JP3838263B2 - Method for producing modified rosin ester resin composition for lithographic ink varnish and method for producing lithographic ink varnish - Google Patents
Method for producing modified rosin ester resin composition for lithographic ink varnish and method for producing lithographic ink varnish Download PDFInfo
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Description
本発明は、平版インキワニス用変性ロジンエステル樹脂組成物の製造方法、および、この製造方法で得れる平版インキワニス用変性ロジンエステル樹脂組成物を用いる平版インキワニスの製造方法に関する。 The present invention relates to a method for producing a modified rosin ester resin composition for a lithographic ink varnish, and a method for producing a lithographic ink varnish using the modified rosin ester resin composition for a lithographic ink varnish obtained by this production method.
オフセット平版インキ用樹脂およびワニスの原料として、ロジン変性フェノール樹脂が主に使用されているが、生活環境や作業環境の改良のために、樹脂中に内在するアルキルフェノール成分やホルムアルデヒド成分の除去を目的とした新規な樹脂類が、近年開発されるようになってきた。 Rosin-modified phenolic resins are mainly used as raw materials for offset lithographic ink resins and varnishes, but the purpose is to remove alkylphenol components and formaldehyde components present in the resins in order to improve the living and working environments. These new resins have been developed in recent years.
このようなアルキルフェノール成分やホルムアルデヒド成分を含有しないオフセット平版インキ用樹脂の製造方法としては、例えば、ロジン等の樹脂酸とα，β−エチレン性不飽和カルボン酸またはその無水物のディールス・アルダー反応物（酸変性樹脂酸と未反応樹脂酸の混合物）に炭素原子数６〜６０の二価アルコールまたは炭素原子数６〜６０の二価アルコールと三価以上のポリオールを反応させて成る樹脂の製造方法が提案されている（例えば、特許文献１参照。）。 Examples of a method for producing an offset lithographic ink resin containing no alkylphenol component or formaldehyde component include, for example, a resin acid such as rosin and a Diels-Alder reaction product of an α, β-ethylenically unsaturated carboxylic acid or its anhydride. A method for producing a resin obtained by reacting (a mixture of an acid-modified resin acid and an unreacted resin acid) a dihydric alcohol having 6 to 60 carbon atoms or a dihydric alcohol having 6 to 60 carbon atoms and a trihydric or higher polyol. Has been proposed (see, for example, Patent Document 1).
しかし、ここで使用される炭素原子数６〜６０の２価アルコール類は沸点が低いため、通常の樹脂酸類の反応温度２２０〜２７０℃では、反応系中に留まり難く、かつ系中から揮散しやすいため反応し難く、反応に著しく長時間を要する上に、高粘度になり難いという問題がある。そのため、これらの樹脂を主成分としたワニスでは平版インキ用として充分な粘弾性が得られ難い。また、反応系中の炭素原子数６〜６０の２価アルコール比率を減じて、その代わりに３価以上のポリオールを併用して合成した樹脂をワニス化して平版インキとした場合には、環境対応としてより好ましい芳香族化合物成分１重量％以下の印刷インキ用溶剤への溶解性が不足し、インキ流動性、転移性が不十分となり印刷物の光沢が低下する。また、これらを改良するために植物油、亜麻仁油、桐油、大豆油等の植物油を使用して合成したアルキド樹脂を、ワニス調製段階で加えた場合には、印刷作業環境を汚染するミスチングが発現する等、充分な問題解決には至っていない。 However, since the dihydric alcohol having 6 to 60 carbon atoms used here has a low boiling point, it does not easily stay in the reaction system at the reaction temperature of 220 to 270 ° C. of ordinary resin acids and is volatilized from the system. There is a problem that it is difficult to react because it is easy, the reaction takes a very long time, and it is difficult to increase the viscosity. Therefore, it is difficult to obtain sufficient viscoelasticity for lithographic inks with varnishes mainly composed of these resins. In addition, when the ratio of dihydric alcohol having 6 to 60 carbon atoms in the reaction system is reduced and a resin synthesized by using a trihydric or higher polyol instead is varnished to form a lithographic ink, it is environmentally friendly. As a result, the solubility in a printing ink solvent having a preferred aromatic compound component of 1% by weight or less is insufficient, the ink fluidity and transferability are insufficient, and the gloss of the printed matter is lowered. In addition, when an alkyd resin synthesized using vegetable oils such as vegetable oil, linseed oil, tung oil, and soybean oil is added in the varnish preparation stage to improve these, misting that contaminates the printing work environment appears. The problem has not been solved sufficiently.
本発明の課題は、生活環境や作業環境を悪化させる環境上の問題のあるアルキルフェノール等のフェノール類やホルムアルデヒド類をその合成過程で使用しなくとも高分子量、高粘度の樹脂を含有する組成物として製造できる環境に優しい平版インキワニス用樹脂組成物であって、平版インキ用としての充分な分子量と粘度を有していながら非芳香族系溶剤に対する良好な溶解性を有し、平版インキワニス用として好適な変性ロジンエステル樹脂組成物と、この樹脂組成物を用いてなる平版インキワニスを提供することにある。 An object of the present invention is to provide a composition containing a high molecular weight, high viscosity resin without using phenols such as alkylphenol and formaldehydes, which have environmental problems that deteriorate the living environment and work environment, in the synthesis process. An environmentally friendly resin composition for lithographic ink varnishes that can be produced and has good solubility in non-aromatic solvents while having sufficient molecular weight and viscosity for lithographic inks and is suitable for lithographic ink varnishes The object is to provide a modified rosin ester resin composition and a lithographic ink varnish comprising the resin composition.
本発明者らは、前記の課題を解決すべく鋭意研究した結果、以下の知見（１）〜（４）を見出し、本発明を完成するに至った。 As a result of earnest research to solve the above-mentioned problems, the present inventors have found the following findings (1) to (4) and have completed the present invention.
（１）ロジン（Ａ）とα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）を反応させて未反応のロジン（Ａ）と酸変性ロジン（Ｂ）を含有する反応混合物とした後、ヨウ素価１４０以上の植物油（ｃ）を反応させ、次いで３価以上のポリオール（Ｄ）を反応させると、フェノール類やホルムアルデヒド類を全く含有しない条件下の反応であっても比較的容易により短時間で高分子量化、高粘度化すると共に、合成段階で植物油（ｃ）に起因する高級炭化水素基が組み込まれるため、非芳香族系溶剤にも良好な溶解性を持つ変性ロジンエステル樹脂と、未反応の植物油（ｃ）および／または未反応のポリオール（Ｄ）を含有する変性ロジンエステル樹脂組成物が製造できること。 (1) A reaction mixture containing unreacted rosin (A) and acid-modified rosin (B) by reacting rosin (A) with α, β-unsaturated dicarboxylic acid and / or anhydride (b) thereof. After that, when the vegetable oil (c) having an iodine value of 140 or more is reacted, and then the polyol (D) having a trivalent or higher value is reacted, it is relatively easy even in a reaction that does not contain any phenols or formaldehydes. A modified rosin ester resin having a high solubility in a non-aromatic solvent because it has a high molecular weight and a high viscosity in a short time and a higher hydrocarbon group derived from the vegetable oil (c) is incorporated in the synthesis stage. A modified rosin ester resin composition containing unreacted vegetable oil (c) and / or unreacted polyol (D) can be produced.
（２）前記変性ロジンエステル樹脂組成物の製造方法としては、前記（１）の製造方法に限定されるものではなく、ロジン（Ａ）と、ロジン（Ａ）をα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）で変性して得られる酸変性ロジン（Ｂ）と、ロジン（Ａ）をヨウ素価１４０以上の植物油（ｃ）で変性して得られる油変性ロジン（Ｃ）と、３価以上のポリオール（Ｄ）を反応させる製造方法であればよいこと。 (2) The production method of the modified rosin ester resin composition is not limited to the production method of the above (1), and rosin (A) and rosin (A) are converted to α, β-unsaturated dicarboxylic acid. And / or an acid-modified rosin (B) obtained by modification with the anhydride (b), and an oil-modified rosin (C) obtained by modifying the rosin (A) with a vegetable oil (c) having an iodine value of 140 or more; It should just be a manufacturing method with which the polyol (D) more than trivalence is made to react.
（３）前記変性ロジンエステル樹脂組成物の工業的製造方法としては、ロジン（Ａ）とα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）を未反応のロジン（Ａ）と酸変性ロジン（Ｂ）を含有する反応混合物と、ヨウ素価１４０以上の植物油（ｃ）と、３価以上のポリオール（Ｄ）を、１６０℃以上２３０℃未満で反応させた後、さらに２３０〜２７０℃で反応させる製造方法が特に好適であること。 (3) As an industrial production method of the modified rosin ester resin composition, rosin (A) and α, β-unsaturated dicarboxylic acid and / or anhydride (b) thereof are converted into unreacted rosin (A) and acid. After the reaction mixture containing the modified rosin (B), the vegetable oil (c) having an iodine value of 140 or more, and the polyol (D) having a valence of 3 or more are reacted at 160 ° C. or higher and lower than 230 ° C., further 230-270 ° C. The production method in which the reaction is performed is particularly suitable.
（４）前記変性ロジンエステル樹脂組成物は、非芳香族系溶剤に良好な溶解性を持つため、平版インキワニス用として好適であり、炭化水素系溶剤（Ｅ）に溶解させることにより容易に平版インキワニスとすることができ、得られたワニスを用いてなるインキはフリーの植物油が少なく、ミスチングや過乳化等による印刷適性不良等の劣化現象が発生しにくいこと。 (4) Since the modified rosin ester resin composition has good solubility in a non-aromatic solvent, it is suitable for a lithographic ink varnish, and can be easily dissolved in a hydrocarbon solvent (E). The ink made from the obtained varnish has a small amount of free vegetable oil, and deterioration phenomenon such as poor printability due to misting or overemulsification is difficult to occur.
即ち、本発明は、ロジン（Ａ）と、ロジン（Ａ）をα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）で変性して得られる酸変性ロジン（Ｂ）と、ロジン（Ａ）をヨウ素価１４０以上の植物油（ｃ）で変性して得られる油変性ロジン（Ｃ）と、３価以上のポリオール（Ｄ）を反応させることを特徴とする平版インキワニス用変性ロジンエステル樹脂組成物の製造方法を提供するものである。 That is, the present invention relates to rosin (A), an acid-modified rosin (B) obtained by modifying rosin (A) with an α, β-unsaturated dicarboxylic acid and / or an anhydride thereof (b), and rosin ( A modified rosin ester resin composition for a lithographic ink varnish characterized by reacting an oil-modified rosin (C) obtained by modifying A) with a vegetable oil (c) having an iodine value of 140 or more and a polyol (D) having a valence of 3 or more The manufacturing method of a thing is provided.
また、本発明は、前記平版インキワニス用変性ロジンエステル樹脂組成物を炭化水素系溶剤（Ｅ）に溶解させることを特徴とする平版インキワニスの製造方法、および、前記平版インキワニス用変性ロジンエステル樹脂組成物を炭化水素系溶剤（Ｅ）に溶解させた後、ゲル化剤（Ｆ）を反応させることを特徴とする平版インキワニスの製造方法を提供するものである。 The present invention also relates to a method for producing a lithographic ink varnish characterized by dissolving the modified rosin ester resin composition for a lithographic ink varnish in a hydrocarbon solvent (E), and the modified rosin ester resin composition for the lithographic ink varnish. Is dissolved in a hydrocarbon solvent (E), and then the gelling agent (F) is reacted.
本発明の製造方法で得られる平版インキワニス用変性ロジンエステル樹脂組成物および平版インキワニスは、アルキルフェノール類やホルムアルデヒド類等を樹脂合成の段階で全く使用しなくても製造できるため、製造環境においても、また印刷作業環境においても、環境汚染物質を全く排出しない環境保全の面でも優れた特性を有している。また、本発明の製造方法で得られる平版インキワニス用変性ロジンエステル樹脂組成物は、前記特許文献１では用いていないヨウ素価１４０以上の植物油（ｃ）を樹脂中に組み込むことで高分子量化、高粘度化した変性ロジンエステル樹脂を含有するものであるため、平版インキワニス用として充分な粘度と重量平均分子量を有しており、これを使用してなる平版インキはミスチングや過乳化等による印刷適性不良等を抑制できること、かつ、非芳香族系溶剤への高い樹脂溶解性を持つことから、顔料分散性に優れ光沢等の良好な平版インキを調製することができる。この特性は平版インキ用途として従来から使用されているロジン変性フェノール樹脂と比較してもそのインキ特性に何ら遜色が無く、代替使用が可能である。かつ、環境汚染成分を放出しないことから環境改善にも有効である。 The modified rosin ester resin composition for lithographic ink varnishes and the lithographic ink varnish obtained by the production method of the present invention can be produced without using any alkylphenols or formaldehydes at the stage of resin synthesis. Even in the printing work environment, it has excellent characteristics in terms of environmental protection that does not emit any environmental pollutants. In addition, the modified rosin ester resin composition for lithographic ink varnish obtained by the production method of the present invention has a high molecular weight by incorporating a vegetable oil (c) having an iodine value of 140 or more, which is not used in Patent Document 1, into the resin. Because it contains a modified rosin ester resin with viscosity, it has sufficient viscosity and weight average molecular weight for lithographic ink varnishes, and lithographic inks using this have poor printability due to misting or over-emulsification. Etc. and high resin solubility in non-aromatic solvents, it is possible to prepare a lithographic ink having excellent pigment dispersibility and good gloss. Compared with rosin-modified phenolic resins conventionally used for lithographic ink applications, this characteristic has no inferiority in ink characteristics and can be used as an alternative. In addition, it is effective in improving the environment because it does not release environmental pollutants.
本発明で用いるロジン（Ａ）としては、ガムロジン、ウッドロジン、トール油ロジン、これらの混合物等のディールス・アルダー反応が可能な共役二重結合を持つロジンが挙げられる。一般にロジンは、松科植物の樹脂液を留去した後の残留樹脂成分を言う。その組成はアビエチン酸を主成分とした樹脂酸と中性成分の各種異性体であり、それらは共役二重結合を持つテルペン類の４量体である。なお、本発明で用いるロジン（Ａ）としては、必要により、不均化されたロジン、二量化されたロジン、水素化されたロジン等の共役二重結合を持たないロジンを２０重量％以下の含有率となる範囲で、前記共役二重結合を持つロジンと併用することができるが、高分子量化、高粘度化が容易なことから共役二重結合を持たないロジンの使用比率は小さいことが好ましく、共役二重結合を持たないロジンを使用しないことがより好ましい。共役二重結合を持たないロジンの含有率が２０重量％を越えるロジンを用いた場合、高分子量化、高粘度化が困難となるため好ましくない。 Examples of the rosin (A) used in the present invention include rosin having a conjugated double bond capable of Diels-Alder reaction, such as gum rosin, wood rosin, tall oil rosin, and mixtures thereof. In general, rosin refers to a residual resin component after the resin solution of a pine plant is distilled off. Its composition is a resin acid mainly composed of abietic acid and various isomers of a neutral component, which are tetramers of terpenes having a conjugated double bond. In addition, as the rosin (A) used in the present invention, if necessary, a rosin having no conjugated double bond such as disproportionated rosin, dimerized rosin, hydrogenated rosin or the like is 20% by weight or less. The rosin having a conjugated double bond can be used in combination with the rosin having the conjugated double bond within the range of the content, but the use ratio of the rosin having no conjugated double bond is small because of high molecular weight and high viscosity. Preferably, it is more preferable not to use a rosin having no conjugated double bond. Use of a rosin having a content of rosin having no conjugated double bond exceeding 20% by weight is not preferable because it is difficult to increase the molecular weight and increase the viscosity.
本発明で用いる酸変性ロジン（Ｂ）としては、α，β−不飽和ジカルボン酸および／またはその無水物（ｂ）で前記ロジン（Ａ）を変性してなるものであればよく、例えば、ロジン（Ａ）が有する共役二重結合と、α，β−不飽和カルポン酸またはその無水物（ｂ）が有する不飽和基をディールス・アルダー反応させて得られるカルボキシル基を分子内に３個有する酸変性ロジンが挙げられる。この際の反応温度は通常１６０℃以上２３０℃未満、好ましくは１８０〜２２０℃であり、反応時間は通常１５分間〜４時間、好ましくは２０分間〜２時間である。 The acid-modified rosin (B) used in the present invention may be any one obtained by modifying the rosin (A) with an α, β-unsaturated dicarboxylic acid and / or its anhydride (b). Acid having three carboxyl groups in the molecule obtained by Diels-Alder reaction of the conjugated double bond of (A) and the unsaturated group of α, β-unsaturated carboxylic acid or its anhydride (b) Examples include modified rosin. The reaction temperature at this time is usually 160 ° C. or higher and lower than 230 ° C., preferably 180 to 220 ° C., and the reaction time is usually 15 minutes to 4 hours, preferably 20 minutes to 2 hours.
前記α，β−不飽和ジカルボン酸および／またはその無水物（ｂ）としては、ディールス・アルダー反応が可能な種々のα，β−不飽和ジカルボン酸および／またはその無水物を用いることができる。例えば、マレイン酸（ｃｉｓ−ブテン二酸）、無水マレイン酸、フマル酸（ｔｒａｎｓ−ブテン二酸）、イタコン酸（メチレンコハク酸）、無水イタコン酸、クロトン酸（ｔｒａｎｓ−２−ブテン酸）等のような炭素原子数３〜５の鎖状ジカルボン酸および／またはそれらの無水物などが挙げられ、なかでも変性ロジンエステル樹脂組成物を製造する際に高分子量化と高粘度化が容易でゲル化しにくいことから、フマル酸を８０重量％以上含有するものが好ましく、フマル酸のみがより好ましい。前記α，β−不飽和ジカルボン酸および／またはその無水物は、２官能酸であり、ロジンとのディールス・アルダー反応によりロジン骨格を多官能化し架橋構造を構築することができ、これにより変性ロジンエステル樹脂の高分子量化、高粘度化が可能となる。酸変性ロジン（Ａ）を得る際のα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）の使用量は、変性ロジンエステル樹脂組成物を製造する際に高分子量化と高粘度化が容易でゲル化しにくいことから、ロジン１００重量部に対して５〜３０重量部となる量であることが好ましく、５〜２０重量部であることがより好ましい。 As the α, β-unsaturated dicarboxylic acid and / or anhydride (b) thereof, various α, β-unsaturated dicarboxylic acids capable of Diels-Alder reaction and / or anhydrides thereof can be used. For example, maleic acid (cis-butenedioic acid), maleic anhydride, fumaric acid (trans-butenedioic acid), itaconic acid (methylenesuccinic acid), itaconic anhydride, crotonic acid (trans-2-butenoic acid), etc. Examples thereof include chain dicarboxylic acids having 3 to 5 carbon atoms and / or their anhydrides, and in particular, when producing a modified rosin ester resin composition, high molecular weight and high viscosity are easily gelled. Since it is difficult, what contains 80 weight% or more of fumaric acid is preferable, and only fumaric acid is more preferable. The α, β-unsaturated dicarboxylic acid and / or anhydride thereof is a bifunctional acid, and a rosin skeleton can be polyfunctionalized by a Diels-Alder reaction with rosin to form a crosslinked structure, whereby a modified rosin It is possible to increase the molecular weight and viscosity of the ester resin. The amount of α, β-unsaturated dicarboxylic acid and / or its anhydride (b) used in obtaining the acid-modified rosin (A) is increased in molecular weight and viscosity when the modified rosin ester resin composition is produced. However, the amount is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of rosin.
なお、本発明で用いる前記ロジン（Ａ）および前記酸変性ロジン（Ｂ）としては、前記酸変性ロジン（Ｂ）の製造を、前記ロジン（Ａ）が未反応で残存する条件、すなわち前記ロジン（Ａ）中の共役二重結合がα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）中の不飽和基に対して過剰となる条件で行った際に得られる未反応のロジン（Ａ）と酸変性ロジン（Ｂ）の混合物を用いることが好ましい。また、この混合物としては、なかでも変性ロジンエステル樹脂組成物を製造する際に高分子量化と高粘度化が容易でゲル化しにくいことから、酸価２００〜３００ＫＯＨｍｇ／ｇの混合物であることが好ましく、酸価２２０〜２６０ＫＯＨｍｇ／ｇの混合物であることがより好ましく、ロジン（Ａ）１００重量部に対して炭素原子数３〜５のα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）５〜２０重量部を反応させてなる酸価２２０〜２６０ＫＯＨｍｇ／ｇの反応混合物であることが更に好ましい。最も好ましい混合物は、ロジン（Ａ）１００重量部に対してフマル酸含有率８０重量％以上のα，β−不飽和ジカルボン酸および／またはその無水物５〜２０重量部を反応させてなる酸価２２０〜２６０ＫＯＨｍｇ／ｇの反応混合物である。 In addition, as the rosin (A) and the acid-modified rosin (B) used in the present invention, the production of the acid-modified rosin (B) is performed under the condition that the rosin (A) remains unreacted, that is, the rosin ( An unreacted rosin obtained when the conjugated double bond in A) is excessive with respect to the unsaturated group in the α, β-unsaturated dicarboxylic acid and / or its anhydride (b) ( It is preferable to use a mixture of A) and acid-modified rosin (B). In addition, the mixture is preferably a mixture having an acid value of 200 to 300 KOHmg / g because, when producing a modified rosin ester resin composition, high molecular weight and high viscosity are easy and gelation is difficult. , An acid value of 220 to 260 KOH mg / g, and more preferably an α, β-unsaturated dicarboxylic acid having 3 to 5 carbon atoms and / or its anhydride (b) per 100 parts by weight of rosin (A). It is more preferable that the reaction mixture has an acid value of 220 to 260 KOHmg / g obtained by reacting 5 to 20 parts by weight. The most preferable mixture is an acid value obtained by reacting 5 to 20 parts by weight of an α, β-unsaturated dicarboxylic acid and / or its anhydride having a fumaric acid content of 80% by weight or more with respect to 100 parts by weight of rosin (A). 220-260 KOH mg / g reaction mixture.
本発明で用いる油変性ロジン（Ｃ）としては、ヨウ素価１４０以上の植物油（ｃ）でロジン（Ａ）を変性してなるものであればよく、例えば、ロジン（Ａ）が有する共役二重結合と、ヨウ素価１４０以上の植物油（ｃ）が有する共役二重結合をディールス・アルダー反応させて得られる植物油変性ロジンが挙げられ、なかでもロジン（Ａ）をヨウ素価１４０〜２００の植物油で変性して得られる油変性ロジンが好ましい。なお、油変性ロジン（Ｃ）の製造に際しては、変性に使用した植物油（ｃ）の全部をロジン（Ａ）と反応させる必要はなく、油変性ロジン（Ｃ）と共に、未反応の植物油（ｃ）が残存していてもよい。また、この際の反応温度は通常１６０℃以上２３０℃未満、好ましくは１８０〜２２０℃であり、これらの反応温度内での反応時間は通常１〜４時間、好ましくは１．５〜３時間である。なお、本発明におけるヨウ素価の単位はＩ２ｇ／１００ｇである。 The oil-modified rosin (C) used in the present invention may be any one obtained by modifying rosin (A) with a vegetable oil (c) having an iodine value of 140 or more. For example, a conjugated double bond possessed by rosin (A) And vegetable oil-modified rosin obtained by subjecting a conjugated double bond of vegetable oil (c) having an iodine value of 140 or more to Diels-Alder reaction. Among them, rosin (A) is modified with vegetable oil having an iodine value of 140 to 200. The oil-modified rosin obtained in this way is preferred. In the production of the oil-modified rosin (C), it is not necessary to react the whole vegetable oil (c) used for modification with the rosin (A), and together with the oil-modified rosin (C), unreacted vegetable oil (c). May remain. In this case, the reaction temperature is usually 160 ° C. or higher and lower than 230 ° C., preferably 180 to 220 ° C., and the reaction time within these reaction temperatures is usually 1 to 4 hours, preferably 1.5 to 3 hours. is there. The unit of iodine value in the present invention is I 2 g / 100 g.
前記油変性ロジン（Ｃ）を製造する際に用いる植物油（ｃ）としては、ヨウ素価１４０以上の植物油であればよく、例えば、ヨウ素価１４０以上の乾性油である桐油、桐油脂肪酸、アマニ油、アマニ油脂肪酸等が挙げられる。また、半乾性油である大豆油、大豆油脂肪酸等の変性物でも混合後のヨウ素価が１４０以上となる量であれば、ヨウ素価１４０以上の乾性油と併用できる。ヨウ素価が１４０未満の植物油を用いたのでは変性ロジンエステル樹脂組成物の分子量が大きくならず、この樹脂組成物を使用したワニスは充分な粘度を得られないため、好ましくない。ヨウ素価１４０以上の植物油（ｃ）としては、なかでも、ヨウ素価１４０〜２００の植物油が好ましい。 The vegetable oil (c) used when producing the oil-modified rosin (C) may be any vegetable oil having an iodine value of 140 or more, such as tung oil, tung oil fatty acid, linseed oil, which is a drying oil having an iodine value of 140 or more, And linseed oil fatty acid. In addition, modified products such as soybean oil and soybean oil fatty acid which are semi-drying oils can be used in combination with drying oil having an iodine value of 140 or more as long as the iodine value after mixing is 140 or more. Use of vegetable oil having an iodine value of less than 140 is not preferable because the molecular weight of the modified rosin ester resin composition does not increase, and a varnish using this resin composition cannot obtain a sufficient viscosity. As the vegetable oil (c) having an iodine value of 140 or more, a vegetable oil having an iodine value of 140 to 200 is preferable.
本発明で用いるポリオール（Ｄ）としては、３価以上のポリオールであればよく、特に限定されないが、３〜４価のポリオールが好ましく、その使用割合はポリオール（Ｄ）の全量１００重量％に対して、通常７０重量％以上、好ましくは８０重量％以上、特に好ましくは１００重量％である。３〜４価のポリオールとしては、例えば、グリセリン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリトリトール〔Ｃ(ＣＨ２ＯＨ)４〕、ジペンタエリトリトール、Ｄ−ソルビトール（Ｄ−グルシトール）などが挙げられる。なお、本発明では、３価以上のポリオール（Ｄ）と共に、２価のポリオールを併用することも可能であるが、２価のポリオールを多量に使用したものでは高粘度型の樹脂を得ることが困難となるため、２価のポリオールの使用量は３価以上のポリオール（Ｄ）１００重量部に対して３０重量部以下に制限することが必要である。 The polyol (D) used in the present invention is not particularly limited as long as it is a tri- or higher valent polyol, but a tri- or tetravalent polyol is preferable, and its use ratio is based on 100% by weight of the total amount of the polyol (D). The amount is usually 70% by weight or more, preferably 80% by weight or more, and particularly preferably 100% by weight. Examples of the trivalent to tetravalent polyol include glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol [C (CH 2 OH) 4 ], dipentaerythritol, D-sorbitol (D-glucitol), and the like. In the present invention, it is possible to use a divalent polyol together with a trivalent or higher polyol (D), but a high viscosity resin can be obtained with a large amount of a divalent polyol. Since it becomes difficult, it is necessary to restrict the amount of the divalent polyol used to 30 parts by weight or less with respect to 100 parts by weight of the trivalent or higher polyol (D).
本発明の平版インキワニス用変性ロジンエステル樹脂組成物の製造方法は、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）と３価以上のポリオール（Ｄ）を反応させる方法であり、例えば、ロジン（Ａ）と、α，β−不飽和ジカルボン酸および／またはその無水物（ｂ）と、ヨウ素価１４０以上の植物油（ｃ）を反応させて、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）を含有し、未反応の植物油（ｃ）を含有していてもよい反応混合物とした後、この反応混合物と３価以上のポリオール（Ｄ）を、好ましくはエステル化反応触媒の存在下で、反応させる方法等が挙げられる。なお、本発明の製造方法で得られる反応生成物には、未反応の植物油（ｃ）および／または未反応のポリオール（Ｄ）が残存していてもよい。また、本発明の製造方法における各成分の使用量としては、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）の合計１００重量部に対して、ロジン（Ａ）が０．５〜６重量部で、酸変性ロジン（Ｂ）が２１〜７５重量部で、油変性ロジン（Ｃ）が２１〜７５重量部で、かつ、３価以上のポリオール（Ｄ）が４〜２０重量部であることが好ましく、なかでも、ロジン（Ａ）が１〜４重量部で、酸変性ロジン（Ｂ）が３１〜６５重量部で、油変性ロジン（Ｃ）が３１〜６５重量部で、かつ、３価以上のポリオール（Ｄ）が６〜１５重量部であることがより好ましい。 The method for producing a modified rosin ester resin composition for a lithographic ink varnish of the present invention is a method in which a rosin (A), an acid-modified rosin (B), an oil-modified rosin (C), and a trivalent or higher polyol (D) are reacted. For example, rosin (A), α, β-unsaturated dicarboxylic acid and / or its anhydride (b), and vegetable oil (c) having an iodine value of 140 or more are reacted to produce rosin (A) and acid-modified rosin. (B) and an oil-modified rosin (C), and after making a reaction mixture that may contain unreacted vegetable oil (c), this reaction mixture and a trivalent or higher polyol (D) are preferably Examples thereof include a method of reacting in the presence of an esterification reaction catalyst. In the reaction product obtained by the production method of the present invention, unreacted vegetable oil (c) and / or unreacted polyol (D) may remain. In addition, the amount of each component used in the production method of the present invention is such that the rosin (A) is 0.1% relative to a total of 100 parts by weight of the rosin (A), the acid-modified rosin (B) and the oil-modified rosin (C). 5 to 6 parts by weight, 21 to 75 parts by weight of the acid-modified rosin (B), 21 to 75 parts by weight of the oil-modified rosin (C), and 4 to 20 parts by weight of a trivalent or higher valent polyol (D) The rosin (A) is preferably 1 to 4 parts by weight, the acid-modified rosin (B) is 31 to 65 parts by weight, and the oil-modified rosin (C) is 31 to 65 parts by weight. In addition, it is more preferable that the trivalent or higher polyol (D) is 6 to 15 parts by weight.
前記本発明の製造方法としては、なかでも、ロジン（Ａ）とα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）を反応させてロジン（Ａ）と酸変性ロジン（Ｂ）を含有する反応混合物とした後、ヨウ素価１４０以上の植物油（ｃ）を反応させ、次いで３価以上のポリオール（Ｄ）を反応させる方法が、α，β−不飽和ジカルボン酸および／またはその無水物（ｂ）と植物油（ｃ）の反応が防止でき、変性ロジンエステル樹脂の高分子量化と高粘度化が容易でゲル化しにくいことから好ましい。なお、３価以上のポリオール（Ｄ）を反応させる前の系内の反応混合物としては、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）を含有し、未反応の植物油（ｃ）を含有していてもよい反応混合物であることが好ましい。 Among the production methods of the present invention, rosin (A) and acid-modified rosin (B) are obtained by reacting rosin (A) with α, β-unsaturated dicarboxylic acid and / or its anhydride (b). A method of reacting a vegetable oil (c) having an iodine value of 140 or more after reacting with a reaction mixture to be contained, and then reacting a polyol (D) having a trivalence or more is an α, β-unsaturated dicarboxylic acid and / or an anhydride thereof. The reaction between (b) and vegetable oil (c) can be prevented, and the modified rosin ester resin can be easily increased in molecular weight and viscosity and is not easily gelled. The reaction mixture in the system before reacting the trivalent or higher polyol (D) contains rosin (A), acid-modified rosin (B) and oil-modified rosin (C), and contains unreacted vegetable oil ( It is preferable that it is a reaction mixture which may contain c).
前記製造方法において、ロジン（Ａ）と酸変性ロジン（Ｂ）を含有する反応混合物を得る際、および、得られた前記反応混合物と植物油（ｃ）の反応の際の反応条件は、いずれもロジン（Ａ）が未反応で残存する条件であれば良く、例えば、ロジン（Ａ）中の共役二重結合がα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）中の不飽和基、および、植物油（ｃ）中の共役二重結合に対していずれも過剰となる条件であることが好ましい。 In the production method, the reaction conditions for obtaining a reaction mixture containing rosin (A) and acid-modified rosin (B) and for the reaction of the obtained reaction mixture and vegetable oil (c) are all rosin. For example, the conjugated double bond in rosin (A) is an unsaturated group in α, β-unsaturated dicarboxylic acid and / or its anhydride (b). It is preferable that the conditions are both excessive with respect to the conjugated double bond in the vegetable oil (c).
前記本発明の製造方法として工業的に好適な製造方法は、ロジン（Ａ）とα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）を反応させてなるロジン（Ａ）と酸変性ロジン（Ｂ）を含有する反応混合物〔以下、反応混合物（１）と略記する。〕と、ヨウ素価１４０以上の植物油（ｃ）と、３価以上のポリオール（Ｄ）を混合し、１６０℃以上２３０℃未満、好ましくは１８０〜２２０℃で反応させた後、２３０〜２７０℃、好ましくは２４０〜２６０℃でさらに反応させる方法が挙げられる。なお、反応混合物（１）としては、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）と３価以上のポリオール（Ｄ）を含有し、未反応の植物油（ｃ）を含有していてもよい反応混合物であることが好ましい。 The industrially preferred production method as the production method of the present invention is a rosin (A) obtained by reacting rosin (A) with an α, β-unsaturated dicarboxylic acid and / or an anhydride (b) thereof, and an acid modification. Reaction mixture containing rosin (B) [hereinafter abbreviated as reaction mixture (1). And a vegetable oil (c) having an iodine value of 140 or higher and a polyol (D) having a trivalent or higher value are mixed and reacted at 160 ° C. or higher and lower than 230 ° C., preferably 180 to 220 ° C., then 230 to 270 ° C., The method of making it react further at 240-260 degreeC preferably is mentioned. The reaction mixture (1) contains rosin (A), acid-modified rosin (B), oil-modified rosin (C), and trivalent or higher polyol (D), and contains unreacted vegetable oil (c). It is preferable that the reaction mixture be an optional one.
前記工業的に好適な製造方法では、前記反応混合物（１）１００重量部に対して、ヨウ素価１４０以上の植物油（ｃ）を通常４〜８０重量部、好ましくは５〜５０重量部となる範囲で使用し、３価以上のポリオール（Ｄ）を通常５〜３０重量部、好ましくは１０〜２０重量部となる範囲で使用する。また、前記反応混合物（１）としては、前記したように、変性ロジンエステル樹脂の高分子量化と高粘度化が容易でゲル化しにくいことから、ロジン（Ａ）１００重量部に対して炭素原子数３〜５のα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）５〜２０重量部を反応させてなる酸価２２０〜２６０ＫＯＨｍｇ／ｇの反応混合物であることが好ましく、ロジン（Ａ）１００重量部に対してフマル酸含有率８０重量％以上のα，β−不飽和ジカルボン酸および／またはその無水物５〜２０重量部を反応させてなる酸価２２０〜２６０ＫＯＨｍｇ／ｇの反応混合物であることが最も好ましい。 In the industrially suitable production method, the vegetable oil (c) having an iodine value of 140 or more is usually 4 to 80 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the reaction mixture (1). The trivalent or higher valent polyol (D) is usually used in an amount of 5 to 30 parts by weight, preferably 10 to 20 parts by weight. In addition, as described above, the reaction mixture (1) is easy to increase the molecular weight and viscosity of the modified rosin ester resin and is difficult to gel. Therefore, the number of carbon atoms is 100 parts by weight of rosin (A). A reaction mixture having an acid value of 220 to 260 KOHmg / g obtained by reacting 5 to 20 parts by weight of 3 to 5 α, β-unsaturated dicarboxylic acid and / or anhydride (b) thereof is preferable. ) A reaction mixture having an acid value of 220 to 260 KOHmg / g obtained by reacting 5 to 20 parts by weight of an α, β-unsaturated dicarboxylic acid and / or its anhydride having a fumaric acid content of 80% by weight or more with respect to 100 parts by weight. Most preferably.
さらに前記工業的に好適な製造方法では、前記反応混合物（１）と、ヨウ素価１４０以上の植物油（ｃ）と、３価以上のポリオール（Ｄ）を混合した後、まず１６０℃以上２３０℃未満、好ましくは１８０〜２２０℃という比較的低温で反応させるため、この反応で得られる反応混合物中のロジン（Ａ）と植物油（ｃ）が主に反応して油変性ロジン（Ｃ）が生成するが、ロジン（Ａ）や酸変性ロジン（Ｂ）と３価以上のポリオール（Ｄ）の反応はほとんど進行しない。この際に得られる反応混合物〔以下、反応混合物（２）と略記する。〕としては、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）と３価以上のポリオール（Ｄ）を含有し、未反応の植物油（ｃ）を含有していてもよい反応混合物であることが好ましい。次いで、この製造方法では、前記反応混合物（２）を２３０〜２７０℃、好ましくは２４０〜２６０℃でさらに反応させるため、ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）と３価以上のポリオール（Ｄ）の反応による高分子量化、高粘度化が進行する。 Further, in the industrially suitable production method, the reaction mixture (1), the vegetable oil (c) having an iodine value of 140 or more, and the polyol (D) having a trivalence or more are first mixed, and then firstly 160 ° C. or higher and lower than 230 ° C. Since the reaction is preferably performed at a relatively low temperature of 180 to 220 ° C., the rosin (A) and the vegetable oil (c) in the reaction mixture obtained by this reaction mainly react to produce an oil-modified rosin (C). The reaction of rosin (A) or acid-modified rosin (B) with a trivalent or higher polyol (D) hardly proceeds. Reaction mixture obtained at this time [hereinafter abbreviated as reaction mixture (2). ] Includes a rosin (A), an acid-modified rosin (B), an oil-modified rosin (C), a trivalent or higher polyol (D), and may contain an unreacted vegetable oil (c). A mixture is preferred. Next, in this production method, the reaction mixture (2) is further reacted at 230 to 270 ° C., preferably 240 to 260 ° C., so that rosin (A), acid-modified rosin (B), and oil-modified rosin (C) High molecular weight and high viscosity are advanced by reaction of a trivalent or higher polyol (D).
なお、前記工業的に好適な製造方法において、前記反応混合物（１）と植物油（ｃ）とポリオール（Ｄ）の１６０℃以上２３０℃未満、好ましくは１８０〜２２０℃での反応時間は、通常１〜４時間、好ましくは１．５〜３時間である。次いで、得られた反応混合物（２）の２３０〜２７０℃、好ましくは２４０〜２６０℃での反応時間は、酸価が１０〜３０ＫＯＨｍｇ／ｇ、好ましくは１６〜３０ＫＯＨｍｇ／ｇとなるまでの時間であり、通常５〜２４時間、好ましくは８〜１５時間である。また、この製造方法での反応は、それぞれの温度範囲内で一定とする必要はなく、反応温度をそれぞれの温度範囲内で変化させながら行ってもよく、例えば、ロジン（Ａ）とα，β−不飽和ジカルボン酸および／またはその無水物（ｂ）を１６０℃以上２３０℃未満で反応させてなる１６０℃以上２３０℃未満の反応混合物に、常温の植物油（ｃ）と常温のポリオール（Ｄ）を混合して温度１１０〜１７０℃の混合物とした後、昇温速度１０〜５０℃／ｈｒ、好ましくは２０〜４０℃／ｈｒの条件で昇温することにより、反応混合物（１）と植物油（ｃ）とポリオール（Ｄ）の１６０℃以上２３０℃未満での反応を行って反応混合物（２）とし、次いで２３０〜２７０℃の温度範囲内まで昇温し、さらに反応させることが好ましい。 In the industrially suitable production method, the reaction time of the reaction mixture (1), the vegetable oil (c) and the polyol (D) at 160 ° C. or higher and lower than 230 ° C., preferably 180 to 220 ° C. is usually 1 -4 hours, preferably 1.5-3 hours. Next, the reaction time of the obtained reaction mixture (2) at 230 to 270 ° C., preferably 240 to 260 ° C. is the time until the acid value becomes 10 to 30 KOH mg / g, preferably 16 to 30 KOH mg / g. Yes, usually 5 to 24 hours, preferably 8 to 15 hours. The reaction in this production method does not have to be constant within each temperature range, and may be performed while changing the reaction temperature within each temperature range. For example, rosin (A) and α, β -Normal temperature vegetable oil (c) and normal temperature polyol (D) to a reaction mixture of 160 ° C or higher and lower than 230 ° C obtained by reacting unsaturated dicarboxylic acid and / or its anhydride (b) at 160 ° C or higher and lower than 230 ° C Are mixed to obtain a mixture having a temperature of 110 to 170 ° C., and then heated at a temperature rising rate of 10 to 50 ° C./hr, preferably 20 to 40 ° C./hr, whereby the reaction mixture (1) and vegetable oil ( It is preferable that the reaction between c) and the polyol (D) is carried out at 160 ° C. or more and less than 230 ° C. to obtain a reaction mixture (2), and then the temperature is raised to 230 to 270 ° C. for further reaction.
前記本発明の製造方法では、前記ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）と３価以上のポリオール（Ｄ）の４成分と共に、必要に応じてフェノール類、ホルムアルデヒド類およびこれらを反応させてなるフェノール系樹脂を併用することもできるが、必ずしも必要ではない。このため、本発明の製造方法では、生活環境や作業環境の改良のために、フェノール類やホルムアルデヒド類の非存在下で製造することが好ましい。 In the production method of the present invention, together with the four components of the rosin (A), acid-modified rosin (B), oil-modified rosin (C), and trivalent or higher polyol (D), if necessary, phenols and formaldehydes A phenolic resin obtained by reacting these can also be used in combination, but it is not always necessary. For this reason, in the manufacturing method of this invention, it is preferable to manufacture in absence of phenols and formaldehydes for the improvement of a living environment or a working environment.
本発明の製造方法におけるロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）と３価以上のポリオール（Ｄ）を反応は、ロジン（Ａ）、酸変性ロジン（Ｂ）および油変性ロジン（Ｃ）中のカルボキシル基と３価以上のポリオール（Ｄ）中の水酸基のエステル化反応と、ロジン（Ａ）および酸変性ロジン（Ｂ）中のカルボキシル基と油変性ロジン（Ｃ）中のエステル基のエステル交換反応等であるため、得られる変性ロジンエステル樹脂は容易に高分子量化、高粘度化し、ミスチングや過乳化等の発生しにくい印刷適性の改善された平版インキの調製に寄与できるものとなると共に、油変性ロジン（Ｂ）中の植物油（ｃ）由来成分が組み込まれて、非芳香族系溶剤への溶解性も向上したものとなる。 In the production method of the present invention, the reaction of rosin (A), acid-modified rosin (B), oil-modified rosin (C), and trivalent or higher polyol (D) comprises rosin (A), acid-modified rosin (B) and oil. Esterification reaction of carboxyl group in modified rosin (C) with hydroxyl group in trivalent or higher polyol (D), carboxyl group in rosin (A) and acid-modified rosin (B) and oil-modified rosin (C) The resulting modified rosin ester resin easily contributes to the preparation of a lithographic ink with high molecular weight, high viscosity, and improved printability that is less likely to cause misting and over-emulsification. In addition, the component derived from the vegetable oil (c) in the oil-modified rosin (B) is incorporated, and the solubility in a non-aromatic solvent is also improved.
本発明の製造方法では、通常、得られる平版インキワニス用変性ロジンエステル樹脂組成物〔変性ロジンエステル樹脂と未反応の植物油（ｃ）および／または未反応のポリオール（Ｄ）を含有する樹脂組成物。以下、同様。〕の重量平均分子量が２万〜３５万となるまで反応させるが、なかでも高粘度で非芳香族系溶剤への溶解性に優れ、過乳化等の印刷適性不良が生じにくい平版インキが得られることから、重量平均分子量が４万〜３０万となるまで反応させることが好ましく、７万〜２７万となるまで反応させることがより好ましい。なお、この際に得られる変性ロジンエステル樹脂組成物の酸価は、１０〜３０ＫＯＨｍｇ／ｇであることが好ましく、１６〜３０ＫＯＨｍｇ／ｇであることがより好ましい。また、変性ロジンエステル樹脂組成物の粘度（濃度６０重量％トルエン溶液の２５℃におけるガードナー・ホルツ粘度）は、Ｍ〜Ｚ４であることが好ましく、Ｐ〜Ｚ２であることがより好ましい。変性ロジンエステル樹脂組成物中の未反応の植物油（ｃ）および／または未反応のポリオール（Ｄ）は、いずれも含有しないことが望ましいが、残存してしまうことが通常である。 In the production method of the present invention, a modified rosin ester resin composition for a lithographic ink varnish usually obtained [a resin composition containing a modified rosin ester resin and an unreacted vegetable oil (c) and / or an unreacted polyol (D). The same applies hereinafter. ], A lithographic ink is obtained that has a high viscosity, excellent solubility in non-aromatic solvents, and poor printability such as overemulsification. Therefore, the reaction is preferably performed until the weight average molecular weight reaches 40,000 to 300,000, and more preferably 70,000 to 270,000. In addition, the acid value of the modified rosin ester resin composition obtained at this time is preferably 10 to 30 KOH mg / g, and more preferably 16 to 30 KOH mg / g. Further, the viscosity of the modified rosin ester resin composition (Gardner-Holtz viscosity at 25 ° C. in a 60 wt% toluene solution) is preferably M to Z 4 , and more preferably P to Z 2 . Although it is desirable that none of the unreacted vegetable oil (c) and / or unreacted polyol (D) in the modified rosin ester resin composition is contained, it usually remains.
前記エステル化反応触媒としては、例えば、水酸化カルシウム、酸化マグネシウム、酸化亜鉛、酸化力ルシウムなどの２価金属化合物、パラトルエンスルホン酸、メタンスルホン酸、硫酸等の酸触媒等が好ましく、なかでも２価金属化合物がより好ましい。２価金属化合物の使用量としては、前記ロジン（Ａ）と酸変性ロジン（Ｂ）と油変性ロジン（Ｃ）とポリオール（Ｄ）の４成分の合計１００重量部に対して、２価金属化合物が０．０５〜２重量部となる範囲が好ましい。 As the esterification reaction catalyst, for example, divalent metal compounds such as calcium hydroxide, magnesium oxide, zinc oxide and oxidative power, and acid catalysts such as paratoluenesulfonic acid, methanesulfonic acid and sulfuric acid are preferable. A divalent metal compound is more preferable. The amount of the divalent metal compound used is a divalent metal compound with respect to a total of 100 parts by weight of the four components of the rosin (A), acid-modified rosin (B), oil-modified rosin (C) and polyol (D). Is preferably in the range of 0.05 to 2 parts by weight.
本発明の平版インキワニスは、本発明の製造方法で得られる平版インキワニス用変性ロジンエステル樹脂組成物を炭化水素系溶剤（Ｅ）に溶解させることで得られる。この際、必要に応じて植物油（ｃ′）、アルキド樹脂等を添加することができる。さらに、本発明の平版インキワニスとしては、平版インキワニス用変性ロジンエステル樹脂組成物を炭化水素系溶剤（Ｅ）に溶解させた後、ゲル化剤（Ｆ）を添加し、反応させることにより、さらに高分子量化、高粘度化することが好ましい。このようにゲル化剤（Ｆ）により高分子量化、高粘度化させた平版インキワニスとしては、光沢に優れ、ミスチング、過乳化等が発生しにくい平版インキが得られることから、レオメータ（Ｒｅｏｍｅｔｒｉｃｓ社製Ｓｔｒｅｓｓ Ｒｈｅｏｍｅｔｅｒ）を用いた粘弾性測定（温度＝２５℃、試験方法＝Ｆｒｅｑｕｅｎｃｙ Ｓｗｅｅｐ、測定様式＝パラレルプレート、Ｓｔｒａｉｎ＝２０％）により求めた周波数が１ｒａｄ／ｓｅｃの時のＥｔａ＊が５００〜２０，０００ｄＰａ・ｓで、Ｔａｎδが０．６〜１０で、周波数が１００ｒａｄ／ｓｅｃの時のＥｔａ＊が５０〜８，０００ｄＰａ・ｓで、Ｔａｎδが０．６〜１０であるものが好ましく、なかでも周波数が１ｒａｄ／ｓｅｃの時のＥｔａ＊が１，０００〜１０，０００ｄＰａ・ｓで、Ｔａｎδが１〜７で、周波数が１００ｒａｄ／ｓｅｃの時のＥｔａ＊が１００〜４，０００ｄＰａ・ｓで、Ｔａｎδが１〜５であるものがより好ましい。 The lithographic ink varnish of the present invention can be obtained by dissolving the modified rosin ester resin composition for a lithographic ink varnish obtained by the production method of the present invention in a hydrocarbon solvent (E). At this time, vegetable oil (c ′), alkyd resin or the like can be added as necessary. Furthermore, as the lithographic ink varnish of the present invention, the rosin ester modified rosin ester resin composition for lithographic ink varnish is dissolved in a hydrocarbon solvent (E), and then the gelling agent (F) is added and reacted. It is preferable to increase the molecular weight and viscosity. As a lithographic ink varnish having a high molecular weight and a high viscosity with a gelling agent (F) as described above, a lithographic ink that is excellent in gloss and hardly generates misting, over-emulsification, etc. can be obtained. Eta * when the frequency obtained by viscoelasticity measurement using a stress rheometer (temperature = 25 ° C., test method = Frequency Sweep, measurement style = parallel plate, strain = 20%) is 1 rad / sec is 500 to 20, 000 dPa · s, Tan δ is 0.6 to 10, and Eta * is 50 to 8,000 dPa · s and Tan δ is 0.6 to 10 when the frequency is 100 rad / sec. in Eta * is 1,000~10,000dPa · s at the time of but 1rad / sec Tanδ is 1 to 7, frequency at Eta * is 100~4,000dPa · s when the 100 rad / sec, is more preferable Tanδ is 1-5.
ここで用いる前記炭化水素系溶剤（Ｅ）としては、特に限定はないが、なかでも沸点２００〜３６０℃の石油系炭化水素系溶剤が好ましい。これは平版インキの粘度調整と平版インキの乾燥性を早めるために添加される。近年は作業環境の改善を目的に芳香族成分を全く含まないか、またはその含有量が１重量％以下であるナフテン系溶剤、パラフィン系溶剤が好ましく使用される。市販品としては、例えば、０号ソルベントＬ、０号ソルベントＭ、０号ソルベントＨ、ＡＦ４号ソルベント、ＡＦ５号ソルベント、ＡＦ６号ソルベント、ＡＦ７号ソルベント〔以上、新日本石油(株)製〕等が挙げられる。 The hydrocarbon solvent (E) used here is not particularly limited, but a petroleum hydrocarbon solvent having a boiling point of 200 to 360 ° C. is particularly preferable. This is added in order to adjust the viscosity of the lithographic ink and accelerate the drying property of the lithographic ink. In recent years, naphthenic solvents and paraffinic solvents that do not contain any aromatic components or have a content of 1% by weight or less are preferably used for the purpose of improving the working environment. Examples of commercially available products include No. 0 Solvent L, No. 0 Solvent M, No. 0 Solvent H, AF No. 4 Solvent, AF No. 5 Solvent, AF No. 6 Solvent, AF No. 7 Solvent (manufactured by Nippon Oil Corporation). Can be mentioned.
また、前記植物油（ｃ′）としては、前記したヨウ素価１４０以上の植物油（ｃ）やヨウ素価１４０未満の植物油、例えば半乾性油である大豆油、大豆油脂肪酸等の変性物が挙げられるが、なかでもヨウ素価１４０以上の植物油（ｃ）であることが好ましい。ただし、近年の環境対応用平版インキワニスには大豆油の使用が好まれている。前記植物油（ｃ′）の使用量としては、光沢に優れ、ミスチング、過乳化等が発生しにくい平版インキが得られる点で、前記本発明の平版インキワニス用変性ロジンエステル樹脂から製造時に使用した植物油（ｃ）成分を除いた樹脂分１００重量部に対して、製造時に使用した植物油（ｃ）成分と前記植物油（ｃ′）の合計が４〜１００重量部となる範囲が好ましく、なかでも５〜８０重量部となる範囲がより好ましい。 Examples of the vegetable oil (c ′) include the above-described vegetable oil (c) having an iodine value of 140 or more, and vegetable oils having an iodine value of less than 140, such as soybean oil that is a semi-drying oil, soybean oil fatty acid and the like. Of these, vegetable oils (c) having an iodine value of 140 or more are preferred. However, the use of soybean oil is preferred for recent environmentally friendly lithographic ink varnishes. The vegetable oil (c ′) is used at the time of production from the modified rosin ester resin for lithographic ink varnish of the present invention in that a lithographic ink having excellent luster and less prone to misting and over-emulsification is obtained. The range in which the total of the vegetable oil (c) component and the vegetable oil (c ′) used during production is 4 to 100 parts by weight is preferable with respect to 100 parts by weight of the resin component excluding the component (c). A range of 80 parts by weight is more preferable.
さらに、前記ゲル化剤（Ｆ）としては、例えば、オクチル酸アルミニウム、ステアリン酸アルミニウム、オクチル酸ジルコニウム、アルミニウムトリイソプロポキサイド、アルミニウムジプロポキサイドモノアセチルアセトナート等が挙げられる。その使用量は、平版インキワニス用変性ロジンエステル樹脂を炭化水素系溶剤（Ｅ）に溶解させた溶液とゲル化剤（Ｆ）の合計１００重量部に対して、ゲル化剤（Ｆ）が０．１〜５重量部となる範囲が好ましく、０．２〜３重量部となる範囲がより好ましい。 Furthermore, examples of the gelling agent (F) include aluminum octylate, aluminum stearate, zirconium octylate, aluminum triisopropoxide, aluminum dipropoxide monoacetylacetonate, and the like. The amount used is such that the gelling agent (F) is 0.1% relative to a total of 100 parts by weight of the solution obtained by dissolving the modified rosin ester resin for lithographic ink varnish in the hydrocarbon solvent (E) and the gelling agent (F). A range of 1 to 5 parts by weight is preferable, and a range of 0.2 to 3 parts by weight is more preferable.
本発明の平版インキワニスの調製方法としては、例えば、温度計付き四つ口フラスコに本発明の平版インキワニス用変性ロジンエステル樹脂組成物４０〜８０重量部、前記植物油（ｃ′）０〜３０重量部、炭化水素溶剤（Ｅ）１０〜７０重量部等を仕込み、不活性ガス気流下、１８０〜２２０℃で溶解させ、オフ輪インキ用、枚葉インキ用、水無インキ用、新聞インキ用等の各種平版印刷用途に合わせてＢ型粘度計による粘度が５００〜８０００ｄＰａ・ｓ／２５℃になるように調整する方法が挙げられる。 As a method for preparing the lithographic ink varnish of the present invention, for example, 40 to 80 parts by weight of the modified rosin ester resin composition for a lithographic ink varnish of the present invention and 0 to 30 parts by weight of the vegetable oil (c ′) in a four-necked flask equipped with a thermometer. , 10 to 70 parts by weight of hydrocarbon solvent (E) is charged, dissolved in an inert gas stream at 180 to 220 ° C., for off-wheel ink, sheet-fed ink, waterless ink, newspaper ink, etc. The method of adjusting so that the viscosity by a B-type viscometer may be 500-8000 dPa * s / 25 degreeC according to various lithographic printing uses is mentioned.
本発明の平版インキワニスを用いた平版インキの調製方法としては、例えば、本発明の平版インキワニスと顔料、さらに必要により乾燥促進剤、その他の添加剤等を、三本ロールやジェットミル等の混練機を用いて混練りして、平版インキワニス中に顔料を分散させる方法が好ましい。 As a method for preparing a lithographic ink using the lithographic ink varnish of the present invention, for example, a lithographic ink varnish of the present invention and a pigment, and further, if necessary, a drying accelerator, other additives, etc., a kneader such as a three-roll or jet mill Is preferably used to disperse the pigment in the lithographic ink varnish.
前記顔料としては、各種の顔料がいずれも使用でき、例えばベンジジンイエロー、レーキレッドＣ、カーミン６Ｂ、フタロシアニン青、カーボン黒等が挙げられる。さらに無機顔料や、流動性調整剤等の体質顔料も用いることができる。 Various pigments can be used as the pigment, and examples thereof include benzidine yellow, lake red C, carmine 6B, phthalocyanine blue, and carbon black. Further, extender pigments such as inorganic pigments and fluidity modifiers can also be used.
以下に実施例と比較例を挙げて、本発明の平版インキワニス用変性ロジンエステル樹脂組成物と平版インキワニス、さらにこれらを用いた平版インキについて、より詳細に説明する。 The modified rosin ester resin composition for lithographic ink varnish and the lithographic ink varnish of the present invention, and further the lithographic ink using these will be described in more detail with reference to Examples and Comparative Examples below.
実施例１
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４２ＫＯＨｍｇ／ｇの反応混合物を得た後、亜麻仁油３１７ｇとペンタエリスリトール１６２ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを添加して撹拌・混合したところ、反応容器内の温度は１６１℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２０ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の亜麻仁油とペンタエリスリトールを含有した本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第１表（１）に示す。
Example 1
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOH mg / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and the acid value of 242 KOH mg / mg containing acid-modified gum rosin and unreacted gum rosin. After the reaction mixture of g was obtained, 317 g of linseed oil and 162 g of pentaerythritol were added and mixed, and further 1.5 g of magnesium oxide was added as a catalyst and stirred and mixed. As a result, the temperature in the reaction vessel was 161 ° C. It was. Next, the reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value became 20 KOH mg / g or less, thereby modifying the modified rosin ester. A modified rosin ester resin composition (R-1) for a lithographic ink varnish of the present invention containing a resin, unreacted linseed oil and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (R-1), the acid value, the weight average molecular weight, the viscosity and the solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 1 (1).
なお、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）の測定は、以下のように行った。
・酸価：ＪＩＳ Ｋ ５６０１−２−１（１９９９）に準拠して測定した。
・重量平均分子量：東ソー（株）製ゲルパーミエイションクロマトグラフィー（ＨＬＣ８０２０）を使用し、ポリスチレン換算の検量線から求めた。
・粘度：平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）をトルエンに溶解させて６０重量％のトルエン溶液とした後、ガードナー・ホルツ粘度管に詰めて、２５℃での粘度を求めた。
・溶剤溶解性（ＡＦソルベント７号溶解性）：平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）をＡＦソルベント７号〔新日本石油(株)製石油系溶剤〕に加熱下で溶解し、２５℃に冷却したときに溶液が白濁するまでに要したＡＦソルベント７号の前記変性ロジンエステル樹脂組成物（Ｒ−１）１ｇ当たりの容量（ｍｌ／ｇ）で示す。
The acid value, weight average molecular weight, viscosity, and solvent solubility (AF Solvent No. 7 solubility) were measured as follows.
Acid value: measured in accordance with JIS K 5601-2-1 (1999).
-Weight average molecular weight: It calculated | required from the calibration curve of polystyrene conversion using the gel permeation chromatography (HLC8020) by Tosoh Corporation.
-Viscosity: The modified rosin ester resin composition (R-1) for lithographic ink varnish was dissolved in toluene to give a 60 wt% toluene solution, and then packed in a Gardner-Holtz viscosity tube, and the viscosity at 25 ° C was determined. .
Solvent solubility (AF Solvent No. 7 solubility): The modified rosin ester resin composition (R-1) for lithographic ink varnish is dissolved in AF Solvent No. 7 (petroleum solvent manufactured by Nippon Oil Corporation) under heating. The volume (ml / g) per gram of the modified rosin ester resin composition (R-1) of AF Solvent 7 required until the solution became cloudy when cooled to 25 ° C.
実施例２
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２００℃にて３０分間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４０ＫＯＨｍｇ／ｇの反応混合物を得た後、亜麻仁油２４０ｇとペンタエリスリトール１６２ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを添加して撹拌・混合したところ、反応容器内の温度は１５５℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２６０℃まで昇温しながら反応させた後、さらに２６０℃で酸価が２５ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の亜麻仁油とペンタエリスリトールを含有した本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−２）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−２）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第１表（１）に示す。
Example 2
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOHmg / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 200 ° C. for 30 minutes under a nitrogen stream, and an acid value of 240 KOHmg / mg containing acid-modified gum rosin and unreacted gum rosin. After the reaction mixture of g was obtained, 240 g of linseed oil and 162 g of pentaerythritol were added and mixed, and further 1.5 g of magnesium oxide was added as a catalyst and stirred and mixed. As a result, the temperature in the reaction vessel became 155 ° C. It was. Next, the reaction vessel was heated and reacted while raising the temperature to 260 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 260 ° C. until the acid value was 25 KOH mg / g or less. A modified rosin ester resin composition (R-2) for a lithographic ink varnish of the present invention containing a resin, unreacted linseed oil and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (R-2), acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 1 (1).
実施例３
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２００℃にて３０分間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４０ＫＯＨｍｇ／ｇの反応混合物を得た後、亜麻仁油１６０ｇとペンタエリスリトール１６２ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを添加して撹拌・混合したところ、反応容器内の温度は１６０℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２６０℃まで昇温しながら反応させた後、さらに２６０℃で酸価が３０ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の亜麻仁油とペンタエリスリトールを含有した本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−３）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−３）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第１表（１）に示す。
Example 3
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOHmg / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 200 ° C. for 30 minutes under a nitrogen stream, and an acid value of 240 KOHmg / mg containing acid-modified gum rosin and unreacted gum rosin. After the reaction mixture of g was obtained, 160 g of linseed oil and 162 g of pentaerythritol were added and mixed, and further 1.5 g of magnesium oxide as a catalyst was added and stirred, and the temperature in the reaction vessel was 160 ° C. It was. Next, the reaction vessel was heated and reacted while raising the temperature to 260 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 260 ° C. until the acid value was 30 KOH mg / g or less. A modified rosin ester resin composition (R-3) for a lithographic ink varnish of the present invention containing a resin, unreacted linseed oil and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (R-3), acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 1 (1).
実施例４
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２００℃にて３０分間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４０ＫＯＨｍｇ／ｇの反応混合物を得た後、亜麻仁油２２２ｇと大豆油９５ｇとペンタエリスリトール１６２ｇを添加・混合し、更に触媒として酸化マグネシウム１．６ｇを添加して撹拌・混合したところ、反応容器内の温度は１４５℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２６０℃まで昇温しながら反応させた後、さらに２６０℃で酸価が２０ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の亜麻仁油と大豆油とペンタエリスリトールとを含有した本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−４）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−４）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第１表（２）に示す。
Example 4
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOHmg / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 200 ° C. for 30 minutes under a nitrogen stream, and an acid value of 240 KOHmg / mg containing acid-modified gum rosin and unreacted gum rosin. After the reaction mixture of g was obtained, 222 g of linseed oil, 95 g of soybean oil, and 162 g of pentaerythritol were added and mixed, and 1.6 g of magnesium oxide as a catalyst was further added and stirred and mixed. It became 145 degreeC. Next, the reaction vessel was heated and reacted while raising the temperature to 260 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 260 ° C. until the acid value was 20 KOH mg / g or less. A modified rosin ester resin composition (R-4) for a lithographic ink varnish of the present invention containing a resin, unreacted linseed oil, soybean oil and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (R-4), the acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 1 (2).
実施例５
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４２ＫＯＨｍｇ／ｇの反応混合物を得た後、亜麻仁油１５７ｇと桐油１６０ｇとペンタエリスリトール１６２ｇを添加・混合し、更に触媒として酸化マグネシウム１．６ｇを添加して撹拌・混合したところ、反応容器内の温度は１５８℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２０ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の亜麻仁油と大豆油とペンタエリスリトールとを含有した本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−５）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−５）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第１表（２）に示す。
Example 5
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOH mg / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and the acid value of 242 KOH mg / mg containing acid-modified gum rosin and unreacted gum rosin. After adding 157 g of linseed oil, 160 g of tung oil, and 162 g of pentaerythritol, 1.6 g of magnesium oxide was added as a catalyst and stirred and mixed. The temperature in the reaction vessel was 158. It became ℃. Next, the reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value became 20 KOH mg / g or less, thereby modifying the modified rosin ester. A modified rosin ester resin composition (R-5) for a lithographic ink varnish of the present invention containing a resin, unreacted linseed oil, soybean oil and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (R-5), the acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent 7 solubility) were measured. The results are shown in Table 1 (2).
実施例６
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇと無水マレイン酸７５．７ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２３５ＫＯＨｍｇ／ｇの反応混合物を得た後、亜麻仁油３１７ｇとペンタエリスリトール１５２．５ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを撹拌・混合したところ、反応容器内の温度は１５２℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２０ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の亜麻仁油とペンタエリスリトールを含有した本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−６）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−６）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第１表（２）に示す。
Example 6
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOH mg / g) and 75.7 g of maleic anhydride are added, and the mixture is heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and contains acid-modified gum rosin and unreacted gum rosin. After obtaining a reaction mixture having a value of 235 KOH mg / g, 317 g of linseed oil and 152.5 g of pentaerythritol were added and mixed, and 1.5 g of magnesium oxide was further stirred and mixed as a catalyst. It became. Next, the reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value became 20 KOH mg / g or less, thereby modifying the modified rosin ester. A modified rosin ester resin composition (R-6) for lithographic ink varnish of the present invention containing a resin, unreacted linseed oil and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (R-6), the acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 1 (2).
比較例１
反応容器中に、ガムロジン（酸価１６５ｍｇＫＯＨ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４５ＫＯＨｍｇ／ｇの反応混合物を得た後、大豆油３１７ｇとペンタエリスリトール１７０ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを添加して撹拌・混合したところ、反応容器内の温度は１５５℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２５ＫＯＨｍｇ／ｇ以下になるまで反応させて、比較用の平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−１）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−１）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第２表に示す。
Comparative Example 1
Into a reaction vessel, 1000 g of gum rosin (acid value 165 mgKOH / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and an acid value of 245 KOHmg / mg containing acid-modified gum rosin and unreacted gum rosin. After the reaction mixture of g was obtained, 317 g of soybean oil and 170 g of pentaerythritol were added and mixed, and 1.5 g of magnesium oxide was further added as a catalyst, followed by stirring and mixing. As a result, the temperature in the reaction vessel became 155 ° C. It was. Next, this reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value was 25 KOH mg / g or less. A modified rosin ester resin composition (CR-1) for lithographic ink varnish was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (CR-1), the acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 2.
比較例２
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１０６ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２４２ＫＯＨｍｇ／ｇの反応混合物を得た後、ペンタエリスリトール２４３ｇを添加・混合し、更に触媒として酸化マグネシウム１．６ｇを添加して撹拌・混合したところ、反応容器内の温度は１８５℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２５ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応のペンタエリスリトールを含有した比較用の平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−２）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−２）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第２表に示す。
Comparative Example 2
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOH mg / g) and 106 g of fumaric acid were added, and the mixture was heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and the acid value of 242 KOH mg / mg containing acid-modified gum rosin and unreacted gum rosin. After the reaction mixture of g was obtained, 243 g of pentaerythritol was added and mixed, and 1.6 g of magnesium oxide as a catalyst was further added and stirred and mixed. As a result, the temperature in the reaction vessel became 185 ° C. Next, the reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value was 25 KOH mg / g or less. A comparative modified rosin ester resin composition (CR-2) for lithographic ink varnish containing a resin and unreacted pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (CR-2), acid value, weight average molecular weight, viscosity, and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 2.
比較例３
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇと無水マレイン酸１１１ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２６３ＫＯＨｍｇ／ｇの反応混合物を得た後、１，８−オクタンジオール１９４ｇとペンタエリスリトール９７ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを添加して撹拌・混合したところ、反応容器内の温度は１５８℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２５ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の１，８−オクタンジオールとペンタエリスリトールとを含有した比較用の平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−３）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−３）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号）を測定した。結果を第２表に示す。
Comparative Example 3
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOHmg / g) and 111 g of maleic anhydride were added, and the mixture was heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and the acid value of 263 KOHmg containing acid-modified gum rosin and unreacted gum rosin. / G of 194 g of 1,8-octanediol and 97 g of pentaerythritol were added and mixed, and 1.5 g of magnesium oxide was added as a catalyst and stirred and mixed. Was 158 ° C. Next, the reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value was 25 KOH mg / g or less. A comparative modified rosin ester resin composition (CR-3) for lithographic ink varnish containing a resin, unreacted 1,8-octanediol and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (CR-3), the acid value, weight average molecular weight, viscosity and solvent solubility (AF Solvent No. 7) were measured. The results are shown in Table 2.
比較例４
反応容器中に、ガムロジン（酸価１６５ＫＯＨｍｇ／ｇ）１０００ｇとフマル酸１３２ｇを投入し、窒素気流下で２２０℃にて１時間加熱攪拌して酸変性ガムロジンと未反応ガムロジンを含有する酸価２６０ＫＯＨｍｇ／ｇの反応混合物を得た後、１，８−オクタンジオール１９４ｇとペンタエリスリトール９７ｇを添加・混合し、更に触媒として酸化マグネシウム１．５ｇを添加して撹拌・混合したところ、反応容器内の温度は１７６℃となった。次いで、この反応容器を加熱し、昇温速度３０℃／ｈｒで２７０℃まで昇温しながら反応させた後、さらに２７０℃で酸価が２５ＫＯＨｍｇ／ｇ以下になるまで反応させて、変性ロジンエステル樹脂と未反応の１，８−オクタンジオールとペンタエリスリトールとを含有した比較用の平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−４）を得た。得られた平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−４）について、酸価、重量平均分子量、粘度および溶剤溶解性（ＡＦソルベント７号溶解性）を測定した。結果を第２表に示す。
Comparative Example 4
In a reaction vessel, 1000 g of gum rosin (acid value: 165 KOH mg / g) and 132 g of fumaric acid were added, and the mixture was heated and stirred at 220 ° C. for 1 hour under a nitrogen stream, and the acid value of 260 KOH mg / mg containing acid-modified gum rosin and unreacted gum rosin. After obtaining 194 g of the reaction mixture, 194 g of 1,8-octanediol and 97 g of pentaerythritol were added and mixed, and 1.5 g of magnesium oxide as a catalyst was added and stirred and mixed. It became 176 degreeC. Next, the reaction vessel was heated and reacted while raising the temperature to 270 ° C. at a rate of temperature rise of 30 ° C./hr, and then further reacted at 270 ° C. until the acid value was 25 KOH mg / g or less. A comparative modified rosin ester resin composition (CR-4) for lithographic ink varnish containing a resin, unreacted 1,8-octanediol and pentaerythritol was obtained. About the obtained modified rosin ester resin composition for lithographic ink varnish (CR-4), the acid value, weight average molecular weight, viscosity and solvent solubility (AF solvent No. 7 solubility) were measured. The results are shown in Table 2.
実施例７〜１２および比較例５
攪拌機、水分離冷却管、温度計付き四つ口フラスコに、平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）〜（Ｒ−６）または（ＣＲ−１）５６重量部と、亜麻仁油９重量部と、ＡＦソルベント５号〔新日本石油(株)製石油系非芳香族溶剤〕３０重量部を投入し、窒素ガスを吹き込みながら昇温し、２００℃で攪拌しながら３０分間保温して粘度を１，０００〜２，０００ｄＰａ・ｓの範囲内に調整した。その後１６０℃に冷却し、ゲル化剤〔ホープ製薬(株)製Ｃｈｅｌｏｐｅ−Ａｌ〕１．０重量部を添加した後、２００℃に昇温し、６０分間保温して本発明の平版インキワニス（Ｖ−１）〜（Ｖ−６）と比較用の平版インキワニス（ＣＶ−１）を得、それぞれについて２５℃におけるＢ型粘度計による粘度を測定すると共に、レオメータ（Ｒｅｏｍｅｔｒｉｃｓ社製Ｓｔｒｅｓｓ Ｒｈｅｏｍｅｔｅｒ）を用いた粘弾性測定（温度＝２５℃、試験方法＝Ｆｒｅｑｕｅｎｃｙ Ｓｗｅｅｐ、測定様式＝パラレルプレート、Ｓｔｒａｉｎ＝２０％）により、周波数が１ｒａｄ／ｓｅｃの時と１００ｒａｄ／ｓｅｃの時のＥｔａ＊とＴａｎδを求めた。それぞれの結果を第３表（１）〜（２）と第４表に示す。
Examples 7-12 and Comparative Example 5
In a four-necked flask equipped with a stirrer, a water separation condenser, and a thermometer, 56 parts by weight of modified rosin ester resin composition (R-1) to (R-6) or (CR-1) for lithographic ink varnish, and linseed oil 9 Part by weight and 30 parts by weight of AF Solvent No. 5 [Shin Nippon Oil Co., Ltd. petroleum-based non-aromatic solvent] are added, the temperature is increased while blowing nitrogen gas, and the temperature is kept at 200 ° C. for 30 minutes while stirring. The viscosity was adjusted within the range of 1,000 to 2,000 dPa · s. Thereafter, the mixture was cooled to 160 ° C., 1.0 part by weight of a gelling agent [Chelope-Al, manufactured by Hope Pharmaceutical Co., Ltd.] was added, the temperature was raised to 200 ° C., and the mixture was kept warm for 60 minutes. -1) to (V-6) and a comparative lithographic ink varnish (CV-1) were obtained, and the viscosity of each was measured with a B-type viscometer at 25 ° C., and a rheometer (Reometrics Stress Rheometer) was used. By measuring viscoelasticity (temperature = 25 ° C., test method = Frequency Sweep, measurement mode = parallel plate, strain = 20%), Eta * and Tan δ at a frequency of 1 rad / sec and 100 rad / sec were obtained. The respective results are shown in Tables (1) to (2) and Table 4.
なお、実施例７〜１２と比較例５において用いた平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）〜（Ｒ−６）と（ＣＲ−１）の仕込み量５６重量部は、植物油変性量を勘案し樹脂分〔実施例１〜６と比較例１で得た平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）〜（Ｒ−６）と（ＣＲ−１）の５６重量部から、製造時に使用した亜麻仁油、大豆油等の植物油成分１１重量部を除いた樹脂成分〕が、後記する比較例６〜８において用いた植物油成分を含有しない比較用の平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−２）〜（ＣＲ−４）の仕込み量４５重量部と同量の４５重量部になる様に調整した。さらに、亜麻仁油の仕込み量９重量部も、前記変性ロジンエステル樹脂組成物（Ｒ−１）〜（Ｒ−６）と（ＣＲ−１）中に含有されている亜麻仁油、大豆油等の植物油成分１１重量部を勘案してワニス系全体で植物油成分が、後記する比較例６〜８において用いた植物油成分２０重量部と同量の２０重量部になる様に調整した。 In addition, 56 weight part of preparation amounts of the modified rosin ester resin compositions (R-1) to (R-6) and (CR-1) for lithographic ink varnish used in Examples 7 to 12 and Comparative Example 5 were modified with vegetable oil. Resin content in consideration of the amount [from 56 parts by weight of modified rosin ester resin compositions for lithographic ink varnish (R-1) to (R-6) and (CR-1) obtained in Examples 1 to 6 and Comparative Example 1 The resin component excluding 11 parts by weight of vegetable oil components such as linseed oil and soybean oil used at the time of manufacture] does not contain the vegetable oil component used in Comparative Examples 6 to 8 to be described later. It adjusted so that it might become 45 weight part of the same amount as preparation amount 45 weight part of composition (CR-2)-(CR-4). Furthermore, 9 parts by weight of linseed oil is also added to vegetable oils such as linseed oil and soybean oil contained in the modified rosin ester resin compositions (R-1) to (R-6) and (CR-1). In consideration of 11 parts by weight of the component, the vegetable oil component was adjusted to 20 parts by weight in the same amount as the vegetable oil component used in Comparative Examples 6 to 8 described later in the entire varnish system.
比較例６〜８
本発明の平版インキワニス用変性ロジンエステル樹脂組成物（Ｒ−１）〜（Ｒ−６）および（ＣＲ−１）５６重量部の代わりに、比較用の平版インキワニス用変性ロジンエステル樹脂組成物（ＣＲ−２）〜（ＣＲ−４）４５重量部を用い、亜麻仁油の使用量を２０重量部に変更した以外は実施例６〜１２および比較例５と同様にして、比較用の平版インキワニス（ＣＶ−２）〜（ＣＶ−４）を得、次いで同様にして、それぞれの粘度と、周波数が１ｒａｄ／ｓｅｃの時と１００ｒａｄ／ｓｅｃの時のＥｔａ＊とＴａｎδを求めた。それぞれの結果を第４表に示す。
Comparative Examples 6-8
Modified rosin ester resin composition for lithographic ink varnish for comparison (CR-1) instead of 56 parts by weight of modified rosin ester resin composition for lithographic ink varnish (R-1) to (R-6) and (CR-1) of the present invention -2) to (CR-4) 45 parts by weight, and a lithographic ink varnish for comparison (CV) in the same manner as in Examples 6 to 12 and Comparative Example 5 except that the amount of linseed oil was changed to 20 parts by weight. -2) to (CV-4) were obtained, and in the same manner, the respective viscosities, Eta * and Tan δ when the frequency was 1 rad / sec and 100 rad / sec were obtained. Each result is shown in Table 4.
試験例１〜６および比較試験例１〜４
実施例７〜１２および比較例５〜８で得られた平版インキワニス（Ｖ−１）〜（Ｖ−６）および（ＣＶ−１）〜（ＣＶ−４）のそれぞれ６０重量部に対して、紅顔料としてブリリアントカーミン６Ｂ−２３３〔大日本インキ化学工業(株)製〕１７重量部をそれぞれ加えて三本ロールで混練して顔料を分散させた後、ＡＦソルベント５号と追加の平版インキワニスを合計で２３重量部（ＡＦソルベント５号５〜２３重量部、追加の平版インキワニス０〜１８重量部、第５表および第６表参照）と、ドライヤーとしてのナフテン酸コバルト１重量部を添加してさらに混練して、タック値が９．０〜９．５／２５℃の平版インキ（Ｉ−１）〜（Ｉ−６）と（ＣＩ−１）〜（ＣＩ−４）を得た。得られた平版インキの特性（タック値、流動性、乾燥時間、光沢、ミスチング、最大乳化率）を以下のようにして測定または評価した。その結果を第５表（１）〜（２）および第６表に示す。
Test Examples 1-6 and Comparative Test Examples 1-4
With respect to 60 parts by weight of each of the lithographic ink varnishes (V-1) to (V-6) and (CV-1) to (CV-4) obtained in Examples 7 to 12 and Comparative Examples 5 to 8, red After adding 17 parts by weight of brilliant carmine 6B-233 (Dainippon Ink Chemical Co., Ltd.) as a pigment and kneading with three rolls to disperse the pigment, AF Solvent No. 5 and additional lithographic ink varnish are combined And 23 parts by weight (5 to 23 parts by weight of AF solvent 5, additional lithographic ink varnish 0 to 18 parts by weight, see Tables 5 and 6) and 1 part by weight of cobalt naphthenate as a dryer. By kneading, lithographic inks (I-1) to (I-6) and (CI-1) to (CI-4) having a tack value of 9.0 to 9.5 / 25 ° C. were obtained. The properties (tack value, fluidity, drying time, gloss, misting, maximum emulsification rate) of the obtained lithographic ink were measured or evaluated as follows. The results are shown in Tables 5 (1) to (2) and Table 6.
・タック値：デジタルインコメーター〔東洋精機(株)製〕を用い、ロール温度３２℃、ロール回転数４００ｒｐｍ、室温２５℃の条件で、ＪＩＳ Ｋ ５７０１（２０００）に準拠して、平版インキを投入してから６０秒後のタック値を求めた。 ・ Tack value: A lithographic ink was introduced in accordance with JIS K 5701 (2000) using a digital incometer (manufactured by Toyo Seiki Co., Ltd.) at a roll temperature of 32 ° C., a roll rotation speed of 400 rpm, and a room temperature of 25 ° C. Then, the tack value 60 seconds after was determined.
・流動性：平行板粘度計〔東洋精機(株)製〕を用い、室温２５℃でＪＩＳ Ｋ ５７０１（２０００）に準拠して、平版インキを投入してから６０秒後のインキの広がり（直径：ｍｍ）を求めた。 -Fluidity: Ink spread (diameter after 60 seconds from introduction of lithographic ink in accordance with JIS K 5701 (2000) using a parallel plate viscometer (manufactured by Toyo Seiki Co., Ltd.) at room temperature of 25 ° C. : Mm).
・乾燥時間：大蔵省印刷局朝陽会式乾燥方法に準拠してインキ付着が確認できなくなるまでの時間を求めた。室温２５℃、湿度６０％ＲＨの条件下で朝陽会式乾燥試験器を用い、硫酸紙に平版インキを展色して上質紙を上に重ね、ドラムに巻き付け押圧車を上に載せてドラムを回転させて、インキの跡がつかなくなるまでの時間を求めた。 -Drying time: The time until ink adhesion could not be confirmed in accordance with the Ministry of Finance Printing Bureau Chaoyangkai drying method was determined. Using a Chaoyang-style drying tester under conditions of room temperature 25 ° C. and humidity 60% RH, lithographic ink is developed on sulfuric acid paper, high quality paper is stacked on top, wound around a drum, and a pressing wheel is placed on the drum. It was rotated and the time until the ink trace was not found was determined.
・光沢：片面アートコート紙〔王子製紙(株)製〕のコート面上に、回転式インキ展色機ＲＩ−２〔（株）明製作所製〕２分割ロールで平版インキ０．１５ｍｌ展色し、１００℃のオーブンを１０秒間通過させ、１日間放置した後の展色された平版インキの光沢値を、光沢計ＶＧ−２０００〔日本電色工業(株)製〕を用いて、反射角６０°、室温２５℃の条件で測定した。 ・ Gloss: On a coated surface of single-sided art-coated paper [Oji Paper Co., Ltd.], 0.15 ml of lithographic ink was developed with a rotary ink color developing machine RI-2 (manufactured by Akira Seisakusho Co., Ltd.) with two split rolls. The gloss value of the developed lithographic ink after passing through an oven at 100 ° C. for 10 seconds and leaving it to stand for 1 day was measured using a gloss meter VG-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) with a reflection angle of 60 Measured under the conditions of ° C and room temperature of 25 ° C.
・ミスチング：デジタルインコメーター〔東洋精機(株)製〕に平版インキ１．３１ｍｌを投入し、室温２５℃、ロール温度４２℃、１２００ｒｐｍで１０分間ロールを回転させた後のロールの下面と前面に配置した白色紙への平版インキも飛散状態を観察し、インキの飛散がないか、あってもほんの僅かで実用上全く問題のないものを○、インキの飛散が若干あるものを△、インキの飛散が著しいものを×と評価した。 ・ Missing: 1.31 ml of lithographic ink is put into a digital incometer (manufactured by Toyo Seiki Co., Ltd.), and the roll is rotated on the bottom and front of the roll after rotating the roll at room temperature 25 ° C., roll temperature 42 ° C., 1200 rpm for 10 minutes. Observe the scattered state of the lithographic ink on the white paper placed, ○ if there is no ink scattering, or if there is only a little and no practical problem at all, △ if there is a little ink scattering, △ The thing with remarkable scattering was evaluated as x.
・最大乳化率：リソトロニック乳化試験機〔独国ノボコントロール(Ｎｏｖｏｃｏｎｔｒｏｌ)社製〕に平版インキ２５ｇを投入し、４０℃に昇温した後、攪拌機回転数１２００ｒｐｍの攪拌下で攪拌トルクを測定しながら蒸留水を４ｍｌ／分の割合で添加し、添加した水分が飽和量に達した時点（インキと水が分離して攪拌トルクが低下を開始した時点）の水分量を最大乳化率（重量％）として求めた。 ・ Maximum emulsification rate: 25 g of lithographic ink was put into a lithotronic emulsification tester (manufactured by Novocontrol, Germany), heated to 40 ° C., and then the stirring torque was measured with stirring at a stirring speed of 1200 rpm. While adding distilled water at a rate of 4 ml / min, the water content at the time when the added water reaches the saturation amount (when the ink and water are separated and the stirring torque starts to decrease) is the maximum emulsification rate (wt% ).
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