JP2005134657A - Method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing solution and a method for forming an image by which an image with excellent developing property and plate wear can be formed, development sludge accumulating in a developing bath in a developing process can be significantly decreased, and the process can be stably carried out for a long period. <P>SOLUTION: A negative image forming material is developed by using the following developing solution. The developing solution contains at least one kind of carbonate and at least one kind of hydrogen carbonate and a nonion aromatic ether-based surfactant expressed by formula of X-Y-O-(A)n-(B)m-H, wherein X represents an aromatic group, Y represents a single bond or a 1-10C alkylene group, A and B are different groups from each other and represent either -CH<SB>2</SB>CH<SB>2</SB>O- or -CH<SB>2</SB>CH(CH<SB>3</SB>)O-, and each of n and m represents 0 or an integer of 1 to 100, by 1.0 mass% to 10 mass%, and the solution has pH 8.5 to 11.5 and the electric conductivity x in the range of 30<x<100 mS/cm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a developer useful for a negative type image forming material capable of direct plate making by scanning a visible light laser based on a digital signal from a computer or the like, and an image forming method using the developer. About.

Conventionally, as a lithographic printing plate, a PS plate having a configuration in which a lipophilic photosensitive resin layer is provided on a hydrophilic support is widely used. The desired printing plate was obtained by dissolving and removing the image area.
In recent years, digitization technology for electronically processing, storing, and outputting image information by a computer has become widespread, and various new image output methods corresponding to it have come into practical use. As a result, CTP technology that scans highly directional light such as laser light in accordance with digitized image information and directly produces a printing plate without using a lith film is desired. Obtaining the original edition is an important technical issue.
As this light source, an Ar laser (488 nm), an FD-YAG laser (532 nm), or an InGaN-based semiconductor laser (violet laser, 350 nm to 450 nm) is employed, and this light source has photosensitivity and can ensure considerable productivity. A lithographic printing plate having a sensitive photopolymerizable photosensitive layer has been developed and put into practical use.

Most of the high-sensitivity technologies relate to photopolymerization initiation systems. For example, a combination of titanocene and coumarin dye (for example, patents) is used as a photopolymerization initiation system that is highly sensitive to Ar laser and FD-YAG laser. References 1 to 3), a combination of a styryl dye and titanocene (for example, see Patent Document 4), and a combination of a dye having a five-membered heterocyclic acidic nucleus and titanocene (for example, see Patent Document 5). It is disclosed.
Photopolymerization initiation systems with high sensitivity to violet laser include combinations of naphthofuranone dyes and titanocene (for example, see Patent Document 6), combinations of carbazolyl styryl dyes and titanocene (for example, Patent Documents). 7, etc.) are known.

On the other hand, in order to stably develop the function as a lithographic printing plate, the development processability is required to have a large solubility difference (discrimination) between the exposed and unexposed areas. Although it is disclosed that it is improved to some extent by adding a specific surfactant (see, for example, Patent Document 8), it is important to further reduce the damage to the image area in order to impart performance. And the developer always maintains stable activity.
However, for example, it has been reported that a strongly alkaline aqueous solution containing potassium silicate or the like and having a pH exceeding 12.5 is used for developing a negative type image forming material using a photopolymerizable composition (Patent Document). 9), such a high pH developer has a problem in that the image portion is greatly damaged and the printing durability is insufficient. In addition, if the development process is continued for a long period of time, the carbon dioxide gas absorption amount of the developer changes due to changes in the environment, for example, the concentration of carbon dioxide, and the developer activity fluctuates. In addition, the plate material component accumulates in the development layer, causing problems such as clogging of piping.
On the other hand, the photosensitive resin composition layer formed on the surface of the glass substrate is developed with, for example, a mixed aqueous solution of sodium carbonate and sodium bicarbonate having a pH of about 10 in order to suppress the deterioration of the development performance due to the repeated use over time. (For example, refer to Patent Document 10 and Patent Document 11).

  However, when the present inventors applied these developers to a lithographic printing plate precursor having a photosensitive layer of a photopolymerizable photosensitive resin composition on the surface of an aluminum support, the developability in non-image areas was sufficient. I could not say. Moreover, in order to solve the problem of developability of a photoresist in which a pigment is dispersed, an alkali developer added with an alkylphenol surfactant has been reported (see Patent Document 12), but still sufficient developability and Printing durability was not obtained.

JP-A-9-268185 JP-A-6-192309 Japanese Patent Laid-Open No. 10-204085 Japanese Patent Laid-Open No. 9-80750 JP-A-10-101719 JP 2000-206690 A JP 2001-42524 A JP 2003-43703 A JP-A-8-108621 JP-A-5-88377 JP-A-11-65126 Japanese Patent Laid-Open No. 10-239858

  An object of the present invention is to form an image with excellent printing durability, excellent stain resistance, hardly cause deterioration in developability over time due to the characteristics of the developer, and accumulate in a developing bath during development processing. It is an object of the present invention to provide an image forming method capable of remarkably reducing development waste and performing stable processing for a long period of time.

  The present inventor has disclosed a photopolymerization type in which an image recording layer comprising a photopolymerization initiation system sensitive to light in the visible light to ultraviolet wavelength region, a polymerizable compound having at least one ethylenically unsaturated group, and a binder polymer is formed. After image exposure of the image forming material, the non-image area developability is developed by developing with a carbonate-based developer containing a specific nonionic surfactant and having a conductivity within a certain range and a pH of 8.5 to 11.5. As a result, the present inventors have found that sufficient developability, printing durability and stain resistance can be ensured, and have achieved the above-mentioned problems and completed the present invention.

Therefore, the present invention forms on the support an image recording layer comprising a photopolymerization initiation system sensitive to light in the visible to ultraviolet wavelength range, a polymerizable compound having at least one ethylenically unsaturated group, and a binder polymer. After the image-exposed photopolymerizable image-forming material is image-exposed, it is selected from the group consisting of a nonionic aromatic ether surfactant of the following formula (1), which contains at least one carbonate and at least one bicarbonate. And developing at least one kind of a surfactant having a pH of 8.5 to 11.5 and a conductivity x of 30 <x <100 mS / cm. The present invention relates to an image forming method.
X-Y-O- (A) n- (B) m-H (1)
(In the formula, X represents an aromatic group which may have a substituent, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, A and B are groups different from each other, and- Represents either CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, n and m each represents 0 or an integer of 1 to 100, provided that n and m are not 0 at the same time, and n Or, when either m is 0, n and m are not 1.)

  When a developer containing the compound represented by the above formula is used for developing an exposed photopolymerization type image forming material, it is excellent in developability even in a relatively low pH state that is not easily affected by carbon dioxide gas, and can be applied to an image area. It has been found that there is an effect of improving printing durability by reducing damage and remarkably improving resolution. Further, since it also acts as a dispersion improver for the insoluble component of the image recording layer, it has been found that the development residue accumulated in the development layer can be significantly reduced even during long-term processing.

  According to the image forming method of the present invention, sufficient developability can be secured at a low pH with little damage to the image forming material, so that both printing durability and developability can be achieved. It is difficult to lower even with gas, and there is no problem with development residue.

The image forming method of the present invention will be described in detail below. First, the developer used in the image forming method of the present invention will be described.
[Developer]
The developer used in the present invention contains at least one carbonate and at least one bicarbonate, and contains 1.0 mass% to 10 mass% of a nonionic aromatic ether surfactant having a specific structure, The pH is 8.5 to 11.5, and the conductivity x is 30 <x <100 mS / cm.

(Nonionic aromatic ether surfactant)
The nonionic aromatic ether surfactant contained in the developer that can be used in the present invention is represented by the following general formula (1).
X-Y-O- (A) n- (B) m-H (1)
(In the formula, X represents an aromatic group which may have a substituent, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, A and B are groups different from each other, and- Represents either CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, n and m each represents 0 or an integer of 1 to 100, provided that n and m are not 0 at the same time, and n Or, if either m is 0, n and m are not 1.)
In the compound represented by the above formula, examples of the aromatic group of X include a phenyl group, a naphthyl group, and an anthranyl group. These aromatic groups may have a substituent. Examples of the substituent include an organic group having 1 to 100 carbon atoms. Examples of the organic group include all organic groups described for the following general formulas (IA) and (IB). In the formula, when both A and B are present, they may be random or block copolymers.

More specifically, examples of the compound represented by the above formula (1) include compounds represented by the following general formulas (IA) and (IB).

(In the above formula, R ₁ and R ₂ each represent a hydrogen atom or an organic group having 1 to 100 carbon atoms; p and q each represent 1 or 2; Y ₁ and Y ₂ each represent a single bond or a carbon atom. Represents an alkylene group of 1 to 10; r and s each represent 0 or an integer of 1 to 100, provided that r and s are not 0 at the same time, and when either r or s is 0, r And s are not 1, and r ′ and s ′ each represent 0 or an integer of 1 to 100, provided that r ′ and s ′ are not 0 at the same time and either r ′ or s ′ is 0. R 'and s' are not 1.
When p is 2 and R ₁ is an organic group having 1 to 100 carbon atoms, R ₁ may be the same or different and R ₁ may be combined to form a ring, , Q is 2 and R ₂ is an organic group having 1 to 100 carbon atoms, R ₂ may be the same or different and R ₂ may be combined to form a ring.

  Specific examples of the organic group having 1 to 100 carbon atoms include aliphatic hydrocarbon groups, aromatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, which may be saturated or unsaturated, and may be linear or branched. , Aryl group, aralkyl group, etc., alkoxy group, aryloxy group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N -Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N- Arylcarbamoyloxy group, acylamino group, N-alkylacylamino group, N-arylacyl Amino group, acyl group, alkoxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group , N-alkyl-N-arylcarbamoyl groups, polyoxyalkylene chains, and the above organic groups to which polyoxyalkylene chains are bonded. The alkyl group may be linear or branched.

Preferred examples of R ₁ and R ₂ include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group, an N-alkylamino group, N, N-dialkylamino group, N-alkylcarbamoyl group, acyloxy group or acylamino group, polyoxyalkylene chain having about 5 to 20 repeating units, aryl group having 6 to 20 carbon atoms, poly having about 5 to 20 repeating units There are aryl groups to which an oxyalkylene chain is bonded.

  In the compounds of the general formulas (IA) and (IB), the number of repeating units of the polyoxyethylene chain is preferably 3-50, more preferably 5-30. The number of repeating units of the polyoxypropylene chain is preferably 0 to 10, more preferably 0 to 5. The polyoxyethylene part and the polyoxypropylene part may be random or block copolymers.

Examples of the compound represented by the general formula (IA) include polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like.
Examples of the compound represented by the general formula (IB) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, and polyoxyethylene nonyl naphthyl ether.
Nonionic aromatic ether surfactants may be used alone or in combination of two or more in the developer.

The content of the nonionic aromatic ether surfactant in the developer is suitably 1 to 10% by mass in the developer, and more preferably 2 to 8% by mass. Here, if the addition amount is too small, the developability and the solubility of the image recording layer components are lowered. On the other hand, if the addition amount is too large, the printing durability of the printing plate is lowered.
Examples of the nonionic aromatic ether surfactant represented by the general formula (IA) or (IB) are shown below.

  In addition to the nonionic aromatic ether surfactants represented by the above general formulas (IA) and (IB), the developer used in the plate making method of the present invention may further include other interfaces described below. An active agent may be added.

Other surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, Sorbitan alkyl esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, monoglyceride alkyl esters such as glycerol monostearate, glycerol monooleate, etc. Nonionic surfactants: alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate Alkyl phthalene sulfonates such as sodium pentylnaphthalene sulfonate, sodium hexyl naphthalene sulfonate, sodium octyl naphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, dilauryl sulfosuccinate Anionic surfactants such as sulfosuccinic acid ester salts such as sodium acid salt: alkylbetaines such as lauryl betaine and stearyl betaine, and amphoteric surfactants such as amino acids can be used, but alkyl naphthalene sulfonates are particularly preferable. An anionic surfactant.
These surfactants can be used alone or in combination. The content of these surfactants in the developer is preferably from 0.1 to 20% by mass in terms of active ingredients.

  The developer used in the image forming method of the present invention contains 1.0% by mass to 10% by mass of at least one surfactant selected from the group consisting of the nonionic aromatic ether surfactants described above, and further at least one type. And at least one bicarbonate, and has a pH of 8.5 to 11.5 and a conductivity x of 30 <x <100 mS / cm. In addition, pH and electrical conductivity are the values measured at normal temperature (about 25 degreeC).

At least one carbonate and at least one bicarbonate act as an alkaline agent in the developer. Examples of the carbonate include at least one compound selected from the group consisting of inorganic alkali and organic alkali carbonates, more preferably at least one compound selected from the group consisting of inorganic alkali carbonates. Specific examples of the carbonate include sodium carbonate, potassium and ammonium, and more preferably sodium carbonate and potassium carbonate.
Examples of the hydrogen carbonate include at least one compound selected from an inorganic alkali and an organic alkali hydrogen carbonate, more preferably at least one compound selected from the group consisting of an inorganic alkali hydrogen carbonate. Specific examples of the bicarbonate include sodium bicarbonate, potassium and ammonium, and more preferably sodium bicarbonate and potassium bicarbonate.
By adjusting the concentration of carbonate in the developer to 0.005 to 1 mol / L and the concentration of bicarbonate in the developer to 0.001 to 1 mol / L, pH buffering properties can be obtained in the range of pH 8.5 to 11.0. In addition, carbon dioxide absorption is also preferable because it can be reduced.

  Moreover, it is essential that pH is 8.5-11.5, and it is preferable that it is 9.0-11.0. In addition, the conductivity x must be 30 <x <100 mS / cm, preferably 31 to 80 mS / cm, and more preferably 35 to 60 mS / cm.

Further, the conductivity can be adjusted by further adding an alkali metal salt of an organic acid or an alkali metal salt of an inorganic acid to the developer as a conductivity adjusting agent.
When the developer is made of an alkali metal salt other than a mixture of carbonate and hydrogen carbonate, the development performance deteriorates with time and repeated use even if the pH and conductivity are in the above ranges. Further, even in the case of a mixture of carbonate and bicarbonate, if the pH falls below the above range, image formation becomes impossible, and if it exceeds the above range, the development performance is deteriorated due to deterioration due to carbon dioxide gas in the air. A decrease occurs. Further, if the conductivity is lower than the above range, elution of the image recording layer composition on the surface of the aluminum plate support becomes difficult and image formation cannot be performed, and if it exceeds the above range, a remaining film is formed in the non-image area. In both cases, the development performance deteriorates.

  The developer may be prepared by adding and dissolving both alkali metal carbonate and hydrogen carbonate in the same water, or may be prepared by mixing respective aqueous solutions of both. .

  Further, the developer includes an inorganic agent such as tribasic sodium phosphate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium, and lithium as an alkaline agent. Alkaline agents and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropyl Use organic alkali agents such as panolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide alone or in combination. It may be mixed and used together look.

The developer may contain a chelating agent. Examples of the chelating agent include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , calgon (sodium polymetaphosphate), etc. Polyethylene salt of, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; hydroxyethylethylenediaminetriacetic acid, its Potassium salt, sodium salt thereof; nitrilotriacetic acid, potassium salt thereof, sodium salt thereof; 1,2-diaminocyclohexanetetraacetic acid, potassium salt thereof, sodium salt thereof; 1,3-diamino-2-propanoltetraacetic acid, potassium salt thereof Aminopolycar, such as its sodium salt 2-phosphonobutanetricarboxylic acid-1,2,4, its potassium salt, its sodium salt; 2-phosphonobutanone tricarboxylic acid-2,3,4, its potassium salt, its sodium salt; Phosphonoethanetricarboxylic acid-1,2,2, potassium salt, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt thereof; aminotri (methylenephosphonic acid), potassium salt thereof And organic phosphonic acids such as sodium salts thereof. The optimum amount of such a chelating agent varies depending on the hardness of the hard water used and the amount used, but is generally 0.01 to 5% by mass, more preferably 0.01 to 0.5% in the developer at the time of use. It is made to contain in the range of mass%.

  In addition to the above components, the following components can be used in combination in the developer of the present invention as necessary. For example, benzoic acid, phthalic acid, p-ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, pn-butylbenzoic acid, pt-butylbenzoic acid, pt-butylbenzoic acid Organic carboxylic acids such as p-2-hydroxyethylbenzoic acid, decanoic acid, salicylic acid, 3-hydroxy-2-naphthoic acid; isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, etc. In addition, chelating agents, reducing agents, dyes, pigments, water softeners, preservatives and the like can be mentioned.

  The developer described above can be used as a developer and a developer replenisher for the exposed negative type image forming material, and is preferably applied to an automatic developing machine. When developing using an automatic developing machine, the developing solution becomes fatigued according to the amount of processing. Therefore, the processing capability may be restored using a replenishing solution or a fresh developing solution. This replenishment method is also preferably applied to the image forming method of the present invention. The effect of the present invention is particularly remarkable when the developer is used for developing an image forming material described later.

The image forming material in the present invention is formed by sequentially laminating an image recording layer and optionally a protective layer on a support, and the image recording layer is sensitive to light in the visible light to ultraviolet wavelength region. And a photopolymerization initiating system, a polymerizable compound having at least one ethylenically unsaturated group, and a binder polymer.
Here, “sequentially laminate” means that an undercoat layer, an image recording layer, and a protective layer are provided in this order on the support, and the undercoat layer and the protective layer can be provided as necessary. In addition, the existence of other layers (for example, an intermediate layer, a back coat layer, etc.) provided according to the purpose is not denied.

[Photopolymerization initiation system sensitive to light in the visible to ultraviolet wavelength range]
The photopolymerization initiation system sensitive to light in the visible light to ultraviolet wavelength range means a system containing a compound that can absorb light in the visible light to ultraviolet wavelength range and initiate photopolymerization. More specifically, a combination of a sensitizing dye having a maximum absorption wavelength in the visible light to ultraviolet wavelength region, preferably 330 to 700 nm, and a photopolymerization initiator may be mentioned. Two or more photopolymerization initiators may be used as the photopolymerization initiator (combination system). As such a photopolymerization initiation system, various sensitizing dyes (dyes) known in patents, literatures, and the like depending on the wavelength of the light source used, and a combination system of a photoinitiator or two or more photoinitiators are used. It can be appropriately selected and used. Specific examples are listed below, but are not limited thereto.

  Various photoinitiating systems have been proposed in the case of using visible light of 400 nm or more, Ar laser, second harmonic of a semiconductor laser, and SHG-YAG laser as a light source, for example, US Pat. No. 2,850,445. Certain photoreducible dyes as described in, for example, rose bengal, eosin, erythrosine, etc., or a combination of a dye and an initiator, for example, a combined initiator system of a dye and an amine (Japanese Patent Publication No. 44-20189), Combination system of hexaarylbiimidazole, radical generator and dye (Japanese Patent Publication No. 45-37377), System of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-Open No. 54-155292) No.), cyclic cis-α-dicarbonyl compound and dye system (Japanese Patent Laid-Open No. 48-84183), cyclic to Liazine and merocyanine dye systems (JP 54-151024), 3-ketocoumarin and activator systems (JP 52-112681, JP 58-15503), biimidazole, styrene derivatives, thiols System (JP 59-140203 A), organic peroxide and dye system (JP 59-1504, JP 59-140203, JP 59-189340, JP 62-174203). No. 6, JP-B 62-1641, US Pat. No. 4,766,055), dyes and active halogen compounds (JP-A 63-258903, JP-A 2-63054, etc.), dyes and borate compounds (JP A) JP-A-62-143044, JP-A-62-1050242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-6464 13143, JP-A 64-13144, JP-A 64-17048, JP-A 1-222903, JP-A-1-298348, JP-A 1-138204, etc.) A dye having a rhodanine ring and a radical generator Systems (JP-A-2-17943, JP-A-2-244050), titanocene and 3-ketocoumarin dyes (JP-A 63-221110), titanocene and xanthene dyes, addition polymerization containing amino groups or urethane groups A combination of possible ethylenically unsaturated compounds (JP-A-4-221958, JP-A-4-219756), titanocene and a specific merocyanine dye system (JP-A-6-295061), having a titanocene and a benzopyran ring And dye systems (Japanese Patent Laid-Open No. 8-3344897).

  Recently, a laser having a wavelength of 400 to 410 nm (violet laser) has been developed, and a photopolymerization initiation system exhibiting high sensitivity at a wavelength of 450 nm or less that is sensitive to it has been developed, and these photoinitiation systems are also used. For example, cationic dye / borate system (JP-A-11-84647), merocyanine dye / titanocene system (JP-A 2000-147663), carbazole type dye / titanocene system (JP-A 2001-42524), and the like. be able to. In the present invention, it is particularly preferable that the photopolymerization initiating system contains a titanocene compound because of excellent sensitivity.

  Various titanocene compounds can be used. For example, various titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used. . More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti -Bis-2,6-difluoropheny 1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl and the like can be mentioned.

  The photopolymerization initiation system preferably contains the above-mentioned titanocene compound and further a triazine compound. Examples of the triazine compound used in combination with the titanocene compound include halomethyltriazine compounds represented by the following general formula (I).

In the formula, Q ₁ and Q ₂ each independently represent a halomethyl group, X represents an electron-withdrawing substituent having a Hammett's σ value ranging from 0 to +0.8, excluding the COOH group, n represents an integer of 0 to 5.
In the present invention, Hammett's σ value is defined by JE Leffler, translated by Yunan Tono, “Organic Reaction Kinetics” (Tokyo, Yodogawa Shoten, 1968).
In the triazine compound represented by the general formula (I) used in the present invention, specific examples of the substituent X having a Hammett's σ value ranging from 0 to +0.8 are substituted with a phenyl group or an electron withdrawing group. phenyl group, a naphthyl group, a trifluoromethyl group, a cyano group, an acetyl group, an ethoxycarbonyl group, -PO ₃ H group, an alkyl-substituted phosphonyl group, thiocyano group, methylsulfonyl group, ethylsulfonyl group, dimethyl sulfonyl group, fluorine An atom, a chlorine atom, a bromine atom, an iodine atom, an iodoyl group, etc. can be mentioned.
Among these, preferred are a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, a trifluoromethyl group, an acetyl group, a phenyl group, and a phenyl group substituted with an electron withdrawing group.
Specific examples of the compound represented by the general formula (I) include the following compounds, but are not limited thereto.

  Furthermore, if necessary for the photoinitiating system, thiol compounds such as 2-mercaptobenzthiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, and amines such as N-phenylglycine and N, N-dialkylamino aromatic alkyl esters It is known that the photoinitiating ability can be further enhanced by adding a hydrogen-donating compound such as a compound. The amount of these photopolymerization initiation systems used is 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.2 to 50 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound described later. Used in the range of parts.

[Polymerizable compound having at least one ethylenically unsaturated group]
The polymerizable compound having at least one ethylenically unsaturated group (hereinafter also referred to as an ethylenically unsaturated bond-containing compound) is a photopolymerization initiator when the image recording layer forming composition is irradiated with actinic rays. It is a compound having at least one ethylenically unsaturated group which undergoes addition polymerization by action, crosslinks and cures. The compound containing at least one ethylenically unsaturated group capable of addition polymerization can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

  Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and aliphatic polyvalent amine compounds. Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate There are oligomers and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p -(3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,5-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

  Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, the mixture of the above-mentioned ester monomer can also be mentioned. Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, and 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

  As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708 contains a hydroxyl group represented by the following general formula (A). Examples thereof include a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer is added.

CH ₂ = C (R) COOCH ₂ CH (R ') OH (A)
(However, R and R ^′ represent H or CH _3. )

  Further, urethane acrylates as described in JP-A-51-37193 and JP-B-2-32293, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, as described in each publication. Furthermore, those introduced as photo-curable monomers and oligomers in the Japan Adhesion Association magazine Vo 1.20, No. 7, pages 300 to 308 (1984) can also be used. In addition, the usage-amount of these ethylenically unsaturated bond containing compounds is 5-80 mass% of the image recording layer whole component, Preferably it is used in 30-70 mass%.

[Binder polymer]
The binder polymer (polymer binder) in the image recording layer of the image forming material used in the method of the present invention is not only used as a film forming agent for the image recording layer but also needs to be dissolved in an alkaline developer. An organic polymer that is soluble or swellable in alkaline water is used.
Examples of such an organic polymer include addition polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-. No. 25957, JP 54-92723, JP 59-53836, JP 59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer Examples include polymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful. Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate (meth) acrylic acid / as required Other addition polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
JP-B-7-120040, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271741 And JP-A-11-352691 are also useful for the use of the present invention.

  These polymer polymers can improve the strength of the cured film by introducing a radical reactive group into the side chain. Functional groups that can undergo an addition polymerization reaction include ethylenically unsaturated bond groups, amino groups, and epoxy groups, and functional groups that can become radicals upon light irradiation include mercapto groups, thiol groups, halogen atoms, triazine structures, and onium salt structures. In addition, examples of the polar group include a carboxyl group and an imide group. The functional group capable of undergoing addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acryl group, a methacryl group, an allyl group, or a styryl group, but also an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, or a carbamoyl group. A functional group selected from an isocyanate group, a ureido group, a ureylene group, a sulfonic acid group, and an ammonio group is also useful.

In order to maintain the developability of the image recording layer, the binder polymer preferably has an appropriate molecular weight and acid value, and a high molecular weight polymer having a weight average molecular weight of 5000 to 300,000 and an acid value of 20 to 200 is effective. used.
These binder polymers can be mixed in an arbitrary amount in the entire composition of the image recording layer. Preferably it is 10 to 90%, More preferably, it is 30 to 80%. In the case of 90% by weight or less, it is preferable because a preferable result is given in terms of the strength of the formed image. The ethylenically unsaturated bond-containing compound and the binder polymer are preferably in the range of 1/9 to 9/1 by weight. A more preferable range is 2/8 to 8/2, still more preferably 3/7 to 7/3.

[Other ingredients]
Further, in the image recording layer of the image forming material, in addition to the above basic components, ethylenic unsaturation that can be polymerized during the production or storage of the composition for image recording layer (hereinafter also referred to as photosensitive composition). It is desirable to add a small amount of a thermal polymerization inhibitor to prevent unwanted thermal polymerization of the bond-containing compound. Suitable thermal polymerization inhibitors include haloid quinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% with respect to the solid content of the image recording layer. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, and unevenly distributed on the surface of the image recording layer in the drying process after coating. Good. The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% with respect to the solid content of the image recording layer.

  Furthermore, a colorant may be added for the purpose of coloring the image recording layer. Examples of the colorant include phthalocyanine pigments (CI Pigment Blue 15: 3, 15: 4, 15: 6, etc.), azo pigments, pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, There are azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% to about 20% of the total composition for the image recording layer. In addition, in order to improve the physical properties of the cured film, an additive such as an inorganic filler or a plasticizer such as dioctyl phthalate, dimethyl phthalate, or tricresyl phosphate may be added. These addition amounts are preferably 10% or less of the total composition for the image recording layer.

[Method of forming image forming material]
In the present invention, when an image recording layer composition of an image forming material is applied on an aluminum support described later, it is dissolved in various organic solvents and used. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate-3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 1 to 50% by weight.

In the present invention, a surfactant can be added to the image recording layer in order to improve the coating surface quality. The coverage of the image recording layer is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably from 0.3 to 5 g / m ^2. More preferably, it is 0.5-3 g / m < ² >.

[Protective layer]
Usually, when exposure is performed in the air, it is preferable to further provide a protective layer on the image recording layer. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the image recording layer to the image recording layer. Make it possible. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and furthermore, transmission of light used for exposure is not substantially inhibited, and adhesion to the image recording layer is improved. It is desirable that it is excellent and can be easily removed in the development process after exposure. Such a device for the protective layer has been conventionally devised, which is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729.

  As a material that can be used for the protective 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 protective 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% and a molecular weight in the range of 300 to 2400.

  Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

  Components of the protective 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 oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs 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, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization.

  On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, U.S. Pat. No. 292,501 and U.S. Pat. No. 44,563 disclose an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesion can be obtained by mixing by weight% and laminating on the polymerized layer. Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that is excellent in the transmission of light from 350 nm to 450 nm and that can absorb light of 500 nm or more, which is used for exposure, it is safe light without causing a decrease in sensitivity. The aptitude can be further enhanced.

(Support)
Next, the support for the image forming material will be described. The support is not particularly limited, but an aluminum support is preferable. Aluminum supports are dimensionally stable aluminum or alloys thereof (eg, alloys with silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel), or aluminum or aluminum alloys laminated or deposited. It means a plastic film or paper, and its thickness is usually about 0.05 mm to 1 mm. A composite sheet described in JP-A-48-18327 can also be used.

The aluminum support is preferably appropriately subjected to a surface treatment described later.
(Graining treatment)
Examples of the graining method include mechanical graining, chemical etching, and electrolytic grain as disclosed in JP-A-56-28893. Furthermore, electrochemical graining method that electrochemically grains in hydrochloric acid or nitric acid electrolyte, and wire brush grain method that scratches aluminum surface with metal wire, and ball grain method that graines aluminum surface with abrasive balls and abrasives Further, a mechanical graining method such as a brush grain method in which the surface is grained with a nylon brush and an abrasive can be used, and the above graining methods can be used alone or in combination. The method is a method of chemically graining in a hydrochloric acid or nitric acid electrolytic solution, suitable current density of 100C / dm ² ~400C / dm ² ranges to make the surface roughness usefully employed in the present invention among them It is. More specifically, in the electrolytic solution containing from 0.1 to 50% hydrochloric acid or nitric acid, the temperature 20 to 100 ° C., for 1 second to 30 minutes, electrolysis at a current density of 100C / dm ² ~400C / dm ² It is preferable to carry out.

The grained aluminum support is chemically etched with acid or alkali. When an acid is used as an etching agent, it takes time to destroy the fine structure, which is disadvantageous when the present invention is applied industrially, but it can be improved by using an alkali as the etching agent. As the alkali agent suitably used in the present invention, caustic soda, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide and the like are used, and preferred ranges of concentration and temperature are 1 to 50 respectively. %, 20 to 100 ° C., and conditions such that the dissolution amount of Al is 5 to 20 g / m ³ are preferable. Pickling is performed to remove dirt (smut) remaining on the surface after etching. As the acid used, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borohydrofluoric acid and the like are used. In particular, as a method for removing smut after the electrochemical surface roughening treatment, contact with 15 to 65% by weight sulfuric acid at a temperature of 50 to 90 ° C. as described in JP-A-53-12739 is preferable. And the alkali etching method described in Japanese Patent Publication No. 48-28123. In addition, the surface roughness (Ra) of the Al support effectively used in the present invention is 0.3 to 0.7 μm.

(Anodizing treatment)
The aluminum support treated as described above is preferably further subjected to an anodizing treatment. The anodizing treatment can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution by combining sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. An anodized film can be formed. The conditions for anodizing treatment vary depending on the electrolyte used, and therefore cannot be determined in general. In general, the concentration of the electrolyte is 1 to 80%, the solution temperature is 5 to 70 ° C., and the current density is 0.5. A range of ˜60 amperes / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 to 100 seconds is appropriate.

Among these anodizing treatments, a method for anodizing at a high current density in sulfuric acid and U.S. Pat. No. 3,511,661, particularly described in British Patent 1,412,768. A method of anodizing the described phosphoric acid as an electrolytic bath is preferred. In the present invention, the anodized film is preferably from ^{1~10g / m 2, 1g / m} 2 or more plate on difficult to enter scratches If it is, a great deal power production and is 10 g / m ² or less This is unnecessary and is economically advantageous. Preferably, a 1.5~7g / m ^2. More preferably 2-5 g / m ^2.

  Furthermore, in the present invention, the aluminum support may be subjected to sealing treatment after graining treatment and anodizing. Such sealing treatment is performed by immersing the substrate in hot water or a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like. The aluminum support of the present invention may be subjected to a surface treatment such as a silicate treatment with an alkali metal silicate or a treatment other than the silicate treatment, for example, an immersion treatment in an aqueous solution of potassium fluorinated zirconate or phosphate.

  An image recording material of the present invention is produced by forming an image recording layer comprising the photopolymerizable composition on the aluminum support that has been surface-treated as described above. An organic or inorganic intermediate layer may be provided as necessary before the treatment.

[Middle layer]
In the image forming material of the present invention, an intermediate layer may be provided for the purpose of improving the adhesion and soiling between the image recording layer and the support. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, JP-A-10-69092, JP-A-10-115931, Kaihei 11-38635, JP-A-11-38629, JP-A-10-282645, JP-A-10-301262, JP-A-11-24277, JP-A-11-109641, JP-A-10-319600, JP-A-10-319600 11-84684, JP-A-11-327152, JP-A-2000-10292, JP-A-2000-235254, JP-A-2000-352824, Japanese Patent Application No. 11-284091, JP-A-2001-209170. And the like.

[Exposure and development processing]
The image forming material in the present invention is, for example, a carbon arc lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, an argon ion laser, an FD / YAG laser, a helium neon laser, a semiconductor. An image can be formed on the surface of the aluminum plate support by exposing the image with a conventionally known actinic ray such as a laser (350 nm to 600 nm) and then developing it. In order to increase the curing rate of the polymerizable image recording layer after image exposure and before development, a heating process may be performed at a temperature of 50 ° C. to 150 ° C. for a period of 1 second to 5 minutes.

  In addition, as described above, a protective layer having an oxygen barrier property is usually provided on the image recording layer in the present invention. Using the developer in the present invention, the protective layer is removed and the image recording layer is not coated. A method of simultaneously removing the exposed portion, or a method of removing the protective layer first with water and warm water and then removing the image recording layer of the unexposed portion by development is known. These water or warm water can contain a preservative described in JP-A-10-10754, an organic solvent described in JP-A-8-278636, and the like.

  In the present invention, the image forming material is developed according to a conventional method at a temperature of 0 to 60 ° C., preferably about 15 to 40 ° C., for example, by immersing the exposed image forming material in a developer and rubbing with a brush. To do.

  Further, when developing using an automatic developing machine, the developing solution becomes fatigued according to the amount of processing, so that the processing capability may be restored using a replenishing solution or a fresh developing solution. The image forming material thus developed is washed with water, a surfactant and the like as described in JP-A Nos. 54-8002, 55-1115045, 59-58431, and the like. And a desensitizing solution containing gum arabic, starch derivatives and the like. In the present invention, these treatments can be used in various combinations for the post-treatment of the image forming material. When the image forming material is a lithographic printing plate precursor, the printing plate obtained by the above treatment is subjected to a heat treatment such as post-exposure treatment or burning by the method described in JP-A-2000-89478. Printing durability can be improved. The planographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

  In the present invention, when the image forming material is a lithographic printing plate precursor, the lithographic printing plate obtained by the above processing is applied to an offset printing machine and used for printing a large number of sheets. During printing, a plate cleaner may be used to remove stains on the plate. As the plate cleaner, a conventionally known plate cleaner for PS plate can be used. For example, CL-1, CL-2, CP, CN-4, CN, CG-1, PC-1, SR, IC (manufactured by Fuji Photo Film Co., Ltd.) and the like.

EXAMPLES The present invention will be specifically described below with reference to examples, but of course, the scope of the present invention is not limited by these examples.
First, lithographic printing plate precursors (1) to (4) were prepared as image forming materials as follows.
[Lithographic printing plate precursor (1)]
A 0.3 mm thick material 1S aluminum plate was thoroughly washed with water, etched by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, then neutralized and washed with 20% nitric acid, and washed with water. . This was subjected to an electrolytic surface roughening treatment in a 1.5% nitric acid aqueous solution with an electric quantity at the anode of 270 coulomb / dm ² using a sinusoidal alternating current under the condition of V _A = 12.7V. When the surface roughness was measured, it was 0.30 μm (Ra indication). Subsequently, after dipping in a 30% aqueous sulfuric acid solution and desmutting at 40 ° C. for 2 minutes, a cathode was placed on the grained surface in a 33 ° C., 20% aqueous sulfuric acid solution at a current density of 5 A / dm ² . When anodized for 50 seconds, the thickness was 2.7 g / m ² .
On the aluminum plate thus treated, an intermediate layer coating solution having the following composition was applied, applied to a dry coating weight of 2 mg / m ^2, and dried at 100 ° C. for 3 minutes.

<Coating liquid for intermediate layer>
The following composition was mixed and stirred. After about 5 minutes, exotherm was observed, and after reacting for 60 minutes, 20,000 g of methanol was added.

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

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

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

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied on the photopolymerizable photosensitive layer thus formed so that the dry coating weight was 2.5 g / m ^2. The plate was dried at 100 ° C. for 90 seconds to obtain a lithographic printing plate precursor (1).

[Lithographic printing plate precursor (2)]
The lithographic printing plate precursor (1) is the same as the lithographic printing plate precursor (1) except that the photopolymerizable composition 2 in which C-1 in the photopolymerizable composition 1 is changed to C-2 (described later) is used. (2) was created.

[Lithographic printing plate precursor (3)]
The planographic printing plate precursor (2) is the same as the planographic printing plate precursor (2) except that the photopolymerizable composition 3 obtained by adding 0.1 g of the triazine compound (I) -1 to the photopolymerizable composition 2 is used. (3) was created.

[Lithographic printing plate precursor (4)]
An aluminum plate made of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an aqueous suspension of 800 mesh Pamiston, and its surface was grained and washed thoroughly with water. After etching by immersing in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, neutralized and washed with 20% HNO ₃ and washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% nitric acid aqueous solution with a quantity of electricity at the anode of 300 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Subsequently, after dipping in a 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, a cathode was placed on the grained surface in a 33 ° C., 20% H ₂ SO ₄ aqueous solution. When anodization was performed for 50 seconds at a density of 5 A / dm ² , an anodized film having a thickness of 2.7 g / m ² was formed.

On the aluminum plate on which the anodized film is formed, methyl methacrylate / ethyl acrylate / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (60/25/15 molar ratio, molecular weight Mn = 30,000) A support obtained by applying a solution dissolved in water / methanol = 5 g / 95 g so that the coating amount was 3 mg / m ² and drying at 80 ° C. for 30 seconds was used.

On this intermediate layer, a photopolymerizable composition 4 having the following composition was applied such that the dry coating weight was 1.5 g / m ² and dried at 100 ° C. for 90 seconds to form a photosensitive layer.

<Photopolymerizable composition 4>
Ethylenically unsaturated bond-containing compound (A2) 1.5 g
Binder polymer (B2) 1.8g
Sensitizing dye (C2) 0.1g
0.2 g of the above photopolymerization initiator (D1)
β-phthalocyanine (F1) dispersion 0.2 g
Fluorine nonionic surfactant Megafac F177 (manufactured by DIC) 0.03g
Methyl ethyl ketone 10g
10g of propylene glycol monomethyl ether acetate

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied on the photopolymerizable photosensitive layer thus formed so that the dry coating weight was 2.5 g / m ^2. And dried at 100 ° C. for 90 seconds to obtain a planographic printing plate precursor (4).

  Among these lithographic printing plate precursors, the lithographic printing plate precursor (1) (photopolymerizable composition 1) is an FD • YAG laser (plate jet 4 manufactured by CSI), and the lithographic printing plate precursors (2) to (4) (Photopolymerizable compositions 2 to 4) were subjected to image exposure under conditions of 175 lines at 2400 dpi with a Violet laser (Luxel Vx9600CTP manufactured by Fuji Photo Film Co., Ltd.) with different exposure amounts.

  For development, standard processing was performed with an automatic processor (LP-850PII, manufactured by Fuji Photo Film Co., Ltd.) charged with a developer having the following composition and finishing gum solution FP-2W (Fuji Photo Film Co., Ltd.).

<Developer>
The following components were dissolved in water to prepare a developer.
Carbonate a mol / L
Bicarbonate b mol / L
Surfactant cg / L
Additive dg / L
Ethylenediaminetetraacetic acid, 4Na salt (chelating agent) 2 g / L

[Evaluation]
The development speed of the non-image area with an alkaline developer was measured as an index for evaluation of developability, and the penetration speed of the alkaline developer into the image recording layer was measured as an index for evaluation of printing durability.
Hereinafter, a method for measuring the “development speed of the non-image area with the alkali developer” and the “penetration speed of the alkali developer into the image recording layer” in the present invention will be described in detail.

<Measurement of development speed of non-image area with alkali developer>
Here, the development speed of the non-image area with the alkali developer is a value obtained by dividing the film thickness (m) of the image recording layer (non-image area) by the time (sec) required for development. As a measuring method of the developing speed in the present invention, as shown in FIG. 1, the one provided with an unexposed image recording layer on an aluminum support is immersed in a certain alkaline developer (30 ° C.) in a range, The dissolution behavior of the image recording layer was investigated with a DRM interference wave measuring device. FIG. 1 shows a schematic diagram of a DRM interference wave measuring apparatus for measuring the dissolution behavior of an image recording layer. In the present invention, a change in film thickness was detected by interference using light of 640 nm. When the development behavior is non-swelling development from the surface of the image recording layer, the film thickness gradually decreases with respect to the development time, and an interference wave corresponding to the thickness can be obtained. Further, in the case of swelling dissolution (film removal dissolution), the film thickness changes due to the penetration of the developer, so that a clean interference wave cannot be obtained.

The measurement is continued under these conditions, and the development speed is determined from the time until the image recording layer is completely removed and the film thickness becomes zero (development completion time) (s) and the film thickness (μm) of the image recording layer. It can obtain | require by the type | formula. It is determined that the higher the development speed, the easier the film is removed by the developer and the better the developability.
Development speed (of unexposed area) = [Image recording layer thickness (μm) / Recording completion time (sec)]
In order to obtain correspondence with practical performance, the developability test of the plate material was performed (see developability evaluation).

<Measurement of penetration rate of alkali developer into image recording layer>
Further, the permeation speed of the alkali developer into the image recording layer is a value indicating the change speed of the capacitance (F) when the image recording layer is formed on a conductive support and immersed in the developer. It is.
As shown in FIG. 2, the method of measuring the electrostatic capacity, which is a measure of permeability in the present invention, is exposed to an alkali developer (28 ° C.) (the photopolymerizable composition 1 is an FD / YAG laser). (CSI Co., Ltd., plate jet 4), the exposure amount was 0.25 mJ / cm ² , and the photopolymerizable compositions 2 and 3 were Violet laser (Fuji Photo Film's Raxel Vx9600CTP), and the exposure amount was 0.05 mJ / cm ² exposure), an aluminum support provided with a cured image recording layer is immersed as one electrode, a lead wire is connected to the aluminum support, and a voltage is applied to the other using a normal electrode. After the voltage is applied, the developer permeates the interface between the support and the image recording layer as the immersion time elapses, and the capacitance changes.

From the time (s) required until the capacitance changes and the film thickness (μm) of the image recording layer, it can be obtained by the following equation. It is determined that the smaller the permeation rate, the lower the permeability of the developer.
Developer penetration rate (of exposed area) =
[Image recording layer thickness (μm) / Time required for capacitance change to be constant (s)]
In order to obtain correspondence with practical performance, the obtained plate material was subjected to a printing durability test on a printing press (see printing durability evaluation).

  As the physical properties of the image recording layer in the lithographic printing plate precursor according to the invention, the development rate of the unexposed portion with respect to the alkaline developer is preferably 80 nm / sec or more, more preferably 80 to 400 nm / sec, and still more preferably 90 to 200 nm / sec. The penetration rate of the alkali developer in the exposed area is preferably 100 nF / sec or less, more preferably 90 nF / sec or less, and still more preferably 80 nF / sec or less.

(Developability evaluation)
Using LP-850PII manufactured by Fuji Photo Film Co., Ltd., developed with the developer shown in Table 1 at 28 ° C. for 18 seconds, and the actual developability of the non-image area was observed.
(Evaluation of printing durability)
The lithographic printing plate precursors (1) to (3), the photopolymerizable composition 1 is FD / YAG laser (CSI plate jet 4), 2400 dpi, 175 lines, 0.25 mJ / cm ² , image exposure, photopolymerization The composition compositions 2 and 3 were image-exposed with a violet laser (Laxel Vx9600CTP manufactured by Fuji Photo Film Co., Ltd.) at 2400 dpi at 175 lines and 0.05 mJ / cm ² .
After the exposure, the protective layer was removed by rinsing with tap water, and then developed at 28 ° C. for 18 seconds using LP-850PII manufactured by Fuji Photo Film Co., Ltd. As the finisher, a 1: 1 water dilution of FP-2W manufactured by Fuji Film Co., Ltd. was used.
The obtained lithographic printing plate was printed using a printing press Lithron manufactured by Komori Corporation, and the number of finished sheets was used as an index of printing durability.

(PH drop due to carbon dioxide in the air)
Each developer was charged into LP-850PII manufactured by Fuji Photo Film Co., Ltd., and the plate material was not processed for 1 day, and the pH fluctuation after standing was determined.

(Evaluation of development residue)
The above-mentioned coated photosensitive material 20 m ² was developed in the above-mentioned developer (1 liter) and left for 1 month to investigate the presence or absence of development residue. This result is also shown.

上記表中、現像性評価において○は残膜なしを表し、現像カス評価において○は沈殿なし、△は微量沈殿あり、×は沈殿多量を表す。

In the above table, in evaluation of developability, ◯ indicates no remaining film, in development residue evaluation, ◯ indicates no precipitation, Δ indicates a slight amount of precipitation, and X indicates a large amount of precipitation.

  As is apparent from the results in Tables 2 to 5, the image forming method of the present invention provides sufficient developability even at a relatively low pH (8.5 to 11.5) with little damage to the image forming material, and good printing durability. Sex was obtained. Further, since the pH fluctuation of the developer is small, it is considered that the decrease in development activity due to carbon dioxide gas is small. Moreover, almost no problems due to development residue occurred (Tables 2 to 5, Developers 1 to 13). On the other hand, when image formation is performed regardless of the image forming method of the present invention, a residual film is formed, and sufficient developability cannot be ensured, the printing durability is lowered, and the development residue is further developed in the developing bath. Phenomenon of sedimentation was observed (Tables 2 to 5, Comparative developers 14 to 19).

It is a schematic block diagram which shows an example of the DRM interference wave measuring apparatus for measuring the melt | dissolution behavior of an image recording layer. It is a schematic block diagram which shows an example of the measuring method of the electrostatic capacitance used in evaluating the permeability to the image recording layer of a developing solution.

Claims (8)

A photopolymerization type in which an image recording layer containing a photopolymerization initiation system sensitive to light in the visible light to ultraviolet wavelength region, a polymerizable compound having at least one ethylenically unsaturated group, and a binder polymer is formed on a support. After image exposure of the image forming material, at least one interface selected from the group consisting of a nonionic aromatic ether surfactant represented by the following formula (1), which contains at least one carbonate and at least one bicarbonate. An image forming method comprising developing with a developer containing 1.0% to 10% by weight of an activator, having a pH of 8.5 to 11.5, and a conductivity x of 30 <x <100 mS / cm:
X-Y-O- (A) n- (B) m-H (1)
(In the formula, X represents an aromatic group which may have a substituent, Y represents a single bond or an alkylene group having 1 to 10 carbon atoms, A and B are groups different from each other, and- Represents either CH ₂ CH ₂ O— or —CH ₂ CH (CH ₃ ) O—, n and m each represents 0 or an integer of 1 to 100, provided that n and m are not 0 at the same time, and n Or, if either m is 0, n and m are not 1.) 2. The image formation according to claim 1, wherein the carbonate is at least one selected from the group consisting of inorganic alkali carbonates, and the hydrogen carbonate is at least one selected from the group consisting of inorganic alkali hydrogen carbonates. Method. The carbonate is at least one selected from the group consisting of potassium carbonate, sodium carbonate, and ammonium carbonate, and the bicarbonate is at least selected from the group consisting of potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate. The image forming method according to claim 1, which is a kind. 4. The developer according to claim 1, wherein the developer further contains at least one compound selected from the group consisting of an alkali metal salt of an organic acid and an alkali metal salt of an inorganic acid. Image forming method. The image forming method according to any one of claims 1 to 4, wherein the developer contains at least a compound represented by the following formula (IA) and / or (IB) as a surfactant.

(In the above formula, R ₁ and R ₂ each represent a hydrogen atom or an organic group having 1 to 100 carbon atoms; p and q each represent 1 or 2; Y ₁ and Y ₂ each represent a single bond or a carbon atom. Represents an alkylene group of 1 to 10; r and s each represent 0 or an integer of 1 to 100, provided that r and s are not 0 at the same time, and when either r or s is 0, r And s are not 1, and r ′ and s ′ each represent 0 or an integer of 1 to 100, provided that r ′ and s ′ are not 0 at the same time and either r ′ or s ′ is 0. And r ′ and s ′ are not 1.) The photopolymerization initiation system that is sensitive to light in the visible light to ultraviolet wavelength region contains a sensitizing dye having a maximum absorption wavelength at 330 to 700 nm and a photopolymerization initiator, according to any one of claims 1 to 5. Image forming method. The image forming method according to claim 6, wherein the photopolymerization initiation system contains a titanocene compound. The image forming method according to claim 6, wherein the photopolymerization initiation system contains a titanocene compound and a triazine compound.

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