JP2009251582A - Development processing liquid, and photosensitive lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a development processing liquid whose pH is within a relatively low pH range of pH 9.0 to 11.5, and which has long-period development stability and a prolonged processing lifetime and contains no silicate, and a photosensitive lithographic printing plate material. <P>SOLUTION: Disclosed are the development processing liquid, containing no silicate, which develops the photosensitive lithographic printing plate material containing at least an alkali-soluble polymer on an aluminum base having been subjected to roughening and anode oxidation processing, the development processing liquid not containing an alkylene oxide chain and containing 0.5 to 10.0 mass% of a surfactant having a group of any of a carboxylic acid and a carboxylic acid alkali metal salt; and the photosensitive lithographic printing plate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a developing solution and a photosensitive lithographic printing plate material, and more particularly to a developing solution and a photosensitive lithographic printing plate material substantially free of silicate.

  In recent years, CTP recording digital image data directly on a photosensitive lithographic printing plate with a laser light source has been developed and is being put to practical use in the technology for producing printing plates for offset printing.

  Among these, in the field of printing that requires a relatively high printing durability, it is known to use, for example, a negative photosensitive lithographic printing plate material having a polymerizable photosensitive layer containing a polymerizable compound. (See, for example, Patent Documents 1 and 2).

  Furthermore, a photosensitive lithographic printing plate material is known which has an improved safe light property from the viewpoint of handleability of the printing plate and can be image-exposed with a laser having a wavelength of 390 nm to 430 nm.

  Then, a high-power and small-sized blue-violet laser with a wavelength of 390 to 430 nm can be easily obtained. By developing a photosensitive lithographic printing plate material suitable for this laser wavelength, the bright room has been developed. (See Patent Document 3).

  Also known is a photosensitive lithographic printing plate material containing a biimidazole compound in the photosensitive layer, which has improved safelight properties under yellow light (see, for example, Patent Document 4), and has high sensitivity and low sublimation. As a photopolymerizable composition, a photopolymerizable composition containing a hexaarylbiimidazole compound containing an aryl group having a substituent such as an alkyl group is known (see, for example, Patent Document 5).

  If importance is attached to the maintainability of the development processing solution and the self-supporting machine, development processing of a development processing solution that is an alkaline aqueous solution having a pH of 9.0 or more and 12.4 or less that does not substantially contain silicate is desired. In the examination of the low pH alkaline developing solution substantially containing no silicate so far, the developability of the nonionic surfactant and the ethylene oxide-containing surfactant is greatly lowered when the pH is 11.0 or less. Although technical disclosure of a developing solution substantially free of silicate has been increased, it is mainly in the range of nonionic activator and pH 11.0 to 12.5. For example, it contains a development processing solution having a nonionic surfactant as a main component and having a pH of 13.0 or less (see, for example, Patent Document 6), an anionic surfactant in an amount of 1.0 to 10% by mass, and a pH of 11.0 to 12.2. No. 5 development processing solution (for example, see Patent Document 7), pH 10 to 12.5 development processing solution and the like are described (for example, see Patent Document 8).

  Moreover, the technique which mixes two types of anionic activators and a nonionic activator as a sludge suppression technique is disclosed (for example, refer patent document 9). However, in the study of a low pH alkaline developer substantially free of silicate, there has been a problem that the developability of the nonionic surfactant and the ethylene oxide-containing surfactant is greatly reduced when the pH is 11.0 or lower.

Further, in order to achieve both bright yellow safelight properties and high sensitivity, the technique using the biimidazole compound described above is advantageous, but a plate having a photosensitive layer containing the biimidazole compound is developed substantially free of silicate. When processing with a processing solution, there is a problem that development stability and processing life in a long term are short in a relatively low pH range of pH 9.0 to 11.5.
JP-A-1-105238 JP-A-2-127404 JP 2001-264978 A JP 2001-194882 A JP 2004-137152 A JP 2002-214782 A JP 2005-196143 A JP 2006-243394 A JP 2005-115376 A

  The object of the present invention is to use a surfactant that eliminates a factor that destabilizes development processing, and in a relatively low pH range of pH 9.0 to 11.5, long-term development stability and processing life. An object of the present invention is to provide a development solution and a photosensitive lithographic printing plate material which are substantially free of silicate and which are prolonged.

  The above object of the present invention can be achieved by the following configuration.

  1. A developing solution substantially free of silicate for developing a lithographic printing plate material having at least an alkali-soluble polymer on a roughened and anodized aluminum support contains an alkylene oxide chain. And 0.5 to 10.0% by mass of a surfactant having at least one group selected from a carboxylic acid group and a carboxylic acid alkali metal base.

  2. 2. The developing solution as described in 1 above, wherein the content of the silicate is 0.1% by mass or less.

  3. 3. The developing solution as described in 1 or 2 above, wherein at least one of the surfactants is an amphoteric surfactant and contains 0.1 to 10.0% by mass of the amphoteric surfactant. .

  4). In the above 1 or 2, wherein the surfactant is a fatty acid alkali metal salt, and the fatty acid of the fatty acid alkali metal salt has a fatty acid having 12 carbon atoms of 60 mass% or more of the total fatty acid. The developing processing solution as described.

  5). The surfactant has at least two groups selected from a carboxylic acid group and a carboxylic acid alkali metal base in one molecule, and an anionic surfactant having a hydrophobic group having 10 to 30 carbon atoms. 5. The developing solution according to any one of 1 to 4 above, wherein

  6). 6. The developing solution according to any one of 1 to 5, wherein the pH of the developing solution is in a range of 9.0 to 11.5.

  7. The photosensitive lithographic printing plate material, which is developed with the developing solution according to any one of 1 to 6 above, contains a compound having a polymerizable unsaturated double bond. Plate material.

  8). 8. The photosensitive lithographic printing plate material as described in 7 above, wherein the mass ratio of the alkali-soluble polymer and the compound having a polymerizable unsaturated double bond is in the range of 1: 1.4 to 1: 2.9. .

  According to the present invention, a development processing solution and a photosensitive lithographic printing plate substantially free of silicate having a long development stability and a long processing life in a relatively low pH range of pH 9.0 to 11.5. Material could be provided.

  The present invention will be described in more detail. When a surfactant containing an alkylene oxide chain is contained in the developing solution of the photosensitive lithographic printing plate material, the alkylene oxide chain is chemically adsorbed on the outermost surface of the photosensitive lithographic printing plate material, and alkali development and penetration of the surfactant are performed. In order to suppress this, the developability is destabilized. In the case of an anionic surfactant containing a sulfate ester alkali metal salt or an alkali metal sulfate salt, the dispersion and solubilization of the photosensitive composition eluted in the processing solution is insufficient, and sludge and precipitate are developed in the developing bath. In addition, the plate material is soiled due to deposition, redeposition during development processing, or clogging is caused in the filter filtration mechanism in the development processing liquid circulation mechanism, thereby destabilizing the development processing. In the present invention, by using a surfactant that eliminates the factors that destabilize the development processing, long-term development stability and long processing life can be achieved in a relatively low pH range of pH 9.0 to 11.5. Achieved.

  In the present invention, “substantially free of silicic acid or alkali metal silicate” means that the content of silicate in the developer is 0.1% by mass or less. Preferably, it is 0.01 mass% or less.

  Hereinafter, the surfactant that can be used in the developing solution of the present invention will be described first.

(Surfactant)
The surfactant having no alkylene oxide group of the present invention and having a carboxylic acid is an amphoteric surfactant, a fatty acid alkali metal salt, or two or more carboxylic acid groups in one molecule, and carbon. An anionic surfactant having several to 30 hydrophobic groups can be exemplified.

  Hereinafter, each surfactant will be described.

(Amphoteric surfactant)
Examples of the amphoteric surfactant that can be used in the present invention include fatty acid amide betaines such as sodium lauroylmethylalanine, sodium lauroylmethylglycine, alkylamino fatty acids, amidopropyl betaine laurate, alkylbetaines, and 2-alkyl-N. -Carboxymethyl-N-hydroxyethylimidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium, N -Imazolium betaines such as coconut oil fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine sodium, amide propyl dimethylamine oxide laurate, dimethyl Uril amine oxide, dimethyl stearyl amine oxide, amine oxides, such as shaped hydroxyethyl lauryl amine oxide, such as hydroxyalkyl (C12-14) hydroxyethyl methyl glycine and the like.

(Fatty acid alkali metal salt)
The fatty acid of the fatty acid alkali metal salt that can be used in the present invention includes butyric acid (butyric acid), valeric acid (valeric acid), caproic acid, enanthic acid (heptylic acid), caprylic acid, pelargonic acid, capric acid, lauric acid , Myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, 6,9,12-linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid, 5,8 , 11-icosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melissic acid, coconut oil fatty acid, beef fat acid, soybean oil acid and the like. Examples of fatty acid alkali metal salts that can be used in the invention include these alkali metal salts, and alkali metal salts of coconut oil fatty acid, lauric acid, and soybean oil acid are particularly preferable. Among these, fatty acid alkali metal salts containing 90% or more of all fatty acids are preferred.

(Anionic surfactant having two or more of at least one selected from a carboxylic acid group and a carboxylic acid alkali metal base in one molecule and a hydrophobic group having 10 to 30 carbon atoms)
An anionic surfactant having at least any two selected from carboxylic acid groups and carboxylic acid alkali metal bases in one molecule that can be used in the present invention and having a hydrophobic group having 10 to 30 carbon atoms Specific examples are given below.

Alkali metal salt of laurylaminodiacetic acid,
An alkali metal salt of an ester of ethylenediaminetetraacetic acid and an alcohol having 10 to 30 carbon atoms,
Alkali metal salts of the following 2-chain 2-hydrophilic surfactants, etc.

  The developing solution of the present invention is preferably an alkaline aqueous solution having a pH of 9 to 11.5 containing an alkaline agent. Hereinafter, components contained in the developing solution of the present invention will be described.

(Alkaline agent)
Examples of the alkaline agent include dibasic sodium phosphate, potassium, and ammonium; sodium bicarbonate, potassium, and ammonium; sodium carbonate, potassium, and ammonium; sodium bicarbonate, potassium, and ammonium; sodium borate, Examples thereof include inorganic alkaline agents such as potassium and ammonium; sodium hydroxide, potassium, ammonium and lithium.

  Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.

  Examples of these alkali salts include phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid and sugar alcohols and saccharose of non-reducing sugars. Particularly, carbonic acid and non-reducing sugar sugar alcohols have a buffering action in an appropriate pH range. preferable.

  The proportion of these acidic substances in the developing solution is preferably 0.1 to 10% by mass, and more preferably 0.1 to 4% by mass.

(Organic carboxylic acid)
An organic carboxylic acid can be further added to the development processing solution and replenisher used in the present invention, if necessary.

  The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring or the like, and specifically includes o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3, There are 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Naphthoic acid is particularly effective.

  The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility. The content of the organic carboxylic acid in the development processing solution used in the present invention is not particularly limited, but if it is less than 0.1% by mass, the effect is not sufficient, and if it is 10% by mass or more, the effect can be further improved. Not only can it interfere with dissolution when used in combination with other additives. Therefore, a preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution at the time of use.

(Other)
In addition to the above, the following additives can be added to the developing solution and replenisher used in the present invention in order to improve the developing performance. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, complexes such as [Co (NH) ³ ] ₆ Cl ₃ described in JP-A-59-121336, JP-A-56 Ampholytic polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-142258, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, JP And organic boron compounds described in JP-A-59-84241. The development processing solution and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softening agent, and the like, if necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, methyliminodiacetic acid, β-alaninediacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetrimethyl. Aminopolycarboxylic acids such as acetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), Ethylenediaminetetra (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 and the hardness and amount of hard water used. It is 5 mass%, More preferably, it is the range of 0.01-0.5 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 developing solution and replenisher is water. The conductivity of the obtained developing solution is more preferably in the range of 3 to 20 mS / cm.

(Automatic processor)
The automatic processor that can be used in the present invention is preferably provided with a mechanism for automatically replenishing a replenisher with a required amount in a developing bath, and preferably provided with a mechanism for discharging a developing solution exceeding a certain amount. Preferably, a mechanism for automatically replenishing the required amount of water to the developing bath is provided, and preferably a mechanism for detecting plate passing is provided, preferably based on detection of plate passing. A mechanism for estimating the processing area of the plate is provided, and preferably the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on the detection of the plate and / or the estimation of the processing area is provided. A mechanism for controlling, preferably a mechanism for controlling the temperature of the developing solution, and preferably a mechanism for detecting the pH and / or conductivity of the developing solution. Ku is a mechanism for controlling the replenishment amount and / or replenishment timing of replenishment solution and / or water attempts to replenish the pH and / or conductivity of the developing solution based has been granted.

  The automatic processor may have a pretreatment unit that immerses the plate in the pretreatment liquid before the development step. The pretreatment unit is preferably provided with a mechanism for spraying the pretreatment liquid onto 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. Preferably, a mechanism for rubbing the plate surface with a roller-like brush is provided. Moreover, water etc. are used as this pretreatment liquid.

(Post-processing)
The developed plate 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. For the post-treatment of the PS plate of the present invention, these treatments can be used in various combinations. For example, a post-development → water wash → surfactant-containing rinse solution treatment or development → water wash → finisher solution treatment is a rinse solution. And less finisher fluid fatigue. 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 an automatic developing machine 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. A method is also known in which a small amount of washing water after development is supplied to the plate surface for washing, and the waste solution is reused as dilution water for the developing solution 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 buffer to the gum solution to remove an alkali component of the developing solution, and in addition, a hydrophilic polymer compound, a chelating agent, a lubricant, a preservative, a solubilizer, 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.

(Protective layer-washing water before development)
In the present invention, a photosensitive lithographic printing plate material in which an overcoat layer is provided on a photosensitive layer is preferably used.

  As the overcoat layer, the one whose main component is polyvinyl alcohol can be used, and by controlling the other additives to an appropriate mixing ratio, it is excellent in handleability without film peeling and has an effect of improving printing durability. To be obtained.

In particular, the content of polyvinyl alcohol is preferably 50 to 85% by mass with respect to the total solid content of the overcoat layer, and preferably within the range of 0.5 to 10 g / m ² , and further the content is 70 to 85. The mass% is particularly preferably in the range of 1 to 5 g / m ² .

  In the plate making method according to the present invention, in the case of a photosensitive lithographic printing plate material having an overcoat layer, it is preferable to have a water washing step of removing the overcoat layer before the development treatment, but the water temperature during the water washing treatment is 10 It is particularly preferable to set the temperature to ˜40 ° C. from the viewpoint of maintaining a long-term stable development processing.

  As described above, in the plate making method according to the present invention, the photosensitive lithographic printing plate material has an overcoat layer containing 50 to 85% by mass of polyvinyl alcohol, and before the development treatment, before development at 10 to 40 ° C. A plate making method including a step of treating with washing water is a preferred embodiment.

  The washing water temperature is more preferably within a range of ± 10 ° C. with respect to the temperature of the developing solution.

  The cleaning solution used in the cleaning step before development is usually water, but various additives can be added as necessary.

  The development treatment may be performed immediately after completion of the pre-development washing step, or the development treatment may be carried out 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.

(printing)
The photosensitive lithographic printing plate material of the present invention is subjected to printing after plate making. In recent years, the printing industry has been screaming for environmental protection, and in printing inks, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are becoming popular. This is particularly noticeable when the printing inks are used. Examples of environmentally friendly printing inks include soybean oil ink “Naturalis 100” manufactured by Dainippon Ink and Chemicals, VOC zero ink “TK Hi-Echo NV” manufactured by Toyo Ink, and process ink “Soyselbo” manufactured by Tokyo Ink. It is done.

(Photosensitive planographic printing plate material)
(Aluminum support)
An aluminum plate is used as the support for the photosensitive lithographic printing plate material used in the present invention. 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, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. . Further, the aluminum support having a roughened surface is used for water retention.

  Prior to roughening (graining treatment), it is preferable to perform 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. In this case, the substrate is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof and desmutted. 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 electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable.

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 amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . 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 roughing, or the mechanical surface roughening method followed by the electrochemical surface roughening method. You may roughen.

  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.

  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 the present invention, it is preferable to perform a hydrophilic treatment after performing these treatments. Hydrophilization treatment is not particularly limited, but a water-soluble resin such as polyvinylphosphonic acid, a polymer and copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or Undercoat with yellow dye or amine salt can be used. Furthermore, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-5-304358 is covalently used.

  Preferably, the support surface is hydrophilized with polyvinylphosphonic acid. The 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 0.05 to 3% aqueous solution. The treatment temperature is preferably 20 to 90 ° C., and 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 arithmetic average roughness (Ra) of the surface on the photosensitive layer side of the obtained aluminum support is preferably 0.4 to 0.6 μm, and is controlled by a combination of hydrochloric acid concentration, current density, and electric quantity in the roughening treatment. I can do it.

(Alkali-soluble polymer)
Examples of the alkali-soluble polymer used in 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, shellacs, and others. Natural resins can be used. Two or more of these may be used in combination.

  A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Further, the copolymer composition of the alkali-soluble polymer 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 preferable.

  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 alkali-soluble polymer 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.

  The vinyl polymer can be produced by ordinary solution polymerization. It can also be produced by bulk polymerization or suspension polymerization. The polymerization initiator is not particularly limited, and examples thereof include azobis-based radical generators such as 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyro). Nitrile) and the like. Moreover, the usage-amount of these polymerization initiators is 0.05-10.0 mass parts normally with respect to 100 mass parts of whole monomers used for forming a copolymer (preferably 0.1-5 mass). Part). Examples of the solvent used for the solution polymerization include ketone-based, ester-based, and aromatic-based organic solvents, among which toluene, ethyl acetate, benzene, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, and the like. In general, a good solvent for an acrylic polymer is used, and a solvent having a boiling point of 60 to 120 ° C. is particularly preferable. In the case of solution polymerization, the above solvent is used, and the reaction temperature is usually 40 to 120 ° C. (preferably 60 to 110 ° C.) and the reaction time is usually 3 to 10 hours (preferably 5 to 8 hours). it can. After completion of the reaction, the solvent is removed to obtain a copolymer. Further, the double bond introduction reaction described later can be carried out without removing the solvent.

  The molecular weight of the resulting copolymer can be adjusted by adjusting the solvent used and the reaction temperature. The solvent, reaction temperature, and the like used to obtain the desired molecular weight copolymer can be appropriately determined depending on the monomer used. Moreover, the molecular weight of the copolymer obtained can also be adjusted by mixing a specific solvent with the said solvent. Examples of such a solvent include mercaptans (for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, etc.), carbon tetrachloride (for example, carbon tetrachloride, butyl chloride, propylene chloride). Etc.). The ratio of mixing these solvents with the solvent used in the above reaction can be appropriately determined depending on the monomer, solvent, reaction conditions, etc. used in the reaction.

  Furthermore, the alkali-soluble polymer of the present invention is preferably a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain. For example, 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. Are also preferred as alkali-soluble polymers.

  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. An unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer is also an alkali. Preferred as a soluble polymer. Compounds having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α'-dimethylbenzyl. Isocyanates are preferred, and (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate and the like can be mentioned.

  A known method can be used for the addition reaction of 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. For example, the reaction temperature is 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is 2 to 10 hours, preferably 3 to 6 hours. Can do. Examples of the solvent to be used include those used in the polymerization reaction of the vinyl copolymer. In addition, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the alicyclic epoxy group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary.

  Here, the catalyst is preferably an amine-based or ammonium chloride-based material, and specifically, the amine-based material is triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, n-propylamine. , Isopropylamine, 3-methoxypropylamine, butylamine, allylamine, hexylamine, 2-ethylhexylamine, benzylamine, and the like, and ammonium chloride-based substances include triethylbenzylammonium chloride and the like.

  When using these as a catalyst, what is necessary is just to add in 0.01-20.0 mass% with respect to the alicyclic epoxy group containing unsaturated compound to be used. In addition, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone 2,5-diphenyl-p-benzoquinone and the like, and the amount used is 0.01 to 5.0% by mass with respect to the alicyclic epoxy group-containing unsaturated compound to be used. The progress of the reaction may be determined by measuring the acid value of the reaction system and stopping the reaction when the acid value becomes zero.

  A known method can be used for the addition reaction of a compound having a (meth) acryloyl group and an isocyanate group in the molecule to a hydroxyl group present in the molecule of the vinyl polymer. For example, the reaction temperature is usually 20 to 100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point (under reflux) of the solvent used, and the reaction time is usually 2 to 10 hours, preferably 3 to 6 hours. It can be carried out. Examples of the solvent to be used include solvents used in the polymerization reaction of the polymer copolymer. Further, after the polymerization reaction, the solvent can be used as it is for the introduction reaction of the isocyanate group-containing unsaturated compound without removing the solvent. The reaction can be performed in the presence of a catalyst and a polymerization inhibitor as necessary. Here, the catalyst is preferably a tin-based or amine-based substance, and specific examples include dibutyltin laurate and triethylamine.

  The catalyst is preferably added in the range of 0.01 to 20.0 mass% with respect to the compound having a double bond to be used. In addition, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone 2,5-diphenyl-p-benzoquinone and the like, and the amount used is usually 0.01 to 5.0% by mass with respect to the isocyanate group-containing unsaturated compound to be used. The progress of the reaction may be determined by determining the presence or absence of an isocyanato group in the reaction system using an infrared absorption spectrum (IR), and stopping the reaction when the absorption disappears.

  The vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain used in the present invention is preferably 50 to 100% by mass, and 100% by mass in the total alkali-soluble polymer. Is more preferable.

  The content of the alkali-soluble polymer in the photosensitive composition applied and formed as the photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and in the range of 20 to 50% by mass. It is particularly preferable from the viewpoint of sensitivity.

  The molecular weight of the alkali-soluble polymer according to the present invention is preferably 10,000 to 150,000, particularly preferably 25,000 to 60,000 in terms of weight average molecular weight.

  The content of the alkali-soluble polymer in the photopolymerizable photosensitive layer applied and formed as the photosensitive layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and 20 to 50% by mass. It is particularly preferable from the viewpoint of sensitivity to use in the above range.

  The alkali-soluble polymer according to the present invention is a resin that dissolves in an aqueous potassium hydroxide solution having a pH of 11 at a concentration of 0.1 g / L or more at 25 ° C.

  The acid value of the alkali-soluble polymer is preferably in the range of 20 to 200 mgKOH / g, particularly preferably 40 to 130 mgKOH / g.

  The acid value is measured according to the neutralization value test method (JIS K2501), and is expressed in mg of potassium hydroxide corresponding to the amount of acidic substance contained in the alkali-soluble polymer.

(Compound having a polymerizable unsaturated double bond)
The compound having a polymerizable unsaturated double bond used in the present invention is a compound that can be polymerized by image exposure. General radical polymerizable monomers, polyfunctional monomers having a plurality of polymerizable unsaturated double bonds generally used for ultraviolet curable resins, and polyfunctional oligomers can be used.

  Preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, Monofunctional acrylic acid esters such as acrylate of 1,3-dioxane alcohol ε-caprolactone adduct, 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, or maleate , Crotonic acid, maleic acid esters such as ethylene glycol diacrylate, triethylene glycol Diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypentylate neopentyl glycol diacrylate, neopentyl glycol adipate di Acrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexanediol Difunctional acrylates such as diacrylate of diglycidyl ether, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester such as trimethylolpropane triacrylate in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone of dipentaerythritol hexaacrylate Additives, pyrogallol triacrylate, propionic acid / dipipe Polyfunctional acrylic acid such as taerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate , Itaconic acid, crotonic acid, maleic acid ester and the like.

  Particularly preferably, it is a polymerizable compound containing a tertiary amino group in the molecule, and there is no particular limitation on the structure, but a tertiary amine compound having a hydroxyl group is selected from glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride, etc. Those modified with are preferably used.

  Specifically, polymerizable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Further, in the present invention, 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 also preferably used. . In particular, a compound having a tertiary amino group and an amide bond is preferably used.

  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) -1,2-propanediol - but Le and the like, but are not limited thereto.

  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- 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. In Not a constant.

  As a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3- Examples include dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.

  Specific examples of these 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. .

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) M-6: Reaction product of triethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-7: ethylenediaminetetraethanol (1 mol), 1,3-bis (1-isocyanate-1-methylethyl) benzene (4 mol), reaction product of 2-hydroxyethyl methacrylate (4 mol) Addition having a tertiary amine group in the molecule The content of the polymerizable ethylenically unsaturated bond-containing compound is preferably 30 to 80% by mass, preferably 30 to 60% by mass with respect to the photosensitive layer. There it is more preferable.

(Photopolymerization initiator)
The photopolymerization initiator according to the present invention generates radicals by light irradiation, electron transfer from the sensitizer, or energy transfer, but the generated radicals have a small contribution as a polymerization initiation point and are more than the peripheral hydrogen donor compound. It is a compound capable of generating radicals with high polymerization initiation ability through electron transfer and proton transfer.

  Examples of the photopolymerization initiator include biimidazole compounds, aromatic carbonyl compounds, and thioxanthone compounds, and biimidazole compounds are particularly preferably used.

  Preferable examples of the aromatic carbonyl compound include “RADIATION CURING IN POLYMERSCIENCE AND TECHN OLOGY”, J. Org. P. FOUASSIER J.M. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in RABEK (1993), p77 to 117.

  More preferable examples of aromatic carbonyls include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, benzoin derivatives described in JP-B-47-23664, Examples thereof include aroylphosphonic acid esters described in Japanese Utility Model Publication No. 57-30704 and dialkoxybenzophenones described in Japanese Patent Publication No. 60-26483.

  A biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426.

  In the present invention, a hexaarylbiimidazole (HABI, triaryl-imidazole dimer) compound can be preferably used as the biimidazole compound.

  Processes for the production of HABIs are described in DE 1,470,154 and their use in photopolymerizable compositions is described in EP 24,629, EP 107,792, US 4,410,621, EP 215,453 and DE 3, 211 and 312.

  Preferred derivatives are, for example, 2,4,5,2 ′, 4 ′, 5′-hexaphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole. Imidazole, 2,2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4' , 5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) biimidazole, 2,2'-bis (2- Chlorophenyl) -4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -biimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4 ' -Bis (3,4-dimethyl) Xylphenyl) biimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,5 , 4 ', 5'-tetraphenylbiimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (2-ethoxyphenyl) -4,5,4 ', 5'-tetraphenylbiimidazole and 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbiimidazole.

  As the photopolymerization initiator, other polymerization initiators may be included in addition to the biimidazole compound.

  Examples of these polymerization initiators include titanocene compounds, monoalkyltriaryl borate compounds, iron arene complex compounds, and polyhalogen compounds.

  Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -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 (cyclopentadienyl) -Ti-bis-2 , 6-difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bi -2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti -Bis-2,6-difluorophenyl (IRGACURE727L: manufactured by Ciba Japan), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRGACURE784: Ciba Japan), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2, 4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-154024 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n- Butyl-trinaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-tert-butylphenyl) -borate Tetra-n-butylammonium · n-hexyl-tri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium · n-hexyl-tri- (3-fluorophenyl) -borate and the like. Can be mentioned.

  Examples of the iron arene complex compound include compounds described in JP-A-59-219307, and more preferable 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 -Xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate and the like.

(Overcoat layer)
In the lithographic printing plate precursor for scanning exposure of the present invention, an overcoat layer can be further provided on the photosensitive layer because normal exposure is performed in the air. The overcoat layer prevents exposure of low molecular weight compounds such as basic substances present in the atmosphere that interfere with the image formation reaction caused by exposure in the photosensitive layer, and enables exposure in the air. . Therefore, the characteristics desired for such an overcoat layer are low permeability of the low molecular weight compound, and further, transmission of light used for exposure is not substantially inhibited, and adhesion to the photosensitive layer is excellent, and It is desirable that it can be easily removed in the development step after exposure. Such an overcoat layer has been conventionally devised and described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the overcoat layer, for example, a water-soluble polymer compound that is relatively excellent in crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as polyacrylic acid are known, but among these, the use of polyvinyl alcohol as the main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the overcoat layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100 mol% and a molecular weight in the range of 300 to 2400 in terms of weight average molecular weight.

  Specifically, Mowiol 3-85, Mowiol 4-88, Mowiol 8-88, Mowiol 13-88, Mowiol 40-88, Mowiol 30-92, Mowiol 4-98, Mowiol 4-98, Mowiol manufactured by Kuraray Co., Ltd. 10-98, Mowiol 20-98, Mowiol 30-98, Mowiol 56-98, Mowiol 15-99, Mowiol 28-98, Mowiol 4-88 low ash, Mowiol 8-88 low ash, Mowiol 40-88 low ash, Mowiol 4-98 low ash, Mowiol 56-98 low ash, Mowiol 28-98 low ash, KL-118, KL318, KL-506, SD-1000, CM-3 18, R-1130, R-2105, R-3109, and the like.

  The components of the overcoat layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to low molecular substance blocking properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the overcoat layer), the higher the film thickness, the higher the blocking of low-molecular substances and the more advantageous in terms of sensitivity. is there. However, if the blocking property of the low molecular weight substance is extremely increased, problems such as unnecessary polymerization reaction during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic polymer layer, film peeling due to insufficient adhesion tends to occur. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, in U.S. Pat. Nos. 292501 and 44563, 20-60 mass% of an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer is mixed in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesion can be obtained by laminating on a polymerized layer. Any of these known techniques can be applied to the overcoat layer in the present invention. Such an overcoat layer coating method is described in detail, for example, in US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the overcoat layer. For example, when laser light is used as the light source, the photosensitive composition is excellent in photosensitivity at the wavelength of the light source, but may not be sensitized at other wavelengths. For example, if the light source is in the infrared region of 750 nm or more, it can be used in a substantially bright room, but in fact, it may be sensitive to short-wave light such as light from a fluorescent lamp. In that case, it is preferable to add a colorant (such as a water-soluble dye) that is excellent in light transmittance of the light source and can efficiently absorb light having a wavelength of less than 700 nm. As another example, if the light source is in the ultraviolet region of 450 nm or less, it can be used under a safelight substantially. However, in actuality, there are cases where exposure is made with visible light of 500 nm or more. In that case, the addition of a colorant (such as a water-soluble dye) that excels in light transmittance of the light source and can efficiently absorb light of 500 nm or more can further enhance the suitability for safelight without causing a decrease in sensitivity. be able to.

The amount of polyvinyl alcohol in the overcoat layer according to the present invention is preferably 50 to 99% by mass and the dry mass is 0.5 to 10 g / m ² with respect to the total solid content of the overcoat layer. .

In particular, it is preferable that polyvinyl alcohol is 70 to 95% by mass with respect to the total solid content of the overcoat layer and is in the range of 0.5 to 3 g / m ² .

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

"Synthesis of alkali-soluble polymers"
In a three-necked flask under a nitrogen stream, put 18 parts of methacrylic acid, 82 parts of methyl methacrylate, 400 parts of propylene glycol monomethyl ether acetate and 3 parts of α, α'-azobisisobutyronitrile, and oil at 80 ° C. in a nitrogen stream. The reaction was performed for 6 hours in the bath. Thereafter, the mixture was refluxed for 1 hour at the boiling point of propylene glycol monomethyl ether acetate to obtain polymer-1. The weight average molecular weight measured using GPC was about 45,000, and the acid value was 115 mgKOH / g. (Solid content 20% solution)
"Synthesis of compounds with polymerizable unsaturated double bonds"
In a 2 liter four-necked separable flask equipped with a stirrer, temperature controller, thermometer and condenser, 431 g of propylene glycol methyl ether acetate, 168 g of hexamethylene diisocyanate (1.0 mol), 2-hydroxyethyl methacrylate 182 g (1.4 mol) was added, 0.2 g of hydroquinone monomethyl ether was added, and 0.3 g of di-n-butyltin dilaurate was added at 40 to 50 ° C. and reacted for 30 minutes. Further, 38.8 g (0.3 mol) of 2- (2-hydroxyethyl) piperidine was added and reacted for 3 hours, and 50% by mass of propylene glycol methyl ether of a compound having a polymerizable unsaturated double bond (the following oligomer 1). An acetate solution was obtained.

(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, this aluminum plate was subjected to electrolytic surface roughening with an alternating current for 20 seconds under conditions of 28 ° C. and a current density of 100 A / dm ^{2 in} a 0.3 mass% hydrochloric 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, and further 0.3% polyvinylphosphone Hydrophilic treatment was performed at 75 ° C. with an acid solution to prepare a support. A support having a center line average roughness (Ra) of 0.45 microns was obtained.

(Preparation of photosensitive lithographic printing plate material 1)
On the above support, a photosensitive layer coating solution having the following composition was applied with a wire bar so that the drying rate was 1.6 g / m ² , dried at 95 ° C. for 1.5 minutes, and then an oxygen barrier layer coating solution. Was coated with a wire bar so as to be 2.0 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes to obtain a photosensitive lithographic printing plate material 1.

(Photosensitive layer coating solution)
Compound having a polymerizable unsaturated double bond: pentaerythritol tetraacrylate
10.0 parts Oligomer 1 solution 87.2 parts Alkali-soluble polymer: Polymer-1 solution 148.9 parts Polymerization initiator: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5 ′ -Tetraphenylbisimidazole 4.0 parts Chain transfer agent-1: 1.2 parts of the following compound 1.2 parts Visible image agent: MHI # 454 (methyl ethyl ketone dispersion with a solid content of 35%) (manufactured by Mikuni Dye Co., Ltd.) 15.4 Part Sensitizing dye: Sensitizing dye 1 below 6 parts Solvent: Propylene glycol monomethyl ether 727.2 parts

(Overcoat layer coating solution)
Polyvinyl alcohol (Mowiol 4-98: manufactured by Kuraray Europe)
40.0 parts polyvinyl alcohol (Mowiol 4-88: manufactured by Kuraray Europe Ltd.)
40.0 parts vinylpyrrolidone / vinyl acetate copolymer (Rubitec VA64W: manufactured by BASF)
20.0 parts Surfinol 465 (produced by Air Products) 0.2 parts Water 900 parts (Preparation of photosensitive lithographic printing plate materials 2 to 7)
Using the photosensitive layer coating solutions 2 to 7 shown in Table 1 below, the photosensitive lithographic printing plate material 1 was prepared in the same manner as described above to obtain photosensitive lithographic printing plate materials 2 to 7.

(Image formation)
The produced photosensitive lithographic printing plate materials 1 to 7 have a plate setter (MAKO4: manufactured by ECRM) equipped with a light source having a laser of 405 ± 5 nm and 60 mW, and the area ratio of the image part to the non-image part is , Exposure energy: 35 μJ / cm ² , image exposure at a resolution of 2540 dpi / 175 lpi (exposure pattern is 100% image area, 98%, 97%, 96%, 95%, 93%, 90%, 85%, 80%, 50%, 20% 10%, 8%, 5%, 4%, 3%, 2%, 1% square dots (dpi is 1 inch, ie 2.54cm In this case, lpi represents the number of lines per inch, that is, 2.54 cm).

Next, a preheating portion that is heated so that the plate surface temperature becomes 100 ° C., a pre-water washing portion that removes the overcoat layer before development, a developing portion that is filled with a developing solution having the composition described in Tables 2 to 4 below, and the plate surface CTP automatic developing machine (Raptor 68P: GLUNZ & JENSEN) equipped with a washing section for removing the developing solution adhering to the surface and a gum solution (GW-3: manufactured by Mitsubishi Chemical Corporation) for protecting the image area And a replenishment solution having a pH higher by 0.1 or more than the development processing solution so that the pH of the development processing solution is the same as the initial value. A development process of 600 m ² was performed for 4 weeks with a combination of photosensitive lithographic printing plate materials to obtain a lithographic printing plate. The plate surface temperature during actual plate making was 95 to 105 ° C. The time during which the photosensitive lithographic printing plate material was in contact with the developing solution was defined as the development time, and the development time using the automatic processor was 18 seconds.

(Development processing solution 1) (1 l aqueous solution formulation)
50g potassium laurate
Ethylenediaminetetraacetic acid disodium salt 0.6g
Potassium hydroxide Addition amount at the following pH The remaining components are water pH 10.5
(Development processing solutions 2-31 and comparative development processing solutions 1-8)
In developing solution 1, potassium laurate and pH were changed as shown in Tables 2 to 4 to prepare developing solutions 2 to 31 and comparative developing solutions 1 to 8 (Comparative 1 to 8 in Table 3).

(Evaluation of printing stains)
The lithographic printing plate produced and developed using the automatic developing machine was coated with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), coated paper, printing ink (manufactured by Dainippon Ink & Chemicals, Inc. Printing was performed using soybean oil ink “Naturalis 100”) and fountain solution (Tokyo liquid ink H liquid SG-51 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 of development stability)
The dot area of 5%, 50%, and 90% was measured with a dot meter for every 100 m ^{2 of the} development treatment, and halftone dot repeat reproduction was evaluated.

(Evaluation of clogging of liquid life filter)
Using a 50 micron cartridge filter in the developing solution circulating system of the automatic developing machine, the amount of the circulating solution was measured after 600 m ² treatment to evaluate filter clogging. When the amount of liquid was less than 80%, the filter was clogged, and it was judged that there was a high possibility of printing stains unless the filter was washed or replaced.

A: 90% or more B: 85% or more, less than 90% Δ: 80% or more, less than 85% ×: less than 80% The results obtained above are shown in Tables 5-7.

  As is clear from Tables 5 to 7, the surfactant having no alkylene oxide chain and having a carboxylic acid group or a carboxylic acid alkali metal base is excellent in reproducibility of halftone dots without printing stains. It is a long-life developing solution with little clogging and excellent development stability.

  This is a development processing solution having a small variation with respect to pH, which is an index of the activity of the development processing solution. Especially, in the range of pH = 9.0 to 11.5, printing smear does not occur, and it is excellent in repeated dot reproduction. It can be seen that the developing solution has a long life with little filter clogging.

  Further, a long-life developing processing solution which is dependent on the carbon number distribution of the fatty acid salt, and particularly excellent in development stability and halftone dot reproducibility when the laurate is 60% or more can be obtained.

Claims (8)

A developing solution substantially free of silicate for developing a lithographic printing plate material having at least an alkali-soluble polymer on a roughened and anodized aluminum support contains an alkylene oxide chain. And 0.5 to 10.0% by mass of a surfactant having at least one group selected from a carboxylic acid group and a carboxylic acid alkali metal base. 2. The developing solution according to claim 1, wherein the content of the silicate is 0.1% by mass or less. The development processing according to claim 1, wherein at least one of the surfactants is an amphoteric surfactant and contains 0.1 to 10.0% by mass of the amphoteric surfactant. liquid. The surfactant is a fatty acid alkali metal salt, and the fatty acid of the fatty acid alkali metal salt has a fatty acid having 12 carbon atoms of 60 mass% or more of the total fatty acid. The development processing solution as described in 1. The surfactant has at least two groups selected from a carboxylic acid group and a carboxylic acid alkali metal base in one molecule, and an anionic surfactant having a hydrophobic group having 10 to 30 carbon atoms. The development processing solution according to any one of claims 1 to 4, wherein The development processing solution according to any one of claims 1 to 5, wherein the pH of the development processing solution is in a range of 9.0 to 11.5. The photosensitive lithographic printing plate material developed by the developing solution according to any one of claims 1 to 6 contains a compound having a polymerizable unsaturated double bond. Printing plate material. The photosensitive lithographic printing plate according to claim 7, wherein the mass ratio of the alkali-soluble polymer and the compound having a polymerizable unsaturated double bond is in the range of 1: 1.4 to 1: 2.9. material.