JP2002278085A - Developing solution for photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing solution for a photosensitive planographic printing plate material having good leachability of a non-image area and excellent in ink receptivity and printing resistance. SOLUTION: The developing solution for a photosensitive planographic printing plate having a photopolymerizable layer contains an alkanolamine having a 1-10C alkyl group and at least one compound having a 2-10C alkyl group and a polyalkyleneoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a developer for a photosensitive lithographic printing plate using a photosensitive composition. More specifically, the present invention relates to a developer for a photosensitive lithographic printing plate using a photosensitive composition capable of forming an image using a laser. In addition, the present invention relates to a negative photosensitive lithographic printing plate developer having sensitivity to light in the wavelength range of near infrared light to infrared light of 750 nm or more.

[0002]

2. Description of the Related Art In addition to a conventional photosensitive resin for forming an image by being exposed by ultraviolet light exposure and a lithographic printing plate using the same, a high-sensitivity which has greatly improved the sensitivity to light in the visible light region is provided. A photosensitive resin system was developed, and an argon ion laser (488 nm) and FD-YAG (532n
m) and the like, and a system capable of direct drawing and plate making by these lasers has been put to practical use. These have a photopolymerization initiator, a dye sensitizer, and a polymerizable compound, and use the light energy absorbed by the dye sensitizer for radical cleavage of the photopolymerization initiator to polymerize the polymerizable compound by generated radicals. Is used.

[0003] In addition to visible light lasers, 7
High-power semiconductor lasers and YAG lasers that emit light in the region of 50 nm or more have been used as light sources,
Development of a photosensitive material adapted to the output of these light sources and a printing plate using the same has been actively performed.

With respect to a specific combination of a photopolymerization initiator and a sensitizer constituting the photopolymerization system, for example, a combination of an organic boron anion and a cationic dye is disclosed in
Nos. -143044 and 62-150242,
-5988, JP-A-2000-89455, and the like. As another example of the photopolymerization initiator, a combination of a titanocene compound and a sensitizer is disclosed in
221110 and the like. Further, a combination of a trihaloalkyl-substituted triazine compound and a cyanine dye is found in JP-A-2-189548 and the like, and a combination of a hexaarylbiimidazole compound and a dye is described in JP-A-1-279903. .

However, the subject of the photosensitive composition as described above is development stability. That is, depending on development conditions, elution failure of an unexposed portion may occur. This problem is likely to occur particularly when the sensitivity is increased, and it is desired to achieve both high sensitivity and development stability. This tendency is particularly remarkable when a sensitizing dye sensitive to light having a wavelength of 750 nm or more is added. When the elution failure occurs, there arises a problem that a non-image portion is easily stained during printing. On the other hand, for example, as described in JP-B-56-39464, benzene alcohol or JP-A No. 2000-1980.
Use of a polyoxyethylene-polyoxyfluoropolypropylene copolymer or the like described in No. 12147 inhibits ink acceptability,
Or, a problem such as a decrease in the number of printed sheets during printing occurs.
Accordingly, there is a need for a dissolution promoter for the non-image portion that promotes dissolution of the non-image portion and does not inhibit the ink receptivity of the image portion or reduce the strength of the image portion.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a developer for a photosensitive lithographic printing plate which has improved development stability, that is, improved dissolution of the non-image area without impairing the printing performance of the image area. Is to do.

[0007]

An object of the present invention is to provide a photosensitive lithographic printing plate developer having a photopolymerizable layer,
A photosensitive lithographic printing plate development comprising an alkanolamine having an alkyl group having 1 to 10 carbon atoms and at least one compound having an alkyl group having 2 to 10 carbon atoms and a polyalkyleneoxy group. Achieved by liquid.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The alkanolamine of the present invention is
Preferred are compounds represented by the following general formula.

[0009]

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In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms. R ₂ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have a hydrophilic substituent such as a hydroxyl group, a carboxylic acid group, and a sulfonic acid group.
R ₁ and R ₂ preferably have 1 to 6 carbon atoms. n ₁ and n ₂ may be the same or different represent an integer of 2 or more. A preferred range of n ₁ and n ₂ is 2-6.

Examples of the compound represented by Chemical formula 1 in the present invention are shown below, but are not limited thereto.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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Preferred compounds of the present invention having an alkyl group having 2 to 10 carbon atoms and a polyalkyleneoxy group are represented by the following general formula.

[0026]

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R ₃ and R _{4 each} represent a hydrogen atom or a compound having 2 or more carbon atoms;
It represents an alkyl group having 0 or less, and at least one of R ₃ and R ₄ is an alkyl group having 2 to 10 carbon atoms. This alkyl group preferably has 2 to 6 carbon atoms. Also, R
_The alkyl group represented by ₃ or R ₄ may have a hydrophilic substituent such as a hydroxyl group, a carboxylic acid group or a sulfonic acid group.
AO represents ethylene oxide, propylene oxide, or random polymerization or block polymerization of ethylene oxide and fluorene oxide. m represents an integer of 2 or more. The preferred range of m is 2 to 1.
0, more preferably 2 to 6.

Examples of the compound of formula (15) are shown below, but are not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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The content of the compound having an alkanolamine or a compound having a polyalkyleneoxy group contained in the developer is from 0.001 to 5% by weight, particularly preferably from 0.01 to 2% by weight.

As the alkaline aqueous solution used in the developer of the present invention, a developer composed of an alkali silicate or a base is used, and the pH is preferably in the range of 12.5-13.5. The alkali silicate used in the present invention preferably shows alkalinity when dissolved in water, and examples thereof include alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate, and ammonium silicate. They can be used alone or in combination of two or more.

In a preferred embodiment of the present invention, the alkali silicate is an alkali metal silicate or ammonium silicate, and its SiO ₂ / M ₂ O molar ratio (M represents an alkali metal atom or an ammonium group) is 0.5 to 3.0. Is preferred, especially 0.5
~ 2.0 is preferred.

Various surfactants can be added to the developer used in the present invention, if necessary, for the purpose of accelerating the developing property, dispersing the developing residue, and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic and
Nonionic and amphoteric surfactants are included. Preferred examples of the surfactant include polyoxyethylene alkyl phenyl ethers,
Polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxyfluorophenol alkyl ethers, polyglycerin fatty acid partial esters, sorbitan fatty acid partial esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol Fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenated castor oils, polyoxyethylene polyglycerin fatty acid esters, polyoxyethylene-polyoxyphenylene block copolymer, ethylenepolyamine polyoxyethylene -Polyoxyphenylene block copolymer adduct, fatty acid dye Non-ionic surfactants such as ureamites, N, N-bis-2-human peroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxytotes, fatty acid salts, adietate salts, human peroxyalkanes Sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl Taurine sodium salt, N-alkylsulfosuccinic acid monoamido disodium salt, petroleum sulfonates, sulfated tallow oil, sulfates of fatty acid alkyl esters, phosphate Diethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl sulfates, alkyl phosphates, polyoxyethylene alkyl ethers Phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, styrene /
Partially saponified maleic anhydride copolymers, partially saponified olefin / maleic anhydride copolymers, anionic surfactants such as naphthalenesulfonate formalin condensates, alkylamine salts, tetrabutylammonium phenolite, etc. Cationic surfactants such as quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylenepolyamine derivatives; amphoteric surfactants such as carboxyheptaines, aminocarboxynic acids, sulfobetaines, aminosulfuric esters, imitadazolines, etc. Is mentioned.
Among the surfactants listed above, there is polyoxyethylene,
Polyoxyalkylenes such as polyoxymethylene, polyoxypropylene, and polyoxyethylene can be read, and their surfactants are also contained. Further preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such a fluorine-based surfactant include an anionic type such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate and perfluoroalkyl phosphate, an amphoteric type such as perfluoroalkyl heptane, and perfluoroalkyltrimethylammonium salt. Cation- and perfluoroalkylamine oxide adducts, perfluoroalkylethylene oxide adducts, perfluoromers containing perfluoroalkyl groups and hydrophilic groups, perfluoromers containing perfluoroalkyl groups and lipophilic groups, perfluoroalkyl groups, hydrophilic and lipophilic Nonionic forms such as group-containing oligomers, perfluoroalkyl groups and lipophilic group-containing urethanes are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

Various developing stabilizers are preferably used in the developer used in the present invention. Preferred examples thereof include poly (ethylene glycol) adducts of sugar alcohols described in JP-A-6-282079, phosphonium salts such as tetrabutylphosphonium chromite, and iodonium salts such as diphenyliodinium chlorite. Further, Japanese Patent Application Laid-Open
Anionic or amphoteric surfactants described in JP-A-51324, water-soluble cationic polymers described in JP-A-55-95946, and water-soluble amphoteric surfactants described in JP-A-56-142528. There is a molecular electrolyte. Further, an organic boron compound to which an alkylene glycol is added as disclosed in JP-A-59-84241, JP-A-61-21
5554, a polyethylene glycol having a weight average molecular weight of 300 or more, a fluorinated surfactant having a cationic group described in JP-A-63-175858, JP-A 2-3
No. 9157, a water-soluble ethylene oxide adduct obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol, and a water-soluble polyalkylene compound.

It is advantageous from the viewpoint of transportation that the developing solution used in the present invention is a concentrated solution having a smaller water content than at the time of use, and is diluted with water at the time of use. In this case, the degree of concentration is appropriately such that each component does not cause separation or precipitation, and although it depends on the content, usually, a concentrated liquid: water =
It can be concentrated to about 1: 0 to 1:10. Further, since the container is alkaline, it is preferable to use a material which does not transmit carbon dioxide gas and which is not damaged during transportation for safety, and a resin container such as a hard bottle and a cue filter is preferably used.

In the processing method of the present invention, after exposure, the processing is usually performed by an automatic developing machine. An automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate, each processing solution tank and a spray tank, and assembles with a pump while horizontally transporting the exposed printing plate. Each processing liquid is sprayed from a spray nozzle to perform development and post-processing. Recently, a method has been developed in which a printing plate is immersed and conveyed by a submerged kit roll or the like in a developing tank filled with a developing solution to perform development processing, and such a developing method can also be suitably applied to the present invention. . In such an automatic developer,
Processing can be performed while replenishing the replenisher in accordance with the development processing amount, operating time, and the like.

The printing plate developed with a developer having such a composition is post-treated with washing water, a rinsing solution containing a surfactant or the like, a finisher or a protective gum solution containing aradium gum or a starch derivative as a main component. Is given. The post-treatment of the printing plate of the present invention can be used in various combinations of these treatments, for example, development → washing → rinsing solution treatment containing a surfactant or development → washing → treatment with a finisher solution is a rinsing solution or finisher It is preferable because the fatigue of the liquid is small. Further, a countercurrent multistage treatment using a rinsing liquid or a finisher liquid is also a preferred embodiment. These post-processings are generally performed using an automatic developing machine including a developing section and a post-processing section. A method of spraying the post-treatment liquid from a spray nozzle and a method of transporting the post-treatment liquid through a treatment tank filled with the treatment liquid are used. There is also known a method in which a fixed amount of a small amount of aqueous water is supplied to a plate surface after development, washed with water, and the waste liquid is reused as dilution water of a developer undiluted solution. In such automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher in accordance with the processing amount and the operating time. In addition, a so-called disposable processing method in which treatment is performed with a substantially unused post-treatment liquid is also applicable. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing.

The photosensitive lithographic printing plate having a photopolymerizable layer according to the present invention is a lithographic printing plate having at least a layer comprising a photopolymerization initiator and a polymerization composition applied on a support, and irradiating the polymer composition with light. Is a lithographic printing plate in which a polymerized portion is an ink-accepting portion by causing a crosslinking and a polymerization reaction and removing an unreacted portion.

In the printing plate of the present invention, any compound can be used as the photopolymerization initiator as long as it is a compound capable of generating a radical upon irradiation with light. For example, trihaloalkyl-substituted compounds (eg, s-triazine compounds and oxadiazole derivatives as trihaloalkyl-substituted nitrogen-containing heterocyclic compounds, trihaloalkylsulfonyl compounds), hexaarylbisimidazole, titanocene compounds, ketoxime compounds, thio compounds, Organic peroxides and the like can be mentioned, but an organic boron salt is particularly preferably used. As the organic boron salt, it is particularly preferable to use a compound having an organic boron anion represented by Chemical formula 27.

[0050]

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In the above formula, R ₅ , R ₆ , R ₇ and R ₈
May be the same or different, and represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or a heterocyclic group. Of these, it is particularly preferred that one of R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group and the other substituent is an aryl group.

In the above-mentioned organic boron anion, a cation forming a salt with the organic boron anion simultaneously exists. Examples of the cation in this case include an alkali metal ion and an onium ion. Onium salts include ammonium, sulfonium, phodonium and phosphonium compounds. When a salt of an alkali metal ion or an onium compound with an organic boron anion is used, a sensitizing dye is separately added to impart photosensitivity in the wavelength range of light absorbed by the dye.

One of preferred embodiments according to the present invention is a photosensitive composition containing an organic boron salt together with a sensitizing dye which sensitizes to a wavelength range of 380 nm to 1300 nm,
In this case, the organic boron salt does not exhibit photosensitivity in the wavelength region from visible light to infrared light, and exhibits photosensitivity to light in such a wavelength region only by adding a sensitizing dye.

The organic boron salt in this case is a salt containing an organic boron anion represented by the above-mentioned chemical formula 27. As the cation forming the salt, an alkali metal ion and an onium compound are preferably used. Particularly preferred examples are as onium salts with organic boron anions,
Examples include ammonium salts such as tetraalkylammonium salts, sulfonium salts such as triarylsulfonium salts, and phosphonium salts such as triarylalkylphosphonium salts. Examples of particularly preferred organic boron salts are shown below.

[0055]

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[0056]

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There is a preferred range for the proportion of the organic boron salt in the photosensitive composition, and the organic boron salt is used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total photosensitive composition. Preferably, it is included.

The photosensitive composition of the present invention is preferably used in combination with a trihaloalkyl-substituted compound together with the above organic boron salt as a photopolymerization initiator. By using these together, higher sensitivity can be realized. The trihaloalkyl-substituted compound referred to herein is, specifically, a compound having at least one trihaloalkyl group such as a trichloromethyl group and a tribromomethyl group in a molecule. Preferred examples include the trihaloalkyl group. Examples of the compound bonded to the nitrogen heterocyclic group include an s-triazine derivative and an oxadiazole derivative, or
And a trihaloalkylsulfonyl compound in which the trihaloalkyl group is bonded to an aromatic ring or a nitrogen-containing heterocyclic ring via a sulfonyl group.

Particularly preferred examples of the trihaloalkyl-substituted nitrogen-containing heterocyclic compound and trihaloalkylsulfonyl compound are shown below.

[0060]

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[0061]

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When the above-mentioned trihaloalkyl-substituted compound is used in combination, the ratio of the trihaloalkyl-substituted compound to the organic boron salt is in the range of 0.1 to 50 parts by weight per 1 part by weight of the organic boron salt. Is preferred.

As for the sensitizing dye according to the present invention, 38
It sensitizes the decomposition of the photopolymerization initiator in the wavelength range of 0 nm to 1300 nm, and includes merocyanine, coumarin, xanthene, thioxanthene, as various cationic dyes, anionic dyes, and neutral dyes having no charge.
Azo dyes and the like can be used. Among these, particularly preferred examples are cyanine as a cationic dye, carbocyanine,
It is a dye selected from hemicyanine, methine, polymethine, triarylmethane, indoline, azine, thiazine, xanthene, oxazine, acridine, rhodamine, and azamethine dyes. In combination with these cationic dyes, they are particularly preferably used because of their high sensitivity and excellent storage stability. Furthermore, in recent years 380-4
An output device (plate setter) equipped with a violet semiconductor laser having an oscillation wavelength in a range of 10 nm has been developed. As a photosensitive system having high sensitivity corresponding to this output device, a system containing a pyrylium compound or a thiopyrylium compound as a sensitizing dye is preferable. Examples of preferred sensitizing dyes according to the present invention are shown below.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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Among the above-mentioned sensitizing dyes, particularly, in a system for imparting photosensitivity to light in the near-infrared to infrared wavelength region of 750 nm or more, which is one of the objects of the present invention, It is necessary that the dye has absorption in such a wavelength region as a sensitizing dye, and particularly preferred examples used for such a purpose are shown below.

[0071]

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[0072]

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There is a preferable range in the quantitative ratio between the sensitizing dye and the photopolymerization initiator as described above. Sensitizing dye
The photopolymerization initiator is used in an amount of from 0.01 part by weight to 1 part by weight.
It is preferably used in the range of 00 parts by weight, and more preferably the photopolymerization initiator is used in the range of 0.1 to 50 parts by weight.

In the present invention, a polymer having a polymerizable double bond in the side chain and a carboxyl group-containing monomer as a copolymer component is used as the polymer binder. The polymer is preferably an alkali-soluble polymer. In this case, the proportion of the carboxyl group-containing monomer contained in the copolymer composition is preferably 5% by weight or more and 99% by weight or less in 100% by weight of the total composition. May not be dissolved in an alkaline aqueous solution. More preferably, the ratio of the carboxyl group-containing monomer contained in the copolymer composition is 10% by weight or more and 80% by weight in the total composition of 100% by weight.
% By weight, particularly preferably from 20% by weight to 70% by weight. The proportion of the monomer having a polymerizable double bond contained in the copolymer composition is preferably from 1% by weight to 95% by weight, more preferably 10% by weight, based on 100% by weight of the total composition. 80% by weight or more
Or less, and particularly preferably from 20% by weight to 75% by weight.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, crotonic acid, maleic acid, fumaric acid, monoalkyl maleate, and fumaric acid. Examples include acid monoalkyl esters, 4-carboxystyrene, and the like.

When a polymer having a polymerizable double bond introduced into the side chain of an alkali-soluble polymer having a carboxyl group is used, a highly sensitive negative photosensitive composition can be obtained in combination with the above-mentioned organic boron salt. In addition, since high sensitivity in a wide wavelength range can be realized in combination with the above-described sensitizing dye, it becomes possible to cope with scanning exposure using various laser beams. Monomers for introducing a polymerizable double bond into the polymer side chain include allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, 1-
Propenyl-acrylate, 1-propenyl-methacrylate, β-phenyl-vinyl-methacrylate, β-
Phenyl-vinyl-acrylate, vinyl methacrylamide, vinyl acrylamide, α-chloro-vinyl-methacrylate, α-chloro-vinyl-acrylate, β
-Methoxy-vinyl-methacrylate, β-methoxy-
Vinyl-acrylate, vinyl-thio-acrylate,
Vinyl-thio-methacrylate and the like.

Particularly preferred as the polymer used in the present invention is a polymer having a phenyl group substituted by a vinyl group in a side chain and having a carboxy group-containing monomer as a copolymer component. The phenyl group substituted by the vinyl group is bonded directly or via a linking group to the main chain, and the linking group is not particularly limited, and includes an arbitrary group, an atom, or a complex group thereof. Further, the phenyl group may be substituted with a substitutable group or atom, and the vinyl group is a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group, It may be substituted with an aryl group, an alkoxy group, an aryloxy group or the like. More specifically, the polymer having a phenyl group in which a vinyl group is substituted in the side chain has a group represented by the following formula 17 in the side chain.

[0078]

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In the formula, Z ₁ represents a linking group, and R ₁₁ , R ₁₂ ,
And R ₁₃ are a hydrogen atom, a halogen atom, a carboxy group,
Sulfo group, nitro group, cyano group, amide group, amino group,
An alkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like, and these groups may be further substituted with an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, a hydroxy group, or the like. . R ₁₄ represents a substitutable group or atom. n ₁ represents 0 or 1, m ₁ represents an integer of 0 to 4, k ₁ is an integer of 1-4.

The above general formula will be described in more detail.
As the linking group for Z ₁ , an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, an arylene group, —N (R ₁₅ )
-, - C (O) -O -, - C (R 16) = N -, - C
(O)-, a sulfonyl group, a heterocyclic group, a group represented by the following formula 41 alone or in combination of two or more. Here, R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group, an aryl group, or the like. Further, the linking group described above includes
It may have a substituent such as an alkyl group, an aryl group or a halogen atom.

[0081]

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The heterocyclic group includes a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isoxazole ring, an oxazole ring, an oxadiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, and a thiatriazole ring. , Indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring,
Benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, nitrogen-containing heterocycle such as quinoline ring, quinoxaline ring, furan ring, thiophene ring and the like. A substituent may be bonded to the ring. Examples of the group represented by Chemical formula 40 are shown below, but it should not be construed that the invention is limited thereto.

[0083]

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[0084]

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[0085]

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[0086]

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Among the groups represented by the above formulas 40, preferred
Things exist. That is, R₁₁And R ₁₂Is a hydrogen atom and R₁₃
Is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (meth
Butyl, ethyl and the like). Furthermore, Z
₁The linking group is preferably a group containing a heterocyclic ring, and k₁Is
Those which are 1 or 2 are preferred.

Examples of the polymer having the group represented by Chemical formula 40 and having a carboxy group-containing monomer as a copolymer component are shown below. In the formula, the number is the copolymer total composition 1
Represents the weight percent of each repeat unit in 00 weight percent.

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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The polymer of the present invention may further contain another monomer as a copolymer component. Other monomers include styrene, 4-methylstyrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-carboxystyrene, 4-aminostyrene, chloromethylstyrene, styrene derivatives such as 4-methoxystyrene, methyl methacrylate Ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, etc .; alkyl methacrylates such as phenyl methacrylate, benzyl methacrylate or alkyl aryl Esters, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methoxydiethylene glycol methacrylate monoester, methoxypolyethylene methacrylate Methacrylates having an alkyleneoxy group such as phenol monoester and polypropylene glycol methacrylate, amino-containing methacrylates such as 2-dimethylaminoethyl methacrylate and 2-diethylaminoethyl methacrylate, or acrylic acid esters. Examples similar to the corresponding methacrylic acid ester, or, as a monomer having a phosphate group, vinylphosphonic acid or the like, or allylamine, amino group-containing monomers such as diallylamine, or vinylsulfonic acid and a salt thereof, allylsulfonic acid and Monomers having a sulfonic acid group, such as salts thereof, methallylsulfonic acid and its salts, styrenesulfonic acid and its salts, 2-acrylamido-2-methylpropanesulfonic acid and its salts, Monomers having a nitrogen-containing heterocycle such as n-pyridine, 2-vinylpyridine, N-vinylimidazole and N-vinylcarbazole, or 4-vinylbenzyltrimethylammonium chloride and acryloyloxyethyltrimethylammonium chloride as monomers having a quaternary ammonium base , Methacryloyloxyethyltrimethylammonium chloride, quaternized dimethylaminopropylacrylamide with methyl chloride, quaternized N-vinylimidazole with methyl chloride, 4-vinylbenzylpyridinium chloride, etc., or acrylonitrile, methacrylonitrile, or acrylamide, Methacrylamide, dimethylacrylamide, diethylacrylamide, N-isopropylacrylamide, dia Acrylamide or methacrylamide derivatives such as tonacrylamide, N-methylolacrylamide, N-methoxyethylacrylamide, 4-hydroxyphenylacrylamide, and further acrylonitrile, methacrylonitrile, phenylmaleimide, hydroxyphenylmaleimide, vinyl acetate, vinyl chlorovinyl acetate, and probion Vinyl esters such as vinyl acrylate, vinyl butyrate, vinyl stearate, and vinyl benzoate, and methyl vinyl ether;
Vinyl ethers such as butyl vinyl ether, and others,
Various monomers such as N-vinylpyrrolidone, acryloylmorpholine, tetrahydrofurfuryl methacrylate, vinyl chloride, vinylidene chloride, allyl alcohol, vinyltrimethoxysilane, and glycidyl methacrylate are exemplified.

There is a preferred range of the molecular weight of the polymer according to the present invention.
It is preferably in the range of 0 to 1,000,000, and more preferably 5
More preferably, it is in the range of 000 to 500,000.

The photosensitive composition of the present invention preferably further contains an ethylenically unsaturated compound. By combining these, higher sensitivity can be realized, and a lithographic printing plate excellent in printing performance can be obtained.

The ethylenically unsaturated compound according to the present invention includes a polymerizable compound having two or more polymerizable double bonds in a molecule. Examples of preferred ethylenically unsaturated compounds include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, trisacryloyloxyethyl isocyanurate, and tripropylene. Examples thereof include polyfunctional acrylic monomers such as glycol diacrylate, ethylene glycol glycerol triacrylate, glycerol epoxy triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.

Alternatively, instead of the above polymerizable compounds, oligomers having radical polymerizability are also preferably used, and polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate can be used as various oligomers having acryloyl or methacryloyl groups introduced therein. ) Acrylates and the like are similarly used, but these can also be preferably used as ethylenically unsaturated compounds.

A more preferred embodiment of the ethylenically unsaturated compound is a polymerizable compound having two or more phenyl groups substituted by a vinyl group in the molecule. When this compound is used, styryl radicals generated by the generated radicals are effectively cross-linked by recombination with each other, which is extremely preferable for producing a highly sensitive negative photosensitive material.

The polymerizable compound having two or more phenyl groups substituted by a vinyl group in the molecule is typically represented by the following general formula.

[0101]

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In the formula, Z ₂ represents a linking group, and R ₂₁ , R ₂₂ and R ₂₃ represent a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an amide group, an amino group, an alkyl group , An aryl group, an alkoxy group, an aryloxy group, and the like, and these groups may be further substituted with an alkyl group, an amino group, an aryl group, an alkenyl group, a carboxy group, a sulfo group, a hydroxy group, or the like. R ₂₄ represents a substitutable group or atom. m ₂ represents an integer of 0 to 4, k ₂ is an integer of 2 or more.

This will be described in more detail. Examples of the linking group for Z ₂ include an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, an arylene group, —N (R ₂₅ ) —, and —C (O) —O
—, —C (R ₂₆ ) ＝ N—, —C (O) —, a sulfonyl group, a heterocyclic group, and the like, alone or in combination of two or more. Here, R ₂₅ and R ₂₆ represent a hydrogen atom, an alkyl group, an aryl group, or the like. Further, the linking group described above includes
It may have a substituent such as an alkyl group, an aryl group or a halogen atom.

Examples of the heterocyclic group include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an isoxazole ring, an oxazole ring, an oxadiazole ring, an isothiazole ring, a thiazole ring, a thiadiazole ring, and a thiatriazole ring. , Indole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring,
Benzselenazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, nitrogen-containing heterocycle such as quinoline ring, quinoxaline ring, furan ring, thiophene ring, and the like. The groups may be attached.

Preferred compounds exist among the compounds represented by the above formula (51). That is, a compound in which R ₂₁ and R ₂₂ are hydrogen atoms, R ₂₃ is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (eg, a methyl group or an ethyl group) and k ₂ is 2 to 10 is preferable. Specific examples of the compound represented by Chemical Formula 51 are shown below, but it should not be construed that the invention is limited thereto.

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There is a preferred range for the proportion of the above ethylenically unsaturated compound in the photosensitive composition, and 1 part by weight to 60 parts by weight of the ethylenically unsaturated compound in 100 parts by weight of the total photosensitive composition. It is preferably contained in the range of 5 parts by weight, more preferably in the range of 5 parts by weight to 50 parts by weight.

In the above-described photosensitive composition containing a photopolymerization initiator, a sensitizing dye, and an ethylenically unsaturated compound in the polymer complex salt, such an additive is uniformly dispersed using the polymer complex salt as a matrix. This is presumed to prevent the diffusion of additives. One of the features of the present invention is that the storage stability of the photosensitive composition is significantly improved.

The photosensitive composition of the present invention is immediately cured by light irradiation without being affected by oxygen in the air, and becomes insoluble in a developing solution. Therefore, there is no need to provide an overlayer on the photosensitive layer. It also has the advantage that development and printing can be performed well without performing any heat treatment after exposure.

As another element constituting the photosensitive composition, a polymerization inhibitor can be preferably added. For example,
Compounds such as quinones and phenols are preferably used, and hydroquinone, p-methoxyphenol, catechol, t-butylcatechol, 2-naphthol, 2,6
Compounds such as -di-t-butyl-p-cresol are preferably used. The preferred ratio of these polymerization inhibitors to the above-mentioned ethylenically unsaturated compound is preferably in the range of 0.001 to 0.1 part by weight per 1 part by weight of the ethylenically unsaturated compound.

A coloring agent can be preferably added as another element constituting the photosensitive composition. The colorant is used for the purpose of enhancing the visibility of the image area after the exposure and development processing, and various kinds of colorants such as carbon black, phthalocyanine dye, triarylmethane dye, anthraquinone dye, azo dye, etc. Dyes and pigments can be used, and can be preferably added in the range of 0.005 part by weight to 0.5 part by weight with respect to 1 part by weight of the binder.

The components constituting the photosensitive composition may contain other components in addition to the components described above for various purposes. For example, it is also preferable to add inorganic fine particles or organic fine particles for the purpose of preventing blocking of the photosensitive composition or improving the sharpness of an image after development.

With respect to the thickness of the photosensitive layer itself when used as a lithographic printing plate material, it is preferable to form the photosensitive layer on a support with a dry thickness in the range of 0.5 to 10 microns, and more preferably 1 to 5 microns. It is extremely preferable that it is within the range, in order to greatly improve the printing durability.
The photosensitive layer is prepared by preparing a solution in which the above three components are mixed, coating the solution on a support using various known coating methods, and drying the solution. As the support, for example, a film or a polyethylene-coated paper may be used, but a more preferable support is an aluminum plate having a polished and anodized film.

In order to use the material having the photosensitive layer formed on the support as described above as a printing plate, the material is subjected to contact exposure or laser scanning exposure, and the exposed portion is crosslinked. Since the solubility in the alkaline developing solution is reduced, the unexposed portion is eluted with the alkaline developing solution described later to form a pattern.

Particularly preferred laser light sources used for laser scanning exposure according to the present invention are lasers having an oscillation wavelength in the near infrared region, and various semiconductor lasers, YAG
Solid lasers such as lasers and glass lasers are most preferred.

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EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as well as the effects. Parts in Examples are parts by weight.

Example 1 As a polymer, P-1 (Japanese Patent Application No. 2000-223304) was used.
In accordance with the method described in JP-A No. 5-2, a monomer obtained by equimolarly reacting chloromethylstyrene and bismuthiol and methacrylic acid are neutralized with triethylamine and polymerized in ethanol, and after the polymerization is completed, chloromethylstyrene is added. The resulting composition was used to prepare a photosensitive composition solution having the following formulation, and the thickness of the composition was reduced to 0.
The sample was coated on a 24 mm grained aluminum plate that had been subjected to graining treatment and anodizing treatment so that the dry film thickness became 3 μm, thereby preparing a sample coated with the photosensitive composition.

<Photosensitive Composition Solution> 100% by weight of 10% solution of alkali-soluble polymer (P-1) in dioxane 5 parts by weight of ethylenically unsaturated compound (C-1) 2 parts by weight of (BC-6) as a photopolymerization initiator Part (BS-2) 1 part by weight As a sensitizing dye (S-34) 0.3 part by weight As a polymerization inhibitor 2,6-di-t-butylcresol 0.1 part by weight As a solvent 1,3-dioxolane 20 parts by weight Cyclohexanone 20 parts by weight

After exposing the above photosensitive material with a thermal plate setter (PT-R4000 (manufactured by Dainippon Screen)), the processor P
Development processing was performed with D-912-M (manufactured by Dainippon Screen Mfg. Co., Ltd.), and a gum solution having the following formulation was applied.

<Developer> KOH 30 g 20% potassium silicate aqueous solution (containing 20% SiO2) 25 g solvent 20 g 1 L with water

Among the above formulas, those containing no solvent at all were used in Comparative Example 1, and the following general formulas (55), (56) and (5) were used as solvents.
Comparative Examples 2 to 7 using the compounds of Chemical Formula 7, Chemical Formula 58, Chemical Formula 59, and Chemical Chemical Formula 60, respectively. As a solvent, Chemical formula 7, Chemical formula 10,
The inventions 1 to 6 are obtained by adding the chemical formulas 12, 12, 20, 25 and 26. 1 g was added per liter because of low solubility.

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In the formula, (b + c): a = 2: 8 and the average molecular weight is 13
00.

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<Gum Solution> 1 g of phosphoric acid 5 g 30 g of arachidicadium 0.5 g of sodium dehydroacetate 1 g of 1 g of EDTA 2 Na 1 L with water

The lithographic printing plate thus obtained was first evaluated for solubility in the non-image area. A non-image portion eluted without any problem was visually evaluated as A, a slightly blue color of the applied material remained as a whole, and a hardly eluted one as C.

The lithographic printing plate prepared in this manner was used as a printing machine for Hightelberg KORD (trademark of offset printing machine manufactured by Heidelberg), ink (New Champion Ink H manufactured by Dainippon Ink Co., Ltd.) and commercial PS plate. Printing was performed using the humidifying solution, and ink acceptability and printing durability were evaluated. With respect to those having an evaluation of C, the printing test was not carried out because the non-image portion hardly eluted.

The ink receptivity was evaluated based on the number of printed sheets until a printed matter having a good image density was obtained while simultaneously starting paper feeding while bringing the ink roller into contact with the plate surface. The printing durability was evaluated by the number of printed sheets when printing became impossible due to either poor ink application of the image area or line skipping. Table 1 shows the results.

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[Table 1] 溶出 Leachability Ink acceptability Printing durability ───── ──────────────────────────── Comparative Example 1 C − − Comparative Example 2 A 100 sheets 10,000 sheets Comparative Example 3 C − − Comparison Example 4 C--Comparative example 5 B 100 sheets 50,000 sheets Comparative example 6 A 200 sheets 200,000 sheets or more Comparative example 7 C--Invention 1A 15 sheets or less 200,000 sheets or more Invention 2A 15 sheets or less 200,000 3 or more of the present invention 3A 15 or less 200,000 or more The present invention 4 A 15 or less 200,000 or more The present invention 5A 15 or less 200,000 or more The present invention 6A 15 or less 200,000 or more ─────────────────────────────

As can be seen from the above results, in the sample using the developing solution to which the solvent of the present invention is not added, the dissolution of the non-image portion is poor, and even if the non-image portion is dissolved, the ink acceptability and the printing durability are improved. However, it can be seen that the developer of the present invention has a good dissolution property in the non-image area, and also has good ink acceptability and printing durability.

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According to the present invention, there is provided a photosensitive lithographic printing plate material developer having good dissolution of non-image areas, excellent ink receptivity and excellent printing durability.

Claims (4)

[Claims] 1. A developer for a photosensitive lithographic printing plate having a photopolymerizable layer, comprising: an alkanolamine having an alkyl group having 1 to 10 carbon atoms and an alkyl group having 2 to 10 carbon atoms and a polyalkyleneoxy group. A photosensitive lithographic printing plate developer comprising at least one compound selected from the group consisting of: 2. The developer for a photosensitive lithographic printing plate according to claim 1, wherein the photopolymerizable layer is a photosensitive negative photosensitive composition for an infrared laser. 3. The photosensitive lithographic printing plate wherein the photopolymerizable layer contains at least a polymer having a polymerizable double bond in a side chain and a carboxyl group-containing monomer as a copolymer component, and an organic boron salt. Item 2. A photosensitive lithographic printing plate developer according to Item 1. 4. The photosensitive lithographic printing plate developer according to claim 3, wherein the photopolymerizable layer of the photosensitive lithographic printing plate further contains an ethylenically unsaturated compound.