JPH0625577A - Desensitizing ink - Google Patents
Desensitizing inkInfo
- Publication number
- JPH0625577A JPH0625577A JP18257292A JP18257292A JPH0625577A JP H0625577 A JPH0625577 A JP H0625577A JP 18257292 A JP18257292 A JP 18257292A JP 18257292 A JP18257292 A JP 18257292A JP H0625577 A JPH0625577 A JP H0625577A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- chemical formula
- desensitizing
- monomer
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Color Printing (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は各種印刷適性に優れた減
感インキに関するものであり、特に感圧複写紙用に適し
た減感インキに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a desensitizing ink excellent in various printability, and more particularly to a desensitizing ink suitable for pressure-sensitive copying paper.
【０００２】[0002]
【従来の技術】減感インキは一般に減感剤、白色顔料、
ワニス、インキ溶剤の構成成分からなっている。特に白
色顔料についてはその白色性、隠ぺい性等から酸化チタ
ンが主に用いられており、減感インキを製造するにあた
り酸化チタンを何等かの方法でワニス中、減感剤中、イ
ンキ溶剤中もしくはこれらの混合物中に分散しなければ
ならない。一般に酸化チタンはその製造の関係で表面が
水酸基等の親水性基で覆われているため、こうした有機
溶剤への親和性が乏しくこのままの状態では分散がきわ
めて困難である。こうした酸化チタンをインキ中に分散
させるために酸化チタン粒子表面を界面活性剤その他有
機物で表面処理を行うことが従来よりなされている。し
かしながら、上記の様な方法で表面処理した酸化チタン
を使用した場合、酸化チタン表面に存在する界面活性剤
等の表面処理剤が減感インキ自体の親水性−疎水性のバ
ランスを崩し、実際の印刷にを於て地汚れ、乳化、イン
キミストの発生その他種々のトラブルが発生することが
多々あり、こうした表面処理剤自体のインキ物性への影
響が問題となっている。Desensitizing inks generally include desensitizing agents, white pigments,
It consists of varnish and ink solvent components. Especially for white pigments, titanium oxide is mainly used because of its whiteness, hiding property, etc.When manufacturing desensitizing ink, titanium oxide is used in a varnish, desensitizing agent, ink solvent or It must be dispersed in these mixtures. In general, titanium oxide has a surface covered with a hydrophilic group such as a hydroxyl group due to its production, and therefore has a poor affinity for such an organic solvent and is extremely difficult to disperse in such a state. In order to disperse the titanium oxide in the ink, it has been conventionally performed that the surface of the titanium oxide particles is surface-treated with a surfactant or other organic substance. However, when titanium oxide surface-treated by the method as described above is used, the surface-treating agent such as a surfactant present on the titanium oxide surface disrupts the hydrophilic-hydrophobic balance of the desensitizing ink itself, and In printing, various problems such as scumming, emulsification, generation of ink mist, etc. often occur, and the influence of the surface treating agent itself on the physical properties of the ink is a problem.
【０００３】さらに、酸化チタンに表面処理を行い粉体
の形で供給した場合、減感インキ製造工程での酸化チタ
ンの粉砕、分散に多大な熱及び機械エネルギーを要する
ものであった。したがって、実際の減感インキの製造及
び品質向上のために酸化チタンの有効かつ簡便なインキ
中への導入方法及び印刷適性を改善するような酸化チタ
ン表面処理剤の開発が切望されているのが現状である。Further, when titanium oxide is surface-treated and supplied in the form of powder, a great deal of heat and mechanical energy are required for pulverizing and dispersing titanium oxide in the desensitizing ink manufacturing process. Therefore, for the actual production and quality improvement of desensitizing ink, there is a strong demand for the development of a titanium oxide surface treatment agent that improves the printability and an effective and convenient method of introducing titanium oxide into the ink. The current situation.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は実際の
印刷に於て地汚れ、乳化、インキミストが少なく、より
印刷適正に優れた減感インキを提供をすることにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a desensitizing ink which has less background stains, emulsification and ink mist in actual printing and is excellent in printability.
【０００５】[0005]
【課題を解決するための手段】上記目的は以下に述べる
本発明によって達成される。すなわち、化１で示される
モノマーから成る重合体、または化１で示されるモノマ
ー及び、化２、化３、化４から選ばれる少なくとも１種
のモノマーを共重合成分として含む共重合体を含有する
減感インキにより解決される。化１中、Ｒ1は水素原子
またはメチル基、Ｒ2は炭素数４〜３０のアルキル基を
表わす。化２中、Ｘは炭素原子、窒素原子、Ｙは炭素原
子、窒素原子、酸素原子、硫黄原子を表わし、Ｒ3は水
素原子、メチル基、エチル基、プロピル基を表わし、Ｒ
4は水素原子、メチル基を表わす。また、ｎ＝０、１、
２、３である。化４中、Ｚは炭素原子、窒素原子、Ｒ5
は水素原子、メチル基、エチル基を表わす。The above object can be achieved by the present invention described below. That is, it contains a polymer composed of the monomer represented by Chemical Formula 1, or a copolymer containing the monomer represented by Chemical Formula 1 and at least one monomer selected from Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 as a copolymerization component. It is solved by desensitizing ink. In Chemical Formula 1 , R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 4 to 30 carbon atoms. In Chemical Formula 2, X represents a carbon atom, a nitrogen atom, Y represents a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, R 3 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, and R
4 represents a hydrogen atom or a methyl group. Also, n = 0, 1,
A few. In Chemical formula 4, Z is a carbon atom, a nitrogen atom, R 5
Represents a hydrogen atom, a methyl group, or an ethyl group.
【０００６】本発明の減感インキの構成物で特に重要と
なるのは化１で示されるモノマーから成る重合体、また
は化１で示されるモノマー及び、化２、化３、化４から
選ばれる少なくとも１種のモノマーを共重合成分として
含む共重合体であり、まずこれについて詳しく説明す
る。Particularly important in the composition of the desensitizing ink of the present invention is a polymer comprising the monomer represented by Chemical formula 1, or a monomer represented by Chemical formula 1, and selected from Chemical formula 2, Chemical formula 3, and Chemical formula 4. It is a copolymer containing at least one kind of monomer as a copolymerization component. First, this will be described in detail.
【０００７】減感インキの主要成分である減感剤は親水
性が高いため減感インキ自体が親水性の高い物になって
おり、また白色顔料として主に用いられてる酸化チタン
もその表面が親水性基で覆われているためさらに親水性
の高いインキになっている。このため、実際の印刷に於
て地汚れ、乳化、インキミストなど種々のトラブルに見
舞われる。この親水性からくるトラブルを解決するのに
化１で示されるモノマーから成る重合体、または化１で
示されるモノマー及び、化２、化３、化４から選ばれる
少なくとも１種のモノマーを共重合成分として含む共重
合体を成分として加えるとこれに対して非常に有効であ
る。The desensitizing agent, which is the main component of the desensitizing ink, has a high hydrophilicity, so that the desensitizing ink itself has a high hydrophilicity, and the surface of titanium oxide, which is mainly used as a white pigment, is also high. The ink is more hydrophilic because it is covered with hydrophilic groups. Therefore, in actual printing, various problems such as background stain, emulsification, and ink mist are encountered. In order to solve this trouble caused by hydrophilicity, a polymer comprising a monomer represented by the chemical formula 1 or a monomer represented by the chemical formula 1 and at least one monomer selected from the chemical formulas 2, 3, and 4 are copolymerized. It is very effective for this to add the copolymer containing as a component as a component.
【０００８】まず、化１で示されるモノマーから成る重
合体は適度な極性を持つエステル結合を持っており、こ
れが非常に有効に酸化チタンに働いていると考えられ
る。このエステル結合によりこの重合体は酸化チタン表
面に吸着して、結果的に酸化チタン表面が長鎖のアルキ
ル基で覆われていると考えられる。これにより親水性の
高い酸化チタンは有機媒体中への分散が容易になり、親
水性の高い減感剤との混合物に成ることにより減感イン
キ全体の親水性−疎水性の丁度良いバランスが得られる
と考えられる。First, the polymer composed of the monomer shown in Chemical formula 1 has an ester bond having an appropriate polarity, and it is considered that this acts very effectively on titanium oxide. It is considered that this polymer is adsorbed to the titanium oxide surface by this ester bond, and as a result, the titanium oxide surface is covered with a long-chain alkyl group. As a result, titanium oxide with high hydrophilicity can be easily dispersed in an organic medium, and by forming a mixture with a desensitizer with high hydrophilicity, a good balance of hydrophilicity-hydrophobicity of the entire desensitizing ink can be obtained. It is thought to be done.
【０００９】次に、化１で示されるモノマー及び、化
２、化３、化４から選ばれる少なくとも１種のモノマー
を共重合成分として含む共重合体は、化２、化３、化４
の様に窒素原子を有する異節環状のモノマーを含んでい
るため、丁度良い極性を持ち、表面に水酸基をもった酸
化チタンや減感インキの主成分である減感剤と親和性が
あると考えられる。まず、酸化チタンへのこの共重合体
の作用であるが、上記した様に化１のエステル結合が酸
化チタン表面に吸着し、且つ共重合体成分である化２、
化３、化４のモノマーが適度に極性を持ちこれにより酸
化チタン表面に作用していとる考えられる。これにより
酸化チタン表面はすぐ近傍には化２、化３、化４の窒素
原子を有する異節環状モノマーがあり、その外側に長鎖
のアルキル基が存在するモデルが考えられる。極性の高
い減感剤への作用は化２、化３、化４の窒素原子を有す
る異節環状モノマーの親和と考えられ、窒素原子を含む
減感剤の場合、より親和性が高いと考えられる。そし
て、この共重合体は疎水性の高い成分として化１で示す
ようなモノマーも含んでいるので、これにより親水性の
高い減感インキ全体の親水性−疎水性のバランスをとっ
ていると考えられる。Next, a copolymer containing the monomer represented by Chemical Formula 1 and at least one monomer selected from Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 as a copolymerization component is represented by Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4
Since it contains a heterocyclic monomer having a nitrogen atom like that, it has a good polarity and has affinity with titanium oxide having a hydroxyl group on the surface and a desensitizer which is the main component of desensitizing ink. Conceivable. First, regarding the action of this copolymer on titanium oxide, as described above, the ester bond of the chemical formula 1 is adsorbed on the titanium oxide surface, and the chemical formula 2, which is a copolymer component,
It is considered that the monomers of Chemical formula 3 and Chemical formula 4 have appropriate polarities and thus act on the surface of titanium oxide. Therefore, a model in which a heterocyclic cyclic monomer having nitrogen atoms of Chemical formulas 2, 3, and 4 is present in the immediate vicinity of the titanium oxide surface and a long-chain alkyl group is present outside thereof is considered. The action on the highly polar desensitizer is considered to be the affinity of the heterocyclic monomer having the nitrogen atoms of Chemical formula 2, Chemical formula 3 and Chemical formula 4, and the desensitizer containing the nitrogen atom is considered to have higher affinity. To be Since this copolymer also contains the monomer shown in Chemical formula 1 as a highly hydrophobic component, it is considered that this balances the hydrophilicity and hydrophobicity of the entire highly desensitizing ink. To be
【００１０】この様な働きをする共重合体は疎水性の高
いモノマー成分と少なくとも一つの窒素原子を有する異
節環状のモノマーとから構成されている。化１で示され
る疎水性成分のモノマーとしてはブチルメタクリレー
ト、ヘキシルメタクリレート、ドデシルメタクリレー
ト、ステアリルメタクリレート、ブチルアクリレート、
ヘキシルアクリレート、ドデシルアクリレート、ステア
リルアクリレートなが挙げられる。化２で示すモノマー
としてＮ−ビニルイミダゾール、Ｎ−ビニル−２−メチ
ルイミダゾール、Ｎ−ビニル−２−エチルイミダゾー
ル、Ｎ−ビニル−２−プロピルイミダゾール、４−ビニ
ルイミダゾール、Ｎ−ビニル−２−ブチルイミダゾー
ル、１−ビニルピロール、３、５−ジメチルビニルピラ
ロゾール、３−メチル−５−イソプロペニルピラロゾー
ル、５−ビニル−４−メチルチアゾール、２−ビニル−
４−メチルチアゾール、Ｎ−α−アクリロキシエチルイ
ミダゾール、Ｎ−β−アクリロキシプロピルイミダゾー
ル、Ｎ−β−アクリロキシエチルピロール等が挙げら
れ、化３に示すモノマーはＮ−ビニル−２−ピロリドン
であり、化４に示すモノマーとしては２−ビニルピラジ
ン、４−ビニルピリジン、２−メチル−５−ビニルピリ
ジン等がある。The copolymer having such a function is composed of a highly hydrophobic monomer component and a heterocyclic monomer having at least one nitrogen atom. As the monomer of the hydrophobic component represented by Chemical formula 1, butyl methacrylate, hexyl methacrylate, dodecyl methacrylate, stearyl methacrylate, butyl acrylate,
Examples include hexyl acrylate, dodecyl acrylate, and stearyl acrylate. As the monomer shown in Chemical formula 2, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-2-ethylimidazole, N-vinyl-2-propylimidazole, 4-vinylimidazole, N-vinyl-2-butyl Imidazole, 1-vinylpyrrole, 3,5-dimethylvinylpyrrolozole, 3-methyl-5-isopropenylpyrrolozole, 5-vinyl-4-methylthiazole, 2-vinyl-
4-methylthiazole, N-α-acryloxyethyl imidazole, N-β-acryloxypropyl imidazole, N-β-acryloxyethyl pyrrole and the like are mentioned, and the monomer shown in Chemical formula 3 is N-vinyl-2-pyrrolidone. There are 2-vinylpyrazine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like as the monomer shown in Chemical formula 4.
【００１１】先に挙げたような働きをさせるために化１
で示されるモノマー及び、化２、化３、化４から選ばれ
る少なくとも１種のモノマーを共重合成分として含む共
重合体は疎水性モノマーと少なくとも一つの窒素原子を
有する異節環状のモノマーとの適度なバランスが必要と
なり、以上に挙げたような化１で示されるモノマーの中
でも適当な長さの長鎖アルキル基を持つ疎水性モノマー
としてｎ−ドデシルメタクリレート、また化２〜４の中
で適当な極性を持つ少なくとも一つの窒素原子を有する
異節環状のモノマーとして化２ではＮ−ビニルイミダゾ
−ル、化３ではＮ−ビニル−２−ピロリドン、化４では
２−ビニルピリジンを用いた共重合体が好ましい。ま
た、その中でも化３で示すＮ−ビニル−２−ピロリドン
が特に好ましい。共重合比としては化１が８０〜９０重
量部、化２、化３、化４の少なくとも１種が２０〜１０
重量部の様に疎水性モノマーが大過剰の共重合比の方が
親水性の高い減感インキに対しより好ましい。化１で示
されるモノマーの重合体の場合もモノマーとしてｎ−ド
デシルメタクレレートが好ましい。本発明において、こ
の様な共重合体を用いて有機溶剤および／または減感剤
中に白色顔料を分散するのが好ましい。In order to make the above-mentioned functions work,
And a copolymer containing at least one monomer selected from Chemical formula 2, Chemical formula 3, and Chemical formula 4 as a copolymerization component is a hydrophobic monomer and a heterocyclic monomer having at least one nitrogen atom. A proper balance is required, and among the monomers shown in Chemical formula 1 mentioned above, n-dodecyl methacrylate is suitable as a hydrophobic monomer having a long-chain alkyl group of an appropriate length, and suitable among Chemical formulas 2 to 4. As a heterocyclic monomer having at least one nitrogen atom with different polarity, N-vinyl imidazole in Chemical formula 2, N-vinyl-2-pyrrolidone in Chemical formula 3, and 2-vinyl pyridine in Chemical formula 4 are used. Coalescence is preferred. Among them, N-vinyl-2-pyrrolidone shown in Chemical formula 3 is particularly preferable. As a copolymerization ratio, 80 to 90 parts by weight of Chemical formula 1 and 20 to 10 of at least one of Chemical formula 2, Chemical formula 3, and Chemical formula 4 are used.
A copolymerization ratio in which the hydrophobic monomer is in a large excess, such as parts by weight, is more preferable for the desensitizing ink having high hydrophilicity. Also in the case of the polymer of the monomer represented by Chemical formula 1, n-dodecyl methacrylate is preferable as the monomer. In the present invention, it is preferable to use such a copolymer to disperse a white pigment in an organic solvent and / or a desensitizer.
【００１２】また、この共重合体の使用量としては白色
顔料に対して３〜７％重量部使用するのが好ましい。そ
の理由として、上記したように顔料表面への吸着、減感
剤中への分散だけではなく、減感インキの界面での親水
性−疎水性のコントロールするためにこの位の使用量が
好ましい。もし、この使用量より少なすぎたり多すぎた
りすると減感インキの親水性−疎水性等のバランスを崩
す恐れがある。The amount of the copolymer used is preferably 3 to 7% by weight based on the white pigment. The reason for this is that not only the adsorption on the pigment surface and the dispersion in the desensitizer as described above, but also the amount used in this amount is preferable in order to control the hydrophilicity-hydrophobicity at the interface of the desensitizing ink. If the amount used is too small or too large, the desensitizing ink may lose its hydrophilic-hydrophobic balance.
【００１３】つぎに減感インキの構成要素としての有機
溶剤であるが、インキの一成分というだけではなく白色
顔料を分散するための分散媒体としても見ることもでき
る。よって、先の共重合体により顔料を容易に分散でき
る有機溶媒として以下のものが挙げられる。ヘキサン、
ヘプタン、ベンゼン、トルエン、キシレン、酢酸エチ
ル、メチルエチルケトン、エタノール、メタノール、プ
ロパノール、ブタノール、パラフィン系高沸点溶剤、パ
ラフィン系低沸点溶剤、イソパラフィン系高沸点溶剤、
イソパラフィン系低沸点溶剤、亜麻仁油、桐油、大豆
油、綿実等が使用できる。上記に挙げた中でも、減感イ
ンキが親水性が高いため、例えばアルコール系溶媒等の
極性溶媒よりヘキサン、パラフィン系低沸点溶剤等の非
極性溶媒の方が好ましい。Next, the organic solvent as a constituent element of the desensitizing ink can be seen not only as one component of the ink but also as a dispersion medium for dispersing the white pigment. Therefore, the following can be mentioned as organic solvents in which the above-mentioned copolymer can easily disperse the pigment. Hexane,
Heptane, benzene, toluene, xylene, ethyl acetate, methyl ethyl ketone, ethanol, methanol, propanol, butanol, paraffin high boiling solvent, paraffin low boiling solvent, isoparaffin high boiling solvent,
Isoparaffin low boiling point solvent, flaxseed oil, tung oil, soybean oil, cottonseed, etc. can be used. Among the above, since the desensitizing ink has high hydrophilicity, nonpolar solvents such as hexane and paraffinic low boiling point solvents are preferable to polar solvents such as alcoholic solvents.
【００１４】減感インキの主な役割をする減感剤として
はドデシルメチルアンモニウムクロライド，オクタドデ
シルアンモニウムクロライドの第四級アンモニウム塩，
ポリアミン誘導体とアルキレンオキサイドとの付加反応
物，ポリオキシエチレンアルキルアミン，ポリオキシエ
チレンアルキルエーテル，ポリオキシエチレンアルキル
フェニルエーテル，ポリエチレングリコール，ポリプロ
ピレングリコール，ポリオキシプロピレンアルキルアミ
ン，グルタミン酸−γ−アルキル残基を有する重合体，
スピロアセタール系ジアミン，Ｎ−（アミノアルキル）
−ラクタム類，アミン類のグリシジエーテル付加体等が
挙げられる。以上の様な有機溶剤および／または減感剤
に白色顔料を分散することにより好ましく減感インキが
製造されるが、減感インキの主役（減感インキの約５０
％を占める）である減感剤に分散した方がより好まし
い。その理由として、インキ溶剤は樹脂との混合物であ
るワニスのかたちで用いられるのが一般的であり、減感
剤での分散に比べ困難な面があるからである。As the desensitizer which plays a main role in the desensitizing ink, dodecylmethylammonium chloride, quaternary ammonium salt of octadodecylammonium chloride,
Addition reaction product of polyamine derivative and alkylene oxide, polyoxyethylene alkylamine, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol, polypropylene glycol, polyoxypropylene alkylamine, glutamic acid-γ-alkyl residue Having polymer,
Spiroacetal type diamine, N- (aminoalkyl)
-Lactams, glycidyl ether adducts of amines, and the like. The desensitizing ink is preferably produced by dispersing the white pigment in the organic solvent and / or the desensitizing agent as described above.
%) Is more preferable. The reason for this is that the ink solvent is generally used in the form of a varnish that is a mixture with a resin, and it is more difficult than dispersion with a desensitizer.
【００１５】通常、溶剤及び／または樹脂より成るビヒ
クルは顔料を分散させインキに流動性を与え印刷面に顔
料を固着させる役目をする液成分で、その中の樹脂とし
てはロジン変性マレイン酸樹脂、ロジン変性フェノール
樹脂、ケトン樹脂、ポリアミド樹脂、マレイン酸樹脂、
フェノール樹脂、エポキシ樹脂、アルキッド樹脂、メラ
ミン樹脂、尿素樹脂等が挙げられる。Usually, a vehicle composed of a solvent and / or a resin is a liquid component which serves to disperse a pigment and impart fluidity to the ink to fix the pigment on a printing surface. The resin therein is a rosin-modified maleic acid resin. Rosin-modified phenol resin, ketone resin, polyamide resin, maleic acid resin,
Phenolic resins, epoxy resins, alkyd resins, melamine resins, urea resins and the like can be mentioned.
【００１６】次に減感インキの粘度を調節したり、減感
印刷部分に不透明性、不光沢性、加筆性等を与える為に
加えられる白色顔料としては酸化チタン、硫酸バリウ
ム、炭酸バリウム、タルク、カオリン等が挙げられるが
白色性、隠ぺい性等から酸化チタンを使用する方が好ま
しい。また、この酸化チタンはルチル形、アナタース形
どちらでも使用出来る。さらに、上記の共重合体を酸化
チタン表面に吸着させるため酸化チタンを有機化合物等
で処理したものも使用可能であり、或はアルミやシリカ
で処理した親水性表面を持つ酸化チタンも好ましく使用
することが出来る。Next, white pigments which are added to adjust the viscosity of the desensitizing ink or to impart opacity, non-glossiness, writing property, etc. to the desensitized printing portion include titanium oxide, barium sulfate, barium carbonate and talc. , Kaolin, etc., but it is preferable to use titanium oxide because of its whiteness and hiding property. Further, this titanium oxide can be used in either rutile type or anatase type. Further, titanium oxide treated with an organic compound or the like can be used to adsorb the above-mentioned copolymer on the titanium oxide surface, or titanium oxide having a hydrophilic surface treated with aluminum or silica is also preferably used. You can
【００１７】添加剤としては必要に応じて乾燥剤、沈降
防止剤、酸化防止剤等やパラフィンワックス、カルパナ
ワックス等のワックス類を添加してもよい。If desired, additives such as desiccants, anti-settling agents, antioxidants, and waxes such as paraffin wax and carpana wax may be added.
【００１８】以上に挙げたような重合体あるいは共重合
体、減感剤、白色顔料、有機溶剤、樹脂を使用した減感
インキにより上記の問題を解決できる。また、この減感
インキの製造上の特徴として酸化チタンを減感剤および
／または有機溶剤中にホモミキサーにて高速剪断分散し
て得られたペーストを用いて減感インキを作成すること
にある。また、高速剪断分散する時に加温すると分散媒
体の粘度が下がり分散効率が高まりより好ましい。この
様にして得た酸化チタンと減感剤及び／または有機溶剤
との分散物に所定量の樹脂、必要に応じてその他添加物
を加えよく混合した後、三本ロール等にてよく混練し減
感インキを得る。The above problems can be solved by the desensitizing ink using the above-mentioned polymers or copolymers, desensitizing agents, white pigments, organic solvents and resins. In addition, as a characteristic of the production of this desensitizing ink, a desensitizing ink is prepared by using a paste obtained by high-speed shearing dispersion of titanium oxide in a desensitizing agent and / or an organic solvent with a homomixer. . Further, it is more preferable to heat the dispersion medium at a high speed when it is dispersed by high speed, because the viscosity of the dispersion medium is lowered and the dispersion efficiency is increased. A predetermined amount of the resin and, if necessary, other additives are added to the dispersion of the titanium oxide thus obtained and the desensitizer and / or the organic solvent, and the mixture is thoroughly mixed and then well kneaded with a three-roll mill or the like. Get desensitizing ink.
【実施例】以下実施例により本発明を具体的に説明する
が本発明はこれらに限定されるものではない。なお以下
に示す部及び％はいずれも重量基準である。尚、実施例
としては化２、化３、化４いずれも良いのだが、特に良
かった化３、化４について実施例に示す。EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited thereto. The parts and% shown below are based on weight. Although any of Chemical Formulas 2, 3, and 4 may be used as an embodiment, the particularly preferable Chemical Formulas 3 and 4 will be shown in the embodiment.
【００１９】重合体の合成例１ ドデシルメタクリレート１００部、ヘプタン２００部を
５００ｍｌの四つ口フラスコに仕込み、Ｎ2 置換しなが
ら７０℃まで加熱してから重合開始剤ＡＩＢＮ１部を加
えて重合を開始する。約３時間反応させた後ドデシルメ
タクリレートの重合体を得た。Polymer Synthesis Example 1 100 parts of dodecyl methacrylate and 200 parts of heptane were placed in a 500 ml four-necked flask and heated to 70 ° C. while substituting with N 2, and then 1 part of a polymerization initiator AIBN was added to initiate polymerization. To do. After reacting for about 3 hours, a polymer of dodecyl methacrylate was obtained.
【００２０】重合体の合成例２ ドデシルメタクリレート９０部、Ｎ−ビニル−２−ピロ
リドン１０部、キシレン２１０部を５００ｍｌの四つ口
フラスコに仕込み、Ｎ2 置換しながら７０℃まで加熱し
てから重合開始剤ＡＩＢＮ１部を加えて重合を開始す
る。約３時間反応させた後ドデシルメタクリレートとＮ
−ビニル−２−ピロリドンの共重合体を得た。Polymer Synthesis Example 2 90 parts of dodecyl methacrylate, 10 parts of N-vinyl-2-pyrrolidone and 210 parts of xylene were placed in a 500 ml four-necked flask, heated to 70 ° C. while being replaced with N 2 , and then polymerized. Polymerization is started by adding 1 part of AIBN initiator. After reacting for about 3 hours, dodecyl methacrylate and N
A copolymer of vinyl-2-pyrrolidone was obtained.
【００２１】重合体の合成例３ ステアリルメタクリレート８０部、２−ビニルピリジン
２０部、キシレン２００部を５００ｍｌの四つ口フラス
コに仕込み、Ｎ2 置換しながら７０℃まで加熱してから
重合開始剤ＡＩＢＮ１部を加えて重合を開始する。約３
時間反応させた後ステアリルメタクリレートと２−ビニ
ルピリジンの共重合体を得た。Polymer Synthesis Example 3 80 parts of stearyl methacrylate, 20 parts of 2-vinyl pyridine and 200 parts of xylene were charged into a 500 ml four-necked flask and heated to 70 ° C. while substituting with N 2, and then the polymerization initiator AIBN1. Add parts to start the polymerization. About 3
After reacting for a time, a copolymer of stearyl methacrylate and 2-vinylpyridine was obtained.
【００２２】実施例１、２、３ 酸化チタンペーストの製造例：重合体の合成例１、２、
３で合成した重合体をそれぞれアルミで表面処理された
市販の酸化チタン５００部に対して５％重量部（２５
部）と減感剤としてＮ、Ｎ−ジ−ポリオキシプロピレン
−３−デシルオキシプロピルアミン５００部を１０００
ｍｌのステンレス製ビーカーに仕込み、ヒーターにてこ
の混合物を約１００℃まで加熱する。つぎにこのままヒ
ーターで加熱しながら高速剪断分散機（ホモミキサー）
で５０００〜６０００r.p.mにて攪拌しながら上記酸化
チタン５００部を徐々に加えて、約３０分間混合分散し
て３種類の酸化チタンのぺーストを得た。Examples 1, 2 and 3 Production Example of Titanium Oxide Paste: Polymer Synthesis Examples 1 and 2,
5% by weight (25% by weight) of the polymer synthesized in 3 with 500 parts of commercially available titanium oxide surface-treated with aluminum.
Part) and 500 parts of N, N-di-polyoxypropylene-3-decyloxypropylamine as a desensitizer to 1000 parts.
A ml beaker made of stainless steel is charged and the mixture is heated to about 100 ° C. with a heater. Then, while heating with a heater as it is, a high-speed shearing disperser (homo mixer)
While stirring at 5000 to 6000 rpm, 500 parts of the above titanium oxide was gradually added and mixed and dispersed for about 30 minutes to obtain a paste of three kinds of titanium oxide.
【００２３】減感インキの製造例：酸化チタンペースト
の製造例で得られた２種類の酸化チタンのペースト５０
０部にロジン変性フェノール樹脂（荒川化学工業製商品
名；タマノル３５０）と亜麻仁油を主成分とするワニス
２５０部、減感剤としてＮ、Ｎ−ジ−ポリオキシプロピ
レン−３−デシルオキシプロピルアミン２５０部を約１
３０℃で均一に混合する。そしてこれを三本ロールに通
してよく混練し３種類の減感インキを得た。合成例１、
２、３に対応した減感インキをそれぞれ実施例１、２、
３とする。Manufacturing Example of Desensitizing Ink: Two kinds of titanium oxide paste 50 obtained in the manufacturing example of titanium oxide paste
250 parts of a varnish containing 0 parts of a rosin-modified phenol resin (trade name of Arakawa Chemical Industry Co., Ltd .; Tamanor 350) and linseed oil as main components, and N, N-di-polyoxypropylene-3-decyloxypropylamine as a desensitizer. About 250 parts
Mix uniformly at 30 ° C. Then, this was passed through a triple roll and well kneaded to obtain three types of desensitizing inks. Synthesis example 1,
Desensitizing inks corresponding to 2 and 3 are prepared in Examples 1 and 2,
Set to 3.
【００２４】比較例１ 重合体の合成例１、２、３で得られた重合体を使用しな
い以外実施例１と同様の手順で減感インキを製造しよう
と試みたが、酸化チタンのペーストを製造する際、酸化
チタンの粗大粒子があるため、同様の方法で製造するこ
とはできなかった。そこで、ロジン変性フェノール樹脂
（荒川化学工業製商品名；タマノル３５０）と亜麻仁油
を主成分とするワニス２５０部、減感剤（Ｎ、Ｎ−ジ−
ポリオキシプロピレン−３−デシルオキシプロピルアミ
ン）５００部を加え、約１５０℃で２時間加熱溶解し、
これにアルミで表面処理された市販の酸化チタン２５０
部を加え、均一に混合してこれを三本ロールに通してよ
く混練し減感インキを得た。Comparative Example 1 An attempt was made to produce a desensitizing ink by the same procedure as in Example 1 except that the polymers obtained in Polymer Synthesis Examples 1, 2 and 3 were not used, but a titanium oxide paste was used. Since there were coarse particles of titanium oxide during the production, it could not be produced by the same method. Therefore, 250 parts of a varnish containing rosin-modified phenol resin (trade name of Arakawa Chemical Industry Co., Ltd .; Tamanor 350) and linseed oil as main components, a desensitizer (N, N-di-).
500 parts of polyoxypropylene-3-decyloxypropylamine), and heated and dissolved at about 150 ° C. for 2 hours,
Commercially available titanium oxide 250 with aluminum surface treatment
Parts were added and mixed uniformly, and this was passed through a three-roll and kneaded well to obtain a desensitized ink.
【００２５】比較例２ 重合体の合成例１、２、３で得られた重合体の代わりに
ポリエチレングリコールノニルフェニルエーテルを用い
て実施例の酸化チタンペースト及び減感インキの製造例
と同様の手順で減感インキを製造した。COMPARATIVE EXAMPLE 2 Polyethylene glycol nonyl phenyl ether was used in place of the polymers obtained in Polymer Synthesis Examples 1, 2 and 3 and the same procedure as in the production examples of titanium oxide paste and desensitizing ink of Example. Manufactured desensitizing ink.
【００２６】比較方法 実施例及び比較例で得られた５種の減感インキをオフセ
ット印刷機で市販の感圧複写紙下用紙（三菱製紙製ＮＣ
Ｒ紙）に印刷してその印刷適性を比較した。その印刷適
性の判断基準としてインキの水幅を用いた。オフセット
印刷に於てオフセット印刷機の湿し水の供給量が過剰な
場合は減感インキが乳化し転写不良を起こし、反対に湿
し水が少なすぎるときは減感インキが転写過多のため非
画像部までインキが転写され、地汚れと言う現象を引き
起こす。この乳化、地汚れの現象の起こらない様な適切
な水の供給量の幅を水幅と言い、個々の減感インキによ
り異なり、この水幅が広いと言うことは乳化、地汚れが
起こり難く、印刷適性に優れた扱い易い減感インキと言
える。Comparative Method The five types of desensitizing inks obtained in Examples and Comparative Examples were used in an offset printing machine to produce commercially available pressure-sensitive copying paper under paper (Mitsubishi Paper Mill NC
R paper) was printed and the printability was compared. The water width of the ink was used as a criterion for determining the printability. In offset printing, if the amount of dampening water supplied from the offset printing machine is excessive, the desensitizing ink will emulsify and transfer defects will occur.On the contrary, if the amount of dampening water is too small, the desensitizing ink will not transfer because of excessive transfer. Ink is transferred to the image area, causing a phenomenon called scumming. The width of the appropriate amount of water supply that does not cause the phenomenon of emulsification and scumming is called the water width, and it depends on the individual desensitizing ink. The wide water width means that emulsification and scumming are less likely to occur. It can be said to be a desensitizing ink that has excellent printability and is easy to handle.
【００２７】比較方法としてはオフセット印刷機の湿し
水（連続給水方式 イソプロピルアルコール１０％重量
部含有）の供給量を変化させて乳化、地汚れの現象が起
き始めた湿し水の相対的な供給量を求めその幅を水幅と
してこれを比較し、結果を表１に示した。尚、乳化、地
汚れの判断方法として減感インキ印刷物に減感チェッカ
ー（三菱製紙製）を噴霧して判断した。この減感チェッ
カーは感圧複写紙下用紙に塗られている顕色剤と反応し
て発色する。すなわち、減感インキが画像部へ適切に印
刷されておれば画像部は発色せずに白色、非画像部が発
色する。しかし、乳化の場合は転写不良のため画像部が
発色し、反対に地汚れの場合は転写過多のため非画像部
に減感インキが写り発色しない所がでてくる。これによ
り乳化、地汚れの始まりが判断できる。また、減感イン
キの盛り量が３ｇ／m2と なるようにオフセット印刷し
た。As a comparison method, the relative amount of the dampening water in which the phenomena of emulsification and scumming began to occur by changing the supply amount of the dampening water of the offset printing machine (continuous water supply system containing 10% by weight of isopropyl alcohol). The amount of supply was determined, and the width was defined as the water width, and the results were compared and the results are shown in Table 1. As a method for determining emulsification and background stain, a desensitization checker (manufactured by Mitsubishi Paper Mills) was sprayed on the desensitized ink printed matter. This desensitization checker reacts with the color developer coated on the pressure-sensitive copy paper to develop color. That is, if the desensitizing ink is appropriately printed on the image area, the image area does not develop color, but the non-image area develops color. However, in the case of emulsification, the image portion develops color due to poor transfer, and in the case of background stain, desensitizing ink appears in the non-image portion due to excessive transfer, and there is a place where no color develops. From this, the start of emulsification and background stain can be determined. In addition, offset printing was performed so that the amount of desensitizing ink was 3 g / m 2 .
【００２８】[0028]
【表１】 ＊数字が大きい程湿し水の供給量が多いことを示す。[Table 1] * The higher the number, the greater the supply of dampening water.
【００２９】[0029]
【発明の効果】本発明の減感インキは、従来の減感イン
キと比較し水幅が大幅に広がり非常に刷り易く、扱い易
いインキである。従来、減感インキ自体非常に水幅が狭
く、刷りにくいインキであり、実際の印刷に於いては熟
練したオペレーターが必要であった。しかし、減感イン
キの水幅が広がることにより熟練したオペレーターは必
要なくなり、誰でも容易に減感インキが刷れるようにな
る。また、減感インキの製造工程上、酸化チタンが分散
が容易になる等コストダウンにもつながる。INDUSTRIAL APPLICABILITY The desensitizing ink of the present invention is an ink that is much easier to print and easier to handle than the conventional desensitizing ink. Conventionally, the desensitizing ink itself has a very narrow water width and is difficult to print, and a skilled operator was required in actual printing. However, since the water width of the desensitizing ink is widened, no skilled operator is needed, and anyone can easily print the desensitizing ink. Further, in the manufacturing process of the desensitizing ink, titanium oxide is easily dispersed, which leads to cost reduction.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 11/10 ＰＴＮ 7415−4Ｊ 139/04 ＰＧＬ 7921−4Ｊ Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C09D 11/10 PTN 7415-4J 139/04 PGL 7921-4J
Claims (4)
として含有する減感インキ。 【化１】 （化１中、Ｒ1は水素原子またはメチル基、Ｒ2は炭素数
４〜３０のアルキル基を表わす。）1. A desensitizing ink containing a monomer represented by the following chemical formula 1 as a polymerization component. [Chemical 1] (In Chemical Formula 1 , R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 4 to 30 carbon atoms.)
及び、化２、化３、化４から選ばれる少なくとも１種の
モノマーを共重合成分として含む共重合体を含有する減
感インキ。 【化２】 （化２中、Ｘは炭素原子、窒素原子、Ｙは炭素原子、窒
素原子、酸素原子、硫黄原子を表わし、Ｒ3は水素原
子、メチル基、エチル基、プロピル基を表わし、Ｒ4は
水素原子、メチル基を表わす。また、ｎ＝０、１、２、
３である。） 【化３】 【化４】 （化４中、Ｚは炭素原子、窒素原子、Ｒ5は水素原子、
メチル基、エチル基を表わす。）2. A desensitizing ink containing a monomer represented by Chemical Formula 1 according to claim 1 and a copolymer containing at least one monomer selected from Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4 as a copolymerization component. [Chemical 2] (In Chemical Formula 2, X represents a carbon atom, a nitrogen atom, Y represents a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, R 3 represents a hydrogen atom, a methyl group, an ethyl group and a propyl group, and R 4 represents hydrogen. Represents an atom or a methyl group, and n = 0, 1, 2,
It is 3. ) [Chemical 3] [Chemical 4] (Wherein Z is a carbon atom, a nitrogen atom, R 5 is a hydrogen atom,
Represents a methyl group and an ethyl group. )
白色顔料を有機溶剤および／または減感剤中に混合分散
することで得られる白色顔料分散液を含有することを特
徴とする減感インキ。3. Use of the copolymer according to claim 1,
A desensitizing ink containing a white pigment dispersion obtained by mixing and dispersing a white pigment in an organic solvent and / or a desensitizing agent.
白色顔料を有機溶剤および／または減感剤中に高速剪断
混合分散することで得られる白色顔料分散液を含有する
ことを特徴とする減感インキ。4. Use of the copolymer according to claim 1,
A desensitizing ink comprising a white pigment dispersion obtained by mixing and dispersing a white pigment in an organic solvent and / or a desensitizing agent under high speed shearing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18257292A JP3251644B2 (en) | 1992-07-09 | 1992-07-09 | Desensitizing ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18257292A JP3251644B2 (en) | 1992-07-09 | 1992-07-09 | Desensitizing ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0625577A true JPH0625577A (en) | 1994-02-01 |
| JP3251644B2 JP3251644B2 (en) | 2002-01-28 |
Family
ID=16120626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18257292A Expired - Fee Related JP3251644B2 (en) | 1992-07-09 | 1992-07-09 | Desensitizing ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3251644B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000006564A (en) * | 1998-06-23 | 2000-01-11 | Dainippon Printing Co Ltd | Forgery preventive printed medium and manufacture thereof |
| US6051678A (en) * | 1996-12-20 | 2000-04-18 | Hyundai Electronics Industries Co., Ltd. | Copolymers containing N-vinyllactam derivatives, preparation methods thereof and photoresists therefrom |
| JP2007107013A (en) * | 1999-12-17 | 2007-04-26 | E I Du Pont De Nemours & Co | Graft copolymer having amide functional group, used as pigment dispersant |
-
1992
- 1992-07-09 JP JP18257292A patent/JP3251644B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6051678A (en) * | 1996-12-20 | 2000-04-18 | Hyundai Electronics Industries Co., Ltd. | Copolymers containing N-vinyllactam derivatives, preparation methods thereof and photoresists therefrom |
| JP2000006564A (en) * | 1998-06-23 | 2000-01-11 | Dainippon Printing Co Ltd | Forgery preventive printed medium and manufacture thereof |
| JP2007107013A (en) * | 1999-12-17 | 2007-04-26 | E I Du Pont De Nemours & Co | Graft copolymer having amide functional group, used as pigment dispersant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3251644B2 (en) | 2002-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5158606A (en) | Low rub printing ink | |
| EP0819738A2 (en) | Aqueous ink jet ink compositions | |
| US6156109A (en) | Water-in-oil type emulsion ink for stencil printing | |
| JPH09165543A (en) | Ink composition and production | |
| JP2002501966A (en) | Inkjet printer ink | |
| JPH0337587B2 (en) | ||
| US4604952A (en) | Quick drying fountain solutions | |
| US6806301B2 (en) | Lithographic printing inks | |
| US6121365A (en) | Polymer fine particles and ink composition containing the same | |
| DE69007159T2 (en) | Resin binder with improved dilution. | |
| DE69608723T2 (en) | Polymers, usable as printing plates | |
| JP3251644B2 (en) | Desensitizing ink | |
| US3398113A (en) | Thermosetting resin pigment composition and process therefor | |
| JP3369348B2 (en) | Oil-based pigment ink composition for writing implements | |
| US6011083A (en) | Emulsion ink for stencil printing | |
| EP1414916B1 (en) | Lithographic printing inks | |
| JP3803715B2 (en) | Anionic water-based printing ink with improved deinking properties | |
| JPH06128516A (en) | Emulsion ink for stencil printing and stencil printing method | |
| JPH05246136A (en) | Desentisized ink | |
| US6840175B2 (en) | Lithographic printing method using a single fluid ink | |
| JP2706560B2 (en) | Aqueous printing ink composition | |
| JP2007106896A (en) | Water-based ink composition and printed matter using the same | |
| JPS6377977A (en) | Pigment composition | |
| US3963501A (en) | Process for preparing anti-mist compounds for printing inks and process for preparing printing inks containing same | |
| JPH04233980A (en) | Emulsion ink for stencil printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |