JP2006250994A - Development processor, method for producing photosensitive planographic printing plate, and photosensitive planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a development processor capable of performing a stable developing process and free from operation errors in a removing process of a water-soluble oxygen blocking layer prior to a developing process of a photosensitive planographic printing plate having a water-soluble oxygen blocking layer as the uppermost layer, and to provide a platemaking method and a photosensitive planographic printing plate. <P>SOLUTION: The development processor for processing a photosensitive planographic printing plate having an image forming layer and an oxygen blocking layer on a supporting body processes the removed oxygen blocking layer dissolved in washing water by the following means (A) and (B). They are: (A) a means to monitor the quality of the washing water; and (B) a means to display degradation in the water quality. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a development processing apparatus in which development processing is stable, a method for making a photosensitive lithographic printing plate, and a photosensitive lithographic printing plate (hereinafter also referred to as PS plate).

  Many studies have been made on developing methods for printing plate materials having a water-soluble oxygen-blocking layer on the photosensitive layer. At present, the plate is washed with water before development to remove the oxygen-blocking layer and then developed. The method to do is common.

  Further, the processing solution used in the water washing treatment before development is used by pouring tap water. In this case, since water is used wastefully, a method of circulating and repeatedly using water has been proposed.

  Usually, water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, etc.) are commonly used in the oxygen barrier layer, which dissolves in water but emits a strange odor when left for a long time, and dissolves in water at a high concentration. However, there is a problem that the removal ability is gradually lowered and development defects and stains on non-image portions are generated.

In addition, the addition of organic solvents, chelating agents or surfactants to prevent a reduction in removal ability, and the addition of preservatives and bactericides to suppress off-flavors have been proposed. Since the composition of the developer is changed by being brought in, stable development processing is difficult. (For example, see Patent Documents 1 and 2)
In the case of the circulation type, regular water replacement is required and when the processing amount is small, water is replaced early, resulting in waste. When the processing amount is large, the removal capacity is insufficient. In some cases, there is a risk of developing defects and smearing of non-image areas, which may result in unusable materials as printing plates and printed materials. (For example, see Patent Document 3)
Japanese Patent Laid-Open No. 10-10754 Japanese Patent Laid-Open No. 2001-281872 JP 2001-166488 A

  The object of the present invention is to provide a stable development process especially in the removal process of a water-soluble oxygen barrier layer that is carried out before the development process of a photosensitive lithographic printing plate having a photopolymerizable layer having a water-soluble oxygen barrier layer as the uppermost layer. An object of the present invention is to provide a development processing apparatus, a plate making method, and a photosensitive lithographic printing plate that are capable of being operated without any fear of an operation error.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In a development processing apparatus for processing a photosensitive lithographic printing plate having an image forming layer and an oxygen blocking layer on a support, the oxygen blocking layer removed and dissolved in washing water is removed by the following means A) and B): A development processing apparatus for processing.

A) Means for monitoring water quality of flush water B) Means for displaying water quality deterioration (Claim 2)
In a development processing apparatus for processing a photosensitive lithographic printing plate having an image forming layer and an oxygen blocking layer on a support, the oxygen blocking layer removed and dissolved in washing water is removed by the following means A) and C): A development processing apparatus for processing.

A) Means for monitoring water quality of flush water C) Means for automatically supplying and draining flush water (Claim 3)
The means for monitoring the water quality of the rinsing water performs at least one measurement selected from pH measurement, conductivity measurement, visible light transmittance measurement, and transparency measurement. 2. The development processing apparatus according to 2.

(Claim 4)
A method for making a photosensitive lithographic printing plate, comprising processing the photosensitive lithographic printing plate with the development processing apparatus according to any one of claims 1 to 3.

(Claim 5)
A photosensitive lithographic printing plate which is processed by the development processing apparatus according to claim 1.

  That is, when washing water is used repeatedly, it is essential to monitor the state of the washing water, and the operator can grasp the water quality to enable stable treatment.

  By providing a means for monitoring the water quality and a means for notifying the operator, stable development processing can be performed. In addition, when water quality is monitored and the oxygen barrier layer removal capability declines, continuous drainage and water supply can be performed automatically and stable processing is possible, due to poor development and contamination of non-image areas. It is possible to drastically reduce the waste of producing printing plates and printed matter that cannot be used.

  The development processing apparatus, plate-making method, and photosensitive lithographic printing plate according to the present invention are particularly water-soluble before the development processing of a photosensitive lithographic printing plate having a photopolymerization layer having a water-soluble oxygen-blocking layer as the uppermost layer. In the removal process of the oxygen blocking layer, stable development processing is possible, and there is an excellent effect that there is no fear of an operation error or the like.

(Development processing equipment)
As shown in a schematic diagram of a schematic example of the development processing apparatus of the present invention in FIG. 3, the development processing device 60 is, for example, a pre-development washing unit 100 for developing a printing plate precursor or a discarded plate precursor, A washing unit 63 for washing away the developer adhering to the later plate, a finisher unit 65 for applying the gum solution, and a drying unit 67 for drying the plate after applying the gum solution are arranged in this order.

  The insertion port 70 of the development processing apparatus is equipped with a sensor 68 for detecting the loading of the plate material (PS plate). When the loading of the plate material is detected by the sensor 68, the conveying means 72 It is sequentially sent to the developing unit 61, the water washing unit 63, the finisher unit 65, and the drying unit 67, and is discharged from the discharge port 74.

  The conveying means 72 is configured to convey the plate material along a predetermined path by a plurality of conveying rollers 76. Each transport roller 76 constituting the transport means 72 is driven by a motor drive unit 78. The operation of the motor drive unit 78 is controlled by the control unit 80.

  FIG. 2 is a schematic view showing an example of a water circulation type pre-development washing section.

  The pre-development pre-development washing section 100 in the development processing apparatus of the present invention is provided with any one or a plurality of measuring means for pH, electrical conductivity, absorbance, and transparency as means 200 for monitoring water quality. Is provided on the control panel 300 of the development processing apparatus (control panel 300) for displaying a warning of water quality deterioration when the value exceeds or falls below the set value.

  Furthermore, in addition to means for displaying a warning about water quality deterioration, if one or more of the measured values exceed or fall below the set values, the water before the development is automatically forcibly drained and then supplied Means are provided.

In the monitoring means 200,
1. The pH measurement measures the hydrogen ion concentration in the washing water, and fluctuates under the influence of the acid-base contained in the oxygen barrier layer composition as the oxygen barrier layer dissolves in water. The effect increases as the amount of processing increases, and a value deviating from the initial value is measured. Although depending on the composition of the oxygen barrier layer, if the polyvinyl alcohol has a value different from ± 0.5 from the initial value in the main component, the oxygen barrier layer composition becomes extremely difficult to dissolve, and the removal of the oxygen barrier layer is difficult. It will be enough. For this reason, poor development and ink stains in the non-image area are caused.

  2. The electrical conductivity measurement varies depending on the amount of electrolyte dissolved in the washing water (salt concentration). When the oxygen barrier layer is dissolved in water, it varies under the influence of the acid-base contained in the oxygen barrier layer composition. The measured value increases as the throughput increases. Although depending on the oxygen barrier layer composition component, when polyvinyl alcohol has a value greater than 70 μS / cm than the initial value in the main component, the oxygen barrier layer composition becomes extremely difficult to dissolve, and the removal of the oxygen barrier layer is insufficient. become. For this reason, poor development and ink stains in the non-image area are caused.

  3. The visible light transmittance is measured by measuring the amount of the compound dissolved in the washing water, and is preferably observed at the absorption wavelength in the oxygen barrier layer composition. When the transmittance is smaller than a certain value, the oxygen barrier layer composition becomes extremely difficult to dissolve and the removal of the oxygen barrier layer becomes insufficient. For this reason, poor development and ink stains in the non-image area are caused.

  4). Permeability measurement measures the transparency of washing water and is sensitive when the washing water rots or mold occurs, and when rot or mold occurs, not only odor is generated but also hygienic undesirable . In addition, spoilage and mold cause particulate matter, which hinders circulation of washing water, clogs the shower, insufficiently removes the oxygen barrier layer, and causes poor development and ink stains in non-image areas. cause.

  The monitoring means 200 is connected to the control panel monitored by the person, and the various measured values are input from the monitoring means 200 to the control panel 300. The washing water is poured into the portion 111 generated on the shower PS plate, and the PS plate is washed with the shower-like washing water and the brush 102. Water is supplied from the water supply port and sent to the pre-development washing section 100 to wash the PS plate before development, thereby achieving the object of the present invention.

  FIG. 3 is a schematic view of a developing device that shows an example of the present invention in which the water circulation type cleaning section of FIG. 2 is provided in front of the insertion port of FIG.

  The development processing apparatus of the present invention is provided with a mechanism that automatically replenishes the developer bath with a replenisher in a required amount, a mechanism that discharges a developer exceeding a certain amount, and a developer bath. A mechanism for automatically replenishing the required amount of water, a mechanism for detecting plate passing, and a mechanism for estimating the processing area of the plate based on detection of plate passing are provided. A mechanism for controlling the amount and / or timing of replenishment of the replenisher and / or water to be replenished based on detection of the plate and / or estimation of the processing area, A mechanism for controlling the temperature is added, a mechanism for detecting the pH and / or conductivity of the developer is added, and replenishment is attempted based on the pH and / or conductivity of the developer. Liquid and / or water supplements It is preferable in that exhibits greater effects of the present invention that a mechanism for controlling the amount and / or replenishment timing has been granted.

  Moreover, when there exists a washing process after a image development process, the washing water after use can be used as a dilution water of the concentrate of a development concentrate and a development replenisher.

  The development processing apparatus of the present invention may have a pre-development washing unit that immerses the plate in the pre-development processing solution before the development unit. The pre-development washing section is preferably provided with a mechanism for spraying the pretreatment liquid on the plate surface, and preferably provided with a mechanism for controlling the temperature of the pretreatment liquid to an arbitrary temperature of 25 ° C. to 55 ° C. A mechanism for rubbing the plate surface with a roller-like brush is preferably provided. Moreover, water etc. are used as this pretreatment liquid.

  Further, the development processing apparatus of the present invention may have a heating unit in front of the pre-development washing unit. In this heating section, the plate surface temperature of the printing plate material can be heated to an arbitrary temperature of 90 to 130 ° C. As the heating means, an IR heater, heated hot air, or the like can be used.

Pre-development washing / rinsing water In the present invention, the washing solution used in the washing step before development is usually water, but the following additives may be added as necessary.

  As the chelating agent, a compound that forms a chelate compound by coordination with a metal ion is used. Ethylenediaminetetraacetic acid, its potassium salt, its sodium salt, ethylenediaminedisuccinic acid, its potassium salt, its sodium salt, triethylenetetramine hexaacetic acid, its potassium salt, its sodium salt, diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt Hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof, nitriotriacetic acid, potassium salt thereof, sodium salt thereof, 1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodium salt thereof, aminotri (methylenephosphone) Acid), potassium salt thereof, sodium salt thereof, phosphonoalkanetricarboxylic acid, ethylenediamine disuccinic acid, potassium salt thereof, sodium salt thereof and the like. Those chelating agents having an organic amine salt instead of the potassium salt and sodium salt are also effective.

  The addition amount of the chelating agent is usually in the range of 0 to 3.0% by mass.

  As the surfactant, any of anionic, nonionic, cationic and amphoteric surfactants can be used, but those used as developer components are more preferable.

  Examples of anionic surfactants include fatty acid salts, abichenates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates , Polyoxyethylene alkylsulfophenyl ether salts, sodium N-methyl-N-oleyl taurate, disodium N-alkylsulfosuccinic acid monoamide, petroleum sulfonates, sulfated castor oil, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene naphthyl ether sulfates, fatty acid monoglyceride sulfates Salts, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, partially saponified styrene-maleic anhydride copolymers , Partially saponified products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate, and the like.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene naphthyl ethers, polyoxyethylene phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid esters. , Sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, iethylene glycol fatty acid ester, polyiglycerin fatty acid partial ester , Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N- Scan - hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides and the like.

  In the cleaning step of the present invention, the cleaning solution used for the pre-development cleaning is preferably used by adjusting the temperature, and the temperature is preferably in the range of 10 to 60 ° C. As a cleaning method, known processing liquid supply techniques such as spraying, dipping, and coating can be used, and processing promoting means such as a brush, a drawing roll, and a submerged shower in the dip processing can be used as appropriate.

  In the present invention, the development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be performed after drying before the pre-development washing step. After the development step, known post-treatments such as washing with water, rinsing and gumming can be performed. The pre-development rinse water that has been used once or more can be reused in post-development rinse water, rinse solution, or gum solution.

Development processing solution (alkali agent)
As the inorganic alkaline agent contained in the developer used in the processing method of the present invention, sodium hydroxide, potassium and lithium are preferably used. These alkali agents are used alone or in combination of two or more.

  The pH is preferably pH 10.5 to 12.7. Particularly preferably, the pH is in the range of 11.0 to 12.5. When the pH of the developer is less than 10.5, the image portion of the printing plate obtained from the photosensitive lithographic printing plate that can be developed with such a developer is physically fragile, and wears quickly during printing. Printing durability is not obtained. Further, the image portion is chemically weak, and an image of a portion wiped with an ink washing solvent or a plate cleaner is damaged during printing, and as a result, sufficient chemical resistance cannot be obtained. A developer having a high pH such that the pH exceeds 12.7 is strongly irritating when adhering to the skin or mucous membrane, and is not preferable because it requires sufficient care in handling.

  In addition to the alkali agent, it is preferable to contain the following buffering agent in order to have plate surface cleaning properties and developer pH buffering properties. For example, potassium silicate, sodium silicate, lithium silicate, ammonium silicate, metametasilicate, sodium metasilicate, lithium metasilicate, ammonium metasilicate, tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, dipotassium phosphate, Disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, ammonium bicarbonate, potassium borate, sodium borate, lithium borate, boric acid Ammonium is mentioned, and it is preferable to contain at least one compound selected from the above.

Most preferred are potassium silicate and potassium carbonate. The concentration of silicate is preferably 0.5 to 3.5% by mass in terms of SiO ₂ concentration. Further, the concentration of carbonate is preferably 0.5 to 3.5% by mass in terms of CO ^{3 −} concentration.

  Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used in combination.

  The developer referred to in the present invention is not only an unused solution used at the start of development, but also supplemented with a replenisher in order to correct the activity of the solution that decreases due to the processing of the photosensitive lithographic printing plate, Includes a liquid having a maintained activity (so-called running liquid). The replenisher therefore needs to have a higher activity (alkali concentration) than the developer, so the pH of the replenisher may exceed 13.0.

(Surfactant)
As for the surfactant, it is essential to use at least one surfactant represented by Compound A, Compound B, and Compound C, anionic and nonionic polymer surfactant, and the image forming property is impaired. Therefore, it is possible to achieve both the stain during printing and the printing durability, and excellent processing stability.

  Compound A is an anionic surfactant containing a polyoxyalkylene group characterized in that the molecular weight of the saturated alkyl group in the hydrophobic group portion is 25% or less of the molecular weight of the entire hydrophobic group, and is a water-insoluble photosensitive compound. In order to stably disperse and solubilize the layer composition for a long period of time, it is preferable to have a polyoxyethylene group. In addition, a surfactant having an unsaturated hydrophobic group such as an aryl group is more preferable because the solubilizing power of the dissolved photosensitive layer component is high.

  Specific examples of Compound A include the compounds shown below, but the present invention is not limited thereto.

Compound _{B R 1 -O- (C 3 H} 6 O) m- (C 2 H 4 O) n-H
The molecular weight of the hydrophobic group portion (R ₁ ) is preferably large to some extent, and preferably 70 or more. Particularly preferred are a naphthyl group, a benzyl group, and an alkyl group having 8 to 12 carbon atoms. If the molecular weight of the hydrophobic group is too large, the solubility of the photosensitive layer is poor and a large amount of sludge is generated. When this compound is added in a small amount, the solubility of the photosensitive layer is poor and a large amount of sludge is generated. If the amount is too large, the foaming property becomes too large, or the film thickness of the photosensitive layer is reduced.

The polyoxypropylene part (C ₃ H ₆ O) n of Compound B is (CH ₂ CH ₂ CH ₂ O) n, (CH (CH ₂ ) CH ₂ O) n, (CH ₂ CH (CH ₂ ) O). ) Three ways of n can be considered. Any structure may be used, but the structure of (CH ₂ CH (CH ₂ ) O) n is most preferable. The value of m is most preferably 2-3. The value of n is most preferably 5-30. n / m is most preferably in the range of 5 or more and 20 or less. If each value of m, n, and n / m is too large or too small, the balance between the hydrophilic group and the hydrophobic group of the active agent is lost, and sludge increases and developability deteriorates.

  Specific examples of Compound B include the compounds shown below, but are not limited thereto.

  Compound C is a nonionic surfactant, wherein the molecular weight of the saturated alkyl group in the hydrophobic group portion is 25% or less of the molecular weight of the entire hydrophobic group. If the molecular weight of the saturated alkyl group exceeds 25%, foaming tends to occur and the developing tank is contaminated, which is not preferable.

  In order to stably disperse and solubilize the water-insoluble photosensitive layer composition for a long period of time, it preferably has a polyoxyethylene group. In addition, the surfactant having an unsaturated hydrophobic group such as an aryl group has excellent penetrating power into non-image areas and good developability.

  Specific examples of Compound C include the compounds shown below, but are not limited thereto.

  The nonionic polymer activator is not particularly limited as long as it is a polymer activator containing a polyoxyalkylene group having 2 to 4 carbon atoms. In particular, polyoxyethylene / polyoxypropylene block copolymers or water-soluble polymer surfactants of alkyl-polyoxyalkylene copolymers described in claim 1 of USP-5972572 are preferred. These polymeric surfactants improve the dispersibility of the photosensitive layer components in the developer, and improve the stability of dispersion and solubilization of the components eluted from the photosensitive layer by the amide group-containing surfactant. There is an effect of suppressing reattachment. In particular, when a urethane group-containing monomer is used as a component of the photosensitive layer, this component exhibits an effect of suppressing the precipitation of the component in the developing solution to generate residue and reattachment to the plate.

  The polyoxyethylene / polyoxypropylene block copolymer is represented by the following structural formula.

_{HO (C 2 H 4 O)} a (C 3 H 6 O) b (C 2 H 4 O) cH
In the above formula a. b. c shows the integer of 1-10000. The range of the polymer suitable for the present invention is 10 to 90% by mass, preferably 40 to 60% by mass of ethylene oxide in the total molecule, and the molecular weight of polyoxypropylene is in the range of 1000 to 4000, preferably 2000 to 3500. Is particularly good.

In the present invention, the polyoxyalkylene-containing polymeric surfactant is used in a mixed system with an amide group-containing surfactant, and may contain other active agents. The addition amount of each activator is preferably in the range of 0.5 to 5.0% by mass of the total amount of the developer, and particularly preferably 1 to 3% by mass.
The anionic polymer activator has an effect of suppressing reattachment of components eluted from the photosensitive layer to the plate by improving the dispersibility of the photosensitive layer component in the developer. In particular, when a urethane group-containing monomer is used as a component of the photosensitive layer, this component exerts a great effect in suppressing the deposition of the component in the developing solution to cause residue and reattachment to the plate. As the polymer having a carboxyl group used in the present invention, a polymer having at least a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) is preferably used.

In the general formula (1) and general formula (2), R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A in the general formula (1) represents a hydrogen atom or a carboxyl group. X ⁺ represents a potassium ion, a sodium ion, or an ammonium ion. B in the general formula (2) is —COOR ₂ , —CONHR ₂ , an aromatic hydrocarbon group having 6 to 15 carbon atoms which may have a substituent (the substituent is an alkyl group having 1 to 20 carbon atoms, Halogen atoms such as Br, Cl and I, aromatic hydrocarbon groups having 6 to 15 carbon atoms, aralkyl groups having 7 to 17 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and alkoxy-carbonyl groups having 2 to 20 carbon atoms And an acyl group having 2 to 15 carbon atoms). R ₂ may have a substituent having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms (the same as the above-mentioned substituent), and an aromatic carbon atom having 6 to 15 carbon atoms that may have a substituent. A hydrogen group (the substituent is the same as above) and an allyl group are shown.

  As long as it is a high molecular weight activator containing the structural unit, it may be a unipolymer, a k-binary copolymer, a ternary copolymer, a quaternary copolymer, or a quaternary copolymer. It preferably has a molecular weight and an acid value. The weight average molecular weight is preferably 5,000 to 300,000, more preferably 5,000 to 50,000. In the present invention, the carboxyl group-containing polymer is used in a complex system with an amide group-containing nonionic surfactant or an amide group-containing anion surfactant, and 0.5 to 5.0% by mass in an aqueous alkaline solution. The addition of 1 to 3% by mass is effective. If the amount is less than the above range, the effect of suppressing development residue is small, and if the amount is too large, a problem of precipitation of the polymer itself occurs.

  In addition, the developer used in the present invention includes not only the compound A, compound B, compound C, nonionic polymer surfactant and anionic polymer surfactant, but also promotes developability and disperses development residue. Various surfactants may be added for the purpose of improving the ink affinity of the printing plate image area.

Surfactants include anionic, cationic, nonionic and amphoteric surfactants. Examples include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ethers, polyoxyethylene polyoxyethylenes. Styryl phenyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol Fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycol Phosphorus fatty acid partial esters, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene-polyoxypropylene block copolymer adduct of ethylenediamine, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamine , Nonionic surfactants such as polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide,
Fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene aryl ethers Carboxylic acid, polyoxyethylene naphthyl ether sulfate, alkyl diphenyl ether sulfonate, alkyl phenoxy polyoxyethylene propyl sulfonate, polyoxyethylene alkyl sulfophenyl ether, polyoxyethylene aryl ether sulfate, N-methyl- N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, Fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl Phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkylphenyl ether phosphate salts, partially saponified styrene / maleic anhydride copolymers, olefin / maleic anhydride copolymer parts Saponified products, anionic surfactants such as naphthalene sulfonate formalin condensates, alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, Polyoxyethylene alkylamine salts, cationic surfactants such as polyethylene polyamine derivatives, carboxy betaines, aminocarboxylic acids, sulfobetaines, amino sulfate esters, amphoteric surfactants such as imidazolines.

  Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included.

  Said surfactant can be used individually or in combination of 2 or more types, and is added in 0.05-10 mass% in a developing solution, More preferably, it is added in 0.1-5 mass%.

(Chelating agent)
Examples of chelating agents include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alanine diacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid Aminopolycarboxylic acids such as nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediamine Tetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid) Hydroxyethyl ethylene diamine tri (methylene phosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts. The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass.

  If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water.

(Post-processing)
The plate developed with the developer having these compositions is subjected to post-processing with a washing water, a rinse solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. In the post-treatment of the photopolymerization type photosensitive printing plate of the present invention, these treatments can be used in various combinations, for example, after development → washing → rinsing solution containing a surfactant or development → water washing → finisher The treatment with the liquid is preferable because the rinse liquid and the finisher liquid are less fatigued. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment.

  These post-processing are generally performed using a development processing apparatus including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used.

  There is also known a method in which a small amount of washing water after development is supplied to the plate surface and washed, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, processing can be performed while each replenisher is replenished with each replenisher according to the processing amount, operating time, and the like.

  In addition, a so-called disposable processing method in which treatment is performed with a substantially unused post-treatment liquid can also be applied. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

(Gum solution)
It is preferable to add an acid or a buffering agent to the gum solution in order to remove alkali components from the developer, and in addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizing agent, and the like can be added. When the gum solution contains a hydrophilic polymer compound, it also has a function as a protective agent for preventing scratches and stains on the developed plate.

  By adding a surfactant to the gum solution preferably used in the present invention, the surface condition of the coating layer is improved. Surfactants that can be used include anionic surfactants and / or nonionic surfactants. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones. Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamido disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalenesulfonate formalin condensates Etc. Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial ester. , Sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters , Polyglycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid part Esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides and the like. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used.

  Fluorine-based and silicon-based anions and nonionic surfactants can also be used. Two or more of these surfactants can be used in combination. For example, two or more different from each other can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable.

  The amount of the surfactant used is not particularly limited but is preferably 0.01 to 20% by mass of the post-treatment liquid.

  In the gum solution used in the present invention, polyhydric alcohols, alcohols and aliphatic hydrocarbons can be used as lubricants as necessary in addition to the above components.

  Among the polyhydric alcohols, preferred specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, sorbitol and the like. Examples of the alcohol include propyl alcohol, butyl alcohol, and pen. Examples include alkyl alcohols such as tanol, hexanol, heptanol, and octanol, and alcohols having an aromatic ring such as pendyl alcohol, phenoxyethanol, and phenylaminoethyl alcohol.

  Examples of the aliphatic hydrocarbon include n-hexanol, methyl amyl alcohol, 2-ethylbutanol, n-heptanol, 3-heptanol, 2-octanol, 2-ethylhexanol, nonanol, 3,5,5-trimethylhexanol, n-decanol, undecanol, n-dodecanol, trimethylnonyl alcohol, tetradecanol, heptadecanol, 2-ethyl-1,3-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,4 -Hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and the like. The content of these lubricants is suitably 0.1 to 50% by mass, more preferably 0.5 to 3.0% by mass in the composition.

In addition to the above components, ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin and the like are suitably used as a lubricant if necessary. These wetting agents may be used alone or in combination of two or more. In general, the wetting agent is preferably used in an amount of 1 to 25% by weight.
Various hydrophilic polymers can be contained for the purpose of improving the film-forming property.

  As such a hydrophilic polymer, any hydrophilic polymer that can be conventionally used in a gum solution can be preferably used. For example, gum arabic, fiber derivatives (eg, carboxymethylcellulose, carboxyethylcellulose, methylcellulose etc.) and modified products thereof, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and copolymers thereof, vinyl methyl ether / maleic anhydride copolymer Examples thereof include a polymer, a vinyl acetate / maleic anhydride copolymer, and a styrene / maleic anhydride copolymer.

In general, it is advantageous to use the gum solution preferably used in the present invention in the acidic range of pH 3 to 6. In order to adjust the pH to 3 to 6, it is generally adjusted by adding a mineral acid, an organic acid, an inorganic salt, or the like in the post-treatment liquid. The addition amount is preferably 0.01 to 2% by mass. Examples of mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid.
Examples of the organic acid include citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, and organic phosphonic acid. Further, examples of the inorganic salt include magnesium nitrate, primary sodium phosphate, secondary sodium phosphate, nickel sulfate, sodium hexamethanoate, sodium tripolyphosphate, and the like. You may use together at least 1 sort (s) or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt.
A preservative, an antifoaming agent, etc. can be added to the gum solution used in the present invention.

  For example, as a preservative, phenol or a derivative thereof, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzisothiazolin-3-one, benztriazole derivative, amiding anidine derivative, quaternary ammonium salt, pyridine, Examples thereof include derivatives such as quinoline and guanidine, diazine, triazole derivatives, oxazole, and oxazine derivatives.

  A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the type of bacteria, molds, yeasts, but 0.01% with respect to the plate surface protective agent at the time of use. The range of ˜4% by mass is preferable, and it is preferable to use two or more kinds of preservatives in combination so as to be effective against various molds and sterilization.

  Moreover, as an antifoamer, a silicon antifoamer is preferable. Among them, emulsification dispersion type and solubilization can be used. Preferably, the range of 0.01 to 1.0% by mass with respect to the gum solution at the time of use is optimal.

  Further, a chelate compound may be added. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, sodium salt thereof; ethylenediamine disuccinic acid, potassium salt thereof. Triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof: nitrilotriacetic acid, sodium salt thereof; 1-hydroxyethane-1,1-diphosphone Acids, potassium salts, sodium salts; organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salts, sodium salts, etc. It can be mentioned.

  An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. These chelating agents are selected so that they are stably present in the gum solution composition and do not impair the printability. The addition amount is suitably 0.001 to 1.0 mass% with respect to the gum solution at the time of use.

  In addition to the above components, a sensitizer can be added as necessary.

  For example, hydrocarbons such as turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosene, mineral spirit, petroleum fraction having a boiling point of about 120 ° C to about 250 ° C, such as dibutyl phthalate, dihebutyl phthalate, di-n-octyl Phthalic acid diester agents such as phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di ( 2-ethylhexyl) aliphatic dibasic acid esters such as sebacate and dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, such as tricresyl phosphate, trioctylfolate Feto, phosphoric acid esters such as tris chloroethyl phosphate, for example, freezing point, such as benzoic acid esters of benzyl benzoate and at 15 ℃ below boiling point at one atmosphere include 300 ° C. or more plasticizers.

  In addition, caproic acid, enanthic acid, caprylic acid, helargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoserine Saturated fatty acids such as acid, serotic acid, heptacosanoic acid, montanic acid, melicinic acid, lactelic acid, isovaleric acid, and acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, nillic acid, buteticidin Examples also include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, sardine acid, talylic acid and licanoic acid. More preferably, it is a fatty acid that is liquid at 50 ° C., more preferably 5 to 25 carbon atoms, and most preferably 8 to 21 carbon atoms. These sensitizers can be used alone or in combination of two or more. A preferable range for the amount used is 0.01 to 10% by mass of the gum, and a more preferable range is 0.05 to 5% by mass.

  The sensitizers as described above may be prepared by emulsifying and dispersing the gum as an oil phase, or may be solubilized with the help of a solubilizer.

In the present invention, the solid content concentration of the gum solution is preferably 5 to 30 g / l. The film thickness of the gum can be controlled by the conditions of the squeeze means of the automatic machine. In the present invention, the gum application amount is preferably 1 to 10 g / m ² . If the amount of gum application exceeds 10, the plate surface needs to be very hot in order to dry in a short time, which is disadvantageous in terms of cost and safety, and the effects of the present invention cannot be sufficiently obtained. If it is less than 1 g / m ² , uniform coating becomes difficult and stable processability cannot be obtained.

  In the present invention, the time from the end of the application of the gum solution to the start of drying is preferably 3 seconds or less. More preferably, it is 2 seconds or less, and the shorter the time is, the better the ink deposition property is.

  In the present invention, the drying time is preferably 1 to 5 seconds. When the drying time is 5 seconds or more, the effect of the present invention cannot be obtained. When the drying time is 1 second or less, it is necessary to make the plate surface very hot in order to sufficiently dry the photosensitive lithographic printing plate, which is not preferable in terms of safety and cost.

  In the present invention, as a drying method, a known drying method such as a warm air heater or a far infrared heater can be used.

  In the drying step, the solvent in the gum solution needs to be dried. Therefore, it is necessary to ensure sufficient drying temperature and heater capacity. The temperature required for drying varies depending on the components of the gum solution, but in the case of a gum solution in which the solvent is water, the drying temperature is preferably 55 ° C. or higher. The heater capacity is often more important than the drying temperature, and the capacity is preferably 2.6 kW or more in the case of the hot air drying method. The larger the capacity, the better, but 2.6-7 kW is preferable in terms of balance with cost.

(Support)
As the support, an aluminum plate is preferably used. In this case, a pure aluminum plate, an aluminum alloy plate, or the like may be used.

  Various aluminum alloys can be used as the support, such as alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. Aluminum plates manufactured by various rolling methods can be used. In addition, a recycled aluminum plate obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.

  Prior to roughening (graining treatment), the support is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface. As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. It is preferable to perform the treatment.

  Examples of the roughening method include a mechanical method and a method of etching by electrolysis.

The mechanical roughening method used is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to neutralize by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used.

As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent No. 896,563 and Japanese Patent Laid-Open No. 53-67507 can be used. This roughening method can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.

When electrochemical surface roughening is performed using a nitric acid-based electrolyte as the electrolyte, it can be generally performed by applying a voltage in the range of 1 to 50 volts, but is selected from the range of 10 to 30 volts. Is preferred. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 2 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 50 to 150 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably 100~2000c / dm ^2, and more and more preferably selected from the range of 200~1000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.

After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.

  The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughening, or the mechanical surface roughening treatment method followed by the electrochemical surface roughening method may be used for roughening. You may face it.

Following the roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. For the anodizing treatment, a method of electrolyzing an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% as an electrolytic solution at a current density of 1 to 10 A / dm ² is preferably used. The method of electrolyzing at high current density in sulfuric acid described in Japanese Patent No. 1,412,768, the method of electrolyzing using phosphoric acid described in Japanese Patent No. 3,511,661, chromic acid, Examples thereof include a method using a solution containing one or more acids, malonic acids and the like. The formed anodic oxidation coating amount is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² . The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is determined from the measurement of mass change before and after dissolution of the coating on the plate.

  The anodized support may be sealed as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, water vapor treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment. Furthermore, in this invention, after performing these processes, the process which coat | covers a support body surface with polyvinylphosphonic acid can be performed. The coating treatment is not limited to a coating method, a spray method, a dip method, or the like, but a dip method is suitable for making the equipment inexpensive.

  In the case of a dip type, it is preferable to treat polyvinylphosphonic acid with a 0.01 to 35% aqueous solution, and a 0.1 to 5% aqueous solution is particularly preferable. The treatment temperature is preferably 20 ° C or higher and 90 ° C or lower, and more preferably 40 ° C or higher and 80 ° C or lower. If it is lower than 20 ° C., printing stains are bad, and if it is higher than 90 ° C., printing durability is deteriorated.

  The treatment time is preferably 10 to 180 seconds. After the treatment, it is preferable to perform a squeegee treatment or a water washing treatment in order to remove the excessively laminated polyvinylphosphonic acid. Furthermore, it is preferable to perform a drying process. As a drying temperature, 20-95 degreeC is preferable.

The amount of polyvinylphosphonic acid applied to the surface of the aluminum support of the present invention is preferably 3 to ²⁰ mg / m2. Particularly, 4 to 15 mg / m ² is preferable. If it is less than 3 mg / m ² , printing stains in the non-image area occur, and if it exceeds 20 mg, the printing durability deteriorates. Various concentrations of polyvinylphosphonic acid aqueous solution concentration, treatment temperature, and treatment time can be combined to obtain a desired coating amount.

  The surface phosphorus atom concentration (atm%) in the state where the surface of the aluminum support of the present invention is coated with polyvinyl sulfonic acid is preferably 3 to 15 atm%. Particularly preferably, 5 to 9 atm%.

(Polymer binder)
The photosensitive lithographic printing plate of the present invention contains a polymer binder in the photopolymerizable photosensitive layer.

  Examples of the polymer binder of the present invention include acrylic polymers, polyvinyl butyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, and other natural materials. Resin etc. can be used. Two or more of these may be used in combination.

  A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferred.

  Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

  Furthermore, in the polymer binder of the present invention, monomers described in the following (1) to (14) can be used as other copolymerization monomers.

  1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.

  2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

  3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p -Aminosulfonylphenyl) acrylamide and the like.

  4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

  6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N- Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

  7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

  14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

  Further, other monomers that can be copolymerized with these monomers may be copolymerized.

  Furthermore, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder.

  Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  These copolymers preferably have a weight average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.

  The content of the high molecular polymer in the photosensitive layer composition is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and the sensitivity to use in the range of 20 to 50% by mass. Particularly preferred from the viewpoint.

  Furthermore, the acid value of the resin is preferably used in the range of 10 to 150, more preferably in the range of 30 to 120, and the use in the range of 50 to 90 from the viewpoint of balancing the polarity of the entire photosensitive layer. Particularly preferred, this can prevent pigment aggregation in the photosensitive layer coating solution.

(Addition-polymerizable ethylenic double bond-containing monomer)
These compounds containing an addition-polymerizable ethylenic double bond according to the present invention include general radical-polymerizable monomers and ethylenic monomers that can be addition-polymerized in a molecule generally used for ultraviolet curable resins. Polyfunctional monomers having a plurality of double bonds and polyfunctional oligomers can be used. The compound is not limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol diacrylate , Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of hydroxypentylate neopentyl glycol, Diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1, Ε-caprolactone adduct of 3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Difunctional acrylic acid esters such as diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, For example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Ε-caprolactone adduct of hexaacrylate, pyrogallol triacrylate Polyfunctional acrylic acid esters such as propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or these acrylates with methacrylate, itaconate, crotonate, Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of maleate.

  Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  The photosensitive composition used in the present invention includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylol propane acrylic. It can contain monomers such as acid benzoic acid esters, alkylene glycol-type acrylic acid-modified, urethane-modified acrylates, and addition-polymerizable oligomers and prepolymers having structural units formed from the monomers.

  Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include phosphate ester compounds containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  In the present invention, it is preferable to use an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, collectable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, the present invention uses a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule. Is preferred.

  Examples of the polyhydric alcohol containing a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'-tetra- 2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N , N-di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino)- Although 1,2-propanediol etc. are mentioned, it is not limited to this.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not. Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include compounds such as MH-1 to MH-13, but are not limited thereto. Preferable examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, and the like.

  These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

  Specific examples of reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. Shown in

M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) An acrylate or an alkyl acrylate described in JP-A-1-105238 and JP-A-2-127404 can be used.

(Spectral sensitizing dye)
When laser light is used as the light source, a sensitizing dye is preferably added to the photosensitive layer. It is preferable to use a dye having an absorption maximum wavelength in the vicinity of the wavelength of the light source.

Compounds that sensitize wavelengths from visible light to near infrared, that is, dyes having an absorption maximum between 350 nm and 1300 nm include, for example, cyanine, phthalocyanine, merocyanine, porphyrin, spiro compounds, ferrocene, fluorene, fulgide, imidazole, and perylene. , Phenazine, phenothiazine, polyene, xanthene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivative, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbi Examples thereof include ketoalcohol borate complexes such as tool acid derivatives and thiobarbituric acid derivatives, and further include European Patent No. 568,993 and US Patent No. 4,508. 811 No., 5,227,227 JP, JP 2001-125255, compounds described in JP-A 11-271969 Patent etc. are also used.
Specific examples of the combination of the photopolymerization initiator and the sensitizing dye include combinations described in JP-A Nos. 2001-125255 and 11-271969.

Further, when recording is performed using a semiconductor laser having a light emission wavelength in the range of 380 nm to 430 nm, that is, a so-called violet laser as a laser beam of the light source, it is desirable to include a dye having an absorption maximum between 350 nm and 450 nm. The dye having an absorption maximum between 350 nm and 450 nm is not particularly limited in terms of structure, but cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, Polyene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin, coumarin derivative, ketocoumarin, quinacridone, indigo, styryl, pyrylium compound, pyromethene compound, pyrazolotriazole compound, benzothiazole compound, barbituric acid derivative, thiobarbitur tool Any dye group such as an acid derivative and a keto alcohol borate complex can be used as long as the absorption maximum satisfies the requirement. Specifically, JP-A No. 2002-296664, JP-A No. 2002-268239, JP-A No. 2002-268238, JP-A No. 2002-268204, JP-A No. 2002-221790, JP-A No. 2002-202598, JP-A No. 2001-042524, JP-A No. 2000 are disclosed. Although the dyes described in JP-A-309724, JP-A-2000-258910, JP-A-2000-206690, JP-A-2000-147663, JP-A-2000-098605 and the like can be used, the present invention is not limited thereto.
Although the compounding quantity of these polymerization initiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 polymerization parts of compound which can be addition-polymerized or bridge | crosslinked. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.

  Specifically, it is a compound represented by the following D-1 to D-8.

(Photopolymerization initiator composition)
Examples of the photopolymerization initiator composition of the present invention include titanocene compounds, iron arene complex compounds, trihaloalkyl compounds, and monoalkyltriaryl borate compounds.

(Titanocene compound)
The photopolymerization initiator composition of the present invention contains a titanocene compound, and examples thereof include compounds described in JP-A-63-41483 and JP-A-2-291. More preferable specific examples include bis (cyclo Pentadienyl) -Ti-di-chloride, bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl Bis (cyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclo Pentadienyl) -Ti-bis-2,6-difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclo Ntadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclo Pentadienyl) -Ti-bis-2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) ) Phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopenta) Dienyl) -bis (2,4,6-trifluoro-3- (2-5-dimethylpyridin-1-) ) Phenyl) titanium, and the like.

(Iron arene complex compound)
Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferred specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η-cumene. -(Η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η- Examples include xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate.

  Specifically, it is a compound represented by I-1, I-2, I-3.

(Monoalkyl aryl borate compound)
Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n-butyl-tri. Naphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n- Examples include butylammonium n-hexyl-tri- (3-chloro-4-methylphenyl) -borate and tetra-n-butylammonium n-hexyl-tri- (3-fluorophenyl) -borate.

(Trihaloalkyl compound)
The photosensitive composition and photosensitive lithographic printing plate material of the present invention contain a compound containing a photodegradable trihaloalkyl group known as a free radical forming photoinitiator for a photopolymerizable mixture. As this type of combination initiator, compounds containing chlorine and bromine as halogen are particularly suitable. The trihaloalkyl group is preferably a trihalomethyl group, and is preferably bonded to an aromatic carbocycle or a heterocycle directly or via a continuously conjugated chain. Preferred are those having a triazine ring having two trihalomethyl groups as a mother nucleus, particularly the compounds described in EP-A-1374552, DE-A-2118259 and 2243621. These compounds exhibit strong light absorption in the near ultraviolet region, for example, 350 to 400 nm. Combination initiators that do not absorb themselves or absorb very little light in the spectral region of the copying light, for example trihalomethyltriazines containing substituents with short electronic systems or aliphatic substituents that allow mesomeries; Is also appropriate. Likewise suitable are compounds having different basic skeletons and absorbing light in the short-wave ultraviolet region, such as phenyl trihalomethyl sulfone or phenyl trihalomethyl ketone, such as phenyl tribromomethyl sulfone.

  More specific compounds include the following compounds.

  In addition, any photopolymerization initiator can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.

  That is, the following can be used as a photopolymerization initiator that can be used in combination.

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, 61-9621 and JP-A-60-60104 Triazine derivatives; organic peroxides described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, JP-A-47-1604, and US patents Diazonium compounds described in US Pat. No. 3,567,453; organic azide compounds described in US Pat. Nos. 2,848,328 and 2,852,379 and 2,940,853; O-quinonediazides described in JP-A Nos. 13109, 38-18015 and 45-9610; JP-B-55-39162, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1307 Various onium compounds described on page 1977; azo compounds described in JP-A-59-142205 Compound: described in JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag. Sci.)”, Vol. 30, 174 (1986) (Oxo) sulfonium organoboron complexes described in Japanese Patent Application Nos. 4-56831 and 4-89535; ("Coordination Chemistry Review" vol. 84, pages 85-277) 1988) and transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701; 2,4,5-triarylimidazole dimer described in JP-A-3-209477; carbon tetrabromide, Organohalogen compounds described in JP-A-59-107344 .

(Oxygen barrier layer)
For the oxygen barrier layer, a water-soluble polymer capable of forming a film having low oxygen permeability is used. Specifically, it contains polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

  In the lithographic printing plate material of the present invention, the peeling force between the photosensitive layer and the water-soluble oxygen barrier layer is preferably 35 g / 10 mm or more, more preferably 50 g / 10 mm or more, and still more preferably 75 g / 10 mm or more. As a preferable composition of the water-soluble oxygen barrier layer, there can be mentioned those described in Japanese Patent Application No. 8-161645.

  The peeling force in the present invention is such that an adhesive tape having a predetermined width is applied on a water-soluble oxygen barrier layer, and the water-soluble oxygen barrier is applied at an angle of 90 degrees to the plane of the planographic printing plate material. The force when peeling with the layer was measured.

  The water-soluble oxygen barrier layer can further contain a surfactant, a matting agent and the like as necessary. The above water-soluble oxygen barrier layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form a water-soluble oxygen barrier layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol, i-propanol.

  The thickness of the water-soluble oxygen barrier layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited to these examples.

  “Parts” in the examples represents “parts by mass” unless otherwise specified.

Example 1
(Binder synthesis)
(Synthesis of acrylic copolymer 1)
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile are placed in a nitrogen stream. The mixture was reacted for 6 hours in an oil bath at 0 ° C. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3% by mass nitric acid aqueous solution, and then kept at 60 ° C. Desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution. The surface-roughened aluminum plate subjected to desmut treatment was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute. Furthermore, after the anodic acid value treatment, a surface treatment was performed in a polyvinyl phosphonic acid aqueous solution at 75 ° C. for 20 seconds to prepare a support. The dry weight of polyvinylphosphonic acid was 8 mg / m ² , and the center line average roughness (Ra) of the surface was 0.65 μm.

(Preparation of photosensitive lithographic printing plate material 1)
On the support, a photopolymerizable photosensitive layer coating solution having the following composition was prepared, applied with a wire bar so as to be 1.6 g / m ² when dried, dried at 95 ° C. for 1.5 minutes, and photopolymerized. A photosensitive layer-coated sample was obtained.

(Photopolymerizable photosensitive layer coating solution)
Addition-polymerizable ethylenic double bond-containing monomer 1 M-3 30.6 parts Addition-polymerizable ethylenic double bond-containing monomer 2 NK ester 4G
(Polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 17.6 parts Polymerization initiator I-1 2.9 parts Trihaloalkyl compound CI-1 1.5 parts Spectral sensitizing dye D-1 4.0 parts Acrylic copolymer Compound 1 40.0 parts N-phenylglycine benzyl ester 0.3 part Phthalocyanine pigment (MHI454: manufactured by Gokoku Color Co., Ltd.) 3.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M Co., Ltd.) 0.1 part Fluorine-based surfactant (F-178K; manufactured by Dainippon Ink Co., Ltd.) 0.1 part A photopolymerized photosensitive layer coating solution 1 was prepared by diluting with an organic solvent.

Methyl ethyl ketone 80 parts Cyclohexanone 820 parts M-3 is as follows.
: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Reaction product of the above-mentioned photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with an applicator so as to be 1.8 g / m ² when dried, and at 65 ° C. for 1.5 minutes. It dried and the photosensitive lithographic printing plate material 1 which has an oxygen interruption | blocking layer on a photosensitive layer was produced. The produced photosensitive lithographic printing plate material was deposited and packaged so that the outermost surface of the photosensitive layer surface and the support surface opposite to the photosensitive layer surface were in contact with each other.

(Oxygen barrier layer coating solution 1)
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 70.0 parts Polyvinylpyrrolidone (K-30: manufactured by BAFS) 29.5 parts Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 900 parts water (image formation)
About the photosensitive printing plate material produced and packed in this way, the area ratio of the image part and the non-image part is 1: 9 using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source. Exposure energy: 150 μJ / cm ² , image exposure at a resolution of 2400 dpi (dpi means the number of dots per 2.54 cm) (exposure pattern is 100% image part, 175 LPI 98, 96, 94, 92, 90, 88, 86, 84, 82, 80, 70, 60, 50, 40, 30, 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1% square dots were used).

  Next, before development, in the development processing apparatus provided with a heating unit in front of the development processing apparatus of the present invention of FIG. 3, a development section filled with the following developer composition, a water washing section for removing the developer attached to the plate surface, A lithographic printing plate was obtained by carrying out development processing with a finisher solution for protecting the image area (GW-3: a product obtained by diluting Mitsubishi Chemical Co., Ltd.). At this time, the heating unit was set so that the plate surface temperature was 110 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating device of the self-machine after the exposure was completed within 60 seconds.

  The amount of water in the pre-rinsing section of the development processing apparatus in FIG. 3 was adjusted to 20 L.

Developer composition (aqueous solution containing the following additives) (20L developer)
Potassium silicate aqueous solution (SiO ₂ : 26%, K ₂ O: 13.5%) 40.0 g / L
Potassium hydroxide 4.0g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether sulfonate 20.0 g / L
Made up to 1 L with deionized water. The pH was 12.1.

<Evaluation of printing stains>
The developed lithographic printing plate was coated with a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) on a coated paper, printing ink (soybean oil ink “Naturalis manufactured by Dainippon Ink & Chemicals, Inc.”). 100 ") and dampening water (Tokyo ink Co., Ltd. H liquid SG-51 density | concentration 1.5%). About the 100th printed matter from the start of printing, the spotted ink stains in the non-image area 100 cm ² were visually evaluated.

A: Ink smudge is not observed in non-image area (number of ink smudges on spots: 0)
○: Ink stains are hardly observed in non-image areas (number of spotted ink stains: 1 to 10)
Δ: Slight ink stains are observed in the non-image area, but can be used as printed matter (number of spotted ink stains: 11 to 30)
×: Ink stains are observed in the non-image area and cannot be used as printed matter (number of spotted ink stains: 31 or more)
Evaluation 1
A pH meter is used as a means of monitoring the water quality of the washing water, and the operator when the measured value of the washing water becomes a pH value that differs by ± 0.5 or more compared to the initial value (value that has never been treated). water warning display degradation, to the case of 10 m ² treated by replacing the washing water, were evaluated contamination of non-image portion of the further printing plate which is manufactured by 10 m ² treated without replacing the.

Evaluation 2
An electrical conductivity meter is used as a means of monitoring the water quality of the washing water. When the measured value of the washing water is 70 μS / cm or more compared to the initial value (value when no treatment has been performed), the water quality is given to the operator. a warning of degradation, to the case of 10 m ² treated by replacing the washing water, were evaluated contamination of non-image portion of the further printing plate which is manufactured by 10 m ² treated without replacing.

Evaluation 3
As a means of monitoring the water quality of the washing water, the transmittance is measured using an absorptiometer. When the measured value of the washing water becomes 95% or less, a warning about the deterioration of the water quality is displayed to the operator, and the washing water is replaced. to the case of ² treatment was evaluated contamination of non-image portion of the further printing plate which is manufactured by 10 m ² treated without replacing.

(Transmittance) = (Transmittance at the time of processing) ÷ (Transmittance at the time of no processing) × 100
The transmittance was measured with light having a wavelength of 500 to 550 nm.

Evaluation 4
When using a fluorometer as a means of monitoring the water quality of the washing water, when the measured value of the washing water becomes 75 cm or less, a warning of water quality deterioration is displayed to the operator, and the washing water is replaced and treated with 10 m ² The stain on the non-image area of the printing plate produced by further processing 10 m ² without replacement was evaluated. The transparency was measured using a semiconductor laser beam of 600 to 1000 nm.

Example 2
(Binder synthesis)
(Synthesis of acrylic copolymer 1)
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile are placed in a nitrogen stream. The mixture was reacted for 6 hours in an oil bath at 0 ° C. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3% by mass nitric acid aqueous solution, and then kept at 60 ° C. Desmutting treatment was performed for 10 seconds in a 5% aqueous sodium hydroxide solution. The surface-roughened aluminum plate subjected to desmut treatment was anodized in a 15% sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute. Furthermore, after the anodic acid value treatment, a surface treatment was performed in a polyvinyl phosphonic acid aqueous solution at 75 ° C. for 20 seconds to prepare a support. The dry weight of polyvinylphosphonic acid was 8 mg / m ² , and the center line average roughness (Ra) of the surface was 0.65 μm.

(Preparation of photosensitive lithographic printing plate material 2)
On the support, a photopolymerizable photosensitive layer coating solution having the following composition was prepared, applied with a wire bar so as to be 1.6 g / m ² when dried, dried at 95 ° C. for 1.5 minutes, and photopolymerized. A photosensitive layer-coated sample was obtained.

(Photopolymerizable photosensitive layer coating solution 2)
Addition-polymerizable ethylenic double bond-containing monomer 1 (M-3) 30.6 parts Addition-polymerizable ethylenic double bond-containing monomer 2 NK ester 4G
(Polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) 17.6 parts Polymerization initiator I-1 2.9 parts Trihaloalkyl compound CI-1 1.5 parts Spectral sensitizing dye D-4 4.0 parts Acrylic copolymer Compound 1 40.0 parts N-phenylglycine benzyl ester 0.3 part Phthalocyanine pigment (MHI454: manufactured by Gokoku Color Co., Ltd.) 3.5 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5 -Methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M Co., Ltd.) 0.1 part Fluorine-based surfactant (F-178K; manufactured by Dainippon Ink Co., Ltd.) 0.1 part A photopolymerized photosensitive layer coating solution 1 was prepared by diluting with an organic solvent.

Methyl ethyl ketone 80 parts Cyclohexanone 820 parts On the photopolymerized photosensitive layer-coated sample, an oxygen barrier layer coating solution having the following composition was coated with an applicator so as to be 1.8 g / m ² when dried. It was dried for 5 minutes to produce a photosensitive lithographic printing plate material 1 having an oxygen blocking layer on the photosensitive layer. The produced photosensitive lithographic printing plate material was deposited and packaged so that the outermost surface of the photosensitive layer surface and the support surface opposite to the photosensitive layer surface were in contact with each other.

(Oxygen barrier layer coating solution 1)
Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 70.0 parts Polyvinylpyrrolidone (K-30: manufactured by BAFS) 29.5 parts Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 900 parts water (image formation)
About the photosensitive printing plate material produced and packed in this way, the area ratio of the image part and the non-image part is determined by using a CTP exposure apparatus (Tigercat: a modified product manufactured by ECRM) equipped with an LED having an oscillation wavelength of 405 nm / 30 mW. , 1: 9 exposure energy: 150 μJ / cm ² , image exposure with a resolution of 2400 dpi (exposure pattern is 100% image area and 175 LPI 98, 96, 94, 92, 90, 88, 86, 84 82, 80, 70, 60, 50, 40, 30, 20, 18, 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1% square dots) It was.

  Next, before development, a heating device part, a pre-water washing part for removing the protective layer, a development part filled with the following developer composition, a water washing part for removing the developer adhering to the plate surface, a finisher solution for protecting the image line part ( GW-3: a product obtained by diluting Mitsubishi Chemical Co., Ltd. twice) to obtain a lithographic printing plate. At this time, the heating unit was set so that the plate surface temperature was 110 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating device of the self-machine after the exposure was completed within 60 seconds.

  The amount of water in the pre-rinsing section of the development processing apparatus in FIG. 3 was adjusted to 20 L.

Developer composition (aqueous solution containing the following additives)
Potassium silicate aqueous solution (SiO ₂ : 26%, K ₂ O: 13.5%) 40.0 g / L
Potassium hydroxide 4.0g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether sulfonate 20.0 g / L
Made up to 1 L with deionized water. The pH was 12.1.

<Evaluation of printing stains>
The developed lithographic printing plate was coated with a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.) on a coated paper, printing ink (soybean oil ink “Naturalis manufactured by Dainippon Ink & Chemicals, Inc.”). 100 ") and dampening water (Tokyo ink Co., Ltd. H liquid SG-51 density | concentration 1.5%). About the 100th printed matter from the start of printing, the spotted ink stains in the non-image area 100 cm ² were visually evaluated.

A: Ink smudge is not observed in non-image area (number of ink smudges on spots: 0)
○: Ink stains are hardly observed in non-image areas (number of spotted ink stains: 1 to 10)
Δ: Slight ink stains are observed in the non-image area, but can be used as printed matter (number of spotted ink stains: 11 to 30)
×: Ink stains are observed in the non-image area and cannot be used as printed matter (number of spotted ink stains: 31 or more)
Evaluation 5
A pH meter is used as a means of monitoring the water quality of the washing water, and the operator when the measured value of the washing water becomes a pH value that differs by ± 0.5 or more compared to the initial value (value that has never been treated). water warning display degradation, to the case of 10 m ² treated by replacing the washing water, were evaluated contamination of non-image portion of the further printing plate which is manufactured by 10 m ² treated without replacing the.

Evaluation 6
An electrical conductivity meter is used as a means of monitoring the water quality of the washing water. When the measured value of the washing water is 70 μS / cm or more compared to the initial value (value when no treatment has been performed), the water quality is given to the operator. a warning of degradation, to the case of 10 m ² treated by replacing the washing water, were evaluated contamination of non-image portion of the further printing plate which is manufactured by 10 m ² treated without replacing.

Evaluation 7
As a means of monitoring the water quality of the washing water, the transmittance is measured using an absorptiometer. When the measured value of the washing water becomes 95% or less, a warning about the deterioration of the water quality is displayed to the operator, and the washing water is replaced. to the case of ² treatment was evaluated contamination of non-image portion of the further printing plate which is manufactured by 10 m ² treated without replacing.

(Transmittance) = (Transmittance at the time of processing) ÷ (Transmittance at the time of no processing) × 100
The transmittance was measured with light having a wavelength of 380 to 430 nm.

Evaluation 8
When using a fluorometer as a means of monitoring the water quality of the washing water, when the measured value of the washing water becomes 75 cm or less, a warning of water quality deterioration is displayed to the operator, and the washing water is replaced and treated with 10 m ² The stain on the non-image area of the printing plate produced by further processing 10 m ² without replacement was evaluated. The transparency was measured using a semiconductor laser beam of 600 to 1000 nm.

  From the table of the above examples, it can be seen that the present invention is superior to the comparison.

It is the schematic which shows an example of a part of developing processing apparatus used for this invention. It is the schematic which shows an example of the pre-development water washing part of this invention. FIG. 3 is a schematic view of a development processing apparatus showing an example of the present invention provided with the water circulation type cleaning unit of FIG. 2 in front of the insertion port of FIG. 1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 51 Control part 60 Development processing apparatus 61 Developing part 63 Washing part 65 Finisher part 67 Drying part 68 Sensor 72 Conveying means 76 Conveying roller 78 Motor drive part 80 Control part 92 Discharge port

Claims (5)

In a development processing apparatus for processing a photosensitive lithographic printing plate having an image forming layer and an oxygen blocking layer on a support, the oxygen blocking layer removed and dissolved in washing water is removed by the following means A) and B): A development processing apparatus for processing.
A) Means for monitoring water quality of flush water B) Means for displaying water quality deterioration In a development processing apparatus for processing a photosensitive lithographic printing plate having an image forming layer and an oxygen blocking layer on a support, the oxygen blocking layer removed and dissolved in washing water is removed by the following means A) and C): A development processing apparatus for processing.
A) Means for monitoring the quality of flush water C) Means for automatically supplying and draining flush water The means for monitoring the water quality of the rinsing water performs at least one measurement selected from pH measurement, conductivity measurement, visible light transmittance measurement, and transparency measurement. 2. The development processing apparatus according to 2. A method for making a photosensitive lithographic printing plate, comprising processing the photosensitive lithographic printing plate with the development processing apparatus according to any one of claims 1 to 3. A photosensitive lithographic printing plate which is processed by the development processing apparatus according to claim 1.

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