JP2013139551A - Lithographic printing ink composition - Google Patents
Lithographic printing ink composition Download PDFInfo
- Publication number
- JP2013139551A JP2013139551A JP2012239094A JP2012239094A JP2013139551A JP 2013139551 A JP2013139551 A JP 2013139551A JP 2012239094 A JP2012239094 A JP 2012239094A JP 2012239094 A JP2012239094 A JP 2012239094A JP 2013139551 A JP2013139551 A JP 2013139551A
- Authority
- JP
- Japan
- Prior art keywords
- ink composition
- lithographic printing
- printing ink
- calcium carbonate
- oil
- 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
- 238000007639 printing Methods 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 55
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000049 pigment Substances 0.000 claims abstract description 21
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 21
- 239000008158 vegetable oil Substances 0.000 claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000011164 primary particle Substances 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 239000012188 paraffin wax Substances 0.000 claims description 7
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical group C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 5
- 238000007645 offset printing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 41
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- 230000000052 comparative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
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- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 fatty acid esters Chemical class 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 235000019438 castor oil Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
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- 239000002540 palm oil Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
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- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- WXHWJILFBPXYTF-UHFFFAOYSA-N 1-heptoxynonane Chemical compound CCCCCCCCCOCCCCCCC WXHWJILFBPXYTF-UHFFFAOYSA-N 0.000 description 1
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- PFBGAPDKJFEGOV-UHFFFAOYSA-N 1-hexoxynonane Chemical compound CCCCCCCCCOCCCCCC PFBGAPDKJFEGOV-UHFFFAOYSA-N 0.000 description 1
- DKZRLCHWDNEKRH-UHFFFAOYSA-N 1-nonoxynonane Chemical compound CCCCCCCCCOCCCCCCCCC DKZRLCHWDNEKRH-UHFFFAOYSA-N 0.000 description 1
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- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
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- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、書籍、チラシ、カタログ、ポスター等を印刷する平版印刷に使用される平版印刷インキ組成物（以下、「インキ」と略す。）に関するものであり、特に、印刷品質の向上と印刷作業環境の改善に関するものであり、更には、着肉性、光沢に優れ、ミスチングを低減できるインキに関するものである。 The present invention relates to a lithographic printing ink composition (hereinafter abbreviated as “ink”) used for lithographic printing for printing books, flyers, catalogs, posters, etc., and in particular, improving printing quality and printing work. The present invention relates to improvement of the environment, and further relates to an ink that has excellent inking properties and gloss and can reduce misting.
近年、オフセット印刷では生産性向上を目的として印刷速度が益々高速化し、インキのプリンティングタックが上昇するような印刷条件になる一方、古紙の再利用や輸入紙の増加により紙面強度が低下する傾向が見られ、紙剥け等による着肉不良が誘発され易い事からインキのタック値を高く設定できない。更に印刷速度の高速化に伴って、ローラーのニップの出口からのインキのミスチング量が増加し、作業環境の汚染が促進される。 In recent years, offset printing has increased printing speed for the purpose of improving productivity, and printing conditions have led to an increase in ink printing tack. On the other hand, paper strength tends to decrease due to reuse of used paper and an increase in imported paper. As seen, it is easy to induce poor walling due to paper peeling, etc., so the ink tack value cannot be set high. Further, as the printing speed increases, the amount of ink misting from the exit of the nip of the roller increases, and contamination of the work environment is promoted.
石油系溶剤や植物油の添加により単純にタック値を低下させると、インキの粘度も低下し、地汚れ、ブランケットでの非画線残り、給水ローラーの汚れ等の印刷トラブルを誘発し、また、ドットゲインの増大等により印刷品質への影響も懸念される。着肉性を維持しつつ地汚れ等の汚れ耐性を維持する為にはいかにプリンティングタックを低下させ、かつ、粘度を高く維持するかが処方設計上肝要である。 If the tack value is simply reduced by the addition of petroleum solvent or vegetable oil, the viscosity of the ink also decreases, causing printing troubles such as background smudges, blanket remaining on the blanket, dirt on the water supply roller, etc. There is also a concern about an influence on print quality due to an increase in gain or the like. In order to maintain dirt resistance such as soiling while maintaining the inking property, it is important in the formulation design to reduce the printing tack and maintain the viscosity high.
特許文献１にはオフセットインキへの炭酸カルシウムなどの体質顔料の効果的な添加方法が示され、印刷インキの品質への影響が比較的少ない体質顔料として記載されている。しかしながら、炭酸カルシウムを添加する事によりインキ生産時における分散の為の負荷が増大し、かつ、粗大粒子の残存により耐刷性不良並びに光沢の低下が誘発される事から、いかに容易に炭酸カルシウムを分散させて、光沢を損なわないかが課題である。 Patent Document 1 discloses an effective method for adding extender pigments such as calcium carbonate to offset ink, and describes as an extender having a relatively small influence on the quality of printing ink. However, the addition of calcium carbonate increases the load for dispersion during ink production, and the remaining coarse particles induce poor printing durability and reduced gloss. The problem is whether to disperse and maintain gloss.
また、特許文献２には、ロジン変性フェノール樹脂と炭酸カルシウムが一体化した樹脂を利用し、ミスチングを低減する方法が提案されている。しかしながら、多量の体質顔料存在下で合成される樹脂は溶解性等の調整が難しく、印刷機上での安定性等に課題がある。 Patent Document 2 proposes a method for reducing misting by using a resin in which a rosin-modified phenolic resin and calcium carbonate are integrated. However, resins synthesized in the presence of a large amount of extender pigments are difficult to adjust solubility and the like, and there are problems with stability on a printing press.
本発明は、このような従来の技術における問題点を解決する為になされたものであり、その課題とするところは、特に、印刷品質の向上と印刷作業環境の改善に関するものであり、更には、着肉性、光沢に優れ、ミスチングを低減できるインキに関するものである。 The present invention has been made in order to solve such problems in the prior art, and the problem is particularly related to the improvement of the printing quality and the improvement of the printing work environment. Further, the present invention relates to an ink that has excellent inking properties and gloss and can reduce misting.
顔料、炭酸カルシウム、バインダー樹脂、石油系溶剤及び植物油を含有する平版印刷インキ組成物において、一定範囲の一次粒子径を有し、特定の物質にて表面処理されている炭酸カルシウムを使用し、一定範囲の重量平均分子量、溶解性を有するロジン変性フェノール樹脂を使用する事により、着肉性、光沢に優れ、ミスチングを低減できる事を特徴とするオフセット印刷インキ組成物を発明するに至った。 In a lithographic printing ink composition containing pigment, calcium carbonate, binder resin, petroleum-based solvent and vegetable oil, it uses calcium carbonate that has a primary particle diameter in a certain range and is surface-treated with a specific substance. By using a rosin-modified phenolic resin having a weight average molecular weight and solubility within a range, the inventors have invented an offset printing ink composition characterized by excellent inking properties and gloss and being able to reduce misting.
即ち本発明は、顔料、炭酸カルシウム、バインダー樹脂、石油系溶剤、植物油を含有する平版印刷インキ組成物において、
炭酸カルシウムが、
一次粒子径が０．０２〜０．１０μｍ
表面処理がロジン酸および／または脂肪酸
バインダー樹脂が、
重量平均分子量が２００００〜１０００００
ノルマルパラフィン白濁温度４０〜１１０℃
であることを特徴とする平版印刷インキ組成物に関するものである。
That is, the present invention relates to a lithographic printing ink composition containing a pigment, calcium carbonate, a binder resin, a petroleum solvent, and a vegetable oil.
Calcium carbonate
Primary particle size is 0.02-0.10 μm
Surface treatment is rosin acid and / or fatty acid binder resin,
Weight average molecular weight is 20000-100,000
Normal paraffin cloudiness temperature 40-110 ° C
The present invention relates to a lithographic printing ink composition.
さらに、本発明は、炭酸カルシウムが、全インキ組成物中０．１〜８重量％であることを特徴とする請求項１記載の平版印刷インキ組成物に関するものである。 Further, the present invention relates to the lithographic printing ink composition according to claim 1, wherein the calcium carbonate is 0.1 to 8% by weight in the total ink composition.
また、本発明は、上記の平版印刷インキ組成物を基材に印刷してなる印刷物に関するものである。 Moreover, this invention relates to the printed matter formed by printing said lithographic printing ink composition on a base material.
従来では、印刷機の高速化に対応する為にタック値をレジューサー等の添加により単純に低下させる場合があるが、地汚れやブラン残りが生じ易く、ミスチングも生じ易くなる点が課題であり、また、炭酸カルシウム等の体質顔料を添加しタックを低下させる事も実施されているが、光沢が低下し印刷品質が損なわれる事が課題である。本発明によって、光沢を損なうことなくミスチングも低減できる高速印刷に適したインキを提供する事が可能となった。 Conventionally, the tack value may be simply reduced by adding a reducer or the like in order to cope with the speeding up of the printing press. However, it is a problem that background stains and blanc residue are likely to occur, and misting is also likely to occur. Further, an extender pigment such as calcium carbonate is also added to lower the tack, but the problem is that the gloss is lowered and the print quality is impaired. According to the present invention, it is possible to provide an ink suitable for high-speed printing capable of reducing misting without impairing gloss.
本発明で使用されるバインダー樹脂とはロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂、アルキド樹脂、ポリエステル樹脂及び石油樹脂等を示し、それらは任意に単独または２種類以上を組み合わせて使用でき、好ましくは、ロジン変性フェノール樹脂を使用することが望ましい。 The binder resin used in the present invention includes rosin-modified phenolic resin, rosin-modified maleic acid resin, alkyd resin, polyester resin, petroleum resin, and the like, which can be used alone or in combination of two or more, preferably It is desirable to use a rosin modified phenolic resin.
バインダー樹脂であるロジン変性フェノール樹脂の重量平均分子量は、２００００〜１０００００の範囲が望ましく、更に好ましくは３００００〜７００００の範囲である。２００００未満では弾性が低くなりミスチングを低減できる効果が損なわれ、１０００００を超える重量平均分子量では樹脂を溶解させてワニス化する工程に過度な熱量を必要とする。 The weight average molecular weight of the rosin-modified phenol resin that is a binder resin is preferably in the range of 20000 to 100,000, and more preferably in the range of 30000 to 70000. If it is less than 20000, the elasticity becomes low and the effect of reducing misting is impaired, and if the weight average molecular weight exceeds 100000, an excessive amount of heat is required for the step of dissolving the resin to form a varnish.
本発明に関するロジン変性フェノール樹脂のノルマルパラフィン白濁温度は４０〜１１０℃の範囲が望ましく、更に好ましくは５０〜９０℃の範囲である。本発明において、ノルマルパラフィン白濁温度とは、樹脂１０重量％と１４〜１６の炭素数を有するノルマルパラフィン９０重量％を加熱混合した際に、白濁する下限の温度をいう（それ以上の温度では白濁が観察されない。）。４０℃未満では樹脂の溶解性が高すぎるのでインキのタックが高くなり、１１０℃を超える白濁温度では樹脂の溶解性が低すぎるので溶剤が離脱し易く機上でインキが締まり易くなる。 The normal paraffin white turbidity temperature of the rosin-modified phenolic resin relating to the present invention is preferably in the range of 40 to 110 ° C, more preferably in the range of 50 to 90 ° C. In the present invention, the normal paraffin white turbidity temperature refers to the lower limit temperature at which white turbidity occurs when 10% by weight of resin and 90% by weight of normal paraffin having 14 to 16 carbon atoms are heated and mixed. Is not observed.) If the temperature is lower than 40 ° C., the resin solubility is too high, so that the tackiness of the ink is increased. If the clouding temperature is higher than 110 ° C., the solubility of the resin is too low, so that the solvent is easily removed and the ink is easily tightened on the machine.
本発明に関する炭酸カルシウムは、一次粒子径が０．０２〜０．１０μｍの範囲が望ましく、更に好ましくは０．０３〜０．０８の範囲である。０．０２μｍ未満では表面積が大きくなり分散工程で多大なエネルギーを要する。０．１０μｍを超える一次粒子径では、インキ皮膜の表面に存在する粒子サイズが大きい炭酸カルシウムにより反射光が散乱し光沢が損なわれる。 The calcium carbonate relating to the present invention preferably has a primary particle size in the range of 0.02 to 0.10 μm, more preferably in the range of 0.03 to 0.08. If it is less than 0.02 μm, the surface area becomes large and a large amount of energy is required in the dispersion step. When the primary particle diameter exceeds 0.10 μm, reflected light is scattered by the calcium carbonate having a large particle size present on the surface of the ink film, and the gloss is impaired.
本発明に関する炭酸カルシウムは、表面処理がロジン酸および／または脂肪酸が望ましい。印刷インキにはロジン変性フェノール樹脂、脂肪酸エステル等が常用されており、ロジン酸、脂肪酸は極めて印刷インキと親和性が良好で、安定した分散状態を保持する事が出来る。 The calcium carbonate relating to the present invention is preferably treated with rosin acid and / or fatty acid. Rosin-modified phenolic resins, fatty acid esters, and the like are commonly used for printing inks, and rosin acid and fatty acids have extremely good affinity with printing inks and can maintain a stable dispersed state.
本発明に関する炭酸カルシウムは、全インキ組成物中０．１〜８重量％であることが望ましく、更に好ましくは１〜６％の範囲である。０．１重量％未満ではタックを低下させる効果が乏しく、８重量％を超える添加量では光沢を維持する事が困難になる。 The calcium carbonate relating to the present invention is desirably 0.1 to 8% by weight in the total ink composition, and more preferably in the range of 1 to 6%. If it is less than 0.1% by weight, the effect of lowering tack is poor, and if it is more than 8% by weight, it is difficult to maintain gloss.
本発明の印刷インキ組成物を製造するには、従来公知の方法で実施する事が出来る。一例としてバインダー樹脂、石油系溶剤、植物油類、必要に応じてゲル化剤を加えて、１９０℃１時間のクッキング条件でワニスを製造する。次いで、例えば、前記のワニスに顔料、石油系溶剤、植物油類、顔料分散剤または顔料分散樹脂を加え、ビーズミルや３本ロール等で分散する事により印刷インキ用ベースを得る事が出来る。次いで、石油系溶剤、植物油類、その他の添加剤を加え、所定粘度に調整し印刷インキ組成物を得る事が出来る。インキの種類としては、オフセット輪転印刷機用インキ、枚葉印刷機用インキが主なものであるが、これに限定されるものではない。 The printing ink composition of the present invention can be produced by a conventionally known method. As an example, a binder resin, petroleum-based solvent, vegetable oil, and a gelling agent as necessary are added, and varnish is produced under cooking conditions of 190 ° C. for 1 hour. Next, for example, a base for printing ink can be obtained by adding a pigment, petroleum solvent, vegetable oil, pigment dispersant or pigment dispersion resin to the varnish and dispersing with a bead mill or three rolls. Subsequently, petroleum-based solvents, vegetable oils, and other additives are added to adjust to a predetermined viscosity to obtain a printing ink composition. The main types of ink are offset rotary printing press ink and sheet-fed printing press ink, but are not limited thereto.
本発明において使用される顔料としては、一般的な無機顔料及び有機顔料を示すことができる。無機顔料としては炭酸カルシウム以外に黄鉛、亜鉛黄、紺青、硫酸バリウム、カドミムレッド、酸化チタン、亜鉛華、弁柄、アルミナホワイト、群青、カーボンブラック、グラファイト、アルミニウム粉、などを示すことができる。有機顔料としては、アゾ系として、Ｃ系（βナフトール系）、２Ｂ系および６Ｂ系（βオキシナフトエ系）などの溶性アゾ顔料、βナフトール系、βオキシナフトエ酸アニリド系、モノアゾイエロー系、ジスアゾイエロー系、ピラゾロン系などの不溶性アゾ顔料、アセト酢酸アリリド系などの縮合アゾ顔料、フタロシアニン系として、銅フタロシアニン（αブルー、βブルー、εブルー）、塩素、臭素などのハロゲン化銅フタロシアン、金属フリーのフタロシアニン顔料、多環顔料としてペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系顔料を挙げることができる。顔料の添加量は、印刷インキ組成物の全量に対して５〜３０重量％である。 Examples of the pigment used in the present invention include general inorganic pigments and organic pigments. In addition to calcium carbonate, examples of inorganic pigments include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, ultramarine blue, carbon black, graphite, and aluminum powder. Organic pigments include azo pigments, soluble azo pigments such as C-based (β-naphthol-based), 2B-based and 6B-based (β-oxynaphthoic), β-naphthol-based, β-oxynaphthoic acid anilide-based, monoazo yellow-based, disazo Insoluble azo pigments such as yellow and pyrazolone, condensed azo pigments such as acetoacetate allylide, phthalocyanines, copper phthalocyanines (α blue, β blue, ε blue), copper halide phthalocyanines such as chlorine and bromine, metals Examples of free phthalocyanine pigments and polycyclic pigments include perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, and quinophthalone pigments. The addition amount of the pigment is 5 to 30% by weight with respect to the total amount of the printing ink composition.
本発明で使用されるバインダー樹脂は、石油系溶剤、植物油類とアルミニウムキレート化合物のようなゲル化剤を添加して、１９０℃以上で溶解してワニス化したものを使用することができるが、ゲル化剤は必須ではない。バインダー樹脂の添加量は印刷インキ組成物の全量に対して２０〜４０重量％である。 As the binder resin used in the present invention, a gelling agent such as a petroleum solvent, vegetable oil and an aluminum chelate compound can be added, and a resin varnished by melting at 190 ° C. or higher can be used. A gelling agent is not essential. The addition amount of the binder resin is 20 to 40% by weight with respect to the total amount of the printing ink composition.
本発明における植物油類とは植物油および植物油由来の化合物であり、グリセリンと脂肪酸とのトリグリセリドにおいて、少なくとも１つの脂肪酸が炭素−炭素不飽和結合を少なくとも１つ有する脂肪酸であるトリグリセリドと、それらのトリグリセリドから飽和または不飽和アルコールとをエステル反応させてなる脂肪酸モノエステル、あるいは植物油の脂肪酸とモノアルコールを直接エステル反応させた脂肪酸モノエステル、エーテル類が挙げられる。 The vegetable oils in the present invention are vegetable oils and compounds derived from vegetable oils. Among the triglycerides of glycerin and fatty acids, at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond, and those triglycerides. Examples include fatty acid monoesters obtained by ester reaction with saturated or unsaturated alcohols, or fatty acid monoesters obtained by direct ester reaction between fatty acids of vegetable oil and monoalcohols, and ethers.
植物油として代表的ものは、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、脱水ヒマシ油などが挙げられる。 Typical vegetable oils are: Asa seed oil, flaxseed oil, eno oil, psyllium oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil , Safflower oil, radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil Cottonseed oil, palm oil, peanut oil, dehydrated castor oil, and the like.
脂肪酸モノエステルは上記植物油とモノアルコールとをエステル交換したものや植物油の脂肪酸とモノアルコールを直接エステル反応させた脂肪酸モノエステルである。モノアルコールの代表的なものは、メタノール、エタノール、ｎ−又はｉｓｏ−プロパノール、ｎ，ｓｅｃ又はｔｅ ｔ−ブタノール、ヘプチノール、２−エチルヘキサノール、ヘキサノール、オクタノール、デカノール、ドデカノール等の飽和アルコール、オレイルアルコール、ドデセノール、フイセテリアルコール、ゾンマリルアルコール、ガドレイルアルコール、１１−イコセノール、１１−ドコセノール、１５−テトラコセノール等の不飽和脂肪族系アルコールが挙げられる。 The fatty acid monoester is a fatty acid monoester obtained by transesterification of the above vegetable oil and monoalcohol or a direct ester reaction between the fatty acid of the vegetable oil and monoalcohol. Typical monoalcohols are methanol, ethanol, n- or iso-propanol, n, sec or t-butanol, heptynol, 2-ethylhexanol, hexanol, octanol, decanol, dodecanol and other saturated alcohols, oleyl alcohol , Unsaturated fatty alcohols such as dodecenol, huseteri alcohol, somaryl alcohol, gadrelyl alcohol, 11-icosenol, 11-docosenol, 15-tetracosenol.
エーテル類として代表的なものは、ジ−ｎ−オクチルエーテル、ジノニルエーテル、ジへプチルエーテル、ジヘキシルエーテル、ジデシルエーテル、ノニルへキシルエーテル、ノニルヘプチルエーテル、ノニルオクチルエーテル等が挙げられる。 Representative examples of ethers include di-n-octyl ether, dinonyl ether, diheptyl ether, dihexyl ether, didecyl ether, nonyl hexyl ether, nonyl heptyl ether, nonyl octyl ether and the like.
本発明で使用される石油系溶剤は、一般的にアロマフリー溶剤と称される芳香族炭化水素が１重量％未満である石油系溶剤である。アロマフリー溶剤の初留点は２４０℃以上かつ３００℃以下が望ましい。２４０℃を下回る初留点では、印刷機のローラー上において溶剤が蒸発し易く、タックの上昇を招く、３００℃を超える初留点では、オフセット輪転印刷における熱風乾燥工程で乾燥しにくくなり、乾燥不良を誘発する虞が生じる。 The petroleum-based solvent used in the present invention is a petroleum-based solvent having an aromatic hydrocarbon content of less than 1% by weight, generally called an aroma-free solvent. The initial boiling point of the aroma-free solvent is preferably 240 ° C or higher and 300 ° C or lower. At an initial boiling point of less than 240 ° C, the solvent is likely to evaporate on the rollers of the printing press, resulting in an increase in tack. At an initial boiling point of more than 300 ° C, it becomes difficult to dry in the hot air drying step in offset rotary printing. There is a risk of inducing defects.
また、平版印刷インキ組成物中への、その他添加剤として、耐摩擦、ブロッキング防止、スベリ、スリキズ防止を目的とする各種添加剤を使用することができ、必要に応じて、レベリング剤、界面活性剤等を添加してもよい。 In addition, various additives for the purpose of anti-friction, anti-blocking, slip and scratch can be used as other additives in the lithographic printing ink composition. Leveling agents and surface active agents can be used as necessary. An agent or the like may be added.
本発明の平版印刷インキ組成物の組成の一例としては、
・バインダー樹脂 ２０〜４０重量％
・石油系溶剤 ２０〜４５重量％
・植物油類 ７〜２０重量％
・顔料 ５〜３０重量％
・炭酸カルシウム ０．１〜８重量％
・その他添加剤 １〜５重量％
などが好ましい組成として挙げられる。
本発明に使用される基材としてはコート紙、非塗工紙等のような一般的な印刷用紙が挙げられる。
As an example of the composition of the lithographic printing ink composition of the present invention,
・ Binder resin 20-40% by weight
・ Petroleum solvent 20-45% by weight
・ Vegetable oils 7-20% by weight
・ Pigment 5-30% by weight
・ Calcium carbonate 0.1 to 8% by weight
・ Other additives 1 to 5% by weight
Etc. are mentioned as preferred compositions.
Examples of the substrate used in the present invention include general printing paper such as coated paper and non-coated paper.
以下に、実施例により本発明をさらに詳細に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、本発明において、「部」は、「重量部」を表し、「％」は「重量％」を表す。 The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the present invention, “part” represents “part by weight” and “%” represents “% by weight”.
（ロジン変性フェノール樹脂製造例）
反応容器中でガムロジン１５００部に、予めキシレン溶媒中でターシャリーブチルフェノール６００部と９２重量％のパラホルムアルデヒド２１０部を水酸化ナトリウム触媒下で１００℃で４時間反応させ、水分除去したフェノール樹脂を１５０℃で滴下し２時間反応させた。更にペンタエリスリトール１６０部を添加し、触媒として酸化カルシウム１．５部を使用して２５０℃で１２時間反応させた。反応の過程で順次取り出す事により、表1の通り樹脂を得る事が出来た。
(Rosin modified phenolic resin production example)
In a reaction vessel, 1500 parts of gum rosin was previously reacted in a xylene solvent with 600 parts of tertiary butylphenol and 210 parts of 92% by weight paraformaldehyde at 100 ° C. for 4 hours under a sodium hydroxide catalyst, and 150 wt. The solution was dropped at 0 ° C. and reacted for 2 hours. Further, 160 parts of pentaerythritol was added and reacted at 250 ° C. for 12 hours using 1.5 parts of calcium oxide as a catalyst. By sequentially removing in the course of the reaction, a resin was obtained as shown in Table 1.
（ロジン変性フェノール樹脂ワニス製造例）
撹拌機、水分離器付還流冷却器、温度計付き４つ口フラスコに、バインダー樹脂として前記ロジン変性フェノール樹脂（Ａ〜F）５０部、大豆油１５部、高沸点石油系溶剤（ＪＸ日鉱日石エネルギー株式会社製ＡＦソルベント７）３５部、を１９０℃で１時間加熱撹拌してロジン変性フェノール樹脂ワニスＡ〜Ｆを得た。
(Rosin modified phenolic resin varnish production example)
A stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer, 50 parts of the rosin-modified phenolic resin (AF), 15 parts of soybean oil, high-boiling petroleum solvent (JX 35 parts of AF Solvent 7) manufactured by Ishienshi Co., Ltd. was heated and stirred at 190 ° C. for 1 hour to obtain rosin-modified phenolic resin varnishes A to F.
（平版印刷インキ組成物実施例１）
ロジン変性フェノール樹脂ワニス、カーボンブラック（三菱化学株式会社製ＭＡ７７）、炭酸カルシウム（実施例１〜３、６、７、比較例１〜３、５においては白石カルシウム株式会社製ハクエンカＴＤＤ、平均粒子径０．０６μｍ、実施例４においては白石カルシウム株式会社製ハクエンカＯ、平均粒子径０．０３μｍ、実施例５においては竹原化学工業製ＳＡ−２００、平均粒子径０．０８μｍ、比較例４においては白石カルシウム株式会社製ハクエンカＰＺ、平均粒子径０．２μｍ）、高沸点石油系溶剤（ＪＸ日鉱日石エネルギー株式会社製ＡＦソルベント７）を表２の配合にて、常法に従い三本ロールを用いて平版印刷インキ組成物の実施例並びに比較例を得た。
(Lithographic printing ink composition Example 1)
Rosin-modified phenolic resin varnish, carbon black (MA77 manufactured by Mitsubishi Chemical Co., Ltd.), calcium carbonate (Examples 1-3, 6, 7, Comparative Examples 1-3-5, Hakuenka TDD manufactured by Shiroishi Calcium Co., Ltd., average particle size) 0.06 μm, in Example 4, Hakuenka O manufactured by Shiraishi Calcium Co., Ltd., average particle size 0.03 μm, in Example 5, Takehara Chemical Industries SA-200, average particle size 0.08 μm, in Comparative Example 4, Shiroishi Calcium Co., Ltd. Hakenka PZ, average particle size 0.2 μm), high boiling point petroleum solvent (JX Nippon Oil & Energy Corporation AF Solvent 7) with the composition shown in Table 2, using three rolls according to conventional methods Examples and comparative examples of lithographic printing ink compositions were obtained.
（性能評価試験１ 光沢）
光沢評価試験は、オフ輪印刷機として三菱重工業株式会社製ＮＥＯ８００にて、一般的な絵柄、
濃度にて、以下の印刷条件にて実施し、得られた印刷物のベタ部分について村上色彩研究所製光沢計ＧＭ２６Ｄにて測定した。
ＣＴＰ版： 富士フイルム製ＸＰ−Ｆ
用紙：三菱製紙株式会社製パールコートＮ
印刷速度：６００ｒｐｍ
チラー設定温度：２５℃
(Performance evaluation test 1 gloss)
The gloss evaluation test is performed with NEO800 manufactured by Mitsubishi Heavy Industries, Ltd.
The density was measured under the following printing conditions, and the solid portion of the obtained printed matter was measured with a gloss meter GM26D manufactured by Murakami Color Research Laboratory.
CTP version: Fujifilm XP-F
Paper: Pearl Coat N manufactured by Mitsubishi Paper Industries Co., Ltd.
Printing speed: 600rpm
Chiller set temperature: 25 ° C
（性能評価試験２ 着肉性の評価）
上記光沢評価試験で得られた印刷物について、目視にて、表３の通り５段階の相対評価を実施した。
(Performance evaluation test 2 Evaluation of inking properties)
The printed matter obtained in the gloss evaluation test was visually evaluated in five stages as shown in Table 3.
（性能評価試験３ ミスチングの評価）
上記印刷時に印刷機の安全カバーの内側に白紙を張り付け、１５０００通し後に白紙を取り出し、インキの飛散の程度を表４の通り５段階の相対評価を実施した。
(Performance evaluation test 3 Evaluation of misting)
At the time of the above printing, a white paper was attached to the inside of the safety cover of the printing press, the white paper was taken out after 15000 passes, and the degree of ink scattering was evaluated in five stages as shown in Table 4.
性能評価試験結果を表５に示す。 The performance evaluation test results are shown in Table 5.
実施例１〜７は光沢並びに着肉性の両者が良好であり、ミスチングも少ない。ロジン変性フェノール樹脂の重量平均分子量が低い比較例１はミスチングの低減が見られない。ロジン変性フェノール樹脂のノルマルパラフィン白濁温度が高い比較例２〜３は光沢並びに着肉性の改善が見られず印刷品質の観点から望ましくない。炭酸カルシウムの粒子径が大きい比較例４は耐ミスチング性は良好ながら光沢並びに着肉性が劣る。炭酸カルシウムが多量に添加されている比較例５は耐ミスチング性は良好ながら光沢並びに着肉性が劣り、実用に供する事は出来ない。炭酸カルシウムが添加されていない比較例６では耐ミスチング性の向上が見られない。 In Examples 1 to 7, both gloss and inking properties are good, and misting is also small. In Comparative Example 1 in which the weight average molecular weight of the rosin-modified phenol resin is low, no reduction in misting is observed. Comparative Examples 2 to 3 in which the normal paraffin clouding temperature of the rosin-modified phenol resin is high are not desirable from the viewpoint of printing quality because neither improvement in gloss nor inking property is observed. Comparative Example 4 having a large particle size of calcium carbonate is inferior in glossiness and inking property while having good misting resistance. In Comparative Example 5 in which a large amount of calcium carbonate is added, the misting resistance is good, but the gloss and the inking property are inferior, and cannot be put to practical use. In Comparative Example 6 in which calcium carbonate was not added, no improvement in misting resistance was observed.
即ち本発明は、顔料、炭酸カルシウム、バインダー樹脂、石油系溶剤、植物油を含有す平版印刷インキ組成物において、下記の（１）〜（３）であることを特徴とする平版印刷インキ組成物に関する。
（１）炭酸カルシウムが、一次粒子径が０．０２〜０．１０μｍであって、表面処理がロジン酸および／または脂肪酸である。
（２）全インキ組成物中、炭酸カルシウムが、０．１〜８重量部％である。
（３）ロジン変性フェノール樹脂が、重量平均分子量２００００〜１０００００、ノルマルパラフィン白濁温度４０〜１１０℃
である。
That is, the present invention relates to a lithographic printing ink composition comprising the following (1) to (3) in a lithographic printing ink composition containing a pigment, calcium carbonate, a binder resin, a petroleum solvent, and a vegetable oil. .
(1) The calcium carbonate has a primary particle size of 0.02 to 0.10 μm, and the surface treatment is rosin acid and / or fatty acid.
(2) In all the ink compositions, calcium carbonate is 0.1 to 8 parts by weight.
(3) The rosin-modified phenol resin has a weight average molecular weight of 20,000 to 100,000 and a normal paraffin turbidity temperature of 40 to 110 ° C.
It is.
Claims (3)
炭酸カルシウムが、
一次粒子径が０．０２〜０．１０μｍ
表面処理がロジン酸および／または脂肪酸
バインダー樹脂が、
重量平均分子量が２００００〜１０００００
ノルマルパラフィン白濁温度４０〜１１０℃
であることを特徴とする平版印刷インキ組成物。 In the lithographic printing ink composition containing pigment, calcium carbonate, binder resin, petroleum solvent, vegetable oil,
Calcium carbonate
Primary particle size is 0.02-0.10 μm
Surface treatment is rosin acid and / or fatty acid binder resin,
Weight average molecular weight is 20000-100,000
Normal paraffin cloudiness temperature 40-110 ° C
A lithographic printing ink composition characterized in that:
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