JP2005202392A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing solution and image forming method capable of forming images having excellent developability and printing resistance and performing stable processing for a long period of time. <P>SOLUTION: In the method for forming the images, a negative-working image-forming material formed with an image-recording layer comprising a photopolymerization initiator system sensitive to light rays whose wavelength falls within the visible to ultraviolet ranges, a polymerizable compound carrying at least one ethylenically unsaturated group and a binder polymer is image-exposed, and then the image-exposed image-forming material is developed with a developing solution which contains at least one carbonate, at least one hydrogen carbonate and at least one alkali silicate and which has a pH value ranging from 9 to 13.0, wherein the ratio of the total molar number a of the carbonate and the hydrogen carbonate to the molar number b of the SiO<SB>2</SB>component present in the alkali silicate: a:b ranges from 1:0.3 to 1:2 and the total molar number of these components: a + b ranges from 0.1 to 2 mole/L. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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

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 are related to photoinitiation systems. For example, photoinitiation systems with high sensitivity to Ar lasers and FD-YAG lasers are combinations of titanocene and coumarin dyes (for example, Patent Document 1). 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). ing.
Further, as a photoinitiating system highly sensitive to a violet laser, a combination of a naphthofuranone dye and titanocene (for example, see Patent Document 6), a combination of a carbazolyl styryl dye and titanocene (for example, Patent Document 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 having excellent printing durability, excellent stain resistance, hardly cause deterioration in developability over time due to the characteristics of the developer, and can stably process for a long period of time. An object of the present invention is to provide an image forming method.

As a result of diligent research, the present inventor has developed 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 on a support. After image exposure of the negative type image forming material on which the image recording layer is formed is developed using a developer in which alkali silicate is mixed at a specific ratio with a developer composed of carbonate and bicarbonate, Even if the pH fluctuates, the performance of the image forming material is stable in a wide latitude, and sufficient developability and stain resistance can be secured, and by containing silicate, it can be removed from a support such as an aluminum substrate during development. It has been found that elution can be suppressed, and the above-described problems have been achieved and the present invention has been completed. Accordingly, the present invention provides an image forming 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 bond group, and a binder polymer on a support. After image exposure of the formed negative type image forming material, at least one kind of carbonate and at least one kind of bicarbonate, and at least one kind of alkali silicate are included, and the total number of moles of carbonate and bicarbonate a and alkali silicate The ratio of mole number b of SiO ₂ component in the salt is a: b = 1: 0.3 to 1: 2, and the total molar concentration of a and b is a + b = 0.1 to 2 mol / L, and the pH is 9 to 13.0. The present invention relates to an image forming method characterized by developing with a developing solution.

  When the above developer is used to develop exposed photopolymerization-type image forming materials, it has excellent developability even at relatively low pH conditions that are not easily affected by carbon dioxide, and improved printing durability by reducing damage to the image area. In addition, it was found that fluctuations in plate performance when the pH fluctuates can be reduced. Therefore, stable processability can be ensured even in an image forming material having a narrow performance latitude during development (small discrimination).

  According to the image forming method of the present invention, since sufficient developability can be secured at a low pH with little damage to the image forming material, it is possible to achieve both printing durability and developability, and an image having excellent printing durability. Thus, there is provided an image forming method which is excellent in stain resistance, hardly deteriorates in developability with time due to the characteristics of the developer, and can be stably processed for a long period of time.

The image forming method of the present invention will be described in detail below. First, the developer will be described.
[Developer]
(Carbonates and bicarbonates)
The developer used in the present invention is an alkaline aqueous solution having a pH of 9 to 13.0 containing at least one carbonate, at least one bicarbonate, and at least one alkali silicate in the proportions shown below. The pH is preferably in the range of 9.0 to 12.5.
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 inorganic alkali carbonates. Specific examples of the carbonate include sodium carbonate, potassium and ammonium. Examples of the bicarbonate include at least one compound selected from inorganic alkali bicarbonates. Specific examples of the bicarbonate include sodium bicarbonate, potassium, and ammonium. 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 region of pH 8.5 to 11.0. Moreover, the amount of carbon dioxide absorption can be reduced, which is preferable.

(Alkali silicate)
The developer used in the present invention further contains at least one alkali metal silicate in addition to the carbonate and bicarbonate.
The alkali silicate to be used exhibits alkalinity when dissolved in water, and examples thereof include sodium silicate, potassium silicate, lithium silicate, and ammonium silicate. These alkali silicates may be used alone or in combination of two or more.
The developer used in the present invention is composed of silicon oxide SiO ₂ which is a silicate component as a hydrophilic component of a substrate and alkali oxide M ₂ O as an alkali component (M represents an alkali metal or an ammonium group). By adjusting the mixing ratio and concentration, it can be easily adjusted to the optimum range. The mixing ratio (SiO ₂ / M ₂ O molar ratio) of silicon oxide SiO ₂ and alkali oxide M ₂ O is 0.75 to 4.0, preferably 0.75 to 3.5.

When the SiO ₂ / M ₂ O is less than 0.75, the alkalinity becomes strong, the anodized film of the aluminum substrate as a support of the lithographic printing plate precursor is excessively dissolved (etched), and the unclean stain occurs. , There is an adverse effect that insoluble residue is formed due to the complex formation of dissolved aluminum and silicic acid, and if it exceeds 4.0 or even 3.0, there is a problem that developability deteriorates or insoluble residue condensed with silicate is generated. Sometimes.

The concentration of the alkali silicate in the developer is preferably 0.01 to 1 mol / L, more preferably 0.05 to 0.8 mol / L as the amount of SiO _{2 with} respect to the mass of the aqueous alkali solution. If this concentration is less than 0.01 mol / L, the effect of inhibiting dissolution (etching) of the anodic oxide film on the aluminum substrate may not be obtained, and developability and development processing ability may deteriorate. If it exceeds 1 mol / L, precipitation occurs. And crystals are easily generated, and gelation is likely to occur during neutralization at the time of waste liquid, which may impede waste liquid treatment.

Here, the total number of moles a of carbonate and bicarbonate a, the ratio of the number of moles b of the SiO ₂ component in the alkali metal silicate is a: b = 1: 0.3 to 1: 2, and the total mole concentration of a and b is a + b = It was found that the addition of 0.1 to 2 mol / L can reduce the fluctuation in plate performance when the pH fluctuates. Accordingly, it is possible to ensure stable processability even in a light-sensitive material having a narrow performance latitude during development (small discrimination). Preferably, a: b = 1: 0.5 to 1: 1.5, and a + b = 0.2 to 1.5 mol / L.

  Even if the developer is prepared by adding and dissolving each component in the same water, the developer is prepared by mixing each component, for example, an aqueous solution of carbonate, bicarbonate, or silicate. May be.

  Further, the developer includes an alkali agent, such as tribasic sodium phosphate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium, lithium, and the like. Inorganic alkaline agent and monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, di Single or two or more organic alkali agents such as isopanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide It may be mixed and used in combination.

(Surfactant)
It is preferable to add at least one surfactant selected from an anionic surfactant and a nonionic surfactant to the developer in the present invention. By adding such a surfactant, developability is promoted, and the dispersibility of the image recording layer composition dissolved in the developer is improved, so that precipitation or the like hardly occurs in the developer. Play. These surfactants are preferably added in the range of 1 to 10% by mass with respect to the developer.

(Anionic surfactant component)
An anionic surfactant is a compound having at least one anionic group in the molecule. Examples of the anion group include a carboxylic acid anion, a sulfonate anion, a sulfinate anion, a sulfate anion, a sulfite anion, a phosphate anion, a phosphite anion, a phosphonate anion, and a phosphinate anion. An anion or a sulfate anion. Specifically, it is a compound having at least one sulfonate anion or sulfate anion. A compound having at least one anionic group of sulfonic acid or anionic group of sulfuric monoester is preferable. More preferred are compounds having at least one anionic group of sulfonic acid or anionic group of sulfuric monoester, and further having at least one aromatic group which may have a substituent.
Preferred examples of the compound having at least one anionic group of sulfonic acid or anionic group of sulfuric monoester include compounds represented by general formula (I) or (II).

In formula, R < ₁ >, R < ₂ > represents the alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group which may have a substituent. M represents a monovalent alkali metal.
Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, and specifically include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and a 2-ethylhexyl group. Preferred examples include octyl group, decyl group, dodecyl group, hexadecyl group, stearyl group and the like.
The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Preferred examples of the polycyclic type include an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, a-pinel group, tricyclodecanyl group and the like.
As an alkenyl group, it is a C2-C20 alkenyl group, for example, Specifically, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group can be mentioned preferably.
As the aralkyl group, for example, an aralkyl group having 7 to 12 carbon atoms, specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably exemplified.
As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, Preferable examples include 9,10-dimethoxyanthryl group.

  As the substituent, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferable examples include a halogen atom (F, Br, Cl, I), a hydroxyl group, an alkoxy group, an aryloxy group, an acyl group, Examples include an amide group, an ester group, an acyloxy group, a carboxy group, a carboxylic acid anion group, and a sulfonic acid anion group.

Specific examples of the alkoxy group in these substituents include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, stearyloxy group, methoxyethoxy group, Examples include poly (ethyleneoxy) and poly (propyleneoxy) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms. The aryloxy group has 6 to 18 carbon atoms such as phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group and naphthyloxy group. Individuals are listed. Examples of the acyl group include those having 2 to 24 carbon atoms such as an acetyl group, a propanoyl group, a butanoyl group, a benzoyl group, and a naphthoyl group. Examples of the amide group include those having 2 to 24 carbon atoms such as an acetamide group, a propionic acid amide group, a dodecanoic acid amide group, a palmitic acid amide group, a stearic acid amide group, a benzoic acid amide group, and a naphthoic acid amide group. . Examples of the acyloxy group include those having 2 to 20 carbon atoms such as an acetoxy group, a propanoyloxy group, a benzoyloxy group, and a naphthoyloxy group. Examples of the ester group include those having 1 to 24 carbon atoms such as methyl ester group, ethyl ester group, propyl ester group, hexyl ester group, octyl ester group, dodecyl ester group, stearyl ester group. The substituent may be a combination of two or more of the above substituents.
Any may be sufficient as the alkali metal represented by M, However, Sodium, potassium, and lithium are especially preferable.

  Of the compounds represented by the formula (I) or the formula (II), the compounds represented by the following formulas (IA) and (IB) are preferable from the viewpoint of the effect of the present invention.

（上記式中、Ｒ₃、Ｒ₅はそれぞれ、直鎖または分岐鎖の炭素原子数１〜５のアルキレン基を表し；Ｒ₄、Ｒ₆は直鎖または分岐鎖の炭素数１〜２０のアルキル基を表し；ｐ、ｑはそれぞれ０、１又は２を表し；Ｘ₁、Ｘ₂はそれぞれ単結合又は炭素原子数１〜１０のアルキレン基を表し；Ｍは一価のアルカリ金属を表し；ｒ、ｓはそれぞれ１〜１００の整数を表し、但しｒ及びｓが２以上の場合には、Ｒ₃またはＲ₅は２種類以上の基から選択されてもよい）。

(In the above formula, R ₃ and R ₅ each represent a linear or branched alkylene group having 1 to 5 carbon atoms; R ₄ and R ₆ are linear or branched alkyl groups having 1 to 20 carbon atoms; P and q each represent 0, 1 or 2; X ₁ and X ₂ each represent a single bond or an alkylene group having 1 to 10 carbon atoms; M represents a monovalent alkali metal; , S each represents an integer of 1 to 100, provided that when r and s are 2 or more, R ₃ or R ₅ may be selected from two or more groups.

  Examples of the compounds represented by the general formulas (I) and (II) are shown below, but the present invention is not limited thereby.

In addition, x and y in the said specific example respectively represent the repeating number of an ethyleneoxy chain and a propyleneoxy chain, and represent the integer of 1-20 (each average value).
The addition amount of the compounds represented by the general formulas (I) and (II) is appropriately 1 to 10% by mass, preferably 2 to 10% by mass in the developer.
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.
The compounds represented by the general formulas (I) and (II) are generally available on the market. Examples of commercially available products include those manufactured by Asahi Denka, Kao Soap, Sanyo Chemical, Shin Nippon Chemical, Daiichi Kogyo Seiyaku, Takemoto Yushi, Toho Chemical, Nippon Yushi.

(Nonionic aromatic ether activator)
Examples of the nonionic surfactant that can be added to the developer of the present invention include nonionic aromatic ether surfactants represented by the following 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 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 (1-A) (1-B). In the formula, when both A and B are present, they may be random or block copolymers.

Specific examples of these compounds include those represented by the following general formulas (1-A) and (1-B).

(In the above formula, R ₁₀ and R ₂₀ each represent a hydrogen atom or an organic group having 1 to 100 carbon atoms; t and u 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; v and w each represent 0 or an integer of 1 to 100, provided that v and w are not 0 at the same time, and v is 0 when either v or w is 0. And w is not 1, and v ′ and w ′ each represent 0 or an integer of 1 to 100, provided that v ′ and w ′ are not 0 at the same time and either v ′ or w ′ is 0. V ′ and w ′ are not 1.
When t is 2 and R ₁₀ is an organic group having 1 to 100 carbon atoms, R ₁ may be the same or different and R ₁₀ may be combined to form a ring, and u And R ₂₀ is an organic group having 1 to 100 carbon atoms, R ₂₀ may be the same or different, and R ₂₀ 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-aryl Silamino 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 ₁₀ and R ₂₀ 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 (1-A) and (1-B), the number of repeating units of the polyoxyethylene chain is preferably 3 to 50, more preferably 5 to 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 (1-A) 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 (1-B) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, and polyoxyethylene nonyl naphthyl ether.
A nonionic aromatic ether type activator may be used individually by 1 type in a developing solution, and may be used in combination of 2 or more type.
The content of the nonionic aromatic ether activator in the developer is suitably 1 to 20% by mass, more preferably 2 to 10% by mass in the developer. 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 activator represented by the general formula (1-A) or (1-B) are shown below.

The developer used in the image forming method of the present invention may further contain other surfactants described below.
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 surfactant.

  These surfactants can be used alone or in combination. Further, the content of these surfactants in the developer is preferably from 0.1 to 20% by mass in terms of active ingredients.

(Defoamer)
The developer may contain an antifoaming agent characterized by containing acetylene alcohol and / or acetylene glycol. When adding an antifoamer to a developing solution, it is preferable that the addition amount is in the range of 0.01 to 1% by mass with respect to the weight of the developing solution.
Acetylene alcohol is an unsaturated alcohol having an acetylene bond (triple bond) in the molecule. Acetylene glycol is also called alkynediol, and is an unsaturated glycol having an acetylene bond (triple bond) in the molecule.
More specifically, there are those represented by the following general formulas (A) and (B).

（式中、Ｒ₁₀₀は炭素原子数１〜５の直鎖又は分岐鎖のアルキル基を表す。）

(In the formula, R ₁₀₀ represents a linear or branched alkyl group having 1 to 5 carbon atoms.)

（式中、Ｒ₂₀₀及びＲ₃₀₀はそれぞれ独立して炭素原子数１〜５の直鎖又は分岐鎖のアルキル基を表し、ａ＋ｂは０〜３０の数である。）

(In the formula, R ₂₀₀ and R ₃₀₀ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, and a + b is a number of 0 to 30.)

  Examples of the linear or branched alkyl group having 1 to 5 carbon atoms in the above formula include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and an isopentyl group.

The following are mentioned as a further specific example of acetylene alcohol and acetylene glycol.
(1) Propargyl alcohol CH≡C-CH ₂ OH
(2) Propargyl carbinol CH≡C—CH ₂ —CH ₂ OH

(3) 3,5-Dimethyl-1-hexyn-3-ol

(4) 3-Methyl-1-butyn-3-ol

(5) 3-Methyl-1-pentyn-3-ol

(6) 1,4-butynediol HO—CH ₂ —C≡C—CH ₂ —OH

(7) 2,5-Dimethyl-3-hexyne-2,5-diol

(8) 3,6-dimethyl-4-octyne-3,6-diol

(9) 2,4,7,9-tetramethyl-5-decyne-4,7-diol

（ｍ＋ｎ＝１〜３０） (10) Ethylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol

(M + n = 1-30)

(11) 2,5,8,11-tetramethyl-6-dodecin-5,8-diol

  These acetylene alcohols and acetylene glycols can be obtained on the market, and for example, the product name Safinol of Air Products and Chemicals Inc. is known as a commercial product. Specific examples of commercially available products include: Safinol 61 as (3) above, Olfin B as (4) above, Olphine P as (5) above, Olphine Y as (7) above, Safinol 82 as above (8), ( 9) Safinol 104, Orphine AK-02, (10) Safinol 400 series, (11) Safinol DF-110, etc.

(Chelating agent)
The developer may further 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 Aminopolycarbonate, such as its sodium salt 2-phosphonobutanetricarboxylic acid-1,2,4, potassium salt, sodium salt thereof; 2-phosphonobutanone tricarboxylic acid-2,3,4, potassium salt, sodium salt thereof; Phosphonoethanetricarboxylic acid-1,2,2, potassium salt, sodium salt thereof; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodium salt; 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% in the developing solution at the time of use. It is made to contain in the range of 0.01-0.5 mass%.

(Other additives)
In addition to the above components, the following components can be used in combination in the developer used in the image forming method of the present invention, if 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 image forming material used in the image forming method of the present invention is an image forming material obtained by sequentially laminating an image recording layer and optionally a protective layer on a support, and the image recording layer is described below. Characterized in that it comprises a composition comprising the stated ingredients.

[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, or SHG-YAG laser as a light source, for example, US Pat. No. 2,850,445. Certain photoreducible dyes described in No. 1, 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) , Hexaarylbiimidazole, radical generator and dye combination system (Japanese Examined Patent Publication No. 45-37377), hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Examined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54- 155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (Japanese Patent Laid-Open No. 48-84183), Azine and merocyanine dye systems (Japanese Patent Laid-Open No. 54-151024), 3-ketocoumarin and activator systems (Japanese Patent Laid-Open Nos. 52-111261, 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-64- 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 (violet laser) having a wavelength of 400 to 410 nm has been developed, and a photoinitiating system exhibiting high sensitivity at a wavelength of 450 nm or less that responds to the laser has been developed, and these photoinitiating systems are also used. For example, a cationic dye / borate system (Japanese Patent Laid-Open No. 11-84647), a merocyanine dye / titanocene system (Japanese Patent Laid-Open No. 2000-147663), a carbazole type dye / titanocene system (Japanese Patent Laid-Open No. 2001-42524), and the like can be mentioned. In the present invention, a system using a titanocene compound is particularly preferable in terms of 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, - difluoro-1-yl, di - cyclopentadienyl -Ti- bis-2,6-difluoro-3- (pyrr-1-yl) - can be exemplified 1-yl and the like.

  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.

  Further, if necessary for the photoinitiating system, thiol compounds such as 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 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, based on 100 parts by weight of the polymerizable compound having at least one ethylenically unsaturated group described later. More preferably, it is used in the range of 0.2 to 50 parts by weight.

[Polymerizable compound having at least one ethylenically unsaturated group]
A 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 that undergoes addition polymerization, crosslinking, and curing by the action of. 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 triacrelane , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester Examples include acrylate oligomers.

  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 [ - (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p-(methacryloxyethoxy) phenyl] dimethyl methane.

  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, 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. The amount of the polymerizable compound having at least one ethylenically unsaturated bond is 5 to 80% by mass, preferably 30 to 70% by mass, based on the total components of the image recording layer.

[Binder polymer]
The binder polymer (polymer binder) used in the image recording layer of the image forming material 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. Organic polymer that is soluble or swellable 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 binder polymer having a weight average molecular weight of 5000 to 300,000 and an acid value of 20 to 200 is effectively used. The
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 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 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]
When the image recording layer composition of the image forming material of the present invention is applied on an aluminum support described later, it is used after being dissolved in various organic solvents. 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.

A surfactant can be added to the image recording layer of the image forming material of the present invention 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]
In the image forming material of the present invention, since the exposure is usually 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, in US Pat. No. 292,501 and US Pat. No. 44,563, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer is added to a hydrophilic polymer mainly composed of polyvinyl alcohol in an amount of 5 to 80. 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 subjected to substrate surface treatment described later as appropriate.
(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 dirtiness between the image recording layer and the substrate. 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 No. 11-84684, No. 11-327152, No. 2000-10292, No. 2000-235254, No. 2000-352824, Japanese Patent Application No. 11-284091, No. 2001-209170, etc. Can be mentioned.

[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 the present invention, as described above, an overcoat layer having oxygen barrier properties is usually provided on the image recording layer, and the developer in the present invention is used to remove the overcoat layer and perform image recording. A method of simultaneously removing the unexposed layer or a method of removing the overcoat 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 about 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. 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 case where the image forming material of the present invention 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 (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>
When the following composition was mixed and stirred, an exotherm was observed after about 5 minutes. 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 high-sensitivity 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 an image recording layer.

<Photopolymerizable composition 1>
1.8g of ethylenically unsaturated bond-containing compound (A1)
Binder polymer (B1) 1.5g
Sensitizer (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 wt% aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) was applied on the photopolymerizable image recording layer thus formed so that the dry application weight was 2.5 g / m ^2. And 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 an image recording layer.

<Photopolymerizable composition 4>
Ethylenically unsaturated bond-containing compound (A2) 1.5 g
Binder polymer (B2) 1.8g
Sensitizer (C2) 0.1g
0.2 g of the above photoinitiator (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 wt% aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) was applied on the photopolymerizable image recording layer thus formed so that the dry application 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.
Development was carried out by standard processing using an automatic processor (LP-850P2 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 (A + B = a mol / L)
Surfactant C g / L
Silicate D g / L (SiO ₂ component b mol / L)
2,4,7,9-Tetramethyl-5-decyne-4,7-diol 1g / L
Ethylenediaminetetraacetic acid, 4Na salt (chelating agent) 2g / 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 developing speed of the non-image area with the alkali developer is a value obtained by dividing the film thickness (μm) 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). (Plate jet 4 manufactured by CSI), the exposure amount is 0.25 mJ / cm ² , and the photopolymerizable compositions 2 to 4 are Violet laser (Fuji Photo Film's Raxel Vx9600CTP), and the exposure amount is 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)
Development was performed at 28 ° C. for 18 seconds using LP-850PII manufactured by Fuji Photo Film Co., Ltd., and the developability of the actual non-image area was observed.
(Evaluation of printing durability)
The resulting lithographic printing plate precursor was subjected to photopolymerization composition 1 using an FD • YAG laser (CSI Co., Ltd., plate jet 4) at 2400 dpi, 175 lines, image exposure at 0.25 mJ / cm ² , and photopolymerizable composition 2 No. 3 was a Violet laser (Laxel Vx9600CTP manufactured by Fuji Photo Film Co., Ltd.) and image exposure was performed 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 developer pH latitude when sensitivity varies ± 10%)
The resulting lithographic printing plate precursor was subjected to photopolymerization composition 1 using an FD • YAG laser (CSI Co., Ltd., plate jet 4) at 2400 dpi, 175 lines, image exposure at 0.25 mJ / cm ² , and photopolymerizable composition 2 No. 3 was a Violet laser (Laxel Vx9600CTP manufactured by Fuji Photo Film Co., Ltd.) and image exposure was performed at 2400 dpi at 175 lines and 0.05 mJ / cm ² . After the exposure, the protective layer was removed by washing with tap water, and then developed with each developer of Examples and Comparative Examples at 30 ° C. for 12 seconds using LP-1310HII 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 density of the image portion of the lithographic printing plate obtained by development was measured using a Macbeth reflection densitometer RD-918, and the cyan density using a red filter equipped in the densitometer. The reciprocal of the exposure necessary to obtain a measured density of 0.8 was used as an index of sensitivity.

上記表中、現像性評価において○は残膜なしを表す。

In the above table, ◯ in the evaluation of developability indicates no remaining film.

  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 the development activity due to carbon dioxide gas is small (Tables 2 to 5, Developers 1 to 13). On the other hand, regardless of the image forming method of the present invention, when image formation was performed, a phenomenon was observed in which a residual film was formed and sufficient developability could not be ensured, or printing durability was reduced (Table 1). 2-5, comparative developers 14-20).

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 (11)

Negative type in which 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 is formed on a support. After image exposure of the image-forming material, it contains at least one carbonate and at least one bicarbonate and at least one alkali silicate, the total number of moles of carbonate and bicarbonate a, and SiO ₂ in the alkali silicate. The ratio of the number of moles b of the components a: b = 1: 0.3 to 1: 2, the total molar concentration of a and b a + b = 0.1 to 2 mol / L, and a pH of 9 to 13.0 An image forming method, wherein the development is carried out using the developer. 2. The image forming method according to claim 1, wherein the developer contains 1 to 10% by mass of at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant. The anionic surfactant is an anionic surfactant having an anionic group of sulfonic acid or an anionic group of sulfuric monoester and having at least one aromatic group which may have a substituent. The image forming method described. The image forming method according to claim 2, wherein the nonionic surfactant is at least one surfactant selected from the group consisting of nonionic aromatic ether surfactants of the following 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.) 5. The method 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. The image forming method according to claim 1. The carbonate is at least one selected from the group consisting of potassium carbonate, sodium carbonate, and ammonium carbonate, and the hydrogen carbonate is at least selected from the group consisting of potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate. The image forming method according to claim 1, wherein the image forming method is one type. The image forming method according to claim 1, wherein the developer further contains an antifoaming agent. The image forming method according to claim 7, wherein the antifoaming agent is at least one selected from the group consisting of acetylene alcohol and acetylene glycol. The photopolymerization initiation system 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. Image forming method. The image forming method according to claim 9, wherein the photopolymerization initiation system contains a titanocene compound. The image forming method according to claim 9, wherein the photopolymerization initiation system includes a titanocene compound and a triazine compound.

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