JP2007186643A - Printing ink - Google Patents
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- JP2007186643A JP2007186643A JP2006007438A JP2006007438A JP2007186643A JP 2007186643 A JP2007186643 A JP 2007186643A JP 2006007438 A JP2006007438 A JP 2006007438A JP 2006007438 A JP2006007438 A JP 2006007438A JP 2007186643 A JP2007186643 A JP 2007186643A
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- 238000007639 printing Methods 0.000 title claims abstract description 48
- 239000000049 pigment Substances 0.000 claims abstract description 53
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000010298 pulverizing process Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 66
- 238000000034 method Methods 0.000 abstract description 35
- 229920005989 resin Polymers 0.000 abstract description 30
- 239000011347 resin Substances 0.000 abstract description 30
- 239000002966 varnish Substances 0.000 abstract description 25
- 239000011164 primary particle Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 102
- 239000013078 crystal Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000003549 soybean oil Substances 0.000 description 9
- 235000012424 soybean oil Nutrition 0.000 description 9
- 238000003801 milling Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- -1 aminophenyl group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000019612 pigmentation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
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- 230000007704 transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 C*Nc1nc(*)nc(*)n1 Chemical compound C*Nc1nc(*)nc(*)n1 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 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 1
- PGEHNUUBUQTUJB-UHFFFAOYSA-N anthanthrone Chemical compound C1=CC=C2C(=O)C3=CC=C4C=CC=C5C(=O)C6=CC=C1C2=C6C3=C54 PGEHNUUBUQTUJB-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 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 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は粗製銅フタロシアニン顔料の印刷インキを製造する際に、粗製銅フタロシアニンから直接印刷インキを製造するために顔料粗製物を用いた印刷インキの製造方法に関するものである。 The present invention relates to a method for producing printing ink using a crude pigment product for producing printing ink directly from crude copper phthalocyanine when producing printing ink of crude copper phthalocyanine pigment.
通常、合成後の銅フタロシアニンは粗製銅フタロシアニンと呼ばれ、１０〜２００μｍ程度の巨大β型結晶粒子のため、そのまま印刷インキ用顔料として使用することはできない。この粗製銅フタロシアニンを印刷インキとして使用可能な大きさ（０．０２〜０．１μｍ程度）まで小さくすることを顔料化と呼ぶ。顔料化にはさまざまな方法がある。 Usually, the synthesized copper phthalocyanine is called crude copper phthalocyanine, and cannot be used as it is as a pigment for printing ink because it is a large β-type crystal particle of about 10 to 200 μm. Making this crude copper phthalocyanine small enough to be usable as a printing ink (about 0.02 to 0.1 μm) is called pigmentation. There are various methods for pigmentation.
最も一般的なのがソルベントソルトミリング法と呼ばれる方法である。この方法は粗製銅フタロシアニンに食塩などの磨砕剤とβ型への結晶転移を促進させる有機溶剤を加え磨砕する方法である。この方法によるβ型銅フタロシアニン顔料はアスペクト比（一次粒子の短径と長径の比）が１〜３で、緑味鮮明で高着色力など印刷インキに適しており、広く使用されている。しかし顔料の数倍量の磨砕剤が必要であり、この磨砕剤や有機溶剤を回収する工程に多くの時間と労力を必要とする。 The most common method is called a solvent salt milling method. This is a method in which crude copper phthalocyanine is ground by adding a grinding agent such as salt and an organic solvent that promotes crystal transition to β-form. The β-type copper phthalocyanine pigment obtained by this method has an aspect ratio (ratio of primary particle minor axis to major axis) of 1 to 3, and is widely used for printing inks such as vivid green and high coloring power. However, a grinding agent several times the amount of the pigment is required, and much time and labor are required for the process of recovering the grinding agent and the organic solvent.
これに対して粗製銅フタロシアニンを乾式で粉砕した後に有機溶剤等で処理するする方法も知られている。この場合、粉砕時に機械的な力を加えることでβ型結晶の一部がα型結晶へ転移するため、再びβ型に転移させるために、この磨砕物を有機溶剤と共に加熱処理しなければならない。この方法はソルベントソルトミリング法に比べて工程が簡略化され、コスト的に有利であるが、有機溶剤で加熱処理する際に粒子が針状に成長しアスペクト比が大きくなり色相が赤味になることや流動性やしまりに問題が生じてしまう。 On the other hand, a method of treating crude copper phthalocyanine with an organic solvent after pulverizing the crude copper phthalocyanine is also known. In this case, since a part of the β-type crystal is transferred to the α-type crystal by applying a mechanical force at the time of pulverization, the ground product must be heat-treated with an organic solvent in order to transfer to the β-type again. . Compared with the solvent salt milling method, this method has a simplified process and is advantageous in terms of cost. However, when heat-treated with an organic solvent, the particles grow into needles, the aspect ratio increases, and the hue becomes reddish. Problems will arise in terms of liquidity and tightness.
低コストの印刷インキを提供するためには、顔料の形態を経由せずに粗製銅フタロシアニンから直接インキ製造することが有効である。粗製銅フタロシアニンを印刷インキ用ワニスまたは印刷インキ用溶剤と混合した後、ビーズミルを用いてインキ化と同時に顔料化を行う方法が知られている。しかしながら、印刷インキワニス中での顔料化は摩砕効率が低いため、超微細なビーズを用いた分散ミルなどを必要とし、エネルギー効率、品質などの点で問題が多い。 In order to provide low-cost printing ink, it is effective to produce ink directly from crude copper phthalocyanine without going through the form of pigment. A method is known in which crude copper phthalocyanine is mixed with a varnish for printing ink or a solvent for printing ink and then pigmented at the same time as inking using a bead mill. However, pigmentation in a printing ink varnish has a low grinding efficiency, and thus requires a dispersion mill using ultrafine beads, which is problematic in terms of energy efficiency and quality.
特公昭５５−６６７０号公報には、粗製銅フタロシアニンを一度乾式で磨砕した後、そのままインキ化する方法が記載されている。乾式の磨砕は効率的に行われるため、非常に有効な方法である。しかしながら乾式粉砕した磨砕物は強固な凝集体であり、またα／β型結晶の混合物となってしまうため、インキ中での磨砕物の分散やβ型結晶への再転移は非常に困難である。 Japanese Examined Patent Publication No. 55-6670 describes a method in which crude copper phthalocyanine is once ground by a dry method and then converted into an ink as it is. Dry grinding is a very effective method because it is performed efficiently. However, the dry pulverized product is a strong agglomerate and becomes a mixture of α / β type crystals. Therefore, it is very difficult to disperse the pulverized product in ink and to re-transfer to β type crystals. .
この様な問題を解決するため、英国特許第１２２４６２７号公報には、粗製銅フタロシアニンを乾式で摩砕する際に１〜８倍量の樹脂を添加する方法が、また特開平２−２９４３６５号公報には粗製銅フタロシアニンを乾式で摩砕する際にロジン変性フェノールなどの樹脂を０．５〜１０重量％添加する方法が記載されている。また、特許第３１５９０４９号公報では、粗製銅フタロシアニンに対して、樹脂を１〜２００重量％、及び溶剤を該樹脂に対して０．５〜２０重量％添加し、７０〜９０℃で乾式粉砕する方法が記載されている。これらの方法は、添加した樹脂の効果により銅フタロシアニン粒子の凝集を防止する意味と添加した樹脂が後に使用する樹脂と同じものを使用できる点で非常に有効な方法と言える。 In order to solve such a problem, British Patent No. 1224627 discloses a method of adding 1 to 8 times the amount of resin when crude copper phthalocyanine is milled in a dry process, and Japanese Patent Application Laid-Open No. 2-294365. Describes a method in which a resin such as rosin-modified phenol is added in an amount of 0.5 to 10% by weight when crude copper phthalocyanine is milled dry. In Japanese Patent No. 3159049, 1 to 200% by weight of a resin and 0.5 to 20% by weight of a solvent are added to crude copper phthalocyanine and dry pulverized at 70 to 90 ° C. A method is described. These methods can be said to be very effective in terms of preventing the aggregation of the copper phthalocyanine particles due to the effect of the added resin and that the added resin can be the same as the resin used later.
しかしながら乾式粉砕した粗製銅フタロシアニンの摩砕物を溶剤処理する方法、または印刷インキ用ワニスまたは印刷インキ用溶剤中で処理することで直接印刷インキを製造する方法に於いて、樹脂と共に乾式粉砕する方法は非常に有効な手段である反面、顔料の一次粒子が針状になってしまう問題は解決せず、色相の赤味や流動性、特にインキ化したときのインキ締まりの問題は残されたままである。 However, the dry pulverized crude copper phthalocyanine grind is processed with a solvent, or directly processed with a printing ink varnish or a printing ink solvent to produce a printing ink. While this is a very effective means, it does not solve the problem that the primary particles of the pigment become needle-like, and the problems of redness and fluidity of the hue, especially ink tightness when inked, remain. .
また、ロジン変性フェノール樹脂は、室温で保存した場合でも酸化による劣化が起こることが知られている。即ち、これらの特許の方法では添加した樹脂は粉砕されることで表面積が増大することや衝撃による瞬間的な熱により、例え冷却したとしても粉砕時の樹脂の酸化を避けることはできない。樹脂は酸化されることでその溶解性や色調、その他の物性が変化してしまうため、従来の使用されてきた樹脂をそのまま適用したとしても同じインキの性能を引き出すことは不可能である。
乾式粉砕した粗製銅フタロシアニンの摩砕物を溶剤処理する方法、または印刷インキ用ワニスまたは印刷インキ用溶剤中で処理することで直接印刷インキを製造する方法に於いて、樹脂と共に乾燥粉砕する方法は非常に有効な方法である反面、顔料の一次粒子の成長が針状になってしまう問題は解決せず、色相の赤味や流動性、特にインキ化したときの顔料粒子の凝集によるインキしまりの問題は残されたままである。 There is a method of dry pulverization with a resin in a method of solvent-treating a dry crushed crude copper phthalocyanine, or a method of directly producing a printing ink by treating it in a varnish for printing ink or a solvent for printing ink. On the other hand, it does not solve the problem that the primary particle growth of the pigment becomes needle-like, but it does not solve the redness and fluidity of the hue, especially the problem of ink retention due to aggregation of the pigment particles when inked. Is left behind.
本発明は、粗製銅フタロシアニンを乾式粉砕する製造方法により製造された顔料組成物に対して、下記一般式（１）または（３）で示される顔料誘導体を添加して製造してなるオフセット用印刷インキに関する。
一般式（１）
Ｙ1 ；−ＮＨ−または−Ｏ−Ｚ；水酸基、アルコキシ基もしくは下記一般式（２）で示される基、あるいはｎ＝１の場合−ＮＨ−Ｘ−Ｑ1であってもよい。
一般式（２）
ｍ；１〜６の整数ｎ；１〜４の整数を表す。
一般式（３）：Ｑ2−（−Ｘ−Ｙ）n
式中、Ｑ2；有機色素残基Ｘ；直接結合，−ＣＯＮＨ−Ｙ2 −，−ＳＯ2 ＮＨ−Ｙ2 −または−ＣＨ2 ＮＨＣＯＣＨ2 ＮＨ−Ｙ2 −（Ｙ2；置換基を有してもよいアルキレン基またはアリーレン基）
Ｙ；下記一般式（４）または（５）で示される基
一般式（４）
Ｙ4 ; 水素原子，ハロゲン原子，−ＮＯ2 ，−ＮＨ2または−ＳＯ3 Ｈｋ；１〜４の整数ｍ；１〜６の整数ｎ；１〜４の整数を表す。
The present invention is an offset printing produced by adding a pigment derivative represented by the following general formula (1) or (3) to a pigment composition produced by a dry pulverization method of crude copper phthalocyanine. It relates to ink.
General formula (1)
Y 1 ; —NH— or —O—Z; a hydroxyl group, an alkoxy group or a group represented by the following general formula (2), or in the case of n = 1, may be —NH—XQ 1 .
General formula (2)
m; an integer n of 1-6; an integer of 1-4.
Formula (3): Q 2 - ( - X-Y) n
In the formula, Q 2 ; organic dye residue X; direct bond, —CONH—Y 2 —, —SO 2 NH—Y 2 — or —CH 2 NHCOCH 2 NH—Y 2 — (Y 2 ; having a substituent May be an alkylene group or an arylene group)
Y: group represented by the following general formula (4) or (5)
Y 4 represents a hydrogen atom, a halogen atom, —NO 2 , —NH 2 or —SO 3 Hk; an integer m of 1 to 4; an integer n of 1 to 6; an integer of 1 to 4.
本発明の方法によって従来の顔料化工程を大幅に簡略化した製法において問題であった、インキ化したときの顔料の一次粒子凝集によるインキしまりの問題は解決され、従来のペースト方により製造されたインキと同品質を得ることが可能となった。 The problem of the ink squeeze due to the primary particle aggregation of the pigment when it was made into an ink, which was a problem in the production method in which the conventional pigmentation process was greatly simplified by the method of the present invention, was solved, and was produced by the conventional paste method. It became possible to obtain the same quality as ink.
以下、本発明について詳細に説明する。
本発明の乾式粉砕は、ビーズ等の粉砕メディアを内蔵した粉砕機を使用して、実質的に液状物質を介在させないで粗製銅フタロシアニンを粉砕するものである。粉砕は、粉砕メディア同士の衝突による粉砕力や破壊力を利用して行なわれる。乾式粉砕装置としては、乾式のアトライター、ボールミル、振動ミルなどの公知の方法を用いることができる。また、必要に応じて窒素ガスなどを流すことで乾式粉砕装置内部を脱酸素雰囲気として乾式粉砕を行なってもよい。
The present invention will be described in detail below.
In the dry pulverization of the present invention, crude copper phthalocyanine is pulverized by using a pulverizer having a built-in pulverization medium such as beads without substantially interposing a liquid substance. The pulverization is performed by using a pulverization force and a destructive force caused by collision between the pulverization media. As the dry pulverizer, known methods such as a dry attritor, a ball mill, and a vibration mill can be used. Further, if necessary, dry pulverization may be performed by flowing nitrogen gas or the like to make the inside of the dry pulverization apparatus a deoxygenated atmosphere.
本発明の乾燥粉砕は加熱下で行う。乾式粉砕を行うことにより粗製銅フタロシアニンのβ型結晶の一部がα型へ結晶転移し、粉砕物はα／β混合型結晶となる。この際、乾式で粉砕する場合の温度を低温で行うと磨砕物中のα型結晶の割合が増加し、後工程で再びβ型結晶へと転移させるための負担が増加するばかりか、最終的なβ型結晶粒子のアスペクト比が大きくなってしまい好ましくない。 The dry pulverization of the present invention is performed under heating. By performing dry pulverization, a part of the β-type crystal of the crude copper phthalocyanine undergoes crystal transition to α-type, and the pulverized product becomes α / β mixed-type crystal. At this time, if the temperature when dry grinding is performed at a low temperature, the proportion of α-type crystals in the ground product increases, and not only does the burden of transferring again to β-type crystals in the subsequent process increase, but finally The aspect ratio of such β-type crystal grains is undesirably increased.
本発明では乾式粉砕時に樹脂と溶剤を存在させる。このことにより乾式粉砕を行って得られるα／β混合結晶型銅フタロシアニン中のα型結晶の割合を少なくすることができ、更に乾式粉砕のアスペクト比が小さくなる。 In the present invention, a resin and a solvent are present during dry pulverization. As a result, the proportion of α-type crystals in the α / β mixed crystal type copper phthalocyanine obtained by dry pulverization can be reduced, and the aspect ratio of dry pulverization is further reduced.
α型結晶は一般的に熱、有機溶剤の存在下でβ型へと転移することが知られている。従って、乾式乾燥時のα型結晶の比率を少なくするための手段のひとつは乾式粉砕を比較的高い温度で行うことである。しかし、あまり高い温度ではフタロシアニン顔料に悪影響は生じるため、本発明の乾式粉砕温度は６０〜１８０度で行う。 It is known that α-type crystals generally transition to β-type in the presence of heat and organic solvents. Therefore, one means for reducing the ratio of α-type crystals during dry drying is to perform dry pulverization at a relatively high temperature. However, since the phthalocyanine pigment is adversely affected at an excessively high temperature, the dry pulverization temperature of the present invention is 60 to 180 degrees.
本発明において、使用される一般式（１）のＱ1、（３）のＱ2における有機色素残基としてはフタロシアニン系色素、アゾ系色素、アントラキノン系色素、キナクリドン系色素、ジオキサジン系色素、アントラピリミジン系色素、アンサンスロン系色素、インダンスロン系色素、フラバンスロン系色素、ペリレン系色素、ペリノン系色素、チオインジコ系色素、イソインドリノン系色素、トリフェニルメタン系色素等の顔料または染料が挙げられる。 In the present invention, the organic dye residues in Q 1 of the general formula (1) and Q 2 of (3) used in the present invention are phthalocyanine dyes, azo dyes, anthraquinone dyes, quinacridone dyes, dioxazine dyes, anthra Pigment or dye such as pyrimidine dye, anthanthrone dye, indanthrone dye, flavanthrone dye, perylene dye, perinone dye, thioindico dye, isoindolinone dye, triphenylmethane dye It is done.
一般式（１）のＱ1 におけるアミノ基を有するアリール基としては、例えばアミノフェニル基、アミノナフチル基などが挙げられ、この時ベンゼン環にはアミノ基に加え、他の置換可能な場所にハロゲン基、アミノ基、ニトロ基、水酸基、カルボキシル基、スルホン基、アルコキシ基、置換または無置換のアルキル基の何れかの置換基を有してもよい。 Examples of the aryl group having an amino group in Q 1 of the general formula (1) include an aminophenyl group and an aminonaphthyl group. At this time, in addition to the amino group, the benzene ring has a halogen atom at other substitutable positions. You may have a substituent in any one of a group, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a sulfone group, an alkoxy group, and a substituted or unsubstituted alkyl group.
本発明において、粗製銅フタロシアニンの乾式粉砕時に添加する一般式（１）または（３）で示される顔料誘導体の添加量は粗製胴フタロシアニン１００重量部に対し０．５〜３０重量部が好ましく、より好ましくは３〜１０重量部である。０．５重量部より少ないと一般式（１）または（３）で示される顔料誘導体の効果が得られず、また３０重量部より多く用いても用いた分の効果は得られない。 In the present invention, the addition amount of the pigment derivative represented by the general formula (1) or (3) added during dry pulverization of the crude copper phthalocyanine is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the crude barrel phthalocyanine. Preferably it is 3-10 weight part. When the amount is less than 0.5 part by weight, the effect of the pigment derivative represented by the general formula (1) or (3) cannot be obtained, and even when the amount is more than 30 parts by weight, the effect of the used amount cannot be obtained.
本発明において、粗製銅フタロシアニンの乾式粉砕時に添加する溶剤と樹脂の添加方法としては、樹脂と有機溶剤をそれぞれ別途添加しても、或いは有機溶剤を予め樹脂中に含有させておいてもよい。 In the present invention, as a method for adding a solvent and a resin to be added during dry pulverization of crude copper phthalocyanine, a resin and an organic solvent may be added separately, or an organic solvent may be previously contained in the resin.
溶剤の種類としては、α型結晶をβ型へ転移させる能力のある有機溶剤であればよく、たとえば、トルエン、キシレン、クロロベンゼン、ニトロベンゼン等の芳香族化合物、ミネラルスピリット、ケロシン、リグロイン等の脂肪族炭化水素化合物、イソプロパノール、ブタノール、イソブタノール、エチルセロソルブ、ブチルセロソルブ、シクロヘキサノール等のアルコー化合物、酢酸エチル、酢酸ブチル、ブチルセロソルブアセテート等のエステル化合物、アセトン、メチルエチルケトン等のケトン化合物の１種または２種以上の混合物が使用できる。 The type of solvent may be an organic solvent capable of transferring α-type crystals to β-type, for example, aromatic compounds such as toluene, xylene, chlorobenzene and nitrobenzene, and aliphatic such as mineral spirits, kerosene and ligroin. One or more of hydrocarbon compounds, alcohol compounds such as isopropanol, butanol, isobutanol, ethyl cellosolve, butyl cellosolve, cyclohexanol, ester compounds such as ethyl acetate, butyl acetate and butyl cellosolve acetate, and ketone compounds such as acetone and methyl ethyl ketone Can be used.
最終製品が印刷インキの場合、印刷インキ用溶剤を使用すれば、溶剤を取り除く工程が必要がないため好ましい。印刷インキ用溶剤としては、高沸点石油系溶剤、脂肪族炭化水素溶剤、高級アルコール系溶剤など印刷インキに適した溶剤であれば芳香族を含まない溶剤であっても単独あるいは２種類以上の組み合わせで任意に使用できる。 When the final product is a printing ink, it is preferable to use a printing ink solvent because there is no need for a step of removing the solvent. Solvents for printing inks are solvents suitable for printing inks, such as high-boiling petroleum solvents, aliphatic hydrocarbon solvents, and higher alcohol solvents. Can be used arbitrarily.
溶剤と共に添加する樹脂の種類としては、ロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂、石油樹脂、アルキド樹脂など印刷インキに適用される樹脂であれば、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が、好ましくはロジン変性フェノール樹脂である。 As the kind of resin added together with the solvent, any resin that can be used for printing inks such as rosin-modified phenolic resin, rosin-modified maleic resin, petroleum resin, alkyd resin can be used alone or in combination of two or more. Is preferably a rosin-modified phenolic resin.
本発明において一般的に樹脂の添加量は粗製銅フタロシアニンに対して１〜２００重量％、溶剤の添加量は樹脂に対して０．５〜２０重量％である。樹脂及び溶剤の添加量は、乾式粉砕温度を加味しながら決定する必要がある。つまり、使用する樹脂の軟化点は溶剤を含有させることで低くなるので、温度が高く処理量が多いと乾式粉砕装置内部での樹脂の付着、固着が生じる危険性が高くなる。粉砕時間はその装置によって、または希望とする粉砕粒径に応じて任意に設定できる。 In the present invention, the addition amount of the resin is generally 1 to 200% by weight based on the crude copper phthalocyanine, and the addition amount of the solvent is 0.5 to 20% by weight based on the resin. It is necessary to determine the addition amount of the resin and the solvent while taking into account the dry grinding temperature. That is, since the softening point of the resin used is lowered by containing a solvent, if the temperature is high and the treatment amount is large, there is a high risk that the resin will adhere and stick inside the dry pulverizer. The pulverization time can be arbitrarily set by the apparatus or according to the desired pulverized particle size.
得られた摩砕物を溶剤処理することでβ型銅フタロシアニン顔料を製造する場合、溶剤処理は通常有機溶剤単独かあるいは有機溶剤と水の混合系で行われる。混合系の場合、水との親和性が高い溶剤であればそのまま混合系で、水との親和性がない溶剤の場合は界面活性剤を用いてエマルションとして用いるのが一般的である。有機溶剤としては、前述した樹脂とともに添加する溶剤が使用できる。 When a β-type copper phthalocyanine pigment is produced by subjecting the obtained ground product to a solvent treatment, the solvent treatment is usually carried out in an organic solvent alone or a mixed system of an organic solvent and water. In the case of a mixed system, it is generally used as a mixed system as long as it is a solvent having a high affinity with water, and is used as an emulsion using a surfactant in the case of a solvent having no affinity with water. As an organic solvent, the solvent added with the resin mentioned above can be used.
この様にして製造された顔料一次粒子のアスペクト比は、ソルベントソルトミリング法による顔料一次粒子とほぼ同じ１〜３の範囲であり、その色相は緑味である。またこの方法により得られた顔料を、従来から行われているソルベントソルトミリング法の顔料と比較したところ、光沢、流動性などの点に於いて同等の品位を有していることが確認された。 The aspect ratio of the primary pigment particles thus produced is in the range of 1 to 3 which is almost the same as that of the primary pigment particles obtained by the solvent salt milling method, and the hue thereof is green. Moreover, when the pigment obtained by this method was compared with the pigment of the conventional solvent salt milling method, it was confirmed that the pigment had the same quality in terms of gloss and fluidity. .
得られた摩砕物を印刷インキ用ワニス或いは印刷インキ用溶剤と混合することで直接β型銅フタロシアニン顔料を含有する印刷インキを製造する場合の印刷インキ用溶剤またはワニス中の溶剤としては、高沸点石油系溶剤、脂肪族炭化水素溶剤、高級アルコール系溶剤など印刷インキに適した溶剤であれば芳香族を含まない溶剤であっても単独あるいは２種類以上の組み合わせで任意に使用できる。 When the obtained ground product is directly mixed with a printing ink varnish or a printing ink solvent to produce a printing ink containing a β-type copper phthalocyanine pigment, the solvent for the printing ink or the varnish has a high boiling point. As long as the solvent is suitable for printing ink, such as petroleum solvent, aliphatic hydrocarbon solvent, and higher alcohol solvent, any solvent that does not contain aromatics can be used alone or in combination of two or more.
また、同様に印刷インキを製造する場合の印刷インキワニス用樹脂としては、ロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂、石油樹脂、アルキド樹脂など印刷インキに適した樹脂と、大豆油、桐油、アマニ油など印刷インキに適した乾性油や重合乾性油などを、その他印刷インキ用の添加剤などと共に任意に単独または２種類以上を組み合わせて使用できる。 Similarly, as a resin for printing ink varnish when producing printing ink, resins suitable for printing ink such as rosin-modified phenol resin, rosin-modified maleic resin, petroleum resin, alkyd resin, soybean oil, tung oil, linseed oil A drying oil or a polymerization drying oil suitable for a printing ink can be used alone or in combination of two or more kinds together with other additives for printing ink.
この様にして製造された印刷インキ中の顔料一次粒子のアスペクト比は、ソルベントソルトミリング法による顔料一次粒子とほぼ同じ１〜３の範囲であり、その色相は緑味である。またこの方法により得られた顔料を、従来から行われているソルベントソルトミリング法の顔料から製造した印刷インキと比較したところ、光沢、流動性などの点に於いて同等の品位を有していることが確認された。
[実施例]
The aspect ratio of the primary pigment particles in the printing ink produced in this way is in the range of 1 to 3 which is almost the same as that of the primary pigment particles by the solvent salt milling method, and the hue is green. In addition, when the pigment obtained by this method is compared with the printing ink produced from the conventional solvent salt milling pigment, it has the same quality in terms of gloss and fluidity. It was confirmed.
[Example]
次に、本発明を実施例に基づいて説明するが、本発明はこれらの実施例に限定されるもではない。なお、以下の例中、「部」及び「％」は、特に断りのない限り、それぞれ「重量部」「重量％」を示す。なお、実施例中で標準インキとして使用しているのは、粗製銅フタロシアニンをソルベントソルトミリング（食塩５倍量）により顔料化したウエットケーキ顔料を用いて、フラッシング法により製造したβ型銅フタロシアニン顔料インキである。また、インキ締まり評価する粘弾性はレオメトリックス社ＤynamicAnalyzer ＲＤＡ−２を用いて評価し、結晶型の測定にはＸ線回折装置を使用した。 Next, the present invention will be described based on examples, but the present invention is not limited to these examples. In the following examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified. The standard ink used in the examples is a β-type copper phthalocyanine pigment produced by a flushing method using a wet cake pigment obtained by pigmenting crude copper phthalocyanine by solvent salt milling (5 times the amount of salt). Ink. In addition, the viscoelasticity for evaluating ink tightness was evaluated using Rheometrics Dynamic Analyzer RDA-2, and an X-ray diffractometer was used to measure the crystal form.
（オフセット用ロジン変性フェノール樹脂ゲルワニスＡの製造）
コンデンサー、温度計、及び攪拌機を装着した四つ口フラスコにロジン変性フェノール樹脂（荒川化学工業（株）製：重量平均分子量１５万、酸価２０、軟化点１６０℃）３８．５部、大豆油３０部、ＡＦソルベント５号（新日本石油（株）製）３０部を仕込み、１８０℃に昇温して、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１．０部（川研ファインケミカル（株）製ＡＬＣＨ）を仕込み、１８０℃で３０分間攪拌してオフセット用ロジン変性フェノール樹脂ゲルワニスＡ（以下ゲルワニスＡと称す）を得た。
(Production of rosin-modified phenolic resin gel varnish A for offset)
38.5 parts of rosin modified phenolic resin (Arakawa Chemical Industries, Ltd .: weight average molecular weight 150,000, acid value 20, softening point 160 ° C.) in a four-necked flask equipped with a condenser, thermometer and stirrer, soybean oil 30 parts, 30 parts of AF Solvent No. 5 (manufactured by Nippon Oil Co., Ltd.) were charged, heated to 180 ° C., stirred at the same temperature for 30 minutes, allowed to cool, and ethyl acetoacetate aluminum as a gelling agent 1.0 part of diisopropoxide (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) was added and stirred at 180 ° C. for 30 minutes to obtain a rosin-modified phenol resin gel varnish A for offset (hereinafter referred to as gel varnish A).
本実施例で用いる顔料誘導体を表１に示す。 The pigment derivatives used in this example are shown in Table 1.
[実施例１]
乾式アトライターに粗製銅フタロシアニン７０重量部とロジン変性フェノール樹脂３０重量部、ＡＦ５号ソルベント（新日本石油（株）製）５重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１８重量部を、ゲルワニスＡ４４重量部、ＡＦ５号ソルベント８重量部、表−１の顔料誘導体１ ３．５重量部（粗製銅フタロシアニンに対し５％）に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロールで一回練肉したところ、顔料粒子は７．５μ以下に分散された。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ１を得た。このインキ１を、同一顔料分を含む標準インキと比較したところ、本実施例のインキは着色力、光沢、色相などの点において標準インキと同等の品位を有していた。また、α型結晶の含有率は１％以下であった。
[Example 1]
70 parts by weight of crude copper phthalocyanine, 30 parts by weight of rosin-modified phenolic resin, and 5 parts by weight of AF5 solvent (manufactured by Nippon Oil Corporation) were added to a dry attritor and pulverized at 160 ° C for 1 hour in a nitrogen stream. It was. Next, 18 parts by weight of the obtained ground product was added to 44 parts by weight of gel varnish A, 8 parts by weight of AF5 solvent, 3.5 parts by weight of pigment derivative 1 in Table 1 (5% with respect to crude copper phthalocyanine), and 120 ° C. After gently stirring for 2 hours, the mixture was kneaded once with three rolls of 60 degrees, and the pigment particles were dispersed to 7.5 μm or less. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. The printing ink 1 for offset adjusted to 1 was obtained. When this ink 1 was compared with a standard ink containing the same pigment component, the ink of this example had the same quality as the standard ink in terms of coloring power, gloss, hue, and the like. The content of α-type crystals was 1% or less.
[実施例２]
乾式アトライターに粗製銅フタロシアニン７０重量部とロジン変性フェノール樹脂３０重量部、ＡＦ５号ソルベント（新日本石油（株）製）５重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１８重量部を、ゲルワニスＡ４４重量部、ＡＦ５号ソルベント８重量部、表−１の顔料誘導体２ ３．５重量部（粗製銅フタロシアニンに対し５％）に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロールで一回練肉したところ、顔料粒子は７．５μ以下に分散された。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ２を得た。このインキ２を、同一顔料分を含む標準インキと比較したところ、本実施例のインキは着色力、光沢、色相などの点において標準インキと同等の品位を有していた。また、α型結晶の含有率は１％以下であった。
[Example 2]
70 parts by weight of crude copper phthalocyanine, 30 parts by weight of rosin-modified phenolic resin, and 5 parts by weight of AF5 solvent (manufactured by Nippon Oil Corporation) were added to a dry attritor and pulverized at 160 ° C for 1 hour in a nitrogen stream. It was. Next, 18 parts by weight of the obtained ground product was added to 44 parts by weight of gel varnish A, 8 parts by weight of AF5 solvent, 3.5 parts by weight of pigment derivative 2 in Table 1 (5% based on crude copper phthalocyanine), and 120 ° C. After gently stirring for 2 hours, the mixture was kneaded once with three rolls of 60 degrees, and the pigment particles were dispersed to 7.5 μm or less. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. Thus, the offset printing ink 2 was obtained. When this ink 2 was compared with a standard ink containing the same pigment component, the ink of this example had the same quality as the standard ink in terms of coloring power, gloss, hue, and the like. The content of α-type crystals was 1% or less.
[実施例３]
乾式アトライターに粗製銅フタロシアニン７０重量部とロジン変性フェノール樹脂３０重量部、ＡＦ５号ソルベント（新日本石油（株）製）５重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１８重量部を、ゲルワニスＡ４４重量部、ＡＦ５号ソルベント８重量部、表−１の顔料誘導体３ ３．５重量部（粗製銅フタロシアニンに対し５％）に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロールで一回練肉したところ、顔料粒子は７．５μ以下に分散された。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ３を得た。このインキ3を、同一顔料分を含む標準インキと比較したところ、本実施例のインキは着色力、光沢、色相などの点において標準インキと同等の品位を有していた。また、α型結晶の含有率は１％以下であった。
[Example 3]
70 parts by weight of crude copper phthalocyanine, 30 parts by weight of rosin-modified phenolic resin, and 5 parts by weight of AF5 solvent (manufactured by Nippon Oil Corporation) were added to a dry attritor and pulverized at 160 ° C for 1 hour in a nitrogen stream. It was. Next, 18 parts by weight of the obtained ground product is added to 44 parts by weight of gel varnish A, 8 parts by weight of AF5 solvent, 3.5 parts by weight of pigment derivative 3 in Table 1 (5% with respect to crude copper phthalocyanine), and 120 degrees. After gently stirring for 2 hours, the mixture was kneaded once with three rolls of 60 degrees, and the pigment particles were dispersed to 7.5 μm or less. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. The offset printing ink 3 adjusted to 1 was obtained. When this ink 3 was compared with a standard ink containing the same pigment, the ink of this example had the same quality as the standard ink in terms of coloring power, gloss, hue, and the like. The content of α-type crystals was 1% or less.
[実施例４]
乾式アトライターに粗製銅フタロシアニン７０重量部とロジン変性フェノール樹脂３０重量部、ＡＦ５号ソルベント（新日本石油（株）製）５重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１８重量部を、ゲルワニスＡ４４重量部、ＡＦ５号ソルベント８重量部、表−１の顔料誘導体３ ７重量部（粗製銅フタロシアニンに対し１０％）に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロールで一回練肉したところ、顔料粒子は７．５μ以下に分散された。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ４を得た。このインキ４を、同一顔料分を含む標準インキと比較したところ、本実施例のインキは着色力、光沢、色相などの点において標準インキと同等の品位を有していた。また、α型結晶の含有率は１％以下であった。
[Example 4]
70 parts by weight of crude copper phthalocyanine, 30 parts by weight of rosin-modified phenolic resin, and 5 parts by weight of AF5 solvent (manufactured by Nippon Oil Corporation) were added to a dry attritor and pulverized at 160 ° C for 1 hour in a nitrogen stream. It was. Next, 18 parts by weight of the obtained ground product was added to 44 parts by weight of gel varnish A, 8 parts by weight of AF5 solvent, and 7 parts by weight of pigment derivative 3 in Table 1 (10% with respect to crude copper phthalocyanine) at 120 degrees. After gently stirring for 2 hours, the mixture was kneaded once with three rolls of 60 degrees, whereby the pigment particles were dispersed to 7.5 μm or less. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. The printing ink 4 for offset adjusted in this way was obtained. When this ink 4 was compared with a standard ink containing the same pigment content, the ink of this example had the same quality as the standard ink in terms of coloring power, gloss, hue, and the like. The content of α-type crystals was 1% or less.
[比較例１]
乾式アトライターに粗製銅フタロシアニン７０重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１６重量部を、ゲルワニスＡ４８重量部、ＡＦ５号ソルベント８重量部に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロール３回の練肉で、顔料粒子は１２．５μであった。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ５を得た。同一顔料分を含む標準インキと比較したところ、得られたインキ５の色相は赤味でα型結晶の含有率が６％であった。
[Comparative Example 1]
70 parts by weight of crude copper phthalocyanine was added to a dry attritor and pulverized at 160 ° C. for 1 hour in a nitrogen stream. Next, 16 parts by weight of the obtained ground product was added to 48 parts by weight of gel varnish A and 8 parts by weight of AF5 solvent and gently stirred at 120 degrees for 2 hours. The pigment particles were 12.5μ. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. A printing ink 5 for offset adjusted to 1 was obtained. When compared with a standard ink containing the same pigment content, the obtained ink 5 had a red hue and a content of α-type crystals of 6%.
[比較例２]
乾式アトライターに粗製銅フタロシアニン７０重量部とロジン変性フェノール樹脂３０重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１８重量部を、ゲルワニスＡ４４重量部、ＡＦ５号ソルベント８重量部に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロール３回の練肉で、顔料粒子は７．５μであった。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ６を得た。同一顔料分を含む標準インキと比較したところ、得られたインキ６の色相は赤味でα型結晶の含有率が３％であった。
[Comparative Example 2]
70 parts by weight of crude copper phthalocyanine and 30 parts by weight of rosin-modified phenolic resin were added to a dry attritor and pulverized at 160 ° C. for 1 hour in a nitrogen stream. Next, 18 parts by weight of the obtained ground product was added to 44 parts by weight of gel varnish A and 8 parts by weight of AF5 solvent, and after gently stirring at 120 degrees for 2 hours, The pigment particles were 7.5 μm. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. A printing ink 6 for offset adjusted to 1 was obtained. When compared with a standard ink containing the same pigment content, the obtained ink 6 had a red hue and a content of α-type crystals of 3%.
[比較例３]
乾式アトライターに粗製銅フタロシアニン７０重量部とロジン変性フェノール樹脂３０重量部とＡＦ５号ソルベント（新日本石油（株）製）５重量部を加え窒素気流下に於いて１６０度で１時間粉砕を行った。次に、得られた摩砕物１８重量部を、ゲルワニスＡ４４重量部、ＡＦ５号ソルベント８重量部に加え１２０度にて２時間緩やかに攪拌した後、６０度の３本ロール３回の練肉で、顔料粒子は７．５μであった。次に、得られたベースインキにゲルワニスＡ１０重量部、再生大豆油１０重量部、ＡＦ５号ソルベント５重量部を加えた後、更にＡＦ５号ソルベントを添加して粘度５．０〜５．５Ｐａ・ｓに調整したオフセット用印刷インキ７を得た。同一顔料分を含む標準インキと比較したところ、得られたインキ７の色相は青味でα型結晶の含有率が１％であった。
[Comparative Example 3]
70 parts by weight of crude copper phthalocyanine, 30 parts by weight of rosin-modified phenolic resin and 5 parts by weight of AF5 solvent (manufactured by Nippon Oil Corporation) were added to a dry attritor and pulverized at 160 degrees for 1 hour under a nitrogen stream. It was. Next, 18 parts by weight of the obtained ground product was added to 44 parts by weight of gel varnish A and 8 parts by weight of AF5 solvent, and after gently stirring at 120 degrees for 2 hours, The pigment particles were 7.5 μm. Next, after adding 10 parts by weight of gel varnish A, 10 parts by weight of regenerated soybean oil, and 5 parts by weight of AF5 solvent to the obtained base ink, AF5 solvent is further added to obtain a viscosity of 5.0 to 5.5 Pa · s. The offset printing ink 7 adjusted to 1 was obtained. When compared with a standard ink containing the same pigment content, the resulting ink 7 had a bluish hue and an α-type crystal content of 1%.
評価結果
上記実施例及び比較例の印刷インキ組成物の内容を表２に示す。そしてその印刷インキ組成物について、α結晶含有率、粘度、インキ流動性（スプレッドメーターによる測定［ＳＲ］、ガラス板流度）、色相、インキしまりについて評価を実施し、結果を表３に示した。
Evaluation results Table 2 shows the contents of the printing ink compositions of the above Examples and Comparative Examples. The printing ink composition was evaluated for α crystal content, viscosity, ink fluidity (measurement with a spread meter [SR], glass plate flow rate), hue, and ink tightness, and the results are shown in Table 3. .
＜α結晶含有率の測定＞
α結晶含有率はＸ線回折装置を使用し、試作インキを測定した。
<Measurement of α crystal content>
The α crystal content was measured using a prototype ink using an X-ray diffractometer.
＜スプレッドメーターによる流動性の評価方法＞
スプレッドメーターに一定容量の試験インキを測り盛り、測定開始後１分後にインキが流動した中心からの距離を計測する［ＳＲ］。測定値の大きいものを流動性が高いと判定する。なお、実施例１で得られたオフセット用印刷インキ１の測定値を１００％とした百分率で測定値を表示した。
<Method of evaluating liquidity using a spread meter>
Measure a certain amount of test ink in a spread meter, and measure the distance from the center where the ink flow 1 minute after the start of measurement [SR]. A sample having a large measured value is determined to have high fluidity. In addition, the measured value was displayed by the percentage which made the measured value of the printing ink 1 for offset obtained in Example 1 100%.
＜ガラス板流度による流動性の評価方法＞
インキピペットに一定容量の試験インキを測り盛り、水平に置いたガラス板流度計の基準線上に滴下させ、直ちにガラス板を垂直に立てる。垂直に立てた時から、１０分後に試験インキが流れた長さを計測する。測定値の大きいものを流動性が高いと判定する。なお、実施例１で得られたオフセット用印刷インキ１の測定値を１００％とした百分率で測定値を表示した。
<Evaluation method of fluidity by glass plate flow rate>
Measure a certain volume of test ink in an ink pipette, drop it on the horizontal line of a glass plate flowmeter placed horizontally, and immediately stand the glass plate vertically. The length of the test ink that flows after 10 minutes from the vertical position is measured. A sample having a large measured value is determined to have high fluidity. In addition, the measured value was displayed by the percentage which made the measured value of the printing ink 1 for offset obtained in Example 1 100%.
＜色相の評価方法＞白い展色紙に、試験インキを展色した後、色相を目視で観察する。 <Evaluation Method of Hue> After the test ink is developed on white colored paper, the hue is visually observed.
＜インキしまりの評価方法＞
粘弾性測定器のレオメトリックス社Dynamic Analyzer RDA-2 を用いて、Dynamic Time Sweep modeにて、貯蔵弾性率G’の経時変化を測定する（測定条件：温度４０度．各周波数(ω)：０．８．Strain：３０．Paralel Plate Gap：１．０ｍｍ．測定時間１時間．）。このとき６分と６０分のG’の比（Ｇ’[60分]／Ｇ’[6分]）を求める。この比率が高い程、インキ中に蓄えられるエネルギーが多くなりインキが締まりやすくなる。なお、実施例１で得られたオフセット用印刷インキ１の比率を１００％とした百分率で測定値を表示した。
<Evaluation method of ink seal>
Measure the time-dependent change of storage elastic modulus G 'in Dynamic Time Sweep mode using Rheometrics Dynamic Analyzer RDA-2, a viscoelasticity measuring instrument (measurement conditions: temperature 40 degrees, each frequency (ω): 0) 8. Strain: 30. Parallel Plate Gap: 1.0 mm. Measurement time: 1 hour. At this time, the ratio of G ′ for 6 minutes to 60 minutes (G ′ [60 minutes] / G ′ [6 minutes]) is obtained. The higher this ratio is, the more energy is stored in the ink and the more easily the ink is tightened. In addition, the measured value was displayed by the percentage which made the ratio of the printing ink 1 for offset obtained in Example 1 100%.
上記のように、本発明で得られるオフセット用インキは従来のインキと比較して、赤味色相や流動性・インキしまりを抑えることが可能となった。
As described above, the offset ink obtained in the present invention can suppress reddish hue, fluidity, and ink tightness as compared with conventional inks.
Claims (1)
一般式（１）
Ｙ1 ；−ＮＨ−または−Ｏ−Ｚ；水酸基、アルコキシ基もしくは下記一般式（２）で示される基、あるいはｎ＝１の場合−ＮＨ−Ｘ−Ｑ1であってもよい。
一般式（２）
ｍ；１〜６の整数ｎ；１〜４の整数を表す。
一般式（３）：Ｑ2−（−Ｘ−Ｙ）n
式中、Ｑ2；有機色素残基Ｘ；直接結合，−ＣＯＮＨ−Ｙ2 −，−ＳＯ2 ＮＨ−Ｙ2 −または−ＣＨ2 ＮＨＣＯＣＨ2 ＮＨ−Ｙ2 −（Ｙ2；置換基を有してもよいアルキレン基またはアリーレン基）
Ｙ；下記一般式（４）または（５）で示される基
一般式（４）
Ｙ4 ; 水素原子，ハロゲン原子，−ＮＯ2 ，−ＮＨ2または−ＳＯ3 Ｈｋ；１〜４の整数ｍ；１〜６の整数ｎ；１〜４の整数を表す。
A printing ink for offset produced by adding a pigment derivative represented by the following general formula (1) or (3) to a pigment composition produced by a production method of dry pulverizing crude copper phthalocyanine.
General formula (1)
Y 1 ; —NH— or —O—Z; a hydroxyl group, an alkoxy group or a group represented by the following general formula (2), or in the case of n = 1, may be —NH—XQ 1 .
General formula (2)
m; an integer n of 1-6; an integer of 1-4.
Formula (3): Q 2 - ( - X-Y) n
In the formula, Q 2 ; organic dye residue X; direct bond, —CONH—Y 2 —, —SO 2 NH—Y 2 — or —CH 2 NHCOCH 2 NH—Y 2 — (Y 2 ; having a substituent May be an alkylene group or an arylene group)
Y: group represented by the following general formula (4) or (5)
Y 4 represents a hydrogen atom, a halogen atom, —NO 2 , —NH 2 or —SO 3 Hk; an integer m of 1 to 4; an integer n of 1 to 6; an integer of 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006007438A JP2007186643A (en) | 2006-01-16 | 2006-01-16 | Printing ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006007438A JP2007186643A (en) | 2006-01-16 | 2006-01-16 | Printing ink |
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| Publication Number | Publication Date |
|---|---|
| JP2007186643A true JP2007186643A (en) | 2007-07-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2006007438A Pending JP2007186643A (en) | 2006-01-16 | 2006-01-16 | Printing ink |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722774B2 (en) | 2008-07-22 | 2014-05-13 | Kao Corporation | Biodegradable resin composition |
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2006
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722774B2 (en) | 2008-07-22 | 2014-05-13 | Kao Corporation | Biodegradable resin composition |
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