JPS60237442A - Developer for photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To enhance hydrophilicness of the surface of aluminum to be exposed without impairing oleophilicness of image parts by incorporating a specified ether compd., an anionic surfactant, an alkaline substance, and a water-soluble reducing agent, and rapidly dissolving off the resin layer of the nonimage parts. CONSTITUTION:The developer contains an ether compd. represented by the formula: R-O-CH2CH2OH, R being phenyl or benzyl; an anionic surfactant, such as alkylnaphthalenesulfonate; an alkaline substance, such as a combination of water glass and sodium metasilicate; and a water-soluble reducing agent, preferably, one of compds., such as sodium bisulfite, sodium biphosphite, and hydrazine. A negative type PS plate prepared by a long term before can be effectively developed by using a developer composed of these 4 as effective components without causing no stain on each nonimage part of the printing plate, and good results can be obtained, too, by applying it to each PS plate avilable in the markets.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field-1 The present invention is a lithographic printing plate material (Offcera) P made by coating a photosensitive composition on the surface of an aluminum support in advance.
This is related to the developer for the negative type S plate (the photosensitive composition is mainly a diazo compound) or the positive type S plate (the photosensitive composition is mainly a quinone azide compound). ``Problem to be Solved by the Invention'' The PS version currently on the market is a negative type, and the iP
- Photosensitive material consisting of a diazo compound such as a formaldehyde condensate of diazophenylamine, and in the case of positive type, an acrylic multi-component copolymer containing a quinonediazide compound and a carboxylic acid blended for the purpose of strengthening the image area. It consists of a hydrophilic composition and an aluminum plate with a hydrophilic surface. The extremely important role of the developer in the process of making lithographic printing plates using PS plates is as follows:
The photosensitive resin layer in the non-image area is quickly dissolved and removed, and the hydrophilicity of the aluminum surface exposed by development is not reduced.
Rather, the aim is to promote this while not impairing the lipophilicity of the resin layer in the image area that has been cured by actinic rays.

The present inventor first developed a negative type developer which fully satisfies the above conditions with the general formula R-0-CH2CH20H (wherein R represents a phenyl group or a benzyl group - hereinafter the same symbols mean the same thing). ), an anionic surfactant, and an alkaline substance. We proposed a developer for both negative and positive use, which uses , and four-hosan salt. However, if you use a negative type developer that has been used for more than one year since its manufacture, it is difficult to develop 1. It has been found that, when stored under adverse conditions such as high temperature and high humidity, there is a problem in that stains occur in non-image areas.

Although the reason for this is not clear, it is thought that oxidation is promoted at the interface between the aluminum layer and the photosensitive resin layer, resulting in a decrease in the hydrophilicity of the aluminum surface.

"Means for Solving the Problems and Their Effects - 1 The present inventors have provided a developer which can eliminate only the above disadvantages without obtaining the advantages of the above-mentioned invention already proposed by the present inventors. As a result of intensive research, we have arrived at the invention of a new developer that can achieve the desired purpose.
The present invention provides a developer for a photosensitive lithographic printing plate, which is characterized by containing an ether compound represented by the following formula, an anionic surfactant, an alkaline substance, and a water-soluble reducing agent.

In this case, the anionic surfactant is fatty acid salt (
(R'Coo)nMm), alkylbenzenesulfonate ((R'+SOs)nMml), alkylsulfonate ((R"03)nMml,
α-olefin sulfonate ((R'-qH2-R'S
O, ) and (R' CH=CHR2S % )n Mm), polyoxyethylene alkyl ether)Y acid salt ([R1-〇-(CH2CH20猜-D -0-1,,
MI+.

naphthalene sulfonate formaldehyde condensate naphthalene sulfonate ((R1-head-So, ) yrn
) (However, in the above chemical formula, R1, R2, key alkyl group, n
, m, o, p indicate the polymer chain length or the number of bonding groups (integer) 1
, 2M indicates an alkali salt. ), among which alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkylphenyl ether sulfates, and especially alkylnaphthalene sulfonates of the general formula shown above can be used. In combination with an ether compound, it is suitable because it has a small amount of 4% and has a developing effect.

The alkaline substances used in the present invention include strong inorganic alkalis such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, and sodium carbonate, sodium bicarbonate, potassium silicate, sodium silicate, sodium metasilicate, and sodium triphosphate 2. Weakly alkaline inorganic substances such as sodium diphosphate, tertiary ammonium phosphate, diammonium diphosphate, and ammonia, as well as monoethylamine, dimethylamine, trimethylamine, monoethylamine,
diethylamine, triethylamine, monoinpropylamine, diisopropylamine, n-butylamines,
There are organic amine compounds such as monoethanolamines, jetanolamine, monoisopropanolamine, ethyleneimine, and ethylenediamine.

When preparing a developer for a negative type P8 plate, it is preferable to use a weakly alkaline inorganic substance among these, but ammonia has a bad odor and is easily dispersed, and as a developer using it is repeatedly used, This is not preferable since its life may be shortened.

This is because organic amines are inappropriate and have a bad odor.
Strong alkaline substances are not suitable because they may corrode image areas and non-image areas.

However, when preparing a developer for both negative and positive PS plates, a strong alkaline substance such as potassium hydroxide is essential. Also, dry with tetraphorate to prevent discoloration of the aluminum surface in the non-image area.

The water-soluble reducing agents used in the present invention include sodium bisulfite, sodium thiosulfate, sodium dithionite,
These include sulfur compounds such as sodium sulfite and potassium sulfite, nitrogen compounds such as hydrazine hydrate, hydrazine sulfate, hydrazine chloride, and sodium nitrite, and phosphorus compounds such as disodium hydrogen phosphate.

Among these, it is particularly preferable to use sodium bisulfite, hydrazine hydrate, and disodium hydrogen phosphate because they are highly effective even when added in small amounts.

Other water-soluble reducing agents include metal hydride compounds such as chlorinated hydrosilane and ethylsilane hydride, metal hydride complex compounds such as lithium aluminum hydride and sodium borohydride, zinc borohydride, and tetraalkylammonium borohydride. Examples include zinc borohydride, phosphorus compounds such as triethylphosphite, triphenylphosphine, diborane, substituted borane, diimide, and salts. When formulating each component in the developer of the invention, when it is used for a negative type, an ether compound of the general formula 10
0 parts (the same below weight parts), 50 to 300 parts of anionic surfactant, 10 to 100 parts of alkaline substance, 100 parts of alkaline substance, and 100 parts of the same ether compound.
The amount of the anionic surfactant is preferably 1 to 5 to 50 parts per part of the water-soluble reducing agent.
The preferred amount of the water-soluble reducing agent is around 10 parts.The preferred amount of the alkaline substance varies depending on the type of alkaline substance. The amount of anionic surfactant, alkaline substance, and water-soluble reducing agent added to the ether compound is not critical, but if the amount of anionic surfactant is too low and too strong, the anionic interface The main action of the activator - the action of improving the solubility of the ether compound in water, and the action of improving the permeability of the ether compound, alkaline substance, and water-soluble reducing agent into the photosensitive resin layer - becomes insufficient. On the other hand, if the amount is too large, it will have a negative effect on the development effect.Alkaline substances, along with the ether compound, have a direct effect of dissolving the photosensitive resin layer, and if the amount is too small, the development speed will be impaired. It will be enough. On the other hand, if the amount of alkaline substances is too large,
Not only does it reduce the hydrophilicity of the aluminum surface in the non-image area,
Damage the image area. The water-soluble reducing agent cleans the aluminum surface at the interface between the aluminum layer and the photosensitive resin layer, and
A stain-free printing plate can be obtained even if the printing plate is stored for a long period of time after the printing plate has been manufactured, and the smaller the amount added, the smaller the effect will be. On the other hand, if the amount is too large, the effect will not change and it will become uneconomical. - Mixing ratio of anionic surfactant, alkaline substance, and water-soluble reducing agent in a developer for both negative and positive PS plates. The meaning of the restriction is the same as in the above case, but the specific amount to be added is slightly different from the above, and is as follows.

That is, for 100 parts of the ether compound, the anionic surfactant is 200 to 800 parts, preferably around 500 parts, and the alkaline substance is 50 to 200 parts, preferably around 100 parts.
The amount of the water-soluble reducing agent is 5 to 50 parts, preferably around 10 parts.7 Among these, when blending the alkaline substance, 20 to 20 parts of the silicate to 100 parts of the alkali metal hydroxide in Group AVcli of the N period table. 200 parts, similarly Siho San salt 5 ~
The preferred amount is around 50 parts for silicate and around 10 parts for tetrahosan salt. ``Advantageous Effects of the Invention'' The present invention has the advantages of the above-mentioned 1. As mentioned above, the four active ingredients are an ether compound, an anionic surfactant, an alkaline substance, and a water-soluble reducing agent. As a result, a good developing effect is achieved without staining the non-image areas of the printing plate.

It also has the feature that it can be commonly applied to PS versions of various companies that have been commercially available.The present invention will be explained in more detail below with reference to Examples.

"Examples and Effect Tests" Example 1゜Butyl cellosolve 4009'' was injected into a clean 11-volume glass reaction vessel equipped with a backflow condenser in advance.
Stir while flowing nitrogen into the reaction vessel and heat it from the outside of the reaction vessel. When the temperature of the butyl cellosolve reaches 80°C, add the following composition to the upper liquid furnace at a rate of 1 g/min. Drop into the reaction container and react. At this time, the reaction temperature is adjusted within the range of 80 to 86°C. Soda product a-1ooo) 2 g of azobisisobutyronitrile The reaction time was 4 to 5 hours from the time when the above composition was first added dropwise. After the noisy reaction, P-diazo 60g of 2-methoxy-4-hydroxy-5-benzoylbenzene sulfonate, a condensate of diphenylamine and paraformaldehyde, and Oil Pruner 603
After adding 005 g of 1.69 g of ethylenediaminetetraacetic acid (EDTA) and 240 g of butyl cellosolve and stirring and mixing at room temperature for 3 hours, the mixture was suction-filtered through Toyo Roshi 1250M-131 using a Buchner PTO.

Next, 255 g of the obtained p solution was diluted with a mixed solvent consisting of 15009 inpropyl alcohol, 200 g of xylene, and 200 g of ethyl leadate to prepare a photosensitive resin composition solution.

Next, this photosensitive resin composition solution was linearized in advance and coated on an aluminum 2S material having a thickness of o and zsm/n which had been subjected to a hydrophilic treatment using a bar coater F6.
A photosensitive resin plate was created by drying in a hot air dryer at 00°C for 1 minute.The dry coating weight was 20? Met. This photosensitive resin plate was left in a hot air dryer at a temperature of 90°C for 8 hours, and then a negative image was printed in a vacuum baking frame.
Exposure for 20 seconds from a distance of 1 m using a double ultra-high pressure water chain lamp.
The plate was immersed in the following developer at 25° C. for 1 minute, taken out, washed with water, and dried to obtain a lithographic printing plate.

Ethylene glycol monophenyl ether 35 g Sodium alkylnaphthalene sulfonate 70 9 Sodium triphosphate 79 Water glass (No. 1183) 8 g Hydrazine hydrate (content 80%) 3 g Water 100
0 f When this printing plate was printed on high-quality paper using a Heidel GTO printing machine, more than 100,000 copies could be printed.

Similarly, when printing was carried out with the printing plate obtained by developing with a developer having a composition other than hydrazine hydrate from the above developer composition, staining occurred in the non-image area after printing 1000 copies. It became impossible to print.

Example 2 A photosensitive resin liquid was prepared in exactly the same manner as in Example 1, and coated on an aluminum plate. 28 plates were created, and after being left in a hot air dryer at a temperature of 90°C for 8 hours under harsh conditions, the negatives were passed through a vacuum printing frame for 20 seconds from a distance of 1 meter using a 4KW ultra-high pressure mercury lamp. Ethylene glycol monophenyl ether 30 9 Sodium alkylnaphthalene sulfonate 60
g Sodium metasilicate 6g Water glass (No. 5183) 7g Sodium bisulfite 2g Water 1000g This printing plate was printed on high-quality paper using a Heidel GTO printing machine.It was possible to print more than 100,000 copies on high-quality paper.Example 5 A PS plate was prepared according to Example 1. It was exposed to light for 20 seconds in the same manner as in 1-1, and then immersed in the following developer at 25°C for 30 seconds and then taken out]-1 Washed with water and dried to form a lithographic printing plate. Obtained.

Ethylene glycol monobenzyl ether 40 9 Alkylnaphthalene sulfonic acid salt p-80 g Sodium sesquicarbonate 6 g Water glass (No. 1185) 8 (7 Sodium biphosphite 4 g Water 1000 g Printing was carried out in the same manner as in Example 1 using this lithographic printing plate. As a result, we were able to print over 100,000 copies without any stains.

Example 4゜A commercially available positive type PS plate (Ulstar PS) and negative type S plate (made by Nippon Foil Co., Ltd.) were used for two years after manufacture.
After stacking the positive and negative image films on a 4KW ultra-high pressure mercury lamp for 50 seconds from a distance of 1 m, they were developed with the following developer, washed with water, and dried to form a lithographic printing plate. Obtained.

Ethylene glycol monophenyl ether 30 f Sodium alkylnaphthalene sulfonate 180 9 Sodium hydroxide 109 Water glass (No. 1186) 25 g Hydrazine hydrate 10 g Shihosanunda 2 g Water 1000 9 This printing plate was printed on high-quality paper using a Heidel GTO printing machine. We were able to print over 50,000 copies using the positive type PS plate (Ulster PS) and over 100,000 copies using the negative 24128 plate (Ulster NS). Similarly, when printing was carried out using a printing plate obtained by developing with a developer having a composition with the above developer composition minus hydrazine, 15,000 copies of the printing plate using a positive pull S plate (Ulster PS) were printed, and a negative 24,128 copies were printed. Edition (Ulster NS
) printing plates began to smudge and became unprintable after 1,000 copies had been printed.

Example 5 Commercially available positive type S plate (FPD) and negative type S plate (FPD) manufactured by Fuji Photo Film @) were used for two years after acquisition.
NS) VCl Positive and negative image films were stacked and exposed for 50 seconds from a distance of 1 m using a 4 KW ultra-high pressure mercury lamp, then developed with the following developer, washed with water and dried (7) to obtain a lithographic printing plate. ter-ethylene glycol monophenyl ether 25 Sodium 9-alkylnaphthalene sulfonate 150 g Potassium hydroxide 109 Water glass (No. 5183) 20 g Sodium bisulfite 109 Four-hothannda 2 g Water 1000 9 This printing plate was prepared using Heidel GTO according to Example 4. When printed using a printing machine, more than 50,000 copies were printed using a positive type PS plate (FPD'), and more than 50,000 copies were printed using a negative type PS plate (CFMS).
) can print more than 100,000 copies. Similarly, printing was carried out using a printing plate obtained by developing with a developer having a composition other than the above-mentioned developer composition except for sodium bisulfite.
In the S version, there are 1. Ground stains occurred from the point of 1.
It became impossible to print.

Test Examples 1 to 17 The PS plate manufactured in Example 1 and subjected to severe treatment at 90°C for 8 hours was exposed in a vacuum printing frame for 20 seconds from a distance of 1 m with a 4KW ultra-high pressure mercury lamp at 1-1000 kHz, and then the front side was exposed. A lithographic printing plate was obtained using the developer shown in -1. The results are shown in the same table. The meanings of rice 1, rice 2, rice 5, rice 4, and rice 5 in the table are as follows.

Rice I A; Ethyne Q-lyl monophenyl ether B
; Sodium alkylnafucrene sulfonate C; Sodium triphosphate D; Water glass (No. 5183) E; Hydrazine aquarium (80% solution) F; Water rice immersed in a developer solution at 225°C to visualize with the naked eye The time it takes to confirm that development is complete.

Contact angle of the non-image area of a 3Pa plate washed with water and dried after development. (Measurement value using a goniometer) A US A PS plate was washed and dried after development, and offset printing ink was applied with a roller to the non-image area at 40°.
C. Pour warm water onto the ink surface and rub the ink surface with a sponge to see how the ink comes off.

1: Ink does not fall off at all 2: Slightly falls off 3 = Most of the ink falls off, but a thin layer remains on the surface of the plate 4: It falls off (wipe it hard with a sponge) 5: It falls off (wipe it lightly with a sponge) ) Rice 5 was developed with an automatic processor (Fuji Photo Film #400-K) and the staining characteristics were measured for each number of PS plates passed through, and the staining characteristics were 4 to 4 in Rice 4.
The number of sheets passed through the range evaluated as 5 is shown in square meters (area) with respect to the developer 11.

Test Example 1B The following six types of commercially available PE 1 plates were subjected to severe treatment at 90°C for 8 hours. After developing for 1 minute and washing with water and drying, a stain test on the plate surface was conducted according to Test Examples 1 to 17. The results are shown in Table 2, showing excellent developability applicable to all of the 28 commercially available plates used, with comparable stain resistance. [PS plates used] (1) Almax TAN Ohka Kogyo @ ) made (2) FN
C-B Manufactured by Fuji Photo Film Co., Ltd. (5) F N E
l Manufactured by Fuji Photo Film Co., Ltd. (4) F N D Manufactured by Fuji Photo Film Co., Ltd. (5) B W IN Manufactured by Konishiroku Photo Industry Co., Ltd. (6) Ulster NS Manufactured by Nippon Seifuku Co., Ltd. Developer] (1) N-200 manufactured by Ohka Kogyo @) (2) D N-3C manufactured by Fuji Photo Film Co., Ltd. (5
) S D N -: 21 Konishiroku Photo Industry C Co., Ltd.) (5
) Go to Test Example 19 of the Present Invention 21 Exposure was carried out according to Example 1 using a PS version Ulster MS that had been manufactured for 3 years, and development was carried out using a developer having the same composition as in Example 1 except for the reducing agent. A printing original plate was prepared using the same method, and the plate properties were measured. As shown in Table 6, although there are differences in effectiveness depending on the type of reducing agent, the developability is improved.

Table-6 Patent applicant Nippon Foil Co., Ltd. Patent attorney Kanji Ida Procedural amendment (spontaneous) 1. Indication of the case Patent No. 93301cl of 1973 2. Name of the invention Developer for photosensitive lithographic printing plates 3. Relationship with the case of the person making the amendment 41JR - Applicant Address 10-70 Higashiomitabicho, Suita City, Osaka Prefecture Name Nippon Foil Co., Ltd. Representative Moto Matsui Giji 6th Amendment Details, Page 5, Line 4 Put it on the 5th line.

Claims (1)

[Claims] ■Characterized by containing an ether compound represented by the general formula R-0+ CH2CH20H (in the formula R represents a phenyl group or a benzyl group), an anionic surfactant, an alkaline substance, and a water-soluble reducing agent. A developer for photosensitive lithographic printing plates. (2) The developer for photosensitive lithographic printing plates according to claim 0, wherein the anionic surfactant is an alkylnaphthalene sulfonate. (2) The photosensitive printing plate preparation according to claim 0, wherein the alkaline substance consists of water glass and sodium metasilicate. (2) The developer for a photosensitive lithographic printing plate according to claim 0, wherein the water-soluble reducing agent is one or more selected from sodium bisulfite, sodium biphosphite, and hydrazine.