシャル、ＳＯＴブラック−１２Ｈ（以上、保土谷化学工業（株）製）、バリファストレッド１３０６，１３０８（以上、オリエント化学工業（株）製）、スピロンレッドＣ−ＢＨ，Ｃ−ＧＨ（以上、保土谷化学工業（株）製）、バリファストブルー１６０３，１６０５（以上、オリエント化学工業（株）製）、ＳＢＮブルー７０１，ＳＰＴブルー２６（以上、保土谷化学工業（株）製）等が挙げられる。
【００３１】
顔料の種類については特に制限はなく、無機系または有機系顔料の中から任意のものを使用することができる。無機系顔料としては、例えば酸化チタン、カーボンブラック、金属粉等が挙げられる。また、有機系顔料としては、例えばアゾレーキ、不溶性アゾ顔料、キレートアゾ顔料、フタロシアニン顔料、ペリレン及びペリノン顔料、アントラキノン顔料、キナクリドン顔料、染料レーキ、ニトロ顔料、ニトロソ顔料等が挙げられる。
これらの着色剤は単独または２種以上併用して用いることができる。
【００３２】
［造膜性樹脂］
本発明で用いられる造膜性樹脂としては、後述する溶剤に可溶であることが好ましく、例としては、アクリル樹脂、フェノール樹脂、ケトン樹脂、マレイン酸樹脂、ロジン樹脂、アミド樹脂、ポリビニルピロリドン等が挙げられる。
【００３３】
アクリル樹脂の例としては、パラロイドＢ−３８（ロームアンドハース社製）、ネオクリルＢ−７００（ゼネカ（株）製）等が挙げられる。フェノール樹脂の例としては、ヒタノール１１３３，１５０１，２５００（以上、日立化成工業（株）製）、タマノル１００Ｓ（荒川化学工業（株）製）等が挙げられる。ケトン樹脂の例としては、ハイラック１１１，２２２，１１０Ｈ（日立化成工業（株）製）等が挙げられる。
これらの造膜性樹脂は単独または２種以上併用して用いることができる。
【００３４】
［溶剤］
本発明で用いられる溶剤としては、親水性溶剤が好ましい。親水性溶剤としては、アルコール系溶剤、グリコールエーテル系溶剤が好ましい。アルコール系溶剤として、エチルアルコール、イソプロピルアルコール、ｎ−プロピルアルコール等の炭素数１〜５の低級アルコール；ベンジルアルコール等の芳香族アルコール；エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン等の多価アルコールが挙げられる。グリコールエーテル系溶剤として、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等が挙げられる。
【００３５】
これらの中では、炭素数１〜５の低級アルコール、芳香族アルコール及び多価アルコールからなるアルコール系溶剤群から選ばれる１種以上を用いることが更に好ましく、炭素数１〜５の低級アルコールが特に好ましい。これらの溶剤は単独または２種以上併用して用いることができる。本発明の効果を損なわない範囲で、非極性の溶剤を用いてもよい。
【００３６】
［油性マーカーインキ及びその製造法］
本発明の油性マーカーインキは、ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンを好ましくは０．１〜３０重量％、さらに好ましくは０．５〜２０重量％含有する。この範囲内では、塗膜性に優れており、良好な筆跡を得ることが出来る。
【００３７】
本発明の油性マーカーインキは、着色剤を好ましくは０．５〜３０重量％、さらに好ましくは１〜２０重量％含有する。この範囲内では、粘度及び筆跡濃度が適度で好ましく、筆記性に優れている。
【００３８】
本発明の油性マーカーインキは、溶剤を好ましくは３０〜９８重量％、さらに好ましくは５０〜９５重量％含有する。この範囲内では、着色剤の溶解又は分散性がよく、粘度及び筆跡濃度が適度で好ましく、筆記性に優れている。溶剤１００重量部に対して、着色剤は、１〜４０重量部であることが好ましく、３〜２０重量部であることが更に好ましい。この範囲内では、着色剤の溶解又は分散性に優れている。
【００３９】
本発明の油性マーカーインキは、更に、塗膜性を向上させるために、造膜性樹脂を含有することが好ましく、造膜性樹脂の含有量は、好ましくは０．５〜２０重量％、さらに好ましくは１〜１５重量％である。
【００４０】
本発明の油性マーカーインキの粘度は、０．５〜５０ｍＰａ・ｓ（測定温度：２０℃、測定器：ＥＬ型粘度計）であることが好ましく、１〜４０ｍＰａ・ｓであることが更に好ましい。これは、粘度が０．５ｍＰａ・ｓ以上であるとマーキングペンからのインキ出が過剰とならず、筆跡がにじみにくくなるためであり、また、５０ｍＰａ・ｓ以下だと筆跡が掠れにくくなるためである。
【００４１】
本発明の油性マーカーインキは、更に、必要に応じて、例えば、粘度調整剤、構造粘性付与剤、染料可溶化剤、乾燥性付与剤等の成分を含有することができる。
【００４２】
本発明の油性マーカーインキは、油性マーカーペン又は油性マーキングペン用のインキ組成物として用いることができる。
【００４３】
本発明の油性マーカーインキの製造方法としては、従来知られている通常の方法によって製造することができる。例えば、溶剤にポリ（Ｎ−アシルアルキレンイミン）変性シリコーン、必要に応じて造膜性樹脂を溶解又は分散させた後、これに着色剤及び、必要に応じて任意成分を添加し、一様に溶解又は分散させることにより製造してもよく、溶剤に着色剤を一様に溶解又は分散させた後、ポリ（Ｎ−アシルアルキレンイミン）変性シリコーン、必要に応じて造膜性樹脂を溶解又は分散させてもよく、あるいは一度にポリ（Ｎ−アシルアルキレンイミン）変性シリコーン、必要に応じて造膜性樹脂、着色剤、及び必要に応じて任意成分を溶剤に混合して製造してもよい。上記の溶解、分散、及び混合は、常温または加熱下（３０〜５０℃）で行うことが好ましい。
【００４４】
【実施例】
以下の例において、「部」及び「％」は、特記しない限り、「重量部」及び「重量％」を示す。尚、アミン当量とは、窒素原子１個あたりの分子量を意味する。
【００４５】
合成例１：ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンＡの合成
硫酸ジエチル６．５部と２−エチル−２−オキサゾリン１００．０部を、脱水した酢酸エチル２００．０部に溶解し、窒素雰囲気下、４時間加熱還流し、末端反応性ポリ（Ｎ−プロピオニルエチレンイミン）を得た。次に、側鎖１級アミノプロピル変性ポリジメチルシロキサン（分子量１１０，０００；アミン当量（ｇ／ｍｏｌ）２０，８００）７２７．０部の５０％酢酸エチル溶液を一括して加え、８時間加熱還流した。反応混合物を減圧濃縮し、ポリ（Ｎ−プロピオニルエチレンイミン）ジメチルシロキサン共重合体（セグメント（Ａ）／セグメント（Ｂ）＝８８／１２）（以下、ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンＡという）を淡黄色ゴム状固体として得た。このもののポリスチレン換算重量平均分子量は１１５，０００であった（クロロホルムを展開溶媒としたゲル浸透クロマトグラフィーによる分子量測定法）。また、溶媒としてメタノールを使用した塩酸による中和滴定の結果、アミノ基が残存していないことを確認した。
【００４６】
合成例２：ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンＢの合成
硫酸ジエチル６．５部と２−エチル−２−オキサゾリン１００．０部を、脱水した酢酸エチル２００．０部に溶解し、窒素雰囲気下、５時間加熱還流し、末端反応性ポリ（Ｎ−プロピオニルエチレンイミン）を得た。ここに、側鎖１級アミノプロピル変性ポリジメチルシロキサン（分子量１１０，０００；アミン当量（ｇ／ｍｏｌ）４，８４０）１００．０部の５０％酢酸エチル溶液を一括して加え、１０時間加熱還流した。反応混合物を減圧濃縮し、ポリ（Ｎ−プロピオニルエチレンイミン）ジメチルシロキサン共重合体（セグメント（Ａ）／セグメント（Ｂ）＝５０／５０）（以下、ポリ（Ｎ−アシルアルキレンイミン）変性シリコーンＢという）を淡黄色ゴム状固体として得た。このもののポリスチレン換算重量平均分子量は１０９，０００であった（クロロホルムを展開溶媒としたゲル浸透クロマトグラフィーによる）。また、溶媒としてメタノールを使用した塩酸による中和滴定の結果、アミノ基が残存していないことを確認した。
【００４７】
実施例１〜４及び比較例１〜４
表１に示す各成分を室温ないし５０℃にて２時間攪拌して均一に溶解させ、必要に応じて濾過して不溶解物を除去し、表１に示す組成を有する黒色の油性マーカーインキを得た。得られた油性マーカーインキを、マーキングペン（商品名「ＡＵＮＯ２　油性マーカーツイン」、セーラー万年筆（株）製）に充填し、下記の評価項目について試験した。結果を併せて表１に示した。
【００４８】
＜試験１＞
荷造り用クラフトテープ（Ｎｏ．２００、リンレイテープ（株）製）の表面に筆記し、筆跡のはじきを以下の基準で判断した。
・評価基準
○…はじきが無い。
×…はじきが有る。
【００４９】
＜試験２＞
その筆跡を乾燥させた後、指でこすり筆跡の密着性を以下の基準で判断した。
・評価基準
◎…密着性が非常に有る。
○…密着性が有る。
×…密着性が無い。
【００５０】
【表１】

【００５１】
＊１：ポリオキシプロピレン変性シリコーン（東芝シリコーン（株）製）
＊２：フェノール樹脂（日立化成工業（株）製）
＊３：アクリル樹脂（ロームアンドハース社製）
＊４：オリエント化学工業（株）製[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to an oil-based ink used for a marker or the like, and more particularly to an oil-based marker ink which is highly safe and does not repel even the surface of a material having poor wettability and has excellent adhesion.
[0002]
Problems to be solved by the prior art and the invention
The oil-based ink used for a marker or the like contains a colorant, an organic solvent, and a film-forming resin as essential components, and a surfactant or the like is added as necessary. Examples of the organic solvent include alcohols such as ethyl alcohol, isopropyl alcohol, n-propyl alcohol and benzyl alcohol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and esters such as ethyl acetate, n-propyl acetate and n-butyl acetate. And petroleum fractions such as petroleum benzine and ligroin; and aromatic hydrocarbons such as xylene and toluene. As the film forming resin, for example, an acrylic resin, an alkyd resin, an alkylphenol resin, a polyester resin, a vinyl acetate-acryl copolymer, or the like is used.
[0003]
Then, when writing on paper or the like, the colorant dissolved in the organic solvent is dispersed in the film-forming resin to form a film, which is dried and adheres to the paper to form handwriting. For this reason, film-forming resins are required to have good film-forming properties and to be quick-drying and rich in adhesion, but when written on the surface of a material having poor wettability, these resins have insufficient adhesion. And could not obtain complete handwriting.
[0004]
By the way, as an example of a material having poor wettability, a kraft tape for packing can be mentioned. This kraft tape for packing is obtained by coating a paper base with a polyethylene film and further covering with a silicone coating. Here, when writing is performed on the surface of the kraft tape for packing with a conventional oil-based ink using the above resin as the film-forming resin, a repelling phenomenon is observed as described above, and good writing is impossible. Furthermore, there is a problem that the adhesion after writing is poor, and the handwriting is erased by rubbing lightly.
[0005]
Other examples of materials having poor wettability include synthetic resin sheets made of polypropylene, polyethylene, nylon, Teflon, polyacetal, etc., or those coated with paper base materials, and even metal surfaces wetted with oil. When writing them, the situation is the same.
[0006]
In order to solve such a problem, Japanese Patent Publication No. Hei 7-91502 discloses a method in which only a silicone-based adhesive is added as a film-forming resin to a colorant and a solvent, and the wettability is increased as in a kraft tape for packing. An oil-based ink having excellent adhesion even to the surface of a bad material is disclosed. However, aromatic oils and ketones are used as solvents in this oil-based ink, and conversion to highly safe solvents is desired.
[0007]
Japanese Patent Application Laid-Open No. 11-21492 discloses that a polar organic solvent having high safety is used, a colorant, an oil-soluble resin, and a polyoxypropylene-modified silicone are further included. An oil-based marking pen ink excellent in fixing property of a coating film upon writing is disclosed. However, with this oil-based ink, when writing on the surface of a poorly wettable material such as kraft tape for packing, repelling phenomena are observed, good writing is impossible, and adhesion after writing However, there is a problem that handwriting is erased by rubbing lightly.
[0008]
The object of the present invention is to solve these problems, to use a highly safe solvent as an ink solvent, and to repel even when writing on the surface of a poorly wettable material such as kraft tape for packing. An object of the present invention is to provide an oil-based marker ink which can obtain a handwriting with good adhesion without any problem.
[0009]
[Means for Solving the Problems]
The present inventors have conducted various tests and studies as a resin for an oil-based marker ink, and as a result, have found that poly (N-acylalkylenimine) -modified silicone is effective, and completed the present invention.
[0010]
That is, the present invention provides an oil-based marker ink containing a poly (N-acylalkyleneimine) -modified silicone, a colorant, and a solvent, and further, an oil-based marker ink containing a film-forming resin.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
[Poly (N-acylalkyleneimine) -modified silicone]
The poly (N-acylalkyleneimine) -modified silicone used in the present invention is not particularly limited, but includes an organopolysiloxane segment (hereinafter, referred to as segment (A)) and a compound represented by the following general formula (1):
[0012]
Embedded image

[0013]
(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, or an arylalkyl group or an alkylaryl group having 7 to 22 carbon atoms, and n is 2 or 3 Indicates the number.)
Having a poly (N-acylalkyleneimine) segment (hereinafter, referred to as a segment (B)) composed of a repeating unit represented by the following formula (hereinafter, referred to as a repeating unit (1)), particularly the terminal or side of the segment (A) An organopolysiloxane in which the segment (B) is bonded to at least one of the silicon atoms of the chain via an alkylene group containing a hetero atom is preferable.
[0014]
In the poly (N-acylalkyleneimine) -modified silicone, the weight ratio of the segment (A) to the segment (B) ((A) / (B)) is controlled from the viewpoint of suppressing repelling of handwriting and improving adhesion. , Preferably 5/95 to 99/1, more preferably 20/80 to 96/4, more preferably 40/60 to 96/4.
[0015]
In addition, the weight average molecular weight of the poly (N-acylalkyleneimine) -modified silicone is preferably 10,000 to 5,000,000, and more preferably 10,000 to 1 from the viewpoint of suppressing repelling of handwriting and improving adhesion. 50,000, more preferably 50,000 to 500,000. In addition, this weight average molecular weight is a polystyrene equivalent weight average molecular weight determined by GPC (gel permeation liquid chromatography) using chloroform as a developing solvent.
[0016]
As the organopolysiloxane forming the segment (A), for example, the general formula (2)
[0017]
Embedded image

[0018]
(In the formula, R represents an alkyl group having 1 to 22 carbon atoms, a phenyl group, or an alkyl group containing a hetero atom, and a plurality of Rs may be the same or different, but at least one contains a hetero atom. An alkyl group; m represents a number from 100 to 5000)
The compound represented by is mentioned.
[0019]
In the general formula (2), the alkyl group having 1 to 22 carbon atoms represented by R is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Examples of the alkyl group containing a hetero atom include an alkyl group having 2 to 20 carbon atoms, preferably containing 1 to 3 nitrogen atoms, oxygen atoms and / or sulfur atoms, and the following groups are preferred.
[0020]
Embedded image

[0021]
The alkyl group containing a hetero atom may be at least one of the terminal or side chain silicon atoms of the organopolysiloxane, and the number of the alkyl group containing a hetero atom in the organopolysiloxane is preferably from 1 to 300, 100 is more preferred.
[0022]
The weight average molecular weight of the organopolysiloxane forming the segment (A) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 500,000. The method for measuring the weight average molecular weight is the same as described above.
[0023]
In the segment (B), R ¹ in the repeating unit (1) is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. As the aryl group, a phenyl group, a naphthyl group, or the like is used. As the arylalkyl group, a phenylalkyl group having 1 to 20 carbon atoms, a naphthylalkyl group, or the like is used. As the alkylaryl group, the number of carbon atoms of the alkyl group is used. Examples thereof include 1 to 20 alkylphenyl groups and alkylnaphthyl groups. N represents 2 or 3.
[0024]
The degree of polymerization of the repeating unit (1) in the segment (B) is not particularly limited, but is preferably, for example, 1 to 500, and more preferably 6 to 100.
[0025]
In the bond between the segment (A) and the segment (B), as the alkylene group containing an intervening hetero atom, an alkylene group having 2 to 20 carbon atoms, preferably containing 1 to 3 nitrogen, oxygen and / or sulfur atoms Is mentioned. Specifically, H ⁺ is added to (1) a secondary amine or a tertiary amine, and (2) a secondary amine or a tertiary amine between carbon-carbon and / or at the terminal of the alkylene chain. Examples of the obtained ammonium salt include (3) a quaternary ammonium salt, (4) an alkylene group having 2 to 20 carbon atoms containing an oxygen atom and / or (5) a sulfur atom. Of these, the following structures are preferred.
[0026]
Embedded image

[0027]
(In the formula, X ⁻ represents a counter ion of an ammonium salt.)
X in the above ^- Specific examples of chlorine, iodine, halogen ion such as bromine, methosulfate, ethosulfate, methemoglobin phosphate, and organic anions such as ethoxy phosphate.
[0028]
The poly (N-acylalkyleneimine) -modified silicone used in the present invention includes, for example, poly (N-acylalkyleneimine) which is a ring-opening polymer of a cyclic imino ether and an organopolysiloxane forming a segment (A). The reaction can be performed by the method described in paragraphs 34 to 42 of JP-A-7-133352. These may be a single compound or a mixture.
[0029]
[Colorant]
Examples of the coloring agent used in the present invention include acid dyes, basic dyes, pigments and the like.
[0030]
The dye is preferably an oil-soluble dye, and more preferably a dye soluble in a solvent described below. Examples of dyes include Varifast Black 3810, 3820, 3830, 3840 (all manufactured by Orient Chemical Industry Co., Ltd.), Spiron Black GMH Special, and SOT Black-12H (all manufactured by Hodogaya Chemical Industry Co., Ltd.) Varifast Red 1306, 1308 (all manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red C-BH, C-GH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), Varifast Blue 1603, 1605 (all manufactured by Orient) Chemical Industry Co., Ltd.), SBN Blue 701, SPT Blue 26 (all made by Hodogaya Chemical Industry Co., Ltd.) and the like.
[0031]
There are no particular restrictions on the type of pigment, and any of inorganic or organic pigments can be used. Examples of the inorganic pigment include titanium oxide, carbon black, and metal powder. Examples of organic pigments include azo lakes, insoluble azo pigments, chelated azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dye lakes, nitro pigments, and nitroso pigments.
These colorants can be used alone or in combination of two or more.
[0032]
[Film forming resin]
The film-forming resin used in the present invention is preferably soluble in a solvent described below, and examples thereof include an acrylic resin, a phenol resin, a ketone resin, a maleic acid resin, a rosin resin, an amide resin, and polyvinylpyrrolidone. Is mentioned.
[0033]
Examples of the acrylic resin include Paraloid B-38 (manufactured by Rohm and Haas), Neoacryl B-700 (manufactured by Zeneca Corporation), and the like. Examples of the phenolic resin include Hitanol 1133, 1501, 2500 (all manufactured by Hitachi Chemical Co., Ltd.), and Tamanol 100S (Arakawa Chemical Industry Co., Ltd.). Examples of the ketone resin include Hiluck 111, 222, 110H (manufactured by Hitachi Chemical Co., Ltd.) and the like.
These film-forming resins can be used alone or in combination of two or more.
[0034]
[solvent]
As the solvent used in the present invention, a hydrophilic solvent is preferable. As the hydrophilic solvent, alcohol solvents and glycol ether solvents are preferred. Examples of the alcohol solvent include lower alcohols having 1 to 5 carbon atoms such as ethyl alcohol, isopropyl alcohol and n-propyl alcohol; aromatic alcohols such as benzyl alcohol; and many alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and glycerin. And polyhydric alcohols. Examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
[0035]
Among these, it is more preferable to use at least one selected from the group consisting of alcoholic solvents consisting of lower alcohols having 1 to 5 carbon atoms, aromatic alcohols and polyhydric alcohols, and lower alcohols having 1 to 5 carbon atoms are particularly preferable. preferable. These solvents can be used alone or in combination of two or more. A non-polar solvent may be used as long as the effects of the present invention are not impaired.
[0036]
[Oil-based marker ink and production method thereof]
The oil-based marker ink of the present invention preferably contains 0.1 to 30% by weight, more preferably 0.5 to 20% by weight of a poly (N-acylalkylenimine) -modified silicone. Within this range, the coating properties are excellent and good handwriting can be obtained.
[0037]
The oil-based marker ink of the present invention contains a colorant preferably in an amount of 0.5 to 30% by weight, more preferably 1 to 20% by weight. Within this range, the viscosity and handwriting density are moderate and preferable, and the writing properties are excellent.
[0038]
The oil-based marker ink of the present invention preferably contains a solvent in an amount of 30 to 98% by weight, more preferably 50 to 95% by weight. Within this range, the dissolution or dispersibility of the colorant is good, the viscosity and handwriting density are moderate and preferable, and the writing properties are excellent. The colorant is preferably 1 to 40 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the solvent. Within this range, the colorant is excellent in dissolution or dispersibility.
[0039]
The oil-based marker ink of the present invention preferably further contains a film-forming resin in order to improve the coating properties, and the content of the film-forming resin is preferably 0.5 to 20% by weight, and more preferably Preferably it is 1 to 15% by weight.
[0040]
The viscosity of the oil-based marker ink of the present invention is preferably 0.5 to 50 mPa · s (measuring temperature: 20 ° C., measuring device: EL type viscometer), and more preferably 1 to 40 mPa · s. This is because if the viscosity is 0.5 mPa · s or more, the ink is not excessively printed from the marking pen, and the handwriting is less likely to bleed, and if it is 50 mPa · s or less, the handwriting is less likely to be blurred. is there.
[0041]
The oil-based marker ink of the present invention may further contain, if necessary, components such as a viscosity modifier, a structural viscosity imparting agent, a dye solubilizing agent, and a dryness imparting agent.
[0042]
The oil-based marker ink of the present invention can be used as an ink composition for an oil-based marker pen or an oil-based marking pen.
[0043]
The oil-based marker ink of the present invention can be produced by a conventionally known ordinary method. For example, after dissolving or dispersing a poly (N-acylalkyleneimine) -modified silicone and, if necessary, a film-forming resin in a solvent, a colorant and, if necessary, an optional component are added thereto, and the mixture is uniformly dispersed. It may be produced by dissolving or dispersing. After uniformly dissolving or dispersing the colorant in the solvent, dissolve or disperse the poly (N-acylalkylenimine) -modified silicone and, if necessary, the film-forming resin. Alternatively, it may be produced by mixing a poly (N-acylalkylenimine) -modified silicone, a film-forming resin if necessary, a colorant, and, if necessary, an optional component in a solvent at a time. The above-described dissolution, dispersion, and mixing are preferably performed at room temperature or under heating (30 to 50 ° C.).
[0044]
【Example】
In the following examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified. In addition, amine equivalent means the molecular weight per nitrogen atom.
[0045]
Synthesis Example 1: Synthesis of poly (N-acylalkyleneimine) -modified silicone A 6.5 parts of diethyl sulfate and 100.0 parts of 2-ethyl-2-oxazoline were dissolved in 200.0 parts of dehydrated ethyl acetate, and nitrogen was dissolved. The mixture was heated under reflux for 4 hours under an atmosphere to obtain a terminal reactive poly (N-propionylethyleneimine). Next, a 50% ethyl acetate solution of 727.0 parts of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight 110,000; amine equivalent (g / mol) 20,800) was added all at once, and the mixture was heated under reflux for 8 hours. did. The reaction mixture was concentrated under reduced pressure to obtain a poly (N-propionylethyleneimine) dimethylsiloxane copolymer (segment (A) / segment (B) = 88/12) (hereinafter referred to as poly (N-acylalkylenimine) -modified silicone A). ) Was obtained as a pale yellow rubbery solid. Its weight average molecular weight in terms of polystyrene was 115,000 (method of measuring molecular weight by gel permeation chromatography using chloroform as a developing solvent). In addition, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was confirmed that no amino group remained.
[0046]
Synthesis Example 2: Synthesis of poly (N-acylalkyleneimine) -modified silicone B 6.5 parts of diethyl sulfate and 100.0 parts of 2-ethyl-2-oxazoline were dissolved in 200.0 parts of dehydrated ethyl acetate, and nitrogen was dissolved. The mixture was heated and refluxed for 5 hours under an atmosphere to obtain terminal-reactive poly (N-propionylethyleneimine). Here, a 50% ethyl acetate solution of 100.0 parts of a side chain primary aminopropyl-modified polydimethylsiloxane (molecular weight: 110,000; amine equivalent (g / mol): 4,840) is added at a time, and the mixture is heated under reflux for 10 hours. did. The reaction mixture was concentrated under reduced pressure to obtain a poly (N-propionylethyleneimine) dimethylsiloxane copolymer (segment (A) / segment (B) = 50/50) (hereinafter referred to as poly (N-acylalkylenimine) -modified silicone B). ) Was obtained as a pale yellow rubbery solid. Its weight average molecular weight in terms of polystyrene was 109,000 (by gel permeation chromatography using chloroform as a developing solvent). In addition, as a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was confirmed that no amino group remained.
[0047]
Examples 1-4 and Comparative Examples 1-4
Each component shown in Table 1 was stirred at room temperature to 50 ° C. for 2 hours to dissolve uniformly, and if necessary, filtered to remove insoluble matter, and a black oil-based marker ink having the composition shown in Table 1 was obtained. Obtained. The obtained oil-based marker ink was filled in a marking pen (trade name “AUNO2 Oil-based Marker Twin”, manufactured by Sailor Fountain Pen Co., Ltd.) and tested for the following evaluation items. The results are shown in Table 1.
[0048]
<Test 1>
Writing was performed on the surface of a packing craft tape (No. 200, manufactured by Linley Tape Co., Ltd.), and the repellency of the handwriting was judged according to the following criteria.
・ Evaluation criteria ○: No repelling.
×: There is repelling.
[0049]
<Test 2>
After the handwriting was dried, it was rubbed with a finger and the adhesion of the handwriting was determined according to the following criteria.
・ Evaluation criteria ◎: Very good adhesion.
…: There is adhesion.
X: No adhesion.
[0050]
[Table 1]

[0051]
* 1: Polyoxypropylene-modified silicone (manufactured by Toshiba Silicone Co., Ltd.)
* 2: Phenolic resin (manufactured by Hitachi Chemical Co., Ltd.)
* 3: Acrylic resin (Rohm and Haas)
* 4: Made by Orient Chemical Industry Co., Ltd.

Claims (5)

An oil-based marker ink containing a poly (N-acylalkyleneimine) -modified silicone, a colorant, and a solvent. A poly (N-acylalkyleneimine) -modified silicone comprising a repeating unit represented by the following general formula (1) through an alkylene group containing a hetero atom on at least one silicon atom of an organopolysiloxane segment. The oil-based marker ink according to claim 1, which is an organopolysiloxane to which an (N-acylalkyleneimine) segment is bonded.

(Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, or an arylalkyl group or an alkylaryl group having 7 to 22 carbon atoms, and n is 2 or 3 Indicates the number.) The poly (N-acylalkylenimine) -modified silicone has a weight ratio ((A) / (B)) of the organopolysiloxane segment (A) to the poly (N-acylalkylenimine) segment (B) of 5/95. The oil-based marker ink according to claim 1 or 2, which is a modified silicone having a weight average molecular weight of 10,000 to 5,000,000. The oil-based marker ink according to claim 1, further comprising a film-forming resin. The oil-based marker ink according to any one of claims 1 to 4, wherein the solvent is a hydrophilic solvent.