JP6963013B2 - Oxidation Polymerization Dry Offset Printing Ink Compositions and Printed Matter - Google Patents
Oxidation Polymerization Dry Offset Printing Ink Compositions and Printed Matter Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/08—Printing inks based on natural resins
Description
本発明は、酸化重合乾燥型オフセット印刷インキ組成物および当該酸化重合乾燥型オフセット印刷インキ組成物を用いて印刷された印刷物に関する。 The present invention relates to an oxidative polymerization dry type offset printing ink composition and a printed matter printed using the oxidative polymerization dry type offset printing ink composition.
酸化重合乾燥型のオフセット印刷インキ組成物は、空気中の酸素によりワニスに含まれる酸化重合性の成分が重合して硬化被膜を形成するものである。酸化重合を促進させるために、オクチル酸などの有機酸と、コバルトやマンガンなどの遷移金属との金属塩のようなドライヤーが一般に配合されている。また、場合により熱乾燥方式を併用することもある。 In the oxidative polymerization dry type offset printing ink composition, the oxidatively polymerizable components contained in the varnish are polymerized by oxygen in the air to form a cured film. In order to promote oxidative polymerization, a dryer such as a metal salt of an organic acid such as octyl acid and a transition metal such as cobalt or manganese is generally blended. In some cases, a heat drying method may be used in combination.
このようにドライヤーを配合したり、熱乾燥方式を併用したりしても、酸化重合乾燥型のオフセット印刷インキ組成物によって印刷された印刷物の乾燥には数時間を要する。この間、印刷物は重ねて保管されるため、印刷直後の印刷面（印刷インキ組成物）が次に印刷して重ねられた印刷物の裏面に付着する、裏移りと呼ばれる問題が生じる。
裏移りを防止する手法として、印刷直後に微粉末を印刷面に散布する、所謂パウダー散布が広く行われている（特許文献１）。Even if a dryer is blended in this way or a heat drying method is used in combination, it takes several hours to dry the printed matter printed by the oxidative polymerization drying type offset printing ink composition. During this period, since the printed matter is stored in layers, a problem called set-off occurs in which the printed surface (printing ink composition) immediately after printing adheres to the back surface of the printed matter that is printed next and overlapped.
As a method for preventing set-off, so-called powder spraying, in which fine powder is sprayed on the printed surface immediately after printing, is widely used (Patent Document 1).
しかしながら、特許文献１のようなパウダー散布は裏移り防止に効果的ではあるが、印刷物の光沢が低下したり、後加工として例えば印刷面にポリプロピレンフィルムを貼る際にフィルムと紙面の密着性が低下したりという不具合が生じるおそれがある。また、パウダーが印刷機周辺に飛散、浮遊して作業環境が悪化するだけでなく、飛散したパウダーが印刷機の磨耗を促進させるおそれもある。 However, although powder spraying as in Patent Document 1 is effective in preventing set-off, the gloss of the printed matter is lowered, and the adhesion between the film and the paper surface is lowered when, for example, a polypropylene film is attached to the printed surface as post-processing. There is a risk of problems such as printing. Further, not only the powder is scattered and floated around the printing machine and the working environment is deteriorated, but also the scattered powder may accelerate the wear of the printing machine.
本発明はこのような事情に鑑みなされたものであって、パウダー散布を行わないか、パウダーの散布量を従来よりも削減した場合であっても裏移りを防止する酸化重合乾燥型オフセット印刷インキ組成物を提供することを目的とする。 The present invention has been made in view of such circumstances, and is an oxidative polymerization dry type offset printing ink that prevents set-off even when powder is not sprayed or the amount of powder sprayed is reduced as compared with the conventional case. It is an object of the present invention to provide a composition.
本発明は、ＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂を含むワニスと、ドライヤーと、顔料と、融点が８０℃以下でありノルマルパラフィンを含む石油系ワックスと、を含み、Ｌ型粘度計で測定した粘度が１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下であり、ノルマルパラフィンの含有量が０．１質量％以上３質量％以下であり、顔料の含有量が規定の範囲内にあることを特徴とする酸化重合乾燥型オフセット印刷インキ組成物に関する。 The present invention comprises a varnish containing a rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C. or higher and 210 ° C. or lower, a dryer, a pigment, and a petroleum wax having a melting point of 80 ° C. or lower and containing normal paraffin. The viscosity measured by an L-type viscometer is 10 Pa · s or more and 60 Pa · s or less, the content of normal paraffin is 0.1% by mass or more and 3% by mass or less, and the pigment content is within the specified range. The present invention relates to an oxidative polymerization dry type offset printing ink composition, which is characterized by being inside.
本発明の酸化重合乾燥型オフセット印刷インキ組成物によれば、印刷物の耐裏移り性を良好なものとすることができる。 According to the oxidative polymerization drying type offset printing ink composition of the present invention, the set-off resistance of the printed matter can be improved.
＜酸化重合乾燥型オフセット印刷インキ組成物＞
本発明の酸化重合乾燥型オフセット印刷インキ組成物は、ワニス、ドライヤー、顔料、石油系ワックスを含むことを特徴とする。以下、本発明の酸化重合乾燥型オフセット印刷インキ組成物について詳述する。また、以下では酸化重合乾燥型オフセット印刷インキ組成物を単に印刷インキともいう。<Oxidation polymerization drying type offset printing ink composition>
The oxidative polymerization dry type offset printing ink composition of the present invention is characterized by containing a varnish, a dryer, a pigment, and a petroleum-based wax. Hereinafter, the oxidative polymerization drying type offset printing ink composition of the present invention will be described in detail. Further, in the following, the oxidative polymerization drying type offset printing ink composition is also simply referred to as a printing ink.
本発明の印刷インキに用いるワニスは、必須の成分としてＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂を含み、必要に応じて他の樹脂類、植物油類または脂肪酸エステル類またはそれらの混合物、石油系溶剤、キレート化剤、その他助剤等を加熱溶解させて得られる。なお、本明細書においてＡＦソルベント６号の曇点とは、ＮＯＢＯＭＡＴＩＣＳ社自動曇点測定器ＣＨＥＭＯＴＯＲＯＮＩＣ ＩＩを使用し、ＡＦソルベント６号（ＪＸＴＧエネルギー株式会社製）１８０質量部と樹脂２０質量部とを加熱混合した際の、白濁下限温度である。 The varnish used in the printing ink of the present invention contains a rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C. or higher and 210 ° C. or lower as an essential component, and other resins, vegetable oils or fatty acid esters as required. It is obtained by heating and dissolving a kind or a mixture thereof, a petroleum solvent, a chelating agent, and other auxiliaries. In the present specification, the cloud point of AF solvent No. 6 is 180 parts by mass of AF solvent No. 6 (manufactured by JXTG Energy Co., Ltd.) and 20 parts by mass of resin using the automatic cloud point measuring instrument CHEMOTORONIC II of NOBOMATICS. This is the lower limit of cloudiness when heated and mixed.
このようなロジン変性フェノール樹脂は、例えば、ホルムアルデヒドおよび／またはパラホルムアルデヒドとフェノール類との加熱反応により得られる平均核体数が１．５〜３．０のレゾールを、ロジン類と多価アルコールとの反応により得られるロジンエステル樹脂と反応させて得られる樹脂や、あるいは、平均核体数が１．５〜３．０のレゾールとロジン類とを反応させた後、多価アルコールでエステル化して得られる樹脂を用いることができる。 Such a rosin-modified phenolic resin is prepared by, for example, using a resol having an average number of nuclei of 1.5 to 3.0 obtained by a heating reaction between formaldehyde and / or paraformaldehyde and phenols, and using rosins and polyhydric alcohols. The resin obtained by reacting with the rosin ester resin obtained by the above reaction, or the resol having an average number of nuclei of 1.5 to 3.0 is reacted with rosins and then esterified with a polyhydric alcohol. The obtained resin can be used.
レゾールの調整に用いるフェノール類としては、例えば、フェノール、クレゾール、アミルフェノール、ｐ−ターシャリーブチルフェノール、ｐ−オクチルフェノール、ｐ−ノニルフェノール、ｐ−ドデシルフェノール、ビスフェノールＡなどが挙げられ、中でもｐ−ターシャリーブチルフェノール、ｐ−オクチルフェノール、ｐ−ノニルフェノール、ｐ−ドデシルフェノール等の、パラ位に炭素原子数が４〜１２の置換基を持つアルキルフェノールを用いることが好ましい。 Examples of the phenols used for adjusting the resole include phenol, cresol, amylphenol, p-terrary butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol, bisphenol A and the like, among which p-tershaly It is preferable to use an alkylphenol having a substituent having 4 to 12 carbon atoms at the para position, such as butylphenol, p-octylphenol, p-nonylphenol, and p-dodecylphenol.
ロジン類としては、従来公知のものを用いることができ特に制限はない。ガムロジン、ウッドロジン、トール油ロジン、重合ロジン、酸変性ロジン、およびこれらのロジン類を蒸留等により精製したものなどが挙げられる。 As the rosins, conventionally known rosins can be used, and there is no particular limitation. Examples thereof include gum rosin, wood rosin, tall oil rosin, polymerized rosin, acid-modified rosin, and those obtained by purifying these rosins by distillation or the like.
酸変性ロジンを用いる場合、ロジンの変性に用いる化合物としては、二塩基酸またはその無水物を用いることが好ましい。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、中でもフマル酸、マレイン酸、無水マレイン酸が好ましく用いられる。 When acid-modified rosin is used, it is preferable to use dibasic acid or an anhydride thereof as the compound used for rosin modification. Examples thereof include fumaric acid, maleic acid, maleic anhydride, adipic acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and trimellitic anhydride, and among them, fumaric acid, maleic acid, and maleic anhydride are preferably used.
多価アルコールとしては、例えば、グリセリン、ジグリセリン、トリメチロールエタン、トリメチロールプロパン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ネオペンチルグリコール、ペンタエリスリトール、ジペンタエリスリトール、ソルビトールなどが挙げられ、中でもグリセリン、ペンタエリスリトールが好ましく用いられる。 Examples of the polyhydric alcohol include glycerin, diglycerin, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol and the like. Of these, glycerin and pentaerythritol are preferably used.
ＡＦソルベント６号の曇点が１００℃以上２１０℃以下であるロジン変性フェノール樹脂の重量平均分子量は１５，０００以上であることが好ましく、３０，０００以上であることがより好ましい。また、１５０，０００以下であることが好ましい。なお、本明細書における重量平均分子量は、下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される値である。 The cloud point of AF solvent No. 6 is 100 ° C. or higher and 210 ° C. or lower. The weight average molecular weight of the rosin-modified phenol resin is preferably 15,000 or more, and more preferably 30,000 or more. Further, it is preferably 150,000 or less. The weight average molecular weight in the present specification is a value measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ；東ソー株式会社製 ＨＬＣ−８３２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫｇｅｌ ４０００ＨＸＬ、ＴＳＫｇｅｌ ３０００ＨＸＬ、ＴＳＫｇｅｌ ２０００ＨＸＬ、ＴＳＫｇｅｌ １０００ＨＸＬ
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）Measuring device; HLC-8320GPC manufactured by Tosoh Corporation
Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)
本発明で用いられるＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂は、さらに、軟化点が１５０℃以上であることが好ましく、１６０℃以上であることがより好ましい。また、軟化点は２００℃以下であることが好ましい。なお、本明細書における軟化点は、ＪＩＳ Ｋ５６０１−２−２に準拠し環球法により測定したもので、具体的には試料を充填した黄銅製環をグリセリン浴中に水平に保持し、試料の中心に一定重量の鋼球をのせ、一定速度で浴温を上昇させ、試料が次第に軟化し、鋼球が下降し、ついに厚さ２５ｍｍの位置の底板に達したときの温度計の示度をもって軟化点とする。 The rosin-modified phenol resin having a cloud point of 100 ° C. or higher and 210 ° C. or lower used in the present invention preferably has a softening point of 150 ° C. or higher, more preferably 160 ° C. or higher. The softening point is preferably 200 ° C. or lower. The softening point in the present specification is measured by the ring-and-ball method in accordance with JIS K5601-2-2. Specifically, the brass ring filled with the sample is held horizontally in the glycerin bath, and the sample is prepared. With a thermometer reading when a constant weight steel ball is placed in the center, the bath temperature is raised at a constant speed, the sample gradually softens, the steel ball descends, and finally reaches the bottom plate at a thickness of 25 mm. Let it be a softening point.
上述した、ＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂と併用可能な他の樹脂としては、従来公知のものを使用することができ特に制限はない。ロジン樹脂、ロジン変性フェノール樹脂、ロジンエステル、石油樹脂、アクリル樹脂、ポリエステル、アルキド樹脂、石油樹脂変性ロジン・フェノール樹脂、石油樹脂変性ロジンエステル、石油樹脂変性アルキド樹脂、アルキド樹脂変性ロジン・フェノール樹脂、アルキド樹脂変性ロジンエステル、アクリル変性ロジン・フェノール樹脂、アクリル変性ロジンエステル、ウレタン変性ロジン・フェノール樹脂、ウレタン変性ロジンエステル、ウレタン変性アルキド樹脂、エポキシ変性ロジン・フェノール樹脂、エポキシ変性ロジンエステル、エポキシ変性アルキド樹脂等が例示される。これらの樹脂は単独で用いてもよいし、二種以上を併用してもよい。 As the other resin that can be used in combination with the above-mentioned rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C. or higher and 210 ° C. or lower, conventionally known resins can be used and are not particularly limited. Rosin resin, rosin-modified phenol resin, rosin ester, petroleum resin, acrylic resin, polyester, alkyd resin, petroleum resin-modified rosin-phenol resin, petroleum resin-modified rosin ester, petroleum resin-modified alkyd resin, alkyd resin-modified rosin-phenol resin, Alkyd resin modified rosin ester, acrylic modified rosin / phenol resin, acrylic modified rosin ester, urethane modified rosin / phenol resin, urethane modified rosin ester, urethane modified alkyd resin, epoxy modified rosin / phenol resin, epoxy modified rosin ester, epoxy modified alkyd Examples include resins. These resins may be used alone or in combination of two or more.
本発明の印刷インキが、ＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂と、それ以外の樹脂とを含む場合、印刷インキに含まれる樹脂の合計のうち、ＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂が占める割合が７５質量％以上であることが好ましく、８５質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。 When the printing ink of the present invention contains a rosin-modified phenolic resin having a cloud point of AF solvent No. 6 of 100 ° C. or higher and 210 ° C. or lower and other resins, AF solvent is out of the total of the resins contained in the printing ink. The proportion of the rosin-modified phenolic resin having a cloud point of No. 6 of 100 ° C. or higher and 210 ° C. or lower is preferably 75% by mass or more, more preferably 85% by mass or more, and more preferably 90% by mass or more. More preferred.
ワニスの調整に用いられる溶剤としては、従来公知のものを用いることができ特に制限はない。
植物油類としては、ヒマシ油、落花生油、オリーブオイルなどの不乾性油、大豆油、綿実油、菜種油、ゴマ油、コーン油などの半乾性油、アマニ油、エノ油、桐油などの乾性油、再生植物油、植物エステル等の植物由来成分などを用いることができる。As the solvent used for adjusting the varnish, conventionally known solvents can be used, and there is no particular limitation.
Vegetable oils include non-drying oils such as castor oil, peanut oil and olive oil, semi-drying oils such as soybean oil, cottonseed oil, rapeseed oil, sesame oil and corn oil, drying oils such as flaxseed oil, eno oil and tung oil, and recycled vegetable oils. , Plant-derived components such as plant ester can be used.
植物油類として、再生植物油を使用することもできる。再生植物油とは、調理等に使用された油を回収し、再生処理された植物油のことである。再生植物油としては、含水率を０．３質量％以下、ヨウ素価を９０以上、酸価を３以下として再生処理した油が好ましく、より好ましくはヨウ素価１００以上である。含水率を０．３質量％以下にすることにより水分に含まれる塩分等のインキの乳化挙動に影響を与える不純物を除去することが可能となり、ヨウ素価を９０以上として再生することにより、乾燥性、すなわち酸化重合性の良いものとすることが可能となり、さらに酸価が３以下の植物油を選別して再生することにより、インキの過乳化を抑制することが可能となる。回収植物油の再生処理方法としては、濾過、静置による沈殿物の除去、および活性白土等による脱色といった方法が例示される。 Recycled vegetable oils can also be used as the vegetable oils. The regenerated vegetable oil is a vegetable oil that has been regenerated by recovering the oil used for cooking or the like. As the regenerated vegetable oil, an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 90 or more, and an acid value of 3 or less is preferable, and an iodine value of 100 or more is more preferable. By setting the water content to 0.3% by mass or less, it is possible to remove impurities such as salts contained in the water that affect the emulsification behavior of the ink, and by regenerating with an iodine value of 90 or more, the drying property That is, it is possible to obtain a good oxidative polymerization property, and further, by selecting and regenerating a vegetable oil having an acid value of 3 or less, it is possible to suppress overemulsification of the ink. Examples of the method for regenerating the recovered vegetable oil include methods such as filtration, removal of precipitates by standing, and decolorization with activated clay or the like.
脂肪酸エステル類としては、例えば、大豆油脂肪酸メチルエステル、大豆油脂肪酸ブチルエステル、大豆油脂肪酸イソブチルエステル、大豆油脂肪酸２−エチルヘキシルエステル、亜麻仁油脂肪酸ブチルエステル、アマニ油脂肪酸イソブチルエステル、トール油脂肪酸ブチルエステル、トール油脂肪酸２−エチルヘキシルエステル、トール油脂オクチルエステル、トール油脂肪酸ペンタエリスリトールエステル、パーム油脂肪酸メチルエステル、パーム油脂肪酸ブチルエステル、パーム油脂肪酸イソブチルエステル、パーム油脂肪酸２−エチルヘキシルエステル、ヒマシ油脂肪酸メチルエステル、ヒマシ油脂肪酸ブチルエステル、ヒマシ油脂肪酸イソブチルエステル、ヒマシ油脂肪酸２−エチルヘキシルエステル等が挙げられる。 Examples of fatty acid esters include soybean oil fatty acid methyl ester, soybean oil fatty acid butyl ester, soybean oil fatty acid isobutyl ester, soybean oil fatty acid 2-ethylhexyl ester, flaxseed oil fatty acid butyl ester, flaxseed oil fatty acid isobutyl ester, and tall oil fatty acid butyl. Estel, Thor Oil Fatty Acid 2-Ethylhexyl Ester, Tall Oil Fatty Acid Octyl Ester, Tall Oil Fatty Acid Pentaerythritol Ester, Palm Oil Fatty Acid Methyl Estel, Palm Oil Fatty Acid Butyester, Palm Oil Fatty Acid Isobutyl Estel, Palm Oil Fatty Acid 2-Ethylhexyl Estel, Himasi Oil Examples thereof include fatty acid methyl ester, bean oil fatty acid butyl ester, bean oil fatty acid isobutyl ester, and bean oil fatty acid 2-ethylhexyl ester.
石油系溶剤としては、炭素数６〜２０の炭化水素が好ましく用いられる。具体的には、ｎ−ペンタン、イソペンタン、ｎ−ヘキサン、２−メチルペンタン、ｎ−ヘプタン、ｎ−オクタン、トリメチルペンタンなどのパラフィン系溶剤、シクロヘキサン、シクロヘキシルメタン、オクタデシルシクロヘキサン、メチルイソプロピルシクロヘキサンなどのナフテン系溶剤、ＪＸＴＧエネルギー株式会社製の「ＡＦソルベント４号」、「ＡＦソルベント５号」、「ＡＦソルベント６号」、「ＡＦソルベント７号」等が挙げられる。 As the petroleum-based solvent, a hydrocarbon having 6 to 20 carbon atoms is preferably used. Specifically, paraffinic solvents such as n-pentane, isopentane, n-hexane, 2-methylpentane, n-heptane, n-octane, and trimethylpentane, and naphthenes such as cyclohexane, cyclohexylmethane, octadecylcyclohexane, and methylisopropylcyclohexane. Examples of the solvent include "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", and "AF Solvent No. 7" manufactured by JXTG Energy Co., Ltd.
キレート化剤としては、例えば、アルミニウムｎ−ブトキシド、アルミニウム−ｉｓｏ−ブトキシド、アルミニウム−ｓｅｃ−ブトキシドの誘導体で、ｎ−ブトキシ基、ｉｓｏ−ブトキシ基、ｓｅｃ−ブトキシ基の各々の基の一つが、エチルアセテート、又は、メチルアセトアセテートで置換された化合物等を使用することができる。 As the chelating agent, for example, it is a derivative of aluminum n-butoxide, aluminum-iso-butoxide, and aluminum-sec-butoxide, and one of each group of n-butoxy group, iso-butoxy group, and sec-butoxy group is used. Ethyl acetate, a compound substituted with methyl acetoacetate, or the like can be used.
本発明の印刷インキに用いる着色顔料としては特に限定されず、種々の有機顔料、無機顔料を用いることができる。例えば、黄顔料としては、ジスアゾイエロー（ピグメントイエロー１２、ピグメントイエロー１３、ピグメントイエロー１７、ピグメントイエロー１）、ハンザイエロー等が挙げられ、紅顔料としては、ブリリアントカーミン６B、レーキレッドC、ウォッチングレッド等が挙げられる。藍顔料としては、フタロシアニンブルー、フタロシアニングリーン、アルカリブルー等が挙げられ、墨顔料としてはファーネスカーボンブラック、チャンネルブラックなどのカーボンブラック、アニリンブラック等が挙げられる。 The coloring pigment used in the printing ink of the present invention is not particularly limited, and various organic pigments and inorganic pigments can be used. For example, examples of yellow pigments include disazo yellow (Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 17, Pigment Yellow 1), Hansa Yellow and the like, and examples of red pigments include Brilliant Carmine 6B, Lake Red C, Watching Red and the like. Can be mentioned. Examples of the indigo pigment include phthalocyanine blue, phthalocyanine green, and alkali blue, and examples of the black pigment include carbon black such as furnace carbon black and channel black, and aniline black.
本発明の印刷インキはＪＩＳ Ｋ５７０１−１に記載のＬ型粘度計による方法にて測定した粘度が１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下となるよう調整して用いられる。その際、本発明の印刷インキに含まれる顔料の含有量は、黄インキにおける黄顔料の含有量は印刷インキの７質量％以上１５質量％以下であり、紅インキにおける紅顔料の含有量は印刷インキの１３質量％以上２０質量％以下であり、藍インキにおける藍顔料の含有量は１６質量％以上２３質量％以下であり、墨インキにおける墨顔料の含有量は１７質量％以上２４質量％以下である。 The printing ink of the present invention is used after adjusting the viscosity measured by the method using an L-type viscometer described in JIS K5701-1 so that the viscosity is 10 Pa · s or more and 60 Pa · s or less. At that time, the content of the pigment contained in the printing ink of the present invention is such that the content of the yellow pigment in the yellow ink is 7% by mass or more and 15% by mass or less of the printing ink, and the content of the red pigment in the red ink is printing. 13% by mass or more and 20% by mass or less of the ink, the content of the indigo pigment in the indigo ink is 16% by mass or more and 23% by mass or less, and the content of the black pigment in the black ink is 17% by mass or more and 24% by mass or less. Is.
着色顔料の他に体質顔料を含んでいてもよい。体質顔料としては特に限定されず、ろう石クレー等のクレー、タルク、硫酸バリウム、炭酸カルシウム、重質炭酸カルシウム、炭酸バリウム、シリカ、ベントナイト、酸化チタン等、公知のものを１種類または２種類以上用いることができる。 In addition to the coloring pigment, an extender pigment may be contained. The extender pigment is not particularly limited, and one or more known ones such as clay such as pyrophyllite clay, talc, barium sulfate, calcium carbonate, heavy calcium carbonate, barium carbonate, silica, bentonite, titanium oxide and the like are used. Can be used.
ドライヤーとしては、酸化重合乾燥型印刷インキに通常用いられるものならば特に制限なく用いることができる。例えば、コバルト、マンガン、鉛、鉄、亜鉛、カルシウム、セリウム、レアアース等の金属と、オクチル酸、ナフテン酸、ネオデカン酸、桐油酸、アマニ油酸、大豆油酸、樹脂酸等のカルボン酸との塩、すなわち金属石鹸、あるいは、コバルト、マンガン、鉛、鉄、亜鉛、カルシウム、セリウム、レアアース等の金属とのホウ酸塩等が挙げられる。これらのドライヤーを単独で用いてもよいし、2種類以上を組み合わせて用いてもよい。 The dryer can be used without particular limitation as long as it is usually used for oxidative polymerization drying type printing ink. For example, metals such as cobalt, manganese, lead, iron, zinc, calcium, cerium and rare earth, and carboxylic acids such as octyl acid, naphthenic acid, neodecanoic acid, tung oil acid, linseed oil acid, soybean oil acid and resin acid. Examples thereof include salts, that is, metal soaps, and borates with metals such as cobalt, manganese, lead, iron, zinc, calcium, cerium, and rare earth. These dryers may be used alone or in combination of two or more.
本発明の印刷インキに用いられる石油系ワックスは、融点が８０℃以下であり、常温で固体のものである。耐裏移り性をより良好なものとするため、融点が５０℃以上のものを用いることが好ましい。石油系ワックスとは、石油の精製により得られる、不定形のものである。ノルマルパラフィン、イソパラフィン、シクロパラフィン、およびこれらの混合物が例示され、本発明ではノルマルパラフィンを８０質量％以上含むものを用いることが好ましく、ノルマルパラフィンを８５質量％以上含むものを用いることがより好ましい。上述した、ＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂と、このような石油系ワックスとを併用することにより、印刷インキの耐裏移り性を良好なものとすることができる。 The petroleum-based wax used in the printing ink of the present invention has a melting point of 80 ° C. or lower and is solid at room temperature. In order to improve the set-off resistance, it is preferable to use one having a melting point of 50 ° C. or higher. Petroleum-based wax is an amorphous wax obtained by refining petroleum. Normal paraffin, isoparaffin, cycloparaffin, and mixtures thereof are exemplified. In the present invention, those containing 80% by mass or more of normal paraffin are preferably used, and those containing 85% by mass or more of normal paraffin are more preferable. By using the above-mentioned rosin-modified phenolic resin having a cloud point of AF Solvent No. 6 of 100 ° C. or higher and 210 ° C. or lower in combination with such a petroleum-based wax, the set-off resistance of the printing ink is improved. be able to.
石油系ワックスはそのまま印刷インキに添加してもよいが、溶剤と加熱攪拌した後、室温まで冷却して得られるコンパウンドとして添加することがより好ましい。このとき用いる溶剤としては、上述したワニスの調整に用いるものと同様のものを適宜用いることができ特に制限はない。 The petroleum wax may be added to the printing ink as it is, but it is more preferable to add it as a compound obtained by heating and stirring with a solvent and then cooling to room temperature. As the solvent used at this time, the same solvent as that used for adjusting the varnish described above can be appropriately used, and there is no particular limitation.
石油系ワックスは、ノルマルパラフィンの含有量が印刷インキの０．１質量％以上となるよう用いることが好ましい。また、ワックスの含有量が多すぎると後加工性が悪くなるため、ノルマルパラフィンの含有量が印刷インキの３質量％以下となる範囲で用いられることが好ましく、１質量％以下であることがより好ましく、０．５質量％以下であることがさらに好ましい。 The petroleum wax is preferably used so that the content of normal paraffin is 0.1% by mass or more of the printing ink. Further, if the wax content is too large, the post-processability deteriorates. Therefore, the normal paraffin content is preferably used in a range of 3% by mass or less of the printing ink, and more preferably 1% by mass or less. It is preferably 0.5% by mass or less, and more preferably 0.5% by mass or less.
本発明の印刷インキは、上述した石油系ワックスに加えて、平均粒子径Ｄ５０が２μｍ以上７μｍ以下の粒子を含むことが好ましい。なお、Ｄ５０とはメディアン径とも呼ばれ、粒度分布において粒径の小さい方から数えて体積基準の累積粒度分布曲線の５０％を表す。
このような粒子としては、真球状であってもよいし、不定形であってもよい。ポリエチレンワックス、ポリテトラフルオロエチレンワックス、フィッシャー・トロプシュワックス、樹脂粒子やこれらの複合体が挙げられ、一種または二種以上を組み合わせて用いることができる。石油系ワックスに加えてこのような粒子を併用することで、耐裏移り性、後加工性（滑性）を良好なものとすることができる。The printing ink of the present invention preferably contains particles having an average particle diameter D50 of 2 μm or more and 7 μm or less in addition to the petroleum-based wax described above. Note that D50 is also called a median diameter, and represents 50% of the volume-based cumulative particle size distribution curve counting from the smallest particle size in the particle size distribution.
Such particles may be spherical or irregular. Examples thereof include polyethylene wax, polytetrafluoroethylene wax, Fischer-Tropsch wax, resin particles and composites thereof, and one kind or a combination of two or more kinds can be used. By using such particles in combination with petroleum-based wax, set-off resistance and post-processability (slipperiness) can be improved.
本発明の印刷インキは、上述した石油系ワックスに加えて、デンプンを併用することがより好ましい。石油系ワックスに加えてデンプンを併用することで、耐裏移り性をさらに良好なものとすることができる。平均粒子径Ｄ５０が１０μｍ以上２０μｍ以下のものを用いることが好ましい。
印刷インキにおける、平均粒子径Ｄ５０が２μｍ以上７μｍ以下の粒子と平均粒子径Ｄ５０が１０μｍ以上２０μｍ以下のデンプンの含有量の合計は、０．５質量％以上であることが好ましく、３．０質量％以下であることが好ましい。In the printing ink of the present invention, it is more preferable to use starch in combination with the above-mentioned petroleum wax. By using starch in addition to petroleum wax, the set-off resistance can be further improved. It is preferable to use one having an average particle size D50 of 10 μm or more and 20 μm or less.
The total content of particles having an average particle size D50 of 2 μm or more and 7 μm or less and starch having an average particle size D50 of 10 μm or more and 20 μm or less in the printing ink is preferably 0.5% by mass or more, preferably 3.0% by mass. % Or less is preferable.
本発明の印刷インキは、リン酸、リン酸のアンモニウム塩、リン酸のアルカリ金属塩、リン酸のアルカリ土類金属二水素塩、クエン酸、クエン酸のアンモニウム塩、クエン酸のアルカリ金属塩、クエン酸のマグネシウム塩から成る群から選ばれる一つ以上の汚れ防止剤粒子を含むことが好ましい。汚れ防止剤粒子の含有量は、印刷インキの０．０１質量％以上０．５質量％以下であることが好ましく、０．０１質量％以上０．２質量％以下であることがより好ましい。印刷中の湿し水の使用量を抑制でき、セット遅延が防止され、耐裏移り性を良好なものとすることができる。 The printing ink of the present invention includes phosphoric acid, an ammonium salt of phosphoric acid, an alkali metal salt of phosphoric acid, an alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, an ammonium salt of citric acid, and an alkali metal salt of citric acid. It preferably contains one or more antifouling agent particles selected from the group consisting of magnesium salts of citric acid. The content of the antifouling agent particles is preferably 0.01% by mass or more and 0.5% by mass or less, and more preferably 0.01% by mass or more and 0.2% by mass or less of the printing ink. The amount of dampening water used during printing can be suppressed, set delay can be prevented, and set-off resistance can be improved.
本発明の印刷インキは、必要に応じて皮張り防止剤、粘度調整剤、分散剤、上述した以外の汚れ防止剤、乳化調整剤、酸化防止剤等の助剤を含んでいてもよい。本発明の効果を損なわない範囲で上述した石油系ワックスや平均粒子径Ｄ５０が２μｍ以上７μｍ以下のワックス粒子以外のワックスを併用してもよい。これらの助剤としては、従来公知のものを好適に用いることができる。 If necessary, the printing ink of the present invention may contain an auxiliary agent such as a skinning inhibitor, a viscosity modifier, a dispersant, a stain inhibitor other than those described above, an emulsion modifier, and an antioxidant. A wax other than the above-mentioned petroleum-based wax and wax particles having an average particle diameter D50 of 2 μm or more and 7 μm or less may be used in combination as long as the effects of the present invention are not impaired. As these auxiliary agents, conventionally known ones can be preferably used.
本発明の印刷インキが耐裏移り性に優れる理由は以下のように推察される。
本発明の印刷インキは、ＡＦソルベント６号の曇点が１００℃以上２１０℃以下のロジン変性フェノール樹脂を用いることにより、コート紙やマットコート紙に印刷した際のセット時間が短くなる。また、本発明のロジン変性フェノール樹脂と石油系ワックスの組み合わせは相溶性が低く、印刷後は分離しやすい。これらの相乗効果で石油系ワックスがインキ塗膜表面に集まりやすくなり、少量のワックスで効果的に裏移りを防止することができる。The reason why the printing ink of the present invention is excellent in set-off resistance is presumed as follows.
The printing ink of the present invention uses a rosin-modified phenolic resin having an AF solvent No. 6 cloud point of 100 ° C. or higher and 210 ° C. or lower, so that the setting time when printing on coated paper or matte coated paper is shortened. Further, the combination of the rosin-modified phenol resin of the present invention and the petroleum-based wax has low compatibility and is easy to separate after printing. Due to these synergistic effects, petroleum-based wax tends to collect on the surface of the ink coating film, and a small amount of wax can effectively prevent set-off.
さらに印刷インキの粘度を１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下とし、その際の顔料濃度を上述した範囲内とすることで、パイリング性と流動性に優れ、また印刷時にインキ塗膜に取り込まれる水の量が適性量となり、セット遅延を防止する事が出来る。これにより、効果的に裏移りを防止することができる。 Further, by setting the viscosity of the printing ink to 10 Pa · s or more and 60 Pa · s or less and setting the pigment concentration at that time within the above-mentioned range, the pilling property and the fluidity are excellent, and the water taken into the ink coating film at the time of printing is excellent. The amount becomes an appropriate amount, and set delay can be prevented. As a result, set-off can be effectively prevented.
本発明の印刷インキは単独で、例えば本発明の黄インキと、通常の（本発明を用いない）紅インキ、藍インキ、墨インキとをセットで用いてもパウダーの散布量を削減し、かつ裏移りを防止することができる。さらに本発明の黄インキ、紅インキ、藍インキ、墨インキをセットで用いると、より効果的に、紙面に印刷された印刷インキがセットするまでの時間を短縮でき、耐裏移り性を良好なものとすることができる。 Even if the printing ink of the present invention is used alone, for example, the yellow ink of the present invention and a normal (not used in the present invention) red ink, indigo ink, and black ink are used as a set, the amount of powder sprayed can be reduced and the amount of powder sprayed can be reduced. It is possible to prevent set-off. Further, when the yellow ink, the red ink, the indigo ink, and the black ink of the present invention are used as a set, the time until the printing ink printed on the paper surface is set can be shortened more effectively, and the set-off resistance is good. Can be.
＜製造方法＞
本発明の印刷インキは、上記の原料を用い、従来公知の方法で製造することができる。一例として、樹脂類、植物油類または脂肪酸エステル類またはそれらの混合物、さらに必要に応じて石油系溶剤、キレート化剤、その他助剤等を加熱溶解させて調整したワニスに、着色顔料、体質顔料、溶剤および他の添加剤を必要に応じて添加し、攪拌機で充分にプレミキシングを行なった後、ショットミル、ロールミル等で練肉を行う。練肉後、ワニス、石油系溶剤、植物油、その他ワックス、酸化防止剤、乳化調整剤等の助剤を添加し、充分に攪拌混合する。石油系ワックスは、プレミキシングの際に添加してもよいし、練肉後に添加してもよい。
これらの原料は印刷インキに必要とされる粘度や流動性に合わせて使用量を調整する。また、これらの原料の添加時期は固定されたものではなく、混合状態に基づいて適切に調整される。<Manufacturing method>
The printing ink of the present invention can be produced by a conventionally known method using the above raw materials. As an example, a coloring pigment, an extender pigment, a coloring pigment, an extender pigment, etc. Solvents and other additives are added as necessary, and after sufficient premixing with a stirrer, the meat is kneaded with a shot mill, a roll mill, or the like. After kneading, varnish, petroleum solvent, vegetable oil, other waxes, antioxidants, emulsion modifiers and other auxiliaries are added, and the mixture is thoroughly stirred and mixed. The petroleum wax may be added at the time of premixing or may be added after kneading.
The amount of these raw materials used is adjusted according to the viscosity and fluidity required for the printing ink. In addition, the timing of addition of these raw materials is not fixed, and is appropriately adjusted based on the mixed state.
＜印刷物＞
本発明の印刷物は、上述したような印刷インキ組成物を用いて平版オフセット印刷機により印刷させて得られる。基材としては特に制限はなく、従来公知のものを用いることができるが、特にコート紙、マットコート紙、上質紙への印刷に適している。本発明の印刷物は、裏移りが少ないものとなる。<Printed matter>
The printed matter of the present invention is obtained by printing with a lithographic offset printing machine using the printing ink composition as described above. The base material is not particularly limited, and conventionally known ones can be used, but it is particularly suitable for printing on coated paper, matte coated paper, and high-quality paper. The printed matter of the present invention has less set-off.
以下、実施例と比較例により本発明を説明するが、本発明はこれに限定されるものではない。配合組成その他の数値は特記しない限り質量基準である。 Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The composition and other values are based on mass unless otherwise specified.
＜ロジン変性フェノール樹脂の合成＞
（ロジン変性フェノール樹脂１の合成）
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、パラターシャルブチルフェノール１０００部、９２％パラホルムアルデヒド３６０部、キシレン１０００部、５０％水酸化ナトリウム１０部を仕込み、９５度に昇温、同温度を維持しながら６時間反応させた後、水３００部と塩酸１３部を混合後加え中和後、さらに水１０００部を加え、上澄みを上記と同様の装置に取り出し、１２０度に昇温して３０分攪拌し、上澄みを取り出して、固形分５７％のレゾール型フェノール樹脂１を得た。レゾール型フェノール樹脂１の重量平均分子量を測定した結果、平均核体数は１．７であった。<Synthesis of rosin-modified phenolic resin>
(Synthesis of rosin-modified phenol resin 1)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device was charged with 1000 parts of paratalital butylphenol, 360 parts of 92% paraformaldehyde, 1000 parts of xylene and 10 parts of 50% sodium hydroxide. After raising the temperature to 95 degrees and reacting for 6 hours while maintaining the same temperature, 300 parts of water and 13 parts of hydrochloric acid are mixed and neutralized, then 1000 parts of water is further added, and the supernatant is taken out to the same apparatus as above. The temperature was raised to 120 ° C. and the mixture was stirred for 30 minutes, and the supernatant was taken out to obtain a resole-type phenol resin 1 having a solid content of 57%. As a result of measuring the weight average molecular weight of the resole-type phenol resin 1, the average number of nuclei was 1.7.
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、酸価１６５ｍｇＫＯＨ／ｇのガムロジン９７０部、無水マレイン酸１４部を仕込み、１８０度に昇温し、ペンタエリスリトール１０７部、酸化亜鉛２部を加え、２５０度に昇温し同温度を維持しながら酸価が２０ｍｇＫＯＨ／ｇ以下になるまで反応させた。その後１８０度に降温し、同温度を維持しながらレゾール型フェノール樹脂１を滴下ロートを用いて滴下速度２．５部／分で滴下し、５０％トルエン溶液の２５℃ガードナー粘度がＦ〜Ｇになった時点で滴下を停止、３０分後樹脂を取り出し、ロジン変性フェノール樹脂１を得た。滴下したレゾール型フェノール樹脂１は５７０部であった。ロジン変性フェノール樹脂１の重量平均分子量は６５０００、ＡＦ−６号ソルベント曇点は１１０、軟化点は１６８度であった。 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device, 970 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 degrees to pentaerythritol 107. 2 parts and 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C., and the reaction was carried out until the acid value became 20 mgKOH / g or less while maintaining the same temperature. After that, the temperature was lowered to 180 ° C., and while maintaining the same temperature, the resole-type phenol resin 1 was added dropwise at a dropping rate of 2.5 parts / minute using a dropping funnel, and the 25 ° C. Gardner viscosity of the 50% toluene solution became FG. The dropping was stopped at that time, and after 30 minutes, the resin was taken out to obtain a rosin-modified phenol resin 1. The amount of the dropped resole-type phenol resin 1 was 570 parts. The weight average molecular weight of the rosin-modified phenol resin 1 was 65,000, the AF-6 solvent cloud point was 110, and the softening point was 168 degrees.
（ロジン変性フェノール樹脂２の合成）
攪拌機および温度計を備えた加圧反応釜に、パラターシャルブチルフェノール１０００部を仕込み１２０度にて加熱溶解し、９２％パラホルムアルデヒド２８５部、水酸化カルシウム８部を加え、１３０度に昇温、同温度を維持しながら２時間反応させた後、脱圧しさらに同温で２０分攪拌し、レゾール型フェノール樹脂２を取り出した。レゾール型フェノール樹脂２の重量平均分子量を測定した結果、平均核体数は３．０であった。(Synthesis of rosin-modified phenol resin 2)
In a pressurized reaction kettle equipped with a stirrer and a thermometer, 1000 parts of paratalital butylphenol was charged and dissolved by heating at 120 ° C., 285 parts of 92% paraformaldehyde and 8 parts of calcium hydroxide were added, and the temperature was raised to 130 ° C. After reacting for 2 hours while maintaining the same temperature, the mixture was depressurized and further stirred at the same temperature for 20 minutes to take out the resol type phenol resin 2. As a result of measuring the weight average molecular weight of the resole-type phenol resin 2, the average number of nuclei was 3.0.
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、酸価１６５ｍｇＫＯＨ／ｇのガムロジン１０５０部、無水マレイン酸１４部を仕込み、１８０度に昇温し、ペンタエリスリトール１１５部、酸化亜鉛２部を加え、２５０度に昇温し同温度を維持しながらで、酸価が２０ｍｇＫＯＨ／ｇ以下になるまで反応させた。その後１８０度に降温し、同温度を維持しながらレゾール型フェノール樹脂２を段階的に投入し、５０％トルエン溶液のガードナー粘度がＦ〜Ｇになった時点で投入を停止、３０分後樹脂を取り出し、ロジン変性フェノール樹脂２を得た。投入したレゾール型フェノール樹脂２は７００部であった。ロジン変性フェノール樹脂２の重量平均分子量は１４５０００、ＡＦ−６号ソルベント曇点は１９５度、軟化点は１７６度であった。 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device, 1050 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 degrees to pentaerythritol 115. 2 parts and 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C. while maintaining the same temperature, and the reaction was carried out until the acid value became 20 mgKOH / g or less. After that, the temperature was lowered to 180 degrees, and the resol type phenol resin 2 was added stepwise while maintaining the same temperature. When the Gardner viscosity of the 50% toluene solution became FG, the addition was stopped, and after 30 minutes, the resin was added. It was taken out to obtain a rosin-modified phenol resin 2. The amount of the resol type phenol resin 2 charged was 700 parts. The weight average molecular weight of the rosin-modified phenolic resin 2 was 145,000, the AF-6 solvent cloud point was 195 degrees, and the softening point was 176 degrees.
（ロジン変性フェノール樹脂３の合成）
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、パラターシャルブチルフェノール１０００部、９２％パラホルムアルデヒド４４５部、キシレン１０００部、５０％水酸化ナトリウム１０部を仕込み、９５度に昇温、同温度を維持しながら６時間反応させた後、水３００部と塩酸１３部を混合後加え中和後、さらに水１０００部を加え、上澄みを取り出して、固形分５８％のレゾール型フェノール樹脂３を得た。レゾール型フェノール樹脂３の重量平均分子量を測定した結果、平均核体数は１．０であった。(Synthesis of rosin-modified phenol resin 3)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device was charged with 1000 parts of paratalital butylphenol, 445 parts of 92% paraformaldehyde, 1000 parts of xylene and 10 parts of 50% sodium hydroxide. After raising the temperature to 95 ° C and reacting for 6 hours while maintaining the same temperature, 300 parts of water and 13 parts of hydrochloric acid were mixed and neutralized, and then 1000 parts of water was added, and the supernatant was taken out to obtain a solid content of 58%. Resol type phenol resin 3 was obtained. As a result of measuring the weight average molecular weight of the resole-type phenol resin 3, the average number of nuclei was 1.0.
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、酸価１６５ｍｇＫＯＨ／ｇのガムロジン９７０部、無水マレイン酸１４部を仕込み、１８０度に昇温し、ペンタエリスリトール１０７部、酸化亜鉛２部を加え、２５０度に昇温し同温度を維持しながら酸価が２０ｍｇＫＯＨ／ｇ以下になるまで反応させた。その後１８０度に降温し、同温度を維持しながらレゾール型フェノール樹脂３を滴下ロートを用いて滴下速度２．５部／分で滴下し、５０％トルエン溶液の２５℃ガードナー粘度がＦ〜Ｇになった時点で滴下を停止、３０分後樹脂を取り出し、ロジン変性フェノール樹脂３を得た。滴下したレゾール型フェノール樹脂３は４８０部であった。ロジン変性フェノール樹脂３の重量平均分子量は５２０００、ＡＦ−６号ソルベント曇点は６０度、軟化点は１６２度であった。 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device, 970 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 degrees to pentaerythritol 107. 2 parts and 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C., and the reaction was carried out until the acid value became 20 mgKOH / g or less while maintaining the same temperature. After that, the temperature was lowered to 180 ° C., and while maintaining the same temperature, the resole-type phenol resin 3 was added dropwise at a dropping rate of 2.5 parts / minute using a dropping funnel, and the 25 ° C. Gardner viscosity of the 50% toluene solution became FG. The dropping was stopped at that time, and after 30 minutes, the resin was taken out to obtain a rosin-modified phenol resin 3. The amount of the dropped resole-type phenol resin 3 was 480 parts. The weight average molecular weight of the rosin-modified phenolic resin 3 was 52000, the AF-6 solvent cloud point was 60 degrees, and the softening point was 162 degrees.
（ロジン変性フェノール樹脂４の合成）
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、パラターシャルブチルフェノール１０００部、９２％パラホルムアルデヒド３００部、キシレン１０００部、５０％水酸化ナトリウム１０部を仕込み、９５度に昇温、同温度を維持しながら６時間反応させた後、水３００部と塩酸１３部を混合後加え中和後、さらに水１０００部を加え、上澄みを上記と同様の装置に取り出し、１２０度に昇温して１４０分攪拌し、上澄みを取り出して、固形分５６％のレゾール型フェノール樹脂４を得た。レゾール型フェノール樹脂４の重量平均分子量を測定した結果、平均核体数は３．８であった。(Synthesis of rosin-modified phenol resin 4)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device was charged with 1000 parts of paratalital butylphenol, 300 parts of 92% paraformaldehyde, 1000 parts of xylene, and 10 parts of 50% sodium hydroxide. After raising the temperature to 95 degrees and reacting for 6 hours while maintaining the same temperature, 300 parts of water and 13 parts of hydrochloric acid are mixed and neutralized, then 1000 parts of water is further added, and the supernatant is taken out to the same apparatus as above. The temperature was raised to 120 ° C. and the mixture was stirred for 140 minutes, and the supernatant was taken out to obtain a resole-type phenol resin 4 having a solid content of 56%. As a result of measuring the weight average molecular weight of the resole-type phenol resin 4, the average number of nuclei was 3.8.
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、酸価１６５ｍｇＫＯＨ／ｇのガムロジン１０１０部、無水マレイン酸１４部を仕込み、１８０度に昇温し、ペンタエリスリトール１１０部、酸化亜鉛２部を加え、２５０度に昇温し同温度を維持しながら、酸価が２０ｍｇＫＯＨ／ｇ以下になるまで反応させた。その後１８０度に降温し、同温度を維持しながらレゾール型フェノール樹脂４を滴下ロートを用いて滴下速度２．５部／分で滴下し、５０％トルエン溶液のガードナー粘度がＦ〜Ｇになった時点で滴下を停止、３０分後樹脂を取り出し、ロジン変性フェノール樹脂４を得た。滴下したレゾール型フェノール樹脂４は１４３０部であった。ロジン変性フェノール樹脂４の重量平均分子量は２１５０００、ＡＦ−６号ソルベント曇点は２２２度、軟化点は１９０℃であった。 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device, 1010 parts of gum rosin having an acid value of 165 mgKOH / g and 14 parts of maleic anhydride were charged, and the temperature was raised to 180 degrees to pentaerythritol 110. 2 parts and 2 parts of zinc oxide were added, and the reaction was carried out until the acid value became 20 mgKOH / g or less while maintaining the same temperature by raising the temperature to 250 ° C. After that, the temperature was lowered to 180 ° C., and the resole-type phenol resin 4 was added dropwise at a dropping rate of 2.5 parts / minute using a dropping funnel while maintaining the same temperature, and the Gardner viscosity of the 50% toluene solution became FG. At that point, the dropping was stopped, and after 30 minutes, the resin was taken out to obtain a rosin-modified phenol resin 4. The amount of the dropped resole-type phenol resin 4 was 1430 parts. The weight average molecular weight of the rosin-modified phenol resin 4 was 215,000, the AF-6 solvent cloud point was 222 degrees, and the softening point was 190 ° C.
＜印刷インキ用樹脂ワニスの調整＞
攪拌機、温度計、還流冷却器および窒素ガス導入装置の付いた４つ口フラスコに、ロジン変性フェノール樹脂１を４５０部、大豆サラダ油（日清オイリオ（株）製）４００部を仕込み、１８０度で１時間過熱攪拌した。その後ＡＦ−６号ソルベント１４０部を加え、１６０度に降温し、エチルアセトアセテートアルミニウムジノルマルブチレート１０部を加え、同温度を１時間保持し印刷インキ用樹脂ワニス１を得た。
ロジン変性フェノール樹脂１にかえて、ロジン変性フェノール樹脂２〜４をそれぞれ用いた以外は同様にして、印刷インキ用樹脂ワニス２〜４を得た。<Adjustment of resin varnish for printing ink>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction device, 450 parts of rosin-modified phenol resin 1 and 400 parts of soybean salad oil (manufactured by Nisshin Oillio Co., Ltd.) were charged at 180 degrees. The mixture was heated and stirred for 1 hour. After that, 140 parts of AF-6 solvent was added, the temperature was lowered to 160 ° C., 10 parts of ethylacetacetate aluminum dinormal butyrate was added, and the same temperature was maintained for 1 hour to obtain a resin varnish 1 for printing ink.
Resin varnishes 2 to 4 for printing ink were obtained in the same manner except that rosin-modified phenolic resins 2 to 4 were used instead of the rosin-modified phenolic resin 1.
＜ベースインキの調整＞
（ベースインキＹの調整）
ＳＹＭＵＬＥＲ Ｆａｓｔ Ｙｅｌｌｏｗ ＧＦｃｏｎｃ（ＤＩＣ（株）製）を１８部、印刷インキ用樹脂ワニス１を７２部、ＡＦ−６号ソルベントを１０部仕込み、ＪＩＳ Ｋ５７０１−１の練和度試験に記載の方法で測定した位置Ａの溝の深さが７．５μｍ以下になるまで３本ロールミルを用いて練肉し、ベースインキＹ１を調整した。印刷インキ用樹脂ワニス１にかえて印刷インキ用樹脂ワニス２〜４をそれぞれ用いた以外は同様にして、ベースインキＹ２〜Ｙ４を得た。<Adjustment of base ink>
(Adjustment of base ink Y)
18 parts of SYMULER Fast Yellow GFconc (manufactured by DIC Corporation), 72 parts of resin varnish 1 for printing ink, 10 parts of AF-6 solvent, and measured by the method described in the kneading degree test of JIS K5701-1. The base ink Y1 was adjusted by kneading the meat using a three-roll mill until the depth of the groove at the position A was 7.5 μm or less. Base inks Y2 to Y4 were obtained in the same manner except that the printing ink resin varnishes 2 to 4 were used instead of the printing ink resin varnish 1.
（ベースインキＭの調整）
ＳＹＭＵＬＥＲ Ｂｒｉｌｌｉａｎｔ Ｃａｒｍｉｎｅ ６Ｂ ２２６（ＤＩＣ（株）製）を２８部、印刷インキ用樹脂ワニス１を６０．４部、ＡＦ−６号ソルベントを１１．６部仕込み、ＪＩＳ Ｋ５７０１−１の練和度試験に記載の方法で測定した位置Ａの溝の深さが７．５μｍ以下になるまで３本ロールミルを用いて練肉し、ベースインキＭ１を調整した。印刷インキ用樹脂ワニス１にかえて印刷インキ用樹脂ワニス２〜４をそれぞれ用いた以外は同様にして、ベースインキＭ２〜Ｍ４を得た。(Adjustment of base ink M)
28 copies of SYMULER Brilliant Carmine 6B 226 (manufactured by DIC Corporation), 60.4 copies of resin varnish 1 for printing ink, and 11.6 copies of AF-6 solvent were used for the kneading test of JIS K5701-1. The base ink M1 was adjusted by kneading with a three-roll mill until the depth of the groove at position A measured by the method described was 7.5 μm or less. Base inks M2 to M4 were obtained in the same manner except that the printing ink resin varnishes 2 to 4 were used instead of the printing ink resin varnish 1.
（ベースインキＣの調整）
ＦＡＳＴＧＥＮ ＢｌｕｅＦＡ５３７５（ＤＩＣ（株）製）を３０部、印刷インキ用樹脂ワニス１を５８部、ＡＦ−６号ソルベントを１２部仕込み、ＪＩＳ Ｋ５７０１−１の練和度試験に記載の方法で測定した位置Ａの溝の深さが７．５μｍ以下になるまで３本ロールミルを用いて練肉し、ベースインキＣ１を調整した。印刷インキ用樹脂ワニス１にかえて印刷インキ用樹脂ワニス２〜４をそれぞれ用いた以外は同様にして、ベースインキＣ２〜Ｃ４を得た。(Adjustment of base ink C)
30 parts of FASTGEN BlueFA5375 (manufactured by DIC Corporation), 58 parts of resin varnish 1 for printing ink, 12 parts of AF-6 solvent, and the positions measured by the method described in the kneading degree test of JIS K5701-1. The base ink C1 was adjusted by kneading the meat using a three-roll mill until the depth of the groove of A became 7.5 μm or less. Base inks C2 to C4 were obtained in the same manner except that the printing ink resin varnishes 2 to 4 were used instead of the printing ink resin varnish 1.
（ベースインキＢの調整）
カーボンブラックＭＡ７（三菱ケミカル（株）製）を２８部、印刷インキ用樹脂ワニス１を６０．４部、ＡＦ−６号ソルベントを１１．６部仕込み、ＪＩＳ Ｋ５７０１−１の練和度試験に記載の方法で測定した位置Ａの溝の深さが７．５μｍ以下になるまで３本ロールミルを用いて練肉し、ベースインキＢ１を調整した。印刷インキ用樹脂ワニス１にかえて印刷インキ用樹脂ワニス２〜４をそれぞれ用いた以外は同様にして、ベースインキＢ２〜Ｂ４を得た。(Adjustment of base ink B)
28 parts of carbon black MA7 (manufactured by Mitsubishi Chemical Corporation), 60.4 parts of resin varnish 1 for printing ink, 11.6 parts of AF-6 solvent, described in the kneading degree test of JIS K5701-1. The base ink B1 was adjusted by kneading the meat using a three-roll mill until the depth of the groove at position A measured by the above method was 7.5 μm or less. Base inks B2 to B4 were obtained in the same manner except that the printing ink resin varnishes 2 to 4 were used instead of the printing ink resin varnish 1.
＜印刷インキの調整＞
ベースインキＹ１を６９．０部、印刷インキ用樹脂ワニス１を２４．５部、石油系ワックスコンパウンド０．３部、ＰＴＦＥワックスを０．１部、オクチル酸コバルト溶液を１．０部、ＡＦ−６号ソルベントを５．１部用いて黄インキＹ１を得た。黄インキＹ１におけるノルマルパラフィンの含有量は０．１３質量％、顔料の含有量は１４．０質量％であった。<Adjustment of printing ink>
69.0 parts of base ink Y1, 24.5 parts of resin varnish 1 for printing ink, 0.3 parts of petroleum wax compound, 0.1 part of PTFE wax, 1.0 part of cobalt octylate solution, AF- Yellow ink Y1 was obtained using 5.1 parts of No. 6 solvent. The content of normal paraffin in the yellow ink Y1 was 0.13% by mass, and the content of the pigment was 14.0% by mass.
同様にして、表１〜表４に示す配合で、黄インキＹ２〜Ｙ１１、紅インキＭ１〜Ｍ１１、藍インキＣ１〜Ｃ１１、墨インキＢ１〜Ｂ１１を調整した。黄インキＹ１〜Ｙ１１、紅インキＭ１〜Ｍ１１、藍インキＣ１〜Ｃ１１、墨インキＢ１〜Ｂ１１の粘度は１０Ｐａ・ｓ〜６０Ｐａ・ｓの範囲内であった。なお、インキの粘度はＬ型粘度計を用い、ＪＩＳ Ｋ ５７０１−１に記載の方法で測定した。インキの調整に用いたベースインキ、印刷インキ樹脂ワニス以外の成分は以下のようなものである。 Similarly, yellow inks Y2 to Y11, red inks M1 to M11, indigo inks C1 to C11, and black inks B1 to B11 were prepared according to the formulations shown in Tables 1 to 4. The viscosities of the yellow inks Y1 to Y11, the red inks M1 to M11, the indigo inks C1 to C11, and the black inks B1 to B11 were in the range of 10 Pa · s to 60 Pa · s. The viscosity of the ink was measured by the method described in JIS K 5701-1 using an L-type viscometer. The components other than the base ink and printing ink resin varnish used for ink adjustment are as follows.
（石油系ワックスコンパウンド）
融点が６１℃、ノルマルパラフィンの比率が９０％の石油系ワックス３５部を、ＡＦ６号ソルベント６５部と加熱攪拌した後、室温まで冷却してコンパウンドとしたものを用いた。
（デンプンコンパウンド）
平均粒子径Ｄ５０が２０μｍのデンプン２０部を、８０部の印刷インキ用樹脂ワニス１で分散したものを用いた。(Petroleum wax compound)
35 parts of petroleum-based wax having a melting point of 61 ° C. and a ratio of normal paraffin of 90% was heated and stirred with 65 parts of AF6 solvent, and then cooled to room temperature to prepare a compound.
(Starch compound)
20 parts of starch having an average particle size D50 of 20 μm was dispersed with 80 parts of resin varnish 1 for printing ink.
（汚れ防止剤コンパウンド）
ヘキサメタリン酸ナトリウム２０部を、８０部の印刷インキ用樹脂ワニス１でＪＩＳ Ｋ５７０１−１の練和度試験に記載の方法で測定した際の位置Ａの溝の深さが７．５μｍ以下になるまで分散、練肉したものを用いた。
（オクチル酸コバルト溶液）
オクチル酸コバルト５０部を大豆油５０部で溶解した溶液を用いた。(Anti-staining agent compound)
Until the depth of the groove at position A is 7.5 μm or less when 20 parts of sodium hexametaphosphate is measured with 80 parts of resin varnish 1 for printing ink by the method described in the kneading degree test of JIS K5701-1. Dispersed and kneaded meat was used.
(Cobalt octylate solution)
A solution in which 50 parts of cobalt octylate was dissolved in 50 parts of soybean oil was used.
＜評価＞
調整した印刷インキを用いて以下の条件にて印刷し、印刷物の性能評価を行った。結果を表５〜表８にまとめた。
（印刷条件）
印刷機；マンローランド社製 ローランド７０４印刷機（セパレート連続給水方式）
湿し水；プレサートＳＤ１００（ＤＩＣグラフィックス（株）製） 濃度２．０％
印刷速度；８，０００枚/時
温度・湿度；室温２５℃、湿度５５％
印刷用紙；OKトップコートN（王子製紙（株）製）<Evaluation>
Printing was performed using the adjusted printing ink under the following conditions, and the performance of the printed matter was evaluated. The results are summarized in Tables 5-8.
(Printing conditions)
Printing machine; Roland 704 printing machine manufactured by Mun Roland (separate continuous water supply system)
Sampling water; Pressart SD100 (manufactured by DIC Graphics Corporation) Concentration 2.0%
Printing speed: 8,000 sheets / hour Temperature / humidity; Room temperature 25 ° C, humidity 55%
Printing paper; OK Top Coat N (manufactured by Oji Paper Co., Ltd.)
（耐裏移り性）
ベタ部分と非画線部分からなる絵柄を３，０００部印刷し、上に積み重ねた。６時間経過後、インキの裏移りがないか目視で評価した。
○…良好。紙面上のインキのしっとり感の高低を＋の数で評価。
＋が多い程しっとり感が低く良好。
△…裏移りが僅かに見られる。
×…裏移りしている部分が多く、印刷物同士がくっついてしまうブロッキング発生。(Set-off resistance)
3,000 copies of the pattern consisting of the solid part and the non-image part were printed and stacked on top of each other. After 6 hours, the ink was visually evaluated for set-off.
○… Good. The level of moistness of the ink on the paper is evaluated by the number of +.
The more +, the lower the moist feeling and the better.
△… Slight set-off is seen.
×… Blocking occurs in which printed matter sticks to each other due to many set-off parts.
（パイリング性）
３，０００枚印刷後の印刷機ローラー上、ブランケット上の堆積状況を目視と指触にて評価した。
○…良好。
△…堆積物が僅かに見られる。
×…堆積物が多い。(Piring property)
After printing 3,000 sheets, the accumulation state on the roller and blanket of the printing press was visually and touch-sensitively evaluated.
○… Good.
Δ… Slight deposits can be seen.
×… There are many deposits.
（流動性）
印刷機のインキつぼにインキを入れ、印刷中のインキの流動状態を目視で評価した。
○…良好。
×…インキが均一に消費されず、つぼの中にインキの動かない部分が発生。(Liquidity)
Ink was put into the ink fountain of the printing machine, and the flow state of the ink during printing was visually evaluated.
○… Good.
×… Ink is not consumed evenly, and some parts of the pot do not move.
（後加工適性）
バーコーターＮ０．６を用いて、印刷物に水性ニス（ＤＩＣグラフィックス（株）製、ディックセーフＣ１１５１）を塗布し、常温で１晩乾燥させた。翌日、セロハンテープによる剥離試験にて後加工適性を評価した。
〇…セロハンテープが印刷物の下地部分から取れる。
△…セロハンテープがインキ面から一部とれる。
×…セロハンテープがインキとニスの界面から剥がれる。(Post-processing suitability)
A water-based varnish (DIC Graphics Co., Ltd., Dick Safe C1151) was applied to the printed matter using a bar coater N0.6, and the printed matter was dried overnight at room temperature. The next day, the post-processing suitability was evaluated by a peeling test using cellophane tape.
〇… Cellophane tape can be removed from the base of the printed matter.
Δ: Part of the cellophane tape can be removed from the ink surface.
×… The cellophane tape peels off from the interface between the ink and the varnish.
表５〜８から明らかなように、本発明の印刷インキは優れた耐裏移り性、パイリング性、流動性、後加工性を示した。 As is clear from Tables 5 to 8, the printing ink of the present invention exhibited excellent set-off resistance, pileing property, fluidity, and post-workability.
Claims (16)
ドライヤーと、
黄顔料と、
融点が８０℃以下でありノルマルパラフィンを含む石油系ワックスと、を含み、
ＪＩＳ Ｋ５７０１−１に記載のＬ型粘度計による方法で測定した粘度が１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下であり、
前記石油系ワックスに含まれる前記ノルマルパラフィンの含有量が０．１質量％以上３質量％以下であり、
前記曇点は、前記ＡＦソルベント６号（ＪＸＴＧエネルギー株式会社製）１８０質量部と前記ロジン変性フェノール樹脂２０質量部とを加熱混合した際の白濁下限温度であり、
前記黄顔料の含有量が７質量％以上１５質量％以下であることを特徴とする酸化重合乾燥型オフセット印刷インキ組成物。 A varnish containing a rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C or higher and 210 ° C or lower,
With a hair dryer
With yellow pigment
Contains petroleum-based wax having a melting point of 80 ° C. or lower and containing normal paraffin.
The viscosity measured by the method using the L-type viscometer described in JIS K5701-1 is 10 Pa · s or more and 60 Pa · s or less.
The content of the normal paraffin contained in the petroleum wax is 0.1% by mass or more and 3% by mass or less.
The cloud point is the lower limit temperature of cloudiness when 180 parts by mass of AF Solvent No. 6 (manufactured by JXTG Energy Co., Ltd.) and 20 parts by mass of the rosin-modified phenol resin are heated and mixed.
An oxidative polymerization dry type offset printing ink composition, wherein the content of the yellow pigment is 7% by mass or more and 15% by mass or less.
ドライヤーと、
紅顔料と、
融点が８０℃以下でありノルマルパラフィンを含む石油系ワックスと、を含み、
ＪＩＳ Ｋ５７０１−１に記載のＬ型粘度計による方法で測定した粘度が１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下であり、
前記石油系ワックスに含まれる前記ノルマルパラフィンの含有量が０．１質量％以上３質量％以下であり、
前記曇点は、前記ＡＦソルベント６号（ＪＸＴＧエネルギー株式会社製）１８０質量部と前記ロジン変性フェノール樹脂２０質量部とを加熱混合した際の白濁下限温度であり、
前記紅顔料の含有量が１３質量％以上２０質量％以下であることを特徴とする酸化重合乾燥型オフセット印刷インキ組成物。 A varnish containing a rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C or higher and 210 ° C or lower,
With a hair dryer
Red pigment and
Contains petroleum-based wax having a melting point of 80 ° C. or lower and containing normal paraffin.
The viscosity measured by the method using the L-type viscometer described in JIS K5701-1 is 10 Pa · s or more and 60 Pa · s or less.
The content of the normal paraffin contained in the petroleum wax is 0.1% by mass or more and 3% by mass or less.
The cloud point is the lower limit temperature of cloudiness when 180 parts by mass of AF Solvent No. 6 (manufactured by JXTG Energy Co., Ltd.) and 20 parts by mass of the rosin-modified phenol resin are heated and mixed.
An oxidative polymerization dry type offset printing ink composition, wherein the content of the red pigment is 13% by mass or more and 20% by mass or less.
ドライヤーと、
藍顔料と、
融点が８０℃以下でありノルマルパラフィンを含む石油系ワックスと、を含み、
ＪＩＳ Ｋ５７０１−１に記載のＬ型粘度計による方法で測定した粘度が１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下であり、
前記石油系ワックスに含まれる前記ノルマルパラフィンの含有量が０．１質量％以上３質量％以下であり、
前記曇点は、前記ＡＦソルベント６号（ＪＸＴＧエネルギー株式会社製）１８０質量部と前記ロジン変性フェノール樹脂２０質量部とを加熱混合した際の白濁下限温度であり、
前記藍顔料の含有量が１６質量％以上２３質量％以下であることを特徴とする酸化重合乾燥型オフセット印刷インキ組成物。 A varnish containing a rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C or higher and 210 ° C or lower,
With a hair dryer
Indigo pigment and
Contains petroleum-based wax having a melting point of 80 ° C. or lower and containing normal paraffin.
The viscosity measured by the method using the L-type viscometer described in JIS K5701-1 is 10 Pa · s or more and 60 Pa · s or less.
The content of the normal paraffin contained in the petroleum wax is 0.1% by mass or more and 3% by mass or less.
The cloud point is the lower limit temperature of cloudiness when 180 parts by mass of AF Solvent No. 6 (manufactured by JXTG Energy Co., Ltd.) and 20 parts by mass of the rosin-modified phenol resin are heated and mixed.
An oxidative polymerization dry type offset printing ink composition, wherein the content of the indigo pigment is 16% by mass or more and 23% by mass or less.
ドライヤーと、
墨顔料と、
融点が８０℃以下でありノルマルパラフィンを含む石油系ワックスと、を含み、
ＪＩＳ Ｋ５７０１−１に記載のＬ型粘度計による方法で測定した粘度が１０Ｐａ・ｓ以上６０Ｐａ・ｓ以下であり、
前記石油系ワックスに含まれる前記ノルマルパラフィンの含有量が０．１質量％以上３質量％以下であり、
前記曇点は、前記ＡＦソルベント６号（ＪＸＴＧエネルギー株式会社製）１８０質量部と前記ロジン変性フェノール樹脂２０質量部とを加熱混合した際の白濁下限温度であり、
前記墨顔料の含有量が１７質量％以上２４質量％以下であることを特徴とする酸化重合乾燥型オフセット印刷インキ組成物。 A varnish containing a rosin-modified phenol resin having a cloud point of AF solvent No. 6 of 100 ° C or higher and 210 ° C or lower,
With a hair dryer
Ink pigment and
Contains petroleum-based wax having a melting point of 80 ° C. or lower and containing normal paraffin.
The viscosity measured by the method using the L-type viscometer described in JIS K5701-1 is 10 Pa · s or more and 60 Pa · s or less.
The content of the normal paraffin contained in the petroleum wax is 0.1% by mass or more and 3% by mass or less.
The cloud point is the lower limit temperature of cloudiness when 180 parts by mass of AF Solvent No. 6 (manufactured by JXTG Energy Co., Ltd.) and 20 parts by mass of the rosin-modified phenol resin are heated and mixed.
An oxidative polymerization dry type offset printing ink composition characterized in that the content of the black pigment is 17% by mass or more and 24% by mass or less.
請求項２に記載の酸化重合乾燥型オフセット印刷インキ組成物と、
請求項３に記載の酸化重合乾燥型オフセット印刷インキ組成物と、
請求項４に記載の酸化重合乾燥型オフセット印刷インキ組成物と、を含むことを特徴とするインキセット。 The oxidative polymerization drying type offset printing ink composition according to claim 1 and
The oxidative polymerization drying type offset printing ink composition according to claim 2 and
The oxidative polymerization drying type offset printing ink composition according to claim 3 and
An ink set comprising the oxidative polymerization drying type offset printing ink composition according to claim 4.
前記基材上に配置された請求項１乃至１４のいずれか一項に記載の酸化重合乾燥型オフセット印刷インキ組成物のインキ塗膜と、を有することを特徴とする印刷物。 With the base material
A printed matter comprising the ink coating film of the oxidative polymerization drying type offset printing ink composition according to any one of claims 1 to 14 arranged on the substrate.
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