JPH0659457A - Treatment of planographic printing plate - Google Patents
Treatment of planographic printing plateInfo
- Publication number
- JPH0659457A JPH0659457A JP4214190A JP21419092A JPH0659457A JP H0659457 A JPH0659457 A JP H0659457A JP 4214190 A JP4214190 A JP 4214190A JP 21419092 A JP21419092 A JP 21419092A JP H0659457 A JPH0659457 A JP H0659457A
- Authority
- JP
- Japan
- Prior art keywords
- printing plate
- added
- silver
- atom
- planographic printing
- 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.)
- Pending
Links
Landscapes
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、銀錯塩拡散転写法によ
る平版印刷版の処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a lithographic printing plate by a silver complex salt diffusion transfer method.
【0002】[0002]
【従来の技術】銀錯塩拡散転写法(DTR)によって得
られる銀画像を利用したオフセット印刷版は、既に特許
公報昭46―43132号あるいは特許公報昭48―3
0562号に記載されており、さらにポジタイプの印刷
原版については公開特許公報昭49―55402号に、
ネガタイプの印刷原版については公開特許公報昭52―
106902号、公開特許公報昭52―112402号
等に詳細に記載されている。2. Description of the Related Art An offset printing plate using a silver image obtained by a silver complex salt diffusion transfer method (DTR) has already been disclosed in Japanese Patent Publication No. 46-43132 or Japanese Patent Publication No. 48-3.
No. 0562, and a positive type printing original plate is disclosed in Japanese Patent Laid-Open Publication No. 49-55402.
Regarding negative type printing original plates, published patent publication Sho 52-
No. 106902, JP-A No. 52-112402, and the like.
【0003】これらのダイレクト印刷版は、支持体およ
びその上にハレーション防止を兼ねた下引き層、ハロゲ
ン化銀写真乳剤層、物理現像核層からなっている。感光
材料を像様露光後、現像薬とハロゲン化銀溶剤を含む現
像液で処理すると潜像が形成されているハロゲン化銀は
乳剤層中で黒化銀となるが、これに対して潜像が形成さ
れいないハロゲン化銀はハロゲン化銀錯化剤の作用で溶
解し、感光材料の表面に拡散してくる。この銀錯塩が表
面層の物理現像核の上に現像主薬の還元作用によって銀
画像として析出する。このプロセスによってダイレクト
印刷版が得られる。These direct printing plates are composed of a support, an undercoat layer also serving as an antihalation layer, a silver halide photographic emulsion layer and a physical development nucleus layer on the support. When a light-sensitive material is imagewise exposed and then treated with a developer containing a developer and a silver halide solvent, the silver halide on which a latent image is formed becomes blackened in the emulsion layer. The silver halide in which the silver halide is not formed is dissolved by the action of the silver halide complexing agent and diffuses to the surface of the light-sensitive material. This silver complex salt is deposited as a silver image on the physical development nuclei of the surface layer by the reducing action of the developing agent. This process results in a direct printing plate.
【0004】この銀画像のインキ受容性を強化させるた
めには現像後、必要ならば感脂化処理を施し、オフセッ
ト印刷機で印刷物へとインキ画像が転写される。このダ
イレクト印刷版は、操作性が良いこと、低価格であるこ
となどの利点を持っているが、その反面写真現像処理に
より印刷用銀画像を形成する性格上、処理時間内に拡散
転写が完結せず、過剰な銀イオンが残存し、それが保存
安定性もしくは耐刷力低下の一因となっていた。In order to enhance the ink receptivity of the silver image, after development, an oil-sensitizing treatment is carried out if necessary, and the ink image is transferred to a printed matter by an offset printing machine. This direct printing plate has advantages such as good operability and low price, but on the other hand, due to the nature of forming a silver image for printing by photographic development processing, diffusion transfer is completed within the processing time. However, excessive silver ions remained, which contributed to a decrease in storage stability or printing durability.
【0005】これらの欠点を改良するために種々の方法
が利用される。そのひとつにハロゲン化銀錯化剤として
種々の適当な化合物を使用する方法がある。特開昭56
―1057号、同56―9750号では、チオサリチル
酸およびその置換誘導体を、処理液または印刷版の構成
層中に添加する方法について述べている。同56―62
37号および56―8145号では、チオサリチル酸お
よびその誘導体と、アルカノールアミンまたは環状イミ
ド化合物を併用する方法について述べているが銀画像の
インクのりの低下などの欠点があり、さらに改良が望ま
れる。Various methods are utilized to remedy these drawbacks. One of them is a method of using various appropriate compounds as a silver halide complexing agent. JP-A-56
Nos. -1057 and 56-9750 describe a method of adding thiosalicylic acid and a substituted derivative thereof to a processing liquid or a constituent layer of a printing plate. Ibid 56-62
Nos. 37 and 56-8145 describe a method in which thiosalicylic acid and its derivative are used in combination with an alkanolamine or a cyclic imide compound, but there are drawbacks such as reduction of ink sticking of silver images, and further improvement is desired.
【0006】また同62−239161号では、現像抑
制剤としてベンゾトリアゾ−ル化合物を使い、DTRの
コントロ−ルにより耐刷性を上げる方法が述べられてい
る。この方法により耐刷力はある程度改良されるが、イ
ンクのりが低下し、まだ充分な水準に達していない。特
に、インクのりを低下させない方法が求められている。Further, Japanese Patent Laid-Open No. 62-239161 describes a method in which a benzotriazole compound is used as a development inhibitor and the printing durability is improved by controlling the DTR. Although the printing durability is improved to some extent by this method, the amount of ink sticking is reduced and it has not yet reached a sufficient level. In particular, there is a need for a method that does not reduce ink sticking.
【0007】[0007]
【発明が解決しようとする課題】本発明の目的は、銀錯
塩拡散転写法を利用するダイレクト平版印刷版の現像処
理に於て耐刷力が良好で、インキ受理能の高い銀画像を
得るための処理方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to obtain a silver image having a good printing durability and a high ink acceptability in the development processing of a direct lithographic printing plate utilizing the silver complex salt diffusion transfer method. Is to provide a processing method.
【0008】[0008]
【課題を解決するための手段】本発明者は、鋭意検討を
重ねた結果、同一分子内にキレ−ト化機能を持つ現像抑
制剤の存在下で現像や、安定化等の処理をすることによ
り、本発明の目的を達成できることを見いだした。Means for Solving the Problems As a result of intensive studies, the present inventor has conducted development and stabilization in the presence of a development inhibitor having a chelating function in the same molecule. It was found that the object of the present invention can be achieved by the above.
【0009】すなわち、本発明は、下記化2で示される
化合物の存在下で銀塩拡散転写平版印刷版を処理する方
法である。That is, the present invention is a method of treating a silver salt diffusion transfer lithographic printing plate in the presence of a compound represented by the following chemical formula 2.
【0010】[0010]
【化2】 化2においてR1、R2は同じでも異なっていてもよく、
それぞれ水素原子、アルキル基又はアルコキシ基を表わ
し、R3は一価のアルカリ金属、水素原子又はアシル基
であり、Xは酸素原子又は窒素原子を含む2価の基であ
り、15員環又は21員環を形成する。本発明に用いら
れる化2の化合物の具体的な例を以下に示す。[Chemical 2] In Chemical formula 2, R 1 and R 2 may be the same or different,
Each represents a hydrogen atom, an alkyl group or an alkoxy group, R 3 represents a monovalent alkali metal, a hydrogen atom or an acyl group, X represents a divalent group containing an oxygen atom or a nitrogen atom, a 15-membered ring or 21 Form a member ring. Specific examples of the compound of Chemical formula 2 used in the present invention are shown below.
【0011】[0011]
【化3】 [Chemical 3]
【0012】[0012]
【化4】 [Chemical 4]
【0013】[0013]
【化5】 [Chemical 5]
【0014】[0014]
【化6】 [Chemical 6]
【0015】[0015]
【化7】 [Chemical 7]
【0016】[0016]
【化8】 [Chemical 8]
【0017】[0017]
【化9】 [Chemical 9]
【0018】[0018]
【化10】 [Chemical 10]
【0019】本発明化合物の合成は母核となるベンゾク
ラウンエーテルをニトロ化、ついで還元して得られるア
ニリン誘導体を原料として、常法に従って容易にでき
る。母核であるベンゾクラウンエーテルは例えば、シン
セシス(Synthesis)680(1986),テトラヘドロン.レター
ズ(Tetrahedron Lett.) 26 2705(1985),ケミカルコミュ
ニケーション(Chem.commun)268(1986),ジャーナル・オ
ブ・ポリマーサイエンス(J.Polymer Sci.A-1 9 817
(1971),ジャーナル・オブ・アメリカンケミカル・ソサ
イティ(J.Amer.Chm.Soc.) 95,3842(1973) ケミカル・コ
ミュニケーション(Chem.commun) 414(1975),639(1976),
640(1976) の方法に従って合成できる。以下に本発明の
代表的化合物の合成例を示す。The compound of the present invention can be easily synthesized by a conventional method using an aniline derivative obtained by nitrating a benzocrown ether as a mother nucleus and then reducing it. The benzocrown ether which is a mother nucleus is, for example, Synthesis 680 (1986), tetrahedron. Letters (Tetrahedron Lett.) 26 2705 (1985), Chemical Communication (Chem.commun) 268 (1986), Journal of Polymer Science (J. Polymer Sci. A-1 9 817)
(1971), Journal of American Chemical Society (J. Amer. Chm. Soc.) 95 , 3842 (1973) Chemical Communication (Chem.commun) 414 (1975), 639 (1976),
It can be synthesized according to the method of 640 (1976). The synthesis examples of representative compounds of the present invention are shown below.
【0020】合成例(化3の合成) ベンゾ−15−クラウン−5 24gをクロロホルム3
30mlに溶かし、酢酸200mlを加え、室温で攪拌しな
がらHNO3(d約1.42)81mlを30分かけて滴
下し、さらに6時間室温で攪拌した。反応液にクロロホ
ルムを加え、水洗し、無水硫酸ナトリウムで乾燥させ
た。クロロホルムを減圧留去し粗製の4−ニトロ体2
0.6g(mp 92−94℃)を淡黄色固体として得
た。Synthetic Example (Synthesis of Chemical Formula 3) 24 g of benzo-15-crown-5 was added to chloroform 3
It was dissolved in 30 ml, 200 ml of acetic acid was added, 81 ml of HNO 3 (d about 1.42) was added dropwise over 30 minutes while stirring at room temperature, and the mixture was further stirred at room temperature for 6 hours. Chloroform was added to the reaction solution, washed with water, and dried over anhydrous sodium sulfate. Chloroform was distilled off under reduced pressure to obtain crude 4-nitro compound 2
0.6 g (mp 92-94 ° C) was obtained as a pale yellow solid.
【0021】鉄粉10gに水10mlを加え110℃に加
熱した後、酢酸2mlを加えて10分間攪拌した。ジオキ
サン50mlに分散させ、内温85℃〜95℃で30分間
攪拌した。同温でニトロ体10gをジオキサン100ml
に溶かした溶液を2時間かけて滴下し、さらに同温で1
時間攪拌した。放冷後、無水酢酸20mlを加えた。不溶
物を濾過後、ジオキサンを減圧留去し、粗生成物を得
た。これをカラムクロマトグラフィ−(シリカゲル/C
HCl3:MeOH=20:1)で分離した。メタノー
ルで再結晶し、4−アセトアミノ体6.2g(mp 15
0−151.5℃)を無色結晶として得た。After adding 10 ml of water to 10 g of iron powder and heating to 110 ° C., 2 ml of acetic acid was added and stirred for 10 minutes. The mixture was dispersed in 50 ml of dioxane and stirred at an internal temperature of 85 ° C to 95 ° C for 30 minutes. At the same temperature, 10 g of the nitro body is 100 ml of dioxane
The solution dissolved in was added dropwise over 2 hours, and then at the same temperature 1
Stir for hours. After cooling, 20 ml of acetic anhydride was added. After filtering the insoluble matter, dioxane was distilled off under reduced pressure to obtain a crude product. Column chromatography (silica gel / C
Separated with HCl 3 : MeOH = 20: 1). The crystals were recrystallized from methanol to give 6.2 g of 4-acetamino compound (mp 15
0-151.5 ° C) was obtained as colorless crystals.
【0022】アセトアミノ体1.8gを無水酢酸5mlに
溶かし、攪拌しながら−10℃で濃HNO3(d=1.
38)1.1mlを2時間かけて滴下した。室温にもどし
さらに1時間攪拌した。無水酢酸を減圧留去し、得られ
た固体をメタノールで洗浄し、粗生成物を得た。クロロ
ホルムとメタノールで再結晶し、4−アセトアミノ−5
−ニトロ体1.45g(mp 179−180℃)を黄色
結晶として得た。1.8 g of acetamino compound was dissolved in 5 ml of acetic anhydride, and concentrated HNO 3 (d = 1.
38) 1.1 ml was added dropwise over 2 hours. The mixture was returned to room temperature and further stirred for 1 hour. Acetic anhydride was distilled off under reduced pressure, and the obtained solid was washed with methanol to obtain a crude product. Recrystallize with chloroform and methanol to give 4-acetamino-5
-1.45 g of nitro compound (mp 179-180 ° C) was obtained as yellow crystals.
【0023】4−アセトアミノ−5−ニトロ体1.8g
をエタノール19mlと水1.9mlに溶かし、水酸化カリ
ウム330mlを加え4時間還流した。放冷後室温で炭酸
ガスを通じ中和した後、溶媒を減圧留去後、残渣をメタ
ノールに溶かし、不溶物を濾過後メタノールを減圧留去
した。残渣をカラムクロマトグラフィー(シリカゲル/
CHCl3:MeOH=20:1)で分離し、4−アミ
ノ−5−ニトロ体0.82g(mp 145.5−147
℃)をオレンジ色結晶として得た。1.8 g of 4-acetamino-5-nitro compound
Was dissolved in 19 ml of ethanol and 1.9 ml of water, 330 ml of potassium hydroxide was added, and the mixture was refluxed for 4 hours. After allowing to cool, the mixture was neutralized with carbon dioxide at room temperature, the solvent was distilled off under reduced pressure, the residue was dissolved in methanol, the insoluble matter was filtered off, and the methanol was distilled off under reduced pressure. Column chromatography of the residue (silica gel /
It was separated with CHCl 3 : MeOH = 20: 1) and 0.82 g of 4-amino-5-nitro compound (mp 145.5-147).
C) was obtained as orange crystals.
【0024】鉄粉1.63gに水1mlを加え110℃ま
で加熱した後、酢酸0.4mlを加えて10分間攪拌し
た。これにジオキサン5mlを加え、さらに内温85〜9
5℃で30分間攪拌した。同温で4−アミノ−5−ニト
ロ体1.47gをジオキサン5mlに溶かした溶液を1.
5時間かけて滴下した。さらに同温で1時間攪拌した。
放冷後不溶物を濾過し、濾液に濃塩酸2.5mlを加え
た。析晶を濾取し、粗製の4,5−ジアミノ体二塩酸塩
0.78gを無色結晶として得た。After adding 1 ml of water to 1.63 g of iron powder and heating to 110 ° C., 0.4 ml of acetic acid was added and stirred for 10 minutes. 5 ml of dioxane was added to this, and the internal temperature was 85-9.
The mixture was stirred at 5 ° C for 30 minutes. A solution prepared by dissolving 1.47 g of 4-amino-5-nitro derivative in 5 ml of dioxane at the same temperature was 1.
It dripped over 5 hours. Further, the mixture was stirred at the same temperature for 1 hour.
After cooling, the insoluble matter was filtered off, and 2.5 ml of concentrated hydrochloric acid was added to the filtrate. The precipitated crystals were collected by filtration to obtain 0.78 g of crude 4,5-diamino dihydrochloride as colorless crystals.
【0025】4,5−ジアミノ体二塩酸塩0.78gに
水1mlと酢酸ナトリウム三水和物0.6gを加えよく攪
拌した後、酢酸0.25gを加えた。この中に室温で、
亜硝酸ナトリウム0.17gを水1mlに溶かした溶液を
一度に加え、1時間攪拌した。反応液をクロロホルムで
抽出し、クロロホルムを減圧留去し粗生成物を得た。こ
れをカラムクロマトグラフィ−(シリカゲル/CHCl
3:MeOH=100:1)で分離し化3を得た。To 0.78 g of 4,5-diamino dihydrochloride, 1 ml of water and 0.6 g of sodium acetate trihydrate were added and well stirred, and then 0.25 g of acetic acid was added. At room temperature,
A solution prepared by dissolving 0.17 g of sodium nitrite in 1 ml of water was added all at once and stirred for 1 hour. The reaction solution was extracted with chloroform, and the chloroform was distilled off under reduced pressure to obtain a crude product. This is subjected to column chromatography (silica gel / CHCl
Separation with 3 : MeOH = 100: 1) gave compound 3.
【0026】収量 0.23g mp 182−183℃ 1HNMR(DMSO,δ) 3.65(8H,S),
3.82,3.84(4H,d.d,J=6.1,6.
7Hz) 4.12,4.14(4H,d.d,J=6.7,6.
1Hz) (以上メチレン水素) 7.2〜7.3(2H,bs,ベンゼン核水素)Yield 0.23 g mp 182-183 ° C. 1H NMR (DMSO, δ) 3.65 (8H, S),
3.82, 3.84 (4H, dd, J = 6.1, 6.
7 Hz) 4.12, 4.14 (4H, dd, J = 6.7, 6.
1 Hz) (above methylene hydrogen) 7.2 to 7.3 (2H, bs, benzene nucleus hydrogen)
【0027】13CNMR(DMSO,δ) 68.2,
68.4,69.0,69.7(以上メチレン炭素) 97.2,136.4,147.1(以上ベンゼン核炭
素) 13 CNMR (DMSO, δ) 68.2
68.4, 69.0, 69.7 (above methylene carbon) 97.2, 136.4, 147.1 (above benzene nucleus carbon)
【0028】合成例(化11の合成) 3,4−メチレンジオキシアニリン24.5gに無水酢
酸67.5mlを加え一晩放置した。無水酢酸を減圧留
去し析出した結晶を濾取し、水洗し、乾燥させ3,4−
メチレンジオキシアセトアニリドの粗生成物29.2g
を褐色結晶として得た。Synthetic Example (Synthesis of Chemical Formula 11) 64.5 ml of acetic anhydride was added to 24.5 g of 3,4-methylenedioxyaniline and left overnight. Acetic anhydride was distilled off under reduced pressure, and the precipitated crystals were collected by filtration, washed with water and dried 3,4-
29.2 g of crude product of methylenedioxyacetanilide
Was obtained as brown crystals.
【0029】3,4−メチレンジオキシアセトアニリド
29gを無水酢酸100mlに溶解させ、攪拌しながら
−10℃で濃硝酸(d=1.38)84mlを2時間か
けて滴下した(10ml加えたところで内容物が固化し
てきたので、溶媒として酢酸88mlを加えた後滴下を
続けた)。室温にもどしさらに1時間攪拌した。得られ
た固体を濾取し、メタノ−ルで洗浄し、粗生成物を得
た。クロロホルム/メタノ−ルで再結晶し、6−ニトロ
−3,4−メチレンジオキシアセトアニリド30gを黄
色結晶として得た。29 g of 3,4-methylenedioxyacetanilide was dissolved in 100 ml of acetic anhydride, and 84 ml of concentrated nitric acid (d = 1.38) was added dropwise over 2 hours at −10 ° C. with stirring (the content was obtained when 10 ml was added). Since the substance had solidified, 88 ml of acetic acid was added as a solvent and the dropping was continued). The mixture was returned to room temperature and further stirred for 1 hour. The obtained solid was collected by filtration and washed with methanol to obtain a crude product. Recrystallization from chloroform / methanol gave 30 g of 6-nitro-3,4-methylenedioxyacetanilide as yellow crystals.
【0030】6−ニトロ−3,4−メチレンジオキシア
セトアニリド25gにエタノ−ル250mlを加えた
後、水酸化カリウム7.5gの水25ml溶液を40℃
で加え30分加温した。分液ロ−トで水洗、クロロホル
ム抽出をし、その際に析出した結晶と、クロロホルム抽
出後クロロホルムを留去して得られた結晶を合わせてメ
タノ−ルで再結晶を行った。6−ニトロ−3,4−ジオ
キシアニリン17.1g(mp 198.5−199.
5℃)をオレンジ色結晶として得た。After adding 250 ml of ethanol to 25 g of 6-nitro-3,4-methylenedioxyacetanilide, a solution of 7.5 g of potassium hydroxide in 25 ml of water was added at 40 ° C.
Then, the mixture was heated for 30 minutes. The mixture was washed with water using a separating funnel and extracted with chloroform. The crystals precipitated at that time were combined with the crystals obtained by extracting chloroform after the extraction with chloroform, and recrystallized with methanol. 17.1 g of 6-nitro-3,4-dioxyaniline (mp 198.5-199.
5 ° C.) was obtained as orange crystals.
【0031】鉄粉33.3gに水17mlを加え110
℃まで加熱した後、酢酸6.8mlを加えて10分間攪
拌した。これにジオキサン70mlを加え、さらに内温
85〜90℃で30分間攪拌した。同温で6−ニトロ−
3,4−ジオキシアニリン16.7gをジオキサン10
0mlに溶かした溶液を1.5時間かけて滴下した。さ
らに同温で1時間攪拌した。放冷後不溶物を濾過し、濾
液に濃塩酸42.5mlを加えた。析晶を濾取し、メタ
ノ−ル:エタノ−ル=1:1の溶液で洗浄し、1,2−
ジアミノ体二塩酸塩19.3g(dec.〜220℃)
を薄紫色結晶として得た。17 ml of water was added to 33.3 g of iron powder, and 110
After heating to ° C, 6.8 ml of acetic acid was added and stirred for 10 minutes. 70 ml of dioxane was added thereto, and the mixture was further stirred at an internal temperature of 85 to 90 ° C for 30 minutes. 6-nitro-at the same temperature
16.7 g of 3,4-dioxyaniline was added to dioxane 10
The solution dissolved in 0 ml was added dropwise over 1.5 hours. Further, the mixture was stirred at the same temperature for 1 hour. After cooling, the insoluble matter was filtered off, and 42.5 ml of concentrated hydrochloric acid was added to the filtrate. The precipitated crystals were collected by filtration and washed with a solution of methanol: ethanol = 1: 1 to give 1,2-
Diamino form dihydrochloride 19.3 g (dec.-220 degreeC)
Was obtained as light purple crystals.
【0032】1,2−ジアミノ体二塩酸塩8.3gに水
4.1mlと酢酸ナトリウム三酸水和物10gを加えよ
く攪拌した後、酢酸4.4gを加えた。この中に室温
下、亜硝酸ナトリウム2.8gを水4.1mlに溶かし
た溶液を一度に加え、1時間攪拌した。反応液をクロロ
ホルムで抽出し、クロロホルムを減圧留去し粗生成物を
得た。これをカラムクロマトグラフィ(シリカゲル/C
HCl3:MeOH=100:1)で分離し5,6−メ
チレンジオキシベンズイミダゾ−ル化11を得た。To 8.3 g of the 1,2-diamino dihydrochloride, 4.1 ml of water and 10 g of sodium acetate trihydrate were added and well stirred, and then 4.4 g of acetic acid was added. At room temperature, a solution of 2.8 g of sodium nitrite in 4.1 ml of water was added all at once, and the mixture was stirred for 1 hour. The reaction solution was extracted with chloroform, and the chloroform was distilled off under reduced pressure to obtain a crude product. Column chromatography (silica gel / C
It was separated with HCl 3 : MeOH = 100: 1) to obtain 5,6-methylenedioxybenzimidazole compound 11.
【0033】収量 1.92g mp 211−212℃ 1HNMR(DMSO,δ) 6.12(2H,s,メ
チレン水素) 7.28(2H,s,ベンゼン核水素) 3.4付近(1H,bs,−NH)Yield 1.92 g mp 211-212 ° C. 1HNMR (DMSO, δ) 6.12 (2H, s, methylene hydrogen) 7.28 (2H, s, benzene nucleus hydrogen) around 3.4 (1H, bs, -NH)
【0034】本発明の化2の化合物の現像液への添加量
は、10-5〜10-1モル/lの範囲であり、好ましくは
10-3〜10-2モル/lがよい。また二種類以上の化合
物の併用もできる。The amount of the compound of formula 2 of the present invention added to the developing solution is in the range of 10 -5 to 10 -1 mol / l, preferably 10 -3 to 10 -2 mol / l. Further, two or more kinds of compounds can be used in combination.
【0035】本発明の化合物は現像液中に添加するのが
最も効果的だが、安定化液等の処理液また、ダイレクト
印刷版のハロゲン化銀乳剤層もしくは物理現像核層、好
ましくはハロゲン化銀乳剤層に添加してもよい。その場
合添加量は10-7〜10-3モル/m2の範囲であり、好
ましくは10-6〜10-4モル/m2 がよい。また二種類
以上の化合物の併用もできる。処理液への添加は、有機
溶剤に溶かし添加するのが好ましい。また、乳剤に添加
する場合も同様である。The compound of the present invention is most effectively added to a developing solution, but a processing solution such as a stabilizing solution, a silver halide emulsion layer or a physical development nucleus layer of a direct printing plate, preferably a silver halide. It may be added to the emulsion layer. In that case, the addition amount is in the range of 10 −7 to 10 −3 mol / m 2 , and preferably 10 −6 to 10 −4 mol / m 2 . Further, two or more kinds of compounds can be used in combination. The addition to the treatment liquid is preferably carried out by dissolving in an organic solvent. The same applies when it is added to the emulsion.
【0036】本発明現像処理液には、アルカリ性物質
(水酸化ナトリウム、水酸化カリウム、第三燐酸ナトリ
ウム等)、保恒剤としての亜硫酸塩(亜硫酸カリウム、
亜硫酸ナトリウムなど)が必須であるが、それ以外の化
合物、例えば硫酸塩(硫酸ナトリウム、硫酸アンモニウ
ムなど)、カブリ防止剤(臭化カリウムなど)、ハロゲ
ン化銀溶剤(チオ硫酸塩、チオシアン酸塩、チオエーテ
ル、環状イミド、チオサリチル酸、アルカノールアミン
など)、現像主薬(ハイドロキノン、1−フェニル−3
−ピラゾリドン、メトールなど)、現像促進剤(ポリオ
キシアルキレン化合物、オニウム化合物など)を含むこ
とが出来る。The developing solution of the present invention contains an alkaline substance (sodium hydroxide, potassium hydroxide, sodium triphosphate, etc.) and a sulfite salt (potassium sulfite, as a preservative).
Sodium sulfite, etc.) is essential, but other compounds such as sulfates (sodium sulfate, ammonium sulfate, etc.), antifoggants (potassium bromide, etc.), silver halide solvents (thiosulfates, thiocyanates, thioethers) , Cyclic imide, thiosalicylic acid, alkanolamine, etc.), developing agent (hydroquinone, 1-phenyl-3)
-Pyrazolidone, methol, etc.) and development accelerators (polyoxyalkylene compounds, onium compounds, etc.).
【0037】更に、界面活性剤(アルギン酸プロピレン
グリコールエステルなど)、アミノポリカルボン酸塩
(エチレンジアミン四酢酸ナトリウムなど)等を一種ま
たは二種以上含有させることも出来る。この他にも本発
明の化合物の溶剤、例えばメタノール、エタノール、プ
ロパノール、イソプロピルアルコール、n−ブチルアル
コール、DMF、ジオキサン等の水混和性有機溶剤を含
ませることが出来る。Further, one or more kinds of surfactants (propylene glycol alginate, etc.), aminopolycarboxylic acid salts (sodium ethylenediaminetetraacetate, etc.) and the like can be contained. In addition to these, a solvent for the compound of the present invention, for example, a water-miscible organic solvent such as methanol, ethanol, propanol, isopropyl alcohol, n-butyl alcohol, DMF, dioxane and the like can be included.
【0038】銀錯塩拡散転写法の実施に当たっては、例
えば英国特許第1000115号、第1012476
号、第1017273号、第1042477号の明細書
に記載されているごとく、ハロゲン化銀乳剤および/ま
たは受像層かそれに隣接する他の水透過性層中に現像主
薬を混入することが行なわれている。したがって、この
ような感光材料では、現像に使われる処理液は、現像主
薬を含まぬ単なるアルカリ溶液を使用しうる。本発明の
化合物は、このようなタイプの感材でも効果がある。In carrying out the silver complex salt diffusion transfer method, for example, British Patent Nos. 1000115 and 1012476.
No. 1017273, 1042477, the incorporation of a developing agent into the silver halide emulsion and / or the image receiving layer or other water permeable layer adjacent thereto has been carried out. There is. Therefore, in such a light-sensitive material, the processing solution used for development may be a simple alkaline solution containing no developing agent. The compound of the present invention is also effective in such a type of sensitive material.
【0039】また本発明の実施に用いられる平版印刷版
のハロゲン化銀乳剤は塩化銀、臭化銀、塩臭化銀、塩沃
化銀、塩臭沃化銀が使用でき、好ましくは塩化銀が50
モル%以上のハロゲン化銀である。これらのハロゲン化
銀乳剤は分光増感剤(光源・用途に応じた分光増感色
素、例えばカメラタイプ、レーザー光タイプ、色分解用
パンクロタイプ等)、ゼラチン硬化剤、塗布助剤、カブ
リ防止剤、可塑剤、現像主薬、マット剤などを含むこと
が出来る。The silver halide emulsion of the lithographic printing plate used in the practice of the present invention may be silver chloride, silver bromide, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide, preferably silver chloride. Is 50
It is a silver halide of mol% or more. These silver halide emulsions are spectral sensitizers (spectral sensitizing dyes depending on the light source and application, such as camera type, laser light type, panchromatic type for color separation), gelatin hardening agents, coating aids, antifoggants. , A plasticizer, a developing agent, a matting agent and the like.
【0040】本発明の平版印刷版のハロゲン化銀乳剤に
用いられるバインダーは、通常ゼラチンであるが、ゼラ
チンはその一部をデンプン、アルブミン、アルギン酸ナ
トリウム、ヒドロキシエチルセルロース(HEC)、ア
ラビアゴム等の天然高分子、ポリビニルアルコール(P
VA)、ポリビニルピロリドン(PVP)、カルボキシ
メチルセルロース(CMC)、ポリアクリルアミド、ス
チレン−無水マレイン酸共重合体などの合成高分子の一
種または二種以上で置換することも出来る。The binder used in the silver halide emulsion of the lithographic printing plate of the present invention is usually gelatin, and a part of gelatin is starch, albumin, sodium alginate, hydroxyethyl cellulose (HEC), natural gums such as gum arabic and the like. Polymer, polyvinyl alcohol (P
VA), polyvinylpyrrolidone (PVP), carboxymethyl cellulose (CMC), polyacrylamide, styrene-maleic anhydride copolymer and the like may be substituted with one or more synthetic polymers.
【0041】ハロゲン化銀乳剤層の下側(支持体面)に
は接着改良および/またはハレーション防止等の目的で
下引層を含むこともでき、この層には現像主薬、マット
剤を含むことが出来る。An undercoat layer may be included on the lower side (support surface) of the silver halide emulsion layer for the purpose of improving adhesion and / or preventing halation. This layer may contain a developing agent and a matting agent. I can.
【0042】ハロゲン化銀乳剤を塗布する支持体は、
紙、各種のフィルム、プラスチックス、樹脂様物質を塗
布した紙、金属板等が利用できる。The support on which the silver halide emulsion is coated is
Paper, various films, plastics, paper coated with resin-like substances, metal plates, etc. can be used.
【0043】物理現像核層に使用される物理現像核は、
周知の薬品であるアンチモン、カドミウム、コバルト、
パラジウム、ニッケル、銀、鉛、亜鉛等の金属およびそ
の硫化物が使用できる。またこの物理現像核層にも現像
主薬を含むことができるし、親水性バインダーを含んで
もよい。The physical development nuclei used in the physical development nuclei layer are
Well-known drugs such as antimony, cadmium, cobalt,
Metals such as palladium, nickel, silver, lead and zinc and their sulfides can be used. The physical development nucleus layer may also contain a developing agent and may contain a hydrophilic binder.
【0044】[0044]
【実施例】以下に実施例を掲げ本発明を更に詳細に説明
するが、これだけに限定されるわけではない。The present invention will be described in more detail with reference to the following examples, but the invention is not limited thereto.
【0045】下引処理したポリエステルフィルム支持体
の片面に平均粒径サイズ5μのシリカ粒子を含有するマ
ット化層を設け、反対側の面に光の反射率を低下させる
カーボンブラックを含み、平均粒径7μのシリカ粉末を
写真用ゼラチンに対して20重量%の割合で含むハレー
ション防止用下塗層(pH4.0に調整)と、化学増感
した後に平均粒径7μのシリカ粉末を写真用ゼラチンに
対して5重量%の割合で添加し、かつ分光増感した高感
度塩化銀乳剤層(pH4.0に調整)とを設けた。下塗
層はゼラチンを3.5g/m2、乳剤層はゼラチン0.
8g/m2とハロゲン化銀(硝酸銀に換算)1.0g/
m2の割合で塗布した。この下塗層と乳剤層は、硬膜剤
としてホルマリンをゼラチンに対して5.0mg/gの割
合で含んでいる。An undercoating-treated polyester film support is provided on one side with a matting layer containing silica particles having an average particle size of 5 μ, and on the opposite side, carbon black is included to reduce the light reflectance. An anti-halation subbing layer (adjusted to pH 4.0) containing silica powder having a diameter of 7μ at a ratio of 20% by weight with respect to photographic gelatin, and a silica powder having an average particle diameter of 7μ after chemically sensitized was used as photographic gelatin. And a spectrally sensitized high-sensitivity silver chloride emulsion layer (adjusted to pH 4.0) were provided. The subbing layer was made of gelatin at 3.5 g / m 2 , and the emulsion layer was made of gelatin.
8 g / m 2 and silver halide (converted to silver nitrate) 1.0 g /
It was applied at a rate of m 2 . The subbing layer and the emulsion layer contain formalin as a hardener at a ratio of 5.0 mg / g with respect to gelatin.
【0046】乾燥後40℃で14日加温した後、この乳
剤層の上に、特開昭54−103104号公報の実施例
2で用いたプレートNO. 31記載の核液を塗布、乾燥
し、平版印刷版を製造する。ハロゲン化銀乳剤は、物理
熟成時にハロゲン化銀1モル当たり4×10-6モルの塩
化ロジウムを添加したものであり、平均粒径0.40μ
であった。このようにして得られた平版印刷版の原版に
像反転機構を有する製版カメラで像露光し、下記の現像
液(使用液)により30℃で30秒間現像処理し、続い
て下記中和液で処理した。After drying, the mixture was heated at 40 ° C. for 14 days, then the emulsion was coated with the nuclear liquid described in Plate No. 31 used in Example 2 of JP-A-54-103104 and dried. , Produce lithographic printing plates. The silver halide emulsion was prepared by adding 4 × 10 −6 mol of rhodium chloride per mol of silver halide during physical ripening, and had an average grain size of 0.40 μm.
Met. The lithographic printing plate precursor thus obtained was image-exposed with a plate-making camera having an image reversal mechanism, developed with the following developer (use solution) at 30 ° C. for 30 seconds, and then with the following neutralizing solution. Processed.
【0047】現像液A 水酸化ナトリウム 24g 水酸化カリウム 8g 無水亜硫酸ナトリウム 50g 2−メチル−アミノ−1−プロパノール 30g ウラシル 0.2g 水を加えて1lとする。Developer A Sodium hydroxide 24 g Potassium hydroxide 8 g Anhydrous sodium sulfite 50 g 2-Methyl-amino-1-propanol 30 g Uracil 0.2 g Water is added to make 1 liter.
【0048】中和液 エチレングリコール 5g コロイダルシリカ(20%水溶液) 1g クエン酸 10g クエン酸ナトリウム 35g 水を加えて1lとする。Neutralizing solution Ethylene glycol 5 g Colloidal silica (20% aqueous solution) 1 g Citric acid 10 g Sodium citrate 35 g Water is added to make 1 liter.
【0049】一方、前記の現像液Aのほかに、下記の比
較化合物化11、12または本発明の例示化合物を現像
液1lあたり2×10-3モルの割合で添加し、現像液B
−Iを調製した。On the other hand, in addition to the developer A, the following comparative compounds 11 and 12 or the exemplified compounds of the present invention were added at a ratio of 2 × 10 -3 mol per liter of the developer, and the developer B was added.
-I was prepared.
【0050】[0050]
【化11】 [Chemical 11]
【0051】[0051]
【化12】 [Chemical 12]
【0052】現像は上記の現像液Aと全く同様にし、製
版処理した。ついで印刷版をオフセット印刷機にセット
し、下記組成のエッチ液で版面を充分に湿し、下記組成
の給湿液を用いて印刷を行なった。The development was carried out in the same manner as the above-mentioned developing solution A, and a plate-making process was carried out. Then, the printing plate was set in an offset printing machine, the plate surface was sufficiently wetted with an etchant having the following composition, and printing was performed using a dampening liquid having the following composition.
【0053】エッチ液 水 600ml イソプロパノール 400ml エチレングリコール 50gEtching solution Water 600 ml Isopropanol 400 ml Ethylene glycol 50 g
【0054】給湿液 水 8l コハク酸 6g 硫酸ナトリウム 25g エチレングリコール 100g コロイダルシリカ(20%水溶液) 28gHumidifying liquid Water 8 l Succinic acid 6 g Sodium sulfate 25 g Ethylene glycol 100 g Colloidal silica (20% aqueous solution) 28 g
【0055】以下の基準により判定した実施例の印刷結
果を、表1に示した。印刷の耐刷力は、次のような方法
で判定した。1,000枚以上50,000枚までの印
刷を続け、銀画像部のインキとびの出るときの印刷枚数
によって、次の4つの水準で評価した。 A 50,000枚以上 B 25,000 C 10,000 D 5,000The printing results of the examples judged according to the following criteria are shown in Table 1. The printing durability of printing was determined by the following method. Printing was continued from 1,000 sheets to 50,000 sheets, and the following four levels were evaluated according to the number of printed sheets when ink bleeding occurred in the silver image area. A 50,000 sheets or more B 25,000 C 10,000 D 5,000
【0056】[0056]
【表1】 [Table 1]
【0057】表1から明らかなように化2の化合物を添
加して得られた平版印刷版は、飛躍的に耐刷力の優れた
銀画像が得られ、原稿の細線部分も良好に再現し、しか
もその細線部の印刷による機械的磨耗もなく長い印刷に
耐えるものであった。As is clear from Table 1, the lithographic printing plate obtained by adding the compound of Chemical formula 2 produced a silver image with dramatically excellent printing durability, and reproduced well the fine line portions of the original. Moreover, it was able to withstand long printing without mechanical abrasion due to printing of the fine line portion.
【0058】[0058]
【発明の効果】本発明の処理方法で製版された平版印刷
版は、転写銀像の欠落が改良され、耐刷力の飛躍的な向
上が図れ、インキ受理能の低下がない。EFFECTS OF THE INVENTION The planographic printing plate produced by the processing method of the present invention is improved in the lack of transferred silver image, the printing durability is remarkably improved, and the ink receiving ability is not deteriorated.
Claims (1)
を、下記化1で示される化合物の少なくとも一種類が存
在する条件下で処理する方法。 【化1】 (式中、R1及びR2はそれぞれ水素原子、アルキル基、
アルコキシ基を表わし、R3は一価のアルカリ金属、水
素原子又はアシル基であり、Xは酸素原子又は窒素原子
を含む2価の基であり、15又は21員環を形成す
る。)1. A method of treating a lithographic printing plate utilizing a silver complex salt diffusion transfer method under conditions in which at least one compound represented by the following chemical formula 1 is present. [Chemical 1] (In the formula, R 1 and R 2 are each a hydrogen atom, an alkyl group,
Representing an alkoxy group, R 3 is a monovalent alkali metal, a hydrogen atom or an acyl group, and X is a divalent group containing an oxygen atom or a nitrogen atom, and forms a 15- or 21-membered ring. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4214190A JPH0659457A (en) | 1992-08-11 | 1992-08-11 | Treatment of planographic printing plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4214190A JPH0659457A (en) | 1992-08-11 | 1992-08-11 | Treatment of planographic printing plate |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0659457A true JPH0659457A (en) | 1994-03-04 |
Family
ID=16651735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4214190A Pending JPH0659457A (en) | 1992-08-11 | 1992-08-11 | Treatment of planographic printing plate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0659457A (en) |
-
1992
- 1992-08-11 JP JP4214190A patent/JPH0659457A/en active Pending
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