JP5958031B2 - Offset printing ink composition and printed matter - Google Patents
Offset printing ink composition and printed matter Download PDFInfo
- Publication number
- JP5958031B2 JP5958031B2 JP2012086325A JP2012086325A JP5958031B2 JP 5958031 B2 JP5958031 B2 JP 5958031B2 JP 2012086325 A JP2012086325 A JP 2012086325A JP 2012086325 A JP2012086325 A JP 2012086325A JP 5958031 B2 JP5958031 B2 JP 5958031B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- printing
- oil
- rosin
- ink composition
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 32
- 238000007645 offset printing Methods 0.000 title description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 75
- 238000007639 printing Methods 0.000 claims description 52
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 41
- 239000008158 vegetable oil Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 26
- 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 claims description 25
- 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 claims description 25
- 239000003208 petroleum Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000000049 pigment Substances 0.000 claims description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011163 secondary particle Substances 0.000 claims description 10
- 229910002029 synthetic silica gel Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 229920005989 resin Polymers 0.000 description 33
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- 238000011156 evaluation Methods 0.000 description 19
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- 230000001965 increasing effect Effects 0.000 description 15
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- 239000004094 surface-active agent Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 5
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- 239000008096 xylene Substances 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
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- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
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- 239000008159 sesame oil Substances 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- KQOMUSLQKQAVTD-UHFFFAOYSA-N sodium 4-hydroxy-3-[(4-nitrophenyl)diazenyl]naphthalene-1,5-disulfonic acid Chemical compound C1=CC2=C(C=C(C(=C2C(=C1)S(=O)(=O)O)O)N=NC3=CC=C(C=C3)[N+](=O)[O-])S(=O)(=O)O.[Na+] KQOMUSLQKQAVTD-UHFFFAOYSA-N 0.000 description 1
- TYVJJYHBZVERDC-UHFFFAOYSA-N sodium 8-hydroxy-7-[(4-nitrophenyl)diazenyl]naphthalene-1,6-disulfonic acid Chemical compound C1=CC2=CC(=C(C(=C2C(=C1)S(=O)(=O)O)O)N=NC3=CC=C(C=C3)[N+](=O)[O-])S(=O)(=O)O.[Na+] TYVJJYHBZVERDC-UHFFFAOYSA-N 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- OJQMPIICCPYCQQ-UHFFFAOYSA-N tetracos-15-en-1-ol Chemical compound CCCCCCCCC=CCCCCCCCCCCCCCCO OJQMPIICCPYCQQ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PPPHYGCRGMTZNA-UHFFFAOYSA-M trifluoromethyl sulfate Chemical compound [O-]S(=O)(=O)OC(F)(F)F PPPHYGCRGMTZNA-UHFFFAOYSA-M 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、非晶質シリカ、バインダー樹脂、植物油類、石油系溶剤および顔料を含有する酸化重合型オフセット印刷インキ組成物、これを用いたおよび印刷方法に関し、より詳しくは、印刷時の乳化適正、乳化安定性に優れた酸化重合型オフセット印刷インキ組成物および印刷物に関する。 The present invention relates to an oxidation polymerization type offset printing ink composition containing amorphous silica, binder resin, vegetable oil, petroleum solvent and pigment, and a printing method using the same, and more particularly, emulsification appropriateness at the time of printing The present invention relates to an oxidation polymerization type offset printing ink composition and a printed matter excellent in emulsion stability.
近年オフセット印刷業界では、印刷時の省人化、省力化、自動化、高速化の要求が高まってきていることに合わせて、様々な印刷条件下においてトラブルレスで長時間安定して高品位な印刷物が得られる印刷インキが望まれている。 In recent years, in the offset printing industry, demands for labor saving, labor saving, automation, and high-speed printing have been increasing. Is desired.
酸化重合型オフセット印刷とは、紙に印刷後、空気中の酸素によって植物油が酸化固化して乾燥する印刷方法である。近年オフセット印刷業界では、印刷物および印刷作業現場における環境配慮への関心が年々増加してきており，高い環境対応性能を有するインキが求められてきている。例えば長いオフセット印刷の歴史の中で、従来より使用してきた揮発性有機溶剤である石油系溶剤が芳香族成分の含有率が１％未満のアロマフリー溶剤になり、さらには、枯渇資源である石油系溶剤の保護および、より一層環境保全を配慮した揮発性の石油系溶剤を一切含有せず、インキ中からの揮発性有機化合物の排出量を1重量％以下に抑えたＶＯＣフリータイプのインキ（Ｎｏｎ−ＶＯＣインキ）のニーズが高まっている。 Oxidation polymerization offset printing is a printing method in which vegetable oil is oxidized and solidified by oxygen in the air and dried after printing on paper. In recent years, in the offset printing industry, interest in environmental considerations in printed materials and printing work sites has been increasing year by year, and ink having high environmental performance has been demanded. For example, in the long history of offset printing, petroleum-based solvents, which are volatile organic solvents that have been used in the past, have become aromatic-free solvents with an aromatic content of less than 1%. VOC-free inks that contain no volatile petroleum solvents that protect environmental solvents and further protect the environment, and that reduce the emission of volatile organic compounds from the ink to less than 1% by weight ( Non-VOC ink) needs are increasing.
また、近年、地球温暖化の問題から日常生活や経済活動において避けることができないＣＯ２等の温室効果ガスの排出量を削減するカーボンオフセットの考え方が普及し、今まで以上にＮｏｎ−ＶＯＣインキの需要が高まってきている。 In recent years, the concept of carbon offset, which reduces emissions of greenhouse gases such as CO 2, which cannot be avoided in daily life and economic activities due to global warming issues, has become widespread. Demand is increasing.
ＶＯＣ（Ｖｏｌａｔｉｌｅ Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄ）とは、常温で揮発しやすい化合物のことであり、米国環境保護庁はＶＯＣ測定方法として、１１０℃１時間の加熱による加熱残分測定を提示しており、実使用に即した測定方法として用いられている。 VOC (Volatile Organic Compound) is a compound that easily volatilizes at room temperature, and the US Environmental Protection Agency presents the measurement of residual heating by heating at 110 ° C. for 1 hour as a VOC measurement method. It is used as an appropriate measurement method.
しかしながら、従来の石油系溶剤成分を使用したオフセット印刷用インキ用樹脂のまま、石油系溶剤成分を植物油類に置き換えただけでは、インキのセット性や乾燥性が著しく低下し、印刷機から出てきた印刷物を積み重ねた際に印刷面が用紙裏面に付着する裏付きや、乾燥した印刷物を高温多湿で保管した際に印刷面が再軟化し他の面に付着するブロッキング現象が発生しトラブルとなる。 However, replacing the oil-based solvent component with vegetable oils while maintaining the conventional resin for offset printing inks that uses a petroleum-based solvent component significantly reduces the ink setting and drying properties and comes out of the printing press. When the printed material is stacked, the printed surface adheres to the back of the paper, and when the dried printed material is stored at high temperature and high humidity, the printed surface re-softens and causes a blocking phenomenon that adheres to the other surface. .
これら防止するために、使用樹脂の溶解性を著しく低下させたり、軟化点を著しく向上させたりしてセット性と乾燥性およびブロッキング性のバランスを保つ方法がとられるが、この場合にはインキの流動性が損なわれインキの転移性も劣化する為、印刷適性が著しく劣る結果になり、印刷面の光沢値も十分に得られない。 In order to prevent these problems, a method of maintaining the balance between setting property, drying property and blocking property by significantly reducing the solubility of the resin used or significantly improving the softening point is employed. Since the fluidity is impaired and the transferability of the ink is deteriorated, the printability is remarkably deteriorated, and the gloss value of the printed surface cannot be sufficiently obtained.
また、Ｎｏｎ−ＶＯＣインキに限らず、近年の印刷機の高速化、短納期化に伴い、一般の酸化重合型インキに関しても使用樹脂の分子量や溶解性バランスの見直しが実施されてきた。樹脂物性の変更はンキの乳化適性にも大きな影響を与える。 In addition to non-VOC inks, the molecular weight and solubility balance of resins used have been reviewed for general oxidation polymerization type inks as printing presses have become faster and shorter in recent years. Changing the resin physical properties has a great influence on the emulsification suitability of the ink.
オフセット水有り印刷では、インキがインキ壷から複数のローラーを経由して版面に供給され、湿し水が水舟から複数のローラーを経由して版面に供給される。版面の画線部は親油性であるのでインキが受理され、版面の非画線部は親水性であるので湿し水で被覆される事により、紙面に画像が形成される。供給されるインキ量と供給される湿し水量が不均衡な場合、印刷トラブルが発生する事がある。例を挙げると、版面の非画線部において湿し水が不足すると非画線残りと一般的に称するパイリング現象や地汚れが発生する。
また、湿し水が過剰に供給されると、水棒絡み、水目、濃度変動、フライング、ローラー余り、ローラー剥げ等の深刻な印刷トラブルが誘発される。これらの印刷トラブルを防止し、優れた印刷紙面を再現する為には、印刷機上でのインキと湿し水の乳化状態を制御し、水幅（印刷機あるいは紙面に対して湿し水に起因するトラブルが発生しない水上がり量の幅）を拡大する印刷インキの処方設計が必要である。近年、オフセット印刷機の性能向上に伴う高速印刷化が益々進行すると共に、印刷用紙の古紙利用比率が上昇しているので、インキと湿し水の需給バランスが変化し、最適かつ安定した乳化状態を保持する事が困難になっている。
In printing with offset water, ink is supplied from the ink fountain to the plate surface via a plurality of rollers, and dampening water is supplied from the water boat to the plate surface via a plurality of rollers. Since the image area on the printing plate is oleophilic, ink is accepted, and since the non-image area on the printing plate is hydrophilic, an image is formed on the paper surface by coating with dampening water. If the amount of ink supplied and the amount of dampening water supplied are imbalanced, printing trouble may occur. For example, if dampening water is insufficient in the non-image area of the printing plate, a piling phenomenon generally referred to as a non-image area residue and background stains occur.
Further, when dampening water is supplied excessively, serious printing troubles such as water rod entanglement, water eyes, density fluctuation, flying, remaining roller, and roller peeling are induced. In order to prevent these printing troubles and to reproduce an excellent printing paper surface, the emulsification state of the ink and the dampening water on the printing machine is controlled, and the water width (the dampening water is applied to the printing machine or the paper surface) It is necessary to design a prescription for printing ink that expands the range of the amount of rising water that does not cause trouble. In recent years, with the progress of high-speed printing accompanying the improvement in the performance of offset printing presses, the ratio of waste paper used for printing paper has increased, so the supply and demand balance of ink and fountain solution has changed, and an optimal and stable emulsification state It is difficult to hold.
特に、植物油類が主体の酸化重合型インキやＮｏｎ-ＶＯＣインキは、湿し水を使用するオフセット印刷において、水と油の反発が大きくなることからインキの乳化適性が劣り、印刷機上でインキ中に取り込めなくなった過剰の水が印刷機のローラーを親水化させローラーストリッピングを引き起こしたり、過乳化して転移性が劣りローラー上に余ったインキが、紙幅外の汚れや水元ローラーの汚れを引き起こしやすいという問題もある。 In particular, oxidative polymerization type inks and non-VOC inks mainly composed of vegetable oils are poor in emulsification of the ink because of the repulsion between water and oil in offset printing using fountain solution. Excess water that can not be taken in causes the roller of the printing press to become hydrophilic, causing roller stripping, or over emulsification and poor transferability, and ink remaining on the roller is stained outside the paper width or dirty on the water source roller There is also a problem that it is easy to cause.
近年では、ローラーストリッピングの改善を目的としてインキ中に取り込めなくなった過剰表面水を減量すべく樹脂面・添加剤面から改良を施し、インキの乳化率を向上させてンキ中に取り込める水の量を多くする方法が取られる場合もあるが、単純にインキの乳化率向上だけでは乳化インキの転移性の劣化からローラー上のインキ余りを引き起こし、最終的にはローラーストリッピングを誘発する現象も起きている。また乳化したインキは版、ブランケットを介して紙に転移されていくが、過剰乳化したインキは紙面上で着肉にムラが発生したり、網点の品質が著しく劣ったりする。 In recent years, the amount of water that can be taken into the tank by improving the emulsification rate of the ink by improving the resin surface and additives in order to reduce excess surface water that can no longer be taken into the ink for the purpose of improving roller stripping. In some cases, simply increasing the emulsification rate of the ink may cause a residual ink on the roller due to a deterioration in the transferability of the emulsified ink, and eventually cause a phenomenon of inducing roller stripping. ing. The emulsified ink is transferred to the paper through the plate and the blanket, but the excessively emulsified ink causes unevenness in the inking on the paper surface and the quality of the halftone dot is remarkably inferior.
従来より、インキの乳化適性を調整する手法としては、アルコールや界面活性剤等の助剤をインキ中に添加する方法が採られてきた。 Conventionally, as a method for adjusting the emulsification suitability of an ink, a method of adding an auxiliary agent such as an alcohol or a surfactant into the ink has been employed.
特許文献１〜２ではインキ組成中に０．１〜５重量％のジオール類を添加することで乳化適性を向上させ、印刷機上でのトラブル、地汚れを改善する手法が開示されているが、アルコール系の添加剤は乳化後のインキ粘弾性を増幅させる為、超高速領域で印刷がなされるオフセット輪転印刷機では有効な手段であるが、一般的な酸化重合型インキが主に使用される枚葉印刷機ではインキ粘弾性の増加はローラー間でのインキの転移不良、印刷後のレベリング性の劣化による光沢不良を招く恐れがあり有効な手段とは言えない。 Patent Documents 1 and 2 disclose a technique for improving emulsification suitability by adding 0.1 to 5% by weight of a diol during the ink composition, and improving troubles on the printing press and background stains. The alcohol-based additive amplifies the ink viscoelasticity after emulsification, and is therefore an effective means for an offset rotary printing press that performs printing in an ultra-high speed region. However, general oxidation polymerization type ink is mainly used. In a sheet-fed printing press, an increase in ink viscoelasticity may cause poor transfer of ink between rollers and poor gloss due to deterioration in leveling after printing, which is not an effective means.
特許文献３では、インキ組成中に０．０１〜１０重量％のダイマージオールを添加する方法が開示されているが、インキに与えられたせん断応力によって乳化のバランスが変化する為、近年の高速化された印刷方式に完全に対応できない。 Patent Document 3 discloses a method in which 0.01 to 10% by weight of dimer diol is added to the ink composition. However, since the balance of emulsification is changed by the shear stress applied to the ink, the speed has been increased in recent years. It is not possible to fully support the printed printing method.
特許文献４〜６では、界面活性剤を添加して乳化適性を向上させる方法が開示されているが、一般的に低表面張力であるカチオン界面活性剤・アニオン界面活性剤・両性界面活性剤・ノニオン界面活性剤を使用するとインキの表面張力が著しく低下し、インキが湿し水に散りやすくなる為、散り汚れや調量絡み等のトラブルが発生しやすくなる。また界面活性剤を使用したインキをインキ壷上に長時間静置すると流動性が失われ易く、一定の外力を付与しないと流動性が回復されず、壷逃げと一般的に称されるトラブルが誘発される。 Patent Documents 4 to 6 disclose a method for improving emulsification suitability by adding a surfactant. Generally, cationic surfactants, anionic surfactants, amphoteric surfactants having a low surface tension, When a nonionic surfactant is used, the surface tension of the ink is remarkably lowered, and the ink is easily dispersed in the fountain solution. Therefore, troubles such as scattering stains and metering tangles are likely to occur. Also, if ink using a surfactant is left on the ink fountain for a long time, the fluidity tends to be lost, and if a certain external force is not applied, the fluidity is not recovered, and there is a problem commonly referred to as wrinkle escape. Be triggered.
加えて、沸点の低いアルコールや界面活性剤等の助剤はＶＯＣ成分として大気中排出される為、Ｎｏｎ-ＶＯＣインキに使用することができないことも挙げられる。 In addition, auxiliary agents such as alcohols and surfactants having a low boiling point are discharged in the atmosphere as VOC components, so that they cannot be used for non-VOC inks.
特許文献７では、粉末状シリカを含有することを特徴とする浸透乾燥型平版印刷インキについて開示されているが、内容に具体性がなく、実施例も乏しい為実用性が見られない。 Patent Document 7 discloses an osmotic drying type lithographic printing ink characterized by containing powdered silica, but its contents are not specific and practical examples are not found because of lack of examples.
特許文献８では、シリカ、高反応性金属有機化合物、バインダー樹脂、植物油および石油系溶剤を含有するヒートセット型オーバープリントニス組成物について開示されているが、シリカをマット化剤として使用し、特定の高反応性有機化合物との組み合わせでマット効果、耐摩擦性、乳化流動性に優れたオーバープリントニスを提供するものであり、本発明とは目的としている課題が異なる。 Patent Document 8 discloses a heat-set overprint varnish composition containing silica, a highly reactive metal organic compound, a binder resin, a vegetable oil, and a petroleum solvent. The present invention provides an overprint varnish excellent in mat effect, friction resistance, and emulsification fluidity in combination with the highly reactive organic compound, and has a different object from the present invention.
本発明の目的は、インキの流動性および印刷時の乳化安定性に優れた酸化重合型オフセット印刷インキ組成物および印刷物を提供することである。 An object of the present invention is to provide an oxidation polymerization type offset printing ink composition and a printed matter excellent in ink fluidity and emulsion stability during printing.
上記課題を解決するために誠意研究した結果、バインダー樹脂、植物油類、石油系溶剤および顔料を含有する酸化重合型オフセット印刷インキ組成物であって、特定の非晶質シリカを含有する酸化重合型オフセット印刷インキ組成物が、インキの流動性、経時安定性および印刷時の乳化安定性に優れ、過乳化やローラー上のインキ余りを防止することで濃度変動等の少ない安定した印刷物を提供できることを見出し本発明を完成するに至った。 As a result of sincere research to solve the above problems, it is an oxidation polymerization type offset printing ink composition containing a binder resin, a vegetable oil, a petroleum solvent and a pigment, and containing a specific amorphous silica. The offset printing ink composition is excellent in ink fluidity, stability over time and emulsification stability during printing, and can provide stable printed matter with less density fluctuations by preventing excessive emulsification and excess ink on the roller. The inventor has completed the present invention.
すなわち、本発明は、非晶質シリカ、バインダー樹脂、植物油類、石油系溶剤および顔料を含有する酸化重合型オフセット印刷インキ組成物であって、
非晶質シリカが、
平均二次粒子径０．０５〜１０μｍ
および
ＢＥＴ比表面積２０〜４００ｍ2／ｇ
であり、
インキ全重量に対して０．１〜１０重量％
含有されていることを特徴とする酸化重合型オフセットインキ組成物に関するものである。
That is, the present invention is an oxidation polymerization type offset printing ink composition containing amorphous silica, a binder resin, a vegetable oil, a petroleum solvent and a pigment,
Amorphous silica
Average secondary particle size 0.05 to 10 μm
And a BET specific surface area of 20 to 400 m 2 / g
And
0.1 to 10% by weight based on the total weight of the ink
The present invention relates to an oxidation polymerization type offset ink composition characterized by being contained.
また、本発明は、非晶質シリカが、湿式法または乾式法で製造された合成非晶質シリカであることを特徴とする上記の酸化重合型オフセットインキ組成物に関するものである。 The present invention also relates to the above oxidation polymerization type offset ink composition, wherein the amorphous silica is a synthetic amorphous silica produced by a wet method or a dry method.
さらに、本発明は、上記バインダー樹脂が、
酸価５〜３０（ｍｇＫＯＨ／ｇ）、
環球法による軟化点１２０〜３００℃
および
重量平均分子量１００００〜１０００００
であることを特徴とする上記の酸化重合型オフセットインキ組成物に関するものである。
Furthermore, the present invention provides the binder resin,
Acid value 5-30 (mgKOH / g),
Softening point 120-300 ° C by ring and ball method
And a weight average molecular weight of 10,000 to 100,000
It is related with said oxidation polymerization type offset ink composition characterized by the above-mentioned.
さらに、本発明は、上記の酸化重合型オフセットインキ組成物を基材上に印刷してなる印刷物に関するものである。 Furthermore, this invention relates to the printed matter formed by printing said oxidation polymerization type offset ink composition on a base material.
本発明が提供する酸化重合型オフセットインキ組成物は、書籍、書籍、チラシ、カタログ等の印刷において、インキの流動性および経時安定性ならびに印刷時の乳化安定性に優れ、従来用いられてきたアルコール系および界面活性剤系の添加剤を使用することなく過乳化やローラー上のインキ余りを防止し濃度変動等の少ない安定した印刷物を提供できる。また過剰な湿し水の供給は印刷物の網点形状の劣化、酸化重合型インキの乾燥不良等引き起こすが、本発明が提供する酸化重合型オフセットインキ組成物はインキの不感脂性を高めることで過剰な湿し水の供給がなくても印刷物の刷り出し汚れを防止できる。 The oxidation polymerization offset ink composition provided by the present invention is an alcohol that has been used in the printing of books, books, leaflets, catalogs, etc., and has excellent fluidity and temporal stability of ink and emulsion stability during printing. Without using a system or surfactant-based additive, it is possible to prevent over-emulsification and residual ink on the roller, and provide a stable printed matter with little variation in density. Excess dampening water causes deterioration of the halftone dot shape of the printed matter and poor drying of the oxidation polymerization type ink. However, the oxidation polymerization type offset ink composition provided by the present invention is excessive by increasing the insensitivity of the ink. Even if no dampening water is supplied, printed matter can be prevented from being smudged.
本発明は、揮発性有機溶剤を使用しない環境に配慮したＮｏｎ−ＶＯＣインキへの展開も可能であり、より環境面に配慮した印刷環境、および印刷物を提供することができる。 The present invention can be applied to an environment-friendly Non-VOC ink that does not use a volatile organic solvent, and can provide a printing environment and printed matter that are more environmentally friendly.
次に、好ましい実施の形態を挙げて本発明をさらに具体的に説明する。 Next, the present invention will be described more specifically with reference to preferred embodiments.
シリカは、二酸化ケイ素（ＳｉＯ２）、または、二酸化ケイ素によって構成される物質の総称であり、天然品、合成品の２つに大別できる。さらに天然品、合成品の中でさらに結晶質と非晶質の２種類に分類され、その種類は多く、多岐に渡る分野で使用されている。 Silica is a general term for silicon dioxide (SiO 2 ) or substances composed of silicon dioxide, and can be broadly divided into two categories: natural products and synthetic products. Furthermore, natural products and synthetic products are further classified into two types, crystalline and amorphous, and there are many types and they are used in various fields.
シリカは圧力や温度などの条件により、様々な形（結晶多形）をとる。天然結晶質シリカとしては、石英、水晶、珪砂等が、非晶質シリカとしては、珪藻土、活性白土等が挙げられる。また、合成非晶質シリカとしては乾式シリカ、湿式シリカ、シリカゲル等が挙げられる。 Silica takes various forms (crystal polymorphs) depending on conditions such as pressure and temperature. Examples of the natural crystalline silica include quartz, quartz, and silica sand, and examples of the amorphous silica include diatomaceous earth and activated clay. Examples of the synthetic amorphous silica include dry silica, wet silica, silica gel and the like.
合成非晶質シリカは、製法の違いによって乾式法シリカと湿式法シリカに分かれる。乾式法シリカは四塩化ケイ素ガスなどを気相中で燃焼させて製造されたものを称し、湿式法シリカはケイ酸ソーダ水溶液の酸またはアルカリ金属塩による中和、分解反応によって製造されたものを称する。 Synthetic amorphous silica is divided into dry silica and wet silica depending on the production method. Dry process silica is produced by burning silicon tetrachloride gas in the gas phase, and wet process silica is produced by neutralization or decomposition reaction of sodium silicate aqueous solution with acid or alkali metal salt. Called.
また、湿式法シリカにおいては、生成過程の違いから沈降法シリカ、ゲル法シリカ等が挙げられる。 Moreover, in the wet method silica, precipitation method silica, gel method silica, etc. are mentioned from the difference in a production | generation process.
沈降法シリカは比較的高温、アルカリ性のｐＨ領域でケイ酸ソーダと鉱酸の中和反応を進めることが特徴であり、シリカ一次粒子の成長を早く進行させ、一次粒子をフロック状に凝集させ沈降させる方法である。近年では、中性のｐＨ領域、低温、高い塩濃度等の条件下で、一次粒子の成長を抑えながら凝集を起させた後、凝集した状態で一次粒子を成長させるような合成手法も取られている。 Precipitated silica is characterized by a neutralization reaction between sodium silicate and mineral acid in a relatively high temperature and alkaline pH range, and the silica primary particles grow rapidly, and the primary particles are agglomerated in the form of flocs and settled. It is a method to make it. In recent years, a synthesis method has been adopted in which primary particles are grown in the aggregated state after causing aggregation while suppressing the growth of primary particles under conditions such as neutral pH range, low temperature, and high salt concentration. ing.
ゲル法シリカは、酸性のｐＨ領域でケイ酸ソーダと鉱酸の中和反応を進めることが特徴であり、一次粒子の成長を抑えた状態で凝集を起こす。この時、凝集体が形成する３次網目構造により反応液全体が一塊のゲルとなる為、ゲル法シリカと呼ばれている。 Gel silica is characterized by a neutralization reaction between sodium silicate and mineral acid in an acidic pH region, and causes aggregation in a state where growth of primary particles is suppressed. At this time, since the whole reaction liquid becomes a lump gel by the tertiary network structure formed by the aggregates, it is called gel method silica.
湿式法シリカ表面は乾式法シリカ表面と比較してシラノール基が多く一定の親水性を有する。表面シラノール基をポリジメチルシロキサン、メチルクロロシラン、ヘキサメチルジシラサン等のシラン類やシリコーン類で表面処理した疎水シリカも存在する。
本発明に用いられる合成非晶質シリカは、請求項１記載の物性範囲を満たせば乾式法、湿式法どの生成過程でも良い。
The wet process silica surface has more silanol groups than the dry process silica surface and has a certain hydrophilicity. There are also hydrophobic silicas whose surface silanol groups are surface-treated with silanes such as polydimethylsiloxane, methylchlorosilane, hexamethyldisilazane, and silicones.
The synthetic amorphous silica used in the present invention may be produced by any of a dry process and a wet process as long as the physical property range of claim 1 is satisfied.
また、合成非晶質シリカは物質の最小構成単位である５〜５５ｎｍの一次粒子が融着あるいは化学結合し一次粒子凝集体（二次粒子構造）となる。さらに一次粒子凝集体が物理的に凝集し二次凝集体として存在しているが、二次凝集体は各種媒体中で物理的なせん断力を与えることで一次粒子凝集体（二次粒子構造）まで分散することが可能である。本発明の平均二次粒子系は一次粒子凝集体（二次粒子構造）のことを指す。 Synthetic amorphous silica forms primary particle aggregates (secondary particle structure) by fusing or chemically bonding the primary particles of 5 to 55 nm, which is the minimum constituent unit of the substance. In addition, primary particle aggregates physically aggregate and exist as secondary aggregates, but secondary aggregates give primary particle aggregates (secondary particle structure) by applying physical shearing force in various media. Can be dispersed. The average secondary particle system of the present invention refers to a primary particle aggregate (secondary particle structure).
本発明におけるシリカは、平均二次粒子径が０．０５〜１０μｍ、好ましくは０．１〜７．５μｍ、さらに好ましくは０．２〜５μｍ、さらに好ましくは０．３〜３μｍであることが望ましい。平均二次粒子径が０．０５μｍ未満であると、より粒径の小さい一次粒子の強い結合から成り立っており、粒子が硬く版磨耗が発生しやすくなる。加えて比表面積も大きくなるため、高い吸油性能を有し、インキ化した際に十分な流動性が得られない。また、平均二次粒子径が１０μｍより大きいと、印刷時のパイリングや、ローラー間での転移不良、インキの着肉不良に繋がる。 The silica in the present invention has an average secondary particle diameter of 0.05 to 10 μm, preferably 0.1 to 7.5 μm, more preferably 0.2 to 5 μm, and further preferably 0.3 to 3 μm. . When the average secondary particle diameter is less than 0.05 μm, it is composed of strong bonds of primary particles having a smaller particle diameter, so that the particles are hard and plate wear tends to occur. In addition, since the specific surface area becomes large, it has high oil absorption performance, and sufficient fluidity cannot be obtained when it is inked. On the other hand, if the average secondary particle diameter is larger than 10 μm, it will lead to piling during printing, poor transfer between rollers, and poor ink deposition.
また、本発明における非晶質シリカ含有率は、０．１〜１０重量％、好ましくは、０．３〜７重量％、さらに好ましくは０．５〜５重量％、さらに好ましくは０．８〜３重量％が望ましい。シリカ含有率が０．１重量％未満であると印刷時の乳化安定性、乳化流動性に効果が見られず、１０重量％より大きいとインキの流動性、転移性が損なわれる為好ましくない。 The amorphous silica content in the present invention is 0.1 to 10% by weight, preferably 0.3 to 7% by weight, more preferably 0.5 to 5% by weight, and still more preferably 0.8 to 3% by weight is desirable. If the silica content is less than 0.1% by weight, no effect is seen in emulsification stability and emulsification fluidity during printing, and if it is more than 10% by weight, the fluidity and transferability of the ink are impaired.
また、本発明におけるシリカは、ＢＥＴ比表面積が２０〜４００ｍ２／ｇ、好ましくは５０〜３００ｍ２／ｇ、さらに好ましくは８０〜２５０ｍ２／ｇであることが望ましい。ＢＥＴ比表面積が２０ｍ２／ｇ未満であると、酸化重合型オフセットインキに必要な粘弾性を得にくく、また粒径が比較的大きくなることにより、パイリング等の問題を招きやすい懸念がある。また、ＢＥＴ比表面積が４００ｍ２／ｇより大きいと、シリカの一次粒子同士の凝集力が強くなりすぎてしまい、分散工程における負荷が大きくなり分散不良、流動性不良、版磨耗性の劣化等の問題が生じる。 The silica in the present invention has a BET specific surface area of 20 to 400 m 2 / g, preferably 50 to 300 m 2 / g, and more preferably 80 to 250 m 2 / g. When the BET specific surface area is less than 20 m 2 / g, it is difficult to obtain viscoelasticity necessary for the oxidation polymerization type offset ink, and there is a concern that problems such as piling are likely to occur due to the relatively large particle size. On the other hand, if the BET specific surface area is larger than 400 m 2 / g, the cohesive force between the primary particles of silica becomes too strong, and the load in the dispersion process increases, resulting in poor dispersion, poor fluidity, deterioration of plate wear, etc. Problems arise.
本発明における微粒子集合体の平均粒径は、一般的なレーザー回折法、散乱法等により測定して求めることができ、その微粒子集合体の投影面積に等しい円を仮定した時の直径の平均値を平均粒径とする。 The average particle diameter of the fine particle aggregate in the present invention can be determined by measurement by a general laser diffraction method, scattering method, etc., and the average value of the diameter when assuming a circle equal to the projected area of the fine particle aggregate Is the average particle size.
また、本発明におけるＢＥＴ比表面積は、ＢＥＴ式（Ｂｒｕｎａｕｅｒ，Ｅｍｍｅｔａｎｄ Ｔｅｌｌｅｒ‘ｓ ｅｑｕａｔｉｏｎ）に従って単分子吸着量を測定した比表面積値である。 Moreover, the BET specific surface area in this invention is a specific surface area value which measured the amount of monomolecular adsorption | suction according to BET type | formula (Brunauer, Emmand Teller's equation).
本発明に用いられるバインダー樹脂としては、ロジン変性フェノール樹脂、石油樹脂、アルキッド樹脂、ロジン変性アルキッド樹脂、石油樹脂変性アルキッド樹脂、ロジンエステル等が挙げられる。好ましくは、ロジン変性フェノール樹脂を使用する。 Examples of the binder resin used in the present invention include rosin-modified phenol resin, petroleum resin, alkyd resin, rosin-modified alkyd resin, petroleum resin-modified alkyd resin, and rosin ester. Preferably, a rosin modified phenolic resin is used.
本発明のロジン変性フェノール樹脂は、ロジンにフェノール‐ホルムアルデヒド初期縮合物（レゾール樹脂）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。一般的にロジン変性フェノール樹脂のロジンとしては、ガムロジン、ウッドロジン、トールロジン、重合ロジン、不均斉化ロジン、水添ロジンなどが挙げられるが、不均斉化ロジン、水添ロジンはそのままではフェノール‐ホルムアルデヒド初期縮合物と反応せず使用できない。重合ロジンはロジン類を重合して得られる樹脂であり、ロジン単体と比較して高い軟化点を有する特徴があるが、コスト面、性能面から単体で使用することは難しい。 The rosin-modified phenolic resin of the present invention is obtained by reacting rosin with a phenol-formaldehyde initial condensate (resole resin) and then esterifying with a polyhydric alcohol. Generally, rosin of rosin-modified phenolic resin includes gum rosin, wood rosin, tall rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, etc. It cannot be used because it does not react with the condensate. Polymerized rosin is a resin obtained by polymerizing rosins and has a higher softening point than rosin alone, but it is difficult to use it alone in terms of cost and performance.
ガムロジンは 松の木の幹に傷をつけて分泌する生松脂を採取し、濾過して不純物をとり除き、その後蒸留することにより、低沸点成分のテレピン油（常温で芳香性を有する液状物質）を分離して得られる。 Gum rosin collects raw pine oil that is damaged by pine tree trunks, collects it, removes impurities by filtration, and then distills it to separate low-boiling turpentine oil (a liquid substance having aromaticity at room temperature). Is obtained.
ウッドロジンは、松を伐採した後の切り株を掘り起こし、チップ状にしたものを溶剤で抽出し、溶媒と低沸点成分であるテレピン油を分離した後得られる成分である。 Wood rosin is a component obtained after digging up a stump after cutting a pine tree, extracting the chips into a chip, and separating the solvent and the low-boiling component turpentine oil.
トールロジンは、木材チップに化学薬品を加え、高い温度と圧力の下で分解してパルプ繊維を取り出すクラフト法において、木材として松を用いた場合、樹脂成分が粗トール油(トールとはスウェーデン語で松の油を意味するＴａｌｌｏｊａに由来する)と呼ばれる副産物として回収され、この粗トール油を精密蒸留することによって得られるロジンである。 Tall rosin is a kraft method in which chemicals are added to wood chips and decomposed under high temperature and pressure to remove pulp fibers.When pine is used as wood, the resin component is crude tall oil. This rosin is recovered as a by-product called tal oil, which means pine oil, and is obtained by precision distillation of this crude tall oil.
多価アルコールとしては、例えば２価の１，６−ヘキサンジオール、１，９−ノナンジオール、３−メチル−１，５−ペンタンジオール、２，２−ジエチル−１，３−プロパンジオ−ル、２−ブチル−２−エチル−１，３−プロパンジオール、１，２−シクロヘキサンジオール、ジエチレングリコールなどが、また３価以上のグリセリン、トリメチロールエタン、トリメチロールプロパン、トリエチレングリコール、１，６−ヘキサンジオール、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、ソルビトール、イノシトール、セルロースなどが挙げられる。これら多価アルコールは単独または複数を任意の量比で組み合わせて使用することが可能である。多価アルコールは、残存するカルボン酸に対しＯＨ等量として好ましくは０．５〜１．５、より好ましくは０．９〜１．２添加する。多価アルコールの添加量は得られる樹脂の重量平均分子量、粘度、溶剤／植物油類への溶解性、乳化適性に大きく影響を与え、多価アルコールの添加量が上記より少ない場合には反応速度が低下し反応に時間がかかる恐れがあり、多い場合には必要とされる性能が得られない恐れがある。 Examples of the polyhydric alcohol include divalent 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-cyclohexanediol, diethylene glycol, etc. are also trivalent or higher glycerin, trimethylolethane, trimethylolpropane, triethylene glycol, 1,6-hexane Examples include diol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, inositol, and cellulose. These polyhydric alcohols can be used singly or in combination in any quantity ratio. The polyhydric alcohol is preferably added in an amount of 0.5 to 1.5, more preferably 0.9 to 1.2 as an OH equivalent to the remaining carboxylic acid. The amount of polyhydric alcohol greatly affects the weight average molecular weight, viscosity, solubility in solvents / vegetable oils, and emulsification suitability of the resulting resin. When the amount of polyhydric alcohol is less than the above, the reaction rate is high. There is a possibility that the reaction will take a long time and the reaction may take a long time, and if it is large, the required performance may not be obtained.
上記多価アルコールによるエステル化反応の温度としては、１８０〜２８０℃、好ましくは２２０〜２８０℃、より好ましくは２４０〜２７０℃であるのがよく、酸価が１５〜３０位になるまで反応させる。さらに必要に応じて、０〜７５ｋＰａの減圧にて反応させることも可能である。 The temperature of the esterification reaction with the polyhydric alcohol is 180 to 280 ° C., preferably 220 to 280 ° C., more preferably 240 to 270 ° C., and the reaction is continued until the acid value reaches 15 to 30 positions. . Furthermore, it is also possible to make it react by the reduced pressure of 0-75 kPa as needed.
上記エステル化反応では、触媒を用いることも可能であり、触媒としては、酸性触媒としてｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸、メタンスルホン酸、エタンスルホン酸等のスルホン酸類、硫酸、塩酸等の鉱酸、トリフルオロメチル硫酸、トリフルオロメチル酢酸、ルイス酸等が、さらにテトラブチルジルコネート、テトライソプロピルチタネート等の金属錯体、酸化マグネシウム、酸化カルシウム、酸化亜鉛等のアルカリ、アルカリ土類金属の酸化物、金属塩触媒等が例示される。これらの触媒は全樹脂中０．０１〜１重量％で２００℃以上の温度で反応させる。しかし、このような条件では反応物が容易に着色するため、還元剤である次亜リン酸、トリフェニルホスファイト、トリフェニルホスフェート等を併用して着色を防止することもできる
フェノール成分としては、フェノール、ｐ−クレゾール、ｐ−ターシャリーブチルフェノール、ｐ−アミルフェノール、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などのフェノール性水酸基を持つ芳香族化合物が挙げられる。
In the esterification reaction, a catalyst can be used. As the catalyst, sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid, sulfuric acid, hydrochloric acid, and the like can be used as acidic catalysts. Mineral acid, trifluoromethyl sulfate, trifluoromethyl acetic acid, Lewis acid, etc., metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, oxidation of alkali and alkaline earth metals such as magnesium oxide, calcium oxide and zinc oxide Products, metal salt catalysts and the like. These catalysts are reacted at a temperature of 200 ° C. or more at 0.01 to 1% by weight in the total resin. However, since the reaction product is easily colored under such conditions, it is possible to prevent coloring by using hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. which are reducing agents. Examples thereof include aromatic compounds having a phenolic hydroxyl group such as phenol, p-cresol, p-tertiary butylphenol, p-amylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol, bisphenol A and the like.
Ｃ４以下のアルキル基を持つフェノール類では、樹脂の軟化点が高くなり、溶解性が著しく劣る。またＣ９以上のアルキル基を持つフェノール類では、樹脂の溶解性が良くなりすぎてセット性、ブロッキング性の劣化を引き起こす。 In phenols having an alkyl group of C4 or lower, the softening point of the resin is increased and the solubility is remarkably inferior. In addition, phenols having an alkyl group of C9 or higher cause the resin solubility to be too good, resulting in deterioration of setting properties and blocking properties.
ホルムアルデヒド成分としては、ホルマリン、パラホルムアルデヒドなどを使用することができる。フェノール成分１モルに対してアルデヒド成分０．５〜３．０モルを常法により付加・縮合反応させる。 As the formaldehyde component, formalin, paraformaldehyde and the like can be used. Addition-condensation reaction of 0.5 to 3.0 moles of aldehyde component is performed by a conventional method with respect to 1 mole of phenol component.
前記フェノール‐ホルムアルデヒド初期縮合物は、レゾール型フェノール樹脂であり、フェノール成分とホルムアルデヒド成分に、これらの合計数量１００重量部に対して５〜１００重量部、好ましくは１０〜５０重量部のトルエンまたはキシレンなどの揮発性有機溶剤を添加してアルカリ触媒中で縮合反応させて得ることができる。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等が挙げられる。 The phenol-formaldehyde initial condensate is a resol type phenol resin, and the phenol component and the formaldehyde component are 5 to 100 parts by weight, preferably 10 to 50 parts by weight of toluene or xylene with respect to 100 parts by weight of the total quantity. It can be obtained by adding a volatile organic solvent such as and condensing reaction in an alkali catalyst. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide and the like.
さらに、第三成分として、α，β‐エチレン性不飽和二塩基酸で変性したロジン変性フェノール樹脂を使用することも可能である。α，β‐エチレン性不飽和二塩基酸は無水物であってもよく、フマル酸、マレイン酸、無水マレイン酸、コハク酸、無水コハク酸、アジピン酸、セバシン酸、アゼライン酸、イタコン酸、無水イタコン酸、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、ピロメリット酸、ダイマー酸、トリマー酸などが挙げられる。特に好ましくはマレイン酸、またはその無水物が例示される。これらの二塩基酸は、予めａ）ロジンと反応させたもの、ｂ）ロジンエステルと反応させたものｃ）その他の合成反応過程で組み込んだものとして変性することができる。 Furthermore, it is also possible to use a rosin-modified phenolic resin modified with an α, β-ethylenically unsaturated dibasic acid as the third component. The α, β-ethylenically unsaturated dibasic acid may be an anhydride, fumaric acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipic acid, sebacic acid, azelaic acid, itaconic acid, anhydrous Itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic acid, dimer acid, trimer acid and the like can be mentioned. Particularly preferred is maleic acid or its anhydride. These dibasic acids can be modified as previously a) reacted with rosin, b) reacted with rosin ester, c) incorporated in other synthetic reaction processes.
樹脂酸とα，β−エチレン性不飽和二塩基酸またはその無水物との反応はディールスアルダーまたは重合反応であり、公知の方法で反応させることができる。例えば、ディールスアルダー反応温度は１２０〜３００℃、好ましくは１８０〜２６０℃、反応時間は１〜４時間である。 The reaction between the resin acid and the α, β-ethylenically unsaturated dibasic acid or its anhydride is a Diels Alder or polymerization reaction, and can be performed by a known method. For example, the Diels-Alder reaction temperature is 120 to 300 ° C, preferably 180 to 260 ° C, and the reaction time is 1 to 4 hours.
α，β−エチレン性不飽和二塩基酸はロジンに対し０．１〜１０重量％、好ましくは０．１〜５重量％添加する。α，β−エチレン性不飽和二塩基酸の添加量は、得られる樹脂の粘度、溶剤／植物油類への溶解性、乳化適性に大きく影響を与え、対ロジンで０．１重量％未満だと、十分な樹脂粘度とインキ化した際の乳化安定性が得られず、１０重量％以上だと溶解性が著しく劣ったり、極性基が多くなることで乳化率が極端に上がり、過乳化によるトラブルを招く。 The α, β-ethylenically unsaturated dibasic acid is added in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on rosin. The amount of α, β-ethylenically unsaturated dibasic acid added greatly affects the viscosity of the resulting resin, solubility in solvents / vegetable oils, and emulsification suitability, and is less than 0.1% by weight based on rosin. , Sufficient resin viscosity and emulsification stability when converted to ink cannot be obtained, and if it is 10% by weight or more, the solubility is remarkably inferior, the emulsification rate is extremely increased due to the increase in polar groups, and trouble due to over-emulsification Invite.
本発明のバインダー樹脂として使用するロジン変性フェノール樹脂は特に限定されず、従来公知のロジン変性フェノール樹脂の製造方法の利用が可能である。具体的には、フェノール‐ホルムアルデヒド付加縮合物は、反応釜に上記フェノール類とアルデヒド類を所定の割合で仕込みさらにトルエン、キシレン等の溶剤をフェノール樹脂の固形分が４０〜７０重量％となるよう添加し、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、３級アミン類等の公知のアルカリ触媒を用い８０〜１２０℃で３〜８時間反応を続けた後、冷却して水を分離、除去することにより得られる。 The rosin-modified phenol resin used as the binder resin of the present invention is not particularly limited, and a conventionally known method for producing a rosin-modified phenol resin can be used. Specifically, in the phenol-formaldehyde addition condensate, the above phenols and aldehydes are charged into a reaction kettle at a predetermined ratio, and a solvent such as toluene and xylene is added so that the solid content of the phenol resin becomes 40 to 70% by weight. Add, continue reaction at 80-120 ° C for 3-8 hours using a known alkali catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, tertiary amines, etc., then cool to separate and remove water Can be obtained.
本発明では、必要に応じて上記ロジン変性フェノール樹脂にロジン変性マレイン酸樹脂、アルキド樹脂、ポリエステル樹脂および石油樹脂等を加えてもよい。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る。 In the present invention, rosin-modified maleic acid resin, alkyd resin, polyester resin, petroleum resin and the like may be added to the rosin-modified phenolic resin as necessary. They can be used alone or in combination of two or more.
本発明で使用するバインダー樹脂は、酸価が５〜３０（ｍｇＫＯＨ／ｇ）、好ましくは５〜２５（ｍｇＫＯＨ／ｇ）、より好ましくは５〜２０（ｍｇＫＯＨ／ｇ）であることが望ましい。バインダー樹脂の酸化が５（ｍｇＫＯＨ／ｇ）未満であると樹脂の極性が低く、ゲルワニス作成時にアルミキレート等のゲル化剤と反応しないことから、インキの弾性が損なわれ流動過多、網点形状の悪化等印刷品質に影響を与える。また湿し水との乳化適性が劣り、印刷適性に影響を及ぼす。バインダー樹脂の酸化が３０（ｍｇＫＯＨ／ｇ）より大きいと、石油系溶剤、植物油との相溶性に劣り、インキの流動性や経時安定性が悪くなることと、極性が高くなるために過乳化のトラブルを引き起こす原因となる。 The binder resin used in the present invention has an acid value of 5 to 30 (mgKOH / g), preferably 5 to 25 (mgKOH / g), more preferably 5 to 20 (mgKOH / g). If the oxidation of the binder resin is less than 5 (mgKOH / g), the polarity of the resin is low, and it does not react with a gelling agent such as aluminum chelate at the time of gel varnish preparation. Affects print quality such as deterioration. Moreover, the emulsification suitability with dampening water is inferior, and the printability is affected. If the oxidation of the binder resin is greater than 30 (mgKOH / g), the compatibility with petroleum-based solvents and vegetable oils will be poor, the fluidity and stability over time of the ink will be poor, and the polarity will be high. It causes trouble.
また本発明で使用するバインダー樹脂は、環球法による軟化点が１２０〜３００℃、好ましくは１４０〜２７０℃、より好ましくは１５０〜２４０℃であることが望ましい。バインダー樹脂の軟化点が１２０℃未満であると印刷物を積み重ねた場合、ブロッキングを起こし易く、実用的でない。軟化点が３００℃より大きいとインキの流動性が損なわれ印刷適性、印刷物の光沢が著しく劣る。 The binder resin used in the present invention desirably has a softening point of 120 to 300 ° C., preferably 140 to 270 ° C., more preferably 150 to 240 ° C. by the ring and ball method. When the printed matter is stacked with the softening point of the binder resin being less than 120 ° C., blocking tends to occur, which is not practical. When the softening point is higher than 300 ° C., the fluidity of the ink is impaired, and the printability and the gloss of the printed matter are remarkably deteriorated.
さらに本発明で使用するバインダー樹脂は、重量平均分子量が１００００〜１０００００、好ましくは１００００〜８００００、より好ましくは１００００〜５００００であることが望ましい。分子量１００００以下ではインキに必要な粘弾性が得られず、１０００００以上ではインキとしての流動性が不十分となる。 Furthermore, the binder resin used in the present invention has a weight average molecular weight of 10,000 to 100,000, preferably 10,000 to 80,000, more preferably 10,000 to 50,000. When the molecular weight is 10,000 or less, the viscoelasticity necessary for the ink cannot be obtained, and when it is 100,000 or more, the fluidity as the ink becomes insufficient.
本発明における植物油類とは、植物油および／または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、再生植物油も使用可能である。植物油類の含有量は印刷インキ組成物の全量に対して１〜６０重量％配合される
本発明に関する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例示できるとともにそれらの熱重合油および酸素吹き込み重合油なども使用できる。また、本発明ではこれら植物油を単独で用いても良いし、２種以上組み合わせて用いることもできる。
The vegetable oils in the present invention are vegetable oils and / or compounds derived from vegetable oils, and in 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 Fatty acid monoesters obtained by ester reaction of saturated or unsaturated alcohols from triglycerides of the above, or fatty acid monoesters obtained by direct ester reaction of fatty acids of vegetable oils and monoalcohols, and ethers, and regenerated vegetable oils can also be used. The content of vegetable oils is 1 to 60% by weight based on the total amount of the printing ink composition. Typical vegetable oils relating to the present invention are: Asa seed oil, flaxseed oil, eno oil, Eutiska 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, daiko oil, camellia oil, corn oil, rapeseed oil , Niger oil, nutka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil and the like, and their thermopolymerized oil and oxygen Blow polymerization oil can also be used. Moreover, in this invention, these vegetable oils may be used independently and can also be used in combination of 2 or more type.
さらに、好適な植物油類を挙げるとすれば、そのヨウ素価が、少なくとも１００以上である植物油類が好ましく、さらにヨウ素価１２０以上の植物油類が、より好ましい。ヨウ素価を１２０以上とすることで、インキ皮膜の酸化重合による乾燥性を高めることができる。但し、ヨウ素価が１００未満の植物油類であっても、インキ中に使用する金属ドライヤーと酸化防止剤の配合比率の調整によりインキ化した際の乾燥性は調整することができる。 Furthermore, if a suitable vegetable oil is mentioned, the vegetable oil whose iodine value is at least 100 or more is preferable, and the vegetable oil whose iodine value is 120 or more is more preferable. By setting the iodine value to 120 or more, it is possible to improve the drying property by oxidative polymerization of the ink film. However, even if the vegetable oil has an iodine value of less than 100, the drying property when the ink is made can be adjusted by adjusting the blending ratio of the metal dryer and the antioxidant used in the ink.
また、本発明に用いられる石油系溶剤は、芳香族炭化水素の含有量が１重量％以下の原油由来の溶剤（石油系溶剤）であり、沸点が２６０〜３５０℃、好ましくは２８０℃〜３４０℃の範囲にあるものがよい。石油系溶剤の沸点が２６０℃未満の場合には、印刷機上でのインキの溶剤蒸発が多くなり、インキの流動性の劣化により、インキがローラー、ブランケット、版等への転移性が悪くなり好ましくない。また、併用する石油系溶剤の沸点が３５０℃を越える場合には、インキの乾燥性が劣るため好ましくない。さらに、石油系溶剤は、アニリン点７５℃〜９５℃が、適当である。アニリン点が７５℃未満の場合には、樹脂を溶解させる能力が高すぎる為インキ粘度が低くなりすぎ、地汚れ耐性が充分でなくなる。またアニリン点が９５℃を超える場合には、樹脂を溶解させる能力が低すぎる為、インキ粘度が高くなりすぎ、インキ流動性も乏しくなり、ローラー、版、ブランケットへのインキの堆積が起こりやすくなる為、好ましく無い。 The petroleum solvent used in the present invention is a crude oil-derived solvent (petroleum solvent) having an aromatic hydrocarbon content of 1% by weight or less, and has a boiling point of 260 to 350 ° C, preferably 280 to 340 ° C. The thing in the range of ° C is good. When the boiling point of petroleum-based solvents is less than 260 ° C, the solvent evaporation of the ink on the printing machine increases, and the transferability of the ink to rollers, blankets, plates, etc. deteriorates due to the deterioration of the fluidity of the ink. It is not preferable. Further, when the boiling point of the petroleum solvent used in combination exceeds 350 ° C., the drying property of the ink is inferior. Further, an aniline point of 75 ° C to 95 ° C is suitable for the petroleum solvent. When the aniline point is less than 75 ° C., the ability to dissolve the resin is too high, the ink viscosity becomes too low, and the stain resistance is not sufficient. Also, if the aniline point exceeds 95 ° C, the ability to dissolve the resin is too low, the ink viscosity becomes too high, the ink fluidity is poor, and ink tends to accumulate on the rollers, plates, and blankets. Therefore, it is not preferable.
本発明に用いられる石油系溶剤は必要に応じて、インキ全量の０〜２５重量％、好ましくは０〜２０重量％、さらに好ましくは０〜１５重量％含有するのが望ましい。但し、環境に配慮したＶＯＣフリーインキの場合には石油系溶剤は使用することができない。 The petroleum solvent used in the present invention is desirably contained in an amount of 0 to 25% by weight, preferably 0 to 20% by weight, more preferably 0 to 15% by weight, based on the total amount of the ink, if necessary. However, petroleum-based solvents cannot be used in the case of environment-friendly VOC-free inks.
一般的に、ＶＣＯフリー以外の印刷インキは、インキ中の不飽和結合を有する植物油類の酸化重合と揮発性の石油系溶剤の浸透により乾燥を行っている事例が多く、印刷時の作業性、印刷後の加工時における作業性等を考慮すると、印刷物上でのセット性、インキの乾燥性についてある程度の速さが必要となる。揮発性の石油系溶剤を一切含まないＶＯＣフリーのインキでは、必然的に溶剤分が全て植物油類になり、石油系溶剤より粘度の高い植物油では紙への毛細管現象による浸透度が遅くなるためインキのセット性が劣るという欠点があった。このような場合、上記記載の植物油に加えて、植物油由来の脂肪酸モノエステルをインキの全重量に対して５〜２０重量％含有することが好ましい。５重量％未満であると、十分なセット性が得られず、２０重量％を超えると、インキが低粘度化することにより印刷適性が劣化する。 In general, printing inks other than VCO-free are often dried by oxidative polymerization of vegetable oils having unsaturated bonds in the ink and penetration of volatile petroleum solvents, workability during printing, Considering workability at the time of processing after printing, a certain degree of speed is required for setability on the printed matter and ink drying property. VOC-free inks that do not contain any volatile petroleum solvents will inevitably contain vegetable oils, and vegetable oils with higher viscosity than petroleum solvents will have a slower penetration due to capillary action on paper. There was a disadvantage that the setability of was inferior. In such a case, in addition to the vegetable oil described above, it is preferable to contain a fatty acid monoester derived from vegetable oil in an amount of 5 to 20% by weight based on the total weight of the ink. If the amount is less than 5% by weight, sufficient setting properties cannot be obtained, and if it exceeds 20% by weight, the ink has a low viscosity and printability is deteriorated.
脂肪酸モノエステルと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−またはｉｓｏ−プロパノール、ｎ，ｓｅｃまたはｔｅｔ−ブタノール、へプチノール、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 the monoalcohol. Typical examples of monoalcohol include methanol, ethanol, n- or iso-propanol, n, sec or tet-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.
本発明に使用される再生植物油は、以上挙げた植物油等で再生処理可能であるものであれば適用可能である。本発明において、再生される植物油（再生植物油）は、飲食物の製造などに用いた植物油として、飲食店や学校給食、惣菜屋などで天ぷらなどの製造に使用した植物油を回収したものが挙げられるが、これらに限定されるものではなく、使用後の植物油で再生可能なものであれば適用可能である。 The regenerated vegetable oil used in the present invention is applicable as long as it can be regenerated with the above-mentioned vegetable oils. In the present invention, the regenerated vegetable oil (regenerated vegetable oil) includes, for example, those recovered from the vegetable oil used for the production of tempura at restaurants, school lunches, vegetable shops, etc. However, it is not limited to these, and it is applicable if it can be regenerated with the vegetable oil after use.
また、本発明における植物油の再生処理の方法としては、ろ過、静置による沈澱、活性白土による脱色といった方法が挙げられるが、特にこれらに限定されるものではなく、適用可能である。 In addition, examples of the method for regenerating vegetable oil according to the present invention include methods such as filtration, precipitation by standing, and decolorization by activated clay, but the method is not particularly limited and is applicable.
さらに、本発明の酸化重合型オフセットインキ組成物には、必要に応じてゲル化剤、顔料分散剤、金属ドライヤー、乾燥抑制剤、酸化防止剤、耐摩擦向上剤、裏移り防止剤、非イオン系界面活性剤、多価アルコールなどの添加剤を適宜使用することができる。
本発明において使用される顔料としては、一般的な無機顔料および有機顔料を示すことができる。無機顔料としては黄鉛、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、炭酸カルシウム、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、オフセット印刷インキの全量に対して５〜３０重量％である。
Furthermore, the oxidative polymerization type offset ink composition of the present invention includes a gelling agent, a pigment dispersant, a metal dryer, a drying inhibitor, an antioxidant, a friction improver, an anti-set-off agent, a non-ion as necessary. Additives such as system surfactants and polyhydric alcohols can be used as appropriate.
Examples of the pigment used in the present invention include general inorganic pigments and organic pigments. Examples of inorganic pigments include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, dial, alumina white, calcium carbonate, ultramarine, 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 offset printing ink.
また、本発明の酸化重合型オフセット印刷インキ組成物は、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、帯電防止剤、界面活性剤、消泡剤、等を添加してもよい。 In addition, the oxidation polymerization type offset printing ink composition of the present invention can use various additives for the purpose of anti-friction, anti-blocking, slip and scratch prevention as other additives. An agent, an antistatic agent, a surfactant, an antifoaming agent, and the like may be added.
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。 Examples of the substrate used in the present invention include general printing paper such as coated paper and non-coated paper.
本発明において、重量平均分子量は、東ソー(株)製ゲルパーミエイションクロマトグラフィ（ＨＬＣ−８０２０。以下ＧＰＣと称す。）で測定した。検量線は標準ポリスチレンサンプルにより作成した。溶離液はテトラヒドロフランを、カラムにはＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｍ（東ソー(株)製）３本を用いた。測定は流速０．６ｍｌ／分、注入量１０μｌ、カラム温度４０℃で行った。 In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8020, hereinafter referred to as GPC) manufactured by Tosoh Corporation. A calibration curve was prepared with a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.
環球法による軟化点の測定は規格試験法において広く採用されている方法であり、ＪＩＳ Ｋ ２０４６があげられる。具体的には試料を充てんした黄銅製環を水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ものである。 The measurement of the softening point by the ring-and-ball method is a method widely used in the standard test method, and JIS K 2046 can be mentioned. Specifically, a brass ring filled with a sample is held horizontally in a water bath, a steel ball of a constant weight is placed on the center of the sample, the bath temperature is increased at a constant speed, the sample gradually softens, and the steel ball is The softening point is determined by the reading of the thermometer when it descends and finally reaches the bottom plate at a thickness of 25 mm.
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、特に断らない限り、「部」は、「重量部」を表し、「％」は「重量％」を表す。
（ロジン変性フェノール樹脂製造例１）
撹拌機、冷却器、温度計をつけた４つ口フラスコにＰ−オクチルフェノール１０００部、３５％ホルマリン８５０部、９３％水酸化ナトリウム６０部、トルエン１０００部を加えて、９０℃で６時間反応させた。その後６Ｎ塩酸１２５部、水道水１０００部の塩酸溶液を添加し、撹拌、静置し、上層部を取り出し、不揮発分４９％のレゾールタイプフェノール樹脂のトルエン溶液２０００部を得て、これをレゾール液Ｘとした。
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” unless otherwise specified.
(Rosin modified phenolic resin production example 1)
P-octylphenol 1000 parts, 35% formalin 850 parts, 93% sodium hydroxide 60 parts and toluene 1000 parts were added to a four-necked flask equipped with a stirrer, cooler and thermometer, and reacted at 90 ° C. for 6 hours. It was. Thereafter, 125 parts of 6N hydrochloric acid and 1000 parts of tap water were added, stirred and allowed to stand, and the upper layer part was taken out to obtain 2000 parts of a toluene solution of a resol type phenol resin having a nonvolatile content of 49%. X.
次いで、撹拌機、水分分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１０００部を仕込み、窒素ガスを吹き込みながら２００℃で溶解し、上記で製造したレゾール液Ｘを１８００部添加し、トルエンを除去しながら２３０℃で４時間反応させた後、グリセリン１１０部を仕込み、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のロジン変性フェノール樹脂ＡおよびＢを得た。 Next, 1000 parts of gum rosin was charged into a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, dissolved at 200 ° C. while blowing nitrogen gas, and 1800 parts of the resole liquid X produced above was dissolved. After adding and reacting at 230 ° C. for 4 hours while removing toluene, 110 parts of glycerin was added and reacted at 250 ° C. for 12 hours. By sequentially taking out in the course of the reaction, rosin-modified phenol resins A and B shown in Table 1 were obtained.
（ロジン変性フェノール樹脂製造例２）
撹拌機、冷却器、温度計をつけた４つ口フラスコにｐ−ターシャリーブチルフェノール１０００部、３５％ホルマリン８５０部、９３％水酸化ナトリウム６０部、キシレン１０００部を加えて、９５℃で４時間反応させる。その後６Ｎ塩酸１２５部、水道水１０００部の塩酸溶液を添加し、撹拌、静置し、上層部を取り出し、不揮発分５２％のレゾールタイプフェノール樹脂のキシレン溶液２０００部を得て、これをレゾール液Ｙとした。
(Rosin modified phenolic resin production example 2)
To a four-necked flask equipped with a stirrer, a cooler, and a thermometer, add 1000 parts of p-tertiary butylphenol, 850 parts of 35% formalin, 60 parts of 93% sodium hydroxide, and 1000 parts of xylene, and at 95 ° C. for 4 hours. React. Then, 125 parts of 6N hydrochloric acid and 1000 parts of tap water were added, stirred and allowed to stand, and the upper layer was taken out to obtain 2000 parts of a xylene solution of a resol type phenol resin having a nonvolatile content of 52%. Y.
次いで、撹拌機、水分分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１０００部を仕込み、窒素ガスを吹き込みながら２００℃で溶解し、レゾール液Ｙを１４００部を添加し、キシレンを除去しながら２３０℃で４時間反応させた後、ペンタエリスリトール１２０部を仕込み、２４０℃で１６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のロジン変性フェノール樹脂ＣおよびＤを得た。 Next, in a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 1000 parts of gum rosin was charged and dissolved at 200 ° C. while blowing nitrogen gas, and 1400 parts of resole liquid Y was added. After reacting at 230 ° C. for 4 hours while removing xylene, 120 parts of pentaerythritol was added and reacted at 240 ° C. for 16 hours. By sequentially taking out in the course of the reaction, rosin-modified phenol resins C and D shown in Table 1 were obtained.
（ワニス製造例１）
撹拌機、冷却器、温度計をつけた４つ口フラスコにロジン変性フェノール樹脂Ａ（酸価２５、軟化点１４０、重量平均分子量１０５００）４３部、大豆油３６部、ＡＦソルベント５号（新日本石油（株）製、アニリン点８８℃、沸点範囲２７９〜３０７℃）２０部を仕込み、１９０℃に昇温、同温で３０分間攪拌した後、放冷し、ゲル化剤としてエチルアセトアセテートアルミニウムジイソプロポキシド１部（川研ファインケミカル（株）製ＡＬＣＨ、以下ＡＬＣＨと称す）を仕込み、１９０℃で６０分間攪拌して酸化重合型オフセット印刷インキ用ゲルワニス１（以下ワニス１と称す）を得た。
(Varnish production example 1)
A four-necked flask equipped with a stirrer, a cooler and a thermometer, 43 parts of rosin-modified phenolic resin A (acid value 25, softening point 140, weight average molecular weight 10500), 36 parts of soybean oil, AF Solvent No. 5 (New Japan) Petroleum Co., Ltd., aniline point 88 ° C, boiling range 279-307 ° C) 20 parts, charged to 190 ° C, stirred at the same temperature for 30 minutes, allowed to cool, and ethyl acetoacetate aluminum as a gelling agent Charge 1 part of diisopropoxide (ALCH manufactured by Kawaken Fine Chemical Co., Ltd., hereinafter referred to as ALCH) and stir at 190 ° C. for 60 minutes to obtain gel varnish 1 (hereinafter referred to as varnish 1) for oxidation polymerization type offset printing ink. It was.
さらに、表２の組成に基づいて、上記と同等のゲルワニス製造方法により、ゲルワニス２〜４（以下ワニス２〜４と称す）を得た。 Furthermore, based on the composition of Table 2, the gel varnishes 2-4 (henceforth varnishes 2-4) were obtained with the gel varnish manufacturing method equivalent to the above.
（ワニス製造例２）
撹拌機、冷却器、温度計をつけた４つ口フラスコにロジン変性フェノール樹脂Ａ４６部、再生植物油３８部、大豆油脂肪酸ブチルエステル１５部を仕込み、１９０℃に昇温、同温で３０分間攪拌した後、放冷し、ＡＬＣＨ１部（川研ファインケミカル（株）製ＡＬＣＨ、以下ＡＬＣＨと称す）を仕込み、１９０℃で６０分間攪拌して酸化重合型オフセット印刷インキ用ゲルワニス５（以下ワニス５と称す）を得た。
(Varnish production example 2)
A four-necked flask equipped with a stirrer, cooler, and thermometer was charged with 46 parts of rosin-modified phenolic resin A, 38 parts of regenerated vegetable oil, and 15 parts of soybean oil fatty acid butyl ester, heated to 190 ° C., and stirred at the same temperature for 30 minutes. After cooling, 1 part of ALCH (ALCH manufactured by Kawaken Fine Chemicals Co., Ltd., hereinafter referred to as ALCH) was added, and stirred for 60 minutes at 190 ° C., and gel varnish 5 for oxidation polymerization type offset printing ink (hereinafter referred to as varnish 5). )
さらに、表３の組成に基づいて、上記と同等のゲルワニス製造方法により、ゲルワニス５〜８（以下ワニス５〜８と称す）を得た。 Furthermore, based on the composition of Table 3, gel varnishes 5-8 (hereinafter referred to as varnishes 5-8) were obtained by the same gel varnish production method as above.
（インキの製造例）
ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ７３３０（東洋インキ（株）製）を１７部、市販の湿式法シリカ１（平均二次粒子径８．５μｍ、ＢＥＴ比表面積２１０ｍ2／ｇ）を１部、ワニス１を７０部、大豆油４．５部、ワックスコンパウンド（東洋インキ（株）製 ニュー耐摩擦コンパウンド）５部、金属ドライヤー（東洋インキ（株）製ＭＫドライヤー）１．５部、乾燥抑制剤（東洋インキ（株）製 乾燥抑制剤ＣＰ）1部を添加仕込み、常法に従い
三本ロールを用いて酸化重合型平オフセットインキ組成物の実施例１を得た。
さらに、表４の組成に基づいて、常法に従い三本ロールを用いて酸化重合型平オフセットインキ組成物の実施例２〜８を得た。なお本明細書において実施例７および８は、参考例である。
(Ink production example)
17 parts of LIONOL BLUE FG7330 (manufactured by Toyo Ink Co., Ltd.), 1 part of commercially available wet method silica 1 (average secondary particle size 8.5 μm, BET specific surface area 210 m 2 / g), 70 parts of varnish 1 and large 4.5 parts soybean oil, 5 parts wax compound (manufactured by Toyo Ink Co., Ltd.), 1.5 parts metal dryer (MK dryer made by Toyo Ink Co., Ltd.), drying inhibitor (manufactured by Toyo Ink Co., Ltd.) Example 1 of an oxidation polymerization type flat offset ink composition was obtained by adding 1 part of a drying inhibitor CP) and using three rolls according to a conventional method.
Furthermore, based on the composition of Table 4, Examples 2 to 8 of oxidation polymerization type flat offset ink compositions were obtained using three rolls according to a conventional method. In this specification, Examples 7 and 8 are reference examples.
同様に、表５の組成に基づいて、常法に従い三本ロールを用いて酸化重合型平オフセットインキ組成物の実施例９〜１６を、表６の組成に基づいて比較例１〜８を得た。 Similarly, based on the composition of Table 5, Examples 9 to 16 of the oxidation polymerization type flat offset ink composition using three rolls according to a conventional method are obtained, and Comparative Examples 1 to 8 are obtained based on the composition of Table 6. It was.
以下作製した酸化重合型平オフセットインキ組成物の評価を行った。 The produced oxidation polymerization type flat offset ink composition was evaluated below.
＜性能評価試験（１） インキ流動性＞
生インキを２．１ｃｃの半球状の容器にセットし、６０°に傾けた傾斜版の上にインキを垂らし、１０分間で流れた長さを測定し以下の評価基準に基づいて評価を行った。値が高いほどインキの流動性が良好であることを示す。
（評価基準）
○：３０ｍｍ以上
△：５ｍｍ以上、３０ｍｍ未満
×：５ｍｍ未満
実用レベルは、△以上である。
<Performance evaluation test (1) Ink fluidity>
The raw ink was set in a 2.1 cc hemispherical container, the ink was dropped on an inclined plate inclined at 60 °, the length that flowed in 10 minutes was measured, and the evaluation was performed based on the following evaluation criteria. . Higher values indicate better ink fluidity.
(Evaluation criteria)
○: 30 mm or more Δ: 5 mm or more and less than 30 mm ×: less than 5 mm The practical level is Δ or more.
＜性能評価試験（２） 乳化率＞
インキ１０ｇをディスパーで攪拌しながら蒸留水１０ｇを徐々に添加し、１２００ｒｐｍ、３分間強制乳化させる。その後、銅板上でナイフベラを用いて余分な水をかき取り、カールフィッシャー水分系にて乳化率を測定し、以下の評価基準に基づいて評価を行った。
（評価基準）
○：５％以上、１５％未満
△：１５以上、２０％未満
×：２０％以上
実用レベルは、△以上である。
<Performance evaluation test (2) Emulsification rate>
While stirring 10 g of ink with a disper, 10 g of distilled water is gradually added and forcedly emulsified at 1200 rpm for 3 minutes. Then, excess water was scraped off on the copper plate using a knife spatula, the emulsification rate was measured with a Karl Fischer moisture system, and evaluation was performed based on the following evaluation criteria.
(Evaluation criteria)
○: 5% or more and less than 15% Δ: 15 or more and less than 20% ×: 20% or more The practical level is Δ or more.
＜性能評価試験（３） 乳化流動性＞
インキ１８ｇをディスパーで攪拌しながら蒸留水２ｇを徐々に添加し、１２００ｒｐｍ、３分間強制乳化させる。乳化インキを２．１ｃｃの半球状の容器にセットし、６０°に傾けた傾斜版の上にインキを垂らし、１０分間で流れた長さを測定し以下の評価基準に基づいて評価を行った。値が高いほど乳化したインキの流動性が良好であることを示す。
（評価基準）
○：３０ｍｍ以上
△：５ｍｍ以上、３０ｍｍ未満
×：５ｍｍ未満
実用レベルは、△以上である。
<Performance Evaluation Test (3) Emulsification Fluidity>
While stirring 18 g of ink with a disper, 2 g of distilled water is gradually added and forcedly emulsified at 1200 rpm for 3 minutes. The emulsified ink was set in a 2.1 cc hemispherical container, the ink was dropped on an inclined plate inclined at 60 °, and the length that flowed in 10 minutes was measured and evaluated based on the following evaluation criteria. . The higher the value, the better the fluidity of the emulsified ink.
(Evaluation criteria)
○: 30 mm or more Δ: 5 mm or more and less than 30 mm ×: less than 5 mm The practical level is Δ or more.
＜性能評価試験（４） インキ余り＞
小森コーポレーション株式会社製枚葉印刷機リスロン２６にて、一般的な絵柄、濃度にて、地汚れが解消する水ダイヤル値から２ポイント上げて印刷し、濃度が安定したところから水ダイヤル値をさらに２０ポイント上昇させて印刷機を停止させ、インキローラー上のインキ余りを目視にて観察し以下の評価基準に基づいて評価を行った。
（評価基準）
○：インキ余りが認められず、安定した印刷品質を確保できる
△：インキ余りが認められる
×：インキ余りが顕著に多く、印刷品質に影響を与える
実用レベルは、△以上である。
<Performance evaluation test (4) Ink residue>
Komori Corporation sheet-fed printing press Lislon 26 prints with a general pattern and density, increasing the water dial value by 2 points from the water dial value that eliminates background stains. The printing press was stopped by raising the point by 20 points, and the ink remaining on the ink roller was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: Ink residue is not recognized, and stable printing quality can be secured. Δ: Ink residue is recognized. X: Ink residue is remarkably large, and the printing quality is affected.
＜性能評価試験（５） 濃度安定性＞
小森コーポレーション株式会社製枚葉印刷機リスロン２６にて、一般的な絵柄、濃度にて、地汚れが解消する水ダイヤル値から２ポイント上げて印刷し、濃度が安定したところから水ダイヤル値をさらに５ポイント、１０ポイント上昇させ、その時の濃度の変化から以下の評価基準に基づいて評価を実施した。
（評価基準）
○：濃度変化の平均が、水ダイヤル５ポイント上昇で±０．０５以下、１０ポイント 上昇で±０．１以下
△：濃度変化の平均が、水ダイヤル５ポイント上昇で±０．１１以下、１０ポイント 上昇で±０．２以下
×：濃度変化の平均が、水ダイヤル５ポイント上昇で±０．２１以下、１０ポイント 上昇で±０．３以下
実用レベルは、△以上である。
<Performance evaluation test (5) Concentration stability>
Komori Corporation sheet-fed printing press Lislon 26 prints with a general pattern and density, increasing the water dial value by 2 points from the water dial value that eliminates background stains. The point was raised by 5 points and 10 points, and the evaluation was carried out based on the following evaluation criteria from the change in concentration at that time.
(Evaluation criteria)
○: The concentration change average is ± 0.05 or less when the water dial increases by 5 points, 10 points is increased by ± 0.1 or less △: The average concentration change is ± 0.11 or less when the water dial increases by 5 points, 10 Point rise: ± 0.2 or less ×: The average concentration change is ± 0.21 or less when the water dial rises 5 points, 10 points rises ± 0.3 or less The practical level is Δ or more.
（印刷条件）
版：平版用ＣＴＰ版 ＨＰ−Ｆ（富士フィルムグラフィックシステムズ株式会社製）
用紙：ＯＫコート（王子製紙株式会社製）
印刷速度：１００００枚／時
湿し水：アクワユニティＣ ２．０％（東洋インキ株式会社製）
濃度：Ｘ−Ｒｉｔｅ９３８、ＳｔａｔｕｓＥ、白紙基準、偏光フィルターなしで測定
黄１．４０、紅１．５０、藍１．６０、墨１．７５（±０．０５の範囲内で調 整）
性能評価試験結果を表７に示す。
(Printing conditions)
Version: CTP plate for flat plate HP-F (Fuji Film Graphic Systems Co., Ltd.)
Paper: OK coat (Oji Paper Co., Ltd.)
Printing speed: 10,000 sheets / hour Dampening water: AQUAUNITY C 2.0% (manufactured by Toyo Ink Co., Ltd.)
Density: X-Rite 938, Status E, blank paper standard, measured without polarizing filter Yellow 1.40, Red 1.50, Indigo 1.60, Black 1.75 (adjusted within ± 0.05)
Table 7 shows the results of the performance evaluation test.
合成非晶質シリカが未添加または添加量が少ないと、乳化流動性が著しく悪くなる。逆に添加しすぎると乳化率が極端に上がり乳化後の流動性は問題ないが、生インキの流動性が悪くインキの経時安定性が悪くなる。
以上の様に本発明に関する実施例により、インキの流動性および経時安定性ならびに印刷時の乳化安定性に優れたオフセットインキを提供することを見出した。
When synthetic amorphous silica is not added or is added in a small amount, the emulsification fluidity is remarkably deteriorated. On the contrary, if it is added too much, the emulsification rate is extremely increased and there is no problem with the fluidity after emulsification, but the fluidity of the raw ink is poor and the stability with time of the ink is deteriorated.
As described above, it has been found that the examples relating to the present invention provide an offset ink having excellent fluidity and stability with time and emulsification stability during printing.
Claims (3)
インキ全重量に対して、前記合成非晶質シリカを０．１〜１０重量％含有する、酸化重合型オフセットインキ組成物の製造方法。The manufacturing method of the oxidation polymerization type offset ink composition which contains the said synthetic amorphous silica 0.1 to 10weight% with respect to the total weight of ink.
酸価５〜３０（ｍｇＫＯＨ／ｇ）、
環球法による軟化点１２０〜３００℃
および
重量平均分子量１００００〜１０００００
であることを特徴とする請求項１に記載の酸化重合型オフセットインキ組成物の製造方法。 Rosin modified phenolic resin
Acid value 5-30 (mgKOH / g),
Softening point 120-300 ° C by ring and ball method
And a weight average molecular weight of 10,000 to 100,000
The method for producing an oxidation polymerization type offset ink composition according to claim 1.
The manufacturing method of printed matter obtained by printing on a base material the oxidation polymerization type offset ink composition obtained by the manufacturing method of Claim 1 or 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012086325A JP5958031B2 (en) | 2012-04-05 | 2012-04-05 | Offset printing ink composition and printed matter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012086325A JP5958031B2 (en) | 2012-04-05 | 2012-04-05 | Offset printing ink composition and printed matter |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015166834A Division JP6056922B2 (en) | 2015-08-26 | 2015-08-26 | Offset printing ink composition and printed matter |
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