JP5805149B2 - Lithographic printing method and fountain solution concentrated composition - Google Patents
Lithographic printing method and fountain solution concentrated composition Download PDFInfo
- Publication number
- JP5805149B2 JP5805149B2 JP2013144555A JP2013144555A JP5805149B2 JP 5805149 B2 JP5805149 B2 JP 5805149B2 JP 2013144555 A JP2013144555 A JP 2013144555A JP 2013144555 A JP2013144555 A JP 2013144555A JP 5805149 B2 JP5805149 B2 JP 5805149B2
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- JP
- Japan
- Prior art keywords
- acid
- fountain solution
- water
- printing
- concentrated composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 29
- 239000000243 solution Substances 0.000 claims description 89
- -1 organic acid salts Chemical class 0.000 claims description 53
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- 239000002253 acid Substances 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 235000010338 boric acid Nutrition 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
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- 125000005619 boric acid group Chemical class 0.000 claims description 6
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 4
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- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 4
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 10
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- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
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- 229940093915 gynecological organic acid Drugs 0.000 description 3
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
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- FYGDTMLNYKFZSV-UHFFFAOYSA-N mannotriose Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(O)C(O)C2O)CO)C(O)C1O FYGDTMLNYKFZSV-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- GHTWQCXOBQMUHR-UHFFFAOYSA-M potassium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [K+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O GHTWQCXOBQMUHR-UHFFFAOYSA-M 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 201000008559 xeroderma pigmentosum group F Diseases 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Landscapes
- Printing Plates And Materials Therefor (AREA)
- Detergent Compositions (AREA)
Description
本発明は、平版印刷用湿し水濃縮組成物およびそれを水で希釈した湿し水、特に、無処理(無現像)型平版印刷版を用いた平版印刷においても使用可能な湿し水、当該湿し水を用いた平版印刷方法および印刷物に関する。 The present invention relates to a fountain solution concentrate for lithographic printing and a fountain solution obtained by diluting the fountain solution with water, in particular, a fountain solution that can be used in lithographic printing using an unprocessed (non-development) type lithographic printing plate, The present invention relates to a planographic printing method and printed matter using the fountain solution.
平版印刷版は、印刷過程でインクを受容する親油性の画像部と湿し水を受容する親水性の非画像部とからなる。 従来の平版印刷版は、親水性支持体上に親油性の感光性樹脂層を設けたPS版に、リスフイルムを介してマスク露光した後、非画像部を現像液によって溶解除去することにより製版(PS版)することが一般的であった。
近年では、コンピュータが画像をデジタル情報として電子的に処理し、蓄積して、出力する。 従って、デジタル画像情報に応じた画像形成処理は、レーザー光のような指向性の高い活性放射線を用いる走査露光により、リスフイルムを介することなく、平版印刷原版に対して直接画像を形成する。 このようにデジタル画像情報からリスフイルムを介さずに印刷版を製版する技術は、コンピュータ・トゥ・プレート(CTP)
とよばれている。
The lithographic printing plate is composed of an oleophilic image portion that receives ink in the printing process and a hydrophilic non-image portion that receives dampening water. Conventional lithographic printing plates are made by exposing a non-image area to a PS plate having a lipophilic photosensitive resin layer on a hydrophilic support through a lith film and then dissolving and removing the non-image area with a developer. (PS version) was common.
In recent years, computers electronically process, store, and output images as digital information. Therefore, in the image forming process corresponding to the digital image information, an image is directly formed on the lithographic printing original plate without using a lith film by scanning exposure using active radiation having high directivity such as laser light. In this way, the technology for making a printing plate from digital image information without using a lithographic film is known as computer-to-plate (CTP).
It is called.
しかしながら、これら従来のPS版やCTP版を用いる印刷版では、露光の後、非画像部を溶解除去する工程(現像処理) に加え、現像処理された印刷版を水洗したり、界面活性剤を含有するリンス液で処理したり、アラビアガムや澱粉誘導体を含む不感脂化液で処理する後処理工程が必要であった。 However, in printing plates using these conventional PS plates and CTP plates, after the exposure, in addition to the step of dissolving and removing the non-image area (development treatment), the developed printing plate is washed with water or a surfactant is added. The post-processing process processed with the rinse liquid to contain or processed with the desensitizing liquid containing gum arabic and a starch derivative was required.
そこで、地球環境の保全の観点から、使用材料や廃棄物を削減するため、これらの付加的な湿式の処理を使用しない機上現像型(無処理型)の平版印刷版が開発され使用されてきている。 このような無処理型平版印刷版を用いた平版印刷において、従来の湿し水を用いた場合、機上現像性に問題が生じたり、得られた印刷物の非画像部に汚れが発生しやすいといった問題がある。 Therefore, from the viewpoint of global environmental conservation, on-press development type (non-processing type) lithographic printing plates that do not use these additional wet processes have been developed and used in order to reduce materials and waste. ing. In lithographic printing using such an unprocessed lithographic printing plate, when conventional dampening water is used, problems occur in on-machine developability and stains are likely to occur in the non-image area of the obtained printed matter. There is a problem.
特許文献1〜4には、プロセスレス(無処理型)印刷材料の印刷方法に用いる湿し水が開示され、これを用いると印刷版が印刷機上で現像可能であり、かつ印刷時の汚れ回復性に優れ、耐刷性に優れているとしている。 Patent Documents 1 to 4 disclose fountain solution used for a processless (non-processed) printing material printing method. When this is used, the printing plate can be developed on a printing press, and stains during printing can be obtained. It is said that it has excellent recoverability and printing durability.
また、特許文献5には、リン酸基、ホスホン酸基、スルホン酸基及びそれらの塩の基から選ばれる基を少なくとも一つ有する繰り返し単位を含むビニル共重合体を含有する印刷用湿し水が開示され、良好な機上現像性及び汚れ性が得られる平版印刷用の湿し水ならびに印刷方法を提供することができるとしている。 Patent Document 5 discloses a fountain solution for printing containing a vinyl copolymer containing a repeating unit having at least one group selected from a phosphoric acid group, a phosphonic acid group, a sulfonic acid group and a salt thereof. Is disclosed, and a fountain solution for lithographic printing and a printing method capable of providing good on-press developability and stain resistance can be provided.
しかしながら、これらの特許文献の発明は、特に無処理型平版印刷版に用いたときにその性能を発揮できるものであり、機上現像性および刷り出し汚れへの耐性に関してもまだ不十分なため更なる改良が必要である。
なお、湿し水は一般的には濃縮された形で流通し、印刷現場において水で希釈して使用される。従って、ここでは、濃縮された形のものを「湿し水濃縮組成物」とし、印刷現場で実際に使用されるものを「湿し水」と定義する。
However, the inventions of these patent documents can exhibit their performance particularly when used in an unprocessed lithographic printing plate, and are further insufficient in terms of on-machine developability and resistance to printing stains. An improvement is needed.
The fountain solution generally circulates in a concentrated form and is diluted with water at the printing site. Accordingly, here, the concentrated form is defined as a “fountain solution concentrated composition”, and the actual form used at the printing site is defined as a “fountain solution”.
本発明は、無処理型平版印刷版では優れた機上現像性と版の保護効果、さらに従来のPS版およびCTP版では非画像部の保護効果を有する平版印刷方法、版の種類によらず印刷中に発生する非画像部の汚れおよび印刷機一旦停止後の刷り出し時に発生する刷り出し汚れが発生しにくい平版印刷方法、これらの平版印刷方法に用いる湿し水濃縮組成物並びにそれを希釈した湿し水、さらにこの平版印刷方法により印刷された印刷物を提供することを課題とする。 The present invention relates to a lithographic printing method having an excellent on-press developability and plate protecting effect for a non-process type lithographic printing plate, and a non-image area protecting effect for a conventional PS plate and CTP plate, regardless of the type of plate. Lithographic printing methods in which stains in non-image areas that occur during printing and printing stains that occur when printing is temporarily stopped after printing is stopped, fountain solution concentrated compositions used in these lithographic printing methods, and dilution thereof It is an object of the present invention to provide a fountain solution that has been printed, and a printed matter printed by the planographic printing method.
本発明者は、平版印刷においては従来のPS版およびCTP版に加え、最近では無処理型平版印刷版が使用されてきている状況を踏まえ、これらの版の種類に影響されずに優れた印刷物を与える湿し水について鋭意検討した結果、本発明を完成した。 In light of the situation that non-processed lithographic printing plates have recently been used in addition to conventional PS plates and CTP plates in lithographic printing, the present inventor has excellent printed matter without being affected by the type of these plates. As a result of diligent investigation on the fountain solution that gives water, the present invention was completed.
すなわち、本発明は、
(1) 平版印刷方法に用いる湿し水濃縮組成物であって、
酸、塩類および水溶性有機溶媒を含有し、
前記酸が有機酸および/または無機酸であり、
前記塩類が有機酸の塩および/または無機酸の塩であり、
前記水溶性有機溶媒がグリコール類、グリコール類のモノアルキルエーテル、およびアルコール類から選択される一種または二種以上を含み、
前記水溶性有機溶媒の含有量が10重量%以上であり、
当該湿し水濃縮組成物を水により重量で100倍希釈した水溶液のpHが3〜5で、その水溶液200mlに0.1規定水酸化ナトリウム水溶液を滴下していったとき、pH8になるまでの滴下量が7ml以上であることを特徴とする湿し水濃縮組成物、
(2) 前記水溶性有機溶媒が2個の水酸基を有し、該2個の水酸基間の最短の炭素数が2〜6で、かつ総炭素数が9であるジオール系非環状炭化水素化合物をさらに含む(1)記載の湿し水濃縮組成物、
(3) 前記酸が、リン酸、クエン酸、グルコン酸、リンゴ酸、コハク酸およびマレイン酸から選ばれた少なくとも1つを含有することを特徴とする(1)または(2)記載の湿し水濃縮組成物、
(4) さらに、ホウ酸類またはフタル酸水素カリウムを含有することを特徴とする(3)記載の湿し水濃縮組成物、
(5) 前記ホウ酸類がホウ酸、三酸化二ホウ素および四ホウ酸ナトリウムから選ばれた少なくとも1つであることを特徴とする(4)記載の湿し水濃縮組成物、
(6) (1)から(5)のいずれかに記載の湿し水濃縮組成物を水により重量で25〜200倍に希釈したことを特徴とする湿し水、
(7)(6)に記載の湿し水を用いて印刷する工程を含む平版印刷方法、
(8) (7)に記載の平版印刷方法により得られた印刷物、
である。
That is, the present invention is,
(1) A dampening water concentrate composition used in the flat plate printing method,
Containing acids, salts and water-soluble organic solvents;
The acid is an organic acid and / or an inorganic acid;
The salts are organic acid salts and / or inorganic acid salts;
The water-soluble organic solvent includes one or more selected from glycols, monoalkyl ethers of glycols, and alcohols,
The content of the water-soluble organic solvent is 10 wt% or more,
When the pH of an aqueous solution obtained by diluting the fountain solution concentrated composition 100 times by weight with water is 3 to 5, and 0.1N aqueous sodium hydroxide solution is added dropwise to 200 ml of the aqueous solution, A fountain solution concentrated composition characterized in that the dripping amount is 7 ml or more ,
(2) the water-soluble organic solvent has two hydroxyl groups, the number of carbon atoms in the shortest between the two hydroxyl groups is 2-6, and the diol-based non-cyclic hydrocarbon compound is a total carbon number of 9 Furthermore, the fountain solution concentration composition according to ( 1 ),
( 3 ) The dampening according to ( 1 ) or ( 2 ) , wherein the acid contains at least one selected from phosphoric acid, citric acid, gluconic acid, malic acid, succinic acid and maleic acid Water concentrated composition,
( 4 ) The fountain solution concentrated composition according to ( 3 ), further comprising boric acids or potassium hydrogen phthalate,
( 5 ) The fountain solution concentrated composition according to ( 4 ), wherein the boric acid is at least one selected from boric acid, diboron trioxide and sodium tetraborate.
( 6 ) A fountain solution characterized in that the fountain solution concentrate composition according to any one of ( 1 ) to ( 5 ) is diluted 25 to 200 times by weight with water ,
(7) A lithographic printing method comprising a step of printing using the fountain solution according to (6),
( 8 ) Printed matter obtained by the planographic printing method according to ( 7) ,
It is.
一般に、湿し水は湿し水濃縮組成物を水で25倍から200倍に希釈して用いる。流通時または使用時の取り扱いの簡便性から、湿し水はできるだけ少量の湿し水濃縮組成物を用いて高度に希釈して用いることが望まれる。従って、湿し水濃縮組成物はできるだけ高濃度になるように設計されるが、特に水溶性有機溶媒や水溶性高分子化合物を含む場合は、含有する酸や塩が析出したり、場合によっては不均一な混合物となるため、高濃度にするには限界がある。 In general, the fountain solution is used by diluting the fountain solution concentrated composition with water 25 to 200 times. In view of the ease of handling during distribution or use, it is desirable that the fountain solution be highly diluted with a fountain solution concentrate as small as possible. Therefore, the fountain solution concentrate composition is designed to have a concentration as high as possible, but particularly when it contains a water-soluble organic solvent or a water-soluble polymer compound, the contained acid or salt may precipitate, or in some cases. Since this is a non-uniform mixture, there is a limit to achieving a high concentration.
ここで、湿し水濃縮組成物を水により重量で100倍希釈した水溶液200mlに0.1規定水酸化ナトリウム水溶液を滴下していったとき、pH8になるまでの滴下量をpH緩衝性(単位ml)とする。
pH緩衝性は、湿し水のpH変動の難易性を表す指標である。すなわち、数値が大きいほどpHが変化しにくく、小さいほど変化しやすい。一般には、pHが低いほうが結果としてpH緩衝性が大きくなることもあり得るので、初期のpHを限定している。また、印刷版に対する初期のpHの影響も無視できない。
Here, when a 0.1N sodium hydroxide aqueous solution was dropped into 200 ml of an aqueous solution obtained by diluting the fountain solution concentrated composition 100 times with water, the amount of dripping until reaching pH 8 was adjusted to pH buffering property (unit: ml).
The pH buffering property is an index representing the difficulty of pH change of the fountain solution. That is, the larger the value, the more difficult the pH changes, and the smaller the value, the easier it changes. In general, the lower the pH, the larger the pH buffering property may result, so the initial pH is limited. Also, the influence of the initial pH on the printing plate cannot be ignored.
刷り出し汚れは、版の材料であるアルミニウム表面の局部的な酸化現象により誘発されると推測され、この酸化現象は、pH緩衝性が大きい場合やホウ酸類またはフタル酸水素カリウムが存在することによって抑制されるものと考えられる。 The imprinting stain is presumed to be induced by a local oxidation phenomenon on the surface of the aluminum plate material. This oxidation phenomenon is caused by the presence of boric acids or potassium hydrogen phthalate when pH buffering is large. It is considered to be suppressed.
本発明によると、無処理型平版印刷版では機上現像性に優れ、印刷機一旦停止後の刷り出し汚れが生じにくくなるため損紙を最少にして汚れのない印刷物を与えかつ、その印刷版の保護効果も有する湿し水および湿し水濃縮組成物、その湿し水を用いた印刷方法、その印刷方法による印刷物を提供することができる。
また、従来のPS版およびCTP版においても版の保護効果に優れ、印刷機一旦停止後の刷り出し汚れを生じにくくする効果を有する。 さらに、印刷版の種類によらず、印刷適性に優れる。
According to the present invention, an unprocessed planographic printing plate has excellent on-press developability, and is less likely to cause printing stains after the printing press is stopped. The fountain solution and the fountain solution concentrate having the protective effect of the fountain solution, the printing method using the fountain solution, and the printed matter by the printing method can be provided.
Further, the conventional PS plate and CTP plate are also excellent in plate protecting effect and have the effect of making it difficult to cause printing stains after the printing press is temporarily stopped. Furthermore, it is excellent in printability regardless of the type of printing plate.
以下、本発明を実施するための形態を詳細に説明する。 なお、本実施形態は、本発明を実施するための一形態に過ぎず、本発明は本実施形態によって限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更実施の形態が可能である。 以下の説明において「部」は「重量部」、「%」は「重量%」を示し、希釈倍数は重量で計算された数値である。 Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that this embodiment is merely an embodiment for carrying out the present invention, and the present invention is not limited by this embodiment, and various modified embodiments can be made without departing from the gist of the present invention. Is possible. In the following description, “part” represents “part by weight”, “%” represents “% by weight”, and the dilution factor is a numerical value calculated by weight.
本発明の湿し水濃縮組成物は、水溶性有機溶媒を10重量%以上含有し、当該湿し水濃縮組成物を水により重量で100倍希釈した水溶液のpHが3〜5で、その水溶液200mlに0.1規定水酸化ナトリウム水溶液を滴下していったとき、pH8になるまでの滴下量が5ml以上であることを特徴とする。 The fountain solution concentrate composition of the present invention contains 10% by weight or more of a water-soluble organic solvent, and the aqueous solution obtained by diluting the fountain solution concentrate composition 100 times by weight with water has a pH of 3 to 5, and the aqueous solution. When a 0.1N aqueous sodium hydroxide solution is dropped into 200 ml, the drop amount until reaching pH 8 is 5 ml or more.
本発明の湿し水濃縮組成物は、水で100倍に希釈したときpH3〜5の範囲が好ましい。pH3未満では版に対するエッチング効果が強くなり、耐刷性が低下する。pHを3〜5に調整するためには、水溶性の有機酸、無機酸及びそれらの塩類から選ばれる少なくとも1種を使用する。 The fountain solution concentrate composition of the present invention preferably has a pH range of 3 to 5 when diluted 100 times with water. If the pH is less than 3, the etching effect on the plate becomes strong and the printing durability is lowered. In order to adjust the pH to 3 to 5, at least one selected from water-soluble organic acids, inorganic acids and salts thereof is used.
本発明の湿し水濃縮組成物のpH緩衝性は水で100倍に希釈したとき5ml以上が好ましく、より好ましいのは7ml以上である。pH緩衝性を5ml以上にすることによって、印刷機一旦停止後の刷り出し汚れが生じにくくなり、非画像部の保護効果に優れ、無処理型平版印刷版では機上現像性にも優れ、7ml以上ではこれらの効果が安定する。pH緩衝性を5ml以上とするには、酸の量を増やしながら調整すればよいが、pHが低くなりすぎる場合は、適宜塩類を同時に添加して調整する。 The pH buffering property of the fountain solution concentrated composition of the present invention is preferably 5 ml or more, more preferably 7 ml or more when diluted 100 times with water. By setting the pH buffering property to 5 ml or more, printing stains are less likely to occur after the printing machine has been stopped, and it is excellent in protecting the non-image area. As described above, these effects are stabilized. In order to adjust the pH buffering property to 5 ml or more, it may be adjusted while increasing the amount of acid. However, if the pH is too low, it is adjusted by adding salts at the same time.
用いる酸としては、有機酸では、例えばクエン酸、アスコルビン酸、リンゴ酸、酒石酸、乳酸、酢酸、グルコン酸、コハク酸、マレイン酸、ヒドロキシ酢酸、蓚酸、マロン酸、レブリン酸、スルファニル酸、p−トルエンスルホン酸、フィチン酸、有機ホスホン酸等が挙げられ、無機酸では、例えばリン酸、硝酸、硫酸、ポリリン酸が挙げられる。
これらの酸の中でも特に、リン酸、クエン酸、リンゴ酸、コハク酸、グルコン酸およびマレイン酸が好ましく用いられる。
さらに、これら有機酸および/または無機酸のアルカリ金属塩、アルカリ土類金属塩あるいはアンモニウム塩、有機アミン塩も用いられ、これらの有機酸、無機酸及びこれらの塩から1種を単独で使用しても、あるいは2種以上の混合物として使用してもよい。これらの中でも、特に硝酸アンモニウム、リン酸塩、クエン酸塩、p−トルエンスルホン酸塩が好ましく用いられ、その含有量は湿し水濃縮組成物に対し1〜10%である。
As the acid used, for example, citric acid, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, gluconic acid, succinic acid, maleic acid, hydroxyacetic acid, succinic acid, malonic acid, levulinic acid, sulfanilic acid, p- Examples include toluenesulfonic acid, phytic acid, and organic phosphonic acid. Examples of inorganic acids include phosphoric acid, nitric acid, sulfuric acid, and polyphosphoric acid.
Among these acids, phosphoric acid, citric acid, malic acid, succinic acid, gluconic acid and maleic acid are preferably used.
Furthermore, alkali metal salts, alkaline earth metal salts or ammonium salts of these organic acids and / or inorganic acids, and organic amine salts are also used. One of these organic acids, inorganic acids and salts thereof is used alone. Or you may use as a mixture of 2 or more types. Among these, ammonium nitrate, phosphate, citrate, and p-toluenesulfonate are particularly preferably used, and the content thereof is 1 to 10% with respect to the fountain solution concentrated composition.
本発明の湿し水濃縮組成物は、さらにホウ酸類を含有することができる。ホウ酸類としては、ホウ酸、三酸化二ホウ素(無水または水和物)、四ホウ酸ナトリウム(無水物または水和物)、メタホウ酸ナトリウム等が挙げられ、その1種または2種以上を使用できるが、特に、ホウ酸、三酸化二ホウ素、四ホウ酸ナトリウムが好ましく用いられる。その含有量は湿し水濃縮組成物に対して0.5〜3%が好ましい。 The fountain solution concentrated composition of the present invention can further contain boric acids. Examples of boric acids include boric acid, diboron trioxide (anhydrous or hydrate), sodium tetraborate (anhydride or hydrate), sodium metaborate, etc., one or more of which are used. In particular, boric acid, diboron trioxide, and sodium tetraborate are preferably used. The content is preferably 0.5 to 3% with respect to the fountain solution concentrated composition.
本発明の湿し水濃縮組成物には、ホウ酸類の他にフタル酸水素カリウムを併用または単独で用いることができる。その含有量は湿し水濃縮組成物に対して0.5〜2%が好ましい。 In the fountain solution concentrated composition of the present invention, potassium hydrogen phthalate can be used in combination or alone in addition to boric acids. The content is preferably 0.5 to 2% with respect to the fountain solution concentrated composition.
本発明の湿し水濃縮組成物には、グリコール類および/またはアルコール類などの水溶性有機溶媒を用いる。
このような水溶性有機溶媒として、例えばエチレングリコールモノメチルエーテル、ジ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メチルエーテル、テトラ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、ジエチレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、テトラ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、ジエチレングリコールモノプロピルエーテル、トリエチレングリコールモノプロピルエーテル、テトラ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イソプロピルエーテル、ジエチレングリコールモノイソプロピルエーテル、トリエチレングリコールモノイソプロピルエーテル、テトラエチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、テトラ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イソブチルエーテル、ジエチレングリコールモノイソブチルエーテル、トリエチレングリコールモノイソブチルエーテル、テトラエチレングリコールモノイソブチルエーテル、エチレングリコールモノターシャリブチルエーテル、ジエチレングリコールモノターシャリブチルエーテル、トリエチレングリコールモノターシャリブチルエーテル、テトラエチレングリコールモノターシャリブチルエーテル、プロピレングリコールモノメチルエーテル、ジ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メチルエーテル、テトラ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、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノエチルエーテル、テトラ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プロピルエーテル、トリプロピレングリコールモノプロピルエーテル、テトラプロピレングリコールモノプロピルエーテル、プロピレングリコールモノイソプロピルエーテル、ジプロピレングリコールモノイソプロピルエーテル、トリプロピレングリコールモノイソプロピルエーテル、テトラプロピレングリコールモノイソプロピルエーテル、プロピレングリコールモノブチルエーテル、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ブチルエーテル、テトラプロピ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イソブチルエーテル、ジプロピレングリコールモノイソブチルエーテル、トリプロピレングリコールモノイソブチルエーテル、テトラプロピレングリコールモノイソブチルエーテル、プロピレングリコールモノターシャリブチルエーテル、ジプロピレングリコールモノターシャリブチルエーテル、トリプロピレングリコールモノターシャリブチルエーテル、テトラプロピレングリコールモノターシャリブチルエーテル、分子量200〜1000のポリプロピレングリコールおよびそれらのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノイソプロピルエーテルおよびモノブチルエーテル、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコールおよびペンタプロピレングリコール、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、ブチレングリコール、ヘキシレングリコール、1,2−オクタンジオール、エチルアルコール、イソプロピルアルコール、n−プロピルアルコール、ベンジルアルコール、エチレングリコールモノフェニルエーテル、2−エチル−1,3−ヘキサンジオール、3−メトキシ−3−メチル−1−ブタノール、1−ブトキシ−2−プロパノール、ジグリセリン、ポリグリセリン、トリメチロールプロパン、ペンタエリスリトール、メトキシエタノール、エトキシエタノール、ブトキシエタノール、3−メトキシブタノールなどが挙げられ、好ましくはグリコール類またはそのアルキルエーテルである。
The fountain solution concentrated composition of the present invention uses a water-soluble organic solvent such as glycols and / or alcohols.
Examples of such water-soluble organic solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, tetraethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl Ether, tetraethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, tetraethylene Glycol monoisobutyl ether, ethylene glycol monotertiary butyl ether, diethylene glycol monotertiary butyl ether, triethylene glycol monotertiary butyl ether, tetraethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether, dipropylene glycol Monomethyl ether, tripropylene glycol monomethyl ether, tetrapropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetrapropylene glycol monoethyl ether, propylene glycol monopropyl ether, di Propylene glycol monopropyl ether, tripropylene glycol monopropyl ether, tetrapropylene glycol monopropyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, tetrapropylene glycol monoisopropyl ether, propylene Lenglycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, tetrapropylene glycol monoisobutyl ether, Propylene glycol monotertiary butyl ether, dipropylene glycol monotertiary butyl ether, tripropylene glycol monotertiary butyl ether, tetrapropylene glycol monotertiary butyl ether, polypropylene glycol having a molecular weight of 200 to 1000 and their monomethyl ether, monoethyl ether Monopropyl ether, monoisopropyl ether and monobutyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and pentapropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butylene glycol, hexylene glycol, 1 , 2-octanediol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, benzyl alcohol, ethylene glycol monophenyl ether, 2-ethyl-1,3-hexanediol, 3-methoxy-3-methyl-1-butanol, 1 -Butoxy-2-propanol, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol Lithol, methoxyethanol, ethoxyethanol, butoxyethanol and 3-methoxybutanol and the like, preferably glycols or their alkyl ethers.
これらの水溶性有機溶媒を単独または2種以上を、湿し水濃縮組成物中10〜70%で使用するのが好ましい。特に好ましくは30〜60%である。 These water-soluble organic solvents are preferably used alone or in combination of two or more at 10 to 70% in the fountain solution concentrated composition. Especially preferably, it is 30 to 60%.
また、2個のOH基を有し、該2個のOH基間の最短の炭素数が2〜6であり、かつ総炭素数が9であるジオール系非環状炭化水素化合物を上記水溶性有機溶媒と併用してもよい。特に、2−ブチル−2−エチル−1,3−プロパンジオールおよび2,4−ジエチル−1,5−ペンタンジオールから選ばれた少なくとも1つが好ましく用いられる。 In addition, the diol-type acyclic hydrocarbon compound having two OH groups, the shortest carbon number between the two OH groups is 2 to 6, and the total carbon number is 9, You may use together with a solvent. In particular, at least one selected from 2-butyl-2-ethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol is preferably used.
本発明の湿し水濃縮組成物には、水溶性高分子化合物を添加してもよい。 A water-soluble polymer compound may be added to the fountain solution concentrated composition of the present invention.
このような水溶性高分子化合物の具体的な例としてはアラビアゴム、澱粉誘導体(例えばデキストリン、酵素分解デキストリン、ヒドロキシプロピル化酵素分解デキストリン、カルボキシメチル化澱粉、燐酸澱粉、オクテニルコハク化澱粉など)、アルギン酸塩、繊維素誘導体(例えばカルボキシメチルセルロース、カルボキシエチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、ヒドロキシプロピルメチルセルロース、それらのグリオキサール変性体など)の天然物とその変性体およびポリビニルアルコールおよびその誘導体、ポリビニルピロリドン、ポリアクリルアミドおよびその共重合体、ポリアクリル酸およびその共重合体、ビニルメチルエーテル/無水マレイン酸共重合体、酢酸ビニル/無水マレイン酸共重合体などの合成物が挙げられる。これらの高分子化合物は単独でまたは混合して使用でき、その含有量の範囲は湿し水濃縮組成物中、0〜2%、より好ましくは、0.5〜1%である。 Specific examples of such water-soluble polymer compounds include gum arabic, starch derivatives (eg, dextrin, enzymatically degraded dextrin, hydroxypropylated enzymatically degraded dextrin, carboxymethylated starch, phosphate starch, octenyl succinated starch), alginic acid. Natural products such as salts, fiber derivatives (such as carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose, glyoxal modified products thereof) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and Copolymer, polyacrylic acid and its copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer What compounds, and the like. These polymer compounds can be used alone or in admixture, and the content range is 0 to 2%, more preferably 0.5 to 1% in the fountain solution concentrated composition.
本発明の湿し水濃縮組成物にはまた、糖類およびグリセリンからなる群から選ばれる少なくとも1種を添加してもよい。使用する糖類としては、単糖類、二糖類及びオリゴ糖類などから選択することができ、水素添加によって得られる糖アルコールもこれに含まれる。具体例としてD−エリトロース、D−スレオース、D−アラビノース、D−リボース、D−キシロース、D−エリスロ−ペンテュロース、D−アルロース、D−ガラクトース、D−グルコース、D−マンノース、D−タロース、β−D−フラクトース、α−L−ソルボース、6−デオキシ−D−グルコース、D−グリセロ−D−ガラクトース、α−D−アルロ−ヘプチュロース、β−D−アルトロ−3−ヘプチュロース、サッカロース、ラクトース、D−マルトース、イソマルトース、イヌロビオース、ヒアルビオウロン、マルトトリオース、D,L−アラビット、リビット、キシリット、D,L−ソルビット、D,L−マンニット、D,L−イジット、D,L−タリット、ズルシット、アロズルシット、マルチトール、還元水あめなどが挙げられる。これらの糖類は1種単独または2種以上を併用してもよい。 You may add at least 1 sort (s) chosen from the group which consists of saccharides and glycerin to the fountain solution concentration composition of this invention. The sugar to be used can be selected from monosaccharides, disaccharides, oligosaccharides, and the like, and includes sugar alcohols obtained by hydrogenation. Specific examples include D-erythrose, D-throse, D-arabinose, D-ribose, D-xylose, D-erythro-pentulose, D-allulose, D-galactose, D-glucose, D-mannose, D-talose, β -D-fructose, α-L-sorbose, 6-deoxy-D-glucose, D-glycero-D-galactose, α-D-allo-heptulose, β-D-alto-3-heptulose, saccharose, lactose, D Maltose, isomaltose, inulobiose, hyalbiouron, maltotriose, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-digit, D, L-talit, zulcit , Allozulcit, maltitol, reduced water candy, etc. It is. These saccharides may be used alone or in combination of two or more.
湿し水濃縮組成物において、糖類およびグリセリンからなる群から選ばれる少なくとも1種の含有量の範囲は0〜5%が適当であり、好ましくは1〜3%である。 In the fountain solution concentrated composition, the content range of at least one selected from the group consisting of saccharides and glycerin is suitably 0 to 5%, preferably 1 to 3%.
以上の成分の他に、本発明の湿し水濃縮組成物にはキレート化合物を添加することができる。通常、濃縮液である湿し水濃縮組成物に水道水、井戸水等を加えて希釈し、湿し水として使用する。この際希釈する水道水や井戸水に含まれているカルシウムイオン等が印刷に影響を与え、印刷物を汚れ易くする原因となることもある。このような場合、キレート化合物を添加しておくことにより、上記欠点を解消することができる。好ましいキレート化合物としては例えば、エチレンジアミンテトラ酢酸、そのカリウム塩、そのナトリウム塩;ジエチレントリアミンペンタ酢酸、そのカリウム塩、そのナトリウム塩;トリエチレンテトラミンヘキサ酢酸、そのカリウム塩、そのナトリウム塩;ヒドロキシエチルエチレンジアミントリ酢酸、そのカリウム塩、そのナトリウム塩;ニトリロトリ酢酸、そのカリウム塩、そのナトリウム塩;1,2−ジアミノシクロヘキサンテトラ酢酸、そのカリウム塩、そのナトリウム塩;1,3−ジアミノ−2−プロパノールテトラ酢酸、そのカリウム塩、そのナトリウム塩などのようなアミノポリカルボン酸類や2−ホスホノブタントリカルボン酸−1,2,4,そのカリウム塩、そのナトリウム塩;2−ホスホノブタントリカルボン酸−2,3,4,そのカリウム塩、そのナトリウム塩;1−ホスホノエタントリカルボン酸−1,2,2,そのカリウム塩、そのナトリウム塩;1−ヒドロキシエタン−1,1−ジホスホン酸、そのカリウム塩、そのナトリウム塩;アミノトリ(メチレンホスホン酸)、そのカリウム塩、そのナトリウム塩などのような有機ホスホン酸類あるいはホスホノアルカントリカルボン酸類を挙げることができる。
上記のキレート剤のナトリウム塩あるいはカリウム塩の代わりに有機アミンの塩も有効である。
これらのキレート剤は湿し水濃縮組成物中に安定に存在し、印刷性を阻害しないものが選ばれる。含有する量の範囲としては湿し水濃縮組成物中0.01〜1%、好ましくは0.05〜0.5%である。
In addition to the above components, a chelate compound can be added to the fountain solution concentrated composition of the present invention. Usually, tap water, well water, etc. are added and diluted to the fountain solution concentrated composition which is a concentrate, and used as the fountain solution. At this time, calcium ions or the like contained in the tap water or well water to be diluted may affect the printing and cause the printed matter to be easily stained. In such a case, the above disadvantages can be eliminated by adding a chelate compound. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof; hydroxyethylethylenediaminetriacetic acid Nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its Aminopolycarboxylic acids such as potassium salt and sodium salt thereof, 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt and sodium salt thereof; 2-phosphonobutanetricarboxylic acid- , 3,4, its potassium salt, its sodium salt; 1-phosphonoethanetricarboxylic acid-1,2,2, its potassium salt, its sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt Organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salt, sodium salt, and the like.
Organic amine salts are also effective in place of the sodium or potassium salts of the above chelating agents.
These chelating agents are selected so that they are stably present in the fountain solution concentrated composition and do not inhibit the printability. The range of the content is 0.01 to 1%, preferably 0.05 to 0.5% in the fountain solution concentrated composition.
本発明の湿し水濃縮組成物には、さらに着色剤、防錆剤、消泡剤などを含有させてもよい。着色剤として食品用色素等が好ましく使用できる。例えば、黄色色素としてはCINo.19140、15985、赤色色素としてはCINo.16185、45430、16255、45380、45100、紫色色素としてはCINo.42640、青色色素としてはCINo.42090、73015、緑色色素としてはCINo.42095、等が挙げられる。 The fountain solution concentrated composition of the present invention may further contain a colorant, a rust inhibitor, an antifoaming agent and the like. Food coloring agents and the like can be preferably used as the colorant. For example, CINo. 19140, 15985 and CI No. 16185, 45430, 16255, 45380, 45100, and purple pigments such as CI No. 42640, as a blue pigment, CI No. 42090 and 73015, CINo. 42095, and the like.
防錆剤としては、例えばベンゾトリアゾール、5−メチルベンゾトリアゾール、チオサリチル酸、ベンゾイミダゾール及びその誘導体等が挙げられる。 Examples of the rust preventive include benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole and derivatives thereof.
消泡剤としてはシリコン消泡剤が好ましく、その中で乳化分散型及び可溶化型などのいずれも使用することができる。 As the antifoaming agent, a silicon antifoaming agent is preferable, and any of an emulsified dispersion type and a solubilized type can be used.
本発明の湿し水濃縮組成物には更に少量の界面活性剤を含有してもよい。 The fountain solution concentrated composition of the present invention may further contain a small amount of a surfactant.
例えば、アニオン型界面活性剤としては、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホこはく酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、N−メチル−N−オレイルタウリンナトリウム類、N−アルキルスルホこはく酸モノアミド2ナトリウム塩類、石油スルホン酸塩類、硬化ひまし油、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸エステル塩類、スチレン−無水マレイン酸共重合物の部分ケン化物類、オレフィン−無水マレイン酸共重合物の部分ケン化物類、ナフタレンスルホン酸塩ホルマリン縮合物類等が挙げられる。これらの中でもジアルキルスルホこはく酸塩類、アルキル硫酸エステル塩類及びアルキルナフタレンスルホン酸塩類が特に好ましく用いられる。 For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid salts, alkylnaphthalene. Sulfonates, alkylphenoxy polyoxyethylenepropyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, Hydrogenated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride Acid ester salts, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, styrene Examples thereof include partially saponified products of maleic anhydride copolymers, partially saponified products of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Of these, dialkylsulfosuccinates, alkylsulfate esters and alkylnaphthalenesulfonates are particularly preferably used.
また非イオン型界面活性剤としては、ポリオキシアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリスチリルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、グリセリン脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸部分エステル類、蔗糖脂肪酸部分エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシエチレンソルビトール脂肪酸部分エステル類、ポリグリセリン脂肪酸部分エステル類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、N,N−ビス−2−ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸エステル、トリアルキルアミンオキシドなどが挙げられる。その中でもポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレン−ポリオキシプロピレンブロックポリマー類等が好ましく用いられる。 Nonionic surfactants include polyoxyalkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial esters, sorbitan fatty acid moieties. Esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid partial esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyglycerin fatty acid partial esters, poly Oxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxy Alkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, such as trialkylamine oxides. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used.
カチオン界面活性剤としては、アルキルアミン塩類、第4級アンモニウム塩類、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体等が挙げられる。また両性界面活性剤の例としては、アルキルイミダゾリン類が挙げられる。さらに、フッ素系界面活性剤が挙げられる、例えば、フッ素系アニオン界面活性剤としては、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルリン酸エステル、フッ素系ノニオン界面活性剤としては、パーフルオロアルキルエチレンオキサイド付加物、パーフルオロアルキルプロピレンオキサイド付加物、フッ素系カチオン界面活性剤としては、パーフルオロアルキルトリメチルアンモニウム塩等が挙げられる。
これらの界面活性剤の含有量は発泡の問題やインキとの乳化を考慮すると、湿し水濃縮組成物中5%以下、好ましくは0.1〜2%の範囲が適当である。
Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like. Examples of amphoteric surfactants include alkyl imidazolines. In addition, examples of the fluorine-based anionic surfactant include fluorine-based surfactants, such as perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, and fluorine-based nonionic surfactants. Examples of the perfluoroalkylethylene oxide adduct, perfluoroalkylpropylene oxide adduct, and fluorine-based cationic surfactant include perfluoroalkyltrimethylammonium salts.
Considering the problem of foaming and emulsification with ink, the content of these surfactants is 5% or less, preferably 0.1 to 2% in the fountain solution concentrated composition.
本発明の湿し水濃縮組成物の残余は水である。
従って、上述の各種成分を水、好ましくは脱塩水に溶解し、湿し水の濃縮液である湿し水濃縮組成物を得ることができる。この湿し水濃縮組成物は低温にさらされたりすると場合によっては含有している塩類が析出したり、不均一となることがあるので適宜水で希釈して希釈された湿し水濃縮組成物としてもよい。これらの湿し水濃縮組成物を、水道水、井戸水等で25〜200倍に希釈し、使用時の湿し水とする。
The balance of the fountain solution concentrate of the present invention is water.
Therefore, the various components described above can be dissolved in water, preferably demineralized water, to obtain a fountain solution concentrated composition that is a concentrate of fountain solution. The fountain solution concentrated composition may be diluted with water as appropriate, since salt contained may precipitate or become uneven in some cases when exposed to low temperatures. It is good. These fountain solution concentrated compositions are diluted 25 to 200 times with tap water, well water, etc., and used as a fountain solution during use.
本発明の湿し水は、種々の平版印刷版に対して使用することができる。
例えば、アルミニウム板を支持体とし、その上に感光層を有する感光性平版印刷版(予め感光性を付与した印刷板で、PS版と呼ばれる。)を画像露光及び現像して得られた平版印刷版に対して好適に使用できる。
The fountain solution of the present invention can be used for various lithographic printing plates.
For example, a lithographic printing obtained by image exposure and development of a photosensitive lithographic printing plate having a photosensitive layer on the aluminum plate as a support (previously photosensitized printing plate called PS plate). It can be suitably used for a plate.
また、可視や赤外線のレーザーで直接露光するCTP用の平版印刷版(CTPプレート)にも好適に使用することができる。具体例としてはフォトポリマータイプデジタルプレート(例えば、コダックGC(株)製:エクスサーモTP−W)や、サーマルポジタイプデジタルプレート(例えば、富士フイルムグラフィックシステムズ(株)製:XPシリーズ)などが挙げられる。 Further, it can be suitably used for a lithographic printing plate (CTP plate) for CTP that is directly exposed with a visible or infrared laser. Specific examples include a photopolymer type digital plate (for example, Kodak GC Co., Ltd .: Exthermo TP-W) and a thermal positive type digital plate (for example, Fuji Film Graphic Systems Co., Ltd .: XP series). It is done.
さらに、無処理型平版印刷版にも好適に使用できる。無処理型平版印刷版では、印刷機上で可視や赤外線のレーザーで直接露光し、露光部分以外の非画像部を湿し水で洗い流し、その後、通常の平版印刷方法により印刷する。従って、無処理型平版印刷版では、従来のPS版やCTP版で使用されてきた現像処理、水洗、リンス液処理等の後処理工程が不要となるため、これらの廃棄物が排出されない。無処理型平版印刷版としては、例えば、ブルーアース(コニカミノルタビジネスソリューションズ(株)製)、XZ−R(富士フイルムグラフィックシステムズ(株)製)などが挙げられる。 Furthermore, it can be suitably used for an unprocessed planographic printing plate. In an unprocessed planographic printing plate, direct exposure is performed with a visible or infrared laser on a printing machine, non-image portions other than the exposed portion are washed away with dampening water, and then printing is performed by a normal planographic printing method. Accordingly, in the non-process type lithographic printing plate, post-treatment steps such as development processing, water washing, and rinsing liquid processing that have been used in conventional PS plates and CTP plates are not required, and these wastes are not discharged. Examples of the unprocessed planographic printing plate include Blue Earth (manufactured by Konica Minolta Business Solutions Co., Ltd.), XZ-R (manufactured by Fuji Film Graphic Systems Co., Ltd.), and the like.
従来のPS版、CTP版および無処理型平版印刷版を用いて印刷するには、これらの版に対して画像を露光して得られた印刷版を用いて一般的な平版印刷を行えばよい。 In order to print using conventional PS plates, CTP plates, and non-processed lithographic printing plates, general lithographic printing may be performed using printing plates obtained by exposing images to these plates. .
以下、本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
「湿し水濃縮組成物の製造」
本発明で用いた材料の製品名および製造(販売)会社を表1に記載した。
"Manufacture of fountain solution concentrate"
Table 1 shows the product names and manufacturing (sales) companies of the materials used in the present invention.
実施例1〜5
表2の組成(重量部)で混合し、実施例1〜5の湿し水濃縮組成物を得た。
Examples 1-5
The compositions (parts by weight) shown in Table 2 were mixed to obtain fountain solution concentrated compositions of Examples 1 to 5.
実施例6〜16
表3の組成(重量部)で混合し、実施例6〜16の湿し水濃縮組成物を得た。
Examples 6-16
The compositions (parts by weight) shown in Table 3 were mixed to obtain fountain solution concentrated compositions of Examples 6 to 16.
比較例1〜8
表4の組成(重量部)で混合して比較例1〜5の湿し水濃縮組成物を得た。また、比較例6〜8は市販の湿し水濃縮組成物であるが、比較例7で水溶性有機溶媒を使用していないことを除いて、これらの組成は不明である。
Comparative Examples 1-8
The fountain solution concentrated compositions of Comparative Examples 1 to 5 were obtained by mixing with the compositions (parts by weight) shown in Table 4. Moreover, although Comparative Examples 6-8 is a commercially available fountain solution concentration composition, these compositions are unknown except the comparative example 7 not using the water-soluble organic solvent.
「CTP版による印刷および刷り出し汚れの評価」
富士フイルムグラフィックシステムズ(株)製のCTP版であるXP−Fを用いて印刷版を作成し、印刷機はハイデルベルグ製SM102、印刷インキは東京インキ(株)製ZIPSET ニューセルボ墨、湿し水は上記実施例および比較例の湿し水濃縮組成物を50倍に希釈した湿し水を用い、通常の方法によりコート紙に印刷した。
1時間以上印刷した後、印刷機を停止し、30分以上後に印刷を再開した。再開後の印刷物の非画像部にインキによる汚れが生じているかを目視で観察し、汚れが発生しないものを○、汚れる場合があるものを△、汚れが必ず発生するものを×、として評価した。
"Evaluation of printing and printing stains with CTP plate"
A printing plate was created using XP-F, a CTP version manufactured by Fujifilm Graphic Systems Co., Ltd., the printing machine was SM102 made by Heidelberg, the printing ink was ZIPSET made by Tokyo Ink Co., Ltd. Using the fountain solution obtained by diluting the fountain solution concentrate compositions of Examples and Comparative Examples 50 times, printing was performed on the coated paper by a normal method.
After printing for 1 hour or more, the printing machine was stopped, and printing was resumed after 30 minutes or more. The non-image area of the printed material after restarting was visually observed to see if it was smudged with ink, and was evaluated as ◯ if no smudge occurred, △ if smudged, and x if smudge always occurred. .
「無処理型平版印刷版による印刷および刷り出し汚れの評価」
コニカミノルタビジネスソリューションズ(株)製の無処理型平版印刷版であるブルーアースを用いて画像を形成し、印刷機はハイデル(株)製SM102、印刷インキは東京インキ(株)製ZIPSET ニューセルボ墨、湿し水は上記実施例および比較例の湿し水濃縮組成物を50倍に希釈した湿し水を用い、通常の機上印刷の方法によりコート紙に印刷した。
1時間以上印刷した後、印刷機を停止し、30分以上後に印刷を再開した。再開後の印刷物の非画像部にインキによる汚れが生じているかを目視で観察し、汚れが発生しないものを○、汚れる場合があるものを△、汚れが必ず発生するものを×、として評価した。
"Evaluation of printing and printing stains with unprocessed planographic printing plates"
An image is formed using Blue Earth, which is an unprocessed lithographic printing plate manufactured by Konica Minolta Business Solutions, Inc., the printing machine is SM102 manufactured by Heidel, and the printing ink is ZIPSET New Cellbo ink manufactured by Tokyo Ink. The fountain solution used was a fountain solution obtained by diluting the fountain solution concentrates of the above-mentioned Examples and Comparative Examples 50 times, and the fountain solution was printed on coated paper by a normal on-press printing method.
After printing for 1 hour or more, the printing machine was stopped, and printing was resumed after 30 minutes or more. The non-image area of the printed material after restarting was visually observed to see if it was smudged with ink, and was evaluated as ◯ if no smudge occurred, △ if smudged, and x if smudge always occurred. .
「印刷適性」
印刷適性は、以下に記載の方法のとおり1)給水ローラ汚れ適性、2)乳化適性の2項目で評価した。
"Printability"
The printability was evaluated according to the following two methods: 1) water roller contamination and 2) emulsification.
1)給水ローラ汚れ適性
前記「無処理型平版印刷版による印刷および刷り出し汚れの評価」で用いた印刷方法により10,000枚印刷した。10,000枚の印刷後、給水ローラ上の汚れを目視により、ほとんど汚れなしを○、やや汚れが見られるものを△、汚れるものを×として評価した。
1) Water supply roller stain suitability 10,000 sheets were printed by the printing method used in the above-mentioned "printing with an unprocessed planographic printing plate and evaluation of printing stains". After printing 10,000 sheets, the stain on the water supply roller was visually evaluated as ◯ when there was almost no stain, Δ when there was some stain, and × when it was dirty.
2)乳化適性
前記「無処理型平版印刷版による印刷および刷り出し汚れの評価」で用いた印刷方法により10,000枚印刷した。10,000枚の印刷後、インキローラ上のインキの乳化状態を目視により、 適性な乳化が見られるものを○、やや過剰乳化が見られるものを△、過剰な乳化が見られ、印刷に耐えられないものを×として評価した。
2) Emulsification suitability 10,000 sheets were printed by the printing method used in the above-mentioned “printing with unprocessed lithographic printing plate and evaluation of printing stains”. After printing 10,000 sheets, visually check the emulsified state of the ink on the ink roller, ○ if the proper emulsification is seen, △ if the slightly emulsified is seen, excessive emulsification is seen and endure printing. What was not evaluated was evaluated as x.
以上の評価試験の結果を表5および6にまとめた。 The results of the above evaluation tests are summarized in Tables 5 and 6.
表5および表6から、実施例では明らかに刷り出し汚れが起こりにくく、印刷適性(給水ローラ汚れ適性、乳化適性)にも優れている。一方、比較例では市販の湿し水濃縮組成物を含め刷り出し汚れが起こりやすかったり、印刷適性に問題があったりすることが分かる。 From Tables 5 and 6, it is apparent that printing stains hardly occur in the examples, and the printability (water supply roller stain suitability and emulsification suitability) is excellent. On the other hand, it can be seen that, in the comparative example, imprinting stains easily occur including a commercially available fountain solution concentrated composition, and there is a problem in printability.
本発明の湿し水は、従来のPS版、CTP版および無処理型平版印刷版を用いた平版印刷において優れた印刷物を与え有用である。 The fountain solution of the present invention is useful because it provides excellent printed matter in lithographic printing using conventional PS plates, CTP plates, and non-processed lithographic printing plates.
Claims (8)
酸、塩類および水溶性有機溶媒を含有し、
前記酸が有機酸および/または無機酸であり、
前記塩類が有機酸の塩および/または無機酸の塩であり、
前記水溶性有機溶媒がグリコール類、グリコール類のモノアルキルエーテル、およびアルコール類から選択される一種または二種以上を含み、
前記水溶性有機溶媒の含有量が10重量%以上であり、
当該湿し水濃縮組成物を水により重量で100倍希釈した水溶液のpHが3〜5で、その水溶液200mlに0.1規定水酸化ナトリウム水溶液を滴下していったとき、pH8になるまでの滴下量が7ml以上であることを特徴とする湿し水濃縮組成物。 A fountain solution concentrate composition used in the flat plate printing method,
Containing acids, salts and water-soluble organic solvents;
The acid is an organic acid and / or an inorganic acid;
The salts are organic acid salts and / or inorganic acid salts;
The water-soluble organic solvent includes one or more selected from glycols, monoalkyl ethers of glycols, and alcohols,
The content of the water-soluble organic solvent is 10 wt% or more,
When the pH of an aqueous solution obtained by diluting the fountain solution concentrated composition 100 times by weight with water is 3 to 5, and 0.1N aqueous sodium hydroxide solution is added dropwise to 200 ml of the aqueous solution, A fountain solution concentrated composition, wherein the dripping amount is 7 ml or more.
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