JP5309433B2 - Lithographic ink composition - Google Patents
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- JP5309433B2 JP5309433B2 JP2006263621A JP2006263621A JP5309433B2 JP 5309433 B2 JP5309433 B2 JP 5309433B2 JP 2006263621 A JP2006263621 A JP 2006263621A JP 2006263621 A JP2006263621 A JP 2006263621A JP 5309433 B2 JP5309433 B2 JP 5309433B2
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- 239000000203 mixture Substances 0.000 title description 16
- 239000000976 ink Substances 0.000 claims description 143
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 36
- 229940097275 indigo Drugs 0.000 claims description 36
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 36
- 239000000049 pigment Substances 0.000 claims description 34
- 238000007639 printing Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 16
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 phthalocyanine compound Chemical class 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 8
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000985 reflectance spectrum Methods 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims 1
- 239000003086 colorant Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 19
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- 238000009472 formulation Methods 0.000 description 12
- 239000002966 varnish Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- 229910052751 metal Inorganic materials 0.000 description 9
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
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- 229920003002 synthetic resin Polymers 0.000 description 2
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- 239000001052 yellow pigment Substances 0.000 description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- CPUMJJMOTBXNBQ-UHFFFAOYSA-N [6-amino-9-(2-ethoxycarbonylphenyl)-7-methylxanthen-3-ylidene]-dimethylazanium;chloride Chemical compound [Cl-].CCOC(=O)C1=CC=CC=C1C(C1=CC(C)=C(N)C=C1O1)=C2C1=CC(=[N+](C)C)C=C2 CPUMJJMOTBXNBQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 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
- 239000003831 antifriction material Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 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 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、黄、紅、藍、墨のプロセス４色からなる平版インキセットであって、４色で高彩度の色再現性に優れた平版インキセットに関する。
The present invention is, yellow, red, blue, a lithographic ink set of process four colors black, about good lithographic ink set color reproduction of high chroma in four colors.
９０年代より始まったＩＴ革命は、印刷現場を取り巻く環境を著しくデジタル化の方向へと導いてきており、このデジタル化によって、従来の印刷方式のワークフロー（撮影・ポジ・スキャン・データ・デザイン・ＥＰＳ・面付け・フィルム・刷版・印刷）が多段階式過程であったのに対し、デジタルカメラによる撮影・ＤＴＰ・ＣＴＰ・印刷とその過程を飛躍的に短縮することに成功した。それによって、入稿データの「ＲＧＢ」化が標準化しつつあり、取り扱われるデータがより色再現領域の広いものへとシフトしつつあるのが現状である。
しかし、現在主流となっている黄、紅、藍、墨のプロセス４色（ＣＭＹＫ）からなる平版オフセット印刷では、減色混合による色相となるため、色を重ねるごとに色相に濁りが生じ、必然的に色再現領域がＲＧＢのそれよりも狭いものとなりデジタルデータと印刷物との間の色再現性の差異が問題となっていった。特に、印刷の最終色として印刷されることが一般的な黄インキが不透明であると黄かぶり現象を起こし、下刷りのインキ各色へ与える影響が大きい為、黄インキはできる限り透明であることが望ましく、他の色と刷り重ねた時に、濁りのない二次色、三次色が得られることが望ましい。
これらを解決する手段として、特許文献１では高彩度の印刷システムとして５〜７色のインキセットを使用する印刷方法が確立され、それぞれの特定した色相を持つインキセットを用いる印刷方法として、プロセス４色に橙、緑を加えた６色（ヘキサクロム印刷）やプロセス４色に橙、緑、紫を加えた７色（ハイファイ印刷）等が確立されている。また、ヘキサクロムインキに代表されるように、二次色、三次色の濁りを抑え、色再現領域を広げる手段として一部の色に蛍光顔料を含有させる等の手法もとられるが、印刷適性の劣化（転移不良、光沢低下等）や耐光性不足による印刷物の褪色等のデメリットもある。更に、使用するインキの色数が６色、７色となり、印刷機の胴数が６胴以上の高価な多色印刷機を必要とする事に加え、それと同数の多色分解した版数が必須条件となり、新たに始めるには巨額な設備投資と、色調管理の複雑化などで本システムを用いるには限られた範囲に止まっている。
However, lithographic offset printing consisting of four process colors (CMYK) of yellow, red, indigo, and black, which is currently the mainstream, has a hue due to subtractive color mixing. In addition, the color reproduction area becomes narrower than that of RGB, and the difference in color reproducibility between digital data and printed matter has become a problem. In particular, when yellow ink, which is generally printed as the final color of printing, is opaque, it causes yellow fogging and has a large effect on each color of underprinting. Therefore, yellow ink must be as transparent as possible. Desirably, it is desirable to obtain secondary and tertiary colors without turbidity when overprinted with other colors.
As means for solving these problems, in Patent Document 1, a printing method using an ink set of 5 to 7 colors is established as a high-saturation printing system. As a printing method using an ink set having each specified hue, process 4 colors are used. 6 colors (hexachrome printing) with orange and green added to 7 colors and 7 colors (high fidelity printing) with orange, green and purple added to 4 process colors have been established. In addition, as represented by hexachrome ink, methods such as adding fluorescent pigments to some colors as a means of suppressing secondary and tertiary turbidity and expanding the color reproduction range are also available. There are also disadvantages such as deterioration of the image quality (transfer defect, gloss reduction, etc.) and fading of printed matter due to insufficient light resistance. Furthermore, the number of ink colors used is 6 or 7, and an expensive multicolor printing machine with 6 or more printing cylinders is required. It is an indispensable condition, and it is limited to using this system due to huge capital investment and complicated color management to start a new one.
本発明は、このような従来の技術における問題点を解決する為になされたものであり、その課題とするところは、従来多く普及している４色印刷機を用いて、ＲＧＢの色再現領域を限りなく表現することができる、黄、紅、藍、墨のプロセス４色からなる平版インキセットを提供する事である。
The present invention has been made in order to solve such problems in the prior art, and the problem is that an RGB color reproduction region using a four-color printing machine that has been widely used in the past. Is to provide a lithographic ink set consisting of four processes of yellow, red, indigo and black.
一般的に、色再現領域を広げるためには、各色の理想的な分光反射率曲線に近づける必要がある。すなわち、人が色を認識する波長領域は４００nm〜７００nmの光（この波長を可視光線という）において、黄インキでは、５００nm〜７００nmの波長領域での反射率が１００％、４００nm〜５００nmの波長領域での反射率が０％であり、紅インキでは、４００nm〜５００nm、６００nm〜７００nmの波長領域での反射率が１００％、５００nm〜６００nmの波長領域での反射率が０％であり、藍インキでは、４００nm〜６００nmの波長領域での反射率が１００％、６００nm〜７００nmの波長領域での反射率が０％であることが理想であると言われている（理想のプロセスインキの分光反射率曲線を表６に示す）。 In general, in order to expand the color reproduction region, it is necessary to approximate the ideal spectral reflectance curve of each color. That is, the wavelength range in which a person recognizes color is 400 nm to 700 nm light (this wavelength is referred to as visible light). In yellow ink, the reflectance in the wavelength range of 500 nm to 700 nm is 100%, and the wavelength range of 400 nm to 500 nm. The red ink has a reflectance of 0%, and the red ink has a reflectance of 100% in the wavelength region of 400 nm to 500 nm and 600 nm to 700 nm, and a reflectance of 0% in the wavelength region of 500 nm to 600 nm. Therefore, it is said that it is ideal that the reflectance in the wavelength region of 400 nm to 600 nm is 100% and the reflectance in the wavelength region of 600 nm to 700 nm is 0% (the spectral reflectance of the ideal process ink) Curves are shown in Table 6).
しかし、現状使用されているプロセス４色からなる、黄、紅、藍、墨のオフセット印刷用インキ組成物の反射スペクトルは理想の反射スペクトルとはかけ離れている。完全反射しなければならない部分での不必要吸収があるためにインキの濁り成分が存在し、色再現性を狭めている。
すなわち本発明は、黄、紅、藍、墨のプロセス４色からなる平版インキを使用する平版印刷において、黄、紅、藍の３色がジスアゾイエロー系化合物を顔料成分とする黄インキと、顔料成分としてC.I.ピグメントレッド１６９を必須として、さらに、C.I.ピグメントレッド８１またはC.Iピグメントバイオレット１をインキの全重量に対して１５〜３０重量％含有する紅インキと、フタロシアニン系化合物を顔料成分とする藍インキとの組み合わせからなる平版インキセットに関するものである。
However, the reflection spectrum of the ink composition for offset printing of yellow, red, indigo and black, which is currently used in four process colors, is far from the ideal reflection spectrum. Since there is unnecessary absorption in the part that must be completely reflected, a turbid component of the ink exists, and the color reproducibility is narrowed.
That is, the present invention is, yellow, magenta, cyan, the lithographic printing using flat Ban'i Nki consisting process four-color black, and yellow ink yellow, red, three colors of indigo is a disazo yellow compound and pigment components CI pigment red 169 is essential as a pigment component, and a red ink containing 15 to 30% by weight of CI pigment red 81 or CI pigment violet 1 based on the total weight of the ink and a phthalocyanine compound as a pigment component The present invention relates to a lithographic ink set consisting of a combination with indigo ink.
また、また、本発明は、フタロシアニン系化合物として、C.I.ピグメントブルー１５：３またはC.I.ピグメントブルー１５：４をインキの全重量に対して１０〜２５重量％且つ、C.I.ピグメントグリーン７をインキの全重量に対して０．５〜２．０重量％含有する上記記載の平版インキセットに関する。
Further, the present invention also provides CI Pigment Blue 15: 3 or CI Pigment Blue 15: 4 as the phthalocyanine compound in an amount of 10 to 25% by weight based on the total weight of the ink, and CI Pigment Green 7 as the total weight of the ink. The present invention relates to the above-described lithographic ink set containing 0.5 to 2.0% by weight.
更には、上記記載のC.I.ピグメントブルー１５：３またはC.I.ピグメントブルー１５：４の比表面積が７４ｍ2/ｇ以上である平版インキセットに関するものである。
さらに、上記紅インキとしてC.I.ピグメントレッド１６９を含有することを特徴とし、これら（ａ）黄、（ｂ）紅、（ｃ）藍が、下記の反射率を有する上記平版インキセットに関する。
（ａ）４００ｎｍ〜７００ｎｍの波長領域において、最大反射率を１００％としたときに、４００ｎｍ〜４８０ｎｍの波長領域が１〜２０％、５３０ｎｍ〜７００ｎｍの波長領域での反射率が９０〜１００％の反射スペクトルを有することを特徴とする黄色相化合物をインキの全重量に対して５〜１５重量％含有する黄インキ。
Furthermore, the present invention relates to a lithographic ink set in which the specific surface area of CI Pigment Blue 15: 3 or CI Pigment Blue 15: 4 is 74 m 2 / g or more.
Further, CI pigment red 169 is contained as the red ink, and (a) yellow, (b) red, and (c) indigo are related to the above lithographic ink set having the following reflectance.
(A) In the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the wavelength region of 400 nm to 480 nm is 1 to 20%, and the reflectance in the wavelength region of 530 nm to 700 nm is 90 to 100%. A yellow ink containing 5 to 15% by weight of a yellow phase compound having a reflection spectrum with respect to the total weight of the ink.
（ｂ）４００ｎｍ〜７００ｎｍの波長領域において、最大反射率を１００％としたときに、４００ｎｍ〜５００ｎｍの波長領域での最大反射率が５０％〜１００％、５００ｎｍ〜５６０ｎｍの波長領域での反射率が１〜２０％、６３０ｎｍ〜７００ｎｍの反射率が９０％〜１００％の反射スペクトルを有することを特徴とする紅色相化合物をインキの全重量に対して１５〜３０重量％含有する紅インキ。
（ｃ）４００ｎｍ〜７００ｎｍの波長領域において、最大反射率を１００％としたときに、４００ｎｍ〜５３０ｎｍの波長領域の反射率が５０〜１００％、６００ｎｍ〜７００ｎｍの反射率が１〜３０％の反射スペクトルを有することを特徴とする藍色相化合物をインキの全重量に対して１０〜２５重量％含有する藍インキ。
(B) In the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the maximum reflectance in the wavelength region of 400 nm to 500 nm is 50% to 100%, and the reflectance in the wavelength region of 500 nm to 560 nm. A red ink containing 15 to 30% by weight of a red hue compound having a reflection spectrum of 1 to 20%, a reflectance of 630 nm to 700 nm and a reflectance spectrum of 90% to 100% based on the total weight of the ink.
(C) In the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the reflectance in the wavelength region of 400 nm to 530 nm is 50 to 100%, and the reflectance of 600 nm to 700 nm is 1 to 30%. An indigo ink containing 10 to 25% by weight of an indigo hue compound having a spectrum with respect to the total weight of the ink.
本発明が提供する平版インキ組成物を用いることにより、従来黄、紅、藍、墨プロセス４色に加えて、橙、緑、紫等を加えた６色、７色印刷で表現していたＲＧＢの色再現領域を、黄、紅、藍、墨の４色で再現することが可能になる。また、本発明では、印刷物の色再現領域を向上させる手段として蛍光顔料を使用していないため、印刷適性、印刷物の経時での褪色等を劣化させることなく、高彩度の印刷物を得ることができる。
By using the lithographic ink composition provided by the present invention, RGB which has conventionally been expressed by 6-color and 7-color printing including orange, green, purple, etc. in addition to 4 colors of yellow, red, indigo and black ink process The color reproduction area can be reproduced with four colors of yellow, red, indigo and black. Further, in the present invention, since a fluorescent pigment is not used as a means for improving the color reproduction region of the printed material, a highly saturated printed material can be obtained without deteriorating printability, fading with time of the printed material, and the like.
次に、好ましい実施の形態を挙げて本発明を更に具体的に説明する。
本発明は、顔料と、合成樹脂、植物油、石油系溶剤とを必要に応じてステアリン酸アルミニウム、アルミキレート等のゲル化剤と共に加熱溶解したビヒクル成分と、耐摩擦剤等の補助剤とからなる黄、紅、藍、墨の４色からなる平版インキであって、ＩＳＯ規格のジャパンカラー標準用紙、例えば三菱製紙（株）製「特菱アート両面四六版／１１０ｋｇ」に印刷し、黄、紅、藍の各色をグレタグマクベスＤ１９６濃度計にて測定した際の濃度値が、黄が１．４０〜１．４４、紅が１．５２〜１．５６、藍が１．６３〜１．６７の範囲内であるときに単色及び各単色の刷り重ねのＬ*ａ*ｂ*表色系による色度（JIS Z 8729）が、黄インキで、L*：８７〜９５、好ましくは８８〜９３、a*：−４〜−１２、好ましくは−５〜−１０、ｂ*：９０〜１００、好ましくは９２〜９８、紅インキで、L*：５０〜５５、好ましくは５１〜５４、a*：７５〜８３、好ましくは７６〜８１、ｂ*：−１４〜−２０、好ましくは−１５〜−１８、藍インキで、L*：５２〜５８、好ましくは５２〜５７、a*：−４０〜−４５、好ましくは−４１〜−４４、ｂ*：−４５〜−５３、好ましくは−４６〜−５１、更には、紅インキ×黄インキの刷り重ねで、L*：５１〜５６、a*：６５〜７０、ｂ*：５６〜６１、藍インキ×黄インキの刷り重ねで、L*：４７〜５３、a*：−７７〜−８３、ｂ*：２５〜３２、藍インキ×紅インキの刷り重ねで、L*：２３〜２９、a*：２８〜３３、ｂ*：−６３〜−６８の範囲内になることを特徴とする。
Next, the present invention will be described more specifically with reference to preferred embodiments.
The present invention comprises a pigment, a vehicle component obtained by heating and dissolving a synthetic resin, a vegetable oil, and a petroleum solvent together with a gelling agent such as aluminum stearate or aluminum chelate as necessary, and an auxiliary agent such as a friction-resistant agent. It is a lithographic ink consisting of four colors, yellow, red, indigo, and black, and is printed on ISO standard Japan color standard paper, for example, “Special Rhibo Art Double Sided Plate / 110 kg” manufactured by Mitsubishi Paper Industries, Inc. When the red and indigo colors were measured with a Gretag Macbeth D196 densitometer, the density values were 1.40 to 1.44 for yellow, 1.52 to 1.56 for red, and 1.63 to 1.67 for indigo. The chromaticity (JIS Z 8729) according to the L * a * b * color system of the single color and the overprint of each single color is yellow ink, L *: 87 to 95, preferably 88 to 93. A *: −4 to −12, preferably −5 to −10, b *: 90 to 100, Preferably 92-98, red ink, L *: 50-55, preferably 51-54, a *: 75-83, preferably 76-81, b *: -14 to -20, preferably -15 To -18, indigo ink, L *: 52 to 58, preferably 52 to 57, a *: -40 to -45, preferably 41 to -44, b *: -40 to -53, preferably- 46 to -51, and L *: 51 to 56, a *: 65 to 70, b *: 56 to 61, indigo ink x yellow ink, L *: 47 to 53, a *: -77 to -83, b *: 25 to 32, L *: 23 to 29, a *: 28 to 33, b *: − It falls within the range of 63 to -68.
色再現領域の表現方法としては、ＸＹＺ表色系（ＣＩＥ１９３１表色系）、Ｘ10Ｙ10Z10表色系（ＣＩＥ１９６４表色系）、Ｌ*ａ*ｂ*表色系（ＣＩＥ１９７６）、ハンターＬａｂ表色系、マンセル表色系、Ｌ*ｕ*ｖ*表色系（ＣＩＥ１９７６）等挙げられる。
Ｌ*ａ*ｂ*表色系では、色相に関係なく比較できる明るさの度合いとして「明度」をＬ*で表現し、Ｌ*が大きくなるほど色が明るく、小さくなるほど暗くなることを示している。また、各色によって異なる「色相」をａ*、ｂ*の値で示し、ａ*は赤（＋）から緑（−）方向、そしてｂ*は黄（＋）から青（−）方向を示し、各方向とも絶対値が大きくなるに従って色鮮やかになり、０に近づくに従ってくすんだ色になることを示している。これによって一つの色を、Ｌ*、ａ*、ｂ*を用いて数値化することが可能となる。また「明度」「色相」とは別に、鮮やかさの度合いを数値化する方法として「彩度（Ｃ）」があり、以下の計算式にて求めることができる。
As a method for expressing the color reproduction area, an XYZ color system (CIE 1931 color system), an X 10 Y 10 Z 10 color system (CIE 1964 color system), an L * a * b * color system (CIE 1976), Hunter Lab color system, Munsell color system, L * u * v * color system (CIE1976), and the like.
In the L * a * b * color system, “brightness” is expressed by L * as the degree of brightness that can be compared regardless of hue, and indicates that the color becomes brighter as L * increases and becomes darker as it decreases. . In addition, “hue” that differs depending on each color is indicated by a * and b * values, a * indicates a red (+) to green (−) direction, and b * indicates a yellow (+) to blue (−) direction, In each direction, the color becomes brighter as the absolute value increases, and the color becomes dull as it approaches 0. This makes it possible to digitize one color using L *, a *, and b *. In addition to “lightness” and “hue”, there is “saturation (C)” as a method for digitizing the degree of vividness, which can be obtained by the following calculation formula.
Ｃに関しても同様に、絶対値が大きくなるに従って色鮮やかになり、値が小さくなるにつれてくすんだ色になることを示している。
Similarly, C shows that the color becomes brighter as the absolute value increases, and the color becomes dull as the value decreases.
一つの印刷物（印刷物以外のカラースペースも含む）で表現できる全ての色再現領域を演色領域（ガモット）と呼ぶが、ガモットを表す最も簡便な方法として、ａ*を横軸、ｂ*縦軸とした2次元空間に、単色ベタ部（黄、紅、藍）、及び、単色ベタ刷り重ね部（黄×紅、紅×藍、藍×黄）計6色のａ*対ｂ*の値を、プロットした六角形の面積で表現することが可能である。ガモットの面積が広い程、色再現領域が広いことを示している。
本発明で使用される黄インキに関し、濃度値１．８５〜１．９０の範囲内で印刷した墨インキ上に、濃度１．４０〜２．１０の範囲で刷り重ねした場合のＬ*値が１７を超えない透明性を有していれば、二次色、三次色の重ね刷りをした際の下刷りインキへの影響が少なく、良好な色再現領域を得ることができる。更には、補色としてC.I.ピグメントイエロー８３を上記黄顔料の０．５〜１０重量％、好ましくは２〜５重量％加えて使用することも可能である。
All color reproduction areas that can be represented by a single printed matter (including color spaces other than printed matter) are called color rendering regions (gamut). The simplest way to represent gamut is as follows: a * is the horizontal axis, b * vertical axis In the two-dimensional space, the solid color part (yellow, red, indigo) and the solid color overprinting part (yellow x red, red x indigo, indigo x yellow) total of 6 colors a * vs b *, It can be expressed by the plotted hexagonal area. The larger the gamut area, the wider the color reproduction area.
Regarding the yellow ink used in the present invention, the L * value when the ink is printed in the range of density 1.40 to 2.10 on the black ink printed in the range of density value 1.85 to 1.90 is If the transparency does not exceed 17, there is little influence on the underprinting ink when the secondary and tertiary colors are overprinted, and a good color reproduction region can be obtained. Furthermore, it is also possible to use CI pigment yellow 83 as a complementary color by adding 0.5 to 10% by weight, preferably 2 to 5% by weight of the above yellow pigment.
本発明で使用される黄顔料としては、C.I.ピグメントイエロー１２またはC.I.ピグメントイエロー１３をインキの全重量に対して５〜１５重量％使用することが好ましい。 As the yellow pigment used in the present invention, C.I. Pigment Yellow 12 or C.I. Pigment Yellow 13 is preferably used in an amount of 5 to 15% by weight based on the total weight of the ink.
本発明で使用される紅顔料としては、ローダミンＢ、ローダミン３Ｇ、ローダミン６Ｇなどのローダミン系染料のモリブデン、タングステン金属レーキ化合物、又は、フェロシアン化銅レーキ化合物が挙げられ、C.I.ピグメントレッド１６９を必ず含有し、その含有量はインキの全重量に対して１０〜３０重量％、好ましくは１０〜２０重量％、より好ましくは１１〜１８重量％含有することが好ましい。 Examples of the red pigment used in the present invention include rhodamine-based dyes such as rhodamine B, rhodamine 3G, rhodamine 6G, molybdenum, tungsten metal lake compounds, or ferrocyanide copper lake compounds. The content is preferably 10 to 30% by weight, preferably 10 to 20% by weight, more preferably 11 to 18% by weight based on the total weight of the ink.
本発明で使用される紅顔料としては、上記C.I.ピグメントレッド１６９を単独で使用しても良いし、上記顔料を２種類以上組み合わせて使用することも可能である。 As the red pigment used in the present invention, the C.I. Pigment Red 169 may be used alone, or two or more of the above pigments may be used in combination.
本発明で使用する藍顔料である銅フタロシアニン系化合物は、結晶多型（同質異晶）を示す物質であり、その結晶構造の違いによってα、β、γ、ε、π、τ、ρ、χ、Ｒ型などに分類されるが、結晶安定性、分散性が優れているβ型を使用することが好ましく、更には比表面積が７４ｍ2／ｇ以上の微細なβ型銅フタロシアニンであることが好ましい。本発明においては、上記銅フタロシアニン化合物に対し、フタロシアニン分子のベンゼン環上の水素原子をハロゲン化合物で置換したハロゲン化銅フタロシアニン化合物を５〜１５重量％より好ましくは８〜１１重量％加えて使用することにより、藍インキ単色の色再現領域を損なうことなく、黄及び紅インキと刷り重ねた際の緑及び紫の色再現領域を広げることが可能になる。具体的には、C.I.ピグメントブルー１５：３またはC.I.ピグメントブルー１５：４をインキの全重量に対して１０〜２５重量％且つ、C.I.ピグメントグリーン７をインキの全重量に対して０．５〜２．０重量％含有することが好ましい。 The copper phthalocyanine compound, which is a cyan pigment used in the present invention, is a substance exhibiting a crystal polymorphism (homogeneous heterocrystal), and α, β, γ, ε, π, τ, ρ, χ depending on the crystal structure. However, it is preferable to use a β-type having excellent crystal stability and dispersibility, and further a fine β-type copper phthalocyanine having a specific surface area of 74 m 2 / g or more. preferable. In the present invention, a copper halide phthalocyanine compound in which a hydrogen atom on a benzene ring of a phthalocyanine molecule is substituted with a halogen compound is added to the copper phthalocyanine compound in an amount of 5 to 15% by weight, more preferably 8 to 11% by weight. This makes it possible to widen the color reproduction region of green and purple when overprinted with yellow and red ink without impairing the color reproduction region of the indigo ink single color. Specifically, CI Pigment Blue 15: 3 or CI Pigment Blue 15: 4 is 10 to 25% by weight based on the total weight of the ink, and CI Pigment Green 7 is 0.5 to 2 based on the total weight of the ink. It is preferable to contain 0.0% by weight.
墨顔料としては、カーボンブラック、例えばC.I.ピグメントブラック７等が挙げられる。 Examples of the black pigment include carbon black such as C.I. Pigment Black 7.
本発明に用いられる合成樹脂としては、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考えられる。好ましくは、ロジン変性フェノール樹脂を使用する。ロジン変性フェノール樹脂は、特に限定されないが、重量平均分子量１万〜３０万のものを使用するのが好ましい。分子量１万以下ではインキの粘弾性が低下し、４０万以上ではインキとしての流動性が不十分となる。 As the synthetic resin used in the present invention, rosin-modified phenol resin, petroleum resin, alkyd resin, rosin-modified alkyd resin, petroleum resin-modified alkyd resin, rosin ester and the like can be considered. Preferably, a rosin modified phenolic resin is used. The rosin-modified phenol resin is not particularly limited, but it is preferable to use a resin having a weight average molecular weight of 10,000 to 300,000. When the molecular weight is 10,000 or less, the viscoelasticity of the ink is lowered, and when it is 400,000 or more, the fluidity as the ink becomes insufficient.
植物油としては、たとえばパーム核油、ヤシ油、綿実油、落花生油、パーム油、コーン油、オリーブ油、亜麻仁油、コーン油、大豆油、サフラワー油、桐油等の植物油由来のもの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。 Examples of vegetable oils include those derived from vegetable oils such as palm kernel oil, palm oil, cottonseed oil, peanut oil, palm oil, corn oil, olive oil, linseed oil, corn oil, soybean oil, safflower oil, and tung oil, Those thermal polymerized oils and oxygen-blown polymerized oils 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.
また、インキに用いられる石油系溶剤は、芳香族炭化水素の含有率が１％以下でアニリン点が７５〜９５℃好ましくは８０〜９５℃及び、沸点が２６０℃〜３５０℃好ましくは２８０〜３５０℃の範囲にある石油系溶剤である。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、インキのセット性が遅くなり好ましくなく、また９５℃を超える場合には樹脂の溶解性が乏しい為、光沢、着肉等が悪くなり好ましくない。沸点が２６０℃未満に場合には、印刷機上でのインキ溶剤の蒸発が多くなり、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、３５０℃を超える場合には、ヒートセット型のインキの乾燥が劣る為、好ましくない。 The petroleum solvent used in the ink has an aromatic hydrocarbon content of 1% or less, an aniline point of 75 to 95 ° C, preferably 80 to 95 ° C, and a boiling point of 260 to 350 ° C, preferably 280 to 350. It is a petroleum solvent in the range of ° C. If the aniline point is less than 75%, the ability to dissolve the resin is too high, which is not preferable because the ink setting property is slow, and if it exceeds 95 ° C., the resin solubility is poor, so Meat etc. are bad and not preferable. When the boiling point is less than 260 ° C., the evaporation of the ink solvent on the printing press increases, and the transferability of the ink to a roller, a blanket, a plate, or the like deteriorates due to the deterioration of the fluidity of the ink. Moreover, when it exceeds 350 degreeC, since drying of heat set type ink is inferior, it is unpreferable.
更に、本発明の平版インキ組成物には、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。
Further, the lithographic ink composition of the present invention includes a gelling agent, a pigment dispersant, a metal dryer, a drying inhibitor, an antioxidant, an anti-friction agent, an anti-set-off agent, and a nonionic surfactant as required. Additives such as agents and polyhydric alcohols can be used as appropriate.
次に具体例により本発明を更に詳細に説明するが、本発明の範囲はこれら記載実施例に限定されるものではない。なお、以下の記述の部は重量部、％は重量％を表す。
ロジン変性フェノール樹脂の製造例
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、これをレゾール液とした。
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１８００部を添加し、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、２６０℃で１０時間反応させ、酸価２０以下として、重量平均分子量５００００、新日本石油化学（株）ＡＦソルベント６号での白濁温度９０℃のロジン変性フェノール樹脂を得た。
ワニス製造例
ロジン変性フェノール樹脂４５部、大豆油４０部、ＡＦソルベント６号（新日本石油化学（株）製
溶剤）１４部、ＡＬＣＨ（川研ファインケミカル（株）製ゲル化剤）１．０部を１９０℃で１時間
加熱撹拌して、ワニスを得た。
インキ実施例（黄インキ）
表１のような配合にてＣ．Ｉ．ピグメントイエロー１２（東洋インキ製造（株）製ＬＩＯＮＯＬ ＹＥＬＬＯＷ １２３５−Ｐ）をニーダー中で温度７５℃の条件下、ワニスを徐々に添加して混練して一次脱水を行った。次にニーダー温度１００℃〜１２０℃、減圧度７６ｍｍＨｇの条件下で１時間バキュームし、ベースインキ中の水分を０．５％以下になるように二次脱水を行った。脱水後、残りのワニス、石油系溶剤を添加して混練して希釈し、ニーダーより未分散ベースインキを取り出した。取り出したベースインキをロール温度６０℃の３本ロールを用いて、分散粒子系測定機（グラインドメーター）で７．５ミクロン以下になるまで練肉し、黄のベースインキ１を得た。次いで、ベースインキ１に対して、表２の配合でワニス、植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し黄インキ１を得た。
インキ実施例（紅インキ）
黄インキと同様に、表１の配合にてＣ．Ｉ．ピグメントレッド８１（不二化成（株）製ファナルローズＲＮＮ−Ｐ）を用い、紅のベースインキ２を得た。次いで、ベースインキ２に対して、表２の配合で植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し紅インキ２を得た。
インキ実施例（紅インキ）
表１の配合にてＣ．Ｉ．ピグメントレッド１６９（ＢＡＳＦ製FanalPink D 4810）をワニス、石油系溶剤と混合し、分散粒子系測定機（グラインドメーター）で７．５ミクロン以下になるまで練肉、紅のベースインキ３を得た。次いで、このベースインキ３に対して、表２の配合で植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し紅インキ３を得た。
インキ実施例（紅インキ）
表１の配合にて作成したベースインキ２及びベースインキ３を表２の配合にて混合後、更に植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し紅インキ４を得た。
インキ実施例(藍インキ)
表１の配合にて、Ｃ．Ｉ．ピグメントブルー１５：３（東洋インキ製造（株）製ＬＩＯＮＯＬ ＢＬＵＥ ＧＬＡ−ＳＤ）をワニス、石油系溶剤と混合し、分散粒子系測定機（グラインドメーター）で７．５ミクロン以下になるまで練肉、藍のベースインキ４を得た。また、別途表１の配合にてＣ．Ｉ．ピグメントグリーン７（東洋インキ製造（株）製ＬＩＯＮＯＬ ＧＲＥＥＮ ＹＳ−２Ａ）をワニス、石油系溶剤と混合し、分散粒子系測定機（グラインドメーター）で７．５ミクロン以下になるまで練肉したベースインキ５を用い、表２の配合にて上記藍ベースインキ４とベースインキ５とを混合後、更に植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し、藍インキ５を得た。
インキ比較例（黄インキ）
表１のような配合にてＣ．Ｉ．ピグメントイエロー１２（東洋インキ製造（株）製ＬＩＯＮＯＬ ＹＥＬＬＯＷ １２２９−Ｐ）をニーダー中で温度７５℃の条件下、ワニスを徐々に添加して混練して一次脱水を行った。次にニーダー温度１００℃〜１２０℃、減圧度７６ｍｍＨｇの条件下で１時間バキュームし、ベースインキ中の水分を０．５％以下になるように二次脱水を行った。脱水後、残りのワニス、石油系溶剤を添加して混練して希釈し、ニーダーより未分散ベースインキを取り出した。取り出したベースインキをロール温度６０℃の３本ロールを用いて、分散粒子系測定機（グラインドメーター）で７．５ミクロン以下になるまで練肉し、黄のベースインキ６を得た。次いで、ベースインキ６に対して、表２の配合でワニス、植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し黄インキ６を得た。
インキ比較例（紅インキ）
黄インキと同様に、表１の配合にてＣ．Ｉ．ピグメントレッド５７：１（東洋インキ製造（株）製ＬＩＯＮＯＬ ＲＥＤ ６Ｂ ４２４０−Ｐ）を用い、紅のベースインキ７を得た。次いで、ベースインキ７に対して、表２の配合で植物油、石油系溶剤、コンパウンド、金属ドライヤー、乾燥抑制剤を添加し紅インキ７を得た。
黄インキの透明性の評価については、以下の試験法で評価した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited to these description Example. In addition, the part of the following description represents a weight part and% represents weight%.
Example of production of rosin-modified phenolic resin To a four-necked flask equipped with a stirrer, a cooler and a thermometer, 1000 parts of P-octylphenol, 850 parts of 35% formalin, 60 parts of 93% sodium hydroxide, 1000 parts of toluene, The reaction was carried out at 90 ° C. for 6 hours. Then, 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 resole type phenol resin having a nonvolatile content of 49%. It was.
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer was charged with 1000 parts of gum rosin, dissolved at 200 ° C. while blowing nitrogen gas, and 1800 parts of the resole solution produced above was added. After reacting at 230 ° C. for 4 hours while removing toluene, 110 parts of glycerin was added, and reacted at 260 ° C. for 10 hours, with an acid value of 20 or less, a weight average molecular weight of 50000, Shin Nippon Petrochemical Co., Ltd. AF Solvent 6 A rosin-modified phenol resin having a cloudiness temperature of 90 ° C. was obtained.
Varnish production example 45 parts of rosin modified phenolic resin, 40 parts of soybean oil, 14 parts of AF Solvent No. 6 (solvent manufactured by Shin Nippon Petrochemical Co., Ltd.), 1.0 part of ALCH (gelator manufactured by Kawaken Fine Chemicals Co., Ltd.) Was heated and stirred at 190 ° C. for 1 hour to obtain a varnish.
Ink example (yellow ink)
In the formulation shown in Table 1, C.I. I. Pigment Yellow 12 (LIONOL YELLOW 1235-P manufactured by Toyo Ink Manufacturing Co., Ltd.) was subjected to primary dehydration by gradually adding varnish and kneading in a kneader at a temperature of 75 ° C. Next, vacuum dehydration was performed for 1 hour under conditions of a kneader temperature of 100 ° C. to 120 ° C. and a degree of vacuum of 76 mmHg, and secondary dehydration was performed so that the water content in the base ink was 0.5% or less. After dehydration, the remaining varnish and petroleum solvent were added, kneaded and diluted, and the undispersed base ink was taken out from the kneader. The extracted base ink was kneaded using a three roll with a roll temperature of 60 ° C. with a dispersed particle measuring machine (grind meter) to 7.5 μm or less to obtain yellow base ink 1. Next, varnish, vegetable oil, petroleum-based solvent, compound, metal dryer, and drying inhibitor were added to the base ink 1 according to the formulation shown in Table 2 to obtain yellow ink 1.
Ink Example (Red ink)
As with the yellow ink, C.I. I. A red base ink 2 was obtained using Pigment Red 81 (Funal Rose RNN-P manufactured by Fuji Kasei Co., Ltd.). Next, vegetable ink, petroleum solvent, compound, metal dryer, and drying inhibitor were added to the base ink 2 in the formulation shown in Table 2 to obtain red ink 2.
Ink Example (Red ink)
In the formulation of Table 1, C.I. I. Pigment Red 169 (FanalPink D 4810 manufactured by BASF) was mixed with varnish and petroleum solvent, and kneaded meat and red base ink 3 was obtained until the particle size became 7.5 microns or less with a dispersion particle system measuring machine (grind meter). Next, to this base ink 3, vegetable oil, petroleum solvent, compound, metal dryer, and drying inhibitor were added according to the formulation shown in Table 2 to obtain red ink 3.
Ink Example (Red ink)
After mixing the base ink 2 and the base ink 3 prepared according to the formulation of Table 1 with the formulation of Table 2, vegetable oil, petroleum solvent, compound, metal dryer, and drying inhibitor were further added to obtain a red ink 4.
Ink Example (Indigo Ink)
In the formulation of Table 1, C.I. I. Pigment Blue 15: 3 (LIONOL BLUE GLA-SD manufactured by Toyo Ink Mfg. Co., Ltd.) is mixed with varnish and petroleum solvent, and the meat paste is mixed with a dispersion particle measuring machine (grind meter) to 7.5 microns or less. An indigo base ink 4 was obtained. In addition, C.I. I. Pigment Green 7 (LIONOL GREEN YS-2A manufactured by Toyo Ink Manufacturing Co., Ltd.) was mixed with varnish and petroleum solvent, and the base ink was kneaded to 7.5 microns or less with a dispersed particle system measuring machine (grind meter) The indigo base ink 4 and the base ink 5 were mixed in the formulation shown in Table 2, and then vegetable oil, petroleum solvent, compound, metal dryer, and drying inhibitor were added to obtain indigo ink 5.
Ink comparison example (yellow ink)
In the formulation shown in Table 1, C.I. I. Pigment Yellow 12 (LIONOL YELLOW 1229-P manufactured by Toyo Ink Manufacturing Co., Ltd.) was subjected to primary dehydration by gradually adding varnish and kneading in a kneader at a temperature of 75 ° C. Next, vacuum dehydration was performed for 1 hour under conditions of a kneader temperature of 100 ° C. to 120 ° C. and a degree of vacuum of 76 mmHg, and secondary dehydration was performed so that the water content in the base ink was 0.5% or less. After dehydration, the remaining varnish and petroleum solvent were added, kneaded and diluted, and the undispersed base ink was taken out from the kneader. The taken out base ink was kneaded with a three-roll having a roll temperature of 60 ° C. with a dispersed particle measuring machine (grind meter) until it became 7.5 μm or less, and yellow base ink 6 was obtained. Next, varnish, vegetable oil, petroleum solvent, compound, metal dryer, and drying inhibitor were added to the base ink 6 according to the formulation shown in Table 2 to obtain yellow ink 6.
Ink comparison example (red ink)
As with the yellow ink, C.I. I. Red base ink 7 was obtained using CI Pigment Red 57: 1 (LIONOL RED 6B 4240-P manufactured by Toyo Ink Manufacturing Co., Ltd.). Next, vegetable ink, petroleum solvent, compound, metal dryer, and drying inhibitor were added to the base ink 7 in the formulation shown in Table 2 to obtain red ink 7.
The transparency of yellow ink was evaluated by the following test method.
濃度値１．８５〜１．９０の範囲内で印刷した墨インキ上に、濃度１．４０〜２．１０の範囲で黄インキを刷り重ねし、Ｌ*を測定した。結果を表４に示す。
実施例の黄インキは、濃度値を２．２０まで上げてもＬ*が１７を越えず、下刷りの墨インキに影響を与え難く、透明性に優れているといえる（Ｌ*は値が小さいほど黒く、大きくなるほど白くなることを示している）。
一方、比較例はＬ*が高く、上刷りの黄インキが不透明であるために下刷りの墨インキの黒さを阻害してしまっていることがわかる。
印刷評価試験
上記実施例及び比較例のインキについて、下記印刷条件の下、黄、紅、藍の各ベタ濃度値を、黄：１．４０〜１．４４、紅：１．５２〜１．５６、藍：１．６３〜１．６７の範囲内で印刷し、印刷物の評価を実施した。尚、墨インキは、一般的な酸化重合型平版印刷インキを使用し、濃度値１．８５〜１．９０の範囲内で印刷した。
Yellow ink was overprinted at a density of 1.40 to 2.10 on the black ink printed within a density value range of 1.85 to 1.90, and L * was measured. The results are shown in Table 4.
The yellow ink of the example does not exceed L * even when the density value is increased to 2.20, hardly affects the black ink of the underprint, and can be said to have excellent transparency (L * has a value) The smaller the color, the more black it is, and the larger the color, the whiter it is).
On the other hand, L * is high in the comparative example, and it can be seen that the black ink of the underprinted ink is hindered because the yellow ink of the overprinted is opaque.
Printing Evaluation Test With respect to the inks of the above Examples and Comparative Examples, yellow, red, and indigo solid density values under the following printing conditions are yellow: 1.40 to 1.44, red: 1.52 to 1.56. , Indigo: Printing was performed within the range of 1.63 to 1.67, and the printed matter was evaluated. The black ink was printed using a general oxidation polymerization type lithographic printing ink within a density value range of 1.85 to 1.90.
印刷条件
印刷機 ：ハイデルベルグスピードマスター 菊全４色機（ハイデルベルグジャパン（株））
用紙 ：特菱アート両面 １１０Ｋｇ（三菱製紙（株））
湿し水 ：アストロマーク３（（株）日研化学研究所）２．０％水道水溶液
印刷速度：１００００枚／時
印刷物測定条件
濃度 ：グレタグマクベスＤ１９６にて印刷物の単色（黄、紅、藍、墨）ベタ部の濃度値を測定
測色 ：Ｘ−Ｒｉｔｅ９３８にて印刷物の単色ベタ部（黄、紅、藍）、及び、単色ベタ刷 り重ね部（黄×紅、紅×藍、藍×黄）のＬ*、ａ*、ｂ*値を測定。
Printing conditions Printing machine: Heidelberg Speedmaster Kikuzen 4-color machine (Heidelberg Japan Ltd.)
Paper: Tokishi Art Double Sided 110Kg (Mitsubishi Paper Co., Ltd.)
Dampening water: Astro Mark 3 (Niken Chemical Laboratory, Inc.) 2.0% tap water printing speed: 10,000 sheets / hour
Measurement conditions for printed matter: Density: Measure the density value of solid color (yellow, red, indigo, black) on printed matter with Gretag Macbeth D196. Colorimetry: Monochromatic solid portion (yellow, red, indigo) on printed matter with X-Rite938 In addition, L *, a *, and b * values of the single-color solid-printed portion (yellow x red, red x indigo, indigo x yellow) were measured.
Ｃ値はａ*及びｂ*から下記の計算式にて求めた。 The C value was determined from the following formula using a * and b *.
結果を表３に示す。比較例と比べて参考実施例１、２及び実施例３ともＣ値が大きく、印刷物の彩度が高い。また、ａ*を横軸、ｂ*縦軸とした2次元空間に、各ａ*、ｂ*値をプロットし、２次元のガモットで比較した結果、参考実施例１、２及び実施例３の色再現領域が広いことがわかる（表５）。
The results are shown in Table 3. Compared to comparative examples Reference Examples 1, 2 and Example 3 both C value is large, a high saturation of the printed matter. In addition, as a result of plotting each a * and b * value in a two-dimensional space with a * as the horizontal axis and b * vertical axis, and comparing with two-dimensional gamut, the results of Reference Examples 1, 2, and Example 3 were obtained. It can be seen that the color reproduction region is wide (Table 5).
Claims (4)
（ａ）４００ｎｍ〜７００ｎｍの波長領域において、最大反射率を１００％としたときに、４００ｎｍ〜４８０ｎｍの波長領域が１〜２０％、５３０ｎｍ〜７００ｎｍの波長領域での反射率が９０〜１００％の反射スペクトルを有することを特徴とする黄色相化合物をインキの全重量に対して５〜１５重量％含有する黄インキ。
（ｂ）４００ｎｍ〜７００ｎｍの波長領域において、最大反射率を１００％としたときに、４００ｎｍ〜５００ｎｍの波長領域での最大反射率が５０％〜１００％、５００ｎｍ〜５６０ｎｍの波長領域での反射率が１〜２０％、６３０ｎｍ〜７００ｎｍの反射率が９０％〜１００％の反射スペクトルを有することを特徴とする紅色相化合物をインキの全重量に対して１５〜３０重量％含有する紅インキ。
（ｃ）４００ｎｍ〜７００ｎｍの波長領域において、最大反射率を１００％としたときに、４００ｎｍ〜５３０ｎｍの波長領域の反射率が５０〜１００％、６００ｎｍ〜７００ｎｍの反射率が１〜３０％の反射スペクトルを有することを特徴とする藍色相化合物をインキの全重量に対して１０〜２５重量％含有する藍インキ。 In lithographic printing using yellow ink and / or indigo ink, and red ink and black ink, CI pigment red 169 is included as the red ink, and (a) yellow, (b) red, (c) indigo The lithographic ink set according to claim 1, wherein the reflectance of the lithographic ink is as follows.
(A) In the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the wavelength region of 400 nm to 480 nm is 1 to 20%, and the reflectance in the wavelength region of 530 nm to 700 nm is 90 to 100%. A yellow ink containing 5 to 15% by weight of a yellow phase compound having a reflection spectrum with respect to the total weight of the ink.
(B) In the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the maximum reflectance in the wavelength region of 400 nm to 500 nm is 50% to 100%, and the reflectance in the wavelength region of 500 nm to 560 nm. A red ink containing 15 to 30% by weight of a red hue compound having a reflection spectrum of 1 to 20%, a reflectance of 630 nm to 700 nm and a reflectance spectrum of 90% to 100% based on the total weight of the ink.
(C) In the wavelength region of 400 nm to 700 nm, when the maximum reflectance is 100%, the reflectance in the wavelength region of 400 nm to 530 nm is 50 to 100%, and the reflectance of 600 nm to 700 nm is 1 to 30%. An indigo ink containing 10 to 25% by weight of an indigo hue compound having a spectrum with respect to the total weight of the ink.
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