JP2007225819A - Automatic development method and automatic development device therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an automatic development method and an automatic development device in which a developing unit is made into a simple and inexpensive configuration and which can minimize changes in the sensitivity of a developer against changes in development conditions and can deal with even the water vaporization of the developer. <P>SOLUTION: The method includes the following steps: a conductivity reference value at which the activity of a developer is appropriate is set; a development replenisher/development replenishing diluent liquid to compensate a decrease in the development activity during operating/stopping an automatic development device and a decrease in the activity of the developer due to processing a planographic printing plate is replenished under predetermined replenishing conditions; the conductivity of the developer replenished at every given time interval is measured; and if the measured conductivity of the developer exceeds the conductivity reference value, the development replenishing diluent liquid is replenished; in this step, water in an amount based on a water vaporization amount from the developer in every unit time which is preliminarily measured is replenished as a vaporization correction water so as to maintain the developer concentration to an almost constant; the elapsed time after replenishing the vaporization correction water is measured; and the measured conductivity of the developer is corrected based on the elapsed time. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an automatic development method such as a photosensitive lithographic printing plate and an automatic development apparatus thereof, and more particularly to a technique for minimizing fluctuations in developer sensitivity to changes in development processing conditions.

  In general, in an automatic developing device for photosensitive lithographic printing plates, as a method for managing the sensitivity of the developer, the lithographic printing plate to be processed is replenished with time with a developer replenisher in a developer tank in which the developer is stored. A developing replenisher solution aging and processing replenishment method (hereinafter referred to as “area aging reference replenishment method”) is employed in which the plate area is measured and the amount of development replenisher solution is replenished in accordance with the measured value.

  However, such an area chronological reference replenishment method requires a highly accurate planographic printing plate area measuring device in the development processing section of the automatic developing device, resulting in a complicated structure and high cost. . In addition, it is difficult to determine whether the lithographic printing plate to be developed has only one side or both sides (hereinafter referred to as `` one side / both sides '') and the type of plate (plates with different photosensitive layer coating amounts, etc.). is there. For this reason, if the replenishment amount of the required development replenisher changes due to changes in the plate area, single side / both sides, and plate type of the lithographic printing plate, it becomes difficult to properly replenish the development replenishment amount. there were.

  Therefore, conventionally, as described in, for example, Patent Document 1, as a method for replenishing a developing replenisher in an automatic developing device for a photosensitive lithographic printing plate, the conductivity of the developer is measured, and this measured value (hereinafter, "Developer conductivity measured value") is compared with the conductivity value indicating the optimum sensitivity obtained in advance (hereinafter referred to as "appropriate conductivity value"), and the measured value of developer conductivity is the appropriate conductivity value. There has been known a replenishment method (hereinafter referred to as “conductivity reference replenishment method”) for replenishing the developer replenisher when the value is lower than. In such a conductivity reference replenishment method, even if the plate area, single side / both sides, and plate type of the lithographic printing plate to be processed are changed, an appropriate amount of development replenisher can be replenished. The sensitivity of can be kept appropriate.

  However, in general, there is an empirical fact that an appropriate conductivity value is different between a developer that is fatigued only by carbon dioxide gas over time and a developer that is fatigued only by plate processing (silicate-based processing agent / time-dependent fatigue (carbonic acid Gas fatigue) -Recovery recovery: 65 mS / cm, Treatment fatigue-Replenishment recovery: 55 mS / cm, Non-silicate treatment agent / Aging fatigue-Replenishment recovery: 56 mS / cm, Treatment fatigue-Replenishment recovery: 39 mS / cm ). Therefore, in the above-mentioned conductivity reference replenishment method, when the processing frequency, for example, the processing amount per day is different from the expected amount, the ratio between the actual replenishment amount and the processing replenishment amount will also differ from the expected value, The appropriate conductivity value of the entire developer in the developer tank calculated from the appropriate conductivity of the developer changes, and there is a discrepancy between the appropriate conductivity value set in advance, and the developer sensitivity can be maintained appropriately. The problem that it becomes impossible is caused.

  On the other hand, in Patent Document 2, after processing replenishment and replenishment over time, the ratio of processing replenishment and replenishment over time is calculated, thereby realizing calculation of the target conductivity value close to the appropriate conductivity value. When the conductivity is measured and the measured value of the developer conductivity exceeds the target conductivity value, the developer conductivity is approximately equal to the target conductivity value by adding the diluent to the developer. Is controlling. According to this method, even if the plate area, single side / both sides, plate type of the lithographic printing plate to be developed and the environmental carbon dioxide concentration change to some extent, it is possible to estimate the ratio between the replenishment amount and the replenishment amount with time. As a result, an appropriate target conductivity value can be determined.

On the other hand, there has been known a phenomenon in which water evaporates from the developer in the developing tank of the automatic developing device. However, due to the concentration of the developer due to the water evaporation, that is, the increase in the developer conductivity, accurate developer conductivity is achieved. There was a problem that the degree value would be different from the appropriate conductivity value. Therefore, in the developing method described in Patent Document 3, a replenishment based on the developer conductivity value is performed, and an amount of water corresponding to the amount of water evaporated from the developer per unit time examined in advance (hereinafter referred to as “evaporation”). The concentration of the developer in the developer tank due to water evaporation is corrected by replenishing the developer in the developer tank to the developer in the developer tank over time.
Japanese Patent No. 2516022 (Japanese Patent Laid-Open No. 64-21451) JP 2001-290249 A Japanese Patent No. 2729797 (Japanese Unexamined Patent Publication No. 1-180548)

However, in general, an inexpensive replenishment pump used for replenishing evaporation correction water has a characteristic that the discharge accuracy deteriorates when the discharge liquid amount is lowered. This is a method of increasing the amount of discharged liquid that is discharged at one time by adding up and replenishing them together. With this method, the discharge amount accuracy is improved, but as shown in FIG. 11, the evaporation water is not corrected during the fixed time interval, and the developer is delivered even after the developer conductivity is measured. Since this continues, an error occurs between the last measured value of the developer conductivity (measured value of developer conductivity) and the actual developer conductivity that changes every moment.
In particular, as in Patent Document 1 and Patent Document 2, when replenishment is performed or the replenishment amount is adjusted based on developer conductivity, the measured developer conductivity measurement value described above and the correct developer conductivity There is a concern that an error with the degree may adversely affect the operation of the replenishment method itself.

  In view of such circumstances, the present invention can minimize the variation in developer sensitivity with respect to changes in development processing conditions while simplifying and developing the development processing unit of the automatic development apparatus, and can evaporate the developer water. It is an object of the present invention to provide an automatic developing method and an automatic developing apparatus that can cope with the above.

The above object is achieved by the automatic developing method and the automatic developing apparatus according to the present invention.
(1) A developer conductivity value at which the developer activity is appropriate is obtained in advance and set as a conductivity reference value, and development is performed when the automatic developing apparatus is operating and / or stopped based on preset replenishment conditions. In order to compensate for the decrease in the activity, the developer replenisher and / or the developer replenisher diluent that is a diluent of the developer replenisher is replenished, and the developer activity by processing the lithographic printing plate based on preset replenishment conditions The developer replenisher and / or developer replenisher dilution solution is replenished to compensate for the decrease in the flow rate, and the conductivity of the developer replenished with the developer replenisher solution is measured at predetermined time intervals. When the developer conductivity measurement value exceeds the conductivity reference value, the developer replenishment dilution liquid is replenished to the developer until the developer conductivity measurement value falls below the conductivity reference value. The developer concentration is almost constant In order to maintain, replenish the amount of water based on the amount of water evaporation from the developer measured in advance per unit time as evaporation correction water, measure the elapsed time from the previous replenishment of the evaporation correction water to the present time, An automatic developing method, wherein the measured value of the measured developer conductivity is corrected based on the elapsed time.
(2) Using the replenisher replacement rate, which is the ratio of the developer replenisher and / or developer replenisher diluted to the developer in the developer tank, the developer replenisher or developer replenisher diluted (1) The automatic developing method according to (1), wherein the conductivity reference value is sequentially corrected each time the ink is replenished.
(3) The developer replenisher and / or development replenished based on the operation time and / or stop time of the automatic developing device with respect to the total developer replenisher and / or the total developer replenisher diluted to the developer in the developer tank. The conductivity reference value is sequentially corrected each time the development replenisher or the development replenisher is replenished using the replenishment ratio with time, which is the ratio of the replenisher, and the replenisher replacement rate. The automatic developing method according to (1).
(4) a developer dilution rate that is a ratio of the developer replenisher diluted in the developer in the developer tank to a developer replenisher replenished in the developer in the developer tank, the replenishment ratio with time, and In order to always switch and set the conductivity target value, which is an appropriate conductivity of the developer, using the replenisher replacement rate, the conductivity The automatic development method according to (1), wherein the degree reference value is sequentially corrected.
(5) A developer conductivity value at which the developer activity is appropriate is experimentally obtained in advance and set as a conductivity reference value, and the development activity at the time of operation and / or stop based on a preset replenishment condition In order to compensate for the decrease in the degree, a development replenisher and / or a development replenisher dilution which is a dilution of the development replenisher is replenished in the developing tank, and the printing plate is developed based on preset replenishment conditions. The developer in the developer tank is replenished with the developer replenisher and / or developer replenisher diluted solution to compensate for the decrease in developer activity, and is replenished with the developer replenisher at predetermined intervals. After measuring the measured developer conductivity, the automatic developing device replenishes the developer with a developer diluent until the measured developer conductivity falls below the conductivity reference value. A development processing section for developing with the developer in the developing tank; Developer replenishment means for replenishing the developer replenisher in the developer in the developer tank, Developer replenisher diluent replenishing means for replenishing the developer replenisher diluted liquid in the developer tank, and the evaporation correction Evaporation correction water replenishment means for replenishing the developer in the developer tank, elapsed time measurement means for measuring the elapsed time from the last replenishment of the evaporation correction water, and the developer conductivity measurement Conductivity measurement means for measuring the value at predetermined time intervals, and the automatic developing method according to any one of (1) to (4), the measured value of the measured value of the developer conductivity is measured. An automatic developing apparatus comprising: a control unit that performs correction based on time.

  In the present invention, the “developing replenisher” is a processing liquid that is replenished in order to keep development performance constant. In general, as this replenisher, there are those prepared by diluting the replenisher stock solution with a diluent (e.g., water) and those using the replenisher stock solution as it is without being diluted. “Liquid” means a solution prepared by diluting a replenisher stock solution with a diluent. Further, as a replenishment method, there are a method of replenishing the developer with a replenisher prepared by diluting in advance, and a method of directly replenishing the developer with a replenisher stock solution and a diluted solution separately.

  Furthermore, in the present invention, the conductivity sensor for measuring the conductivity value of the developer is a known means such as an AC conductivity meter, an AC bridge meter, or other conductivity meter. The measurement current value and oscillation frequency of the measuring device vary depending on the composition of the developer, but the current value is low to some extent to prevent electrolysis of the water-soluble developer. It is preferably several hundred mA to several μA. The frequency is preferably from several hundred Hz to several hundred kHz in view of the relationship with the electrostatic capacitance component in the developer.

  The conductivity value of the developer containing the electrolyte depends on the temperature of the aqueous solution, and the value increases as the solution temperature increases. Therefore, it is more preferable to measure the conductivity value with a measuring instrument provided with a temperature sensor and a temperature compensation circuit. In the control device that controls replenishment, it is also possible to compensate for the temperature by converting the actually measured liquid resistance value and liquid temperature into a conductivity value at a predetermined temperature. The sensor installation position of the AC conductivity meter, AC bridge meter, or other conductivity meter may be any place where it can be immersed in the developer at the time of measurement and the AC conductivity value of the developer can be measured. A preferred position is in the developer circulation system, particularly in the development tank or circulation pipe. Moreover, as a detection part, the well-known measurement cell which used platinum, stainless steel, etc. for the electrode can be used.

  According to the present invention, the developer conductivity calculated from the measured value of the developer conductivity and the elapsed time since the replenishment of the evaporation correction water is used even when the replenishment method using the conductivity value of the developer is used. By using the corrected measurement value, the replenishment operation is not affected by fluctuations in the measured value of the developer conductivity when the developer is concentrated due to water evaporation or when the evaporation correction water is replenished to compensate for the water evaporation. Automatic development processing with high sensitivity stability can be realized.

  In the automatic developing method of the automatic developing device according to the present invention, the developer conductivity value at which the developer activity is appropriate is obtained in advance and set as the conductivity reference value, and the automatic developing device is set based on a preset replenishment condition. In order to compensate for a decrease in the development activity at the time of operation and / or stoppage, a development replenisher and / or a development replenisher dilution that is a dilution of the development replenisher are replenished, and based on preset replenishment conditions Development in which the developer replenisher and / or developer replenisher diluent is replenished to compensate for the decrease in developer activity due to the processing of the lithographic printing plate, and the developer replenisher is replenished at predetermined time intervals. After measuring the conductivity of the liquid, if the measured value of developer conductivity exceeds the conductivity reference value, the developer is measured until the developer conductivity measured value falls below the conductivity reference value. Automatic replenishment of replenishment diluent In order to keep the developer concentration substantially constant, an amount of water based on the amount of water evaporation from the developer measured in advance per unit time is replenished as evaporation correction water, and the evaporation correction water is replenished last time. Then, the elapsed time up to the present time is measured, and the measured value of the measured developer conductivity is corrected based on the elapsed time. Hereinafter, the automatic developing method of the automatic developing device will be described in detail.

First, an alkali developing solution used for plate making of the lithographic printing plate of the present invention will be described.
An alkali developing solution (hereinafter also simply referred to as “developing solution”) used for the developing process is an alkaline aqueous solution, and can be appropriately selected from conventionally known alkaline aqueous solutions. Examples of the alkaline aqueous solution include a developer composed of an alkali silicate or non-reducing sugar and a base, and those having a pH of 12.5 to 14.0 are particularly preferable. The alkali silicate exhibits alkalinity when dissolved in water, and examples thereof include alkali metal silicates such as sodium silicate, potassium silicate and lithium silicate, and ammonium silicate. The alkali silicate may be used alone or in combination of two or more.

The alkali aqueous solution is easy to develop by adjusting the mixing ratio and concentration of silicon oxide SiO ₂ and alkali oxide M ₂ O (M represents an alkali metal or ammonium group), which is a silicate component. Can be adjusted to. Among the alkaline aqueous solutions, those having a mixing ratio (SiO ₂ / M ₂ O: molar ratio) of silicon oxide SiO ₂ and alkali oxide M ₂ O of 0.5 to 3.0 are preferable, and 1.0 to 2.0 is more preferable.
If the SiO ₂ / M ₂ O is less than 0.5, the alkali strength becomes stronger, which may cause a problem of etching a general-purpose aluminum plate or the like as a support for a lithographic printing plate precursor. If it exceeds 3.0, the developability may be lowered.

  Moreover, as a density | concentration of the alkali silicate in a developing solution, 1-10 mass% is preferable with respect to the mass of alkaline aqueous solution, 3-8 mass% is more preferable, and 4-7 mass% is the most preferable. If this concentration is less than 1% by mass, the developability and processing ability may be lowered. If it exceeds 10% by mass, precipitation and crystals are likely to occur, and further gelation tends to occur during neutralization in the waste liquid. , It may interfere with waste liquid treatment.

In a developer comprising a non-reducing sugar and a base, the non-reducing sugar means a saccharide that has no free aldehyde group or ketone group and therefore has no reducing property, and is a trehalose-type oligosaccharide in which reducing groups are bonded to each other. Glycosides in which saccharide reducing groups and non-saccharides are combined, and sugar alcohols reduced by hydrogenation of saccharides. Any of these can be suitably used in the present invention.
Examples of trehalose type oligosaccharides include saccharose and trehalose, and examples of the glycoside include alkyl glycosides, phenol glycosides, and mustard oil saccharides.
Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, zulsiit, allozulcit and the like. Furthermore, maltitol obtained by hydrogenation of a disaccharide, a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide, and the like can also be suitably exemplified.

  Among the above, as the non-reducing sugar, sugar alcohol and saccharose are preferable, and among them, D-sorbitol, saccharose, and reduced starch syrup are more preferable because they have a buffering action in an appropriate pH region. These non-reducing sugars may be used alone or in combination of two or more. The proportion of the non-reducing sugar in the developer is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass.

  In the alkali silicate or non-reducing sugar, an alkali agent as a base can be appropriately selected from conventionally known compounds and combined. Examples of the alkali agent include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.

Furthermore, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, An organic alkali agent such as ethyleneimine, ethylenediamine, and pyridine can also be suitably exemplified.
These alkaline agents may be used alone or in combination of two or more. Of these, sodium hydroxide and potassium hydroxide are preferred. The reason is that the pH can be adjusted in a wide pH range by adjusting the amount added to the non-reducing sugar. Further, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable because they have a buffering action.
The development replenisher of the present invention can further contain a conductivity adjusting agent. The conductivity adjusting agent as used in the present invention has a function of increasing the conductivity of an alkaline developer, dissolves in an alkaline aqueous solution, does not react with the developer component and the developer replenisher component, and also serves as a photosensitive layer component. Any material may be used as long as it does not react with the undercoat layer component and the backcoat layer component and exhibits electrophoretic properties when dissolved in water, and includes an organic electrolyte and an inorganic electrolyte.

The conductivity adjusting agent used in the present invention, among the above compounds, is added to a developer having an original conductivity of 35 to 80 mS / cm at a concentration of 0.01 to 10.0% by mass. Is preferably 2 to 10 mS / cm, preferably 3 to 8 mS / cm, more preferably 4 to 7 mS / cm 2. Furthermore, in addition to satisfying the above conditions, an inorganic electrolyte and an organic electrolyte having a molecular weight of 1500 or less, preferably a molecular weight of 1000 or less, more preferably a molecular weight of 800 or less and 100 or more are preferable. Furthermore, in addition to the above-mentioned conditions for increasing conductivity and molecular weight, the most preferred is a compound in which a 5% by mass aqueous solution of the compound exhibits a pH of 3 to 10, preferably a pH of 3.5 to 9.5, more preferably a pH of 4 to 9. Used.
Therefore, the most preferable conductivity adjusting agent used in the present invention is (1) dissolved in an alkaline aqueous solution and does not react with the developer component and the developer replenisher component, and the photosensitive layer component, undercoat layer component and It does not react with the backcoat layer components and exhibits electrophoretic properties when dissolved in water. (2) In a developer having an original conductivity of 35 to 80 mS / cm, a concentration of 0.01 to 10.0% by mass Can be increased in conductivity by 4 to 7 mS / cm, (3) an inorganic electrolyte or organic electrolyte having a molecular weight of 800 or less and 100 or more, and (4) a 5% by mass aqueous solution having a pH of 4 to 9. It is.
The above-mentioned conductivity measurement can be carried out, for example, using a conductivity meter manufactured by Toa DKK.

Specific examples of the conductivity adjusting agent used in the present invention include, as an inorganic electrolyte, carbonates such as lithium, sodium, potassium, calcium, magnesium and ammonium, bicarbonates, phosphates, phosphites, hydrochlorides, Sulfates, sulfites, nitrates, nitrites and the like can be mentioned. As the organic electrolyte, carboxylate such as lithium, sodium, potassium, calcium, magnesium and ammonium, sulfonate and phosphonate are used.
More specifically, carboxylates such as formate, acetate, propionate, butanoate, oxalate, malonate, succinate, citrate, benzoate, salicylate, sulfosalicylic acid There are aromatic carboxylates such as salts and phthalates, and sulfonates include lower alkyl sulfonates, benzene sulfonates, styrene sulfonates, xylene sulfonates, lower alkyl benzene sulfonates, and benzene disulfonic acids. Examples include salt.
In the present invention, these conductivity adjusting agents can be used singly or in combination of two or more.

Among them, examples of conductivity adjusting agents that are particularly preferably used include potassium citrate, sodium citrate, lithium citrate, potassium succinate, sodium succinate, lithium succinate, potassium carbonate, sodium carbonate, and lithium carbonate. As described above, a developer containing an alkali silicate or non-reducing sugar and a base is used as the alkali developing solution, but as its cation component, Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ are conventionally used. ing. In particular, a system containing a large number of cations having a small ionic radius has high penetrability into the image recording layer and excellent developability, but dissolves up to the image area and causes image defects. Therefore, there is a certain limit to increasing the alkali concentration, and in order to completely process the image recording layer (residual film) so as not to remain in the non-image area without causing defects in the image area, it is delicate. It was required to set a proper liquid condition.
However, by using a cation having a large ionic radius as the cation component, the penetrability of the developer into the image recording layer can be suppressed, and the image density can be reduced without reducing the alkali concentration, that is, the developability. The dissolution inhibiting effect of the part can also be improved.
As the cation component, in addition to the alkali metal cation and ammonium ion, other cations can be used.

The following additives can be added to the alkaline developing solution of the present invention for the purpose of further improving the development performance.
For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, chelating agents such as EDTA and NTA described in JP-A-58-190952, JP-A-59-121336 [Co (NH ₃ ) ₆ ] Cl ₃ , CoCl ₂ .6H ₂ O and other complexes described in JP-A-50-51324, sodium alkylnaphthalene sulfonate, n-tetradecyl-N, N-dihydroxy Anionic or amphoteric surfactants such as ethylbetaine, nonionic surfactants such as tetramethyldecynediol described in US Pat. No. 4,374,920, p described in JP-A-55-95946 -Cationic polymers such as methyl chloride quaternary compound of dimethylaminomethyl polystyrene, disclosed in JP-A-56-142528 Amphoteric polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described above, reducing inorganic salts such as sodium sulfite described in JP-A-57-192951, JP-A-58-59444 Inorganic lithium compounds such as lithium chloride described in JP-A No. 59-75255, organometallic surfactants including organic Si and Ti described in JP-A-59-75255, and organoboron compounds described in JP-A-59-84241 And quaternary ammonium salts such as tetraalkylammonium oxides described in EP101010.
A lithographic printing plate developed using an alkali developing solution and a replenisher is post-treated with a rinsing solution containing washing water, a surfactant and the like, and a desensitizing solution containing gum arabic and starch derivatives. In this post-treatment, these treatment liquids can be variously combined.

Next, the heat-sensitive positive lithographic printing plate used in the automatic developing apparatus according to the present invention will be described.
[Heat-sensitive positive lithographic printing plate]
The heat-sensitive positive lithographic printing plate used in the plate-making method of the present invention comprises an image recording layer containing an infrared absorbing dye as an essential component on a support and usually containing an alkali-soluble resin or the like.
The heat-sensitive positive lithographic printing plate (also referred to as a lithographic printing plate precursor) is described in detail below. First, the configuration of the image recording layer will be described.

[Infrared absorbing dye]
In the present invention, the infrared absorbing dye used in the image recording layer is not particularly limited as long as it absorbs infrared rays and generates heat, and various dyes known as infrared absorbing dyes can be used.
As the infrared absorbing dye, commercially available dyes and known dyes described in the literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, quinoneimine dyes, methine dyes, and cyanine dyes. In the present invention, among these dyes, those that absorb infrared light or near infrared light are particularly preferred because they are suitable for use in lasers that emit infrared light or near infrared light.
Examples of dyes that absorb such infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, and JP-A-60-78787. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, etc., JP-A-58-112793, Naphthoquinone dyes described in JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-59240, JP-A-60-63744, etc. Examples thereof include squarylium dyes described in JP-A-58-112792, and cyanine dyes described in British Patent 434,875.

Further, a near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used as the dye, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 Pentamethine thiopyrylium salts described in No. 5 and pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 But as the commercially available products, Epolight III-178 of Eporin Co., Epolight III-130, Epolight III-1 25 and the like are particularly preferably used.
Infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 are particularly preferred as infrared absorbing dyes used in the image recording layer. The dye exhibits a very strong interaction with the alkalinized soluble resin, and is excellent in the unexposed area alkaline development resistance of the image recording layer.

The amount of the infrared absorbing dye added to the image recording layer is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, particularly from the viewpoint of sensitivity and uniformity of the image recording layer, with respect to the mass of the image recording layer. Preferably it is 0.1-30 mass%.
Specific examples of the infrared absorbing dye are shown below, but the present invention is not limited thereto.

[Alkali-soluble resin]
The alkali-soluble resin used in the image recording layer is a water-insoluble and alkali-water-soluble resin (hereinafter appropriately referred to as an alkali-soluble polymer), and has an acidic group on the main chain and / or side chain in the polymer. Containing homopolymers, copolymers thereof or mixtures thereof. Therefore, the image recording layer of the lithographic printing plate precursor has a property of dissolving when contacted with an alkaline developer.
The alkali-soluble polymer used in the image recording layer is not particularly limited as long as it is a conventionally known polymer, but any one of (1) phenolic hydroxyl group, (2) sulfonamide group, and (3) active imide group A polymer compound having a functional group in the molecule is preferable. For example, the following are exemplified, but not limited thereto.

  (1) Examples of the polymer compound having a phenolic hydroxyl group include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p Any of-or m- / p-mixing) may be used. Examples thereof include novolak resins such as mixed formaldehyde resins and pyrogallol acetone resins. In addition to this, a polymer compound having a phenolic hydroxyl group in the side chain is preferably used as the polymer compound having a phenolic hydroxyl group. As a polymer compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer comprising a low molecular compound having at least one unsaturated bond polymerizable with the phenolic hydroxyl group is homopolymerized, or other polymerizable property is added to the monomer. Examples thereof include a polymer compound obtained by copolymerizing monomers.

  Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenolic hydroxyl group. Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N -(3-Hydroxyphenyl) methacrylamide, N- (4-Hydroxyphenyl) methacrylamide, o-Hydroxyphenyl acrylate, m-Hydroxyphenyl acrylate, p-Hydroxyphenyl acrylate, o-Hydroxyphenyl methacrylate , M-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) ethyl Acrylate, 2- 4-hydroxyphenyl) ethyl acrylate, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate can be suitably used 2- (4-hydroxyphenyl) ethyl methacrylate. Such resins having a phenolic hydroxyl group may be used in combination of two or more. Furthermore, as described in U.S. Pat. No. 4,123,279, phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, These copolymers may be used in combination.

(2) Examples of the alkali-soluble polymer compound having a sulfonamide group include a polymer compound obtained by homopolymerizing a polymerizable monomer having a sulfonamide group or copolymerizing the monomer with another polymerizable monomer. . The polymerizable monomer having a sulfonamide group includes one or more sulfonamide groups —NH—SO ₂ — in which at least one hydrogen atom is bonded on a nitrogen atom and one or more polymerizable unsaturated bonds in one molecule. And a polymerizable monomer comprising a low molecular weight compound. Among them, a low molecular compound having an acryloyl group, an allyl group, or a vinyloxy group, and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group is preferable.

(3) The alkali-soluble polymer compound having an active imide group preferably has an active imide group in the molecule, and the polymer compound has an unsaturated bond polymerizable with an active imide group in one molecule. Examples thereof include a polymer compound obtained by homopolymerizing a polymerizable monomer composed of one or more low-molecular compounds or copolymerizing the monomer with another polymerizable monomer.
As such a compound, specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used.

  Furthermore, as the alkali-soluble polymer compound, a polymer compound obtained by polymerizing two or more of the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, and the polymerizable monomer having an active imide group is used. Alternatively, it is preferable to use a polymer compound obtained by copolymerizing these two or more polymerizable monomers with another polymerizable monomer. When a polymerizable monomer having a phenolic hydroxyl machine is copolymerized with a polymerizable monomer having a sulfonamide group and / or a polymerizable monomer having an active imide group, the compounding polymerization ratio (mass ratio) of these components is It is preferably in the range of 50:50 to 5:95, particularly preferably in the range of 40:60 to 10:90.

  When the alkali-soluble polymer is a copolymer of a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group and another polymerizable monomer The monomer that imparts alkali solubility is preferably contained in an amount of 10 mol% or more, more preferably 20 mol% or more so that the alkali solubility becomes sufficient and the effect of improving the development latitude is sufficiently achieved.

Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group include the compounds listed in the following (m1) to (m12). However, it is not limited to these.
(M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(M2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, and glycidyl acrylate.
(M3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, and glycidyl methacrylate.
(M4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.

(M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(M7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene.
(M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
(M10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

The alkali-soluble polymer compound preferably has a phenolic hydroxyl group in terms of excellent image-forming properties in exposure with an infrared laser or the like, such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, Preferred examples include novolak resins and pyrogallol acetone resins such as m- / p-mixed cresol formaldehyde resin and phenol / cresol (which may be m-, p-, or m- / p-mixed) mixed formaldehyde resin.
Further, as an alkali-soluble polymer compound having a phenolic hydroxyl group, as described in US Pat. No. 4,123,279, carbon such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin is used. Examples thereof include condensation polymers of phenol and formaldehyde having an alkyl group of 3 to 8 as a substituent.
As a copolymerization method of the alkali-soluble polymer compound, a conventionally known graft copolymerization, block copolymerization, random copolymerization method or the like can be used.

In the present invention, when the alkali-soluble polymer is a homopolymer or copolymer of a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group, Those having an average molecular weight of 2,000 or more and a number average molecular weight of 500 or more are preferred. More preferably, the weight average molecular weight is 5,000 to 300,000, the number average molecular weight is 800 to 250,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 10. .
In the present invention, when the alkali-soluble polymer is a resin such as phenol formaldehyde resin or cresol aldehyde resin, the weight average molecular weight is 500 to 20.000, and the number average molecular weight is 200 to 10,000. Is preferred.
These alkali-soluble polymer compounds may be used alone or in combination of two or more, and are 30 to 99% by mass, preferably 40 to 95% by mass, particularly preferably 50%, based on the total solid content of the image forming layer. Used in an addition amount of ˜90% by mass. From the viewpoint of durability and sensitivity of the image forming layer, the above content range is appropriate.

The image forming layer may also contain an alkali-soluble polymer compound having a carboxyl group (hereinafter sometimes referred to as “component (B1)”).
The polymer compound (B1) may be any alkali-soluble polymer compound having a carboxyl group, but polymer compounds (b1-1) and (b1-2) defined below are preferred.
(B1-1) An alkali-soluble polymer compound having a polymerizable monomer unit represented by the following general formula (i) (hereinafter also referred to as polymer compound (b1-1))

(In the formula, Xm represents a single bond or a divalent linking group, Y represents hydrogen or a carboxyl group, and Z represents hydrogen, an alkyl group or a carboxyl group.)
As a monomer constituting the polymerizable monomer unit represented by the general formula (i), there is a polymerizable monomer having at least one carboxyl group and one polymerizable unsaturated group in the molecule.
Specific examples of such polymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride.

Examples of the monomer to be copolymerized with the polymerizable monomer having a carboxyl group include the following (1) to (11), but are not limited thereto.
(1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylates such as acrylates;
(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl Alkyl methacrylate such as methacrylate.

(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.
(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
(10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
Moreover, the monomer of the following general formula (ii) is also preferably used.

In the formula, X represents O, S, or N—R ¹² . R ^{10 to} R ¹² each independently represents a hydrogen atom or an alkyl group. m, n, and o each independently represents an integer of 2 to 5, and CmH ₂ m, CnH ₂ n, and CoH ₂ o may each be linear or branched. p, q, and r each independently represent an integer of 0 to 3,000, and p + q + r ≧ 2.
The alkyl group in R ¹⁰ to R ^12, preferably one having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, n- propyl group, an isopropyl group. p, q, and r preferably represent an integer of 0 to 500, and more preferably represent an integer of 0 to 100.
Although the example of the monomer corresponding to the repeating unit represented by the said general formula (ii) is given below, it is not this limitation.

The repeating unit represented by the general formula (ii) is a commercially available hydroxypoly (oxyalkylene) material such as a trade name Pluronic (Pluronic (manufactured by Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.) ), Carbowax (Carbowax (Glyco Product)), Triton (Toriton (Rohm and Haas (Rohm and Haas)), and PE (Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by reacting the product with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride in a known manner.
Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  As a commercially available monomer, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, Blemmer AE-200, Blemmer as a hydroxyl-terminated polyalkylene glycol mono (meth) acrylate manufactured by NOF Corporation. AE-400, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50 PEP-300, Blemmer 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 5 PPT-800, Blemmer 70PPT-800, Blemmer APT series, Brenmer 10PPB-500B, and the like Brenmer 10APB-500B. Similarly, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer as alkyl-terminated polyalkylene glycol mono (meth) acrylates manufactured by NOF Corporation. 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASE series, Blemmer PKEP series, Blemmer AKEP series, Blemmer AE-300 , Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANE -500, BLEMMER 70ANEP-550, etc., and Kyoeisha Chemical Co., Ltd. light ester MC, light ester 130MA, light ester 041MA, light acrylate BO-A, light acrylate EC-A, light acrylate MTG-A, light acrylate 130A, light Examples thereof include acrylate DPM-A, light acrylate P-200A, light acrylate NP-4EA, and light acrylate NP-8EA.

The minimum constitutional unit having a polymerizable monomer component having at least one carboxyl group and at least one polymerizable unsaturated group in the polymer compound (b1-1) does not have to be one kind in particular, and is the same. It is also possible to use a copolymer obtained by copolymerizing two or more of the minimum structural units having the above acidic groups or two or more of the minimum structural units having different acidic groups.
As the copolymerization method, conventionally known graft copolymerization, block copolymerization, random copolymerization, and the like can be used.

  (B1-2) A basic skeleton is a reaction product of a diol compound represented by the following general formula (iii), (iv) or (v) having a carboxyl group and a diisocyanate compound represented by the following general formula (viii) And an alkali-soluble polymer compound having a carboxyl group (hereinafter, also referred to as polymer compound (b1-2)).

R ¹³ represents a hydrogen atom, a substituent (for example, an alkyl, aryl, alkoxy, ester, urethane, amide, ureido, or halogeno group is preferable), alkyl, alkenyl, aralkyl, aryl, alkoxy, An aryloxy group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
R ¹⁴ , R ¹⁵ and R ¹⁶ each have the same or different single bond and substituent (for example, alkyl, alkenyl, aralkyl, aryl, alkoxy and halogeno groups are preferred). Divalent aliphatic or aromatic hydrocarbons that may be present. Preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms is shown.
If necessary, R ¹⁴ , R ¹⁵ and R ¹⁶ have other functional groups that do not react with isocyanate groups, such as ester groups, urethane groups, amide groups, ureido groups, and carbon-carbon unsaturated bonds. Also good. In addition, you may comprise a ring by 2 or 3 of R < ¹³ >, R <^14> , R <^15> , R < ¹⁶ >.
Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and preferably an aromatic group having 6 to 15 carbon atoms.

OCN-R ¹⁸ -NCO (viii)
In the formula, R ¹⁸ represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent (for example, an alkyl, alkenyl, aralkyl, aryl, alkoxy, or halogeno group is preferable). If necessary, R ¹⁸ may have another functional group that does not react with an isocyanate group, such as an ester, urethane, amide, ureido group, or carbon-carbon unsaturated bond.

Specific examples of the diol compound having a carboxyl group represented by the general formula (iii), (iv) or (v) include those shown below.
3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide Etc.

  The alkali-soluble polymer compound having a carboxyl group (b1-2) is preferably a reaction product in which a diol represented by the following general formula (vi) or (vii) is combined.

In the formula, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 2 or more. Examples of the alkyl group having 1 to 8 carbon atoms in R ^17, a methyl group, an ethyl group, i- propyl, n- butyl group, etc. i- butyl group.
Specific examples of the diol represented by the general formula (vi) or (vii) are shown below, but the present invention is not limited thereto.

Specific example of (vi) HO — (— CH ₂ CH ₂ O—) ₃ —H
HO — (— CH ₂ CH ₂ O—) ₄ —H
HO — (— CH ₂ CH ₂ O—) ₅ —H
HO — (— CH ₂ CH ₂ O—) ₆ —H
HO — (— CH ₂ CH ₂ O—) ₇ —H
_{HO - (- CH 2 CH 2} O-) 8 -H
HO — (— CH ₂ CH ₂ O—) ₁₀ —H
HO — (— CH ₂ CH ₂ O—) ₁₂ —H
Polyethylene glycol (average molecular weight 1000)
Polyethylene glycol (average molecular weight 2000)
Polyethylene glycol (average molecular weight 4000)
HO — (— CH ₂ CH (CH ₃ ) O—) ₃ —H
HO — (— CH ₂ CH (CH ₃ ) O—) ₄ —H
HO — (— CH ₂ CH (CH ₃ ) O—) ₆ —H
Polypropylene glycol (average molecular weight 1000)
Polypropylene glycol (average molecular weight 2000)
Polypropylene glycol (average molecular weight 4000)

Specific examples of (vii) HO — (— CH ₂ CH ₂ CH ₂ O—) ₃ —H
HO — (— CH ₂ CH ₂ CH ₂ O—) ₄ —H
HO — (— CH ₂ CH ₂ CH ₂ O—) ₈ —H
HO — (— CH ₂ CH ₂ CH (CH ₃ ) O—) ₁₂ —H

Specific examples of the diisocyanate compound represented by the general formula (viii) include those shown below.
That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Aromatic diisocyanate compounds such as 1,5-naphthalene diisocyanate and 3,3′-dimethylbiphenyl-4,4′-diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate Compound, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) -diisocyanate, 1 An aliphatic diisocyanate compound such as 1,3- (isocyanatomethyl) cyclohexane; a diisocyanate compound which is a reaction product of a diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate, and the like. Can be mentioned.

  The molar ratio of the diisocyanate and the diol compound used for the synthesis of the polymer compound (b1-2) is preferably 0.8: 1 to 1.2-1, and when an isocyanate group remains at the polymer terminal, alcohols or By treating with amines or the like, it is finally synthesized in a form in which no isocyanate group remains.

As the component (B1), one type may be used alone from the above polymer compounds (b1-1) and (b1-2), or two or more types may be used in combination.
The content of the repeating unit having a carboxyl group contained in the component (B1) is 2 mol% or more based on the total amount of each monomer of the component (B1), preferably 2 to 70 mol%. Yes, more preferably in the range of 5 to 60 mol%.
The preferred weight average molecular weight of the component (B1) is preferably 3000 to 300,000, more preferably 6,000 to 100,000.

  Furthermore, the preferable addition amount of the component (B1) is in the range of 0.005 to 80% by mass, preferably in the range of 0.01 to 50% by mass, based on the total solid content mass of the image recording layer. Preferably it is the range of 1-20 mass%.

[Additive]
In forming the image recording layer, in addition to the above components, various additives can be further added as necessary as long as the effects of the present invention are not impaired.
-Solubility inhibiting compound-
The lithographic printing plate precursor can contain various inhibitors in the image recording layer for the purpose of enhancing its inhibition (solubility inhibition).
Although it does not specifically limit as this inhibitor, A quaternary ammonium salt, a polyethyleneglycol type compound, etc. are mentioned.

The quaternary ammonium salt is not particularly limited, and examples thereof include tetraalkylammonium salts, trialkylarylammonium salts, dialkyldiarylammonium salts, alkyltriarylammonium salts, tetraarylammonium salts, cyclic ammonium salts, and bicyclic ammonium salts. .
Specifically, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, tetraoctylammonium bromide, tetralaurylammonium bromide, tetraphenylammonium bromide, tetranaphthylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide , Tetrastearyl ammonium bromide, lauryl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium bromide, lauryl triethyl ammonium bromide, phenyl trimethyl ammonium bromide, 3-trifluoromethylphenyl trimethyl ammonium bromide, benzyl trimethyl ammonium bromide De, dibenzyl dimethyl ammonium bromide, distearyl dimethyl ammonium bromide, tristearyl methyl ammonium bromide, benzyl triethyl ammonium bromide, hydroxyphenyl trimethyl ammonium bromide, N- methyl pyridinium bromide, and the like. In particular, quaternary ammonium salts described in Japanese Patent Application Nos. 2001-226297, 2001-370059, and 2001-398047 are preferable.

  The addition amount of the quaternary ammonium salt is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, based on the total solid content of the image recording layer. The range of the content is appropriate in that the solubility inhibiting effect is sufficiently exhibited and the film forming property of the binder is not deteriorated.

  Although it does not specifically limit as a polyethyleneglycol type compound, The thing of the following structure is mentioned.

^{R 1 - {- O- (R} 3 -O-) m-R 2} n
(R ¹ is a polyhydric alcohol residue or polyhydric phenol residue, R ² is a hydrogen atom, an alkyl group, alkenyl group, alkynyl group, alkyloyl group, aryl which may have a substituent of 1 to 25 carbon atoms, aryl Group or aryloyl group, R ³ represents an alkylene residue which may have a substituent, m is an average of 10 or more, and n is an integer of 1 to 4.
Examples of polyethylene glycol compounds having the above structure include polyethylene glycols, polypropylene glycols, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol aryl ethers, polypropylene glycol aryl ethers, polyethylene glycol alkyl aryl ethers. , Polypropylene glycol alkyl aryl ethers, polyethylene glycol glycerin esters, polypropylene glycol glycerin esters, polyethylene sorbitol esters, polypropylene glycol sorbitol esters, polyethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, polyethylene glycolated ethylene Diamines, polypropylene glycolated ethylenediamines, polyethylene glycolated diethylenetriamine, and polypropylene glycol diethylenetriamines.

  Specific examples thereof include polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 10000, polyethylene glycol 20000, polyethylene glycol 5000, polyethylene glycol 100000, polyethylene glycol 200000, polyethylene glycol 500000, polypropylene glycol 1500, polypropylene glycol. 3000, polypropylene glycol 4000, polyethylene glycol methyl ether, polyethylene glycol ethyl ether, polyethylene glycol phenyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol diphenyl ether Polyethylene glycol lauryl ether, polyethylene glycol dilauryl ether, polyethylene glycol nonyl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol distearyl ether, polyethylene glycol behenyl ether, polyethylene glycol dibehenyl ether, polypropylene glycol methyl ether, polypropylene glycol Ethyl ether, polypropylene glycol phenyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diethyl ether, polypropylene glycol diphenyl ether, polypropylene glycol lauryl ether, polypropylene glycol dilauryl ether, polyethylene glycol Propylene glycol nonyl ether, polyethylene glycol acetyl ester, polyethylene glycol diacetyl ester, polyethylene glycol benzoate, polyethylene glycol lauryl ester, polyethylene glycol dilauryl ester, polyethylene glycol nonyl ester, polyethylene glycol cetylate, polyethylene glycol stearoyl ester, polyethylene Glycol distearoyl ester, polyethylene glycol behenate ester, polyethylene glycol dibehenate ester, polypropylene glycol acetyl ester, polypropylene glycol diacetyl ester, polypropylene glycol benzoate ester, polypropylene glycol dibenzoate ester, Ripropylene glycol laurate, polypropylene glycol dilaurate, polypropylene glycol nonyl ester, polyethylene glycol glycerol ether, polypropylene glycol glycerol ether, polyethylene glycol sorbitol ether, polypropylene glycol sorbitol ether, polyethylene glycolated ethylenediamine, polypropylene glycolated ethylenediamine, Examples thereof include polyethylene glycolized diethylenetriamine, polypropylene glycolated diethylenetriamine, and polyethylene glycolated pentamethylenehexamine.

  The addition amount of the polyethylene glycol compound is 0.1 to 50% by mass in terms of solid content with respect to the total solid content of the image recording layer from the viewpoint of exhibiting sufficient solubility inhibiting effect and maintaining good image formability. It is suitable that it is 1-30 mass%.

Further, when the above-described measures for improving the inhibition (solubility inhibition) are performed, the sensitivity is lowered. In this case, it is effective to add a lactone compound. It is considered that the lactone compound reacts with the developer and the lactone compound when the developer penetrates into the exposed area, and a new carboxylic acid compound is generated, contributing to dissolution of the exposed area and improving sensitivity.
Although it does not specifically limit as a lactone compound, The compound represented by the following general formula (LI) and general formula (L-II) is mentioned.

In the general formula (LI) and general formula (L-II), X ¹ , X ² , X ³ and X ⁴ are ring constituent atoms or atomic groups, which may be the same or different, and are independent of each other. And may have a substituent, and at least one of X ¹ , X ² and X ³ in formula (LI) and X ¹ , X ² , X ³ and X in formula (L-II) ^At least one of ⁴ has an electron-withdrawing substituent or a substituent substituted with an electron-withdrawing group.
The constituent atoms or atomic groups of the ring represented by X ¹ , X ² , X ³ and X ⁴ are nonmetallic atoms having two single bonds for forming a ring or atomic groups containing the nonmetallic atoms.
A preferred nonmetallic atom or nonmetallic atomic group is an atom or atomic group selected from a methylene group, a sulfinyl group, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfur atom, an oxygen atom, and a selenium atom, and more preferably, It is an atomic group selected from a methylene group, a carbonyl group and a sulfonyl group.

At least one of X ¹ , X ² and X ^{3 in} the general formula (LI) or at least one of X ¹ , X ² , X ³ and X ^{4 in} the general formula (L-II) is an electron withdrawing group Have In this specification, the electron-withdrawing substituent refers to a group in which Hammett's substituent constant σp takes a positive value. For Hammett's substituent constants, see Journal of Medicinal Chemistry, 1973, Vol. 16, no. 11, 1207-1216 etc. can be referred to. Examples of electron-withdrawing groups in which Hammett's substituent constant σp takes a positive valence include halogen atoms (fluorine atoms (σp value: 0.06), chlorine atoms (σp value: 0.23), bromine atoms (σp value). : 0.23), iodine atom (σp value: 0.18)), trihaloalkyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp) Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0. 72)), aliphatic / aryl or heterocyclic acyl groups (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl groups (for example, C≡CH (σp value: 0)) .23)), Aliphatic Ali Or a heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value: 0.57), sulfoxide groups, heterocyclic groups, oxo groups, phosphoryl groups and the like.

Preferred electron withdrawing groups are amide groups, azo groups, nitro groups, fluoroalkyl groups having 1 to 5 carbon atoms, nitrile groups, alkoxycarbonyl groups having 1 to 5 carbon atoms, acyl groups having 1 to 5 carbon atoms, and carbon numbers. An alkylsulfonyl group having 1 to 9 carbon atoms, an arylsulfonyl group having 6 to 9 carbon atoms, an alkylsulfinyl group having 1 to 9 carbon atoms, an arylsulfinyl group having 6 to 9 carbon atoms, an arylcarbonyl group having 6 to 9 carbon atoms, and thiocarbonyl A group selected from a group, a fluorine-containing alkyl group having 1 to 9 carbon atoms, a fluorine-containing aryl group having 6 to 9 carbon atoms, a fluorine-containing allyl group having 3 to 9 carbon atoms, an oxo group, and a halogen element.
More preferably, a nitro group, a fluoroalkyl group having 1 to 5 carbon atoms, a nitrile group, an alkoxycarbonyl group having 1 to 5 carbon atoms, an acyl group having 1 to 5 carbon atoms, an arylsulfonyl group having 6 to 9 carbon atoms, carbon It is a group selected from an arylcarbonyl group of formulas 6 to 9, an oxo group and a halogen element.
Specific examples of the compounds represented by formula (LI) and formula (L-II) are shown below, but the present invention is not limited to these compounds.

The addition amount of the compounds represented by the general formula (LI) and the general formula (L-II) is preferably 0.1 to 50% by mass in terms of the solid content with respect to the total solid content of the image recording layer. 1-30 mass% is more preferable. In addition, since this compound reacts with a developing solution, it is desirable to contact a developing solution selectively.
These lactone compounds may be used alone or in combination. Two or more compounds of the general formula (LI) or two or more compounds of the general formula (L-II) may be used in combination at an arbitrary ratio within the above range.

  In addition, a substance that is thermally decomposable, such as an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, and an aromatic sulfonic acid ester compound, and that substantially reduces the solubility of the alkaline water-soluble polymer compound without being decomposed. Use in combination is preferable in terms of improving the dissolution inhibition of the image area in the developer. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts.

Preferred examples of the onium salt used in the present invention include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974, TS Balet al, Polymer, 21, 423 (1980), JP-A-5-158230, diazonium salts, U.S. Pat. Nos. 4,069,055 and 4,069. , 056, JP-A-3-140140, the ammonium salt described in DC Necker et al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, JV Crivello et al, Macromolecules, 10 (6) , 1307 (1977), Chem. & Eng News, Nov. 28, p31 (1988), European Patent No. 104,143, US Patent Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-296514. Iodonium salts, JV Crivello et al, Polymer J. 17, 73 (1985), JV Crivello et al. J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivello et al, Polymer Bull., 14, 279 (1985), JV Crivello et al, Macromolecules, 14 ( 5), 1141 (1981), V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 233,567, 297,443, 297,442 U.S. Pat.Nos. 4,933,377, 3,902,114, 410,201, 339,049, 4,760,013, 4,734,444, 2 , 833, 827, German Patent Nos. 2,904, 626, 3,604, 580, 3,604, 581, JV Crivello et al, Macromolecules, 10 ( 6), 1307 (1977), JV Crivello et al, J. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), C.I. S. Wen et al, Teh, Proc. nf. Rad. Curing ASIA, p478 Tokyo, Oct (1988).
Of the onium salts, diazonium salts are particularly preferred. Particularly suitable diazonium salts include those described in JP-A-5-158230.
The counter ion of the onium salt includes tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfone And acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and paratoluenesulfonic acid. Of these, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferred.

  Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide assists the solubility of the sensitive material system by both the effect of losing the inhibition of dissolution of the binder due to thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described in pages 339 to 352 of “Light-sensitive systems” by John Coley (John Wiley & Sons. Inc.) can be used, and in particular, o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. The sulfonic acid esters or sulfonic acid amides are preferred. Further, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403 Esters of benzoquinone- (1,2-diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5 described in US Pat. Nos. 3,046,120 and 3,188,210. Esters of sulfonic acid chloride and phenol-formaldehyde resin are also preferably used.

  Further, esters of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride with phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Ester is also preferably used as well. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481, US Pat. Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, 3,674,495, 3,785,825, British Patents 1,227,602, 1,251,345, 1,267 No. 1,005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890, and the like.

The addition amount of the o-quinonediazide compound is preferably in the range of 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass with respect to the total solid content in the image recording layer. These compounds can be used alone, but may be used as a mixture of several kinds.
Moreover, you may include the alkali-soluble resin by which at least one part of Unexamined-Japanese-Patent No. 11-288089 was esterified.

  Further, for the purpose of enhancing the dissolution inhibiting property on the surface of the image recording layer and enhancing the resistance to scratches on the surface, it is possible to improve the resistance against scratches on the surface as described in JP-A No. 2000-187318. It is preferable to use a polymer having a polymerization component of a (meth) acrylate monomer having 2 or 3 fluoroalkyl groups. The addition amount is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content in the image recording layer.

-Development accelerator-
For the purpose of further improving sensitivity, acid anhydrides, phenols, and organic acids can be used in combination.
As the acid anhydrides, cyclic acid anhydrides are preferable. Specific examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride described in US Pat. No. 4,115,128. Acid, 3,6-endooxy-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of the acyclic acid anhydride include acetic anhydride.

  The phenols include bisphenol A, 2,2′-bishydroxysulfone, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4- Examples include hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane. .

Furthermore, examples of organic acids include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphate esters, and carboxylic acids described in JP-A-60-88942 and JP-A-2-96755. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, Examples include adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like. .
The proportion of the acid anhydride, phenols and organic acids in the image recording layer is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, particularly preferably 0.1 to 10%. % By mass.

-Surfactant-
In the image recording layer, as described in Japanese Patent Application Laid-Open Nos. 62-251740 and 3-208514, in order to improve the coating property and to expand the stability of the processing with respect to the development conditions. Nonionic surfactants, amphoteric surfactants as described in JP-A-59-121044, JP-A-4-13149, siloxane-based compounds as described in EP950517, JP A fluorine-containing monomer copolymer as described in JP-A-62-170950, JP-A-11-288093, and Japanese Patent Application No. 2001-247351 can be added.

  Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of amphoteric activators include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Co., Ltd.).

The siloxane compound is preferably a block copolymer of dimethylsiloxane and polyalkylene oxide. Specific examples include DBE-224, DBE-621, DBE-712, DBP-732, DBP-534, manufactured by Chisso Corporation. And polyalkylene oxide-modified silicones such as Tego Glide 100 manufactured by Tego, Germany.
The proportion of the nonionic surfactant and amphoteric surfactant in the total solid content in the image forming layer is preferably 0.01 to 15% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0. 0.05 to 0.5 mass%.

-Bakeout agent / colorant-
In the image recording layer, a print-out agent for obtaining a visible image immediately after heating by exposure, or a dye or pigment as an image colorant can be added.
Typical examples of the printing-out agent include a combination of a compound that releases an acid by heating by exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, 36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440, and trihalomethyl compounds and salt-forming organic dyes Can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear printout images.

As the image colorant, other dyes can be used in addition to the aforementioned salt-forming organic dyes. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet Lactone, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015), etc. Can do. The dyes described in JP-A-62-293247 are particularly preferred.
These dyes can be added in a proportion of 0.01 to 10% by mass, preferably 0.1 to 3% by mass, based on the total solid content in the image recording layer.

-Plasticizer-
Furthermore, a plasticizer is added to the image recording layer as needed to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.

-Wax agent-
In the image recording layer of the lithographic printing plate precursor, for the purpose of imparting scratch resistance, a compound that lowers the static friction coefficient of the surface can be added. Specifically, esters of long chain alkyl carboxylic acids as used in US Pat. No. 6,117,913, Japanese Patent Application No. 2001-261627, Japanese Patent Application No. 2002-032904, Japanese Patent Application No. 2002-165854 And the like. The amount added is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass in the total solid content forming the layer.

A lithographic printing plate precursor can usually be produced by dissolving a heat-sensitive composition containing the above-described components in a solvent and coating the solution on a suitable support.
[Coating solvent]
Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, water, etc. However, the present invention is not limited to this. These solvents are used alone or in combination.

When selecting the coating solvent, the coating solvent for the upper recording layer is used for the upper recording layer and the lower recording layer in order to prevent compatibility at the interface between the layers when they are provided adjacent to each other. Is preferably selected so as not to substantially dissolve the lower recording layer. The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.
When using an acid anhydride, the water in the coating solution is preferably 0.5% or less.

[Amount of application]
Further, the coating amount (solid content) of the heat-sensitive composition varies depending on the application, but it can be provided at a coating amount of 0.3 to 3.0 g / m ² from the viewpoint of film properties and printing durability. Preferably it is 0.5-2.5 g / m < ² >, More preferably, it is 0.8-1.6 g / m < ² >.

[Multilayer structure]
The lithographic printing plate precursor used in the present invention has an image recording layer containing the above-described components provided on a support, but these image recording layers may have a multilayer structure of at least two layers. Good (for the sake of convenience, the case of two layers consisting of an upper layer and a lower layer will be described below).
In this case, the alkali-soluble resin that constitutes the upper layer and the lower layer can be the alkali-soluble resin described above, but the upper layer has a lower solubility in alkali than the lower layer. Is preferred.

  The infrared absorbing dye may be an infrared absorbing dye different in each layer, or an infrared absorbing dye composed of a plurality of compounds may be used in each layer. The amount to be contained is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, and particularly preferably 0.1% to 50% by mass, based on the total solid content of the layer to be added, as described above, when used in any layer. It can add in the ratio of 0.1-30 mass%. When adding to a several layer, it is preferable to add so that the total of addition amount may become the said range.

In the state of being thermally decomposable and not thermally decomposable, the substance that substantially lowers the solubility of the alkali-soluble resin may be partially decomposed over time, so when the image recording layer has a multilayer structure, Although it is effective to contain it in the lower layer, it may be any layer or both layers. The amount to be contained is as described above. When adding to a several layer, it is preferable to add so that the total of addition amount may become the said range.
In the case of a multilayer structure, the lactone compound is effective to be contained in the upper layer, but it may be any layer or both layers.

[Support]
Examples of the hydrophilic support used in the lithographic printing plate precursor include a dimensionally stable plate having necessary strength and durability, such as paper, plastic (for example, polyethylene, polypropylene, polystyrene). Etc.) laminated paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate) , Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper laminated with a metal as described above, or vapor-deposited paper, or a plastic film.

  As the support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass.

  A particularly suitable aluminum is pure aluminum, but completely pure aluminum is difficult to manufacture in terms of refining technology, and may contain slightly foreign elements. Thus, the composition of the aluminum plate is not specified, and conventionally, an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

  Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing rolling oil on the surface is performed as desired. The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

  The roughened aluminum plate is subjected to an alkali etching treatment and neutralization treatment as necessary, and then subjected to an anodization treatment to enhance the water retention and wear resistance of the surface as desired. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used and cannot be specified. However, in general, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1 to 100 V, electrolysis time 10 seconds to 5 minutes are suitable. The amount of the anodized film is preferably 1.0 g / m ² or more in terms of printing durability. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. Examples of the hydrophilic treatment include alkali metal silicates as disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. (For example, sodium silicate aqueous solution) method. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, it is disclosed in potassium fluoride zirconate disclosed in Japanese Patent Publication No. 36-22063 and US Pat. Nos. 3,276,868, 4,153,461, and 4,689,272. A method of treating with polyvinylphosphonic acid is used.

The lithographic printing plate precursor used in the present invention has at least the above-described image recording layer provided on a support, and an undercoat layer may be provided between the support and the image recording layer as necessary. it can.
As an undercoat layer component, various organic compounds are used. For example, phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, and phenylphosphone which may have a substituent. Acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, organic phosphonic acid such as methylenediphosphonic acid and ethylenediphosphonic acid, optionally substituted phenylphosphoric acid, naphthylphosphonic acid, alkylphosphoric acid and glycerophosphoric acid Of organic phosphoric acid such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and triethanolamine which may have a substituent Hydroxy groups such as hydrochloride Selected from hydrochloride of the amine to be, but may be used by mixing two or more.

  Furthermore, an undercoat layer containing at least one compound selected from the group of organic polymer compounds having a structural unit represented by the following formula is also preferred.

R ¹¹ represents a hydrogen atom, a halogen atom or an alkyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, —OR ^14. , -COOR ¹⁵ , -CONHR ¹⁶ , -COR ¹⁷ or -CN, or R ¹² and R ¹³ may be bonded to form a ring, and R ^{14 to} R ¹⁷ are each independently an alkyl group or Represents an aryl group, X represents a hydrogen atom, a metal atom, or NR ¹⁸ R ¹⁹ R ²⁰ R ²¹ , and R ^{18 to} R ²¹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl. Represents a group, or R ¹⁸ and R ¹⁹ may combine to form a ring, and m represents an integer of 1 to 3.

  This undercoat layer can be provided by the following method. That is, a method in which water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof is dissolved and applied on an aluminum plate and dried, and water, methanol, ethanol, methyl ethyl ketone, etc. In this method, an aluminum plate is immersed in a solution in which the above organic compound is dissolved in the above organic solvent or a mixed solvent thereof to adsorb the above compound, and then washed and dried with water or the like to provide an undercoat layer. In the former method, a solution having a concentration of 0.005 to 10% by mass of the organic compound can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass, the immersion temperature is 20 to 90 ° C., preferably 25 to 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this can be adjusted to a pH range of 1 to 12 with basic substances such as ammonia, triethylamine, potassium hydroxide, and acidic substances such as hydrochloric acid and phosphoric acid.

The coverage of the undercoat layer, from the viewpoint of printing durability, 2 to 200 mg / m ² are suitable, and preferably from 5 to 100 mg / m ^2.

The lithographic printing plate precursor prepared as described above is imagewise exposed, and then subjected to development using the alkali developing solution detailed above.
Examples of the active light source used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser or a semiconductor laser is particularly preferable.

  If the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming has an unnecessary image area, the unnecessary image area is erased. . Such erasing is preferably performed by applying an erasing solution as described in, for example, Japanese Patent Publication No. 2-13293 to an unnecessary image portion, leaving it for a predetermined time, and then washing with water. As described in JP-A-59-174842, a method of developing after irradiating an unnecessary image portion with an actinic ray guided by an optical fiber can also be used.

The lithographic printing plate obtained by the development method of the present invention as described above can be subjected to a printing step after applying a desensitized gum if desired, but a lithographic printing plate having higher printing durability. If it is desired to do so, a burning process is performed. In the case of burning a lithographic printing plate, before burning, the preparations described in JP-B-61-2518, JP-A-55-28062, JP-A-1-31859, and JP-A-61-159655 are prepared. It is preferable to treat with a surface liquid.
As the method, a method of applying the lithographic printing plate with a sponge or absorbent cotton soaked with the surface-adjusting liquid, or immersing the printing plate in a vat filled with the surface-adjusting liquid, or applying an automatic coater Application by, for example, is applied. Further, it is more preferable to make the coating amount uniform with a squeegee or a squeegee roller after coating.

In general, the amount of surface-adjusting solution applied is suitably 0.03 to 0.8 g / m ² (dry weight). The lithographic printing plate coated with the surface-adjusting solution is dried if necessary, and then heated to a high temperature with a burning processor (for example, burning processor “BP-1300” sold by Fuji Photo Film Co., Ltd.). . In this case, the heating temperature and time are in the range of 180 to 300 ° C. and preferably in the range of 1 to 20 minutes, although depending on the type of components forming the image.
The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming as needed, but a surface-conditioning solution containing a water-soluble polymer compound is used. In such a case, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such processing is applied to an offset printing machine and used for printing a large number of sheets.

Hereinafter, the present invention will be described with reference to illustrated embodiments.
FIG. 1 is a block diagram of a first embodiment of an automatic developing apparatus 1 (referred to as an automatic developing apparatus for carrying out an automatic developing method for a photosensitive lithographic printing plate according to the present invention). As shown in FIG. 1, the automatic developing apparatus 1 includes a development processing unit (hereinafter referred to as “developing unit”) 6 for developing a photosensitive lithographic printing plate (hereinafter referred to as “PS plate”) 4. The post-processing unit 8 for washing away the developer adhering to the developed PS plate 4 and applying the gum solution, the drying unit 10 for drying the PS plate 4 after applying the gum solution, and the control device 50 constituting the control means. And.

  In the case of processing the PS plate 4 that needs to be heated before the development processing, a preheating unit can be provided, although not shown in FIG. The preheating unit is installed on the upstream side of the developing unit 6 in the transport direction of the PS plate 4 and has a function of maintaining the specified PS plate surface temperature for a specified time while transporting the PS plate 4. The PS plate 4 inserted in the preheating unit is automatically conveyed to the next process while being heated. Furthermore, although not shown in FIG. 1, it is also possible to provide a pre-water washing part. The pre-washing unit is installed upstream of the developing unit 6 in the transport direction of the PS plate 4 and downstream of the pre-heating unit in the transport direction of the PS plate 4, and the PS plate surface is washed with water while transporting the PS plate 4 Has the function of washing and cooling with water. The PS plate 4 inserted into the pre-water washing section is automatically conveyed to the developing section 6 which is the next process.

  An insertion port 14 is formed in the side plate 12 of the automatic developing device 2, and the PS plate 4 inserted from the insertion port 14 is conveyed to the developing unit 6 by the conveyance roller 16. The insertion port 14 is provided with a rubber blade 18. When the PS plate 4 is not inserted, the insertion port 14 is closed by the rubber blade 18.

  In the developing tank 20 of the developing unit 6, a conveying roller 22, a brush roller 24, and a squeeze roller 26 are sequentially provided from the upstream side in the conveying direction of the PS plate 4, and a backup roller 28 is provided at an appropriate position therebetween. It has been. The PS plate 4 is developed by being immersed in the developer while being conveyed by the conveying roller 22.

  The post-processing unit 8 connected to the developing unit 6 includes a water washing unit 8a and a finisher unit 8b. Among these, the water washing section 8a is provided with rollers 30a 'and 30a for conveying the PS plate 4, a water washing tank 32a, and an injection member 34a for spraying the water washing liquid in the water washing tank 32a onto the PS plate 4. Yes. A flush water supply pump 78a for supplying flush water is provided in the flush tank 32a. On the other hand, the finisher section 8b is provided with a roller 30b for conveying the PS plate 4, a finisher tank 32b, and an injection member 34b for spraying the finisher liquid in the finisher tank 32b to the PS plate 4, respectively. A gum solution supply pump 77 that supplies the gum solution to the tank 32 b and a gum solution dilution pump 78 b that supplies the gum solution dilution liquid from the replenishment diluent storage tank 53 are provided. Then, the PS plate 4 after the development processing is washed with water by spraying a washing solution by the discharge member 34a while being conveyed by the conveyance roller 30a. Further, the PS plate 4 is applied by spraying the finisher liquid by the discharge member 34b while being conveyed by the conveyance roller 30b.

  At this time, the washing liquid 32 is replenished to the washing tank 32a by the washing water supply pump 78a. Next, the finisher tank 32b is replenished with the gum solution in the gum solution tank 56 by the pump 77, and the replenisher 57 in the replenishment diluent storage tank 53 is replenished by the replenishment diluent supply pump 78b. Here, the replenishment ratio of the gum solution and the diluent is, for example, 1: 1. Along with the replenishment, the washing liquid overflowed from the washing tank 32a and the gum waste liquid overflowed from the finisher tank 32b are collected in the waste liquid tank 54 in the same manner as the development waste liquid.

  Moreover, although not shown in FIG. 1, it is also effective to provide the washing part 8a with a washing brush roller. The washing brush roller is installed on the upper surface or upper and lower surfaces of the PS plate 4 between the spray member 34a and the PS plate 4, and rubs and rinses the surface of the PS plate 4 being conveyed while rotating.

  On the other hand, a structure in which the water washing portion 8a is the first finisher portion 8a and the finisher portion 8b is the second finisher portion 8b is also effective. The first finisher portion 8a and the second finisher portion 8b are provided with transport rollers 30a and 30b for transporting the PS plate 4, and injection members 34a and 34b for spraying the gum solution in the finisher tanks 32a and 32b to the PS plate 4. The PS plate 4 after the development processing is applied by spraying the gum solution by the spray members 34a and 34b while being transported by the transport rollers 30a and 30b. At this time, the gum solution in the finisher tank 32b of the second finisher portion 8b on the downstream side in the transport direction of the PS plate 4 is in the finisher tank 32a of the first finisher portion 8a on the upstream side in the transport direction of the PS plate 4. However, instead of such a configuration, it may be supplied in the same manner by a pump or the like. In this case, the flush water supply pump 78a is not used.

  At this time, the gum liquid in the gum liquid tank 56 is replenished to the second finisher tank 32 b by the pump 77, and the dilution liquid 57 in the replenishment dilution liquid storage tank 53 is replenished by the replenishment dilution liquid supply pump 78. . Here, the replenishment ratio of the gum solution and the diluent is, for example, 1: 1. With this replenishment, the gum waste liquid overflowed from the first finisher tank 32a is collected in the waste liquid tank 54 in the same manner as the development waste liquid.

  The drying unit 10 connected to the finisher unit 8 is provided with a guide roller 36 and a pair of skewer rollers 38 in order from the upstream side in the transport direction of the PS plate 4. The drying unit 10 is provided with drying means (not shown) such as hot air supply means and heat generation means. Further, the drying unit 10 is provided with a discharge port 40, and the PS plate 4 dried by the drying means is discharged from the discharge port 40. A shutter 44 is provided in the passage between the drying unit 10 and the finisher unit 8, and the passage 46 is closed by the shutter 44 when the PS plate 4 does not pass through the passage 46.

  The developing tank 20 is provided with a box-shaped shielding lid 60 integrally with the tank wall. The bottom wall of the shielding lid 60 is continuously curved in an arc shape so as not to come into contact with the upper outer peripheral surfaces of the transport roller 22, the brush roller 24, and the backup roller 28, and does not interfere with the roller or the like. . Since the shielding lid 60 is box-shaped, an airtight space is defined in the upper part of the developing tank 20, and the amount of air in the developing unit 6 is reduced as much as possible. Further, since the shielding lid 60 is provided, the contact area between the developer and air is reduced as much as possible.

  In the automatic developing apparatus 1 having the above-described configuration, the rubber blade 62 is provided at an appropriate place, and the developing unit 6 to the finisher unit 8b are substantially airtight with respect to the external atmosphere, so that the outside air does not flow in. ing. Further, a space between the developing unit 6 and the water washing unit 8a is substantially airtight by the rubber blade 62 so that air in the water washing unit 8a does not flow into the developing unit 6. Accordingly, the developing unit 6 has a hermetically sealed structure in which air flows in slightly when the PS plate 4 passes, but is substantially airtight and hardly receives air.

  Next, the developing unit 6 will be described in detail. A developing solution circulation pipe 80 is connected to the developing tank 20. In the circulation pipe 80, a developer circulation pump 71, a conductivity sensor 73 (conductivity measuring means), and a filter (not shown) are provided. The developer circulation pump 71 sucks the developer in the developer tank 20 from the suction hole at the bottom of the developer tank 20 into the circulation pipe 80 and circulates in the circulation pipe 80, and again into the developer tank 20. Discharge. The filter filters the developer flowing in the circulation pipe 80. The conductivity sensor 73 which is a conductivity measuring means measures the conductivity of the developer flowing in the circulation pipe 80.

  Further, the developing unit 6 includes a replenishment pipe 90, 91 that constitutes a replenishment device for replenishing the development replenisher, the development replenishment dilution liquid, and the evaporation correction water, and the replenishment connected to the replenishment pipe 90. A stock solution storage tank 55, a replenishment stock solution supply pump 74 interposed in the replenishment pipe 90, and a replenishment diluent storage tank connected to the replenishment pipe 91 (development replenishment dilution liquid replenishment means and evaporation correction water replenishment means are configured. 53) and a replenishment diluent supply pump (which constitutes a development replenishment diluent replenishing unit and an evaporation correction water replenishment unit) 76 interposed in the replenishment pipe 91 are provided. It functions as a development replenishment dilution liquid replenishment means and an evaporation correction water replenishment means. Further, the developing waste liquid overflowed from the developing tank 20 is collected in the waste liquid tank 54.

  More specifically, a pair of development replenisher replenishment pipes 90 and 91 obtained by diluting the development replenishment stock solution 58 with the replenishment diluent 57 is provided in the vicinity of the developing tank 20. The other end (the lower end in FIG. 1) of the replenishment piping 90 for the development replenishing stock solution 58 is connected to the replenishing stock solution storage tank 55, and a replenishing stock solution supply pump 74 is provided in the piping. The replenishment stock solution supply pump 74 supplies the development replenishment stock solution 58 from the replenishment stock solution storage tank 55 to the developing tank 20. The other end (lower end in FIG. 1) of the replenishment piping 91 for the development replenishment diluent (which is also the evaporation correction water) 57 is connected to the replenishment diluent storage tank 53. 76 is provided. The replenishment dilution liquid supply pump 76 supplies the development replenishment dilution liquid (and evaporation correction water) 57 from the replenishment dilution liquid storage tank 53 to the developing tank 20. That is, the replenishment pipe 91, the replenishment diluent supply pump 76, and the replenishment diluent storage tank 53 constitute a dilution water replenishment device.

  The replenishment stock solution supply pump 74 and the replenishment dilution solution supply pump 76 are provided with a control ROM 51a or control RAM 51b, which is a condition storage means, and a time measurement unit 52 based on signals from the conductivity sensor 73 and the time measurement unit 52. It is controlled by a device (control means) 50. Further, the control device 50 drives the transport roller 22, the brush roller 24, the squeeze roller 26, and the like at appropriate timing based on the signal from the plate detection sensor 27, and transports the PS plate 4.

  Further, the control device 50 measures the time elapsed since the last replenishment of the evaporation correction water as the “elapsed time”, and corrects the measured value of the measured developer conductivity based on the elapsed time. To do.

Next, control by the control device 50 will be described.
2 to 8 are examples of flowcharts showing a control method by the control device 50.
First, a basic control process for replenishing the development replenisher will be described with reference to FIG.
In step 1 (hereinafter abbreviated as S1), if it is not the first start-up after a new replacement of the developer, the stop time of the automatic developing device 1, that is, the time from the previous stop to the current start-up has elapsed. An amount corresponding to the time, that is, a replenishment amount with time, is replenished.

  In S2, if a predetermined time has elapsed, the development replenisher is replenished with a replenishment amount with time calculated from the replenishment amount with time and the time. Next, in S3, if the PS plate 4 has been subjected to development processing of a predetermined fixed area, an amount calculated from the processing replenishment amount set value and the processing area, that is, a replenishment amount of processing replenishment solution is replenished. To do. Next, in S4, it is determined whether the time elapsed since the start or the previous developer conductivity measurement has reached a predetermined time, and if it has reached, the process proceeds to S5, and if not, the process proceeds to S10.

In S5, by measuring the electric conductivity of the developer obtains the electric conductivity of the developer measured value d _M. Next, in S6, the last, to measure the elapsed time T _W from supplemented evaporation correction water. In S7, the developer conductivity correction value is calculated in order to correct the developer conductivity measurement value d _M when the elapsed time Tw has elapsed. For the developer conductivity correction measurement value d _MR , for example, in FIG.

However, in FIG.
d _MR : Developer conductivity correction measurement value (mS / cm)
d _M : Measured value of developer conductivity (mS / cm)
V _T : Amount of developer in developer tank 20 (ml)
V _E : Evaporated water volume per unit time (ml / h) determined in advance by experiment
T _W : Time elapsed since the last replenishment of evaporation correction water (h)
Calculate from Thus, the developer conductivity measurement value d _M is corrected so that the pulsation of the conductivity value due to evaporation does not occur as shown in the graph of the developer solution conductivity correction measurement value d _MR indicated by the solid line in FIG. Is done.

In the next S8, it compares the electric conductivity of developer correction measured value d _MR and electric conductivity reference value dh calculated in S7, the S9 larger the electric conductivity of developer correction measured value d _MR, electric conductivity of developer correction measurements d If _MR is small, proceed to S10. Here, “electric conductivity reference value”: d _H is a value obtained by experimentally obtaining and setting in advance a developer conductivity value at which the developer activity is appropriate. In S9, a predetermined amount of diluent (water) is replenished to the developer in the developing tank 20. Here, “development replenishment diluent” refers to a dilution solution (water) of the development replenisher.
In S10, the state of the operation switch of the automatic developing device 1 is confirmed. If the operation switch is turned on, the process returns to S2. To do.

Next, the first control process specifically showing the basic control process will be described with reference to FIGS.
If S21 is the first start-up after a new replacement of the developing solution, the replenishment integrated value over time: I _H , the processing replenishment integrated value: I _V , the replenisher replacement rate: X, which are variables used during control. Is initialized, that is, 0 is substituted. Here, the replenisher replacement ratio: X is the ratio of the developer replenisher (and / or developer replenisher diluted solution) replenished to the developer to the developer in the developing tank 20.

Next, in S22, if it is not the first start-up time when the developer is newly replaced, the development replenisher of the amount of replenishment with time: V _F corresponding to the stop time: T _F of the automatic developing apparatus 1 is replenished. variable V _F is a time lapse replenishment integrated value described above: integrating the I _H. The calculation at this time is as follows:
V _F = V _CF · T _F (2)
I _H + V _F → I _H (3)
However, V _CF ; when the automatic developing device is stopped experimentally
Amount of replenishment over time per unit time,
It is desirable to do as follows.

Next, in S23, the replenisher replacement rate: X is updated using the replenishment amount with time: V _F and the arithmetic expression. The arithmetic expression used at this time is as follows:
(V _T · X + V _F ) / (V _T + V _F ) → X (4)
Where V _T ; developer volume in the developing tank 20,
Is desirable.

In S24, it is determined whether the time from the start-up or the time when the development replenisher of S22 was replenished last time has reached a predetermined time: Tk. If it has elapsed, the process has passed S25. If not, the process proceeds to S27. In S25, a predetermined time at the time of the automatic developing apparatus 1 runs: T _K required by time lapse replenishment amount: the developer replenisher V _C replenished in the developer in the developing tank 20, further, aging of the V _C S22 variable is replenished accumulated value: integrating the I _H. For example,
V _C = V _CN · T _K (5)
I _H + V _C → I _H (6)
However, V _CN ; when the automatic developing device is operated experimentally
It is calculated like the replenishment amount with time per unit time.

In S26, the replenisher replacement rate: X is updated using the replenishment amount with time: V _C and the arithmetic expression. The arithmetic expression used at this time is as follows:
(V _T · X + V _C ) / (V _T + V _C ) → X (7)
Is desirable.

In S27, it is determined whether the development processing area of the PS plate 4 at the start-up or after replenishment of the processing replenishment solution at the previous time has reached a predetermined processing area: S. If not, the process proceeds to S30. Here, the “treatment replenishment amount” is a replenishment amount of the development replenisher obtained in advance through experiments, which is replenished according to the plate area when the PS plate 4 is developed. In S28, the processing replenishment amount required for processing area: S is replenished with the developer replenisher of V _{B to} the developer in the developing tank 20, and further, V _B is set to a variable: I _H which is a replenishment integrated value over time. Accumulate. For example,
V _B = V _BN · S (8)
I _H + V _B → I _H (9)
However, V _BN is calculated as a processing replenishment amount for each unit area obtained experimentally in advance.

In S29, the processing replenishment amount of S28: using V _B and arithmetic expression, replenisher replacement ratio: Update X. The arithmetic expression used at this time is as follows:
(V _T · X + V _B ) / (V _T + V _B ) → X (10)
The following formula is desirable.

Next, in S30, it is determined whether the time from the start-up or the previous time when the developer conductivity was measured has reached a predetermined time: T _D , and if it has elapsed, it must have elapsed in S31. If so, the process proceeds to S41.

In S31, the developer conductivity is measured to obtain a measured value of developer conductivity. Its value, in S33 after, the electric conductivity of developer correction measurements: d _MR for calculating (1) is substituted for the electric conductivity of developer measured value d _M of the formula. In the next S32, the elapsed time from the previous replenishment of evaporated correction Water: to measure T _W.

Next, in S33, the electric conductivity of developer measurement of S31: d _M and the time elapsed S32: using _{T W,} the electric conductivity of developer correction measured value from the equation (1): calculates a d _MR.

In the next S34, the developer conductivity value at which the developer activity obtained experimentally in advance is appropriate (this corresponds to the “conductivity reference value”): d _H , replenisher replacement rate: X, replenishment with time A conductivity target value: d _T is calculated using a variable: I _H which is an integrated value, a variable: I _w which is a replenishment integrated value of development replenishment diluent (water), and an arithmetic expression. Here, the electric conductivity target value: d _T is the electric conductivity of the developer that can always exhibit an appropriate developer activity. An arithmetic expression for calculating the electrical conductivity target value d _T is as follows:
y = I _H / (I _H + I _W ) −I _W / (I _H + I _W ) · C _r (11)
_{d T = d H + (1} -X) · d M + X · {(1-y) · D W + y · D l}
(12)
Where C _r , D _W , D _l ; constants obtained experimentally in advance,
Is desirable.

Next, at S35, the corrected electric conductivity of developer correction measured value in S33: and d _MR, S34 of electric conductivity target value: Compare d _T. to S36 if d _MR is larger, the process proceeds to S41 The smaller the d _MR. In S36, a predetermined amount: V _W dilution liquid (water) which is the “development replenishment dilution liquid” of the present invention is replenished to the development liquid in the developing tank 20, and in next S37, the development replenishment dilution liquid (water) ): V _W is added to a variable: I _W which is a cumulative value of replenishment over time. At this time, the following equation:
I _W + V _W → I _W (13)
It is desirable to use
Further, in the next S38, the replenisher replacement rate: X is updated using the development replenishment diluent (water): V _W and the arithmetic expression. At this time, the following equation:
(V _T · X + V _W ) / (V _T + V _W ) → X (14)
Where V _T ; developer volume in the developing tank 20,
It is desirable to use

In the next S39, the evaporation correction water previous course from replenishment time: and T _W, the reference value is a predetermined value: comparing T _WS, to S40 if Uwamaware better elapsed time T _W, so If not, the process proceeds to S41. In S40, in order to keep the developing solution concentration in the developing tank 20 substantially constant, an amount V _W of water based on the amount of water evaporated from the developing solution per unit time measured in advance is replenished.

  In S41, the state of the operation switch of the automatic developing device 1 is confirmed. If the operation switch is turned on, the process returns to S24, and if the operation switch is turned off, the processing is ended by stopping the automatic developing device 1. .

As described above, even when the processing conditions such as the plate type, the plate size, and the processing frequency are changed, appropriate replenishment can always be performed, and development processing can be performed with stable and constant sensitivity. Then, using the replenisher replacement rate (X), which is the ratio of the developer replenisher replenished to the developer in the developer tank 20, the conductivity target value (d _T ) is replenished each time the developer replenisher is replenished. By successively calculating, the developing unit 6 of the automatic developing device 1 can be configured in a simple and inexpensive manner, while minimizing fluctuations in developer sensitivity with respect to changes in development processing conditions with a developer containing an electrolyte. it can.

Next, the second control process will be described with reference to FIGS.
In S51, at the first start-up time when the developer is newly replaced, the replenishment integrated value: I _H , processing replenishment integrated value: I _V , replenisher replacement rate: X, replenishment with time, which are variables used during control. Ratio: F is initialized, that is, I _H = 0, I _V = 0, X = 0, and F = C _F are substituted (C _F is a constant obtained experimentally in advance). Here, the replenishment ratio with time: F is the operation time (and / or stop time) of the automatic developing device 1 with respect to the total development replenisher (and / or the total development replenishment dilution liquid) replenished to the developer in the developing tank 20. ) Based on the development replenisher (and / or development replenishment diluent).

Next, in S52, if the first startup after the new interchanged developer, downtime automatic developing apparatus 1: minute time lapse replenishment amount corresponding to T _F: supplemented with developer replenisher V _F , variable this V _F is a time lapse replenishment integrated value described above: integrating the I _H. The calculation of V _F and I _H is the same as the expressions (2) and (3) in the first control process, that is,
V _F = V _CF · T _F (15)
I _H + V _F → I _H (16)
However, V _CF ; when the automatic developing device is stopped experimentally
It is desirable to carry out the replenishment amount over time per unit time.

Next, in S53, the replenisher replacement rate: X and the replenishment ratio with time: F are updated using the replenishment amount with time: V _F and the arithmetic expression. The arithmetic expression used at this time is as follows:
(V _T · X + V _F ) / (V _T + V _F ) → X (17)
(V _T · X · F + V _F ) / (V _T · X + V _F ) → F (18)
However, V _T ; the developer volume in the developing tank 20 is desirable.

In S54, the time elapsed during startup or time lapse replenishment amount of the developer replenisher of S52 from the time of last supplemented, preset predetermined time: determining whether reached T _K, in S55 if passed, passed If not, the process proceeds to S57. In S55, a predetermined time at the time of the automatic developing apparatus 1 runs: T _K required by time lapse replenishment amount: the developer replenisher V _C replenished in the developer in the developing tank 20, further, aging of the V _C S52 Replenishment integrated value: _IH is integrated. For example, V _C and I _H are calculated as follows, similarly to the expressions (5) and (6) in the first control process.
V _C = V _CN · T _K (19)
I _H + V _C → I _H (20)
However, Vcn: when the automatic developing apparatus is operated experimentally obtained in advance
Amount of replenishment over time per unit time

In S56, the replenisher replacement rate: X and the replenishment ratio with time: F are updated using the replenishment amount with time: V _C in S55 and the arithmetic expression. The arithmetic expression used at this time is preferably the following expression.
(V _T · X + V _C ) / (V _T + V _C ) → X (21)
(V _T · X · F + V _C ) / (V _T · X + V _C ) → F (22)

In S57, it is determined whether the development processing area of the PS plate 4 at the start-up or after replenishing the development replenisher of the processing replenishment amount has reached a predetermined processing area: S. If not, the process proceeds to S60. In S58, the processing replenishment amount required for processing area: S is replenished with the developer replenisher of V _{B to} the developer in the developing tank 20, and the V _B is further integrated with the time-dependent replenishment integrated value: I _H. To do. This integration is, for example,
V _B = V _BN · S (23)
I _H + V _B → I _H (24)
However, V _BN is calculated as a processing replenishment amount for each unit area obtained experimentally in advance.

In S59, the processing replenishment amount of S58: using V _B and arithmetic expression, replenisher replacement ratio: and X, time lapse replenishment ratio: Update F. The arithmetic expression used at this time is
(V _T · X + V _B ) / (V _T + V _B ) → X (25)
(V _T · X · F) / (V _T · X + V _B ) → F (26)
The following formula is desirable.

Next, in S60, it is determined whether the time from the start-up or the time when the developer conductivity was measured last time has reached a predetermined time: T _D. If so, the process proceeds to S71.
In S61, the developer conductivity is measured to obtain a measured value of developer conductivity. Its value, in S63 after, the electric conductivity of developer correction measurements: d _MR for calculating (1) is substituted for the electric conductivity of developer measured value d _M of the formula. In the next S62, the elapsed time from the previous replenishment of evaporated correction Water: to measure T _W.

Next, in S63, the electric conductivity of developer measurement of S61: d _M and the time elapsed S62: using T _W, the electric conductivity of developer correction measured value from the equation (1): calculates a d _MR.

In S64, the developer conductivity value (conductivity reference value) at which the developer activity determined experimentally in advance is appropriate: d _H , replenisher replacement rate: X, replenishment ratio with time: F, accumulated replenishment value with time A conductivity target value: d _T is calculated using a certain variable: I _H , a variable: I _W which is an integrated replenishment value of development replenishment diluent (water): I _W and an arithmetic expression. Arithmetic expression for calculating the electric conductivity target value d _T is desirably the following equation.
y = I _H / (I _H + I _W ) −I _W / (I _H + I _W ) · C _r (27)
d _T = d _H + (1-X) · d _M + X · [(1-y) · D _W
+ Y · {(1−F) · D _B + F · D _C }]
... (28)
Where C _r , D _W , D _B , D _C ;

Next, in S65, the developing solution and the electric conductivity correction measured value d _MR corrected in S63, S64 of the electric conductivity target value: Compare d _T. to S66 if d _MR is larger, the process proceeds to S71 The smaller the d _MR. In S66, a predetermined amount: V _W dilution liquid (water) which is the “development replenishment dilution liquid” of the present invention is replenished to the development liquid in the developing tank 20, and in next S67, the development replenishment dilution liquid (water) ): V _W is added to a variable: I _W which is a cumulative value of replenishment over time. At this time, the following equation:
I _W + V _W → I _W (29)
It is desirable to use
Further, in the next S68, the replenisher replacement rate: X is updated using the development replenishment diluent (water): V _W and the arithmetic expression. At this time, the following equation:
(V _T · X + V _W ) / (V _T + V _W ) → X (30)
Where V _T ; developer volume in the developing tank 20,
It is desirable to use

In the next S69, the elapsed time from the previous replenishment of the evaporation correction water: T _M is compared with a predetermined value, that is, the reference time: T _WS , and if the elapsed time T _M exceeds, the process proceeds to S70. If not, the process proceeds to S71. In S70, in order to keep the developer concentration in the developing tank 20 substantially constant, an amount of water: V _W based on the amount of water evaporated from the developer per unit time measured in advance is replenished.

  In S69, the state of the operation switch of the automatic developing device 1 is confirmed. If the operation switch is turned on, the process returns to S70, and if the operation switch is turned off, the processing is ended by stopping the automatic developing device 1. .

As described above, even when the processing conditions such as the plate type, the plate size, and the processing frequency are changed, appropriate replenishment can always be performed, and development processing can be performed with stable and constant sensitivity. A time-dependent replenishment ratio: F, which is a ratio of the development replenisher replenished based on the operation time and / or stoppage time of the automatic developing device with respect to the total replenisher replenishment amount replenished to the developer in the developing tank. Using the replenisher replacement rate (X), the electric conductivity target value (d _T ) is sequentially calculated every time the automatic replenisher 1 is replenished with either the development replenisher or the diluting liquid, thereby developing processing. It is possible to cope with fluctuations in the appropriate conductivity value due to changes in conditions (the ratio between the replenishment amount and the replenishment amount with time) and environmental conditions (humidity), and automatic development processing with high sensitivity stability can be realized.

Next, the third control process will be described with reference to FIGS.
In S81, if it is the first start-up after a new replacement of the developer, the replenisher replacement rate: X, the temporal replenishment ratio: F, and the developer dilution rate: Z, which are variables used during the control, are initialized. That is, X = 0, F = C _F , and Z = C _Z are substituted (C _F and C _Z are constants obtained experimentally in advance). Here, the developer dilution rate: Z is the ratio of the developer replenisher diluted to the developer in the developer tank 20 to the developer replenisher replenished to the developer in the developer tank 20.

Next, in S82, if it is not the first start-up after a new replacement of the developing solution, the developing replenisher with a replenishment amount with time: V _F corresponding to the stop time: T _F of the automatic developing device 1 is developed into the developing tank. The developer in 20 is replenished. The calculation at this time is as follows:
V _F = V _CF · T _F (31)
However, V _CF ; when the automatic developing device is stopped experimentally
It is desirable to carry out the replenishment amount over time per unit time.

Next, in S83, the replenisher replacement rate: X, the replenishment ratio over time: F, and the developer using a time-dependent replenishment amount: V _F corresponding to the stop time: T _F of the automatic developing device 1 and the arithmetic expression. Dilution rate: Z is updated. The arithmetic expression used at this time is as follows:
(V _T · X + V _F ) / (V _T + V _F ) → X (32)
(V _T · X · F + V _F ) / (V _T · X + V _F ) → F (33)
{V _T · X · Z / (Z + 1) + V _F · C _ZH / (C _ZH +1)}
/ {V _T · X / (Z + 1) + V _F / (C _ZH +1)} → Z (34)
Where V _T ; developer volume in the developing tank 20,
C _ZH ; A predetermined constant is desirable.

In S84, startup or time lapse replenishment amount of S82: V _F time the developer correction solution has elapsed from the time of the last replenishment is preset predetermined time: determining whether reached T _K, if the elapsed S85 If not, the process proceeds to S87. In S85, a predetermined time at the time of the automatic developing apparatus 1 run: time lapse replenishment amount required by T _K: a developing correction fluid of V _C replenishing the developer in the developing tank 20. This replenishment amount with time: V _C is, for example,
V _C = V _CN · T _K (35)
However, V _CN ; when the automatic developing device 1 is experimentally determined in advance
Amount of replenishment over time per unit time,
Calculate as follows.

In S86, the replenisher replacement ratio: X, the replenishment ratio over time: F, and the developer dilution ratio: Z are updated using the replenishment amount over time: V _C required for the predetermined time: T _K in S84. . The arithmetic expression used at this time is as follows:
(V _T · X + V _C ) / (V _T + V _C ) → X (36)
(V _T · X · F + V _C ) / (V _T · X + V _C ) → F (37)
{V _T · X · Z / (Z + 1) + V _C · C _ZH / (C _ZH +1)}
/ {V _T · X / (Z + 1) + V _C / (C _ZH +1)} → Z
... (38)
Is desirable.

In S87, it is determined whether the development processing area of the PS plate 4 at the time of start-up or the replenishment of the processing replenishment solution after the previous replenishment has reached a predetermined processing area: S. If not, the process proceeds to S90. In S 88, the developer replenisher of processing replenishment amount: V _B required for the processing area: S is replenished to the developer in the developing tank 20. This V _B is, for example,
V _B = V _BN · S (39)
Where V _BN ; treatment replenishment amount per unit area determined experimentally in advance
Calculate as follows.

In S89, the processing replenishment amount of S88: using V _B and arithmetic expression, replenisher replacement ratio: and X, time lapse replenishment ratio: F, developer dilution: Update Z. The arithmetic expression used at this time is as follows:
(V _T · X + V _B ) / (V _T + V _B ) → X (40)
(V _T · X · F) / (V _T · X + V _B ) → F (41)
{V _T · X · Z / (Z + 1) + V _B · C _ZH / (C _ZH +1)}
/ {V _T · X / (Z + 1) + V _B / (C _ZH +1)} → Z
... (42)
Is desirable.

Next, in S90, the time of startup or the electric conductivity of developer from the time of previous measurement, predetermined prescribed time: determining whether reached T _D, in S91 if passed, it has not elapsed If so, the process proceeds to S100.
In S91, the developer conductivity is measured to obtain a measured value of developer conductivity. That value is substituted into the measured value d _M of the developer conductivity in equation (1) for calculating the developer conductivity corrected measured value: d _MR in S93 later. In the next S92, the elapsed time from the previous replenishment of evaporated correction Water: to measure T _W.

Next, in S93, the electric conductivity of developer measurement of S91: d _M and the time elapsed S92: using T _W, the electric conductivity of developer correction measured value from the equation (1): calculates a d _MR.

In S94, developer conductivity value (conductivity reference value) at which the developer activity obtained experimentally in advance is appropriate: d _H , replenisher replacement rate: X, replenishment ratio with time: F, developer dilution rate: Using Z and an arithmetic expression, the electric conductivity target value: d _T is calculated. An arithmetic expression for calculating the electrical conductivity target value d _T is as follows:
y = (1-C _ZR ) · {(C _ZW +1) / (Z + 1) / (C _ZW −C _ZR )
−1 / (C _ZW −C _ZR )}
... (43)
d _T = d _H + (1−X) · d _M + X · {(1−y) · D _W
+ Y (1-F) · D _B + F × D _C )}
... (44)
Where C _ZR , C _ZW ; predetermined constants,
D _W , D _B , D _C ; constants obtained experimentally in advance
Is desirable.

In S95, the developer and the conductivity correction measured value d _MR corrected in S93, S94 of the electric conductivity target value: Compare d _T. to S96 if d _MR is larger, the process proceeds to S100 the smaller the d _MR. In S96, a predetermined amount: V _W dilution liquid (water) which is the “development replenishment dilution liquid” of the present invention is replenished to the development liquid in the developing tank 20, and in next S97, the development replenishment dilution liquid (water) ): The replenisher replacement ratio: X and the developer dilution ratio: Z are updated using V _W and the arithmetic expression. At this time, the following equation:
(V _T · X + V _W ) / (V _T + V _W ) → X (45)
{V _T · X · Z / (Z + 1) + V _W } / {V _T · X / (Z + 1)} → Z
... (46)
Where V _T ; developer volume in the developing tank 20,
It is desirable to use

In the next S98, the elapsed time from the previous replenishment of the evaporation correction water: T _M is compared with a predetermined value, ie, the reference time: T _WS , and if the elapsed time T _M exceeds, the process proceeds to S99. Proceed to S100. In S99, in order to keep the developer concentration in the developing tank 20 substantially constant, an amount of water: V _W based on the amount of water evaporated from the developer per unit time measured in advance is replenished.

  In S100, the state of the operation switch of the automatic developer is confirmed. If the operation switch is turned on, the process returns to S84, and if the operation switch is turned off, the process is terminated by stopping the apparatus.

  According to the control of the automatic developing device 1 described above, by appropriately switching and setting the conductivity target value, it is always appropriate even if the processing conditions such as the plate type, the plate size, and the processing frequency change in each case. Replenishment can be performed, and development processing can be performed with stable and constant sensitivity. Since the ratio between the replenishment amount with time and the replenishment amount with processing is automatically corrected, the appropriate developer solution is always applied to changes in processing conditions, i.e., changes in the size and processing frequency of the photosensitive material. It is possible to set a conductivity target value and to perform development processing with a stable and constant sensitivity. Therefore, it is possible to minimize the variation in the developer sensitivity with respect to the change in the development processing conditions while making the developing unit 6 of the automatic developing device 1 simple and inexpensive.

  Further, the developer dilution rate, which is the ratio of the diluent replenished to the developer in the developer tank 20 with respect to the developer replenisher stock solution replenished to the developer in the developer tank 20, the replenishment ratio with time, and the replenisher replacement rate Are used to calculate the conductivity target value each time the developer replenisher or diluent is replenished, thereby developing processing conditions (ratio of processing replenishment amount and replenishment amount over time) and environmental conditions (humidity). ), It is possible to deal with fluctuations in the appropriate conductivity value, high sensitivity stability, and automatic development processing that does not generate debris.

(Second embodiment)
Next, a second embodiment of the present invention will be described.
FIG. 9 is a block diagram of an automatic developing device 2 according to the second embodiment of the present invention. As shown in FIG. 9, in the automatic developing device 2 of the present embodiment, the internal processing unit is covered with an outer panel 114. Inside the outer panel 114, a developing tank 118 for developing the PS plate 112, a developing unit 122 having an overflow pipe 120 for collecting the developer overflowed from the developing tank 118, and the PS plate 112 were attached. A water washing part 124 for washing the developer with water and a finisher part 126 for applying a gum solution to the PS plate 112 after washing with water and desensitizing it are disposed. The flushing section 124 is provided with a flushing tank 128, and the finisher section 126 is provided with a gum solution tank 130.

  The side plate of the outer panel 114 is provided with a slit-like insertion port 202 and a discharge port 204, respectively. A reentry insertion port (sub-insertion port) 250 for inserting the PS plate 112 is provided between the developing unit 122 and the water washing unit 124 on the upper surface of the outer panel 114. The sub-insertion opening 250 serves as an insertion opening for the PS plate 112 for performing processing excluding development processing.

  A blade 252 is disposed in the sub insertion port 250. The blade 252 is in contact with the outer panel 114 whose tip is used as a guide support surface of the sub insertion port 250, and the base is fixed to the back side of the outer panel 114 via a bracket 254. For this reason, the sub insertion port 250 is closed by the blade 252.

  The drying unit (not shown) is configured to blow hot air on both sides of the PS plate 112 while drying the PS plate 112 fed from the finisher unit 126 by a plurality of rollers (not shown). .

  A pair of conveying rollers 132 is disposed on the side of the developing unit 122 where the PS plate 112 is inserted into the developing tank 118, and the PS plate 112 is inserted between the pair of conveying rollers 132 from the insertion port 202. It is like that.

  A rubber blade 206 is attached in the vicinity of the downstream side of the conveying roller 132. The tip of the blade 206 is in contact with the side wall of the developing tank 118 of the developing unit 122, and the base is attached to the outer panel 114 via a bracket 256. The bracket 256 includes a fixed portion 256A and a slide portion 256B attached to the fixed portion with a thumbscrew 258, and the blade 206 is fixed to the slide portion 256B. For this reason, the blade 206 is configured such that the tip end portion can be separated from the side wall of the developing tank 118 by loosening the thumbscrew 258 and sliding the slide portion 256B relative to the fixed portion 256A.

  In addition, a plate detection sensor 208 capable of measuring the presence / absence of the PS plate 112 and the plate area of the transported plate is attached in the vicinity of the insertion slot 102.

  The developing tank 118 has a substantially inverted mountain shape with the upper part opened and the bottom center part protruding downward. A pump 260 is provided in the developing tank 118, and the developer in the developing tank 118 is sucked out by the pump 260 and ejected from spray pipes 144 and 272 described later. Thereby, the developer stored in the developing tank 118 is circulated. During this circulation, the developer passes through an electrical conductivity sensor 262 that is an electrical conductivity measuring means for measuring the electrical conductivity of the developer. The developing tank 118 is supplied with a replenishing stock solution from a development replenishing stock solution tank 266 via a replenishing stock solution supply pump 264. As will be described later, the developing tank 118 is supplied with dilution water from a washing tank 128 via a pump 286.

  The pump 264 and the pump 286 are controlled by a control device 50 including a control ROM 51a or a control RAM 51b, which is a condition storage unit, and a time measurement unit 52 based on signals from the conductivity sensor 262 and the time measurement unit 52. In addition, since the effect of the control apparatus 50 is the same as that of 1st Embodiment, the description is abbreviate | omitted.

  In the developing tank 118, a guide plate 268 is disposed on the upstream side, and a number of guide rollers 134 and a rotating brush roller 270 are disposed on the downstream side. The guide roller 134 and the rotating brush roller 270 are rotatably spanned between a pair of side plates of the developing tank 118.

  A guide roller 136 having a relatively large diameter is disposed above the guide plate 268, and rotating brush rollers 138 and 270 and a guide roller 140 are disposed above the guide roller 134. In addition, a pair of squeezing rollers 142 having a function of squeezing the surface of the PS plate 112 are disposed in the center of the developing tank 118.

  The overflow pipe 120 is disposed on the most downstream side in the PS plate 112 conveyance direction of the developing tank 118. When the liquid level of the developing solution in the developing tank 118 exceeds a predetermined level, the developing solution is guided to the waste liquid tank 284. And are going to be discarded.

  A liquid level lid 150 is disposed on the surface of the developer in the developing tank 118. The liquid level cover 150 has a portion corresponding to the rotating brush roller 138 and the guide roller 140 adjacent to the rotary brush roller 138 protruding in a substantially arc shape, and on the level of the developer to minimize the contact between the developer surface and air. The both ends of the liquid surface lid 150 in the transport direction of the PS plate 112 are attached to a side plate (not shown) so as to slide up and down in accordance with the increase and decrease of the developer.

  The tip of the blade 274 is in contact with the downstream end of the liquid level lid 150 in the PS plate 112 conveyance direction. The blade 274 is fixed to the outer panel 114 via a bracket 276. The blade 274 partitions the liquid level of the developer exposed from the downstream end of the PS plate 112 in the conveying direction of the liquid level cover 150 and the upper side of the liquid level cover 150, and the blade 206 (development) in the vicinity of the insertion port 202 is partitioned. The state above the side wall of the tank 118 is completely isolated from the outside air above the liquid level cover 150, and evaporation of the developer can be suppressed.

  A roller pair 154 that sandwiches and conveys the PS plate 112 and squeezes the developer from the surface of the PS plate 112 is disposed on the most downstream side of the developing tank 118 in the conveying direction of the PS plate 112.

  On the other hand, in the automatic developing device 2, a rinsing tank 128 of the rinsing unit 124 is disposed downstream of the developing unit 122 in the conveying direction of the PS plate 112. Two pairs of transport rollers 152 and 153 are disposed above the water washing tank 128.

  The rinsing tank 128 stores rinsing water after the developer is washed out from the PS plate 112 sent out from the developing tank 118. A spray pipe 156 is disposed on the upstream side of the transport direction of the PS plate 112 with respect to the transport roller 153 and on the upper side of the transport path, and a plurality of discharge ports communicating with the inside are provided on the outer periphery of the spray pipe 156. ing. From the spray pipe 156, the washing water pumped up from the washing water tank 278 by the pump 280 is dropped onto the upper roller of the conveying roller 153, and the conveying roller 153 rotates, so that the washing water quickly flows onto the surface of the PS plate 112. And the surface of the PS plate 112 is washed with water.

  The lower part of the lower roller of the transport rollers 152 and 153 is accommodated in the tray 162. Washing water is stored in the tray 162 and is pumped up by the lower roller to clean the back surface of the PS plate 112 and to prevent the upper transport rollers 152 and 153 from drying.

  Further, the washing water diffused in the width direction on the surface of the PS plate 112 falls from the both ends in the width direction of the PS plate 112 to the receiving tray 162 below, and the back surface of the PS plate 112 is washed away by the washing water pumped up from the receiving plate 162. It is configured to be processed. The flush water overflowing from the tray 162 is guided to the flush tank 128. The flush tank 128 is provided with an overflow pipe 282, which is discarded into a waste liquid tank 284 when a predetermined liquid level is exceeded.

  The washing tank 128 and the developing tank 118 are communicated with each other via a pump 286, and the washing water in the washing tank 128 is guided to the developing tank 118 by driving the pump 286, and the replenishing stock solution is supplied to the developing tank 118. Can be used as means for replenishing the developer as evaporation-corrected water at regular intervals, using a diluting solution when supplying water and an amount of water calculated in advance from experiments.

  A pair of transport rollers 178 are provided above the gum solution tank 130 of the finisher portion 126. The PS plate 112 sent out by the transport roller 153 is guided to the transport roller 178.

  Further, spray pipes 182 and 288 are arranged in the up and down direction of the transport path on the upstream side of the transport roller 178 in the transport direction of the PS plate 112. From the spray pipes 182 and 288, the gum solution pumped up from the gum solution tank 290 by the pump 292 is discharged and supplied to the front and back surfaces of the PS plate 112.

  The conveyance roller 178 nips and conveys the PS plate 112 and squeezes the gum solution supplied by the spray pipe 182 to desensitize the surface of the PS plate 112. The gum solution squeezed from the surface of the PS plate 112 is collected in the gum solution tank 130. The gum solution in the gum solution tank 130 is circulated by a pump 294. The gum solution tank 130 is provided with an overflow pipe 296 so that when the gum solution exceeds a predetermined liquid level, it is guided to the waste solution tank 284 and discarded.

  Further, the lower part of the lower conveyance roller 178 is immersed in the gum liquid stored in the gum liquid tank 130, and the lower conveyance roller 178 is connected to the gum liquid tank 130 from the gum liquid tank 130 on the back side of the PS plate 112. The coating process is performed by pumping up. As a result, the conveying roller 178 takes out the gum solution to perform the desensitization process on the back surface of the PS plate 112 and suppresses the drying of the upper conveying roller 178 so that the components of the processing liquid do not deposit on the surface of the conveying roller 178. It has become.

  The PS plate 112 that has been processed by the finisher unit 126 passes through the discharge port 204 of the casing 2A and is sent out to a drying unit (not shown).

  Here, the discharge port 204 is provided with a lid 210 as a partition plate. The lid 210 is fixed to the shaft 212. The shaft 212 can be rotated by driving means (not shown) (for example, a solenoid). The rotation of the shaft 212 is performed based on the detection of the PS plate 112 by the plate detection sensor 208 provided in the vicinity of the insertion port 202. In other words, the lid 210 is substantially horizontal (after the detection of the discharge port 204) while the plate detection sensor 208 is detecting the PS plate 112 and after it is no longer detected (after the rear end is detected) until a predetermined time elapses. It is held in an open state, and the others are vertical (the discharge port 204 is closed).

The operation of this embodiment will be described below.
First, processing tanks such as the developing tank 118, the washing tank 128, and the gum solution tank 130 are covered with a casing 200 such as an upper lid 114 and a main body 108. Further, when the PS plate 112 is not developed by the automatic developing device 2, the insertion port 202 is closed because the blade 206 is in contact with the side wall of the developing tank 118. On the other hand, since the discharge plate 204 does not detect the PS plate 112 by the plate detection sensor 208, the lid 210 is in a vertical state, and the discharge port 204 is also closed. Further, the sub insertion port 250 is also closed by the blade 252, and the liquid level cover 150 of the developing unit 122 is also closed by the blades 206 and 122. For this reason, the developing solution in the developing tank 118, the washing water in the washing unit 124, and the gum solution in the finisher unit 126 are not exposed to the outside air, and there is almost no carbon dioxide fatigue. For this reason, it is possible to suppress a decrease in developing ability due to deterioration over time, and for example, it is possible to drastically reduce the replenishing amount of the replenishing stock solution and the amount of evaporation correction water to be replenished to the developing solution in the developing unit 122. In particular, since the surface of the developer in the developing tank 118 is covered with the liquid level lid 150, the effect of preventing contact between the developer and the outside air is great.

  In order to minimize the contact between the developing solution and the outside air and the evaporation amount of water from the developing solution, it is preferable to shorten the opening time of the lid 210 as much as possible. Therefore, a structure in which the PS plate 112 is open only while it passes and is closed during the other time is preferable.

  The control by the control device 50 is the same as the contents of the flowchart of the replenishing method of the developing replenisher in FIGS. 2 to 8 described in the first embodiment, and the description thereof is omitted here.

  Next, in the case where the development replenisher replenishment method and the conventional developer replenisher replenishment method in the above embodiment were applied, the variation range of the developer sensitivity was obtained by experiments. Production of developer A, B, C, D, replenisher A, B, C, D, photosensitive material A, B, C, D, E used in Examples 1-10 and Comparative Examples 1-20 below Describes the method.

[Developer A]
A developer DP-7 manufactured by Fuji Photo Film Co., Ltd. was diluted 1/9 and used.
[Developer B]
A developer DT-2 manufactured by Fuji Photo Film Co., Ltd. was diluted 1/9 and used.
[Developer C]
The following components were dissolved in water, and a developer was prepared with KOH so as to have the following pH.
Surfactant (see chemical formula 13) ・ ・ ・ 5% by mass
2,4,7,9-Tetramethyl-5-decyne-4,7-diol ... 0.1% by mass
Ethylenediaminetetraacetic acid 4Na salt: 0.2% by mass
Potassium carbonate: 0.2% by mass
pH [25 ° C] 12.0

[Developer D]
The following components were dissolved in water, and a developer was prepared with KOH so as to have the following pH.
Compound (Y) of general formula (I): 5.0 g
Ethylenediaminetetraacetic acid 4Na salt ... 0.1g
Additive 1 (P) ... 1.0 g
Additive 2 (Q) ... 1.0 g
pH [25 ° C] ... 12.0

Y:

P:

Q:

[Replenisher A]
A developer replenisher DP-7RW manufactured by Fuji Photo Film Co., Ltd. was used.
[Replenisher B]
A developer replenisher DT-2R manufactured by Fuji Photo Film Co., Ltd. was used.
[Replenisher C]
The following components were dissolved in water, and a developer was prepared with KOH so as to have the following pH.
Surfactant (see chemical formula 17) 5% by mass
2,4,7,9-Tetramethyl-5-decyne-4,7-diol ... 0.1% by mass
Ethylenediaminetetraacetic acid 4Na salt 0.2 mass%
Potassium carbonate: 0.2% by mass
pH [25 ° C] ... 13.0

Ｐ：

Ｑ：

[Replenisher D]
The following components were dissolved in water, and a developer was prepared with KOH so as to have the following pH.
Compound (Y) of general formula (I): 5.0 g
Ethylenediaminetetraacetic acid 4Na salt ... 0.1g
Additive 1 (P) ... 1.0 g
Additive 2 (Q) ... 1.0 g
pH [25 ° C] 13.0
Y:

P:

Q:

[Photosensitive material A]
It created based on Example 1 of Unexamined-Japanese-Patent No. 2000-231188 specification. The resulting photosensitive plate was subjected to image exposure for 1 minute with a printer FT26V2UPNS (light source: 2 kW metal halide lamp) manufactured by Nuark, USA.
[Photosensitive material B]
It created based on Example 1 of Unexamined-Japanese-Patent No. 7-295212. The obtained photosensitive plate was subjected to 50 count image exposure with a printer FT26V2UPNS (light source: 22 kW metal halide lamp) manufactured by Nuark, USA.
[Photosensitive material C]
A 0.3 mm thick aluminum plate (material 1050) was washed with trichlorethylene and degreased, and then a nylon brush and 400 mesh pumice-water suspension were used to make the surface grainy and washed thoroughly with water. After washing, the aluminum plate was etched by immersing it in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, then immersed in a 20% nitric acid aqueous solution for 20 seconds, and washed again with water. The etching amount of the grained surface at this time was about 3 g / m ² . Next, the aluminum plate was provided with a 3 g / m ² anodic oxide coating with a direct current of 15 A / dm ² using 7% sulfuric acid as an electrolyte, and then washed with water and dried. This was treated with a 2.5% aqueous solution of sodium silicate at 30 ° C. for 10 seconds, the following undercoat layer coating solution was applied, and dried at 80 ° C. for 15 seconds to obtain a support. The dry coating amount of the undercoat layer after drying was 15 mg / m ² .

<Coating liquid for undercoat layer>
The following copolymer P (molecular weight 28000): 0.3 g
Methanol ... 100g
1g of water
Copolymer P

<Synthesis of specific copolymer>
Synthesis example (specific copolymer 1)
A 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel is charged with 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile and cooled in an ice-water bath. The mixture was stirred while. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped with a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes. To this reaction mixture, 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, this mixture was added to 1 liter of water with stirring, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to take out a precipitate, which was slurried with 500 ml of water, and then the slurry was filtered, and the resulting solid was dried to give white N- (p-aminosulfonylphenyl) methacrylamide. A solid was obtained (yield 46.9 g).
Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide (0.0192 mol) and 2.94 g of ethyl methacrylate (0.0258) were added to a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. Mol), 0.80 g (0.015 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. To this mixture, 0.15 g of “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. To this reaction mixture was further added a mixture of 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile, N, N-dimethylacetamide and 0.15 g of “V-65”. It dropped by the dropping funnel over 2 hours. After completion of the dropwise addition, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol is added to the mixture, the mixture is cooled, and the resulting mixture is poured into 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate is removed by filtration and dried. Gave 15 g of a white solid. It was 53,000 when the weight average molecular weight (polystyrene standard) of this specific copolymer was measured by the gel permeation chromatography.

The following image recording layer coating solution was applied onto the obtained support so that the dry coating amount was 1.8 g / m ² to obtain a positive-type infrared-sensitive lithographic printing plate.
<Coating liquid for image recording layer>
The above specific copolymer ... 0.4g
m, p-cresol novolak ・ ・ ・ 0.6g
(M / p ratio = 6/4, weight average molecular weight 8000, containing 0.5% of unreacted cresol)
Cyanine dye A ... 0.1g
Phthalic anhydride ... 0.05g
p-Toluenesulfonic acid 0.002g
Ethyl violet ... 0.02g
(Counterion: 6-hydroxy-β-naphthalenesulfonic acid)
Esterified product of naphthoquinone 1,2-diazide-5-sulfonylcroid and pyrogallol-acetone resin: 0.01 g
Fluorosurfactant ... 0.05g
(Product name: Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)
Methyl ethyl ketone 8g
1-methoxy-2-propanol 4g

[Photosensitive material D]
(Production of support)
<Aluminum plate>
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.001 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: It contains 0.03% by mass, and the balance is prepared by using an aluminum alloy of Al and inevitable impurities. After the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Produced. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, it was kept soaked at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum plate of JIS1050 material. After making this aluminum plate width 1030mm, it used for the surface treatment shown below.

<Surface treatment>
The surface treatment was performed by continuously performing the following various treatments (a) to (j). In addition, after each process and water washing, the liquid was drained with the nip roller.

(A) Mechanical surface roughening treatment While supplying a suspension of a polishing agent (pumice) having a specific gravity of 1.12 and water as a polishing slurry liquid to the surface of the aluminum plate, mechanical rotation is performed by a rotating nylon roller brush. Surface treatment was performed. The average particle size of the abrasive was 30 μm, and the maximum particle size was 100 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 45 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 2.6% by mass, an aluminum ion concentration of 6.5% by mass and a temperature of 70 ° C. / M ^{2 was} dissolved. Then, water washing by spraying was performed.

(C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a process of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 10.5 g / L aqueous solution of nitric acid (containing 5 g / L of aluminum ions and 0.007% by mass of ammonium ions) at a liquid temperature of 50 ° C. The AC power supply waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero and a duty ratio of 1: 1. Went. Ferrite was used for the auxiliary anode.
The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(E) Alkali etching treatment An aluminum plate was subjected to an etching treatment by spraying at 32 ° C. using an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% to dissolve the aluminum plate by 0.50 g / m ^2. The smut component mainly composed of aluminum hydroxide generated when the electrochemical surface roughening process is performed using the alternating current of the previous stage is removed, and the edge portion of the generated pit is melted to smooth the edge portion. I made it. Then, water washing by spraying was performed.

(F) Desmut treatment Desmut treatment was performed by spraying with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 4.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a process of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 5.0 g / L aqueous solution (containing 5 g / L of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform is subjected to electrochemical surface roughening using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero and a duty ratio of 1: 1. went. Ferrite was used for the auxiliary anode.
The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Then, water washing by spraying was performed.

(H) Alkali etching treatment An aluminum plate was sprayed using an aqueous solution having a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C., and the aluminum plate was dissolved at 0.10 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(I) Desmutting treatment A desmutting treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying.

(J) Anodizing treatment Anodizing treatment was performed using an anodizing apparatus to obtain a lithographic printing plate support. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis units. All electrolytes had a sulfuric acid concentration of 170 g / L (containing 0.5 mass% of aluminum ions) and a temperature of 38 ° C. Then, water washing by spraying was performed. The final oxide film amount was 2.7 g / m ² .
The Ra of the support obtained by the above treatment was 0.45.

〔undercoat〕
Next, the following undercoat liquid was applied to this aluminum support with a wire bar, and dried at 90 ° C. for 30 seconds using a hot air drying apparatus. The coating amount after drying was 10 mg / m ² .

<Undercoat liquid>
-Copolymer of ethyl acrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt in a molar ratio of 75:15 0.1 g
・ 2-aminoethylphosphonic acid 0.1g
・ Methanol 50g
・ Ion exchange water 50g

(Photosensitive layer)
Next, the following photosensitive layer coating solution [P-1] was prepared and applied to the above-mentioned undercoated aluminum plate using a wire bar. Drying was performed at 122 ° C. for 43.5 seconds using a hot air drying apparatus to form a photosensitive layer. The coating amount after drying was 1.4 g / m ² .

<Photosensitive layer coating solution [P-1]>
・ Infrared absorber (IR-1) 0.08g
-Polymerization initiator (OS-1) 0.25g
・ Dipentaerythritol hexaacrylate 1.00g
・ Binder polymer (BT-1) 1.00g
・ Ethyl violet chloride 0.04g
・ Fluorine surfactant 0.03g
(Megafuck F-780-F Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 10.4g
・ Methanol 4.83g
・ 10.4 g of 1-methoxy-2-propanol

  The structures of the infrared absorber (IR-1), the polymerization initiator (OS-1), and the binder polymer (BT-1) used in the photosensitive layer coating solution are shown below.

[Protective layer (overcoat layer)]
On the surface of the photosensitive layer, a mixed aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) and polyvinylpyrrolidone (BASF Corp., Rubiscor K-30) was applied using a wire bar, It was dried at 125 ° C. for 75 seconds with a drying apparatus. The content of PVA was 85% by mass, and the coating amount (coating amount after drying) was 2.45 g / m ² . The surface dynamic friction coefficient was 0.45.
A photosensitive lithographic printing plate 1 was obtained as described above.

[Photosensitive material E]
A 0.3 mm thick material 1S aluminum plate was thoroughly washed with water, etched by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, then neutralized and washed with 20% nitric acid, and washed with water. . This was subjected to an electrolytic surface roughening treatment in a 1.5% nitric acid aqueous solution with an electric quantity at the anode of 270 coulomb / dm ² using a sinusoidal alternating current under the condition of V _A = 12.7V. When the surface roughness was measured, it was 0.30 μm (Ra indication). Subsequently, after dipping in a 30% sulfuric acid aqueous solution and desmutting at 40 ° C. for 2 minutes, a cathode was placed on a grained surface in a 33 ° C., 20% sulfuric acid aqueous solution at a current density of 5 A / dm ² . When anodized for 50 seconds, the thickness was 2.7 g / m ² .
On the aluminum plate thus treated, an intermediate layer coating solution having the following composition was applied, a dry coating mass was applied to 2 mg / m ^2, and dried at 100 ° C. for 3 minutes.

<Coating liquid for intermediate layer>
A solution in which the following composition was mixed and stirred, exotherm was observed after about 5 minutes and reacted for 60 minutes, and then 20,000 g of methanol was added.

Methanol 100g
DDP-8 (phosphate compound: manufactured by Nikko Chemical) 15g
10g of water
Phosphoric acid 5g
Tetraethoxysilane 50g
3-Methacryloxypropyltriethoxysilane 50g

On this undercoat layer, a high-sensitivity photopolymerizable composition 1 having the following composition was applied so that the dry coating mass was 1.5 g / m ² and dried at 100 ° C. for 90 seconds to form a photosensitive layer.

<Photopolymerizable composition 1>
1.8g of ethylenically unsaturated bond-containing compound (A1)
Linear organic polymer binder (B1) 1.5g
Sensitizer (C1) 0.15 g
Photoinitiator (D1) 0.2g
β-phthalocyanine (F1) dispersion 0.2 g
Fluorine-based nonionic surfactant Megafac F177 (manufactured by DIC) 0.03g
Methyl ethyl ketone 10g
10g of propylene glycol monomethyl ether acetate

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) was applied on the photopolymerizable photosensitive layer thus formed so that the dry coating weight was 2.5 g / m ^2. And dried at 100 ° C. for 90 seconds to obtain a photosensitive material E.

[Processing of Examples 1 to 4]
As shown in Table 1, Table 2, Table 3, Table 4, Table 5, and Table 6, continuous processing was performed using the replenishing method of the present invention to evaluate developer sensitivity stability. The evaluation of the development sensitivity stability was performed according to how much the image density of an image having a gradation density of 50% exposed by halftoning the photosensitive material changes after the development processing. The results are shown in Table 7.

[Processing of Comparative Examples 1 to 4]
As shown in Table 1, Table 2, Table 3, Table 4, Table 5, and Table 6, continuous processing was performed using the control method described in JP-A-2005-275384, and developer sensitivity stability was evaluated. . The evaluation of the development sensitivity stability was performed according to how much the image density of an image having a gradation density of 50% exposed by halftoning the photosensitive material changes after the development processing. The results are shown in Table 7.

  As a result of the above evaluation, Examples using the method of the present invention were used for Comparative Examples 1 to 4 in which the change in 50% gradation density exceeded the allowable range of −1.0% to + 1.0%. In 1 to 4, it was confirmed that the 50% gradation density change was within the allowable range.

1 is a configuration diagram illustrating a first embodiment of an automatic developing apparatus that performs an automatic developing method according to the present invention. It is a flowchart explaining the basic control processing which replenishes a replenisher with the automatic developing method. It is a flowchart (the 1) explaining a 1st control process. It is a flowchart (the 2) explaining a 1st control process. It is a flowchart (the 1) explaining a 2nd control process. It is a flowchart (the 2) explaining a 2nd control process. It is a flowchart (the 1) explaining a 3rd control process. It is a flowchart (the 2) explaining a 3rd control process. It is a block diagram of 2nd Embodiment of the automatic developing apparatus which implements the automatic developing method of this invention. (A) is an explanatory view showing the principle of the developing method of the present invention, and (B) is an explanatory view for deriving an arithmetic expression used therefor. It is explanatory drawing which shows the shift | offset | difference of the electrical conductivity by the conventional image development method.

Explanation of symbols

1 Automatic development device 4 PS plate 6 Development section (development processing section)
20 Developing tank 50 Control device (control means)
51a Control ROM
51b Control RAM
52 Time measurement unit (elapsed time measurement means)
53 Replenishment dilution liquid storage tank (Development replenishment dilution liquid replenishment means, evaporation correction water replenishment means)
55 Replenishment stock solution storage tank 73 Conductivity sensor (conductivity measuring means)
74 Replenishment stock solution supply pump (Developer replenishment means)
76 replenishment diluent supply pump (development replenishment diluent replenishment means, evaporation correction water replenishment means)
90, 91 Supplementary piping

Claims (5)

The developer conductivity value at which the developer activity is appropriate is obtained in advance and set as a conductivity reference value. Based on the replenishment conditions set in advance, the developer activity value when the automatic developing device is activated and / or stopped is determined. In order to compensate for the decrease, the developer replenisher and / or the developer replenisher diluent that is a diluent of the developer replenisher is replenished, and the decrease in the developer activity due to the processing of the lithographic printing plate is performed based on preset replenishment conditions. In order to compensate, the developer replenisher and / or developer replenisher diluent is replenished, and the conductivity of the developer replenished with the developer replenisher is measured every predetermined time interval. When the measured value of the conductivity exceeds the conductivity reference value, an automatic developing method of replenishing the developer with the developer replenishment diluent until the developer conductivity measured value falls below the conductivity reference value,
In order to keep the developer concentration substantially constant, an amount of water based on the amount of water evaporated from the developer per unit time measured in advance is replenished as evaporation correction water,
Measure the elapsed time from the last replenishment of the evaporation correction water to the present time,
Correcting the measured value of the measured developer conductivity based on the elapsed time;
And an automatic developing method.   The developer replenisher or developer replenisher diluent is replenished using a replenisher replacement rate that is the ratio of the developer replenisher and / or developer replenisher diluent replenished to the developer in the developer tank. 2. The automatic development method according to claim 1, wherein the conductivity reference value is sequentially corrected each time.   The developer replenisher and / or developer replenisher diluted for the total developer replenisher and / or the total developer replenisher diluted to the developer in the developing tank is replenished based on the operation time and / or stop time of the automatic developing device. The conductivity reference value is sequentially corrected each time the development replenisher or the development replenishment dilution is replenished using the replenishment ratio with time and the replenisher replacement rate. Item 2. The automatic development method according to Item 1.   The developer dilution ratio, which is the ratio of the developer replenishment diluent replenished to the developer in the developer tank with respect to the developer replenisher replenished to the developer in the developer tank, the replenishment ratio with time, and the replenisher replacement The conductivity reference value is used every time the development replenisher or the development replenishment diluent is replenished in order to switch and set the conductivity target value, which is always the appropriate conductivity of the developer using the rate. The automatic development method according to claim 1, wherein the correction is sequentially performed. A developer conductivity value at which the developer activity is appropriate is experimentally obtained in advance and set as a conductivity reference value. Based on preset replenishment conditions, a decrease in developer activity during operation and / or stoppage In order to compensate for the above, a development replenisher and / or a development replenisher diluent that is a dilution of the developer replenisher is replenished in the developing tank, and the developer activity by developing the printing plate based on preset replenishment conditions The developer replenisher and / or developer replenisher diluent is replenished in order to compensate for a decrease in the degree, and the developer in the developer tank in which the developer replenisher is replenished at predetermined time intervals. An automatic developing device that replenishes the developer with a developer diluent until the measured conductivity value of the developer falls below the conductivity reference value after measuring the measured conductivity value,
A development processing unit for developing the printing plate with a developer in the developing tank;
A developer replenishing means for replenishing the developer in the developer tank with the developer replenisher;
Development replenishment diluent replenishing means for replenishing the developer replenishment diluent in the developer in the developer tank;
Evaporation correction water replenishing means for replenishing the developer in the developer tank with the evaporation correction water;
An elapsed time measuring means for measuring an elapsed time from the last replenishment of the evaporation correction water to the present time;
Conductivity measurement means for measuring the developer conductivity measurement value at predetermined time intervals;
Control means for correcting the value of the measured value of the developer conductivity based on the measurement time by the automatic development method according to any one of claims 1 to 4,
An automatic developing apparatus comprising:

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