JP2015187231A - Aqueous inkjet ink for plate making and method of making lithographic plate for lithography - Google Patents
Aqueous inkjet ink for plate making and method of making lithographic plate for lithography Download PDFInfo
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- JP2015187231A JP2015187231A JP2014065095A JP2014065095A JP2015187231A JP 2015187231 A JP2015187231 A JP 2015187231A JP 2014065095 A JP2014065095 A JP 2014065095A JP 2014065095 A JP2014065095 A JP 2014065095A JP 2015187231 A JP2015187231 A JP 2015187231A
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- Prior art keywords
- ink
- water
- plate
- printing
- weight
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- 238000001459 lithography Methods 0.000 title abstract 5
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- YQEHHPFEQLDFCN-UHFFFAOYSA-K trisodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].Oc1c(N=Nc2ccccc2S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O YQEHHPFEQLDFCN-UHFFFAOYSA-K 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、平版印刷用原版に直接インクジェット印刷を行うことで、高精細かつ高耐刷性を有する平版印刷用刷版を作成可能な製版用水性インクジェットインキ、およびそれを用いた平版印刷用刷版の製版方法に関する。
The present invention relates to a water-based inkjet ink for plate making capable of producing a lithographic printing plate having high definition and high printing durability by directly performing inkjet printing on a lithographic printing original plate, and a lithographic printing plate using the same. It relates to a plate making method.
平版印刷用刷版は、印刷時に平版印刷用インキが付着する疎水性の画線部と湿し水が付着する親水性の非画線部からなる。平版印刷はインキと湿し水が反発することを利用して、画線部に付着したインキを紙などの印刷媒体に転写する方法である。平版印刷用刷版は親水性の支持体上に疎水性の画線部を形成することで得られる。 The lithographic printing plate comprises a hydrophobic image area to which lithographic ink adheres and a hydrophilic non-image area to which dampening water adheres during printing. Lithographic printing is a method of transferring ink adhering to an image area to a printing medium such as paper by utilizing the repulsion of ink and fountain solution. A lithographic printing plate can be obtained by forming a hydrophobic image area on a hydrophilic support.
平版印刷用刷版を製造することを製版と称するが、現在の製版方法はCTP方式が主流である。これは親水性の支持体上に疎水性の感光性樹脂層を設けたPS版と呼ばれる平版印刷用原版に対して、レーザーを用いて画線部を感光させ、その後、現像処理により未露光の非画線部の樹脂層を除去することで製版する方法である。CTP方式は非常に精細な刷版をデジタルデータから容易に作成することができる方式であるが、現像工程を必要とするためこの時に使用する現像液の廃液が環境に与える影響への懸念もある。 The production of a lithographic printing plate is called plate making, but the current plate making method is mainly the CTP method. This is because the image area is exposed using a laser to a lithographic printing plate called PS plate having a hydrophobic photosensitive resin layer provided on a hydrophilic support, and then unexposed by development processing. This is a method for making a plate by removing the resin layer in the non-image area. The CTP method is a method that makes it possible to easily create a very fine plate from digital data. However, since it requires a development process, there is a concern about the environmental impact of the waste liquid of the developer used at this time. .
そこで現像工程を必要としない製版方式が開発されており、その中の一つがインクジェット方式である。インクジェット方式では親水性の原版に画線部を印刷して、疎水性の画線部、親水性の非画線部を形成する方法である。使用するインキとしてはインキ中に含有する疎水性の樹脂を利用した水性インキ(特許文献1)、油性インキ(特許文献2)や印刷後にUV硬化により疎水性樹脂を形成するUVインキ(特許文献3)などがある。 Therefore, a plate making method that does not require a development process has been developed, and one of them is an ink jet method. The inkjet method is a method in which an image area is printed on a hydrophilic original plate to form a hydrophobic image area and a hydrophilic non-image area. As the ink to be used, water-based ink using a hydrophobic resin contained in the ink (Patent Document 1), oil-based ink (Patent Document 2) and UV ink that forms a hydrophobic resin by UV curing after printing (Patent Document 3) )and so on.
中でも環境への影響の面から水性インキによる製版方法が注目されている。例えば特許文献4では最低造膜温度が40℃以上の樹脂微粒子を使用した水性インキを使用した製版方法が開示されている。この方法では十分に加熱を行った原版上へ印刷することで高い耐刷性を発揮することが可能とある。しかし、原版を加熱する必要があることから、印刷時にインクジェットヘッドのノズル周辺のインキが乾燥し、ノズル欠損が生じる懸念がある。また、描画性に関する記述もなく、十分な品質の刷版を得ることは困難であった。 In particular, a plate making method using water-based ink has attracted attention from the viewpoint of environmental impact. For example, Patent Document 4 discloses a plate making method using water-based ink using resin fine particles having a minimum film forming temperature of 40 ° C. or higher. In this method, it is possible to exhibit high printing durability by printing on a sufficiently heated original plate. However, since it is necessary to heat the original plate, there is a concern that the ink around the nozzles of the inkjet head dries at the time of printing, and nozzle defects occur. In addition, there is no description about drawability, and it has been difficult to obtain a sufficiently high quality printing plate.
本発明の目的は、平版印刷用原版に直接インクジェット印刷を行うことで、高精細かつ高耐刷性を有する平版印刷用刷版を作成可能な製版用水性インクジェットインキ、およびそれを用いた平版印刷用刷版の製版方法を提供することにある。 An object of the present invention is to provide a water-based inkjet ink for plate making capable of producing a lithographic printing plate having high definition and high printing durability by directly performing inkjet printing on a lithographic printing original plate, and lithographic printing using the same. It is to provide a plate making method of a printing plate.
少なくとも着色剤と水分散性樹脂微粒子と有機溶剤と水とを含む平版印刷用刷版の製版に使用される水性インクジェットインキであって、前記有機溶剤として炭素数4以上10以下の1,2-アルカンジオールをインキ中に5重量%以上50重量%以下含むことを特徴とする製版用水性インクジェットインキに関する。 An aqueous inkjet ink used for plate making of a lithographic printing plate comprising at least a colorant, water-dispersible resin fine particles, an organic solvent and water, wherein the organic solvent is a 1,2-carbon having a carbon number of 4 or more and 10 or less The present invention relates to a water-based inkjet ink for plate making, which contains alkanediol in an ink in an amount of 5 wt% to 50 wt%.
また、本発明は、1,2-アルカンジオールとして1,2-ヘキサンジオールを含むことを特徴とする上記製版用水性インクジェットインキに関する。 The present invention also relates to the water-based inkjet ink for plate making described above, which comprises 1,2-hexanediol as 1,2-alkanediol.
また、本発明は、水分散性樹脂微粒子と着色剤のインキ中の配合重量比[水分散性樹脂微粒子/着色剤]が5以上1000以下であることを特徴とする上記製版用水性インクジェットインキに関する。 The present invention also relates to the aqueous inkjet ink for plate making described above, wherein the mixing weight ratio [water-dispersible resin fine particles / colorant] in the ink of the water-dispersible resin fine particles and the colorant is 5 or more and 1000 or less. .
また、本発明は、インキ中に配合される固形分量が5重量%以上20重量%以下であることを特徴とする上記製版用水性インクジェットインキに関する。 The present invention also relates to the above-mentioned water-based inkjet ink for plate making, wherein the solid content in the ink is 5% by weight or more and 20% by weight or less.
また、本発明は、水分散性樹脂微粒子のガラス転移温度(Tg)が60℃以上120℃以下であることを特徴とする上記製版用水性インクジェットインキに関する。 The present invention also relates to the water-based inkjet ink for plate making described above, wherein the water-dispersible resin fine particles have a glass transition temperature (Tg) of 60 ° C. or higher and 120 ° C. or lower.
また、本発明は、さらにシリコン系界面活性剤を含むことを特徴とする上記製版用水性インクジェットインキに関する。 The present invention also relates to the water-based inkjet ink for plate making, further comprising a silicon-based surfactant.
また、本発明は、上記製版用水性インクジェットインキを使用し、親水性表面を有する平版印刷用原版へインクジェット印刷を行い、疎水性の画線部を形成することを特徴とした平版印刷用刷版の製版方法に関する。 Further, the present invention provides a printing plate for lithographic printing, which uses the above-described aqueous inkjet ink for plate making, performs inkjet printing on a lithographic printing original plate having a hydrophilic surface, and forms a hydrophobic image portion. Relates to the plate making method.
また、本発明は、平版印刷用原版へ印刷を行った後、100℃以上250℃以下に印刷された原版を加熱することを特徴とした上記平版印刷用刷版の製版方法に関する。 The present invention also relates to a method for making a lithographic printing plate as described above, wherein the lithographic printing plate is heated to 100 ° C. or more and 250 ° C. or less after printing on the lithographic printing plate.
本発明により、平版印刷用原版に直接インクジェット印刷を行うことで、高精細かつ高耐刷性を有する平版印刷用刷版を作成可能な製版用水性インクジェットインキ、およびそれを用いた平版印刷用刷版の製版方法を提供することが可能となった。
According to the present invention, an aqueous inkjet ink for plate making capable of producing a lithographic printing plate having high definition and high printing durability by performing inkjet printing directly on a lithographic printing original plate, and a lithographic printing using the same It became possible to provide plate making methods.
本発明の刷版用水性インクジェットインキは少なくとも着色剤と水分散性樹脂微粒子と有機溶剤と水とを含み、有機溶剤として炭素数4以上10以下の1,2-アルカンジオールをインキ中に5重量%以上50重量%以下含むことを特徴する。以下、本発明のインキの成分について詳細に説明する。 The water-based inkjet ink for printing plates of the present invention contains at least a colorant, water-dispersible resin fine particles, an organic solvent, and water, and 5 wt.% Of 1,2-alkanediol having 4 to 10 carbon atoms as the organic solvent. It is characterized by containing from 50% to 50% by weight. Hereinafter, the components of the ink of the present invention will be described in detail.
(着色剤)
本発明では刷版の画線部を識別するために着色剤を使用する。着色剤としては、例えば、染料、顔料等が挙げられる。これらの着色剤は1種類を単独で使用してもよく、2種類以上を併用してもよい。刷版の体制を向上させるためにも顔料を使用することが好ましい。刷版の画線部の識別が可能であれば着色剤の含有量は特に制限されないが、着色剤の含有量としてはインキの全量に対して0.1重量%以上5重量%以下、好ましくは0.2重量%以上3重量%以下、より好ましくは0.3重量%以上2重量%以下、最も好ましくは0.5重量%以上1.5重量%以下である。
(Colorant)
In the present invention, a colorant is used to identify the image area of the printing plate. Examples of the colorant include dyes and pigments. These colorants may be used alone or in combination of two or more. In order to improve the system of the printing plate, it is preferable to use a pigment. The content of the colorant is not particularly limited as long as the image area of the printing plate can be identified, but the content of the colorant is 0.1% by weight or more and 5% by weight or less, preferably 0.2% by weight with respect to the total amount of the ink. % To 3% by weight, more preferably 0.3% to 2% by weight, and most preferably 0.5% to 1.5% by weight.
染料を使用する場合には、直接染料、酸性染料、食用染料、塩基性染料、反応性染料、分散染料、建染染料等の通常インクジェット記録に使用する各種染料を使用することができる。 In the case of using a dye, various dyes usually used for ink jet recording, such as a direct dye, an acid dye, a food dye, a basic dye, a reactive dye, a disperse dye, and a vat dye, can be used.
更に詳しくは、シアン染料としてはC. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90, 92, 93, 100, 012, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234, 236, 249, C. I. Direct Blue 1,2, 6, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, C. I. Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33, 34,37, 38, 39, 40, 41, 43, 44, 46, C. I. Food Blue 1, 2, C. I. Basic Blue 9, 25,28, 29, 44等が挙げられる。 More specifically, CI Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78 are used as cyan dyes. , 80, 82, 83, 90, 92, 93, 100, 012, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154 , 158, 161, 166, 167, 168, 170, 171, 182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234, 236, 249, CI Direct Blue 1,2, 6, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 87, 90, 98, 106, 108, 120, 123, 158, 160, 163, 165, 168, 192, 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, CI Reactive Blue 1, 2, 3, 4, 5, 7, 8, 9, 13 , 14, 15, 17, 18, 19, 20, 21, 25, 26, 27, 28, 29, 31, 32, 33, 34,37, 38, 39, 40, 41, 43, 44, 46, CI Food Blue 1, 2, CI Basic Blue 9, 25, 28, 29, 44 and the like.
マゼンタ染料としてはC. I. Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 51, 52, 57, 75, 77, 80, 82, 85, 87, 88, 89, 92, 94, 97, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 180, 183, 184, 186, 194, 198, 209, 211, 215, 219, 249, 252, 254, 262, 265, 274, 282, 289, 303, 317, 320, 321, 322, C. I. Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, 231, C. I. Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32, 33, 34,35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46, 49, 50, 58, 59, 63, 64, C. I. Food Red 7, 9, 14等が挙げられる。 CI Acid Red 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 51, 52, 57, 75, 77, 80, 82, 85, 87 as magenta dye , 88, 89, 92, 94, 97, 106, 111, 114, 115, 117, 118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168, 180 , 183, 184, 186, 194, 198, 209, 211, 215, 219, 249, 252, 254, 262, 265, 274, 282, 289, 303, 317, 320, 321, 322, CI Direct Red 1, 2, 4, 9, 11, 13, 17, 20, 23, 24, 28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99, 113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, 231, CI Reactive Red 1, 2, 3, 4, 5, 6, 7, 8, 11 , 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 24, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42 , 43, 45, 46, 49, 50, 58, 59, 63, 64, CI Food Red 7, 9, 14 and the like.
イエロー染料としてはC. I. Acid Yellow 1, 3, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 70, 72, 75, 76, 78, 79, 98, 99, 110, 111, 127, 131, 135, 142, 162, 164, 165, C. I. Direct Yellow 1, 8, 11, 12, 24, 26, 27, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 110, 132, 142, 144, Reactive Yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37, 42, C. I. Food Yellow 3, 4等が挙げられる。 CI Acid Yellow 1, 3, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 70, 72, 75, 76, 78, 79 , 98, 99, 110, 111, 127, 131, 135, 142, 162, 164, 165, CI Direct Yellow 1, 8, 11, 12, 24, 26, 27, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 110, 132, 142, 144, Reactive Yellow 1, 2, 3, 4, 6, 7, 11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 37, 42, CI Food Yellow 3, 4 and the like.
ブラック染料としてはC. I. Direct Black 1, 7, 19, 32, 51, 71, 108, 146, 154, 166等が挙げられる。 Examples of black dyes include C. I. Direct Black 1, 7, 19, 32, 51, 71, 108, 146, 154, 166 and the like.
シアン、マゼンタ、イエロー、ブラック以外の染料としてはC. I. Acid Green 7, 12, 25, 27, 35, 36, 40, 43, 44, 65, 79, C. I. Direct Green 1, 6, 8, 26, 28, 30, 31, 37, 59, 63, 64, C. I. Reactive Green 6, 7, C. I. Direct Violet 2, 48, 63, 90, C. I. Reactive Violet 1, 5, 9, 10等が挙げられる。 CI Acid Green 7, 12, 25, 27, 35, 36, 40, 43, 44, 65, 79, CI Direct Green 1, 6, 8, 26, 28, as dyes other than cyan, magenta, yellow and black 30, 31, 37, 59, 63, 64, CI Reactive Green 6, 7, CI Direct Violet 2, 48, 63, 90, CI Reactive Violet 1, 5, 9, 10, etc.
顔料を使用する場合には、無機顔料、有機顔料の何れも使用することができる。無機顔料としては、酸化チタン、亜鉛華、硫化亜鉛、鉛白、炭酸カルシウム、沈降性硫酸バリウム、ホワイトカーボン、アルミナホワイト、カオリンクレー、タルク、ベントナイト、黒色酸化鉄、カドミウムレッド、べんがら、モリブデンレッド、モリブデートオレンジ、クロムバーミリオン、黄鉛、カドミウムイエロー、黄色酸化鉄、チタンイエロー、酸化クロム、ビリジアン、チタンコバルトグリーン、コバルトグリーン、コバルトクロムグリーン、ビクトリアグリーン、 群青、紺青、コバルトブルー、セルリアンブルー、コバルトシリカブルー、コバルト亜鉛シリカブルー、マンガンバイオレット、コバルトバイオレット等を 挙げることができる。 When a pigment is used, either an inorganic pigment or an organic pigment can be used. Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, brown rice, molybdenum red, Molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, bituminous, cobalt blue, cerulean blue, Examples thereof include cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.
有機顔料としてはアゾ顔料、フタロシアニン顔料、アントラキノン顔料、キナクリドン顔料、イソインドリノン顔料、キノフタロン顔料、染料レーキ顔料、蛍光顔料等が挙げられる。 Examples of organic pigments include azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, dye lake pigments, and fluorescent pigments.
更に詳しくは、シアン顔料としてはC. I. Pigment Blue 1, 2, 3, 15:1, 15:3, 15:4, 15:6, 16, 21, 22, 60, 64等が挙げられる。マゼンタ顔料としてはC. I. Pigment Red 5, 7, 9, 12, 31, 48, 49, 52, 53, 57, 97, 112, 120, 122, 146, 147, 149, 150, 168, 170, 177, 178, 179, 184, 188, 202, 206, 207, 209, 238, 242, 254, 255, 264, 269, 282、C. I. Pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 40, 50等が挙げられる。イエロー顔料としてはC. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213等が挙げられる。 More specifically, examples of cyan pigments include C. I. Pigment Blue 1, 2, 3, 15: 1, 15: 3, 15: 4, 15: 6, 16, 21, 22, 60, 64 and the like. CI Pigment Red 5, 7, 9, 12, 31, 48, 49, 52, 53, 57, 97, 112, 120, 122, 146, 147, 149, 150, 168, 170, 177, 178 as magenta pigments , 179, 184, 188, 202, 206, 207, 209, 238, 242, 254, 255, 264, 269, 282, CI Pigment Violet 19, 23, 29, 30, 32, 36, 37, 38, 40, 50 etc. are mentioned. CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128 , 129, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213 and the like.
ブラック顔料としては、ファーネス法、チャネル法で製造されたカーボンブラックが挙げられる。例えば、これらのカーボンブラックであって、一次粒子径が11〜40nm、BET法による比表面積が50〜400m2/g、揮発分が0.5〜10%、pH値が2〜10等の特性を有するものが好適である。このような特性を有する市販品としては下記のものが挙げられる。例えば、No.33、40、45、52、900、2200B、2300、MA7、MA8、MCF88（以上、三菱化学製）、RAVEN1255（コロンビアンカーボン製）、REGA330R、400R、660R、MOGUL L、ELFTEX415（以上、キャボット製）、Nipex90、Nipex150T、Nipex160IQ、Nipex170IQ、Nipex75、Printex85、Printex95、Printex90、Printex35、PrintexU（以上、エボニックデグサ製）等があり、何れも好ましく使用することができる。 Examples of the black pigment include carbon black produced by the furnace method and the channel method. For example, these carbon blacks have a primary particle size of 11 to 40 nm, a specific surface area by BET method of 50 to 400 m2 / g, a volatile content of 0.5 to 10%, a pH value of 2 to 10, etc. Is preferred. The following are mentioned as a commercial item which has such a characteristic. For example, No.33, 40, 45, 52, 900, 2200B, 2300, MA7, MA8, MCF88 (Mitsubishi Chemical), RAVEN1255 (Colombian Carbon), REGA330R, 400R, 660R, MOGUL L, ELFTEX415 ( As described above, manufactured by Cabot), Nipex90, Nipex150T, Nipex160IQ, Nipex170IQ, Nipex75, Printex85, Printex95, Printex90, Printex35, PrintexU (above, manufactured by Evonik Degussa) and the like can be preferably used.
シアン、マゼンタ、イエロー、ブラック以外の顔料としてはC. I. Pigment Green 7, 10, 36、C. I. Pigment Brown 3, 5, 25, 26、C. I. Pigment Orange 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 62, 63, 64, 71等が挙げられる。 CI Pigment Green 7, 10, 36, CI Pigment Brown 3, 5, 25, 26, CI Pigment Orange 2, 5, 7, 13, 14, 15, 16, 24 other than cyan, magenta, yellow, and black , 34, 36, 38, 40, 43, 62, 63, 64, 71 and the like.
これらの顔料を使用する場合には長期間のインキ安定性を維持するためにも、インキ媒体中に分散して使用することが好ましい。顔料の分散方法としては、顔料を酸化処理等により表面改質し、分散剤なしで顔料を分散させる方法や、界面活性剤や樹脂を分散剤として顔料を分散させる方法がある。より安定なインキとするためにも分散樹脂を使用して顔料を分散させることが好ましい。 When these pigments are used, it is preferable to use them dispersed in an ink medium in order to maintain long-term ink stability. As a method for dispersing the pigment, there are a method in which the pigment is surface-modified by oxidation treatment or the like and the pigment is dispersed without a dispersant, and a method in which the pigment is dispersed using a surfactant or resin as a dispersant. In order to obtain a more stable ink, it is preferable to disperse the pigment using a dispersion resin.
顔料分散樹脂としてはアクリル樹脂、スチレンアクリル樹脂、マレイン酸樹脂、スチレンマレイン酸樹脂、αオレフィンマレイン酸樹脂、ウレタン樹脂、エステル樹脂等が挙げられる。なかでもアクリル樹脂、スチレンアクリル樹脂を使用することが好ましい。 Examples of the pigment dispersion resin include an acrylic resin, a styrene acrylic resin, a maleic acid resin, a styrene maleic resin, an α-olefin maleic resin, a urethane resin, and an ester resin. Among these, it is preferable to use an acrylic resin or a styrene acrylic resin.
顔料分散樹脂の酸価は50mgKOH/g以上400mgKOH/g以下であることが顔料分散の安定性、インクジェット適性の面から好ましい。酸価が50mgKOH/g以上であると樹脂が水に対し十分に溶解し、インキ粘度を低く保ち、安定な吐出を実現できる。また、400mgKOH/g以下であると顔料-樹脂間の相互作用が樹脂同士や樹脂-水間の相互作用よりも十分に強くなり、分散を良化させ、インキの安定性を保つことができる。顔料分散樹脂の酸価は、より好ましくは100 mgKOH/g以上350mgKOH/g以下であり、更に好ましくは150 mgKOH/g以上300mgKOH/g以下である。 The acid value of the pigment dispersion resin is preferably 50 mgKOH / g or more and 400 mgKOH / g or less from the viewpoint of pigment dispersion stability and ink jet suitability. When the acid value is 50 mgKOH / g or more, the resin is sufficiently dissolved in water, the ink viscosity is kept low, and stable ejection can be realized. Further, if it is 400 mgKOH / g or less, the interaction between the pigment and the resin becomes sufficiently stronger than the interaction between the resins and between the resin and water, the dispersion can be improved, and the stability of the ink can be maintained. The acid value of the pigment-dispersed resin is more preferably from 100 mgKOH / g to 350 mgKOH / g, still more preferably from 150 mgKOH / g to 300 mgKOH / g.
顔料分散樹脂の重量平均分子量は5000以上100000以下であることが好ましい。重量平均分子量5000以上であると分散安定性が良化し、重量平均分子量100000以下であると吐出安定性が良化する。より好ましくは重量平均分子量10000以上50000以下であり、更に好ましくは重量平均分子量15000以上30000以下である。 The weight average molecular weight of the pigment dispersion resin is preferably 5000 or more and 100000 or less. When the weight average molecular weight is 5000 or more, the dispersion stability is improved, and when the weight average molecular weight is 100000 or less, the discharge stability is improved. More preferably, the weight average molecular weight is 10000 or more and 50000 or less, and further preferably the weight average molecular weight is 15000 or more and 30000 or less.
顔料と顔料分散樹脂の重量比率は2/1以上100/1以下であることが好ましい。顔料分散樹脂の重量比率が2/1以上であるとインキの粘度を低く抑えることができる。また、100/1以下であると分散安定性が良化し、インキの安定性を向上させることができる。顔料と顔料分散樹脂の重量比率としてより好ましくは4/1以上50/1以下、更に好ましくは5/1以上25/1以下であり、最も好ましくは10/1以上20/1以下である。 The weight ratio of the pigment to the pigment dispersion resin is preferably 2/1 or more and 100/1 or less. When the weight ratio of the pigment dispersion resin is 2/1 or more, the viscosity of the ink can be kept low. Further, when it is 100/1 or less, the dispersion stability is improved and the stability of the ink can be improved. The weight ratio of the pigment to the pigment dispersion resin is more preferably 4/1 or more and 50/1 or less, further preferably 5/1 or more and 25/1 or less, and most preferably 10/1 or more and 20/1 or less.
(水分散性樹脂微粒子)
本発明のインキでは、刷版の疎水性画線部を形成するためのバインダー樹脂として、水分散性樹脂微粒子を使用する。一般に水性インクジェットインキのバインダー樹脂としては水溶性樹脂と水分散性樹脂微粒子の何れかが使用されるが、水分散性微粒子は樹脂の分子量が高いため、強固な皮膜を形成し、高い耐性を発揮することができる。また、水分散性微粒子はインキの粘度も比較的低く保つことができ、インクジェット適性を損なうことなく配合量を増やせるため、インクジェット用途には好適である。
(Water-dispersible resin particles)
In the ink of the present invention, water-dispersible resin fine particles are used as the binder resin for forming the hydrophobic image area of the printing plate. Generally, either water-soluble resin or water-dispersible resin fine particles are used as the binder resin for water-based inkjet inks. However, water-dispersible fine particles have a high molecular weight, so they form a strong film and exhibit high resistance. can do. Further, the water-dispersible fine particles can keep the viscosity of the ink relatively low, and can increase the blending amount without impairing the ink-jet suitability, so that they are suitable for the ink-jet application.
本発明では水分散性樹脂微粒子のガラス転移温度(Tg)を30℃以上200℃以下の範囲にすることで刷版の画線部の耐刷性を向上させることが可能であり、好ましくは40℃以上150℃以下、より好ましくは50℃以上130℃以下、更に好ましくは60℃以上120℃以下、最も好ましくは70℃以上110℃以下の範囲とするのが良い。上記の範囲内では刷版上に形成された画線部が十分な強度を保つことができるため、繰り返し平版印刷を行っても刷版の欠けや削れが生じず、印刷品質を落とすことなく印刷物を得ることが可能である。 In the present invention, the glass transition temperature (Tg) of the water-dispersible resin fine particles can be in the range of 30 ° C. or more and 200 ° C. or less to improve the printing durability of the image area of the printing plate, preferably 40 It is good to set it as the range of 70 degreeC or more and 150 degrees C or less, More preferably, 50 degreeC or more and 130 degrees C or less, More preferably, they are 60 degreeC or more and 120 degrees C or less, Most preferably, they are 70 degreeC or more and 110 degrees C or less. Within the above range, the image area formed on the printing plate can maintain a sufficient strength, so that even if repeated lithographic printing is performed, the printing plate will not be chipped or scraped, and the printed matter will not deteriorate. It is possible to obtain
水分散性樹脂微粒子の酸価は0mgKOH/g以上100mgKOH/g以下の範囲であることが好ましい。酸価があまりに高い場合には、刷版上に形成された画線部の親水性が高くなることで平版印刷インキの着肉性が低下し、印刷画質に悪影響を与えることがある。好ましくは0 mgKOH/g以上80mgKOH/g以下の範囲であり、より好ましくは0 mgKOH/g以上50mgKOH/g以下の範囲であり、更に好ましくは0 mgKOH/g以上30mgKOH/g以下の範囲であり、最も好ましくは0 mgKOH/g以上10mgKOH/g以下の範囲である。 The acid value of the water-dispersible resin fine particles is preferably in the range of 0 mgKOH / g to 100 mgKOH / g. If the acid value is too high, the image area formed on the printing plate becomes highly hydrophilic and the lithographic printing ink has a poor walling property, which may adversely affect the printing image quality. Preferably it is in the range of 0 mgKOH / g to 80 mgKOH / g, more preferably in the range of 0 mgKOH / g to 50 mgKOH / g, and still more preferably in the range of 0 mgKOH / g to 30 mgKOH / g, Most preferably, it is in the range of 0 mgKOH / g to 10 mgKOH / g.
水分散性樹脂微粒子としてはアクリル樹脂、スチレンアクリル樹脂、ウレタン樹脂、スチレンブタジエン樹脂、塩化ビニル樹脂、ポリオレフィン樹脂等が挙げられる。インキの安定性、耐刷性の面からアクリル樹脂、スチレンアクリル樹脂の水分散性樹脂微粒子を使用することが好ましい。 Examples of the water-dispersible resin fine particles include acrylic resin, styrene acrylic resin, urethane resin, styrene butadiene resin, vinyl chloride resin, polyolefin resin, and the like. In view of ink stability and printing durability, it is preferable to use water-dispersible resin fine particles of an acrylic resin or a styrene acrylic resin.
水分散性樹脂微粒子としてアクリル樹脂、スチレンアクリル樹脂を選択する場合には、構成成分としては汎用のアクリルモノマー、スチレン誘導体等を使用することが出来る。例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、ベヘニル(メタ)アクリレート等のアルキル基含有モノマー、エトキシエチル(メタ)アクリレート、エトキシエトキシエチル(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレート等のアルキレンオキサイド含有モノマー、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ノニルフェノキシエチル(メタ)アクリレート、スチレン、αメチルスチレン等の芳香環含有モノマー、ヒドロキシエチル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート等のヒドロキシル基含有モノマー、(メタ)アクリルアミド、ジメチル(メタ)アクリルアミド、ジメチルアミノプロピル(メタ)アクリルアミド等のアミノ(アミド)基含有モノマー、(メタ)アクリル酸、スチレンスルホン酸等の酸基含有モノマー、から選択することが出来る。 When an acrylic resin or a styrene acrylic resin is selected as the water-dispersible resin fine particles, a general-purpose acrylic monomer, styrene derivative or the like can be used as a constituent component. For example, alkyl groups containing methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. Monomer, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, alkylene oxide-containing monomer such as polypropylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, Contains aromatic ring-containing monomers such as nonylphenoxyethyl (meth) acrylate, styrene, α-methylstyrene, and hydroxyl groups such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate. Monomers, amino (amide) group-containing monomers such as (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and acid group-containing monomers such as (meth) acrylic acid and styrenesulfonic acid I can do it.
更に水分散性樹脂微粒子の構成成分として架橋性単量体を含むことで、インキ中での樹脂微粒子のインキ中での分散安定性の向上や、樹脂微粒子の内部架橋による高い樹脂強度により耐刷性の向上といった効果が得られる。 Furthermore, by including a crosslinkable monomer as a constituent of the water-dispersible resin fine particles, the dispersion stability of the resin fine particles in the ink is improved, and the printing durability is improved due to the high resin strength due to internal crosslinking of the resin fine particles. The effect of improving the property is obtained.
架橋性単量体は樹脂微粒子の製造時に他の原料となる単量体と合わせて用いることで、樹脂微粒子内に導入する。樹脂微粒子中の架橋性単量体の含有量としては、樹脂微粒子全量に対して、0.1重量%以上10重量%以下が好ましく、より好ましくは0.2重量%以上8重量%以下であり、更に好ましくは0.5重量%以上5重量%以下である。含有量がこの範囲であれば、インキの安定性の向上や刷版の耐刷性の向上といった効果を十分に得ることが可能である。 The crosslinkable monomer is introduced into the resin fine particles by being used in combination with other raw material monomers during the production of the resin fine particles. The content of the crosslinkable monomer in the resin fine particles is preferably 0.1% by weight or more and 10% by weight or less, more preferably 0.2% by weight or more and 8% by weight or less, and still more preferably, with respect to the total amount of the resin fine particles. 0.5 wt% or more and 5 wt% or less. If the content is within this range, it is possible to sufficiently obtain the effects of improving the stability of the ink and improving the printing durability of the printing plate.
架橋性単量体としては、例えば、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、グリセリンジメタクリレート、ジメチロールトリシクロデカンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリストールテトラ(メタ)アクリレート、ジビニルベンゼン、アジピン酸ジビニル、イソフタル酸ジアリル、フタル酸ジアリル、マレイン酸ジアリル等の2個以上の不飽和基を有する単量体、γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン、γ-(メタ)アクリロキシプロピルトリブトキシシラン、γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン、γ-(メタ)アクリロキシメチルトリメトキシシラン、γ-(メタ)アクリロキシメチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン等のアルコキシシリル基含有不飽和単量体、N-メチロール(メタ)アクリルアミド、N, N-ジメチロール(メタ)アクリルアミド、アルキルエーテル化-N-メチロール(メタ)アクリルアミド等のメチロール基含有不飽和単量体が挙げられるが、特にこれらに限定されるものではない。これらは１種類または２種以上を併用して用いることができる。 Examples of the crosslinkable monomer include allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, glycerin dimethacrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Divinyl ben Monomers having two or more unsaturated groups such as divinyl adipate, diallyl adipate, diallyl isophthalate, diallyl phthalate, diallyl maleate, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylic Roxypropyltriethoxysilane, γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxy Alkoxysilyl group-containing unsaturated monomers such as methyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, N- Methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamido Although methylol group-containing unsaturated monomers such as alkyl etherified -N- methylol (meth) acrylamide, but it is not particularly limited thereto. These can be used alone or in combination of two or more.
上記の架橋性単量体の中でも、2個のアリル基を有する単量体とアルコキシシリル基含有不飽和単量体が分散安定性向上の面から好ましく、2個のアリル基を有する単量体が更に好ましい。 Among the above crosslinkable monomers, a monomer having two allyl groups and an alkoxysilyl group-containing unsaturated monomer are preferable from the viewpoint of improving dispersion stability, and a monomer having two allyl groups Is more preferable.
本発明に使用する水分散性樹脂微粒子には酸性基としてスルホン酸基含有単量体を含むことで樹脂微粒子の分散安定性を更に向上させることができる。樹脂微粒子中のスルホン酸基含有単量体の含有量としては、樹脂微粒子全量に対して、0.1重量%以上5重量%以下が好ましく、より好ましくは0.2重量%以上3重量%以下であり、更に好ましくは0.5重量%以上2重量%以下である。含有量がこの範囲であれば、樹脂微粒子の分散安定性が良好となる。 When the water-dispersible resin fine particles used in the present invention contain a sulfonic acid group-containing monomer as an acidic group, the dispersion stability of the resin fine particles can be further improved. The content of the sulfonic acid group-containing monomer in the resin fine particles is preferably 0.1% by weight or more and 5% by weight or less, more preferably 0.2% by weight or more and 3% by weight or less, based on the total amount of the resin fine particles. Preferably they are 0.5 weight% or more and 2 weight% or less. When the content is within this range, the dispersion stability of the resin fine particles becomes good.
スルホン酸基含有単量体としてはスチレンスルホン酸、スチレンスルホン酸ナトリウム、スチレンスルホン酸アンモニウム、2-アクリルアミド-2-メチルプロパンスルホン酸、2-アクリルアミド-2-メチルプロパンスルホン酸ナトリウム、メタリルスルホン酸、メタリルスルホン酸、メタリルスルホン酸ナトリウム、アリルスルホン酸、アリルスルホン酸ナトリウム、アリルスルホン酸アンモニウム、ビニルスルホン酸、アリルオキシベンゼンスルホン酸、アリルオキシベンゼンスルホン酸ナトリウム、アリルオキシベンゼンスルホン酸アンモニウム等が挙げられる。 Examples of sulfonic acid group-containing monomers include styrene sulfonic acid, sodium styrene sulfonate, ammonium styrene sulfonate, 2-acrylamido-2-methylpropane sulfonic acid, sodium 2-acrylamido-2-methylpropane sulfonate, and methallyl sulfonic acid. , Methallyl sulfonic acid, sodium methallyl sulfonate, allyl sulfonic acid, sodium allyl sulfonate, ammonium allyl sulfonate, vinyl sulfonic acid, allyloxybenzene sulfonic acid, sodium allyloxybenzene sulfonate, ammonium allyloxybenzene sulfonate, etc. Is mentioned.
上記の水分散性樹脂微粒子のインキ中における含有量は、固形分でインキの全量に対して2重量%以上30重量%以下の範囲であり、好ましくは5重量%以上25重量%以下の範囲であり、より好ましくは8重量%以上20重量%以下の範囲である。 The content of the water-dispersible resin fine particles in the ink is in the range of 2% by weight to 30% by weight and preferably in the range of 5% by weight to 25% by weight with respect to the total amount of the ink in solid content. More preferably, it is in the range of 8 wt% to 20 wt%.
本発明では刷版の画線部を識別するために着色剤を必要とするが、水分散性樹脂微粒子を元とする樹脂成分に着色剤成分が含まれると、樹脂の強度が下がり、平版印刷時に刷版の画線部が欠けたり削れたりすることがある。このような不具合を防ぐために水分散性樹脂微粒子と着色剤のインキ中の配合重量比[水分散性樹脂微粒子/着色剤]を5以上1000以下にすることが好ましい。着色剤の配合量に対して樹脂の割合を増やすことにより、平版印刷時に樹脂強度の低下の影響が生じないようにすることが出来る。より好ましくは配合重量比[水分散性樹脂微粒子/着色剤]が8以上500以下、更に好ましくは10以上100以下、最も好ましくは12以上50以下である。 In the present invention, a colorant is required to identify the image line portion of the printing plate. However, if the colorant component is contained in the resin component based on the water-dispersible resin fine particles, the strength of the resin is reduced, and lithographic printing is performed. Occasionally, the image area of a printing plate may be chipped or scraped. In order to prevent such problems, it is preferable that the blending weight ratio [water-dispersible resin fine particles / colorant] in the ink of the water-dispersible resin fine particles and the colorant is 5 or more and 1000 or less. By increasing the proportion of the resin with respect to the blending amount of the colorant, it is possible to prevent the influence of a decrease in the resin strength during lithographic printing. More preferably, the blending weight ratio [water-dispersible resin fine particles / colorant] is 8 or more and 500 or less, more preferably 10 or more and 100 or less, and most preferably 12 or more and 50 or less.
(固形分量)
更にインキ中の固形分量をインキ全量に対して5重量%以上20重量%以下とすることが好ましい。固形分量が20重量%よりも多い場合には、刷版上に形成された画線部にインクジェット印刷によるドットの凹凸が生じる場合がある。このような凹凸が多くあると、平版印刷インキの着肉性が低下したり、凹凸から画線部が欠ける原因となったりし、平版印刷物の品質低下を生じる可能性がある。固形分量が20重量%以下であれば刷版上に凹凸の少ない画線部を形成することが出来る。固形分量として好ましくは8重量%以上18重量%以下であり、より好ましくは10重量%以上15重量%以下である。
(Solid content)
Furthermore, the solid content in the ink is preferably 5% by weight or more and 20% by weight or less based on the total amount of the ink. When the solid content is more than 20% by weight, dot irregularities may be formed by ink jet printing in the image area formed on the printing plate. If there are many such irregularities, the inking property of the lithographic printing ink may be reduced, or the image area may be missing from the irregularities, which may cause a reduction in the quality of the lithographic printed matter. If the solid content is 20% by weight or less, it is possible to form an image line portion with less unevenness on the printing plate. The solid content is preferably 8% by weight or more and 18% by weight or less, and more preferably 10% by weight or more and 15% by weight or less.
インキ中の固形分量は以下の通り測定することができる。ガラス製のシャーレに1〜3g程度のインキを量りとり、これを180℃のオーブンにて30分間乾燥させる。乾燥後の重量を量り、これを固形分として乾燥前後の重量からインキ中の割合を求める。 The solid content in the ink can be measured as follows. About 1 to 3 g of ink is weighed into a glass petri dish and dried in an oven at 180 ° C. for 30 minutes. The weight after drying is measured, and the ratio in the ink is determined from the weight before and after drying, using this as the solid content.
(有機溶剤)
本発明では有機溶剤として炭素数4以上10以下の1,2-アルカンジオールをインキ中に5重量%以上50重量%以下の割合で配合することを特徴とする。1,2-アルカンジオールはヒドロキシル基の親水部とアルキル基の疎水部とを有する両親媒性構造であることから、界面活性効果を示し高い濡れ広がり性を発揮する。また、2つのヒドロキシル基を有することにより高い保湿性を有するため、インクジェットヘッドのノズル近傍でインキが乾燥条件下におかれても流動性を保ち、ノズル欠損が生じにくくなる。また、この溶剤を使用することでインキの基材上での濡れ広がり性が向上し、製版時にプラテンで基材を加温しなくてもムラ、ニジミのない刷版を得ることが可能となる。更にプラテンを加温することで、より良質な刷版を得ることが出来る。刷版にムラ、ニジミが生じると、これを利用して平版印刷して得られた印刷物にも画質低下の影響を与えることとなる。炭素数4以上10以下の1,2-アルカンジオールを使用しない場合にはムラやニジミにより刷版品質の低下が生じる。また、これを解消するためにプラテン温度を上げると、インクジェットヘッドのノズル近傍のインキが乾燥することによりインキが不吐出となり、画像欠陥が生じてしまう。
(Organic solvent)
In the present invention, 1,2-alkanediol having 4 to 10 carbon atoms as an organic solvent is blended in the ink at a ratio of 5 wt% to 50 wt%. Since 1,2-alkanediol is an amphiphilic structure having a hydrophilic part of a hydroxyl group and a hydrophobic part of an alkyl group, it exhibits a surface active effect and exhibits high wettability. In addition, since it has high moisture retention due to having two hydroxyl groups, fluidity is maintained even when the ink is placed in the vicinity of the nozzle of the inkjet head under dry conditions, and nozzle defects are less likely to occur. In addition, by using this solvent, wetting and spreading properties of the ink on the base material are improved, and it becomes possible to obtain a printing plate free from unevenness and blurring without heating the base material with a platen during plate making. . Further, by heating the platen, a higher quality printing plate can be obtained. If unevenness and blurring occur in the printing plate, the printed matter obtained by lithographic printing using this will also have an effect of lowering the image quality. When 1,2-alkanediol having 4 or more and 10 or less carbon atoms is not used, the printing plate quality deteriorates due to unevenness or blurring. Further, if the platen temperature is raised to solve this problem, the ink near the nozzles of the ink jet head is dried, resulting in non-ejection of the ink and image defects.
炭素数4以上10以下の1,2-アルカンジオールとしては1,2-ブタンジオール、1,2-ペンタンジオール、1,2-ヘキサンジオール、1,2-ヘプタンジオール、1,2-オクタンジオールジオール、1,2-ノナンジオール、1,2-デカンジオール等が挙げられる。中でもインキ中の水との混和性、水分散性樹脂微粒子の分散安定性の点から1,2-ブタンジオール、1,2-ペンタンジオール、1,2-ヘキサンジオールを使用することが好ましい。より好ましくは1,2-ヘキサンジオールである。 1,2-Alkanediol having 4 to 10 carbon atoms is 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol diol 1,2-nonanediol, 1,2-decanediol and the like. Of these, 1,2-butanediol, 1,2-pentanediol, and 1,2-hexanediol are preferably used from the viewpoint of miscibility with water in the ink and dispersion stability of the water-dispersible resin fine particles. More preferred is 1,2-hexanediol.
本発明でインキ中に含まれる炭素数4以上10以下の1,2-アルカンジオールの配合量は、インキ全量に対して、5重量%以上50重量%以下の範囲である。この範囲内であれば上述したとおり、良好な画質の刷版を得ることが可能となる。より好ましくは8重量%以上35重量%以下、更に好ましくは10重量%以上30重量%以下、最も好ましくは12重量%以上25重量%以下である。 In the present invention, the blending amount of 1,2-alkanediol having 4 to 10 carbon atoms contained in the ink is in the range of 5 wt% to 50 wt% with respect to the total amount of the ink. Within this range, it is possible to obtain a printing plate with good image quality as described above. More preferably, they are 8 weight% or more and 35 weight% or less, More preferably, they are 10 weight% or more and 30 weight% or less, Most preferably, they are 12 weight% or more and 25 weight% or less.
本発明では上述した効果に影響を与えない限り、その他の溶剤を併用することが可能である。その他の溶剤としてはエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコール-2-エチルヘキシルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコール-2-エチルヘキシルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、メトキシブタノール、3-メチル-3-メトキシブタノール、ジエチレングリコージメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルブチルエーテル、トリエチレングリコールメチルブチルエーテル、トリプロピレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル等のグリコールエーテル系溶剤、グリセリン、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、1,9-ノナンジオール等の多価アルコール系溶剤、2-ピロリドン、N-メチルピロリドン、N-エチルピロリドン、N-メチルオキサゾリジノン、N-エチルオキサゾリジノン、γ-ブチロラクトン、ε-カプロラクトン、N, N-ジメチル-β-メトキシプロピオンアミド等の含窒素系溶剤、ジエチレングリコールメチルエーテルアセテート、乳酸エチル等が挙げられる。 In the present invention, other solvents can be used in combination as long as the effects described above are not affected. Other solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Diethylene glycol monohexyl ether, diethylene glycol-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether Ter, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, methoxybutanol, 3-methyl-3-methoxybutanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl Glycol ether solvents such as ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol Polyhydric alcohol solvents such as dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, Nitrogen-containing solvents such as 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-methyloxazolidinone, N-ethyloxazolidinone, γ-butyrolactone, ε-caprolactone, N, N-dimethyl-β-methoxypropionamide, Examples include diethylene glycol methyl ether acetate and ethyl lactate.
インキ中の総溶剤量は、インキ全量に対して、5重量%以上70重量%以下が好ましい。より好ましくは8重量%以上50重量%以下、更に好ましくは10重量%以上35重量%以下、最も好ましくは12重量%以上25重量%以下である。 The total amount of solvent in the ink is preferably 5% by weight or more and 70% by weight or less based on the total amount of the ink. More preferably, they are 8 weight% or more and 50 weight% or less, More preferably, they are 10 weight% or more and 35 weight% or less, Most preferably, they are 12 weight% or more and 25 weight% or less.
(界面活性剤)
本発明では界面活性剤をインキに配合することも可能である。界面活性剤を使用することで高い濡れ広がり性を発揮し、良質な刷版を得ることができる。更に印刷後に低温で加熱を行った場合にも高い耐刷性を発揮することが可能となる。この原因は定かではないが、界面活性剤が樹脂微粒子の造膜助剤として働き、低温でも樹脂微粒子の造膜が起こるためと考えられる。
(Surfactant)
In the present invention, it is also possible to add a surfactant to the ink. By using a surfactant, high wettability can be exhibited and a high-quality printing plate can be obtained. Further, even when heating is performed at a low temperature after printing, high printing durability can be exhibited. The reason for this is not clear, but it is considered that the surfactant acts as a film forming aid for the resin fine particles, and the film formation of the resin fine particles occurs even at a low temperature.
界面活性剤としてはシリコン系界面活性剤、アセチレン系界面活性剤、フッ素系界面活性剤、グリコールエーテル系界面活性剤等が使用できる。中でもシリコン系界面活性剤、アセチレン系界面活性剤を使用することが好ましく、より好ましくはシリコン系海面下製剤である。 As the surfactant, a silicon-based surfactant, an acetylene-based surfactant, a fluorine-based surfactant, a glycol ether-based surfactant, or the like can be used. Among these, it is preferable to use a silicon-based surfactant or an acetylene-based surfactant, and more preferably a silicon-based subsea preparation.
シリコン系界面活性剤としては下記一般式1〜3で表される化合物を使用することが好ましい。より好ましくは一般式2または一般式3で表される化合物であり、更に好ましくは一般式2で表される化合物である。界面活性剤の添加量としては、インキ全量に対して、0.1重量%以上5重量%以下が好ましく、より好ましくは0.5重量%以上3重量%以下であり、更に好ましくは0.8重量%以上2重量%以下であり、最も好ましくは1重量%以上1.5重量%以下である。 As the silicon surfactant, it is preferable to use compounds represented by the following general formulas 1 to 3. A compound represented by general formula 2 or 3 is more preferable, and a compound represented by general formula 2 is still more preferable. The addition amount of the surfactant is preferably 0.1% by weight or more and 5% by weight or less, more preferably 0.5% by weight or more and 3% by weight or less, and further preferably 0.8% by weight or more and 2% by weight or less based on the total amount of the ink. And most preferably 1% by weight or more and 1.5% by weight or less.
(D) アルキル基、またはアリール基である。 (D) An alkyl group or an aryl group.
一般式1で表される化合物の市販品としてはエボニックデグサ社製のTegotwin4000やTegotwin4100等が挙げられる。 Examples of commercially available compounds represented by the general formula 1 include Tegotwin 4000 and Tegotwin 4100 manufactured by Evonik Degussa.
一般式2で表される化合物の市販品の例としては、東レ・ダウコーニング社製のBY16-201, SF8427, ビックケミー社製のBYK-331, BYK-333, BYK-UV3500, エボニックデグサ社製のTegoglide410, Tegoglide432, Tegoglide435, Tegoglide440, Tegoglide450等が挙げられる。 Examples of commercially available compounds represented by general formula 2 include BY16-201, SF8427 manufactured by Toray Dow Corning, BYK-331, BYK-333, BYK-UV3500 manufactured by BYK Chemie, and Evonik Degussa Tegoglide410, Tegoglide432, Tegoglide435, Tegoglide440, Tegoglide450 etc. are mentioned.
一般式3で表される化合物の市販品の例としては、東レ・ダウコーニング社製のSF8428, FZ-2162, 8032ADDITIVE, SH3749, FZ-77, L-7001, L-7002, FZ-2104, FZ-2110, F-2123, SH8400, SH3773M, ビックケミー社製のBYK-345, BYK-346, BYK-347, BYK-348, BYK-349, エボニックデグサ社製のTegowet250, Tegowet260, Tegowet270, Tegowet280, 信越化学工業社製のKF-351A, KF-352A, KF-353, KF-354L, KF355A, KF-615A, KF-640, KF-642, KF-643等が挙げられる。 Examples of commercially available compounds represented by general formula 3 include SF8428, FZ-2162, 8032ADDITIVE, SH3749, FZ-77, L-7001, L-7002, FZ-2104, FZ manufactured by Toray Dow Corning. -2110, F-2123, SH8400, SH3773M, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 manufactured by Big Chemie, Tegowet250, Tegowet260, Tegowet270, Tegowet280, Shinetsu Chemical, manufactured by Evonik Degussa Examples thereof include KF-351A, KF-352A, KF-353, KF-354L, KF355A, KF-615A, KF-640, KF-642, and KF-643 manufactured by Kogyo.
アセチレン系界面活性剤としては一般式4で表される化合物を使用することが好ましい。一般式4で表される化合物の市販品としてはエアープロダクツ社製のサーフィノール104, サーフィノール420, サーフィノール440, サーフィノール465, サーフィノール485等が挙げられる。 As the acetylene surfactant, it is preferable to use a compound represented by the general formula 4. Examples of commercially available compounds represented by the general formula 4 include Surfinol 104, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485 and the like manufactured by Air Products.
本発明の水性インクジェットインキに含まれる水としては、種々のイオンを含有する一般の水ではなく、イオン交換水(脱イオン水）を使用するのが好ましい。 As water contained in the water-based inkjet ink of the present invention, it is preferable to use ion-exchanged water (deionized water) instead of general water containing various ions.
本発明で使用することができる水のインキ組成中における含有量は、インキ全量に対して、20重量%以上90重量%以下の範囲が好ましく、40重量%以上85重量%以下の範囲がより好ましく、60重量%以上80重量%以下の範囲が更に好ましい。 The content of water in the ink composition that can be used in the present invention is preferably in the range of 20% by weight to 90% by weight, more preferably in the range of 40% by weight to 85% by weight, based on the total amount of the ink. A range of 60% by weight to 80% by weight is more preferable.
(その他の成分)
本発明のインキは上記成分の他に、必要に応じて所望の物性値を持つインキとするために、消泡剤、増粘剤、pH調整剤、防腐剤等の添加剤を適宜添加することができる。これらの添加剤の添加量としては、インキの全質量に対して0.01重量%以上10重量％以下、好ましくは0.05重量％以上5重量％以下、より好ましくは0.1重量％以上3重量％以下である。
(Other ingredients)
In addition to the above components, the ink of the present invention may be appropriately added with additives such as antifoaming agents, thickeners, pH adjusters, preservatives, etc., in order to obtain inks having desired physical properties as required. Can do. The additive amount of these additives is 0.01% by weight or more and 10% by weight or less, preferably 0.05% by weight or more and 5% by weight or less, more preferably 0.1% by weight or more and 3% by weight or less with respect to the total mass of the ink. .
(平版印刷用原版)
本発明で使用する平版印刷用原版としては、平版印刷に適した親水性表面を有するものであれば従来既知のものが使用できる。平版印刷用原版とは原版の元となる支持体上に、必要に応じて親水化処理、粗面化処理、インキ受理層塗布処理などを行ったものである。
(Original for lithographic printing)
As the lithographic printing original plate used in the present invention, those conventionally known can be used as long as they have a hydrophilic surface suitable for lithographic printing. The lithographic printing original plate is obtained by subjecting a support that is the original of the original plate to a hydrophilic treatment, a roughening treatment, an ink receiving layer coating treatment, and the like as necessary.
平版印刷用原版の支持体としてはアルミニウム板やその合金板のような金属板、ポリエステル、ポリエチレンテレフタラート等のプラスチックフィルム、耐水処理された紙などを使用することが出来る。原版自体の耐性から金属板を支持体として使用することが好ましく、より好ましくはアルミニウム板である。 As the support for the lithographic printing original plate, a metal plate such as an aluminum plate or an alloy plate thereof, a plastic film such as polyester or polyethylene terephthalate, a water-resistant paper, or the like can be used. In view of the resistance of the original plate itself, it is preferable to use a metal plate as a support, more preferably an aluminum plate.
アルミニウム板を使用する際には粗面化処理、ケイ酸ナトリウム、フッ化ジルコニウム酸カリウム、リン酸塩などの水溶液への浸漬処理、陽極酸化処理といった表面処理を行うことが好ましい。これらの処理により平版印刷適性の向上、原版の耐性向上といった効果が得られる。粗面化処理はブラシ研磨の様な機械的に粗面化する方法や、電解エッチングにより凹凸を形成するといった従来既知の方法で行うことが出来る。 When using an aluminum plate, it is preferable to perform a surface treatment such as a surface roughening treatment, an immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or an anodizing treatment. By these treatments, effects such as improvement of lithographic printing suitability and improvement of resistance of the original plate can be obtained. The roughening treatment can be performed by a conventionally known method such as a mechanical roughening method such as brush polishing or a method of forming irregularities by electrolytic etching.
また、本発明のインクジェットインキにより形成される画線部をより精細にするために画像受理層を設けることも好ましい。画像受理層としてはポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、ポリアクリル酸樹脂、スチレンマレイン酸樹脂、カゼイン、ゼラチン等の水溶性樹脂を使用することができる。 It is also preferable to provide an image receiving layer in order to make the image area formed by the inkjet ink of the present invention finer. As the image receiving layer, water-soluble resins such as polyvinyl alcohol resin, polyvinyl pyrrolidone resin, polyacrylic acid resin, styrene maleic acid resin, casein, and gelatin can be used.
(インクジェット製版方法)
本発明のインキをインクジェット方式により平版印刷用原版に画線部を印刷することで平版印刷用刷版を作成することが出来る。本発明のインキを原版へ付着させ、溶剤や水を揮発、乾燥させることで疎水性の樹脂分が原版上へ残り、これが平版印刷時に印刷される画線部となる。
(Inkjet plate making method)
A printing plate for lithographic printing can be prepared by printing the image area on the lithographic printing original plate by the ink jet method of the present invention. By adhering the ink of the present invention to the original plate and volatilizing and drying the solvent and water, the hydrophobic resin remains on the original plate, which becomes the image line portion printed during lithographic printing.
インクジェット記録方式としては一回の走査で画像を形成するワンパス方式と複数回の走査で画像を形成するマルチパス方式の何れも使用することが可能であるが、マルチパス方式を使用することが好ましい。マルチパス方式では複数回の走査で画像を形成するため、インクジェットヘッドのノズル欠損が生じても他のノズルでカバーすることができ、刷版の画線部に欠陥が生じにくい。 As the ink jet recording method, either a one-pass method in which an image is formed by a single scan or a multi-pass method in which an image is formed by a plurality of scans can be used, but it is preferable to use a multi-pass method. . In the multi-pass method, since an image is formed by a plurality of scans, even if a nozzle defect of the ink jet head occurs, it can be covered with another nozzle, and the image line portion of the printing plate is less likely to be defective.
使用するインクジェットヘッドとしてはコンティニュアス方式でもオンデマンド方式でも何れも使用可能である。また、吐出方式としてはピエゾ方式、サーマル方式の何れも使用可能である。 As an inkjet head to be used, either a continuous method or an on-demand method can be used. Further, as a discharge method, either a piezo method or a thermal method can be used.
インクジェットヘッドから吐出されるインキの液適量としては0.5〜20pLが好ましい。より好ましくは1pL以上15pL以下であり、更に好ましくは2 pL以上10pL以下であり、最も好ましくは3 pL以上7pL以下である。液適量を小さくすることで、解像度の高い刷版を作成することが可能となる。但し、あまりに小さい場合には空気抵抗により液滴の着滴位置がばらつくため、画質の低下が生じる場合がある。 The appropriate amount of ink discharged from the inkjet head is preferably 0.5 to 20 pL. More preferably, it is 1 pL or more and 15 pL or less, More preferably, it is 2 pL or more and 10 pL or less, Most preferably, it is 3 pL or more and 7 pL or less. By reducing the appropriate amount of the liquid, it is possible to create a printing plate with high resolution. However, if it is too small, the landing position of the liquid droplets varies due to air resistance, so that the image quality may be deteriorated.
所望するスクリーン線数の刷版を得るために、インクジェット印刷の解像度は適宜変更することが出来るが、600×600dpi以上の解像度で印刷することが好ましい。新聞印刷に必要な60〜80線程度の解像度の刷版であれば、720×720dpiの解像度でインクジェット印刷することで網点の再現が可能である。また、より高品質なカラー印刷に使用される150〜200線の刷版の様な高解像度の網点を再現するには、インクジェット印刷の解像度も1440×1440dpi〜2880×2880dpiといった高解像度にすることが好ましい。 In order to obtain a printing plate having a desired number of screen lines, the resolution of ink jet printing can be changed as appropriate, but printing with a resolution of 600 × 600 dpi or more is preferable. If the printing plate has a resolution of about 60 to 80 lines required for newspaper printing, halftone dots can be reproduced by inkjet printing at a resolution of 720 × 720 dpi. Also, in order to reproduce high-resolution halftone dots such as 150-200 line plates used for higher-quality color printing, the resolution of inkjet printing is also set to high resolution such as 1440 x 1440 dpi to 2880 x 2880 dpi. It is preferable.
本発明のインキは室温で印刷を行っても精細な画像を作成することが可能であるが、プラテンヒーターにより原版を加温しながら印刷することも可能である。加温によりインキの乾燥を速め、ドットのニジミを生じづらくして、より高精細な刷版を作成することが可能となる。但し、プラテンヒーターをあまりに高温にしてしまうと、インクジェットヘッドのノズル近傍のインキが揮発し、ノズル欠損を生じてしまう場合がある。印刷時の温度としては10℃以上60℃以下が好ましく、15℃以上55℃以下がより好ましく、20℃以上50℃以下が更に好ましい。 The ink of the present invention can produce a fine image even when printing at room temperature, but it is also possible to print while heating the original plate with a platen heater. Heating accelerates the drying of the ink and makes it difficult to cause dot blurring, thereby making it possible to create a higher-definition printing plate. However, if the platen heater is too high, the ink near the nozzles of the inkjet head may volatilize and cause nozzle defects. The temperature during printing is preferably 10 ° C or higher and 60 ° C or lower, more preferably 15 ° C or higher and 55 ° C or lower, and further preferably 20 ° C or higher and 50 ° C or lower.
本発明の製版方法では印刷された原版を加熱処理することでより高い耐刷性を発揮することが可能である。加熱処理の温度としては50℃以上300℃以下が好ましく、100℃以上250℃以下がより好ましく、150℃以上230℃以下が更に好ましい。また、乾燥温度としては特に制限されないが、1分以上60分以下であることが好ましく、2分以上30分以下であることがより好ましく、5分以上15分以下であることが更に好ましい。 In the plate making method of the present invention, higher printing durability can be exhibited by heat-treating the printed original plate. The temperature of the heat treatment is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 150 ° C. or higher and 230 ° C. or lower. The drying temperature is not particularly limited, but is preferably 1 minute or more and 60 minutes or less, more preferably 2 minutes or more and 30 minutes or less, and further preferably 5 minutes or more and 15 minutes or less.
以下、実施例及び比較例を挙げて本発明を更に具体的に説明する。尚、以下の記載において、「部」及び「%」とあるものは特に断らない限りそれぞれ「重量部」、「重量%」を表す。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.
(水分散性樹脂微粒子Aの製造例)
攪拌器、温度計、滴下ロート、還流器を備えた反応容器に、イオン交換水40部と界面活性剤としてアクアロンKH-10(第一工業製薬製)0.2部とを仕込み、別途、2-エチルヘキシルアクリレート16部、メチルメタクリレート51部、スチレン30部、ジメチルアクリルアミド2部、アクリル酸1部、イオン交換水53部および界面活性剤としてアクアロンKH-10(第一工業製薬製)1.8部をあらかじめ混合しておいたプレエマルジョンのうちの1%をさらに加えた。内温を60℃に昇温し十分に窒素置換した後、過硫酸カリウムの5%水溶液10部、および無水重亜硫酸ナトリウムの1%水溶液20部の10%を添加し重合を開始した。反応系内を60℃で5分間保持した後、内温を60℃に保ちながらプレエマルジョンの残りと過硫酸カリウムの5%水溶液、および無水重亜硫酸ナトリウムの1%水溶液の残りを1.5時間かけて滴下し、さらに2時間攪拌を継続した。固形分測定にて転化率が98％超えたことを確認後、温度を30℃まで冷却した。ジエチルアミノエタノールを添加して、pHを8.5とし、さらにイオン交換水で固形分を40％に調整して水分散性樹脂微粒子Aの分散液を得た。得られた水分散性樹脂微粒子Aの計算上のガラス転移温度は70℃である。
(Production example of water-dispersible resin fine particles A)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and refluxing vessel, 40 parts of ion-exchanged water and 0.2 part of Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant were charged, and 2-ethylhexyl was separately added. 16 parts of acrylate, 51 parts of methyl methacrylate, 30 parts of styrene, 2 parts of dimethylacrylamide, 1 part of acrylic acid, 53 parts of ion-exchanged water and 1.8 parts of Aqualon KH-10 (Daiichi Kogyo Seiyaku) as a surfactant are mixed in advance. An additional 1% of the pre-emulsion was added. After raising the internal temperature to 60 ° C. and sufficiently purging with nitrogen, 10 parts of a 5% aqueous solution of potassium persulfate and 20 parts of a 1% aqueous solution of anhydrous sodium bisulfite were added to initiate polymerization. After maintaining the reaction system at 60 ° C. for 5 minutes, while maintaining the internal temperature at 60 ° C., the remaining pre-emulsion, 5% aqueous solution of potassium persulfate, and the remaining 1% aqueous solution of anhydrous sodium bisulfite were added over 1.5 hours. The mixture was added dropwise and stirring was continued for another 2 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the temperature was cooled to 30 ° C. Diethylaminoethanol was added to adjust the pH to 8.5, and the solid content was adjusted to 40% with ion-exchanged water to obtain a dispersion of water-dispersible resin fine particles A. The calculated glass transition temperature of the obtained water-dispersible resin fine particles A is 70 ° C.
(水分散性樹脂微粒子B〜Dの製造例)
表1の原料を使用する以外は水分散性樹脂微粒子Aと同様の操作にて樹脂合成を行い、水分散性樹脂微粒子B〜Dの溶液を得た。得られた水分散性樹脂微粒子B〜Dの計算上のガラス転移温度は表1記載の通りである。
(Production example of water-dispersible resin fine particles B to D)
Resin synthesis was performed in the same manner as the water-dispersible resin fine particles A except that the raw materials shown in Table 1 were used to obtain solutions of water-dispersible resin fine particles B to D. The calculated glass transition temperatures of the obtained water-dispersible resin fine particles B to D are as shown in Table 1.
(評価用インキ1の製造例)
顔料としてピグメントブルー15:3を20部、顔料分散樹脂(スチレンアクリル樹脂、酸価200mgKOH/g)を6部、水74部を混合し、ディスパーで予備分散した後、直径0.5mmのジルコニアビーズを充填したサンドミルを用いて2時間本分散を行い、顔料分散液を得た。
(Example of production of ink 1 for evaluation)
20 parts of Pigment Blue 15: 3, 6 parts of pigment dispersion resin (styrene acrylic resin, acid value 200 mgKOH / g) and 74 parts of water were mixed as a pigment, and after pre-dispersion with a disper, zirconia beads with a diameter of 0.5 mm were added. This dispersion was performed for 2 hours using a filled sand mill to obtain a pigment dispersion.
顔料分散液10部、水分散性樹脂微粒子Aの分散液20部、1,2-ブタンジオール16部、残りを水としてインキ全体が100部になるように調整し、これをディスパーで十分に均一になるまで攪拌した。その後、メンブランフィルターで濾過を行い、ヘッドつまりの原因となる粗大粒子を除去し本発明の水性インクジェットインキを作成した。 Adjust 10 parts of pigment dispersion, 20 parts of dispersion of water-dispersible resin fine particles A, 16 parts of 1,2-butanediol, and the rest to be 100 parts of the total ink. Stir until. Thereafter, filtration with a membrane filter was performed to remove coarse particles that would cause clogging of the head, and the aqueous inkjet ink of the present invention was prepared.
(評価用インキ2〜22の製造例)
評価用インキ1の製造例と同様に、表2記載の通りの組成となるように配合を行い評価用インキ2〜22を作成した。
(Production example of evaluation inks 2 to 22)
In the same manner as in the production example of the evaluation ink 1, blending was performed so that the composition was as shown in Table 2 to prepare evaluation inks 2 to 22.
(試験1)
作成した評価用インキ1をプラテンヒーターを具備するインクジェット装置に充填し、粗面化処理したアルミニウム板を平版印刷用原版として用い、解像度1440×1440dpiで印刷を行い、平版印刷用刷版を製造した。この時の印刷時のプラテン温度は25℃であり、原版への印刷後に120℃、10分の条件で加熱処理を行った。
(Test 1)
The prepared ink for evaluation 1 was filled in an inkjet apparatus equipped with a platen heater, and a roughened aluminum plate was used as a lithographic printing original plate, and printing was performed at a resolution of 1440 × 1440 dpi to produce a lithographic printing plate. . The platen temperature during printing at this time was 25 ° C., and after the printing on the original plate, the heat treatment was performed at 120 ° C. for 10 minutes.
(印刷安定性評価)
平版印刷用刷版1枚を製版した後に、ノズルチェックパターンを印刷しノズル欠損の有無を確認することで印刷安定性の評価を行った。
A：印刷後にノズル欠損が生じていない
B：印刷後にノズル欠損が生じている
(Printing stability evaluation)
After making one lithographic printing plate, printing stability was evaluated by printing a nozzle check pattern and checking for the presence or absence of nozzle defects.
A: No nozzle defect after printing
B: Nozzle defect occurs after printing
(描画性)
作成した刷版をオフセット印刷機にセットし、インキとしてヴァンテアンエコー墨 HAS、湿し水としてニュースキング Aly(0.5%)を使用して新聞用紙にサイズの異なる文字列を含む画像の印刷を行った。印刷物の文字列を確認し、識別できる文字列のサイズで描画性の評価を行った。
A：3ptの文字が識別できる
B：5ptの文字が識別できる
C：8ptの文字が識別できる
C：8ptの文字が識別できない
(Drawability)
The created printing plate was set in an offset printing machine, and images containing character strings of different sizes were printed on newsprint using Vantean Echo ink HAS as ink and Newsking Aly (0.5%) as dampening water. . The character string of the printed material was confirmed, and the drawability was evaluated by the size of the character string that can be identified.
A: 3pt characters can be identified
B: Can identify 5pt characters
C: Can identify 8pt characters
C: Character of 8pt cannot be identified
(耐刷性)
作成した刷版をオフセット印刷機にセットし、インキとしてヴァンテアンエコー墨 HAS、湿し水としてニュースキング Aly(0.5%)を使用して新聞用紙に15万枚印刷を行った。印刷途中でおよそ1000枚ごとに印刷物を抜き取り、文字の欠けや潰れなどの画像欠陥が生じているかを確認し、評価を行った。評価基準は以下のとおりである。
A：15万枚まで画像欠陥が生じない
B：10万枚まで画像欠陥が生じない
C：15万枚まで画像欠陥が生じない
D：2万枚まで画像欠陥が生じない
E：2万枚で画像欠陥が生じている
(Print life)
The prepared printing plate was set on an offset printing machine, and 150,000 sheets were printed on newspaper using Vantean Echo ink HAS as ink and Newsking Aly (0.5%) as dampening water. During the printing, the printed matter was extracted about every 1000 sheets, and it was confirmed whether or not image defects such as missing or crushed characters occurred. The evaluation criteria are as follows.
A: Image defects do not occur up to 150,000 sheets
B: Image defects do not occur up to 100,000 sheets
C: No image defects up to 150,000
D: Image defects do not occur up to 20,000 sheets
E: Image defects occur at 20,000 sheets
インキ2〜22についても同様にして、刷版の製造を行い、評価を行った。インキ1〜18を使用して試験を行ったところ、インキに水分散性樹脂微粒子、炭素数4以上10以下の1,2-アルカンジオールを5重量%以上50重量%以下含むため、印刷安定性、描画性、耐刷性いずれも良好な結果が得られた。また、配合量の調整、水分散性樹脂微粒子のガラス転移温度の調整、シリコン系界面活性剤の使用などにより、更に高い効果を発揮している(実施例1〜18)。一方でインキ19では水分散性樹脂微粒子を使用していないため耐刷性が悪く、インキ20〜22では有機溶剤が請求項の範囲外であるため描画性が悪い結果となっている(比較例1〜4)。 Inks 2 to 22 were similarly produced and evaluated. When tested using inks 1 to 18, the ink contains water-dispersible resin fine particles and 1,2-alkanediol having 4 to 10 carbon atoms in an amount of 5 to 50% by weight. Good results were obtained in both drawing and printing durability. Further, higher effects are exhibited by adjusting the blending amount, adjusting the glass transition temperature of the water-dispersible resin fine particles, and using a silicon surfactant (Examples 1 to 18). On the other hand, ink 19 does not use water-dispersible resin fine particles, so printing durability is poor, and inks 20 to 22 have poor drawability because organic solvents are outside the scope of claims (Comparative Example). 1-4).
(試験2)
評価用インキ2, 6, 11, 19を使用して原版への印刷を行い、印刷後の加熱温度、時間を表4記載の通りに変化させ、平版印刷用刷版の製造を行った。評価は試験1と同様に印刷安定性、描画性、耐刷性の評価を行った。
(Test 2)
Printing on the original plate was performed using the evaluation inks 2, 6, 11, and 19, and the heating temperature and time after printing were changed as shown in Table 4 to produce a lithographic printing plate. Evaluation was made in the same manner as in Test 1 in terms of printing stability, drawing performance, and printing durability.
評価用インキ2, 6, 11では印刷後の加熱温度を上げ、加熱時間を長くすることで耐刷性が向上する結果が得られた(実施例19〜33)。特にシリコン系界面活性剤を使用したインキ11では低温での乾燥であっても高い耐刷性を発揮することができている。一方で水分散性樹脂微粒子を使用していないインキ19では乾燥温度を高くしても耐刷性は向上しなかった(比較例5, 6)。 In the evaluation inks 2, 6, and 11, the results were improved by increasing the heating temperature after printing and increasing the heating time (Examples 19 to 33). In particular, the ink 11 using a silicon-based surfactant can exhibit high printing durability even when dried at a low temperature. On the other hand, with the ink 19 which does not use water-dispersible resin fine particles, the printing durability was not improved even when the drying temperature was increased (Comparative Examples 5 and 6).
(試験3)
評価用インキ2, 6, 11, 20, 21, 22を使用して原版への印刷を行い、印刷中のプラテン温度を表5記載の通りに変化させ、平版印刷用刷版の製造を行った。評価は試験1と同様に印刷安定性、描画性、耐刷性の評価を行った。
(Test 3)
Printing was performed on the original plate using evaluation inks 2, 6, 11, 20, 21, and 22, and the platen temperature during printing was changed as shown in Table 5 to produce a lithographic printing plate. . Evaluation was made in the same manner as in Test 1 in terms of printing stability, drawing performance, and printing durability.
評価用インキ2, 6, 11ではプラテン温度を高くすることで、印刷安定性を損なうことなく、描画性が向上する結果が得られた(実施例34〜39)。インキ20, 22ではプラテン温度を高くすることで描画性は向上したが、ノズル欠損が生じてしまった(比較例8, 11, 12)。インキ21では乾燥温度を上げても描画性が向上せず、十分が画質を得ることができなかった(比較例9, 10)。 In the evaluation inks 2, 6, and 11, by increasing the platen temperature, it was possible to obtain the result that the drawing property was improved without impairing the printing stability (Examples 34 to 39). With inks 20 and 22, the drawing performance was improved by increasing the platen temperature, but nozzle defects occurred (Comparative Examples 8, 11 and 12). Ink 21 did not improve the drawability even when the drying temperature was raised, and sufficient image quality could not be obtained (Comparative Examples 9 and 10).
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