JP2001164166A - Preparation process of resin composition for printing ink - Google Patents
Preparation process of resin composition for printing inkInfo
- Publication number
- JP2001164166A JP2001164166A JP35399499A JP35399499A JP2001164166A JP 2001164166 A JP2001164166 A JP 2001164166A JP 35399499 A JP35399499 A JP 35399499A JP 35399499 A JP35399499 A JP 35399499A JP 2001164166 A JP2001164166 A JP 2001164166A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- resin
- parts
- ink
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、オフセット印刷に
おいて優れた印刷適性を有する、印刷インキ用ロジン変
性フェノール樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin-modified phenolic resin composition for printing ink having excellent printability in offset printing.
【０００２】[0002]
【従来の技術】従来、オフセット印刷インキに使用する
ロジン変性フェノール樹脂は、溶融したロジンにフェノ
ール樹脂及び多価アルコールを添加し、２５０〜２７０
℃の高温で反応させる塊状重合法によるのが一般的であ
る。2. Description of the Related Art Conventionally, a rosin-modified phenol resin used for offset printing ink is prepared by adding a phenol resin and a polyhydric alcohol to a molten rosin, and adding the rosin to the rosin in an amount of 250 to 270.
Generally, a bulk polymerization method in which the reaction is carried out at a high temperature of ° C is used.
【０００３】そして当該樹脂を、インキ溶剤と乾性油中
で、場合によってはゲル化剤を添加して、１４０〜２４
０℃に加熱溶解し、クッキングすることにより印刷イン
キ用ワニスを製造している。[0003] The resin is added to an ink solvent and a drying oil, and if necessary, a gelling agent is added to the resin to form a resin of 140 to 24.
The varnish for printing ink is manufactured by heating and dissolving at 0 ° C. and cooking.
【０００４】[0004]
【発明が解決しようとする課題】近年の印刷業界におい
ては、生産性向上の動きに対応して印刷機の高速化が進
んでおり、それに伴い印刷インキ用樹脂としては、ミス
チング抑制、乾燥性向上等の高速印刷適性の向上が求め
られている。高速印刷適性はインキの粘弾性に依存する
と考えられており、このような性能を得るためには、樹
脂の分子量が大きく、軟化点が高く、且つ溶融時の粘度
が高いことが求められる。In the printing industry in recent years, the speed of printing presses has been increasing in response to the trend of improving productivity, and as a result, misting suppression and drying property have been improved as printing ink resins. There is a demand for improvement in high-speed printing suitability. It is considered that the suitability for high-speed printing depends on the viscoelasticity of the ink. In order to obtain such performance, it is required that the resin has a large molecular weight, a high softening point, and a high viscosity when melted.
【０００５】しかしながら従来の塊状重合法では、十分
に高分子量の樹脂を得ようとすると、溶融粘度が高くな
るために撹拌負荷が大きくなり、十分に撹拌されないた
めに反応系が不均一になりやすい。そのため分子量分布
がばらつき、均一な樹脂を得ることができない。However, in the conventional bulk polymerization method, if a resin having a sufficiently high molecular weight is to be obtained, the melt viscosity is high, so that the stirring load is large, and the reaction system is liable to be non-uniform, since the stirring is not sufficient. . Therefore, the molecular weight distribution varies, and a uniform resin cannot be obtained.
【０００６】また反応終了後に反応容器からかかる高粘
度の樹脂を取り出すのは極めて困難である。反応が終了
した後に、樹脂を溶剤に溶解して取り出すことも考えら
れるが、塊状重合により合成された高分子量の樹脂は粘
度が高く、これを溶剤に溶解することは困難である。It is very difficult to remove such a high-viscosity resin from the reaction vessel after the reaction. After completion of the reaction, the resin may be dissolved in a solvent and taken out. However, the high molecular weight resin synthesized by bulk polymerization has a high viscosity, and it is difficult to dissolve the resin in the solvent.
【０００７】本発明はかかる事情に鑑みなされたもので
あって、高分子量で軟化点が高く、高粘度で高速印刷特
性に優れた印刷インキ用樹脂を、容易に製造するための
方法を提供することを目的とするものである。The present invention has been made in view of the above circumstances and provides a method for easily producing a printing ink resin having a high molecular weight, a high softening point, a high viscosity, and excellent high-speed printing characteristics. The purpose is to do so.
【０００８】[0008]
【問題点を解決するための手段】而して本発明は、ロジ
ン又はその誘導体１００重量部に対して、フェノールホ
ルムアルデヒド初期縮合物５０〜１５０重量部及び、前
記ロジン又はその誘導体のカルボン酸に対して０．１〜
１．５モル当量の多価アルコールを混合し、これを加熱
反応させてロジン変性フェノール樹脂を生成するに当た
り、その反応生成物の重量平均分子量が１０００以上と
なった時点で、沸点が１６０℃〜３２０℃のオフセット
印刷インキ用溶剤１〜１００重量部を添加することを特
徴とするものである。Means for Solving the Problems Thus, the present invention relates to 50 to 150 parts by weight of a phenol formaldehyde precondensate and 100 parts by weight of rosin or a derivative thereof and carboxylic acid of the rosin or derivative thereof. 0.1 ~
In mixing 1.5 molar equivalents of a polyhydric alcohol and reacting it by heating to produce a rosin-modified phenolic resin, when the weight average molecular weight of the reaction product becomes 1000 or more, the boiling point is 160 ° C. It is characterized by adding 1 to 100 parts by weight of a solvent for offset printing ink at 320 ° C.
【０００９】本発明においては、前記ロジン変性フェノ
ール樹脂と共に、１〜５０重量部の植物油を添加するこ
とが好ましい。In the present invention, it is preferable to add 1 to 50 parts by weight of vegetable oil together with the rosin-modified phenol resin.
【００１０】すなわち本発明は、ロジン又はその誘導体
と、フェノールホルムアルデヒド初期縮合物と、多価ア
ルコールとを反応させ、ロジン変性フェノール樹脂を合
成する方法において、その合成の初期においては前記三
成分のみによる塊状重合法により行い、生成物の重合平
均分子量が１０００以上となった時点で、溶剤及び必要
に応じて植物油を添加し、それ以後は当該溶剤に溶解し
た状態での溶液重合工程に移行し、反応を完結させるの
である。That is, the present invention relates to a method for synthesizing a rosin-modified phenolic resin by reacting rosin or a derivative thereof, a phenol formaldehyde initial condensate, and a polyhydric alcohol, wherein only the three components are used in the initial stage of the synthesis. Performed by a bulk polymerization method, at the time when the polymerization average molecular weight of the product becomes 1000 or more, add a solvent and, if necessary, vegetable oil, and thereafter, shift to a solution polymerization step in a state of being dissolved in the solvent, The reaction is completed.
【００１１】得られたロジン変性フェノール樹脂は、こ
れをそのまま固体として汲み出すことができ、またさら
に溶剤、乾性油を追加してワニスとしてとりだすことも
できる。さらに、ゲル化剤を添加してゲル化したゲルワ
ニスとして取り出すことも可能である。The obtained rosin-modified phenol resin can be pumped out as it is as a solid, and can be further taken out as a varnish by adding a solvent and a drying oil. Furthermore, it is also possible to take out as a gel varnish gelled by adding a gelling agent.
【００１２】本発明で使用するロジンとしては、ガムロ
ジン、ウッドロジン又はトール油ロジンを使用すること
ができ、それらの蒸留ロジンを使用することもできる。
またそれらのロジンの誘導体としては、不均化ロジン、
水添ロジン、重合ロジンを使用することもでき、さらに
それらを２塩基酸又はその無水物で変性したものを使用
することもできる。As the rosin used in the present invention, gum rosin, wood rosin or tall oil rosin can be used, and their distilled rosins can also be used.
Derivatives of these rosins include disproportionated rosin,
Hydrogenated rosin and polymerized rosin can be used, and those obtained by modifying them with a dibasic acid or its anhydride can also be used.
【００１３】変性に使用する２塩基酸又はその無水物と
しては、フマル酸、マレイン酸、無水マレイン酸、アジ
ピン酸、イタコン酸、無水フタル酸、イソフタル酸、テ
レフタル酸、無水トリメリット酸などが挙げられる。The dibasic acids or anhydrides used for the modification include fumaric acid, maleic acid, maleic anhydride, adipic acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride and the like. Can be
【００１４】本発明で使用するフェノールホルムアルデ
ヒド初期縮合物としては、レゾール化し、若しくはノボ
ラック化した後レゾール化した、１〜８核体の核数を持
つレゾール型フェノール樹脂が好ましい。As the phenol-formaldehyde precondensate used in the present invention, a resol-type phenol resin having a nucleus of 1 to 8 nuclei, which is formed into a resol or a novolak and then into a resol, is preferable.
【００１５】レゾール型フェノール樹脂に使用されるフ
ェノール類としては、フェノール性水酸基を有するすべ
ての芳香族化合物が使用できるが、中でも水酸基のパラ
位に炭素数４〜１２のアルキル置換基を持つアルキルフ
ェノール化合物や、ビスフェノールＡが好ましい。アル
デヒド供給体成分としては、パラホルムアルデヒド及び
ホルマリン水溶液を使用する。As the phenols used in the resole type phenol resin, all aromatic compounds having a phenolic hydroxyl group can be used. Among them, alkylphenol compounds having an alkyl substituent having 4 to 12 carbon atoms at the para position of the hydroxyl group can be used. Alternatively, bisphenol A is preferred. As the aldehyde donor component, paraformaldehyde and an aqueous solution of formalin are used.
【００１６】上記フェノール類とアルデヒド供給体成分
とを、アルカリ触媒を使用してレゾール型フェノール樹
脂を合成する。アルカリ触媒としては、水酸化カリウ
ム、水酸化ナトリウム、水酸化カルシウム、水酸化マグ
ネシウム、アンモニア水溶液、等のアルカリ触媒が用い
られる。A resol type phenol resin is synthesized from the phenols and the aldehyde donor component using an alkali catalyst. As the alkali catalyst, an alkali catalyst such as potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, and an aqueous ammonia solution is used.
【００１７】本発明で使用する多価アルコールとして
は、たとえばグリセリン、トリメチロールエタン、トリ
メチロールプロパン、ジエチレングリコール、トリエチ
レングリコール、トリメチロールプロパン、ペンタエリ
スリトール、ジペンタエリスリトールなどが挙げられ
る。The polyhydric alcohol used in the present invention includes, for example, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, triethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like.
【００１８】かかる多価アルコールの使用量は、得られ
るロジン変性フェノール樹脂の溶解性や軟化点と密接に
関係する。通常はロジン成分のカルボン酸に対し０．１
〜１．５モル当量とするのが適当であり、好ましくは
０．３〜１．１モル当量とするのが好ましい。The amount of the polyhydric alcohol used is closely related to the solubility and softening point of the obtained rosin-modified phenol resin. Usually, 0.1 to carboxylic acid of rosin component
It is suitably from 1.5 to 1.5 molar equivalents, preferably from 0.3 to 1.1 molar equivalents.
【００１９】多価アルコールの添加量が多すぎると、得
られた樹脂に親水性のアルコール性水酸基が残存するこ
ととなり、樹脂の溶解性が低下すると共に、インキにし
た後に耐乳化適性が悪くなるため好ましくない。If the amount of the polyhydric alcohol is too large, hydrophilic alcoholic hydroxyl groups remain in the obtained resin, so that the solubility of the resin decreases and the emulsification resistance after the ink is formed deteriorates. Therefore, it is not preferable.
【００２０】本発明で使用するオフセット印刷インキ用
溶剤としては、沸点１８０℃から３２０℃のパラフィン
系、ナフテン系又は芳香族系の溶剤であって、一般的に
オフセット印刷インキ用溶剤として市販されているもの
を、そのまま使用することができる。The solvent for offset printing ink used in the present invention is a paraffinic, naphthenic or aromatic solvent having a boiling point of 180 ° C. to 320 ° C., and is generally commercially available as a solvent for offset printing ink. Can be used as is.
【００２１】本発明において使用する植物油としては、
アマニ油、重合アマニ油、脱水ヒマシ油、大豆油、トー
ル油、サフラワー油、シナキリ油及びエゴマ油などを使
用することができる。The vegetable oil used in the present invention includes:
Linseed oil, polymerized linseed oil, dehydrated castor oil, soybean oil, tall oil, safflower oil, cinnamon oil and perilla oil can be used.
【００２２】本発明により得られた樹脂は、インキ溶剤
と乾性油と混合し、さらに必要に応じてゲル化剤を添加
し、１４０〜２４０℃に加熱して溶解し、クッキングし
て印刷インキ用ワニスとする。そして当該ワニスに顔料
を分散し、必要に応じて耐摩擦性向上剤、インキドライ
ヤー、乾燥抑制剤などを添加し、粘度を調整して印刷イ
ンキとする。枚葉インキ、オフ輪インキなどのオフセッ
ト印刷用として適しているが、新聞用や凸版のインキと
しても使用できる。The resin obtained according to the present invention is mixed with an ink solvent and a drying oil, and if necessary, a gelling agent is added thereto. Varnish. Then, a pigment is dispersed in the varnish, and if necessary, a friction resistance improver, an ink dryer, a drying inhibitor, and the like are added, and the viscosity is adjusted to obtain a printing ink. It is suitable for offset printing such as sheet-fed ink and web offset ink, but can also be used as newspaper ink or letterpress ink.
【００２３】[0023]
【実施例】次に具体的な実施例により本発明を説明す
る。以下の説明で「部」「％」とは、重量部及び重量％
を表す。Next, the present invention will be described with reference to specific examples. In the following description, “parts” and “%” are parts by weight and weight%.
Represents
【００２４】製造例（レゾール型フェノール樹脂の製
造） 撹拌器、還流冷却器及び温度計を付した四つ口フラスコ
中に、p−オクチルフェノール８２５部と、ビスフェノ
ールＡ２２８部と、９２％パラホルムアルデヒド３２６
部と、キシレン１３０部とを仕込み、６０℃まで加熱し
て溶解した後、水酸化カリウム５．２部を投入する。さ
らに加熱して９０℃にまで昇温し、５時間反応して平均
核体数４核体のレゾールを調製する。それをキシレン１
１０部に溶解し、固形分濃度を８５％に調整した。Production Example (Production of resol type phenol resin) In a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 825 parts of p-octylphenol, 228 parts of bisphenol A and 326 parts of 92% paraformaldehyde were added.
And 130 parts of xylene were charged and dissolved by heating to 60 ° C., and then 5.2 parts of potassium hydroxide were added. The mixture is further heated to 90 ° C. and reacted for 5 hours to prepare a resol having an average of 4 nuclei. Xylene 1
It was dissolved in 10 parts and the solid content concentration was adjusted to 85%.
【００２５】実施例１ 撹拌器、水分離器付き還流冷却器及び温度計を付した四
つ口フラスコに、ガムロジン２２０部と、製造例で製造
したレゾール型フェノール樹脂１７０部と、ペンタエリ
スリトール１９部と、グリセリン５部とを投入し、窒素
ガスを吹き込み撹拌しながら加熱し、樹脂を溶解して均
一状態とする。Example 1 In a four-necked flask equipped with a stirrer, a reflux condenser equipped with a water separator, and a thermometer, 220 parts of gum rosin, 170 parts of the resole-type phenol resin produced in the production example, and 19 parts of pentaerythritol And 5 parts of glycerin, and the mixture is heated while blowing in and stirring with nitrogen gas to dissolve the resin and make it uniform.
【００２６】その後キシレンと水とを水分離器付き還流
冷却器で回収しながら、７時間かけて２６０℃にまで昇
温した。この時点における樹脂組成物の平均分子量は、
１３００であった。Thereafter, the temperature was raised to 260 ° C. over 7 hours while recovering xylene and water with a reflux condenser equipped with a water separator. At this point, the average molecular weight of the resin composition is
1300.
【００２７】この時点で日本石油社製日石ＡＦ６号ソル
ベント３０部を投入し、同温度で８時間反応させ、酸価
２０、平均分子量１８万、n−ヘキサントレランス１．
８g/gの樹脂３５８部を得た。At this time, 30 parts of Nisseki AF No. 6 solvent manufactured by Nippon Oil Co., Ltd. were charged and reacted at the same temperature for 8 hours, acid value 20, average molecular weight 180,000, n-hexane tolerance 1.
358 parts of an 8 g / g resin were obtained.
【００２８】あらかじめ日石ＡＦ６号ソルベント２９０
部、大豆油１６０部及び、川研ファインケミカル社製ゲ
ル化剤ＡＬＣＨ５部を混合した四つ口フラスコに、前記
樹脂組成物を添加し、内温１９０℃で１時間熟成し、粘
度８３Pa.Sのゲルワニス８２０部を得た。Nisseki AF No. 6 Solvent 290
Parts, soybean oil 160 parts and Kawaken Fine Chemical Co., Ltd. gelling agent ALCH5 parts were mixed in a four-necked flask, and the resin composition was added thereto. The mixture was aged at an internal temperature of 190 ° C. for 1 hour, and had a viscosity of 83 Pa.S. 820 parts of gel varnish were obtained.
【００２９】実施例２ 実施例１と同様の反応装置を使用し、四つ口フラスコに
ガムロジン２２０部と、ペンタエリスリトール１９部
と、グリセリン５部とを投入し、窒素ガスを吹き込み撹
拌しながら加熱し、２７０℃で８時間かけてエステル化
反応させ、酸価１５のロジンエステルとした。Example 2 Using the same reactor as in Example 1, 220 parts of gum rosin, 19 parts of pentaerythritol, and 5 parts of glycerin were charged into a four-necked flask, and heated while stirring by blowing in nitrogen gas. Then, an esterification reaction was performed at 270 ° C. for 8 hours to obtain a rosin ester having an acid value of 15.
【００３０】然る後、製造例で製造したレゾール型フェ
ノール樹脂１７０部を、２６０℃で６時間かけて滴下し
た。滴下開始後樹脂組成物の重量平均分子量が１０００
０となった時点で、日石ＡＦ６号ソルベント３０部を投
入した。レゾール樹脂の滴下終了後、２時間同温度で反
応させ、酸価１２、平均分子量３２万、n−ヘキサント
レランス２．６g/gの樹脂３５８部を得た。Thereafter, 170 parts of the resol-type phenol resin produced in the production example was dropped at 260 ° C. over 6 hours. After the start of the dropping, the weight average molecular weight of the resin composition is 1000
When it reached 0, 30 parts of Nisseki AF No. 6 solvent were charged. After completion of the dropping of the resole resin, the mixture was reacted at the same temperature for 2 hours to obtain 358 parts of a resin having an acid value of 12, an average molecular weight of 320,000, and n-hexane tolerance of 2.6 g / g.
【００３１】この樹脂について、実施例１において述べ
たと同様の操作を行い、粘度９２Pa.Sのゲルワニス８２
０部を得た。The same operation as described in Example 1 was performed on this resin to obtain a gel varnish 82 having a viscosity of 92 Pa.S.
0 parts were obtained.
【００３２】実施例３ 実施例１と同様の組成と操作で、樹脂組成物の重量平均
分子量が１３００となった時点で、日石ＡＦ６号ソルベ
ント３０部と共にトール油脂肪酸３０部を投入した。得
られた樹脂の、酸価は２０、平均分子量は１６万、n−
ヘキサントレランスは２．４g/gであった。Example 3 With the same composition and operation as in Example 1, when the weight average molecular weight of the resin composition reached 1300, 30 parts of Nisseki AF6 solvent and 30 parts of tall oil fatty acid were added. The obtained resin had an acid value of 20, an average molecular weight of 160,000 and n-
Hexane tolerance was 2.4 g / g.
【００３３】またこの樹脂から実施例１と同様にしてゲ
ルワニスを得るに当たり、使用する大豆油の量は１３０
部とした。最終的に得られたゲルワニスの粘度は、粘度
７２Pa.Sであった。When a gel varnish was obtained from this resin in the same manner as in Example 1, the amount of soybean oil used was 130
Department. The viscosity of the finally obtained gel varnish was 72 Pa.S.
【００３４】比較例１ 実施例１と同様の操作において、日石ＡＦ７号ソルベン
トを添加することなく樹脂を合成した。この操作におい
ては、２６０℃に昇温後２時間で、樹脂が撹拌機に巻き
上がり、撹拌不能の状態になり汲み出した。Comparative Example 1 In the same operation as in Example 1, a resin was synthesized without adding Nisseki AF7 solvent. In this operation, two hours after the temperature was raised to 260 ° C., the resin was rolled up in a stirrer, and was pumped out in a state where stirring was impossible.
【００３５】比較例２ 実施例１と同様の操作において、ロジンを溶解した後直
ちに日石ＡＦ６号ソルベント３２部を投入して樹脂を合
成した。得られた樹脂は、酸価２０、平均分子量６万、
n−へキサントレランス２．０g/gであった。以下実施例
１と同様の方法で、粘度２６Pa.Sのゲルワニス８２０部
を得た。Comparative Example 2 In the same manner as in Example 1, immediately after dissolving the rosin, 32 parts of Nisseki AF6 Solvent was charged to synthesize a resin. The obtained resin had an acid value of 20, an average molecular weight of 60,000,
The n-hexane tolerance was 2.0 g / g. Thereafter, 820 parts of a gel varnish having a viscosity of 26 Pa.S was obtained in the same manner as in Example 1.
【００３６】比較例３ 実施例２と同様の操作において、レゾール滴下時に日石
ＡＦ７号ソルベントを添加することなく樹脂を合成し、
酸価１４、n−ヘキサントレランス２．０g/gの樹脂を得
た。その樹脂について、日石ＡＦ６号ソルベントの量を
３２０部にした以外は実施例１と同様に操作して、粘度
１２０Pa.Sのゲルワニス８２０部を得た。そのワニスは
不溶解成分が分散した不均一な状態であった。Comparative Example 3 In the same manner as in Example 2, a resin was synthesized without adding Nisseki AF No. 7 solvent at the time of resole dripping.
A resin having an acid value of 14 and n-hexane tolerance of 2.0 g / g was obtained. 820 parts of a gel varnish having a viscosity of 120 Pa.S was obtained by operating the resin in the same manner as in Example 1 except that the amount of Nisseki AF No. 6 solvent was changed to 320 parts. The varnish was in a non-uniform state in which insoluble components were dispersed.
【００３７】比較例４ 実施例１と同様の反応で、ペンタエリスリトール３８部
及びグリセリン１０部に代えてグリセリン４３部を用
い、日石ＡＦ７号ソルベントを添加せずに、２６０℃で
８時間反応させ、酸価２４、平均分子量１２万、n−ヘ
キサントレランス１．２g/gの樹脂３２５部を得た。こ
の樹脂について比較例３と同様に操作して、粘度７０P
a.Sのゲルワニス８２０部を得た。Comparative Example 4 The same reaction as in Example 1 was performed, except that 38 parts of pentaerythritol and 10 parts of glycerin were used, and 43 parts of glycerin was used. The reaction was carried out at 260 ° C. for 8 hours without adding Nisseki AF7 solvent. 325 parts of a resin having an acid value of 24, an average molecular weight of 120,000 and n-hexane tolerance of 1.2 g / g were obtained. This resin was operated in the same manner as in Comparative Example 3 to obtain a resin having a viscosity of 70 P
820 parts of aS gel varnish were obtained.
【００３８】実施例及び比較例で得られたゲルワニスを
使用してインキを調製し、そのインキについて性能を評
価した。Inks were prepared using the gel varnishes obtained in Examples and Comparative Examples, and the performance of the inks was evaluated.
【００３９】ａ．インキの調製 得られた各々のゲルワニス６０部と、東洋インキ製造社
製紅顔料カーミン６Ｂ１８部とを混合し、三本ロールミ
ルを用いて分散した後、ナフテン酸マンガン０．５部及
び、ＡＦ６号ソルベントと各々のゲルワニスとを添加し
て、２５℃のタックが９〜１０、平行板粘度計の６０秒
値直径が３２．０〜３４．０mmとなるように調整し、枚
葉インキを調製した。A. Preparation of Ink 60 parts of each of the obtained gel varnishes and 18 parts of red pigment Carmine 6B manufactured by Toyo Ink Mfg. Co., Ltd. were mixed and dispersed using a three-roll mill, and then 0.5 parts of manganese naphthenate and AF6 Solvent were used. And the respective gel varnishes were added to adjust the tack at 25 ° C. to 9 to 10 and the 60-second diameter of the parallel plate viscometer to 32.0 to 34.0 mm to prepare a sheet-fed ink.
【００４０】ｂ．印刷試験評価 各実施例及び比較例２，４から得られた枚葉インキにつ
いて、インキの光沢、濃度、セット性、ミスチング及び
最大乳化量を測定した。B. Printing Test Evaluation With respect to the sheet ink obtained from each of the examples and Comparative Examples 2 and 4, gloss, density, setting property, misting and maximum emulsification amount of the ink were measured.
【００４１】なお比較例１は樹脂を製造することができ
ず、また比較例３はワニス中に不溶解成分が多くてイン
キを調製することができなかったので、対象から除外し
た。各測定項目の測定方法は次の通りである。In Comparative Example 1, no resin could be produced, and in Comparative Example 3, an ink could not be prepared due to a large amount of insoluble components in the varnish. The measuring method of each measurement item is as follows.
【００４２】光沢：インキ０．２５ccを、明製作所製Ｒ
Ｉテスター全面ロールでアート紙に展色したのち、１日
後の光沢値を６０°−６０°光沢計で測定した。 濃度：光沢を測定したのと同一の展色紙について、反射
濃度計を用いて濃度を測定した。 セット：インキ０．１５ccをＲＩテスター四分割ロール
でアート紙に展色した後、上からアート紙を重ね、一定
の加重をかけて、３分ごとに重ねた紙に転写するインキ
の度合を観察した。 ミスチング：インキ２カップを東洋精機社製インコメー
ターに載せ、ロール温度４０℃で、２０００rpmで２分
間回転させたときの、ロール下面と前面に置いた白色紙
上へのインキの飛散状態を観察した。 最大乳化量：乳鉢にインキ１０．０gと精製水２０．０g
を秤り取り、乳棒で練った時のインキの重量増加を乳化
量として測定した。Gloss: 0.25 cc of ink, R
After the color was spread on the art paper with the whole roll of the I tester, the gloss value one day later was measured with a 60 ° -60 ° gloss meter. Density: The density was measured using a reflection densitometer on the same colored paper as that for which the gloss was measured. Set: 0.15 cc of ink is spread on art paper with a RI tester quadruple roll, then the art paper is overlaid from above, with a certain weight applied, and the degree of ink transferred to the overlaid paper every 3 minutes is observed. did. Misting: Two cups of the ink were placed on an incometer manufactured by Toyo Seiki Co., Ltd., and the state of ink scattering on white paper placed on the lower surface and the front surface of the roll when rotated at 2000 rpm for 2 minutes at a roll temperature of 40 ° C. was observed. Maximum emulsification amount: 10.0 g of ink and 20.0 g of purified water in a mortar
Was weighed, and the weight increase of the ink when kneaded with a pestle was measured as an emulsified amount.
【００４３】試験の結果を表１に示す。Table 1 shows the test results.
【００４４】[0044]
【表１】 [Table 1]
【００４５】評価 表１からも明らかなように、本発明により得られたロジ
ン変性フェノール樹脂を使用した印刷インキは、通常の
ロジン変性フェノール樹脂に比べ、光沢とセットとのバ
ランスが良好で、ミスチング及び最大乳化量において、
優れた改善が見られた。Evaluation As is clear from Table 1, the printing ink using the rosin-modified phenolic resin obtained according to the present invention has a better balance between gloss and set than ordinary rosin-modified phenolic resin, and has a misting. And at the maximum emulsification amount,
Excellent improvement was seen.
【００４６】さらにインキの転移性がよく、印刷試験片
に同量のインキを展色したさいに印刷濃度が高くなる。
すなわち本発明により得られた樹脂は、印刷時の印刷適
性が極めて優れたものになっており、特に高速印刷の際
にこの特異な性能が発揮されるものである。Furthermore, the transferability of the ink is good, and the printing density becomes high when the same amount of the ink is spread on the printed test piece.
That is, the resin obtained by the present invention has extremely excellent printability at the time of printing, and exhibits such a unique performance particularly at the time of high-speed printing.
【００４７】同様の組成のロジン変性フェノール樹脂で
あっても、溶剤を添加することなく合成したものは、比
較例１、３に見られるように適切なインキを調製するこ
とができず、また比較例４のように多価アルコールの等
量数を減らせばインキの調製は可能であるが、インキの
転移性が悪く光沢が不良であって、本発明により得られ
たインキに比べて性能が大幅に劣る。Even if a rosin-modified phenolic resin having the same composition was synthesized without adding a solvent, an appropriate ink could not be prepared as shown in Comparative Examples 1 and 3. Ink can be prepared by reducing the equivalent number of polyhydric alcohols as in Example 4, but the transferability of the ink is poor and the gloss is poor, and the performance is significantly higher than that of the ink obtained by the present invention. Inferior.
【００４８】さらに合成の当初から溶剤を添加した場合
には、比較例２に見られるように、同一組成の実施例１
と比べてワニスの粘度が低く、インキのセット性が悪
く、さらにミスチングが不良である。Further, when a solvent was added from the beginning of the synthesis, as shown in Comparative Example 2, Example 1 having the same composition was used.
The varnish has a lower viscosity than that of the varnish, has poor ink setting properties, and has poor misting.
【００４９】[0049]
【発明の効果】従って本発明によれば、高速印刷適性が
良好なインキ用ロジン変性フェノール樹脂を得ることが
でき、この樹脂をオフセット印刷インキに使用すること
により、光沢、セットのバランスとミスチングと乳化性
にすぐれ、さらにインキの転移性がよく、印刷濃度の高
い優れたインキとなる。Thus, according to the present invention, it is possible to obtain a rosin-modified phenol resin for inks having good suitability for high-speed printing, and by using this resin for offset printing ink, it is possible to obtain a balance between gloss, set and misting. Excellent emulsifiability, good ink transferability, and excellent printing density.
【００５０】そのため枚葉インキとしては乾燥性がすぐ
れ、印刷物の即納対応が可能となり、半乾性油の大豆油
の含有率をあげることができる。また水無しインキでは
凝集力がつき地汚れしにくくなり、オフ輪インキではよ
り印刷機速度を上げることができて生産効率が向上する
など、高速印刷適性を備えた、優れた実用的効果を有す
るものである。Therefore, the sheet-fed ink has excellent drying properties, enables immediate delivery of printed matter, and can increase the content of soybean oil as a semi-dry oil. In addition, waterless inks have a good practical effect with high-speed printing aptitude, such as cohesive strength and less soiling, and off-wheel inks can increase printing machine speed and improve production efficiency. Things.
Claims (2)
して、フェノールホルムアルデヒド初期縮合物５０〜１
５０重量部及び、前記ロジン又はその誘導体のカルボン
酸に対して０．１〜１．５モル当量の多価アルコールを
混合し、これを加熱反応させてロジン変性フェノール樹
脂を生成するに当たり、その反応生成物の重量平均分子
量が１０００以上となった時点で、沸点が１６０℃〜３
２０℃のオフセット印刷インキ用溶剤１〜１００重量部
を添加することを特徴とする、印刷インキ用樹脂組成物
の製造方法1. A phenol formaldehyde precondensate of 50 to 1 based on 100 parts by weight of rosin or a derivative thereof.
50 parts by weight and 0.1 to 1.5 molar equivalents of a polyhydric alcohol with respect to the carboxylic acid of the rosin or a derivative thereof are mixed, and the mixture is heated and reacted to produce a rosin-modified phenol resin. When the weight average molecular weight of the product becomes 1000 or more, the boiling point is 160 ° C to 3 ° C.
A method for producing a resin composition for printing ink, comprising adding 1 to 100 parts by weight of a solvent for offset printing ink at 20 ° C.
〜５０重量部の植物油を添加することを特徴とする、請
求項１に記載の印刷インキ用樹脂組成物の製造方法2. The rosin-modified phenolic resin together with
The method for producing a resin composition for a printing ink according to claim 1, wherein the vegetable oil is added in an amount of 50 to 50 parts by weight.
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|---|---|---|---|
| JP35399499A JP4166394B2 (en) | 1999-12-14 | 1999-12-14 | Method for producing resin composition for printing ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35399499A JP4166394B2 (en) | 1999-12-14 | 1999-12-14 | Method for producing resin composition for printing ink |
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|---|---|
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| JP4166394B2 JP4166394B2 (en) | 2008-10-15 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203975A (en) * | 2002-12-24 | 2004-07-22 | Arakawa Chem Ind Co Ltd | Method for manufacturing resin varnish for printing ink |
| JP2009227785A (en) * | 2008-03-21 | 2009-10-08 | Arakawa Chem Ind Co Ltd | Rosin-modified phenolic resin, resin varnish for printing ink, pigment coating agent, and printing ink |
| JP2012001714A (en) * | 2010-05-19 | 2012-01-05 | Arakawa Chem Ind Co Ltd | Rosin-modified phenolic resin, printing ink varnish, and printing ink |
| CN102321405A (en) * | 2011-07-28 | 2012-01-18 | 黄山新力油墨科技有限公司 | Environmentally-friendly surface printing plastic white ink and preparation method thereof |
-
1999
- 1999-12-14 JP JP35399499A patent/JP4166394B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203975A (en) * | 2002-12-24 | 2004-07-22 | Arakawa Chem Ind Co Ltd | Method for manufacturing resin varnish for printing ink |
| JP4529169B2 (en) * | 2002-12-24 | 2010-08-25 | 荒川化学工業株式会社 | Manufacturing method of resin varnish for printing ink |
| JP2009227785A (en) * | 2008-03-21 | 2009-10-08 | Arakawa Chem Ind Co Ltd | Rosin-modified phenolic resin, resin varnish for printing ink, pigment coating agent, and printing ink |
| JP2012001714A (en) * | 2010-05-19 | 2012-01-05 | Arakawa Chem Ind Co Ltd | Rosin-modified phenolic resin, printing ink varnish, and printing ink |
| CN102321405A (en) * | 2011-07-28 | 2012-01-18 | 黄山新力油墨科技有限公司 | Environmentally-friendly surface printing plastic white ink and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP4166394B2 (en) | 2008-10-15 |
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