JP2021098771A - Color ink for penetration drying-type offset printing - Google Patents
Color ink for penetration drying-type offset printing Download PDFInfo
- Publication number
- JP2021098771A JP2021098771A JP2019230094A JP2019230094A JP2021098771A JP 2021098771 A JP2021098771 A JP 2021098771A JP 2019230094 A JP2019230094 A JP 2019230094A JP 2019230094 A JP2019230094 A JP 2019230094A JP 2021098771 A JP2021098771 A JP 2021098771A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- rosin
- solvent
- offset printing
- modified
- 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
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Landscapes
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Abstract
Description
本発明は、浸透乾燥型オフセット印刷用カラーインキ（以下、単に「印刷インキ」「インキ」ともいう）に関する。 The present invention relates to a color ink for permeation-drying offset printing (hereinafter, also simply referred to as “printing ink” or “ink”).
浸透乾燥型オフセット印刷用インキは、インキを構成している、溶剤や植物油等が毛細管現象によって紙基材の内部に浸透し、一方で顔料や樹脂等の固形分が前記紙基材の表面に残留して画像を形成する、という乾燥及び画像形成メカニズムをとる。ヒートセット型オフセット印刷用インキの様な、加熱オーブンを用いてインキ中の溶剤成分を乾燥させる方式と区別するため、「浸透乾燥型」は「コールドセット型」とも呼ばれ、例えば新聞印刷で使用されている。 In the penetration-drying offset printing ink, the solvent, vegetable oil, etc. that make up the ink permeate into the inside of the paper base material by capillarity, while solids such as pigments and resins permeate the surface of the paper base material. It adopts a drying and image forming mechanism in which it remains to form an image. The "penetration drying type" is also called the "cold set type" to distinguish it from the method of drying the solvent component in the ink using a heating oven, such as the heat set type offset printing ink, and is used for newspaper printing, for example. Has been done.
上述した浸透乾燥型オフセット印刷用インキを印刷機内に供給する方式には、壷方式、レール方式、キーレス方式等がある。近年の印刷高速化及び紙面品質の向上といった市場要求に応えるべく、上記のうち、壷方式及びレール方式の採用が増加傾向にある。 Examples of the method of supplying the above-mentioned permeation-drying offset printing ink into the printing machine include a pot method, a rail method, and a keyless method. Of the above, the pot method and rail method are being increasingly adopted in order to meet market demands such as faster printing speed and improved paper quality in recent years.
一方、インキの重要な物理的性状として流動性がある。壷方式またはレール方式を採用した場合、インキの流動性が高すぎると、壷垂れやレールスリットからの自然吐出、更には、ミスト、汚れなどが発生する原因となる。従って、浸透乾燥型オフセット印刷用インキの流動性のコントロールは、近年その重要度を増しているといえる。 On the other hand, fluidity is an important physical property of ink. When the jar method or the rail method is adopted, if the fluidity of the ink is too high, it may cause dripping of the jar, natural ejection from the rail slit, mist, dirt, and the like. Therefore, it can be said that the control of the fluidity of the permeation-drying offset printing ink has become more important in recent years.
従来、流動性を制御する手段として、炭酸カルシウム、カオリン、有機ベントナイト等の体質顔料の添加が行なわれてきた（特許文献１〜２参照）。しかしながらこれらの材料は粉末あるいは固形状であり、インキ中に添加するとそれだけビヒクル分が減量されることになるため、インキの転移性が低下する恐れがあった。また、上記材料はいずれも乳化しやすい性質を有しているため、印刷機ローラー上で過乳化状態となり、インキ転移性が低下してしまう。加えて、上記の材料を過剰に添加するとインキのチキソトロピー性が強くなり、インキが締まりやすくなるという問題点も存在していた。 Conventionally, as a means for controlling fluidity, extender pigments such as calcium carbonate, kaolin, and organic bentonite have been added (see Patent Documents 1 and 2). However, these materials are in the form of powder or solid, and when added to the ink, the vehicle content is reduced by that amount, so that the transferability of the ink may be lowered. Further, since all of the above materials have a property of being easily emulsified, they are in an overemulsified state on the rollers of the printing machine, and the ink transfer property is lowered. In addition, if the above materials are added in excess, the thixotropy of the ink becomes strong, and there is a problem that the ink becomes easy to tighten.
特に新聞印刷においては、インキ元ローラーとピックアップローラーとのギャップ転移を経て、版面へとインキを供給するタイプの印刷機が主流である。そのため、転移性が低下するとインキの供給が不安定となり、その結果、印刷中に印刷物の濃度が変動するトラブル（濃度変動）を引き起こしやすくなる。 In particular, in newspaper printing, a printing machine of a type that supplies ink to the printing plate surface through a gap transition between an ink source roller and a pickup roller is the mainstream. Therefore, when the transferability is lowered, the ink supply becomes unstable, and as a result, a trouble (density fluctuation) in which the density of the printed matter fluctuates during printing is likely to occur.
濃度変動は特に画像面積が小さい箇所、いわゆる低画線部で発生しやすい傾向にある。低画線部は必要となるインキ量が少なく、印刷機のローラー上の膜厚が薄くなるため、ギャップ転移が不安定になりやすいこと、及び、インキ量が少ないため相対的に水量が多くなりローラー上で乳化が進行しやすいこと、が要因として考えられる。特に近年は、インキの使用量削減を目的として、顔料の含有量を高めた高濃度インキが主流となっており、結果としてローラー上のインキ膜厚が更に薄くなるため、より濃度変動が発生しやすい状況となっている。 Density fluctuation tends to occur especially in a place where the image area is small, that is, a so-called low image area. The low image area requires a small amount of ink, and the film thickness on the rollers of the printing press is thin, so the gap transition tends to be unstable, and the amount of ink is small, so the amount of water is relatively large. It is considered that the factor is that emulsification easily progresses on the rollers. In particular, in recent years, high-density ink with an increased pigment content has become the mainstream for the purpose of reducing the amount of ink used, and as a result, the ink film thickness on the rollers becomes even thinner, causing further density fluctuations. The situation is easy.
加えて最近では、紙面品質向上と管理のため、自動紙面検査装置の導入が進んでおり、今までは見過ごされてきた微妙な紙面の濃度変動が検知できるようになったため、濃度変動によって損紙数及び生産性にも影響が出ることとなる。 In addition, recently, automatic paper surface inspection equipment has been introduced to improve and manage paper quality, and it has become possible to detect subtle changes in paper density that have been overlooked until now. It will also affect the number and productivity.
そのため、インキ転移性の低下やインキ締まりの悪化を抑制しながら前記インキの流動性を制御し、トラブルを発生させることなく安定して使用できる、浸透乾燥型オフセット印刷用インキが要望されていた。 Therefore, there has been a demand for a permeation-drying offset printing ink that can be used stably without causing trouble by controlling the fluidity of the ink while suppressing deterioration of ink transfer property and deterioration of ink tightness.
本出願人は以前、特許文献３にて、一次粒子径が２〜５０ｎｍである粉末状シリカを添加することで、印刷中のローラー含水率上昇を抑制し濃度変動を防止する、という提案を行った。しかしながらこの方法では、併用する材料によってはインキ転移性が低くなる恐れがあり、近年の印刷高速化には対応できない可能性があった。また、併用する材料によっては、インキの保存安定性が悪くなる恐れもあるため、材料選択性の観点からも、必ずしも良好な方策とはいえなかった。 The applicant previously proposed in Patent Document 3 that by adding powdered silica having a primary particle size of 2 to 50 nm, an increase in the water content of the roller during printing is suppressed and a concentration fluctuation is prevented. It was. However, this method may reduce the ink transfer property depending on the material used in combination, and may not be able to cope with the recent increase in printing speed. In addition, depending on the material used in combination, the storage stability of the ink may deteriorate, so that it is not always a good measure from the viewpoint of material selectivity.
また本出願人は、高濃度のカーボンブラック、特定の酸価及び水酸基価を有するアルキッド樹脂、及び、特定の動粘度を有する石油系溶剤を含む印刷インキの提案も行っている（特許文献４参照）。前記特許文献４では、上記アルキッド樹脂と上記石油系溶剤とを用いることで、印刷濃度とインキの転移性の両立を図っている。しかしながら、特許文献４は顔料としてカーボンブラックを使用する墨インキである。一般にカーボンブラックは主として炭素原子のみからなる。それに対してカラーインキで一般に使用される有機顔料の中には、親水性の高い構造を持ったものもあり、墨インキに比べて乳化特性のコントロールが難しい。また一般に、新聞の絵柄構成上、カラーインキは墨インキよりも使用量が少なく、ローラー上の膜厚が薄くなりやすい。結果として、カラーインキは墨インキに比べて濃度変動が発生しやすい傾向にあり、上記構成をそのままカラーインキに転用しても、転移性が十分に向上するとはいえなかった。 The applicant also proposes a printing ink containing a high concentration of carbon black, an alkyd resin having a specific acid value and a hydroxyl value, and a petroleum-based solvent having a specific kinematic viscosity (see Patent Document 4). ). In Patent Document 4, the print density and the transferability of the ink are compatible with each other by using the alkyd resin and the petroleum-based solvent. However, Patent Document 4 is a black ink that uses carbon black as a pigment. In general, carbon black mainly consists of carbon atoms only. On the other hand, some organic pigments generally used in color inks have a highly hydrophilic structure, and it is difficult to control the emulsifying characteristics as compared with black inks. Further, in general, due to the pattern composition of newspapers, the amount of color ink used is smaller than that of black ink, and the film thickness on the roller tends to be thin. As a result, the density of the color ink tends to fluctuate more easily than that of the black ink, and even if the above configuration is directly used for the color ink, the transferability cannot be said to be sufficiently improved.
本発明は、上記課題を解決すべくなされたものであって、その目的は、壺垂れを引き起こすことがなく、また優れたインキ転移性によって安定した紙面品質を確保でき、更にはインキ締まりが抑制された浸透乾燥型オフセット印刷用カラーインキを提供することにある。 The present invention has been made to solve the above problems, and an object of the present invention is to ensure stable paper surface quality due to excellent ink transferability without causing jar dripping, and further to suppress ink tightness. The purpose of the present invention is to provide a color ink for permeation-drying offset printing.
本発明者らが鋭意研究した結果、以下に定める構成を有するロジン変性フェノール樹脂と、特定の動粘度を有する石油系溶剤とを含む浸透乾燥型オフセット印刷用カラーインキによって上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent research by the present inventors, it has been found that the above-mentioned problems can be solved by a color ink for permeation-drying offset printing containing a rosin-modified phenol formaldehyde having the following constitution and a petroleum-based solvent having a specific kinematic viscosity. , The present invention has been completed.
即ち、本発明は、有彩色顔料、ロジン変性フェノール樹脂、及び、石油系溶剤を含む浸透乾燥型オフセット印刷用カラーインキであって、
前記ロジン変性フェノール樹脂が、ロジン類と、フェノール樹脂とを含む樹脂原料の反応物であり、
前記ロジン変性フェノール樹脂原料の固形分全量を基準として、前記ロジン類成分を６０〜８０質量％含み、
前記石油系溶剤が、パラフィン系溶剤またはナフテン系溶剤（Ａ）を含み、
前記パラフィン系溶剤またはナフテン系溶剤（Ａ）の、４０℃における動粘度が１２０ｍｍ2／ｓ以上５０００ｍｍ2／ｓ未満である、浸透乾燥型オフセット印刷用カラーインキに関する。
That is, the present invention is a color ink for permeation-drying offset printing containing a chromatic pigment, a rosin-modified phenol resin, and a petroleum-based solvent.
The rosin-modified phenol resin is a reaction product of a resin raw material containing rosins and a phenol resin.
Based on the total solid content of the rosin-modified phenol resin raw material, the rosin component is contained in an amount of 60 to 80% by mass.
The petroleum-based solvent contains a paraffin-based solvent or a naphthenic solvent (A), and contains
The present invention relates to a color ink for permeation-drying offset printing in which the kinematic viscosity of the paraffin-based solvent or the naphthenic solvent (A) at 40 ° C. is 120 mm 2 / s or more and less than 5000 mm 2 / s.
また、本発明は、前記石油系溶剤が、パラフィン系溶剤を含む、上記浸透乾燥型オフセット印刷用カラーインキに関する。 The present invention also relates to the color ink for permeation-drying offset printing, wherein the petroleum-based solvent contains a paraffin-based solvent.
また、本発明は、前記パラフィン系溶剤またはナフテン系溶剤（Ａ）の、アニリン点が１００℃以上１４０℃以下である、上記浸透乾燥型オフセット印刷用カラーインキに関する。 The present invention also relates to the color ink for permeation-drying offset printing in which the aniline point of the paraffin-based solvent or the naphthen-based solvent (A) is 100 ° C. or higher and 140 ° C. or lower.
また、本発明は、前記ロジン類成分が、α、β−不飽和カルボン酸及び／またはその酸無水物で変性した変性ロジン類を含む、上記浸透乾燥型オフセット印刷用カラーインキに関する。 The present invention also relates to the color ink for permeation-drying offset printing, wherein the rosins component contains modified rosins modified with α, β-unsaturated carboxylic acid and / or an acid anhydride thereof.
また、本発明は、前記ロジン変性フェノール樹脂が、樹脂原料に更にポリオールを含み、
前記ポリオールの量が、前記ロジン類及び前記フェノール樹脂の総量を基準として、５〜１５質量％である、上記浸透乾燥型オフセット印刷用カラーインキに関する。
Further, in the present invention, the rosin-modified phenolic resin further contains a polyol as a resin raw material.
The present invention relates to the color ink for permeation-drying offset printing, wherein the amount of the polyol is 5 to 15% by mass based on the total amount of the rosins and the phenol resin.
また、本発明は、上記浸透乾燥型オフセット印刷用カラーインキにより印刷された印刷物に関する。 The present invention also relates to a printed matter printed by the above-mentioned color ink for permeation-drying offset printing.
本発明により、壺垂れを引き起こすことがなく、また優れたインキ転移性によって安定した紙面品質を確保でき、更にはインキ締まりが抑制された浸透乾燥型オフセット印刷用カラーインキを提供することができた。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a color ink for permeation-drying offset printing, which does not cause jar dripping, can secure stable paper surface quality due to excellent ink transferability, and further suppresses ink tightness. ..
背景技術でも説明したように、従来、流動性のコントロールに用いられている体質顔料は、ローラー上で過乳化を引き起こす原因となり、インキの転移性を悪化させてしまう。 As explained in the background art, the extender pigment conventionally used for controlling the fluidity causes overemulsification on the roller and deteriorates the transferability of the ink.
また単に、使用する溶剤の粘度を調整して、インキの流動性を制御しようとした場合も、本発明の課題の全てを解決できるインキを得ることは難しい。具体的には、低粘度溶剤を使用した場合、微視的に低粘度となったインキによる壺垂れや、ローラー上での乾燥による転移性の悪化が起こる恐れがある。一方で高粘度溶剤を使用した場合、流動性と粘弾性のバランスを取ることができずにインキの転移性が悪化したり、顔料やロジン変性フェノール樹脂といった成分と均一に混ざり合わず、インキ締まりが悪化したりする可能性がある。 Further, even when the viscosity of the solvent used is simply adjusted to control the fluidity of the ink, it is difficult to obtain an ink that can solve all the problems of the present invention. Specifically, when a low-viscosity solvent is used, there is a risk that the ink drips due to the microscopically low-viscosity ink and the transferability deteriorates due to drying on a roller. On the other hand, when a high-viscosity solvent is used, the fluidity and viscoelasticity cannot be balanced and the transferability of the ink deteriorates, or the ink does not mix uniformly with components such as pigments and rosin-modified phenolic resins, resulting in ink tightening. May get worse.
そこで前記課題を同時に解決すべく、本発明者らが鋭意検討した結果、特定構成のロジン変性フェノール樹脂と、４０℃における動粘度が１２０ｍｍ2／ｓ以上５０００ｍｍ2／ｓ未満である、ナフテン系溶剤またはパラフィン系溶剤とを組み合わせることで、壺垂れを引き起こすことがなく、またインキ転移性の向上によって安定した紙面品質が確保でき、更にはインキ締まりが抑制された浸透乾燥型オフセット印刷用カラーインキが得られることを見出した。 Therefore, as a result of diligent studies by the present inventors in order to solve the above problems at the same time, a rosin-modified phenol resin having a specific constitution and a naphthenic solvent having a kinematic viscosity at 40 ° C. of 120 mm 2 / s or more and less than 5000 mm 2 / s. Alternatively, by combining with a paraffin solvent, a color ink for permeation-drying offset printing that does not cause jar dripping, secures stable paper surface quality by improving ink transferability, and suppresses ink tightness. I found that I could get it.
すなわち、本発明のインキに含まれるロジン変性フェノール樹脂は、ロジン類と、フェノール樹脂とを含む樹脂原料の反応物であり、前記ロジン変性フェノール樹脂原料の固形分全量を基準として、前記ロジン類を６０〜８０質量％含む。また、本発明のインキに含まれる石油系溶剤は、４０℃における動粘度が１２０ｍｍ2／ｓ以上５０００ｍｍ2／ｓ未満であるナフテン系溶剤またはパラフィン系溶剤（Ａ）である。ロジン類の量を上記範囲内に収めることで、詳細は不明ながら、動粘度が高く芳香環を構造（ほぼ）有さない、本発明におけるナフテン系溶剤またはパラフィン系溶剤との分子間相互作用の形成により、好適な粘弾性を有するインキとなり、インキ元ローラーとピックアップローラーとの間におけるインキ転移性が向上し、更には壺垂れも抑制できる。また、壺垂れ耐性を付与することを目的とした体質顔料の添加量を減少させることができるため、インキのチキソトロピー性が改善し、インキ締まりが抑制される。ここで、主として芳香環構造を有するアロマ系溶剤を過剰に使用してしまうと、同じく芳香環構造を多数有するロジン変性フェノール樹脂との分子間相互作用が過剰となってしまい、流動性と粘弾性のバランスが崩れ、インキ転移性が悪化する恐れがある。 That is, the rosin-modified phenol resin contained in the ink of the present invention is a reaction product of a resin raw material containing rosins and a phenol resin, and the rosins are used based on the total solid content of the rosin-modified phenol resin raw material. Contains 60-80% by mass. The petroleum-based solvent contained in the ink of the present invention is a naphthenic solvent or a paraffin-based solvent (A) having a kinematic viscosity at 40 ° C. of 120 mm 2 / s or more and less than 5000 mm 2 / s. By keeping the amount of rosins within the above range, although the details are unknown, the intermolecular interaction with the naphthenic solvent or paraffinic solvent in the present invention, which has high kinematic viscosity and does not have an aromatic ring structure (almost). By forming the ink, the ink has suitable viscoelasticity, the ink transferability between the ink source roller and the pickup roller is improved, and the jar dripping can be suppressed. Further, since the amount of the extender pigment added for the purpose of imparting jar dripping resistance can be reduced, the thixotropy of the ink is improved and the ink tightening is suppressed. Here, if an aroma solvent mainly having an aromatic ring structure is used excessively, the intermolecular interaction with the rosin-modified phenol resin which also has a large number of aromatic ring structures becomes excessive, and the fluidity and viscoelasticity become excessive. There is a risk that the balance will be lost and the ink transfer property will deteriorate.
以上のように、壺垂れの抑制、印刷機上でのインキ転移性、及び、インキ締まりの抑制の全てに優れたインキを得るためには、本発明のインキの構成が必須不可欠である。 As described above, the composition of the ink of the present invention is indispensable in order to obtain an ink excellent in all of suppressing jar dripping, ink transferability on a printing machine, and suppressing ink tightness.
続いて以下に、本発明のインキを構成する各材料について、その詳細を説明する。 Subsequently, the details of each material constituting the ink of the present invention will be described below.
［ロジン変性フェノール樹脂］
本発明では、インキ転移性を高め、壺垂れを抑制することを目的に、ロジン類とフェノール樹脂とを樹脂原料に含み、前記ロジン類の量が、原料の固形分全量を基準として６０〜８０質量％であるロジン変性フェノール樹脂を用いる。なお前記ロジン類の量は、樹脂原料の固形分全量を基準として７０〜８０質量％であることが好ましい。
[Rosin-modified phenolic resin]
In the present invention, for the purpose of enhancing ink transferability and suppressing jar dripping, rosins and phenol resin are contained in the resin raw material, and the amount of the rosins is 60 to 80 based on the total solid content of the raw material. A rosin-modified phenolic resin having a mass% is used. The amount of the rosins is preferably 70 to 80% by mass based on the total solid content of the resin raw material.
本発明のロジン変性フェノール樹脂に使用するロジン類とは、環式ジテルペン骨格を有する一塩基酸を指し、共役二重結合を有するアビエチン酸、およびその共役化合物である、ネオアビエチン酸、パラストリン酸、レボピマル酸や、共役二重結合を有さないピマル酸、イソピマル酸、サンダラコピマル酸、及びデヒドロアビエチン酸等が挙げられる。
また、これらのロジン類を含有する天然樹脂として、ガムロジン、トール油ロジン、ウッドロジン、メルクシロジンなどの天然ロジンが使用でき、該天然ロジンから誘導される重合ロジン、天然ロジンや重合ロジンを不均化または水素添加して得られる安定化ロジンなども使用できる。
これらのロジン類は、単独で、または、２種以上を併用して使用することができる。
The rosins used in the rosin-modified phenolic resin of the present invention refer to a monobasic acid having a cyclic diterpene skeleton, abietic acid having a conjugated double bond, and neoavietic acid, palastolic acid, which are conjugated compounds thereof. Examples thereof include levopipmaric acid, pimaric acid having no conjugated double bond, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid.
Further, as a natural resin containing these rosins, natural rosins such as gum rosin, tall oil rosin, wood rosin, and merkushirodin can be used, and polymerized rosins derived from the natural rosins, natural rosins, and polymerized rosins are disproportionated or Stabilized rosin obtained by adding hydrogen can also be used.
These rosins can be used alone or in combination of two or more.
また、インキ転移性の更なる向上の観点から、上記ロジン類として、α、β−不飽和カルボン酸及び／またはその酸無水物で変性した変性ロジン類（以下、単に「酸変性ロジン類」とも呼ぶ）を用いるのが好ましい。酸変性ロジン類とは、上記のロジン類に、α、β−不飽和カルボン酸及び／またはその酸無水物を付加して得られる変性ロジンのことであり、例えば、マレイン酸変性ロジン、無水マレイン酸変性ロジン、フマル酸変性ロジン、イタコン酸変性ロジン、クロトン酸変性ロジン、ケイ皮酸変性ロジン、アクリル酸変性ロジン、メタクリル酸変性ロジンなどが挙げられる。
また、これらの変性を重合ロジンに施したもの（酸変性重合ロジン類）も、「酸変性ロジン類」に含まれるものとする。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。また、酸変性ロジン類と、無変性のロジン類とを混合して使用することもできる。
Further, from the viewpoint of further improving the ink transfer property, the rosins are modified rosins modified with α, β-unsaturated carboxylic acid and / or an acid anhydride thereof (hereinafter, also simply referred to as “acid-modified rosins”). It is preferable to use). The acid-modified rosins are modified rosins obtained by adding α, β-unsaturated carboxylic acid and / or an acid anhydride thereof to the above rosins, and are, for example, maleic acid-modified rosin and maleic anhydride. Examples thereof include acid-modified rosin, fumaric acid-modified rosin, itaconic acid-modified rosin, crotonic acid-modified rosin, silicic acid-modified rosin, acrylic acid-modified rosin, and methacrylate-modified rosin.
Further, those obtained by subjecting these modifications to polymerized rosins (acid-modified polymerized rosins) are also included in "acid-modified rosins". One of these may be used alone, or two or more thereof may be mixed and used. Further, acid-modified rosins and non-modified rosins can be mixed and used.
酸変性ロジン類を用いる場合、変性に用いるα、β−不飽和カルボン酸及び／またはその酸無水物の量は、変性させるロジン類（天然ロジン、重合ロジン、及び、安定化ロジン）１００質量％に対して、１〜１０質量％であることが好ましく、３〜７質量％であることが特に好ましい。上記範囲内に収めることで、ナフテン系溶剤またはパラフィン系溶剤（Ａ）に対する溶解性を好適なものにでき、また適度な量の極性基によって乳化率の極端な上昇を防ぐことで、過乳化によるトラブルも抑制できる。 When acid-modified rosins are used, the amount of α, β-unsaturated carboxylic acid and / or its acid anhydride used for modification is 100% by mass of the rosins to be modified (natural rosin, polymerized rosin, and stabilized rosin). On the other hand, it is preferably 1 to 10% by mass, and particularly preferably 3 to 7% by mass. By keeping it within the above range, the solubility in a naphthenic solvent or a paraffinic solvent (A) can be made suitable, and an appropriate amount of polar groups prevents an extreme increase in the emulsification rate due to overemulsification. Trouble can also be suppressed.
一方、本発明のロジン変性フェノール樹脂を構成するフェノール樹脂は、従来既知のフェノール−アルデヒド付加縮合物が利用できる。当該フェノール−アルデヒド付加縮合物は、レゾール型であってもノボラック型であってもよいが、幅広い性状の付加縮合物が製造でき、本発明の効果の向上に加え、印刷適性などその他の特性にも優れたインキが得られることから、レゾール型であることが好ましい。 On the other hand, as the phenol resin constituting the rosin-modified phenol resin of the present invention, a conventionally known phenol-aldehyde addition condensate can be used. The phenol-aldehyde addition condensate may be of the resol type or the novolak type, but an addition condensate having a wide range of properties can be produced, and in addition to improving the effect of the present invention, it has other properties such as printability. The resol type is preferable because excellent ink can be obtained.
本発明において好適に使用できるレゾール型のフェノール−アルデヒド付加縮合物は、例えば、フェノール類とアルデヒド類を仕込み、揮発性有機溶剤（キシレン等）を添加したのち、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化リチウム、有機アミン等の公知の塩基性触媒の存在下で上記材料を縮合反応させることにより得られる。上記フェノール類としては、フェノール水酸基を持つすべての芳香族化合物が使用でき、例えば、石炭酸（フェノール）、クレゾール、ｐ−アミルフェノール、ビスフェノールＡ、ｐ−ブチルフェノール、ｐ−オクチルフェノール、ｐ−ノニルフェノール、ｐ−ドデシルフェノール等が例示できる。中でも、アルキル置換基の炭素数が４〜９のフェノール類が、転移性向上効果を発現しやすく好ましい。更に好ましくは、アルキル置換基の炭素数が４であるフェノール類を含む。これらのフェノール類は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。またアルデヒド類としては、ホルムアルデヒド（例えばパラホルムアルデヒド等）が使用できる。 The resol-type phenol-aldehyde condensed product that can be suitably used in the present invention is, for example, prepared with phenols and aldehydes, added with a volatile organic solvent (xylene, etc.), and then sodium hydroxide, potassium hydroxide, and water. It is obtained by subjecting the above materials to a condensation reaction in the presence of a known basic catalyst such as calcium oxide, lithium hydroxide, or an organic amine. As the above phenols, all aromatic compounds having a phenol hydroxyl group can be used. For example, coal acid (phenol), cresol, p-amylphenol, bisphenol A, p-butylphenol, p-octylphenol, p-nonylphenol, p- Dodecylphenol and the like can be exemplified. Of these, phenols having an alkyl substituent having 4 to 9 carbon atoms are preferable because they are likely to exhibit a transferability improving effect. More preferably, it contains phenols having 4 carbon atoms in the alkyl substituent. One of these phenols may be used alone, or two or more of these phenols may be mixed and used. As the aldehydes, formaldehyde (for example, paraformaldehyde) can be used.
本発明のロジン変性フェノール樹脂の製造方法としては、従来既知の方法を採用することができる。例えば、ロジン類とフェノール−アルデヒド付加縮合物（好ましくはレゾール型のフェノール−アルデヒド付加縮合物）とを容器中に添加し、１８０〜２８０℃下で１〜３０時間反応させる。その後、必要に応じて、ポリオール、及び、触媒を添加し、１５０〜３００℃下で１〜３０時間エステル化反応させる方法；ロジン類、ポリオール、及び、必要に応じて触媒を容器中に添加し、１５０〜３００℃下で１〜３０時間エステル化反応させたのち、１８０〜２８０℃下でフェノール−アルデヒド付加縮合物（好ましくはレゾール型フェノール−アルデヒド付加縮合物）を添加し、１８０〜３００℃下で１〜２０時間反応させる方法；等があげられる。 As a method for producing the rosin-modified phenol resin of the present invention, a conventionally known method can be adopted. For example, rosins and a phenol-aldehyde addition condensate (preferably a resole-type phenol-aldehyde addition condensate) are added into a container and reacted at 180 to 280 ° C. for 1 to 30 hours. Then, if necessary, a polyol and a catalyst are added, and an esterification reaction is carried out at 150 to 300 ° C. for 1 to 30 hours; rosines, the polyol, and if necessary, the catalyst is added into the container. After an esterification reaction at 150 to 300 ° C. for 1 to 30 hours, a phenol-aldehyde addition condensate (preferably a resole-type phenol-aldehyde addition condensate) was added at 180 to 280 ° C., and 180 to 300 ° C. A method of reacting underneath for 1 to 20 hours; etc. can be mentioned.
本発明で使用するロジン変性フェノール樹脂は、ロジン類及びフェノール樹脂に加えて、樹脂原料にポリオールを使用することが好ましい。そのようなロジン変性フェノール樹脂を使用することで、当該ロジン変性フェノール樹脂の重量平均分子量、粘度、溶剤及び植物油類への溶解性を好適なものにでき、乳化適性の良化及びインキ転移性の向上が実現できる。当該ポリオールとしては、例えば２価のポリオールとして、１，６−ヘキサンジオール、１，９−ノナンジオール、３−メチル−１，５−ペンタンジオール、２，２−ジエチル−１，３−プロパンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，２−シクロヘキサンジオール、ジエチレングリコールなどが、また、３価以上のポリオールとして、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、イノシトール、セルロース等が使用できる。これらのポリオールは、単独または複数を、任意の量比で組み合わせて使用することが可能である。その使用量は、ロジン類成分及びフェノール樹脂成分の総量に対して、５〜１５質量％であることが好ましく、７〜１１質量％であることが特に好ましい。 As the rosin-modified phenol resin used in the present invention, it is preferable to use a polyol as a resin raw material in addition to the rosins and the phenol resin. By using such a rosin-modified phenol resin, the weight average molecular weight, viscosity, solvent and solubility in vegetable oils of the rosin-modified phenol resin can be made suitable, and the emulsification suitability and ink transfer property can be improved. Improvement can be realized. Examples of the polyol include divalent polyols such as 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, and the like. 2-Butyl-2-ethyl-1,3-propanediol, 1,2-cyclohexanediol, diethylene glycol and the like are also trivalent or higher polyols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and dipenta. Ellisritol, sorbitol, inositol, cellulose and the like can be used. These polyols can be used alone or in combination in any amount ratio. The amount used is preferably 5 to 15% by mass, particularly preferably 7 to 11% by mass, based on the total amount of the rosin component and the phenol resin component.
また上記触媒としては、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、ｐ−ドデシルベンゼンスルホン酸、メタンスルホン酸、エタンスルホン酸等の有機スルホン酸類；硫酸、塩酸等の鉱酸；トリフルオロメチル硫酸、トリフルオロメチル酢酸等が例示できる。更に、テトラブチルジルコネート、テトライソブチルチタネート等の金属錯体；酸化マグネシウム、水酸化マグネシウム、酢酸マグネシウム、酸化カルシウム、水酸化カルシウム、酢酸カルシウム、酸化亜鉛、酢酸亜鉛等の金属塩触媒等も使用可能である。これら触媒を添加する場合、ロジン類成分と、フェノール樹脂成分と、ポリオール（使用する場合）との総量に対して０．０１〜５質量％の範囲で使用される。なお、触媒使用による樹脂の着色を抑制するために、次亜リン酸、トリフェニルホスファイト、トリフェニルホスフェート、トリフェニルホスフィン等を併用してもよい。 Examples of the catalyst include organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid; mineral acids such as sulfuric acid and hydrochloric acid; trifluoromethylsulfate and tri. Fluoromethylacetic acid and the like can be exemplified. Further, metal complexes such as tetrabutylzirconate and tetraisobutyltitanate; metal salt catalysts such as magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide and zinc acetate can also be used. is there. When these catalysts are added, they are used in the range of 0.01 to 5% by mass with respect to the total amount of the rosin component, the phenol resin component, and the polyol (when used). In addition, in order to suppress the coloring of the resin due to the use of a catalyst, hypophosphorous acid, triphenylphosphine, triphenylphosphate, triphenylphosphine and the like may be used in combination.
本発明で使用できるロジン変性フェノール樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算値（溶媒：テトラヒドロフラン）で、５，０００〜４０，０００であることが好ましく、より好ましくは５，０００〜３０，０００である。５，０００以上であるとインキの粘弾性が好適となり、壺垂れ及び印刷時の汚れ発生を抑制できる。また４０，０００以下であると、インキ転移性が好適となる。なお上記重量平均分子量は、ＪＩＳ Ｋ ７２５２に基づいて測定できる。 The weight average molecular weight of the rosin-modified phenol resin that can be used in the present invention is preferably 5,000 to 40,000, more preferably 5,000 to 40,000 in terms of polystyrene (solvent: tetrahydrofuran) by gel permeation chromatography (GPC). It is 5,000 to 30,000. When it is 5,000 or more, the viscoelasticity of the ink becomes suitable, and it is possible to suppress the dripping of the jar and the occurrence of stains during printing. Further, when it is 40,000 or less, the ink transfer property becomes preferable. The weight average molecular weight can be measured based on JIS K 7252.
またロジン変性フェノール樹脂の酸価は、５〜３５ｍｇＫＯＨ／ｇであることが好ましく、より好ましくは１０〜３０ｍｇＫＯＨ／ｇである。酸価を前記範囲内とすることで、インキにしたときの乳化適性が好適となる。なお上記酸価は、ＪＩＳ Ｋ ００７０に基づいて測定できる。具体的には、ロジン変性フェノール樹脂１ｇを中和するのに要する水酸化カリウムのｍｇ数によって測定できる。 The acid value of the rosin-modified phenol resin is preferably 5 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. By setting the acid value within the above range, the emulsification suitability when made into an ink becomes suitable. The acid value can be measured based on JIS K 0070. Specifically, it can be measured by the number of mg of potassium hydroxide required to neutralize 1 g of the rosin-modified phenol resin.
［その他の樹脂］
本発明のインキは、ロジン変性フェノール樹脂以外の樹脂を含んでいてもよく、例えばアルキッド樹脂が使用できる。当該アルキッド樹脂としては、合成品を用いてもよいし、市販品を用いてもよいが、どちらの場合についても、インキ締まり抑制の観点から、水酸基価が１０〜６０ｍｇＫＯＨ／ｇであり、酸価が６〜６５ｍｇＫＯＨ／ｇであるものを使用することが好ましい。なお前記水酸基価は１８〜４０ｍｇＫＯＨ／ｇであることがより好ましく、２０〜３５ｍｇＫＯＨ／ｇであることが特に好ましい。また前記酸価は８〜４０ｍｇＫＯＨ／ｇであることがより好ましく、１０〜２５ｍｇＫＯＨ／ｇであることが特に好ましい。また、上記水酸基価はＪＩＳ Ｋ ００７０に基づいて測定でき、酸価は上記ロジン変性フェノール樹脂の場合と同様にして測定できる。
[Other resins]
The ink of the present invention may contain a resin other than the rosin-modified phenol resin, and for example, an alkyd resin can be used. As the alkyd resin, a synthetic product or a commercially available product may be used, but in both cases, the hydroxyl value is 10 to 60 mgKOH / g and the acid value is from the viewpoint of suppressing ink tightness. It is preferable to use an ink having a value of 6 to 65 mgKOH / g. The hydroxyl value is more preferably 18 to 40 mgKOH / g, and particularly preferably 20 to 35 mgKOH / g. The acid value is more preferably 8 to 40 mgKOH / g, and particularly preferably 10 to 25 mgKOH / g. Further, the hydroxyl value can be measured based on JIS K 0070, and the acid value can be measured in the same manner as in the case of the rosin-modified phenol resin.
［石油系溶剤］
本発明のインキは、石油系溶剤として、４０℃における動粘度が１２０ｍｍ2／ｓ以上５，０００ｍｍ2／ｓ未満であるパラフィン系溶剤またはナフテン系溶剤（Ａ）を含む。なお、前記動粘度は２５０〜１，２００ｍｍ2／ｓであることが好ましく、５００〜１，０００ｍｍ2／ｓであることがより好ましい。前記動粘度は、ＪＩＳ Ｋ ２２８３によって測定できる。
[Petroleum solvent]
The ink of the present invention contains, as a petroleum-based solvent, a paraffin-based solvent or a naphthenic solvent (A) having a kinematic viscosity at 40 ° C. of 120 mm 2 / s or more and less than 5,000 mm 2 / s. Incidentally, the kinematic viscosity is preferably from 250~1,200mm 2 / s, more preferably 500~1,000mm 2 / s. The kinematic viscosity can be measured by JIS K 2283.
また本発明では、上記パラフィン系溶剤またはナフテン系溶剤（Ａ）として、アニリン点が１００℃〜１４０℃である溶剤を用いることが好ましく、１１５℃〜１２５℃であることがより好ましい。１００℃以上のアニリン点であれば、インキ転移性が十分なものとなり、濃度変動を引き起こすことがなくなる。なお上記アニリン点は、従来既知の方法、例えばＪＩＳ Ｋ ２２５６によって測定できる。 Further, in the present invention, as the paraffin-based solvent or the naphthenic solvent (A), it is preferable to use a solvent having an aniline point of 100 ° C. to 140 ° C., and more preferably 115 ° C. to 125 ° C. When the aniline point is 100 ° C. or higher, the ink transfer property is sufficient and the concentration does not fluctuate. The aniline point can be measured by a conventionally known method, for example, JIS K 2256.
本発明では、パラフィン系溶剤またはナフテン系溶剤（Ａ）として上記動粘度範囲に収まるパラフィン系溶剤またはナフテン系溶剤を１種以上使用する。なお、パラフィン系溶剤とナフテン系溶剤とを併用してもよい。中でも本発明では、上記に記載した効果、例えばロジン変性フェノール樹脂との分子間相互作用が好適となり、インキ転移性の向上及び壺垂れの抑制が実現できる点から、前記石油系溶剤（Ａ）として、少なくともパラフィン系溶剤を含むことが好ましい。前記パラフィン系溶剤として、ノルマルパラフィン系溶剤、イソパラフィン系溶剤のどちらを用いてもよいし、併用してもよい。また、合成油を用いても、鉱物油等の天然由来のものを用いてもよく、両者を併用してもよい。前記石油系溶剤（Ａ）として、好適に利用できる市販品の一例として、石油系炭化水素溶剤であるＪＸＴＧエネルギー社製スーパーオイルＮ１５０、３２０、４６０、１０００、三共油化工業社製サンキョウＳＮＨ２２０、５４０、谷口石油精製社製ＮＣＬ１５０、２２０、３２０を挙げることができる。 In the present invention, one or more paraffinic solvents or naphthenic solvents within the kinematic viscosity range are used as the paraffinic solvent or naphthenic solvent (A). A paraffin-based solvent and a naphthenic solvent may be used in combination. Above all, in the present invention, the above-mentioned effect, for example, intermolecular interaction with a rosin-modified phenol resin is preferable, and the petroleum-based solvent (A) can be used because it can improve ink transferability and suppress jar dripping. , At least preferably containing a paraffinic solvent. As the paraffin solvent, either a normal paraffin solvent or an isoparaffin solvent may be used, or may be used in combination. Further, synthetic oil may be used, naturally derived oil such as mineral oil may be used, or both may be used in combination. As an example of a commercially available product that can be suitably used as the petroleum-based solvent (A), super oils N150, 320, 460, 1000 manufactured by JXTG Energy Co., Ltd. and Sankyo SNH220, 540 manufactured by Sankyo Yuka Kogyo Co., Ltd., which are petroleum-based hydrocarbon solvents. , NCL150, 220, 320 manufactured by Taniguchi Petroleum Refinery Co., Ltd. can be mentioned.
本発明のインキに含まれるパラフィン系溶剤またはナフテン系溶剤（Ａ）の量は、前記インキ全量に対し、５〜３０質量％であることが好ましく、１０〜２０質量％であることがより好ましい。特に、パラフィン系溶剤またはナフテン系溶剤（Ａ）の量を１５〜２０質量％とすることで、インキ転移性に特段に優れたインキとなる。 The amount of the paraffin-based solvent or the naphthen-based solvent (A) contained in the ink of the present invention is preferably 5 to 30% by mass, more preferably 10 to 20% by mass, based on the total amount of the ink. In particular, by setting the amount of the paraffin-based solvent or the naphthenic solvent (A) to 15 to 20% by mass, the ink has a particularly excellent ink transfer property.
本発明では、石油系溶剤として、上述したパラフィン系溶剤またはナフテン系溶剤（Ａ）に加えて、その他の石油系溶剤を使用してもよい。具体的には、上記動粘度範囲に収まらない、パラフィン系溶剤、ナフテン系溶剤、芳香族炭化水素系溶剤、及びこれらの混合溶剤が挙げられる。また特に、上記記載のように、ロジン変性フェノール樹脂との分子間相互作用が過剰とならないようにするため、芳香族炭化水素系溶剤の含有率が１質量％以下であることが好ましい。本発明において好適に用いることができる、その他の石油系溶剤として、主成分としてナフテンを含む石油系溶剤である、ＪＸＴＧエネルギー社製ＡＦソルベント５号、６号等がある。 In the present invention, as the petroleum-based solvent, in addition to the paraffin-based solvent or the naphthenic solvent (A) described above, other petroleum-based solvents may be used. Specific examples thereof include paraffin-based solvents, naphthenic solvents, aromatic hydrocarbon-based solvents, and mixed solvents thereof that do not fall within the kinematic viscosity range. In particular, as described above, the content of the aromatic hydrocarbon solvent is preferably 1% by mass or less in order to prevent the intermolecular interaction with the rosin-modified phenol resin from becoming excessive. Other petroleum-based solvents that can be suitably used in the present invention include AF solvent Nos. 5 and 6 manufactured by JXTG Energy Co., Ltd., which are petroleum-based solvents containing naphthene as a main component.
［その他］
本発明に用いられる有彩色顔料として、従来既知の有機顔料が使用できる。例えば、アゾ系、フタロシアニン系などオフセットインキに従来用いられる顔料が相当し、銅フタロシアニン系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５、１５：１、１５：２、１５：３、１５：４、１５：６、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７、３６）、モノアゾ系顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３、４、５、２３、４８：１、４８：２、４８：３、４８：４、４９：１、４９：２、５３：１、５７：１）、ジスアゾ系顔料（Ｃ．Ｉ．ＰｉｇｍｅｎｔＹｅｌｌｏｗ １２、１３、１４、１７、８３）等が挙げられる。なお「有彩色」とは、黒（墨）色、灰色、白色のような無彩色を除く任意の色を表す。従って、淡色等も「有彩色」に含まれるものとする。
[Other]
Conventionally known organic pigments can be used as the chromatic pigments used in the present invention. For example, pigments conventionally used for offset inks such as azo pigments and phthalocyanine pigments correspond to copper phthalocyanine pigments (CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15 :. 6, CI Pigment Green 7, 36), monoazo pigments (CI Pigment Red 3, 4, 5, 23, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1) , 49: 2, 53: 1, 57: 1), disazo pigments (CI PigmentYellou 12, 13, 14, 17, 83) and the like. The "chromatic color" represents any color except achromatic colors such as black (ink), gray, and white. Therefore, light colors and the like are also included in "chromatic colors".
本発明のインキにおいて、上述した石油系溶剤に加えて、その他の溶剤を用いる場合、従来既知の溶剤を任意に用いることができる。中でも、上記ロジン変性フェノール樹脂との相溶性やインキ粘弾性、乾燥性を好適なものとし、インキ転移性の向上及びインキ締まりの抑制に有効である点から、植物油、及び、脂肪酸エステルから選ばれる少なくとも１種類を含むことが好ましい。なおこれらの材料は、単独で用いても良いし、２種類以上を併用しても良い。またその配合量は、インキ全量に対し１０〜４０質量％であることが好ましく、１５〜３５質量％であることが特に好ましい。 In the ink of the present invention, when other solvents are used in addition to the above-mentioned petroleum-based solvent, conventionally known solvents can be arbitrarily used. Among them, vegetable oils and fatty acid esters are selected because they have suitable compatibility with the above-mentioned rosin-modified phenolic resin, ink viscoelasticity, and dryness, and are effective in improving ink transferability and suppressing ink tightness. It is preferable to include at least one type. These materials may be used alone or in combination of two or more. The blending amount thereof is preferably 10 to 40% by mass, particularly preferably 15 to 35% by mass, based on the total amount of the ink.
上記「植物油」とは、グリセリンと脂肪酸とのエステル化反応物であるトリグリセライド、エステル交換反応により生成されたモノグリセライド、ジグリセライドを表す。なお、前記脂肪酸は飽和脂肪酸でも不飽和脂肪酸でも良い。 The above-mentioned "vegetable oil" represents triglyceride which is an esterification reaction product of glycerin and a fatty acid, monoglyceride produced by a transesterification reaction, and diglyceride. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid.
植物油として代表的なものは、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、脱水ヒマシ油などが挙げられる。特に大豆油、ヤシ油、アマニ油、菜種油が好ましい。 Typical vegetable oils are asa seed oil, flaxseed oil, eno oil, oyster oil, olive oil, cacao oil, capoc oil, kaya oil, mustard oil, kyonin oil, drilling oil, kukui oil, walnut oil, poppy oil, Sesame oil, safflower oil, daikon seed oil, soybean oil, sardine oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, sunflower oil, sunflower oil, grape seed oil, gentou oil, pine seeds Examples include oil, cottonseed oil, palm oil, peanut oil, and dehydrated castor oil. In particular, soybean oil, coconut oil, linseed oil, and rapeseed oil are preferable.
本発明において使用される「脂肪酸エステル」としては、上記に列挙した１種類以上の植物油、例えば大豆油、綿実油、アマニ油、サフラワー油、トール油、脱水ヒマシ油、カノーラ油、菜種油等から製造される植物油エステルが挙げられる。その他の例としては、脂肪酸モノアルキルエステル化合物が挙げられる。このうちモノエステルを構成する脂肪酸としては、炭素数１６〜２０の飽和または不飽和脂肪酸が好ましく、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、オレイン酸、リノール酸、リノレン酸、エレオステアリン酸等が例示できる。脂肪酸モノエステルを構成するアルコール由来のアルキル基は、炭素数１〜１０のものが好ましく、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔ−ブチル、２−エチルヘキシル等のアルキル基が例示できる。これら脂肪酸モノエステルは、単独で、または２種以上を組み合わせて使用できる。 The "fatty acid ester" used in the present invention is produced from one or more kinds of vegetable oils listed above, for example, soybean oil, cottonseed oil, flaxseed oil, safflower oil, tall oil, dehydrated castor oil, canola oil, rapeseed oil and the like. The vegetable oil ester to be used is mentioned. Other examples include fatty acid monoalkyl ester compounds. Of these, the fatty acids constituting the monoester are preferably saturated or unsaturated fatty acids having 16 to 20 carbon atoms, and stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid and the like are preferable. It can be exemplified. The alcohol-derived alkyl group constituting the fatty acid monoester is preferably one having 1 to 10 carbon atoms, and alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and 2-ethylhexyl can be exemplified. These fatty acid monoesters can be used alone or in combination of two or more.
本発明のインキでは、本発明の効果を阻害しない範囲で体質顔料を使用してもよい。例えば、有機ベントナイト、炭酸カルシウム、硫酸バリウム、カオリンクレー、シリカ等を、適宜使用することができる。 In the ink of the present invention, extender pigments may be used as long as the effects of the present invention are not impaired. For example, organic bentonite, calcium carbonate, barium sulfate, kaolin clay, silica and the like can be appropriately used.
本発明において、必要に応じて用いることができるゲル化剤としては、従来公知の材料、例えば、アルミニウムキレート化合物、金属石鹸、アルカノールアミン等がある。 In the present invention, as the gelling agent that can be used as needed, there are conventionally known materials such as aluminum chelate compounds, metal soaps, alkanolamines and the like.
本発明で使用できる助剤としては、分散剤、乾燥抑制剤、酸化防止剤、耐摩擦剤（ワックス）、裏移り防止剤、非イオン系界面活性剤、多価アルコール等の添加剤がある。 Examples of the auxiliary agent that can be used in the present invention include additives such as dispersants, drying inhibitors, antioxidants, anti-friction agents (waxes), set-off inhibitors, nonionic surfactants, and polyhydric alcohols.
本発明のインキは、上述の通り、浸透乾燥型オフセット印刷に使用されるものである。そのため、印刷に使用する基材としては、紙基材、特に非塗工紙、微塗工紙、更紙のような、浸透乾燥を起こすものが適している。 As described above, the ink of the present invention is used for permeation-drying offset printing. Therefore, as the base material used for printing, a paper base material, particularly a material that causes permeation drying, such as uncoated paper, finely coated paper, and stencil paper, is suitable.
次に、実施例に基づいて本発明を説明する。ただし、本発明の範囲は、以下の実施例に何等限定されるものではない。なお、本明細書において、「部」及び「％」は、特に断りのない限り、それぞれ「質量部」及び「質量％」を意味する。 Next, the present invention will be described based on examples. However, the scope of the present invention is not limited to the following examples. In the present specification, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.
（フェノール樹脂（レゾール型フェノール−アルデヒド付加縮合物）の合成例）
撹拌機、水分離器付き冷却器、温度計を備えた４つ口フラスコに、パラ−ｔ−ブチルフェノール１０００部、９２％パラホルムアルデヒド４８０部、９８％水酸化カルシウム３部、キシレン９６１部を加えて、９０℃で４時間反応させた。その後、水道水２４０部を加え、更に９８％硫酸を１５部滴下した。よく撹拌したのち２相に分離するまで静置し、上相部を取り出した。得られた前記上相部は、不揮発分（固形分）６０％のレゾール型フェノール樹脂のキシレン溶液であり、これをレゾール液Ａとした。
(Synthesis example of phenol resin (resole-type phenol-aldehyde addition condensate))
To a four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer, add 1000 parts of para-t-butylphenol, 480 parts of 92% paraformaldehyde, 3 parts of 98% calcium hydroxide, and 961 parts of xylene. , 90 ° C. for 4 hours. Then, 240 parts of tap water was added, and 15 parts of 98% sulfuric acid was further added dropwise. After stirring well, the mixture was allowed to stand until it was separated into two phases, and the upper phase portion was taken out. The obtained upper phase portion was a xylene solution of a resol-type phenol resin having a non-volatile content (solid content) of 60%, and this was designated as a resol solution A.
（ロジン変性フェノール樹脂１〜３、１１〜１２の製造例）
撹拌機、水分離器付き冷却器、ガス導入管、温度計を備えた４つ口フラスコに、それぞれ下表１の配合量でガムロジンを仕込み、窒素を吹き込みながら１８０℃まで加熱し、前記ガムロジンを融解させた。次いで、前記４つ口フラスコ内の温度を２００℃まで上げたのち、下表１に示した配合量のレゾール液Ａを、３時間かけて滴下した。その後、前記４つ口フラスコ内の温度を２６０℃まで上げ、撹拌しながら、下表１の配合量のグリセリン（ポリオール）及びパラトルエンスルホン酸を添加し、２６０℃で１２時間反応させることで、ロジン変性フェノール樹脂１〜３、１１〜１２を得た。
(Production Examples of Rosin-Modified Phenolic Resins 1-3 to 11-12)
Gum rosin is charged into a four-necked flask equipped with a stirrer, a cooler with a water separator, a gas introduction pipe, and a thermometer in the amounts shown in Table 1 below, and heated to 180 ° C while blowing nitrogen. It was thawed. Next, after raising the temperature in the four-necked flask to 200 ° C., the amount of Resol Solution A shown in Table 1 below was added dropwise over 3 hours. After that, the temperature in the four-necked flask was raised to 260 ° C., and while stirring, glycerin (polyol) and paratoluenesulfonic acid in the amounts shown in Table 1 below were added and reacted at 260 ° C. for 12 hours. Rosin-modified phenolic resins 1-3 to 11-12 were obtained.
（ロジン変性フェノール樹脂４〜１０の製造例）
撹拌機、水分離器付き冷却器、ガス導入管、温度計を備えた４つ口フラスコに、それぞれ下表１の配合量でガムロジンを仕込み、窒素を吹き込みながら１８０℃まで加熱し、前記ガムロジンを融解させた。次いで、下表１の配合量で無水マレイン酸を添加し、１８０℃で更に１時間反応させた。その後、前記４つ口フラスコ内の温度を２００℃まで上げたのち、下表１に示した配合量のレゾール液Ａを、３時間かけて滴下した。そして、前記４つ口フラスコ内の温度を２６０℃まで上げ、撹拌しながら、下表１の配合量のグリセリン及びパラトルエンスルホン酸を添加し、２６０℃で１２時間反応させることで、ロジン変性フェノール樹脂４〜１０を得た。
(Production example of rosin-modified phenolic resin 4 to 10)
Gum rosin is charged into a four-necked flask equipped with a stirrer, a cooler with a water separator, a gas introduction pipe, and a thermometer in the amounts shown in Table 1 below, and heated to 180 ° C while blowing nitrogen. It was thawed. Then, maleic anhydride was added in the blending amount shown in Table 1 below, and the mixture was reacted at 180 ° C. for another 1 hour. Then, after raising the temperature in the four-necked flask to 200 ° C., the amount of Resol Solution A shown in Table 1 below was added dropwise over 3 hours. Then, the temperature inside the four-necked flask was raised to 260 ° C., and while stirring, glycerin and p-toluenesulfonic acid in the amounts shown in Table 1 below were added and reacted at 260 ° C. for 12 hours to cause rosin-modified phenol. Resins 4 to 10 were obtained.
なお表１には、ロジン変性フェノール樹脂１〜１２それぞれの、樹脂原料の固形分全量に対するロジン類成分の量、及び、前記ロジン類及びフェノール樹脂の総量に対するポリオールの量も記載した。 Table 1 also shows the amount of the rosin component with respect to the total solid content of the resin raw material and the amount of the polyol with respect to the total amount of the rosin and the phenol resin of each of the rosin-modified phenolic resins 1 to 12.
（ロジン変性フェノール樹脂ワニス製造例）
撹拌機、水分離器付き冷却器、温度計を備えた４つ口フラスコに、バインダー樹脂として、上記で製造したロジン変性フェノール樹脂１を４５部、大豆油を４４部、大豆油脂肪酸ノルマルブチルエステルを１０部、アルミニウム系ゲル化剤（川研ファインケミカル社製ＡＬＣＨ、アルミニウム分９．８質量％）を１部、それぞれ投入した。そして、前記４つ口フラスコを１９０℃まで加熱し、１時間撹拌・混合して、ロジン変性フェノール樹脂ワニス１を得た。また、ロジン変性フェノール樹脂１をロジン変性フェノール樹脂２〜１２にそれぞれ変更した以外は、上記と同様の方法により、ロジン変性フェノール樹脂ワニス２〜１２を得た。
(Example of manufacturing rosin-modified phenol resin varnish)
In a four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer, 45 parts of the rosin-modified phenol resin 1 produced above, 44 parts of soybean oil, and soybean oil fatty acid normal butyl ester were used as binder resins. 10 parts and 1 part of an aluminum-based gelling agent (ALCH manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum content 9.8% by mass) were added. Then, the four-necked flask was heated to 190 ° C., stirred and mixed for 1 hour to obtain a rosin-modified phenol resin varnish 1. Further, rosin-modified phenol resin varnishes 2 to 12 were obtained by the same method as described above except that the rosin-modified phenol resin 1 was changed to rosin-modified phenol resins 2 to 12, respectively.
（インキの製造例）
上記で製造したロジン変性フェノール樹脂ワニス、アルキッド樹脂、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３（トーヨーカラー社製）、石油系溶剤、及び、大豆油（植物油）を、それぞれ表２に示す配合量で混合した後、三本ロール及びミキサーを用いて混練混合することで、実施例１〜２４、及び比較例１〜６のインキを製造した。
(Ink manufacturing example)
The rosin-modified phenolic resin varnish, alkyd resin, C.I. I. Pigment Blue 15: 3 (manufactured by Toyo Color Co., Ltd.), petroleum solvent, and soybean oil (vegetable oil) are mixed in the blending amounts shown in Table 2, and then kneaded and mixed using a three-roll and a mixer. , Examples 1 to 24, and Comparative Examples 1 to 6 were produced.
また、上記で製造したロジン変性フェノール樹脂ワニスと、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ５７：１（トーヨーカラー社製）とを表２に示す配合量で混合したのち、よく撹拌して水分を十分に取り除いた（フラッシング）。その後、アルキッド樹脂、石油系溶剤、及び、大豆油（植物油）を、それぞれ表３に示す配合量で混合し、更に三本ロール及びミキサーを用いて混練混合することで、実施例２５〜３７、及び比較例７〜１０のインキを製造した。 Further, the rosin-modified phenolic resin varnish produced above and C.I. I. Pigment Red 57: 1 (manufactured by Toyo Color Co., Ltd.) was mixed in the blending amounts shown in Table 2, and then thoroughly stirred to remove water sufficiently (flushing). Then, the alkyd resin, the petroleum-based solvent, and the soybean oil (vegetable oil) are mixed in the blending amounts shown in Table 3, and further kneaded and mixed using a three-roll and a mixer to carry out Examples 25 to 37. And the inks of Comparative Examples 7 to 10 were produced.
更に、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ５７：１を、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １２（トーヨーカラー社製）に変更し、各材料の配合量を表４に示した量とした以外は、上記実施例２５〜３７、及び比較例７〜１０のインキと同様にして、実施例３８〜５０、及び比較例１１〜１４のインキを製造した。 Furthermore, C.I. I. Pigment Red 57: 1, C.I. I. In the same manner as the inks of Examples 25 to 37 and Comparative Examples 7 to 10 above, except that the ink was changed to Pigment Yellow 12 (manufactured by Toyo Color Co., Ltd.) and the blending amount of each material was set to the amount shown in Table 4. Inks of Examples 38 to 50 and Comparative Examples 11 to 14 were produced.
なお、表２〜４中に記載した略称は、以下に示す通りである。
・石油系溶剤１：ＪＸＴＧエネルギー株式会社製スーパーオイルＮ１０００（パラフィン系、４０℃における動粘度９７１ｍｍ2／ｓ、アニリン点：１２３℃）
・石油系溶剤２：ＪＸＴＧエネルギー株式会社製スーパーオイルＮ４６０（パラフィン系、４０℃における動粘度５２３ｍｍ2／ｓ、アニリン点：１２１℃）
・石油系溶剤３：ＪＸＴＧエネルギー株式会社製スーパーオイルＮ３２０（パラフィン系、４０℃における動粘度２６７ｍｍ2／ｓ、アニリン点：１２０℃）
・石油系溶剤４：ＪＸＴＧエネルギー株式会社製スーパーオイルＮ１５０（パラフィン系、４０℃における動粘度１４１ｍｍ2／ｓ、アニリン点：１１２℃）
・石油系溶剤５：三共油化工業株式会社製ＳＮＨ５４０（ナフテン系、４０℃における動粘度５１８ｍｍ2／ｓ、アニリン点：８９℃）
・石油系溶剤６：三共油化工業株式会社製ＳＮＨ２２０（ナフテン系、４０℃における動粘度２１８ｍｍ2／ｓ、アニリン点：８０℃）
・石油系溶剤７：ＪＸＴＧエネルギー株式会社製スーパーオイルＮ１００（パラフィン系、４０℃における動粘度１０１ｍｍ2／ｓ、アニリン点：１０５℃）
・石油系溶剤８：ＪＸＴＧエネルギー株式会社製スーパーオイルＮ４６（パラフィン系、４０℃における動粘度４６ｍｍ2／ｓ、アニリン点：９９℃）
・石油系溶剤９：三共油化工業株式会社製ＳＮＨ４６（ナフテン系、４０℃における動粘度４６ｍｍ2／ｓ、アニリン点：７３℃）
・石油系溶剤１０：当栄ケミカル株式会社製３８０−Ｓ（パラフィン系、４０℃における動粘度７３ｍｍ2／ｓ、アニリン点：１２０℃）
・ＡＦ−５号：ＪＸＴＧエネルギー社製ＡＦソルベント５号（ナフテン系、４０℃における動粘度４ｍｍ2／ｓ、アニリン点：９２℃）
The abbreviations described in Tables 2 to 4 are as shown below.
-Petroleum-based solvent 1: Super oil N1000 manufactured by JXTG Energy Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 971 mm 2 / s, aniline point: 123 ° C.)
-Petroleum-based solvent 2: Super oil N460 manufactured by JXTG Energy Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 523 mm 2 / s, aniline point: 121 ° C.)
-Petroleum-based solvent 3: Super oil N320 manufactured by JXTG Energy Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 267 mm 2 / s, aniline point: 120 ° C.)
-Petroleum-based solvent 4: Super oil N150 manufactured by JXTG Energy Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 141 mm 2 / s, aniline point: 112 ° C.)
-Petroleum solvent 5: SNH540 manufactured by Sankyo Yuka Kogyo Co., Ltd. (naphthenic acid, kinematic viscosity at 40 ° C. 518 mm 2 / s, aniline point: 89 ° C.)
-Petroleum-based solvent 6: SNH220 manufactured by Sankyo Yuka Kogyo Co., Ltd. (naphthenic acid, kinematic viscosity at 40 ° C. 218 mm 2 / s, aniline point: 80 ° C.)
-Petroleum-based solvent 7: Super oil N100 manufactured by JXTG Energy Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 101 mm 2 / s, aniline point: 105 ° C.)
-Petroleum-based solvent 8: Super oil N46 manufactured by JXTG Energy Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 46 mm 2 / s, aniline point: 99 ° C.)
-Petroleum solvent 9: SNH46 manufactured by Sankyo Yuka Kogyo Co., Ltd. (naphthenic acid, kinematic viscosity at 40 ° C. 46 mm 2 / s, aniline point: 73 ° C.)
-Petroleum-based solvent 10: 380-S manufactured by Toei Chemical Co., Ltd. (paraffin-based, kinematic viscosity at 40 ° C. 73 mm 2 / s, aniline point: 120 ° C.)
-AF-5: AF solvent No. 5 manufactured by JXTG Energy Co., Ltd. (naphthenic acid, kinematic viscosity at 40 ° C. 4 mm 2 / s, aniline point: 92 ° C.)
［実施例１〜５０、比較例１〜１４］
表２〜４に示した実施例１〜５０、及び比較例１〜１４のインキを用いて、以下の評価を実施した。なお評価結果は、表２〜４に併せて示した通りであった。
[Examples 1 to 50, Comparative Examples 1 to 14]
The following evaluations were carried out using the inks of Examples 1 to 50 and Comparative Examples 1 to 14 shown in Tables 2 to 4. The evaluation results are as shown in Tables 2 to 4.
＜壺垂れ耐性の評価方法＞
インキ２．１ｃｃを、６０°に傾けた傾斜板の上にゆっくりと垂らし、１０分間で流れた長さを測定した。数値が短いものほど壺垂れ耐性が優れていることを表すため、下記評価基準で２以上のものを、実用上問題ないレベルとした。
［評価基準］
４：３０ｍｍ未満
３：３０ｍｍ以上、６０ｍｍ未満
２：６０ｍｍ以上、９０ｍｍ未満
１：９０ｍｍ以上
<Evaluation method of jar dripping resistance>
2.1 cc of ink was slowly dropped on an inclined plate tilted at 60 °, and the length of the ink flowing in 10 minutes was measured. The shorter the value, the better the pot dripping resistance. Therefore, the ones with 2 or more according to the following evaluation criteria were set to the level where there is no problem in practical use.
[Evaluation criteria]
Less than 4:30 mm 3:30 mm or more, less than 60 mm 2:60 mm or more, less than 90 mm 1:90 mm or more
＜インキ締まりの評価方法＞
各インキを、直径３ｃｍ、円筒状のアルミ製の缶にそれぞれ８０ｇ取り、２５℃で２４時間静置した。その後、質量８０ｇの針を、インキに対して垂直に貫入させ、３ｃｍ浸入するまでにかかった時間を測定した。その時間が短いほど、インキの締まりが小さく、供給適性が高いことを表す。そのため、下記評価基準で２以上のものを、実使用上問題ないレベルとした。
［評価基準］
４：１分未満
３：１分以上、２分未満
２：２分以上、３分未満
１：３分以上
<Evaluation method of ink tightness>
80 g of each ink was taken in a cylindrical aluminum can having a diameter of 3 cm, and the ink was allowed to stand at 25 ° C. for 24 hours. Then, a needle having a mass of 80 g was inserted perpendicularly to the ink, and the time required for the needle to penetrate 3 cm was measured. The shorter the time, the smaller the tightness of the ink and the higher the supply suitability. Therefore, the ones with 2 or more according to the following evaluation criteria were set to the level where there is no problem in actual use.
[Evaluation criteria]
Less than 4: 1 minute 3: 1 minutes or more and less than 2 minutes 2: 2 minutes or more and less than 3 minutes 1: 3 minutes or more
＜インキ転移性の評価方法＞
上記各インキについて、下記印刷条件の下で単色ベタと網点（１０〜１００％の１０％刻み）の絵柄を印刷した際、地汚れが発生しないスプレーダンプナー水量の最低値を調べ、その水量値を０とした。次いで、スプレーダンプナー水量値を２０に設定し、下記印刷条件で５００部印刷した。そして、５０部ごとに単色ベタ部の印刷濃度を測定し、その最大値と最小値との差を求めることで、５００部印刷における印刷濃度の変動幅を求め、転移性の評価を行った。前記印刷濃度の変動幅が小さい程、インキ転移性が良いことを表すため、下記評価基準で２以上のものを、実使用上問題ないレベルとした。
［評価基準］
４：０．０５未満
３：０．０５以上、０．１０未満
２：０．１０以上、０．１５未満
１：０．１５以上
<Evaluation method of ink transferability>
For each of the above inks, when printing a single-color solid and halftone dot (10% increments of 10 to 100%) pattern under the following printing conditions, check the minimum value of the spray dumper water amount that does not cause background stains, and check the water amount. The value was set to 0. Next, the spray dampener water amount value was set to 20, and 500 copies were printed under the following printing conditions. Then, the print density of the solid color solid portion was measured every 50 copies, and the difference between the maximum value and the minimum value was obtained to obtain the fluctuation range of the print density in printing 500 copies, and the transferability was evaluated. The smaller the fluctuation range of the print density, the better the ink transfer property. Therefore, the following evaluation criteria of 2 or more were set as levels that would not cause any problem in actual use.
[Evaluation criteria]
Less than 4: 0.05 3: 0.05 or more, less than 0.10 2: 0.10 or more, less than 0.15 1: 0.15 or more
［印刷条件］
印刷機 ：２Ｎ−７５０型印刷機（東浜精機社製）
用 紙 ：新聞用更紙（日本製紙社製）
湿し水 ：ＮＥＷＳＫＩＮＧ（登録商標）ＡＬＫＹ（東洋インキ社製）の０．５％水道水溶液
印刷速度：１２万部／時
版 ：ＣＴＰ版（富士フイルム社製）
[Printing conditions]
Printing machine: 2N-750 type printing machine (manufactured by Higashihama Seiki Co., Ltd.)
Paper: Newspaper paper (manufactured by Nippon Paper Industries, Ltd.)
Damping water: NEWSKING (registered trademark) ALKY (manufactured by Toyo Ink Co., Ltd.) 0.5% aqueous solution of tap water Printing speed: 120,000 copies / hour Version: CTP version (manufactured by Fujifilm Co., Ltd.)
［測色条件］
分光測色計 ： Ｘ−Ｒｉｔｅ社製 ｅＸａｃｔ
フィルター ： Ｍ０
イルミナント： Ｄ５０
濃度ステータス： ＩＳＯ ステータス Ｔ
濃度白色基準： 絶対値
[Color measurement conditions]
Spectrophotometer: X-Rite eXact
Filter: M0
Illuminant: D50
Concentration status: ISO status T
Density white standard: Absolute value
表２〜４に示したとおり、ロジン類の含有量が低いロジン変性フェノール樹脂を使用した比較例１、７、１１では、インキ転移性が劣っていた。逆にロジン類成分の含有量が高いロジン変性フェノール樹脂を使用した比較例２、８、１２では、インキ締まりが不良であった。また比較例３〜６、９、１０、１３、１４は、パラフィン系溶剤またはナフテン系溶剤（Ａ）の替わりに４０℃における動粘度が１２０ｍｍ2／ｓ未満である石油系溶剤を使用した例であり、全ての例において壷垂れ耐性に劣ることが確認された。また上記のうち比較例４、５、１０、１４は、使用した石油系溶剤のアニリン点が１００℃未満である例であり、壺垂れ耐性に加えインキ転移性も不十分であった。上記、比較例１〜１４のインキに対して、本発明のインキである実施例１〜５０のインキは、インキ転移性、壺垂れ耐性、インキ締まりのすべての評価項目において、実使用上問題なく使用できることが明らかとなった。 As shown in Tables 2 to 4, in Comparative Examples 1, 7 and 11 using the rosin-modified phenol resin having a low content of rosins, the ink transfer property was inferior. On the contrary, in Comparative Examples 2, 8 and 12 in which the rosin-modified phenol resin having a high content of rosin components was used, the ink tightness was poor. Further, Comparative Examples 3 to 6, 9, 10, 13 and 14 are examples in which a petroleum solvent having a kinematic viscosity at 40 ° C. of less than 120 mm 2 / s was used instead of the paraffin solvent or the naphthenic solvent (A). Yes, it was confirmed that the pot dripping resistance was inferior in all cases. Of the above, Comparative Examples 4, 5, 10 and 14 were examples in which the aniline point of the petroleum-based solvent used was less than 100 ° C., and the ink transfer property was insufficient in addition to the pot dripping resistance. In contrast to the inks of Comparative Examples 1 to 14 described above, the inks of Examples 1 to 50, which are the inks of the present invention, have no problem in actual use in all the evaluation items of ink transferability, jar dripping resistance, and ink tightness. It became clear that it could be used.
Claims (6)
前記ロジン変性フェノール樹脂が、ロジン類と、フェノール樹脂とを含む樹脂原料の反応物であり、
前記ロジン変性フェノール樹脂原料の固形分全量を基準として、前記ロジン類成分を６０〜８０質量％含み、
前記石油系溶剤が、パラフィン系溶剤またはナフテン系溶剤（Ａ）を含み、
前記パラフィン系溶剤またはナフテン系溶剤（Ａ）の、４０℃における動粘度が１２０ｍｍ2／ｓ以上５０００ｍｍ2／ｓ未満である、浸透乾燥型オフセット印刷用カラーインキ。 A color ink for permeation-drying offset printing containing chromatic pigments, rosin-modified phenolic resins, and petroleum-based solvents.
The rosin-modified phenol resin is a reaction product of a resin raw material containing rosins and a phenol resin.
Based on the total solid content of the rosin-modified phenol resin raw material, the rosin component is contained in an amount of 60 to 80% by mass.
The petroleum-based solvent contains a paraffin-based solvent or a naphthenic solvent (A), and contains
A color ink for permeation-drying offset printing in which the kinematic viscosity of the paraffin-based solvent or naphthenic solvent (A) at 40 ° C. is 120 mm 2 / s or more and less than 5000 mm 2 / s.
前記ポリオールの量が、前記ロジン類及び前記フェノール樹脂の総量を基準として、５〜１５質量％である、請求項１〜４いずれかに記載の浸透乾燥型オフセット印刷用カラーインキ。 The rosin-modified phenolic resin further contains a polyol as a resin raw material, and the resin raw material further contains a polyol.
The color ink for permeation-drying offset printing according to any one of claims 1 to 4, wherein the amount of the polyol is 5 to 15% by mass based on the total amount of the rosins and the phenol resin.
A printed matter printed by the color ink for permeation-drying offset printing according to any one of claims 1 to 5.
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