JP2011225827A - Binder for publication-grade gravure printing ink and publication-grade gravure printing ink - Google Patents
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Abstract
Description
本発明は出版グラビア印刷インキ用バインダーおよび出版グラビア印刷インキに関する。 The present invention relates to a publication gravure printing ink binder and publication gravure printing ink.
出版グラビア印刷インキは雑誌や週刊誌、広告その他のメディアに使用されており、そのバインダーとしては従来、ロジン類と金属化合物との反応生成物を含有する樹脂組成物が賞用されている。また、近年はインキの転移性や乾燥性、インキ皮膜の光沢といったバインダー性能の更なる向上が要求されており、原料面より種々の改良がなされている。例えば本出願人は、α，β−エチレン性不飽和カルボン酸変性ロジン、多価アルコール、および金属化合物からなる樹脂酸部分エステル化物を大豆油脂肪酸等で変性してなる、高分子量であり且つ架橋状の樹脂組成物を用いたバインダーを提案している（特許文献１を参照）。 Publication gravure printing inks are used in magazines, weekly magazines, advertisements and other media, and as their binders, resin compositions containing reaction products of rosins and metal compounds have been conventionally used. In recent years, further improvements in binder performance such as ink transferability and drying properties and gloss of ink film have been demanded, and various improvements have been made from the raw material side. For example, the present applicant has a high molecular weight and cross-linked product obtained by modifying a resin acid partial esterified product composed of α, β-ethylenically unsaturated carboxylic acid-modified rosin, a polyhydric alcohol, and a metal compound with soybean oil fatty acid or the like. A binder using a resin composition in the form of a resin is proposed (see Patent Document 1).
ところで、従来のバインダーには主にトルエン等の芳香族系有機溶剤が使用されていたが、印刷物の臭気などの理由からメチルシクロヘキサン等の脂環族系有機溶剤が利用される傾向にある。しかし、脂環族系有機溶剤は一般に架橋した高分子量の樹脂の溶解力に劣るため、バインダー中に不溶物が発生しやすく、また、そうしたバインダーは性能面でも劣る傾向にある。よって、有機溶剤を芳香族系のものから脂環族系のものに置換する場合には、原料面で適切な樹脂設計を行う必要がある。 By the way, although aromatic organic solvents, such as toluene, were mainly used for the conventional binder, there exists a tendency for alicyclic organic solvents, such as methylcyclohexane, to be utilized from reasons, such as the odor of printed matter. However, alicyclic organic solvents are generally poor in the solubility of cross-linked high molecular weight resins, so that insolubles are easily generated in the binder, and such binders tend to be inferior in performance. Therefore, when the organic solvent is replaced from an aromatic one to an alicyclic one, it is necessary to design an appropriate resin in terms of raw materials.
そこで本出願人は、例えば特許文献２において、α，β−エチレン性不飽和カルボン酸で変性したロジンと金属化合物との反応物が脂環族系有機溶剤に溶解し、しかも良好なバインダー性能を発揮することを提案したが、昨今は高速印刷化や印刷物に対する高品質化に対する要求が強まっており、性能の更なる向上が求められていた。 Therefore, the present applicant, for example, in Patent Document 2, a reaction product of a rosin modified with an α, β-ethylenically unsaturated carboxylic acid and a metal compound is dissolved in an alicyclic organic solvent, and good binder performance is obtained. Although it has been proposed to demonstrate this, recently there has been an increasing demand for high-speed printing and high quality printing, and further improvement in performance has been demanded.
本発明は、脂環族有機溶剤の均一な溶液として使用可能であり、かつ、インキの転移性やインキ皮膜の乾燥性、光沢等のバインダー性能をバランスよく発揮できる出版グラビア印刷インキ用バインダーを提供することを主たる課題とする。 The present invention provides a binder for publishing gravure printing ink that can be used as a uniform solution of an alicyclic organic solvent and can exhibit a good balance of ink transfer properties, ink film drying properties, gloss and other binder properties. The main task is to do.
本発明者は鋭意検討を重ねた結果、特定の原料を使用して得られる樹脂組成物により前記課題を達成できることを見出した。 As a result of intensive studies, the present inventor has found that the above problems can be achieved by a resin composition obtained using a specific raw material.
すなわち本発明は、重合ロジン（ａ１）を５〜３４重量％含有するロジン類（Ａ）、脂肪酸類（Ｂ）、炭素数１０〜２０のアルキル基を有するモノアミンおよび／または炭素数１０〜２０のアルケニル基を有するモノアミンを含むアミン類（Ｃ）、ならびに金属化合物（Ｄ）を脂環族有機溶剤（Ｅ）中で造塩反応させてなる樹脂組成物を用いた、出版グラビア印刷インキ用バインダー；当該出版グラビア印刷インキ用バインダーを用いてなる、出版グラビア印刷インキ、に関する。 That is, the present invention relates to rosins (A), fatty acids (B) containing 5 to 34% by weight of polymerized rosin (a1), monoamines having an alkyl group having 10 to 20 carbon atoms and / or having 10 to 20 carbon atoms. A binder for publishing gravure printing inks using a resin composition obtained by salt-forming an amine (C) containing a monoamine having an alkenyl group and a metal compound (D) in an alicyclic organic solvent (E); The present invention relates to a publishing gravure printing ink using the publishing gravure printing ink binder.
本発明の出版グラビア印刷インキ用バインダーは脂環族有機溶剤の均一な溶液として利用できる。また、顔料分散性や溶剤脱離性等に優れるため、インキの転移性やインキ皮膜の乾燥性、光沢等において、芳香族系有機溶剤を使用した従来品に匹敵する出版グラビア印刷インキを提供できる。 The binder for publication gravure printing ink of the present invention can be used as a uniform solution of an alicyclic organic solvent. In addition, because of excellent pigment dispersibility and solvent detachability, it is possible to provide publication gravure printing inks that are comparable to conventional products using aromatic organic solvents in terms of ink transferability, ink film drying properties, and gloss. .
また、インキは転移性が良好であることから、例えば、印刷版胴から基材への転移が完了する前にインキが固化してしまう版かぶり現象が減少する。他にもインキ皮膜の乾燥性に優れることから、例えば、多色刷において下塗りインキ皮膜が上塗インキの印刷版胴にとられてしまうバックトラップ現象や、印刷物のブロッキング、裏移り等が低減する。また、皮膜の光沢が良好であること等から、今日の高い品質要求に合致した印刷物を提供することが可能になる。 In addition, since the ink has good transferability, for example, a plate fog phenomenon in which the ink is solidified before the transfer from the printing plate cylinder to the substrate is completed is reduced. In addition, since the drying property of the ink film is excellent, for example, the back trap phenomenon that the undercoat ink film is taken on the printing plate cylinder of the overcoat ink in multi-color printing, the blocking of the printed matter, and the back-off are reduced. In addition, since the gloss of the film is good, it is possible to provide a printed matter that meets today's high quality requirements.
本発明のバインダーは、重合ロジン（ａ１）（以下、（ａ１）成分という）を５〜３４重量％含有するロジン類（Ａ）（以下、（Ａ）成分という）、脂肪酸類（Ｂ）（以下、（Ｂ）成分という）、炭素数１０〜２０のアルキル基を有するモノアミンおよび／または炭素数１０〜２０のアルケニル基を有するモノアミンを含むアミン類（Ｃ）（以下、（Ｃ）成分という）、ならびに金属化合物（Ｄ）（以下、（Ｄ）成分という）を脂環族有機溶剤（Ｅ）（以下、（Ｅ）成分という）中で造塩反応させてなる樹脂組成物を用いたものである。 The binder of the present invention comprises rosins (A) (hereinafter referred to as (A) component), fatty acids (B) (hereinafter referred to as component (A)) containing 5 to 34% by weight of polymerized rosin (a1) (hereinafter referred to as component (a1)). , (B) component), amines (C) (hereinafter referred to as (C) component) containing a monoamine having an alkyl group having 10 to 20 carbon atoms and / or a monoamine having an alkenyl group having 10 to 20 carbon atoms, In addition, a resin composition obtained by subjecting a metal compound (D) (hereinafter referred to as “component (D)”) to a salt formation reaction in an alicyclic organic solvent (E) (hereinafter referred to as “component (E)”) is used. .
（ａ１）成分としては、トール油ロジン、ガムロジン、ウッドロジン等の原料ロジン類を公知の手段で重合処理したものが挙げられ、各種のものを特に制限なく使用できる。また、（Ａ）成分における（ａ１）成分の含有量は通常５〜３４重量％、好ましくは１０〜２５重量％であり、５重量％未満であるとインキ皮膜の光沢が、３４重量％を超えると特にインキの転移性と乾燥性が不十分になる。なお、（ａ１）成分の物性は特に限定されないが、通常、酸価（ＪＩＳ Ｋ ００７０）が１５０〜２００程度である。 Examples of the component (a1) include those obtained by polymerizing raw material rosins such as tall oil rosin, gum rosin, and wood rosin by known means, and various types can be used without particular limitation. Further, the content of the component (a1) in the component (A) is usually 5 to 34% by weight, preferably 10 to 25% by weight, and if it is less than 5% by weight, the gloss of the ink film exceeds 34% by weight. In particular, the transferability and drying properties of the ink are insufficient. In addition, although the physical property of (a1) component is not specifically limited, Usually, an acid value (JISK0070) is about 150-200.
（Ａ）成分には、特にインキ皮膜の乾燥性の観点より、さらにα，β−エチレン性不飽和カルボン酸変性ロジン（ａ２）（以下、（ａ２）成分という）を含ませることができる。該α，β−エチレン性不飽和カルボン酸としては、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、シトラコン酸等のα，β−エチレン性不飽和ジカルボン酸や、アクリル酸、メタクリル酸等のα，β−エチレン性不飽和モノカルボン酸が挙げられる。また、（ａ２）成分をなすロジンとしては前記した原料ロジン類が挙げられる。（ａ２）成分は、当該原料ロジン類と前記α，β−エチレン性不飽和カルボン酸とを通常１８０〜２５０℃程度の温度でディールス・アルダー反応させることにより得られる。なお、（Ａ）成分における（ａ２）成分の含有量は通常９４〜６７重量％程度、好ましくは９０〜７５重量％である。また、（ａ２）成分の物性は特に限定されないが、通常、酸価（ＪＩＳ Ｋ ００７０）が１８０〜３５０程度である。 The component (A) can further contain α, β-ethylenically unsaturated carboxylic acid-modified rosin (a2) (hereinafter referred to as component (a2)), particularly from the viewpoint of the drying property of the ink film. Examples of the α, β-ethylenically unsaturated carboxylic acid include α, β-ethylenically unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid, Examples include α, β-ethylenically unsaturated monocarboxylic acids such as methacrylic acid. Examples of the rosin constituting the component (a2) include the raw material rosins described above. The component (a2) is obtained by subjecting the raw material rosins and the α, β-ethylenically unsaturated carboxylic acid to a Diels-Alder reaction usually at a temperature of about 180 to 250 ° C. In addition, content of (a2) component in (A) component is about 94 to 67 weight% normally, Preferably it is 90 to 75 weight%. The physical properties of the component (a2) are not particularly limited, but usually the acid value (JIS K 0070) is about 180 to 350.
なお、（Ａ）成分とともに、必要に応じて、前記原料ロジン類、その不均化物、および水素化物等を併用できる。その使用量は通常、（Ａ）成分１００重量部に対して０〜５０重量部程度、具体的には０〜２５重量部である。 In addition to the component (A), the raw material rosins, their disproportionates, hydrides, and the like can be used in combination as necessary. The amount of use is usually about 0 to 50 parts by weight, specifically 0 to 25 parts by weight per 100 parts by weight of component (A).
（Ｂ）成分としては、各種公知の脂肪酸類を特に制限なく使用できる。具体的には、炭素数６〜２０程度（好ましくは１４〜１８）のアルキル基を有するモノカルボン酸および／または炭素数６〜２０程度（好ましくは１４〜１８）のアルケニル基を有するモノカルボン酸を含む脂肪酸類が好ましい。アルキル基およびアルケニル基の炭素数が６以上であることにより特にインキ皮膜の光沢が、また、２０以下であることにより特にインキ皮膜の乾燥性が良好になる傾向にある。なお、当該脂肪酸類における該モノカルボン酸の含有量は特に制限されないが、通常８５重量％以上、好ましくは９０〜９８重量％程度である。また、前記「炭素数」は、各モノカルボン酸が有するアルキル基またはアルケニル基一つについての炭素数を意味する。 As the component (B), various known fatty acids can be used without particular limitation. Specifically, a monocarboxylic acid having an alkyl group having about 6 to 20 carbon atoms (preferably 14 to 18) and / or an alkenyl group having about 6 to 20 carbon atoms (preferably 14 to 18). Fatty acids containing are preferred. When the alkyl group and the alkenyl group have 6 or more carbon atoms, the glossiness of the ink film tends to be particularly good, and when it is 20 or less, the drying property of the ink film tends to be particularly good. In addition, the content of the monocarboxylic acid in the fatty acids is not particularly limited, but is usually 85% by weight or more, preferably about 90 to 98% by weight. The “carbon number” means the number of carbon atoms per alkyl group or alkenyl group of each monocarboxylic acid.
当該脂肪酸類の具体例としては、大豆油脂肪酸、トール油脂肪酸、ヤシ油脂肪酸、亜麻仁油脂肪酸等が挙げられる。これらの中でも、バインダー性能のバランスを考慮すると大豆油脂肪酸および／またはトール油脂肪酸が、特にインキの転移性を考慮すると大豆油脂肪酸が好ましい。また、該脂肪酸類をなすモノカルボン酸のうち、前記アルキル基を有するものとしては、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、アラキジン酸等が、また、前記アルケニル基を有するものとしては、パルミトレイン酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、エレオステアリン酸、アラキドン酸等が挙げられる。 Specific examples of the fatty acids include soybean oil fatty acid, tall oil fatty acid, coconut oil fatty acid, linseed oil fatty acid and the like. Among these, soybean oil fatty acid and / or tall oil fatty acid are preferable in consideration of the balance of binder performance, and soybean oil fatty acid is particularly preferable in consideration of ink transferability. Among the monocarboxylic acids constituting the fatty acids, those having the alkyl group include enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearin Examples of the acid, arachidic acid, etc. having the alkenyl group include palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid and the like.
なお、（Ｂ）成分とともに、必要に応じ、ダイマー酸やトリマー酸などのジカルボン酸を含む脂肪酸類を併用してもよい。 In addition to (B) component, you may use together fatty acids containing dicarboxylic acids, such as a dimer acid and a trimer acid, as needed.
（Ｃ）成分は、炭素数１０〜２０（好ましくは１６〜１９）のアルキル基を有するモノアミンおよび／または炭素数１０〜２０（好ましくは１６〜１９）のアルケニル基を有するモノアミンを含むアミン類であれば、各種公知のものを特に制限なく使用できる。アルキル基およびアルケニル基の炭素数が１０未満であると特にインキ皮膜の転移性や乾燥性が、また、２０を超えると特にインキ皮膜の乾燥性や光沢が不十分となる。なお、当該アミン類中の該モノアミンの含有量は特に制限されないが、通常６５重量％以上、好ましくは７０〜９９重量％程度である。また、当該アルキル基およびアルケニル基には活性水素基（水酸基、カルボキシル基等）が含まれない。また、前記「炭素数」は、各モノアミンが有するアルキル基またはアルケニル基一つについての炭素数を意味する。 Component (C) is an amine containing a monoamine having an alkyl group having 10 to 20 carbon atoms (preferably 16 to 19) and / or a monoamine having an alkenyl group having 10 to 20 carbon atoms (preferably 16 to 19 carbon atoms). If it exists, various well-known things can be used without a restriction | limiting in particular. When the alkyl group and alkenyl group have less than 10 carbon atoms, the transferability and drying property of the ink film are particularly poor, and when it exceeds 20, the drying property and gloss of the ink film are particularly insufficient. The monoamine content in the amines is not particularly limited, but is usually 65% by weight or more, preferably about 70 to 99% by weight. The alkyl group and alkenyl group do not include an active hydrogen group (hydroxyl group, carboxyl group, etc.). The “carbon number” means the number of carbon atoms per alkyl group or alkenyl group of each monoamine.
当該モノアミンのうち前記アルキル基を有するものとしては、カプリルアミン、ラウリルアミン、ミリスチルアミン、ステアリルアミン等の第１級脂肪族モノアミンや、ジカプリルアミン、ジラウリルアミン、ジミリスチルアミン、ジステアリルアミン、Ｎ−メチルステアリルアミン等の第２級脂肪族モノアミン、Ｎ，Ｎ−ジメチルデシルアミン、トリデシルアミン、Ｎ，Ｎ−ジメチルカプリルアミン、トリカプリルアミン、Ｎ，Ｎ−ジメチルラウリルアミン、トリラウリルアミン、Ｎ，Ｎ−ジメチルミリスチルアミン、トリミリスチルアミン、Ｎ，Ｎ−ジメチルステアリルアミン等の第３級脂肪族モノアミンが挙げられる。また、前記アルケニル基を有するものとしては、ウンデシルアミン、ミリストイルアミン、オレイルアミン、オクタデセニルアミン等の第１級脂肪族モノアミン、ジメチルオレイルアミン等の第３級脂肪族モノアミンなどが挙げられる。（Ｃ）成分としては、バインダー性能のバランスを考慮すると、Ｎ，Ｎ−ジメチルステアリルアミンやオレイルアミンを主成分とするアミン類が好ましい。 Among the monoamines, those having the alkyl group include primary aliphatic monoamines such as caprylamine, laurylamine, myristylamine, stearylamine, dicaprylamine, dilaurylamine, dimyristylamine, distearylamine, N -Secondary aliphatic monoamines such as methylstearylamine, N, N-dimethyldecylamine, tridecylamine, N, N-dimethylcaprylamine, tricaprylamine, N, N-dimethyllaurylamine, trilaurylamine, N And tertiary aliphatic monoamines such as N, N-dimethylmyristylamine, trimyristylamine and N, N-dimethylstearylamine. Examples of those having the alkenyl group include primary aliphatic monoamines such as undecylamine, myristoylamine, oleylamine and octadecenylamine, and tertiary aliphatic monoamines such as dimethyloleylamine. As the component (C), considering the balance of binder performance, amines mainly composed of N, N-dimethylstearylamine or oleylamine are preferable.
（Ｄ）成分としては、各種の金属化合物を使用できる。具体的には、各種金属（カルシウム、マグネシウム、亜鉛等）の酸化物、水酸化物、有機酸塩類が挙げられる。具体的には、水酸化カルシウム、酢酸カルシウム、水酸化マグネシウム、水酸化亜鉛、酸化亜鉛、酢酸亜鉛等が例示できる。これらの中でも、特にインキ皮膜の光沢の観点より、酸化亜鉛、水酸化カルシウムおよび水酸化マグネシウムの併用が好ましい。 As the component (D), various metal compounds can be used. Specific examples include oxides, hydroxides, and organic acid salts of various metals (calcium, magnesium, zinc, and the like). Specific examples include calcium hydroxide, calcium acetate, magnesium hydroxide, zinc hydroxide, zinc oxide, and zinc acetate. Among these, the combined use of zinc oxide, calcium hydroxide and magnesium hydroxide is particularly preferable from the viewpoint of gloss of the ink film.
（Ｅ）成分としては、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ジメチルシクロヘキサン、メチルエチルシクロヘキサンなどが挙げられる。これらの中でも、特にインキ皮膜の乾燥性の観点より、メチルシクロヘキサンが好ましい。 Examples of the component (E) include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and methylethylcyclohexane. Among these, methylcyclohexane is particularly preferable from the viewpoint of the drying property of the ink film.
（Ａ）成分〜（Ｃ）成分の使用量は特に限定されないが、バインダー性能のバランス、特にインキ皮膜の乾燥性の観点より、（Ａ）成分１００重量部に対し、（Ｂ）成分および（Ｃ）成分の使用量が順に通常５〜１５重量部程度（好ましくは８〜１２重量部）、１０〜２０重量部程度（好ましくは１２〜１８重量部）となる範囲である。 Although the usage-amount of (A) component-(C) component is not specifically limited, (B) component and (C) with respect to 100 weight part of (A) component from a viewpoint of the balance of binder performance, especially the drying property of an ink film. ) The amount of component used is usually in the range of about 5 to 15 parts by weight (preferably 8 to 12 parts by weight) and about 10 to 20 parts by weight (preferably 12 to 18 parts by weight).
（Ｄ）成分の使用量も特に制限されないが、特にインキ皮膜の乾燥性の観点より、（Ａ）成分および（Ｂ）成分におけるカルボキシル基の合計１００モル％に対し通常７０〜１００モル％程度（好ましくは８０〜９５モル％）となる範囲である。 The amount of component (D) used is not particularly limited, but is usually about 70 to 100 mol% with respect to the total of 100 mol% of carboxyl groups in component (A) and component (B), particularly from the viewpoint of the drying properties of the ink film ( The range is preferably 80 to 95 mol%.
（Ｅ）成分の使用量も特に制限されないが、本発明に係る樹脂組成物の不揮発分が通常４５〜６０重量％程度となる範囲である。 Although the usage-amount of (E) component is not restrict | limited in particular, it is the range from which the non volatile matter of the resin composition concerning this invention will be about 45 to 60 weight% normally.
本発明に係る樹脂組成物は、（Ａ）成分〜（Ｄ）成分を（Ｅ）成分中で造塩反応させることにより得られる。なお、本発明において「造塩反応」とは、酸性物質（（Ａ）成分および（Ｂ）成分）と塩基性物質（（Ｃ）成分および（Ｄ）成分）とが塩を形成する中和反応を意味する。また、「塩」の構造としては、例えばカルボキシル基−金属イオン−カルボキシル基、カルボキシル基−アミノ基等のイオン結合が挙げられる。当該樹脂組成物をなす樹脂は、（Ｅ）成分中でそうしたイオン結合を介したネットワークを形成していると考えられ、おそらくそのため、当該樹脂は比較的高分子量でありながらも（Ｅ）成分中で不溶物を発生することなく溶解しているのではないかと考えられる。 The resin composition according to the present invention is obtained by subjecting the components (A) to (D) to a salt formation reaction in the component (E). In the present invention, the “salt-forming reaction” means a neutralization reaction in which an acidic substance (component (A) and component (B)) and a basic substance (component (C) and component (D)) form a salt. Means. Moreover, as a structure of "salt", ionic bonds, such as a carboxyl group-metal ion-carboxyl group, a carboxyl group-amino group, are mentioned, for example. The resin constituting the resin composition is considered to form a network through such ionic bonds in the component (E), which is probably because the resin has a relatively high molecular weight but is in the component (E). It is thought that it is dissolved without generating insoluble matter.
それゆえ、本発明に係る樹脂組成物においては、従来高分子量化成分として使用されていたグリセリンやペンタエリスリトール、ジペンタエリスリトール等の多価アルコールを架橋剤（エステル化反応成分）として使用しなくてもよい。 Therefore, in the resin composition according to the present invention, a polyhydric alcohol such as glycerin, pentaerythritol, dipentaerythritol and the like conventionally used as a high molecular weight component must not be used as a crosslinking agent (esterification reaction component). Also good.
造塩反応時の温度は通常６０〜１４０℃程度、好ましくは７０〜１１０℃である。また、（Ａ）成分〜（Ｄ）成分を（Ｅ）成分に添加する順序も特に限定されず、例えば、［１］（Ａ）成分〜（Ｄ）成分を一度に同温度で造塩反応させるワンポット反応や、［２］（Ａ）成分、（Ｂ）成分および（Ｄ）成分を（Ｅ）成分中で同温度で反応させた後、さらに（Ｃ）成分を添加して同温度で造塩反応させる二段階反応を採用できる。後者の方法で得られるバインダーは、インキ皮膜の乾燥性や光沢等の観点より好ましい。 The temperature during the salt-forming reaction is usually about 60 to 140 ° C, preferably 70 to 110 ° C. Further, the order in which the components (A) to (D) are added to the component (E) is not particularly limited. For example, [1] the components (A) to (D) are salt-formed at the same temperature at the same time. One-pot reaction, [2] (A) component, (B) component and (D) component are reacted in component (E) at the same temperature, and then component (C) is added to form salt at the same temperature. A two-stage reaction can be employed. The binder obtained by the latter method is preferable from the viewpoints of drying properties and gloss of the ink film.
当該造塩反応は、反応促進のために水やその他触媒の存在下で実施できる。当該触媒としては、蟻酸、酢酸、プロピオン酸、酪酸、メタンスルホン酸、パラトルエンスルホン酸、これらの金属塩等が挙げられる。なお、（Ａ）成分〜（Ｄ）成分の合計１００重量部に対し水の使用量は通常０．５〜５重量部程度、触媒の使用量は通常０．５〜１重量部程度である。 The salt formation reaction can be carried out in the presence of water or other catalyst to promote the reaction. Examples of the catalyst include formic acid, acetic acid, propionic acid, butyric acid, methanesulfonic acid, paratoluenesulfonic acid, and metal salts thereof. In addition, the usage-amount of water is about 0.5-5 weight part normally with respect to a total of 100 weight part of (A) component-(D) component, and the usage-amount of a catalyst is about 0.5-1 weight part normally.
こうして得られる樹脂組成物の物性は特に限定されないが、特にインキ皮膜の乾燥性や光沢等の観点より、粘度が通常０．０５〜０．５Ｐａ・ｓ程度（Ｂ形粘度計を用い２５℃、不揮発分５５％で測定した値）、融点（ＪＩＳ Ｋ ００６４）が通常１６０〜２６０℃程度、酸価（ＪＩＳ Ｋ ００７０）が通常３０〜２４０程度、アミン価（ＪＩＳ Ｋ ７２３７）が通常１〜２０程度である。 The physical properties of the resin composition thus obtained are not particularly limited, but the viscosity is usually about 0.05 to 0.5 Pa · s (25 ° C. using a B-type viscometer, particularly from the viewpoints of drying properties and gloss of the ink film). The value measured at a non-volatile content of 55%), the melting point (JIS K 0064) is usually about 160 to 260 ° C., the acid value (JIS K 0070) is usually about 30 to 240, and the amine value (JIS K 7237) is usually 1 to 20. Degree.
本発明の出版グラビア印刷インキ用バインダーは前記方法で得た樹脂組成物を用いたものであり、必要に応じて顔料分散剤や消泡剤等の副資材を配合できる。 The publication gravure printing ink binder of the present invention uses the resin composition obtained by the above-mentioned method, and can contain auxiliary materials such as a pigment dispersant and an antifoaming agent as necessary.
本発明の出版グラビア印刷インキは、前記出版グラビア印刷インキ用バインダーを用いたものであり、他に各種顔料（黄、紅、藍、墨等）および必要に応じてインキ溶剤やワックス、添加剤等を配合できる。インキ溶剤としては芳香族有機溶剤（トルエン、キシレン等）、各種植物油（大豆油、ひまし油、あまに油等）、石油系溶剤（ＡＦ−５号ソルベント、ＡＦ−６号ソルベント、０号ソルベント等）が挙げられる他、前記脂環族有機溶剤も好適に利用できる。 The publishing gravure printing ink of the present invention uses the publishing gravure printing ink binder, in addition to various pigments (yellow, red, indigo, black, etc.) and, if necessary, ink solvents, waxes, additives, etc. Can be blended. Ink solvents include aromatic organic solvents (toluene, xylene, etc.), various vegetable oils (soybean oil, castor oil, linseed oil, etc.), petroleum solvents (AF-5 solvent, AF-6 solvent, 0 solvent, etc.) In addition, the alicyclic organic solvent can also be suitably used.
以下に、製造例、実施例および比較例をあげて本発明を詳細に説明するが、本発明はこれら限定されるものではない。尚、部および％は重量基準である。 Hereinafter, the present invention will be described in detail with reference to production examples, examples and comparative examples, but the present invention is not limited thereto. Parts and% are based on weight.
実施例１
撹拌機、温度計、冷却管、分水器および窒素ガス導入管を備えたフラスコに、トール油ロジン（福建省沙縣林産化工廠（株）製、酸価１６５。以下、トール油ロジンというときは同様である。）１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン（荒川化学工業（株）製、酸価１４８。以下、重合ロジンというときは同様である。）５０４部、大豆油脂肪酸（商品名「ＴＯＥＮＯＬ１１２５」、当栄ケミカル（株）製、酸価１９５、オレイン酸およびリノール酸を主成分とする。以下、大豆油脂肪酸というときは同様である。）４９部、ならびにメチルシクロヘキサン１４１２部を加えて溶液となした後、酸化亜鉛４７．６部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム９５．３部を加え、反応系を徐々に昇温して１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でＮ，Ｎ−ジメチルラウリルアミンを主成分とするアミン類（製品名「ファーミンＤＭ４０９８」、花王（株）製。以下、ファーミンＤＭ４０９８というときは同様である。）を１４６部加えて１５分撹拌し、不揮発分５８％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 1
To a flask equipped with a stirrer, thermometer, cooling pipe, water separator and nitrogen gas introduction pipe, tall oil rosin (manufactured by Shaolin Forest Products Co., Ltd., Fujian Province, acid value 165. Hereinafter, when it is called tall oil rosin, It is the same.) After 1000 parts were charged and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, polymerized rosin (Arakawa Chemical Industries, Ltd., acid value 148, hereinafter referred to as polymerized rosin) 504 parts, soybean oil fatty acid (trade name “TOENOL1125”, manufactured by Toei Chemical Co., Ltd., Acid value 195, oleic acid and linoleic acid as main components (hereinafter referred to as soybean oil fatty acid is the same)) After adding 49 parts and methylcyclohexane 1412 parts to make a solution, 47.6 zinc oxide Part, 2.0 parts of calcium acetate and 15 parts of water were added and kept at 75 ° C. for 1 hour. Next, 95.3 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Subsequently, 146 parts of amines (product name “Farmin DM4098”, manufactured by Kao Corporation. The same applies when referred to as “Farmin DM4098”) containing N, N-dimethyllaurylamine as a main component at 80 ° C. are added. The mixture was stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 58% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例２
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン４５９部、大豆油脂肪酸４９部およびメチルシクロヘキサン１４３６部を加えて溶液となした後、酸化亜鉛４６．５部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム９３．０部を加え、反応系を徐々に昇温して１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃で、オレイルアミンを主成分とするアミン類（製品名「ファーミンＯ」、花王（株）製。以下、ファーミンＯというときは同様である。）を１４７部加えて１５分撹拌し、不揮発分５７％、粘度０．１９Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 2
In a flask similar to Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 459 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1436 parts of methylcyclohexane were added to form a solution, and then 46.5 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water were added, Keep warm for hours. Next, 93.0 parts of magnesium hydroxide was added, and the reaction system was gradually heated and kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the reaction system was cooled. Next, at 80 ° C., 147 parts of amines mainly composed of oleylamine (product name “Farmin O”, manufactured by Kao Co., Ltd., hereinafter referred to as “Farmin O”) are added and stirred for 15 minutes. A resin composition having a nonvolatile content of 57% and a viscosity of 0.19 Pa · s was obtained. The appearance was transparent and no insoluble material could be confirmed.
実施例３
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン３７８部、大豆油脂肪酸４９部およびメチルシクロヘキサン１４８８部を加えて溶液となした後、酸化亜鉛４４．５部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８８．９部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５５％、粘度０．２１Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 3
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 378 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1488 parts of methylcyclohexane were added to form a solution, followed by addition of 44.5 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water, and 75 ° C. And kept warm for 1 hour. Next, 88.9 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 55% and a viscosity of 0.21 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例４
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５７部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８３．３部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＯを１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 4
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 257 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, followed by addition of 41.3 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water, Keep warm for hours. Next, 83.3 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin O was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例５
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．２２Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 5
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a non-volatile content of 53% and a viscosity of 0.22 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例６
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、トール油脂肪酸（商品名「ハートール ＦＡ−1」、ハリマ化成（株）製、酸価１９４、オレイン酸およびリノール酸を主成分とする。以下、トール油脂肪酸というときは同様である。）４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 6
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Subsequently, 256 parts of polymerized rosin, tall oil fatty acid (trade name “Hartol FA-1”, manufactured by Harima Chemicals Co., Ltd., acid value 194, oleic acid and linoleic acid are the main components. It is the same.) After adding 49 parts and 1500 parts of methylcyclohexane to make a solution, 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and kept at 75 ° C. for 1 hour. . Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例７
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃で、Ｎ，Ｎ−ジメチルステアリルアミンを主成分とするアミン類（製品名「ファーミンＤＭ８０９８」、花王（株）製。以下、ファーミンＤＭ８０９８というときは同様である。）を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．１９Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 7
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, at 80 ° C., 147 parts of amines mainly composed of N, N-dimethylstearylamine (product name “Farmin DM8098”, manufactured by Kao Corporation; hereinafter referred to as “Farmin DM8098”) are added. For 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.19 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例８
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＯを１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．１８Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 8
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin O was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.18 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例９
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃で、Ｎ，Ｎ−ジメチルデシルアミンを主成分とするアミン類（製品名「ファーミンＤＭ１０９８」、花王（株）製。以下、ファーミンＤＭ１０９８というときは同様である。）を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 9
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, at 80 ° C., 147 parts of amines mainly composed of N, N-dimethyldecylamine (product name “Farmin DM1098”, manufactured by Kao Corporation. The same applies when referred to as “Farmin DM1098”). For 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例１０
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン１５３部、大豆油脂肪酸４９部およびメチルシクロヘキサン１４６３部を加えて溶液となした後、酸化亜鉛３８．７部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７７．４部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５２％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 10
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 153 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1463 parts of methylcyclohexane were added to form a solution, and then 38.7 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Subsequently, 77.4 parts of magnesium hydroxide was added, and the reaction system was gradually heated and kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the reaction system was cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 52% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例１１
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン７７部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５０６部を加えて溶液となした後、酸化亜鉛３６．８部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７３．５部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５０％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 11
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 77 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1506 parts of methylcyclohexane were added to form a solution, and then 36.8 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 73.5 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 50% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例１２
実施例１と同様のフラスコにガムロジン（荒川化学工業（株）製、酸価１７０。以下、ガムロジンというときは同様である。）１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 12
In a flask similar to Example 1, gum rosin (produced by Arakawa Chemical Industries, Ltd., acid value 170. Hereinafter, the same applies when referred to as gum rosin) 1000 parts was heated and melted, and then 31 parts of fumaric acid was added. The reaction was carried out at 200 ° C. for 1 hour. Next, after adding 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and methylcyclohexane part to make a solution, 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. Incubated for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
実施例１３
実施例１と同様のフラスコにトール油ロジンを１０００部仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジンを６２部、大豆油脂肪酸を４９部、およびメチルシクロヘキサン１４９０部を加えて溶液となした後、酸化亜鉛３６．４部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７２．８部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＯを１４７部加えて１５分撹拌し、不揮発分５０％、粘度０．２１Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Example 13
After adding 1000 parts of tall oil rosin to the same flask as in Example 1 and heating and melting it, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 62 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1490 parts of methylcyclohexane were added to form a solution, and then 36.4 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water were added, and 75 It was kept at 1 ° C. for 1 hour. Next, 72.8 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin O was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 50% and a viscosity of 0.21 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例１
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン５７５部、大豆油脂肪酸４９部およびメチルシクロヘキサン１４０６部を加えて溶液となした後、酸化亜鉛４９．５部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム９８．９部を加え、反応系を徐々に昇温して１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＯ１４７部を加え１５分撹拌し、不揮発分５９％、粘度０．１９Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 1
In a flask similar to Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 575 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1406 parts of methylcyclohexane were added to form a solution, followed by addition of 49.5 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water, and 1 at 75 ° C. Keep warm for hours. Next, 98.9 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin O was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 59% and a viscosity of 0.19 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例２
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン５７５部、大豆油脂肪酸４９部およびメチルシクロヘキサン１４０６部を加えて溶液となした後、酸化亜鉛４９．５部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム９８．９部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分５９％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 2
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 575 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1406 parts of methylcyclohexane were added to form a solution, followed by addition of 49.5 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water, and 75 ° C. And kept warm for 1 hour. Next, 98.9 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 59% and a viscosity of 0.20 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例３
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン４１部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５２８部を加えて溶液となした後、酸化亜鉛３５．８部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７１．７部を加え徐々に昇温後１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＯ１４７部を加え１５分撹拌し、不揮発分４９％、粘度０．２１Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 3
In a flask similar to Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 41 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1528 parts of methylcyclohexane were added to form a solution, then 35.8 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water were added, Keep warm for hours. Next, 71.7 parts of magnesium hydroxide was added, the temperature was gradually raised, and the mixture was kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the mixture was cooled. Next, 147 parts of Farmin O was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 49% and a viscosity of 0.21 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例４
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融した後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン４３部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５３０部を加えて溶液となした後、酸化亜鉛３５．９部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７１．８部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、不揮発分４９％、粘度０．１９Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 4
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 43 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1530 parts of methylcyclohexane were added to form a solution, then 35.9 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 71.8 parts of magnesium hydroxide was added, and the reaction system was gradually heated and kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the reaction system was cooled. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 49% and a viscosity of 0.19 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例５
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、大豆油脂肪酸４９部およびメチルシクロヘキサン１６０８部を加えて溶液となした後、酸化亜鉛３４．８部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム６９．６部を加え徐々に昇温後１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でファーミンＯ１４７部を加え１５分撹拌し、不揮発分４７％、粘度０．２１Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 5
In a flask similar to Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, after 49 parts of soybean oil fatty acid and 1608 parts of methylcyclohexane were added to form a solution, 34.8 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water were added and kept at 75 ° C. for 1 hour. Next, 69.6 parts of magnesium hydroxide was added, the temperature was gradually raised, and the mixture was kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the mixture was cooled. Next, 147 parts of Farmin O was added at 80 ° C. and stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 47% and a viscosity of 0.21 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例６
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、大豆油脂肪酸４９部およびメチルシクロヘキサン１５６５部を加えて溶液となした後、酸化亜鉛３４．８部、酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム６９．６部を加え徐々に昇温後１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却し、不揮発分４５％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 6
In a flask similar to Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, after 49 parts of soybean oil fatty acid and 1565 parts of methylcyclohexane were added to form a solution, 34.8 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water were added and kept at 75 ° C. for 1 hour. Next, 69.6 parts of magnesium hydroxide was added and the temperature was gradually raised and kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the mixture was cooled and cooled to a non-volatile content of 45% and a viscosity of 0.20 Pa · A resin composition of s was obtained. The appearance was transparent and no insoluble material could be confirmed.
比較例７
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、大豆油脂肪酸４３部およびメチルシクロヘキサン１５３０部を加えて溶液となした後、酸化亜鉛３５．９部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７１．８部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った。次いで、８０℃でファーミンＤＭ４０９８を１４７部加えて１５分撹拌し、冷却することにより、不揮発分４９％、粘度０．２１Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 7
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, after 43 parts of soybean oil fatty acid and 1530 parts of methylcyclohexane were added to form a solution, 35.9 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added and kept at 75 ° C. for 1 hour. . Next, 71.8 parts of magnesium hydroxide was added, the reaction system was gradually heated and kept at 100 ° C. for 2 hours, and a dehydration reaction was performed under reflux of methylcyclohexane. Next, 147 parts of Farmin DM4098 was added at 80 ° C. and stirred for 15 minutes, followed by cooling to obtain a resin composition having a nonvolatile content of 49% and a viscosity of 0.21 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例８
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却することにより、不揮発分５３％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 8
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, and the reaction system was gradually warmed and kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, cooling was performed to obtain a nonvolatile content of 53%. A resin composition having a viscosity of 0.20 Pa · s was obtained. The appearance was transparent and no insoluble material could be confirmed.
比較例９
実施例１と同様のフラスコにトール油ロジン１０００部、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１１４３部を加えて溶液となした後、酸化亜鉛３６．５部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７２．９部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行い、冷却することにより、不揮発分５７％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 9
To the same flask as in Example 1, 1000 parts of tall oil rosin, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1143 parts of methylcyclohexane were added to form a solution, and then 36.5 parts of zinc oxide and 2.0 parts of calcium acetate were obtained. And 15 parts of water were added and kept at 75 ° C. for 1 hour. Next, 72.9 parts of magnesium hydroxide is added, and the reaction system is gradually warmed and kept at 100 ° C. for 2 hours, dehydration reaction is performed under reflux of methylcyclohexane, and the mixture is cooled to have a nonvolatile content of 57% and a viscosity. A 0.20 Pa · s resin composition was obtained. The appearance was transparent and no insoluble material could be confirmed.
比較例１０
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃でＮ，Ｎ−ジメチルベヘニルアミンを主成分とするアミン類（製品名「ファーミンＤＭ２２８５」、花王（株）製。以下、ファーミンＤＭ２２８５というときは同様である。）を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．１９Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 10
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, 147 parts of amines (product name “Farmin DM2285”, manufactured by Kao Corporation, hereinafter referred to as “Farmin DM2285”) containing N, N-dimethylbehenylamine as a main component at 80 ° C. are added. The mixture was stirred for 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.19 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例１１
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸３１部を添加し、２００℃で１時間反応させた。次いで、重合ロジン２５６部、大豆油脂肪酸４９部およびメチルシクロヘキサン１５００部を加えて溶液となした後、酸化亜鉛４１．３部、酢酸カルシウム２．０部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム８２．７部を加え、反応系を徐々に昇温して１００℃で２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。次いで、８０℃で、Ｎ，Ｎ−ジメチルオクチルアミンを主成分とするアミン類（製品名「ファーミンＤＭ０８９８」、花王（株）製。以下、ファーミンＤＭ２２８５というときは同様である。）を１４７部加えて１５分撹拌し、不揮発分５３％、粘度０．２１Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Comparative Example 11
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 31 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 256 parts of polymerized rosin, 49 parts of soybean oil fatty acid and 1500 parts of methylcyclohexane were added to form a solution, and then 41.3 parts of zinc oxide, 2.0 parts of calcium acetate and 15 parts of water were added, and 75 ° C. And kept warm for 1 hour. Next, 82.7 parts of magnesium hydroxide was added, the reaction system was gradually warmed and kept at 100 ° C. for 2 hours, dehydrated under reflux of methylcyclohexane, and then cooled. Next, at 80 ° C., 147 parts of amines mainly composed of N, N-dimethyloctylamine (product name “Farmin DM0898”, manufactured by Kao Corporation, hereinafter referred to as “Farmin DM2285”) are added. For 15 minutes to obtain a resin composition having a nonvolatile content of 53% and a viscosity of 0.21 Pa · s. The appearance was transparent and no insoluble material could be confirmed.
比較例１２
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸２７部を添加し、２００℃で１時間反応させた。次いで、ジペンタエリスルトール４部と大豆油脂肪酸１１０部を加え２５０℃にて１時間エステル化を行った。次いでメチルシクロヘキサン１４２０部を加えて溶液となした後、酸化亜鉛４６．６部、酢酸カルシウム２部および水１０部を添加して、７５℃で１時間保温した。次いで、水酸化カルシウム９２．６部を加え徐々に昇温後１００℃にて２時間保温し、メチルシクロヘキサン還流下に脱水反応を行った後、冷却した。不揮発分４０％、粘度０．２０Ｐａ・ｓのポリエステル樹脂組成物を得たが、外観が濁っており、不溶物の発生を確認した。
Comparative Example 12
In a flask similar to that in Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 27 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Subsequently, 4 parts of dipentaerythritol and 110 parts of soybean oil fatty acid were added and esterification was performed at 250 ° C. for 1 hour. Next, 1420 parts of methylcyclohexane was added to form a solution, and then 46.6 parts of zinc oxide, 2 parts of calcium acetate and 10 parts of water were added, and the mixture was kept at 75 ° C. for 1 hour. Next, 92.6 parts of calcium hydroxide was added, the temperature was gradually raised, and the mixture was kept at 100 ° C. for 2 hours. After dehydration reaction under reflux of methylcyclohexane, the mixture was cooled. A polyester resin composition having a nonvolatile content of 40% and a viscosity of 0.20 Pa · s was obtained, but the appearance was cloudy, and the generation of insoluble materials was confirmed.
参照例１
実施例１と同様のフラスコに、トール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸２７部を添加し、２００℃で１時間反応させた。次いで、ジペンタエリスルトール４部と大豆油脂肪酸１１０部を加え２５０℃にて１時間エステル化を行った。次いでトルエン１４２０部を加えて溶液となした後、酸化亜鉛４６．６部、酢酸カルシウム２部及び水１０部を添加して、７５℃で１時間保温した。次いで、水酸化カルシウム９２．６部を加え徐々に昇温後１００℃にて２時間保温し、トルエン還流下に脱水反応を行った後、冷却した。不揮発分４０％、粘度０．２０Ｐａ・ｓのポリエステル樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Reference example 1
In a flask similar to that in Example 1, 1000 parts of tall oil rosin was charged and heated to melt, and then 27 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Subsequently, 4 parts of dipentaerythritol and 110 parts of soybean oil fatty acid were added and esterification was performed at 250 ° C. for 1 hour. Next, 1420 parts of toluene was added to form a solution, and then 46.6 parts of zinc oxide, 2 parts of calcium acetate and 10 parts of water were added, and the mixture was kept at 75 ° C. for 1 hour. Next, 92.6 parts of calcium hydroxide was added, the temperature was gradually raised, the temperature was kept at 100 ° C. for 2 hours, dehydration reaction was performed under reflux of toluene, and then cooled. A polyester resin composition having a nonvolatile content of 40% and a viscosity of 0.20 Pa · s was obtained. The appearance was transparent and no insoluble material could be confirmed.
参照例２
実施例１と同様のフラスコにトール油ロジン１０００部を仕込み加熱溶融させた後、フマル酸４６部を添加し、２００℃で１時間反応させた。次いで大豆油脂肪酸１８部及びトルエン９２０部を加えて溶液となした後、酸化亜鉛３８．６部と酢酸カルシウム２部及び水１５部を添加して、７５℃で１時間保温した。次いで、水酸化マグネシウム７７．２部を加え徐々に昇温後１１０℃にて２時間保温し、トルエン還流下に脱水反応を行い、不揮発分５５％、粘度０．２０Ｐａ・ｓの樹脂組成物を得た。外観は透明であり、不溶物は確認できなかった。
Reference example 2
After 1000 parts of tall oil rosin was charged into the same flask as in Example 1 and heated and melted, 46 parts of fumaric acid was added and reacted at 200 ° C. for 1 hour. Next, 18 parts of soybean oil fatty acid and 920 parts of toluene were added to form a solution, and then 38.6 parts of zinc oxide, 2 parts of calcium acetate and 15 parts of water were added, and kept at 75 ° C. for 1 hour. Next, 77.2 parts of magnesium hydroxide was added and the temperature was gradually raised and kept at 110 ° C. for 2 hours. A dehydration reaction was performed under reflux of toluene to obtain a resin composition having a nonvolatile content of 55% and a viscosity of 0.20 Pa · s. Obtained. The appearance was transparent and no insoluble material could be confirmed.
表１中、ＭＣＨはメチルシクロヘキサンを、ＤＰＥはジペンタエリスリトールを意味する。 In Table 1, MCH means methylcyclohexane and DPE means dipentaerythritol.
（グラビアインキの調製）
実施例１〜１３及び比較例１〜１２で得られた樹脂組成物を、いずれも粘度が０．０３５Ｐａ・ｓ／２０℃となるようにメチルエチルヘキサンで希釈した。また、参照例１〜２で得られた樹脂組成物を、いずれも粘度が０．０３５Ｐａ・ｓ／２０℃となるようにトルエンで希釈した。
(Preparation of gravure ink)
The resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 12 were each diluted with methyl ethyl hexane so that the viscosity was 0.035 Pa · s / 20 ° C. In addition, the resin compositions obtained in Reference Examples 1 and 2 were each diluted with toluene so that the viscosity was 0.035 Pa · s / 20 ° C.
次いで、実施例１に係る樹脂組成物の溶液８８部に紅顔料（カーミン６Ｂ）を１２部混合し、サンドミルを用いて１時間混練した後、メチルエチルヘキサンで希釈して粘度が０．０８５Ｐａ・ｓ／２５℃の紅グラビアインキを得た。実施例２〜１３及び比較例１〜１２に係る溶液についても同様にして紅グラビアインキを得た。また、参照例１〜２に係る溶液については、希釈溶剤としてトルエンを使用した他は同様にして、紅グラビアインキを得た。 Next, 12 parts of red pigment (Kermin 6B) was mixed with 88 parts of the resin composition solution according to Example 1, kneaded for 1 hour using a sand mill, and then diluted with methylethylhexane to obtain a viscosity of 0.085 Pa · A red gravure ink of s / 25 ° C. was obtained. Red gravure ink was obtained in the same manner for the solutions according to Examples 2 to 13 and Comparative Examples 1 to 12. For the solutions according to Reference Examples 1 and 2, red gravure ink was obtained in the same manner except that toluene was used as a diluent solvent.
＜インキの転移性＞
簡易グラビア印刷機（製品名「ＥＣＧＬ−ＳＢ」、和泉電気（株）製版のインキ孔深さ４０μｍ）により、市販のコート紙に各グラビアインキを塗布した後、印刷面の色の濃さの順によりインキの転移性を目視評価した。５＞４＞３＞２＞１の順に良好であることを意味する。その際、参照例２を基準とした。
<Ink transferability>
After applying each gravure ink to commercially available coated paper with a simple gravure printing machine (product name "ECGL-SB", Izumi Denki Co., Ltd., ink hole depth 40 μm), the order of color density on the printed surface Thus, the transferability of the ink was visually evaluated. It means that it is favorable in the order of 5>4>3>2> 1. At that time, Reference Example 2 was used as a standard.
＜インキ皮膜の乾燥性＞
バーコター＃１０を用いて各グラビアインキをコート紙に展色し、１分間放置した後、インキ皮膜に人差し指を押しつけた際の指触により、皮膜の乾燥性を評価した。５＞４＞３＞２＞１の順に良好であることを意味する。その際、参照例２を基準とした。
<Dryness of ink film>
Each gravure ink was developed on coated paper using Barcota # 10 and allowed to stand for 1 minute, and then the drying property of the film was evaluated by finger touch when the index finger was pressed against the ink film. It means that it is favorable in the order of 5>4>3>2> 1. At that time, Reference Example 2 was used as a standard.
＜インキ皮膜の光沢＞
前記乾燥性試験を行なったコート紙におけるインキ皮膜の光沢を目視評価した。５＞４＞３＞２＞１の順に良好であることを意味するその際。その際、参照例２を基準とした。
<Gloss of ink film>
The gloss of the ink film on the coated paper subjected to the drying test was visually evaluated. In that case, it means that it is favorable in the order of 5>4>3>2> 1. At that time, Reference Example 2 was used as a standard.
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| JPH0641486A (en) * | 1991-03-19 | 1994-02-15 | Arakawa Chem Ind Co Ltd | Binder for printing ink and its production |
| JPH0625581A (en) * | 1991-06-13 | 1994-02-01 | Arakawa Chem Ind Co Ltd | Binder for printing ink and its production |
| JPH09291244A (en) * | 1996-04-26 | 1997-11-11 | Dainippon Ink & Chem Inc | Resin composition for printing ink, its production and printing ink |
| JP2001234105A (en) * | 2000-02-25 | 2001-08-28 | Arakawa Chem Ind Co Ltd | Binder for printing ink and printing ink composition |
| JP2001254041A (en) * | 2000-03-09 | 2001-09-18 | Arakawa Chem Ind Co Ltd | Printing ink binder and printing ink composition |
| JP2001279146A (en) * | 2000-03-30 | 2001-10-10 | Arakawa Chem Ind Co Ltd | Binder for printing ink and its production method |
| JP2006063197A (en) * | 2004-08-27 | 2006-03-09 | Toyo Ink Mfg Co Ltd | Alkyd resin, printing ink obtained using the same and printed matter thereof |
| JP2006335923A (en) * | 2005-06-03 | 2006-12-14 | Toyo Ink Mfg Co Ltd | Printing ink and its printed matter |
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