JP2004264838A - Modifying agent for lithographic printing forme - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modifying agent for a lithographic printing forme realizing that: the agent stably shows the erasing function for a long time; deformation or damages of the container storing the agent or leaking of the content from the container is prevented; only a desired image part can be erased and the image part can be rapidly erased independently of the kind of the lithographic printing forme without giving an adverse influences on the nearby necessary image part; no contamination is induced in the erased part; and the agent shows high safeness regarding the health of an operator. <P>SOLUTION: The modifying agent for a lithographic printing forme contains a carbonic acid ester and a basic compound, and further contains a specified sulfoxide compound. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a correction agent for a lithographic printing plate, and in particular, an image portion (lithographic plate) of a lithographic printing plate produced so as to give an image portion and a non-image portion by photolithography and development after laser exposure. The present invention relates to a correction agent used for erasing an area where oil-based ink is received by repelling dampening water used during printing.

Conventionally, various correction agents for lithographic printing plates have been proposed. For example, a correction agent combining a carbonate such as ethylene carbonate and propylene carbonate with an acidic substance and dimethyl sulfoxide as a solvent for dissolving or swelling the image area ( For example, see Patent Document 1.), containing dimethyl sulfoxide as an erasing solution for a lithographic printing plate obtained from a photosensitive lithographic printing plate obtained by providing a photosensitive layer on a grained aluminum substrate that is mechanically roughened (For example, see Patent Document 2), a solvent having an ether bond or a solvent having an amide bond, a metal hexafluoride (IV) acid, a fluorinated fatty acid, an alkali hydrogen difluoride compound, a fluoride. A combination composition such as ammonium (see, for example, Patent Document 3) has been proposed.
Further, a correction agent comprising a combination of benzyl alcohol, amino alcohol and dimethyl sulfoxide (for example, see Patent Document 4), a correction agent containing an organic solvent and an alkaline agent having a quaternary ammonium group soluble in the organic solvent (for example, , And Patent Document 5), and a correcting agent (for example, see Patent Document 6) containing cyclohexanone or ethylene glycol derivative and an amine compound has been proposed.

  However, these known correction agents may gradually deteriorate the erasability due to decomposition of the carbonic acid ester component, and the container containing the correction agent may be deformed or damaged. Further, depending on the components forming the photosensitive layer, there is a drawback that the erasing workability of the image portion is inferior. In other words, in lithographic printing plates that use styrene resin, urethane resin, acrylic resin, etc. as a primer or binder for the photosensitive layer, the erasing time of unnecessary image areas is slow, and the correction agent can be applied over a long period of time. It was necessary to apply external force such as rubbing from above. In addition, there is a drawback that the support is destroyed due to the strong basicity of the correction agent, and the erased portion is stained.

Japanese Patent Laid-Open No. 7-248631 JP-A-7-261408 JP-A-8-324150 Japanese Examined Patent Publication No. 4-53421 JP 2001-147541 A US Pat. No. 4,351,895

  Accordingly, an object of the present invention is to provide a correction agent for a lithographic printing plate which can exhibit an erasing function stably for a long period of time and does not cause deformation and breakage of a container to be stored and leakage of contents from the container. The object of the present invention is not to depend on the type of the lithographic printing plate, but to delete only the desired image portion without adversely affecting the necessary adjacent image portion, and to quickly delete the image portion. Another object of the present invention is to provide a lithographic printing plate correcting agent that does not cause stains in the erased portion. Another object of the present invention is to provide a highly safe correction agent in consideration of the health of the worker.

(式中、Ｒ₁及びＲ₂は同じでも異なっていてもよく、水素原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基又はアリール基を表し、Ｒ₁及びＲ₂が一緒になって環を形成していてもよい。)
本発明の平版印刷版用修正剤の好ましい実施態様では、さらに酸性化合物を含有する。
本発明の平版印刷版用修正剤はまた、ペン型修正剤として使用することができる。従って、本発明はさらに、上記の平版印刷版用修正剤がペン型容器に充填されている平版印刷版用修正ペンに向けられている。 In order to achieve the above object, the present inventors have intensively studied, and as a result, have reached the present invention.
That is, the present invention is a lithographic printing plate correction agent comprising a carbonate and a basic compound. The present invention is also the above lithographic printing plate correcting agent further comprising a compound represented by the following general formula (1).

(Wherein R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ together represent a ring; May be formed.)
In a preferred embodiment of the lithographic printing plate correction agent of the present invention, it further contains an acidic compound.
The correction agent for lithographic printing plates of the present invention can also be used as a pen-type correction agent. Accordingly, the present invention is further directed to a lithographic printing plate correction pen in which a pen-type container is filled with the lithographic printing plate correction agent described above.

（式（２）中、Ｒ₃及びＲ₄は同じでも異なっていてもよく、アルキル基、シクロアルキル基、アルケニル基又はアリール基を表す。式（３）中、Ｒ₅〜Ｒ₈は同じでも異なっていてもよく、水素原子、アルキル基、シクロアルキル基、アルケニル基又はアリール基を表し；Ｒ₅〜Ｒ₈のうちの２つで環を形成していてもよい。）
本発明の平版印刷版用修正剤はその実施態様としてｐＨ１．０〜９．０を有し、好ましくはｐＨ４．０〜９．０を有する。 As a specific embodiment of the lithographic printing plate correction agent of the present invention, the carbonate ester is selected from the compounds represented by the following general formula (2) or (3).

(In the formula (2), R ₃ and R ₄ may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. In the formula (3), R _{5 to} R ₈ may be the same. They may be different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group; two of R _{5 to} R ₈ may form a ring.)
The correction agent for lithographic printing plates of the present invention has a pH of 1.0 to 9.0 as an embodiment thereof, and preferably has a pH of 4.0 to 9.0.

The correction agent of the present invention can be used for a lithographic printing plate obtained by making a plate from any lithographic printing plate precursor. In particular, it is preferably used to correct a lithographic printing plate obtained by developing a positive-type heat-sensitive lithographic printing plate or a heat-polymerization type heat-sensitive lithographic printing plate having an image recording layer containing an infrared absorber after image exposure. It is done. It is also preferably used for correcting a lithographic printing plate obtained by developing a photopolymerization type photosensitive lithographic printing plate after image exposure.
Since the correction agent of the present invention contains a carbonate ester and a basic compound, the decomposition of the carbonate ester is suppressed, and good erasability can be maintained even after long-term storage. The contents will not leak without causing damage. Further, the correction agent of the present invention does not cause the support to be broken, and does not cause the erasure part to become dirty.
The correction agent of the present invention also quickly removes unwanted image areas regardless of the components that form the photosensitive layer of the lithographic printing plate, particularly the type of binder, and the primer component of the photosensitive layer. It has no effect on the image part that can be erased and should not be erased.

The correction agent for a lithographic printing plate of the present invention does not deteriorate the erasing ability even after long-term storage and can exhibit an erasing function stably. Further, the contents are not leaked without causing deformation or breakage of the container to be stored. Further, the correction agent of the present invention does not cause the support to be broken, and does not cause the erasure part to become dirty.
The correction agent for a lithographic printing plate of the present invention does not depend on the type of the lithographic printing plate to be applied, specifically on the component forming the photosensitive layer of the lithographic printing plate, particularly on the type of binder, Regardless of the composition of the primer of the adhesive layer, unnecessary image portions can be quickly erased, and the image portions that should not be erased are not affected at all. This action and effect is better exhibited when the compound represented by the general formula (I) is further blended in a predetermined range in the correction agent of the present invention.
Therefore, the erasing process is shortened and the efficiency of the plate making operation is improved. Further, there is an advantage that a desired image portion can be removed without adversely affecting adjacent image portions. Accordingly, it is possible to easily and completely erase the detailed image portion.
Furthermore, the leaving time after application of the correction agent required for erasing on the plate is equal to the leaving time after application of the correction agent required to prevent the ink from depositing on the erased portion immediately after printing is started. Therefore, if it can be confirmed that the image has been erased on the plate, the ink will not be deposited on the erased portion at the start of printing, and therefore, the trouble of re-erasing during printing can be saved.
Furthermore, the correction agent of the present invention can exhibit an erasing function stably over a long period of time by adjusting the pH range, and leakage of contents due to deformation or breakage of the storage container can be avoided.

Hereinafter, each component contained in the correction agent of this invention is demonstrated in detail.
[1] Carbonic acid ester used in the present invention The carbonic acid ester used in the present invention is preferably a compound represented by the following general formula (2) or (3).

In formula (2), R ₃ and R ₄ may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. The alkyl group, cycloalkyl group, alkenyl group and aryl group include both those having no substituent and those having a substituent. In formula (3), R _{5 to} R ₈ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. The alkyl group, cycloalkyl group, alkenyl group and aryl group include both those having no substituent and those having a substituent. Two of R _{5 to} R ₈ may form a ring.

The alkyl group for R ₃ , R ₄ and R _{5 to} R ₈ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically a methyl group, an ethyl group, which may have a substituent, Preferred examples include propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and the like. The cycloalkyl group may be monocyclic or polycyclic. Preferably, it is monocyclic and has 3 to 8 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like, which may have a substituent. As the alkenyl group, for example, an alkenyl group having 2 to 8 carbon atoms, specifically, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like which may have a substituent may be preferably exemplified. it can. As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl which may have a substituent. Preferred examples include a group, a naphthyl group, and an anthryl group.
The ring formed by combining two of R _{5 to} R ₈ is, for example, a 5- to 8-membered ring, and specifically, a cyclopentane ring, cyclohexane ring, cycloheptane which may have a substituent. A ring, a cyclooctane ring, etc. can be mentioned preferably. In addition, examples of the substituent substituted with these groups include those having active hydrogen such as amide group, ureido group, hydroxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group ( Methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), cyano group, nitro group and the like.

Specific examples of the carbonic acid ester represented by the general formula (2) or (3) include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like. 1 type may be used individually as carbonate ester, and 2 or more types may be used together. Among them, particularly preferred compounds are ethylene carbonate and propylene carbonate. Further, ethylene carbonate and propylene carbonate are used for the purpose of improving the solubility of the image area, improving the washing performance after erasing the image area, and maintaining the liquid at room temperature. And the ability as a corrector can be dramatically improved. In this case, the mixing ratio of ethylene carbonate and propylene carbonate is arbitrary, but is preferably 90:10 to 10:90, more preferably 90:10 to 50:50 in terms of mass ratio.
In the correction agent of the present invention, the amount of carbonate used is suitably 20 to 90% by mass, preferably 30 to 80% by mass, based on the total mass of the correction agent.

[2] Basic compounds used in the present invention Conventionally known bases are preferably used as the basic compounds to be included in the correction agent of the present invention, and are generally called Arrhenius bases, Bronsted-Lowry bases, and Lewis bases. Any of these can be used. Also, salts of weak acids and strong bases can be used.
Specific examples include group 1 element hydroxides, such as sodium oxide, potassium oxide, lithium oxide, and group 2 element water, such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. Magnesium hydroxide, calcium hydroxide which is an oxide, magnesium oxide which is an oxide of a group 2 element, calcium oxide, iron hydroxide, iron oxide and the like are used. Also, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, carbonate Examples thereof include inorganic alkali agents such as ammonium hydrogen, sodium borate, potassium borate, ammonium borate, sodium silicate, potassium silicate, lithium silicate, and ammonium silicate, potassium citrate, tripotassium citrate, sodium citrate and the like.
In addition monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, amino alcohols such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and Organic alkaline agents such as diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, hydroxides of quaternary ammonium compounds such as tetramethylammonium hydroxide can also be used. Particularly preferred are amino alcohols, among which triethanolamine can be preferably used.
These basic compounds may be used alone or in combination of two or more. 0.01-20 mass% is suitable for the usage-amount of a basic compound with respect to the total mass of a correction agent, Preferably it is 0.1-10 mass%.

式（１）中、Ｒ₁及びＲ₂は同じでも異なっていてもよく、水素原子、アルキル基、シクロアルキル基、アルケニル基、アラルキル基又はアリール基を表し。上記アルキル基、シクロアルキル基、アルケニル基、アラルキル基及びアリール基は、置換基を有さないものと置換基を有するものとの双方を包含する。また、Ｒ₁及びＲ₂が一緒になって環を形成していてもよい。 [3] Compound represented by general formula (1) used in the present invention The correcting agent of the present invention may include a compound represented by the following general formula (1).

In formula (1), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. The alkyl group, cycloalkyl group, alkenyl group, aralkyl group and aryl group include both those having no substituent and those having a substituent. R ₁ and R ₂ may be combined to form a ring.

The alkyl group for R ₁ and R ₂ is, for example, an alkyl group having 1 to 12 carbon atoms, and specifically, a methyl group, ethyl group, propyl group, n-butyl which may have a substituent. Preferred examples include a group, sec-butyl group, isobutyl group, isopentyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like. The cycloalkyl group may be monocyclic or polycyclic. Preferably, it is monocyclic and has 3 to 8 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like, which may have a substituent. As the alkenyl group, for example, an alkenyl group having 2 to 8 carbon atoms, specifically, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like which may have a substituent may be preferably exemplified. it can. As the aralkyl group, for example, an aralkyl group having 7 to 11 carbon atoms, specifically, a benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4-dimethyl which may have a substituent. Examples include benzyl group, 3,4-dimethylbenzyl group, 2,5-dimethylbenzyl group, ethylbenzyl group, and diethylbenzyl group.
As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl which may have a substituent. Preferred examples include a group, a naphthyl group, and an anthryl group.
In addition, examples of the substituent substituted with these groups include those having active hydrogen such as amide group, ureido group, hydroxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group ( Methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), cyano group, nitro group and the like.

Specific examples of the compound of the general formula (1) include dibenzyl sulfoxide, dimethyl sulfoxide, diphenyl sulfoxide, dinormal butyl sulfoxide, phenylmethyl sulfoxide, divinyl sulfoxide, vinyl phenyl sulfoxide, tetramethylene sulfoxide, di-p-tolyl sulfoxide, Dodecylmethyl sulfoxide, bis (2-ethylhexyl) sulfoxide, dinormal hexyl sulfoxide, diisobutyl sulfoxide, methyl-p-tolyl sulfoxide, 2-hydroxyphenyl dodecyl sulfoxide, allyl phenyl sulfoxide, benzyl phenyl sulfoxide, ethyl-2-naphthyl sulfoxide, ethyl -P-tolyl sulfoxide, diisopentyl sulfoxide, phenyl normal propyl sulfoxide, di Such Rumaru propyl sulfoxide.
1 type may be used individually as a compound of General formula (1), and 2 or more types may be used together. Among these, dinormal butyl sulfoxide and dimethyl sulfoxide are preferable, and dimethyl sulfoxide is particularly preferable.

5-50 mass% is suitable for content of the compound of General formula (1) in the correction agent of this invention, Preferably it is 10-40 mass%.
The mixing ratio of the carbonate ester and the compound represented by the general formula (1) is such that the mass ratio of the carbonate ester: the compound of the formula (1) ranges from 100: 0 to 1:99, preferably 80:20 to 20: A range of 80. By using the carbonate ester and the compound represented by the general formula (1) within the above-mentioned range, regardless of the type of the lithographic printing plate, the thermal polymerization type thermosensitive lithographic printing plate and the photopolymerization type photosensitive lithographic printing plate can be used. Excellent erasability can be exhibited with respect to the obtained plate.
In the present invention, the total amount of the carbonate ester and the compound of the general formula (1) is appropriately 40 to 90% by mass, preferably 60 to 90% by mass, based on the total mass of the correction agent.

[4] Acidic compound used in the present invention The correcting agent of the present invention may further contain an acidic compound. Suitable acidic compounds include phosphorus-containing acids and fluorine-containing acids.
Specific examples of the phosphorus-containing acid include phosphoric acid compounds such as phosphoric acid, phosphorous acid, phytic acid, and metaphosphoric acid, and phosphonic acid compounds. Examples of the phosphonic acid include 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-diphosphono-1,2-dicarboxyethane, 1,2,2,3-tetraphosphonopropane, 2 (2′- And phosphonoethyl) pyridine, aminotri (methylenephosphonic acid), vinylphosphonic acid, polyvinylphosphonic acid, 2-phosphonoethane-1-sulfonic acid, and a water-soluble copolymer of vinylphosphonic acid with acrylic acid and / or vinyl acetate. . A phosphorus-containing acid may be used individually by 1 type, and may use 2 or more types together. Among these, phosphoric acid is preferably used from the viewpoint of preventing stains on the erased portion. 0.1-20 mass% is suitable with respect to the total mass of a correction agent, and, as for the addition amount of a phosphorus containing acid, More preferably, it is 0.1-10 mass%.

Specific examples of the fluorine-containing acid include hydrofluoric acid compounds (for example, Group 4 element hydrofluoric acid, Group 13 element hydrofluoric acid, Group 14 element hydrofluoric acid), fluorinated fatty acid, and fluorinated dicarboxylic acid. Etc. Specific examples of the hydrofluoric acid compound include titanium hydrofluoric acid, zircon hydrofluoric acid, silicohydrofluoric acid, and borohydrofluoric acid. These may be used alone or in combination of two or more. Of these, Group 4 element hydrofluoric acid is preferred from the viewpoint of stain resistance, and zircon hydrofluoric acid is particularly preferred.
The addition amount of a fluorine-containing acid is 0.01-20 mass% with respect to the total mass of a correction agent, More preferably, it is 0.1-10 mass%.
One of the phosphorus-containing acid and the fluorine-containing acid may be used for the correction agent of the present invention, or both may be used.
As other acidic compounds, any of those generally called Arrhenius acid, Bronsted-Lorry acid, and Lewis acid can be used. Also, strong acid and weak base salts can be used. For example, mineral acids such as sulfuric acid, nitric acid, hydrochloric acid and ammonium salts thereof, malic acid, citric acid, tartaric acid, gluconic acid, tannic acid, succinic acid, acetic acid, lactic acid, p-toluenesulfonic acid and the like may be used.

The pH value of the correction agent of the present invention is generally in the range of 1 to 9, and in order to improve the storage stability of the correction agent, the pH range is particularly preferably pH 4 to 9. When the pH is in the range of 4 to 9, decomposition of the carbonic acid ester can be better suppressed, and deformation, breakage, and liquid leakage of the storage container due to generation of carbon dioxide gas can be prevented. A more preferred pH value is pH 4-7.
The above-mentioned basic compound may be used alone to make the pH of the correction agent in a desired range, or an acidic compound may be used at the same time by a neutralization reaction. It is more preferable to use

[5] Water It is preferable that the correction agent of the present invention also contains water. Water is useful in that it suppresses bleeding around the correction portion (damage of the peripheral image portion due to the correction agent) in combination with the carbonate solvent. Water is also effective as a solubilizing agent for basic compounds and acidic compounds, and the amount of water is suitably in the range of 3 to 20% by mass, more preferably 5 to 15% by mass with respect to the total mass of the correction agent. % Range. In general, a correction agent is prepared by dissolving the above carbonate ester, the compound of the general formula (1), a basic compound, an acidic compound, and the like in water.

[6] Other components used in the correction agent of the present invention (1) Solvents The correction agent of the present invention contains, if necessary, an organic solvent having a boiling point of 120 ° C. or higher that dissolves or swells an image or ink. Can do. Examples include alcohols, ketones, glycol ethers, lactones having 3 to 12 carbon atoms, esters, and hydrocarbon solvents.
Specific examples of the alcohol include n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, nonanol, cyclohexanol, 2-methylcyclohexanol, benzyl alcohol, and tetrahydrofurfuryl alcohol. .
Specific examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl n-hexyl ketone, di-n-propyl ketone, diacetone alcohol, acetonyl acetone, isophorone, phorone, cyclohexanone, methylcyclohexanone, and acetophenone. Can be mentioned.

Examples of the glycol ether include compounds represented by the following general formula [I] or [II].
R ₀₁ O— (CH ₂ CH (R ₀₂ ) —O) _m —R ₀₃ [I]
R ₀₄ O— (CH ₂ CH ₂ —O) _p —CO—CH ₃ [II]
In the formula, R _{01 to} R ₀₄ independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a benzyl group, a phenyl group, or a cycloalkyl group, and m and p represent an integer of 1 to 20. Specific examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether. , Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobenzyl ether Ter, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, di And propylene glycol diethyl ether.

Specific examples of the lactone having 3 to 12 carbon atoms include γ-butyrolactone, methyl-γ-butyrolactone, acetyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprolactone, and γ-laurolactone. , Δ-valerolactone, δ-caprolactone, ε-caprolactone, crotolactone, α-angelica lactone, β-angelica lactone, hexanolactone and the like.
Specific examples of the ester or hydrocarbon include amyl acetate, isoamyl acetate, methyl isoamyl acetate, secondary hexyl acetate, 2-ethyl-butyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, propion Butyl acid, isoamyl propionate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, butyl lactate, amyl lactate, isoamyl lactate, toluene, xylene, mesitylene, tetramethylbenzene, ethylbenzene, methylethylbenzene, methylpropylbenzene, diethylbenzene, boiling point 120 ° C ~ Examples include petroleum fractions near 300 ° C., methylnaphthalene, dimethylnaphthalene, tetrahydronaphthalene, decahydronaphthalene and the like. Among these, mesitylene, tetramethylbenzene, methylethylbenzene, methylpropylbenzene, dimethylnaphthalene, tetrahydronaphthalene, methylisoamyl acetate, cyclohexyl acetate, benzyl acetate, and amyl lactate are particularly preferable.

Examples of amides include dimethylformamide, dimethylacetamide, diethylformamide, diethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N- (2-hydroxyethyl) pyrrolidone, N -Octyl pyrrolidone, tetramethyl urea, dimethyl imidazolidinone and the like.
Other than the above, sulfolane, dioxolane, polyethylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, monomethyl ether, monoethyl ether, monopropyl ether, isopropyl ether, monobutyl ether and the like of these compounds can also be exemplified.
These organic solvents may be used individually by 1 type, or may use 2 or more types together. When the organic solvent is included in the correction agent, the amount thereof is suitably 1 to 20% by mass, preferably 5 to 15% by mass, based on the total mass of the correction agent.

(2) Water-soluble polymer compound By incorporating the water-soluble polymer compound in the correction agent of the present invention, even better performance, that is, ease of spreading when applying the correction agent on a lithographic printing plate using a brush. Properties (such as not fading) and prevention of bleeding can be imparted to the correction agent. The water-soluble polymer compound is highly compatible with the carbonate ester solvent and is suitable for imparting an appropriate viscosity to the correction agent.
Preferred water-soluble polymer compounds include, for example, modified cellulose such as methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose / Na salt, gum arabic, structan, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol And polymer compounds such as vinyl methyl ether-maleic anhydride copolymer and vinyl acetate-maleic anhydride copolymer. Among them, modified cellulose, polyvinyl pyrrolidone, vinyl methyl ether maleic anhydride copolymer, structan and the like are useful. The above water-soluble polymer compounds can be used alone or in combination of two or more. The amount used is 0.1 to 10% by mass, most preferably 0.3 to 5% by mass, based on the total mass of the correction agent.

(3) Surfactant By incorporating a surfactant into the correction agent of the present invention, it is possible to impart performance that allows each component to penetrate better into the image portion of the lithographic printing plate in the correction agent. Surfactants are further effective to allow each component contained in the correction agent to mix well to form a stable solution. Such surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid. Partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, oxyethyleneoxypropylene block copolymer, trimethylolpropane, glycerin, etc. added with oxyethylene, oxypropylene, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene Sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fat Partial ester, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide, N, N-bis-2-hydroxyalkylamine, polyoxyethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, etc. Nonionic surfactants, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinic acid ester salts, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalenes Sulfonate, alkylphenoxy polyoxyethylene propyl sulfonate, polyoxyethylene alkyl sulfophenyl ether salt, N-methyl-N-oleyl taurine sodium, N-a Killsulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated castor oil, sulfated beef oil, sulfate of fatty acid alkyl ester, alkyl sulfate, polyoxyethylene alkyl ether sulfate, fatty acid monoglyceride sulfate, Polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styryl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, styrene-anhydrous Anionic surfactants such as partially saponified products of maleic acid copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate, alkyl Cationic surfactants such as ruamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, amphoteric surfactants such as carboxybetaine, aminocarboxylic acid, sulfobetaine, aminosulfate, and imidazoline, fluorine And silicon-based surfactants. Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene.

  Among these, nonionic surfactants and anionic surfactants are preferable, and surfactants having an HLB of 9 or more are more preferable because the components contained in the correction agent are well mixed. In particular, nonionic surfactants are preferably used from the viewpoint of improving the wettability and penetrability to the image area to increase the correction speed. For example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, oxyethyleneoxy A propylene block copolymer, a polyoxyethylene sorbitan fatty acid partial ester, a polyoxyethylene sorbitol fatty acid partial ester, a polyethylene glycol fatty acid ester, a polyglycerin fatty acid partial ester, and the like are preferable for improving the image area erasing effect of the correction agent.

Examples of the nonionic surfactant used in the present invention include those represented by the following formula (4).
R ₁₀ O- (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) n (CH ₂ CH ₂ O) pR ₁₁ (4)
(Wherein R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 18 carbon atoms, m + p is an integer of 1 to 300, and n is 0 or Represents an integer of 1 to 100.)
An example of the formula (4) is one in which at least one of R ₁₀ and R ₁₁ is a hydrogen atom. Further, one of R ₁₀ and R ₁₁ is a hydrogen atom, and the other is a hydrogen atom, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ or —CH ₂ CH═CH ₂ . There are certain compounds. M + p preferably represents an integer of 1 to 240, and n preferably represents an integer of 2 to 100, and more preferably 2 to 70.
Furthermore, the most preferred nonionic surfactant represented by the formula (4) is an oxyethyleneoxypropylene block copolymer in which both R ₁₀ and R ₁₁ are hydrogen atoms.
The nonionic surfactant used in the present invention preferably has a polypropylene glycol portion having a weight average molecular weight in the range of 1200 to 3500 and an ethylene oxide content of about 40 to 90% by mass.
These surfactants may be used singly or in combination of two or more, and are preferably 0.01 to 40% by mass, more preferably 0.8%, based on the total mass of the correction agent of the present invention. It is made to contain in 1-25 mass%.

(4) Viscosity modifier It is preferable that the modifier of the present invention further contains a viscosity modifier. This gives a better writing property to the correction agent. For example, when the correction agent of the present invention is applied to the image portion of the lithographic printing plate using a brush, there is no inconvenience that the correction agent is dropped or dropped from the brush. It is effective in doing so. As such components, the above water-soluble polymer compounds also partially function, but it is preferable to contain them because fine particles such as silicic acid fine powder, colloidal silica, and zeolite exhibit excellent performance. Moreover, the average particle diameter of these fine powders is preferably in the range of 1 to 200 nm, more preferably in the range of 5 to 100 nm. Such a range of the average particle size of the fine powder is advantageous because it has a high affinity with a carbonate ester solvent and can provide an appropriate thixotropic property.

Preferred fine particles include silicon dioxide fine powder Aerosil 130 (average primary particle diameter of about 16 nm), Aerosil 200 (about 12 nm), Aerosil 300 (about 7 nm), Aerosil 380 (about 7 nm), Aerosil R- 972 (about 16 nm), Aerosil MOX170 (about 15 nm), Aerosil OX50 (about 40 nm), Aerosil TT600 (about 40 nm), Aerosil MOX80 (about 30 nm), Silica K320DS (about 18 nm), SILTEG AS7 ( (About 35 nm), CALSIL (about 40 nm), silica D17 (about 20 nm), aluminum oxide C (about 20 nm), Titanium Oxide P25 (about 30 nm), all manufactured by Nippon Aerosil Co., Ltd., Nissan Chemical Alumina Sol-520 (particle average diameter of about 10-20 nm), Alumina Sol-100 (particle size average 100 nm × 10 nm), and Alumina Sol-200 (particle size average 100 nm × 10 nm), Colloidal Silica manufactured by Nissan Chemical Industries, Ltd. Snowtex 20 (particle diameter 10-20 nm), Snowtex 30 (particle diameter 10-20 nm), Snowtex C (particle diameter 10-20 nm), Snowtex N (particle diameter 10-20 nm), Snowtex O (particle diameter) 10-20 nm) and the like are preferable examples. Of the fine particles, silicon dioxide fine powder is particularly preferred, and a particularly preferred particle size is 5 to 100 nm.
If the particle size is smaller than 1 nm, the particles are likely to aggregate, and the viscosity of the correction agent is likely to fluctuate.
1-10 mass% is suitable with respect to the total mass of a correction agent, and, as for the usage-amount of these viscosity modifiers, More preferably, it is the range of 3-8 mass%.

(5) Fluorine Compound The correction agent of the present invention can further contain a fluorine compound. This is suitable for increasing the hydrophilicity of the erased portion and preventing smearing during printing. Examples of such fluorine compounds include titanium hydrofluoric acid, zircon hydrofluoric acid, silicohydrofluoric acid, borohydrofluoric acid, hydrofluoric acid, and fluorine. Fatty acid salt, fluorinated dicarboxylic acid salt, ammonium fluoride, potassium fluoride, lithium fluoride, sodium fluoride, ammonium hydrogen fluoride, potassium hydrogen fluoride, lithium hydrogen fluoride, sodium hydrogen fluoride, etc. . The addition amount of these fluorine compounds is 0.01-20 mass% with respect to the total mass of a correction agent, More preferably, it is 0.1-15 mass%.

（一般式（５）において、Ｒ²及びＲ³は、各々独立に、水素原子又はアルキル基を表し、Ｘは単結合もしくは２価の連結基を表し、ｍは０又は１以上の整数、ｎは１以上の整数を表す。）
から誘導される繰り返し単位を含むフルオロ脂肪族基含有高分子化合物がある。
上記のフルオロ脂肪族基含有高分子化合物は、画像部での修正剤のはじきと非画像部での修正剤のにじみを防止するために有用である。 (6) Polymer Compound Having Fluoroaliphatic Group in Side Chain The correction agent of the present invention can also contain a polymer compound having a fluoroaliphatic group in the side chain. As such a fluoroaliphatic group-containing polymer compound, a monomer (i) having a partial structure represented by the following general formula (5):

(In General Formula (5), R ² and R ³ each independently represent a hydrogen atom or an alkyl group, X represents a single bond or a divalent linking group, m represents 0 or an integer of 1 or more, n Represents an integer of 1 or more.)
There are fluoroaliphatic group-containing polymer compounds containing repeating units derived from
The above-described fluoroaliphatic group-containing polymer compound is useful for preventing repelling of the correcting agent in the image area and bleeding of the correcting agent in the non-image area.

The alkyl group in R ² and R ³ in the general formula (5) preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. R ² and R ³ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
X represents a single bond or a divalent linking group (organic group) for bonding the substituent represented by the general formula (5) to the polymer side chain. Preferred X represents —O—, —S—, —N (R 4) —, —CO—, and is bonded to the polymer main chain directly or via a divalent linking group. Here, R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group, with a hydrogen atom and a methyl group being preferred. X may be any of the above, but —O— is more preferable.
m is 0 or an integer of 1 or more, preferably an integer of 2 to 8, and particularly preferably m = 2. When m is 2 or more, functional groups on adjacent carbon atoms may be bonded to form an aliphatic ring.
n represents an integer of 1 or more, and an integer of 1 to 10 is preferable. Here, n is particularly preferably 3 to 6.

式中、Ｒ¹は水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子）または置換基を有しても良いメチル基、Ｙ₀は２価の有機基、Ｘ、Ｒ²、Ｒ³、ｍ、ｎは一般式（５）と同義である。Ｙ₀は２価の有機基としては、前述のＸと同様の具体例が挙げられる。 As the monomer (i), a monomer represented by the following general formula (6) is preferable.

In the formula, R ¹ is a hydrogen atom, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom) or a methyl group which may have a substituent, Y ₀ is a divalent organic group, X, R ² , R ³ , m, and n are as defined in general formula (5). Specific examples of Y ₀ as the divalent organic group are the same as those of X described above.

Examples of specific structures (F-1 to F-49) of the perfluoroalkyl group-containing monomer of the general formula (6) used in the present invention are shown below.

The fluoroaliphatic group-containing polymer compound used in the present invention may be a polymer obtained by polymerizing one kind or two or more kinds as the monomer (i). One or more repeating units derived from the monomer (i) may be present.
The fluoroaliphatic group-containing polymer used in the present invention may also be a copolymer of the monomer (i) and another monomer, for example, a repeating unit derived from the monomer (i), There is a copolymer containing a repeating unit represented by the following general formula (7) and / or a repeating unit represented by the following general formula (8).

(In General Formula (7), R ⁴ represents a hydrogen atom or an alkyl group, R ⁵ represents a hydrogen atom, an alkyl group, or an aryl group. T represents an integer of 2 or more, and u represents an integer of 2 to 6. )
In the general formula (7), the alkyl group in R ^4, preferably has 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. The alkyl group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-butyl group, Although i-butyl group etc. are mentioned, these may have a substituent further. Examples of the aryl group in R ⁵ include a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group, and the like, and these may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, and a carboxyl group. t is an integer of 2 or more, preferably an integer of 4 to 100, u represents an integer of 2 to 6, and 2 or 3 is preferable.
In the fluoroaliphatic group-containing polymer compound used in the present invention, two or more repeating units represented by the general formula (7) may be present.

(In the general formula (8), R ⁶ represents a hydrogen atom or an alkyl group. R ⁷ represents a hydrogen atom, an alkyl group or an aryl group. O, p, q, r and s are each independently 1 to 1) And o and p are not the same, a and b are each independently an integer of 4 or more, and c, d and e each independently represent an integer of 0 or 1 or more. )
In general formula (8), the alkyl group in R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, or a propyl group. Group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. The alkyl group for R ⁷ is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, and n-butyl. Group, i-butyl group and the like, and these may further have a substituent. Examples of the aryl group for R ⁷ include a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group, and the like, and these may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, and a carboxyl group. o, p, q, r, and s are each independently an integer of 1 to 4, and an integer of 2 to 3 is preferable. a and b are each independently an integer of 4 or more, and an integer of 10 to 30 is preferable. c, d, and e each independently represent 0 or an integer of 1 or more, and among them, an integer of 10 to 30 is preferable.
In the fluoroaliphatic group-containing polymer compound used in the present invention, two or more repeating units represented by the general formula (8) may be present.

  As described above, in the present invention, as the fluoroaliphatic group-containing polymer compound, the monomer (i) and at least the monomer (ii) corresponding to the repeating unit represented by the general formula (7) and / or the general A fluoroaliphatic group-containing copolymer obtained by copolymerizing the monomer (iii) corresponding to the repeating unit represented by the formula (8) can be used.

Specific examples (O-1 to O-40) of the monomer (ii) corresponding to the repeating unit represented by the general formula (7) that can be used in the present invention are shown below. It is not limited.

Furthermore, specific examples (P-1 to P-23) of the monomer (iii) corresponding to the repeating unit represented by the general formula (8) that can be used in the present invention are shown below. It is not limited to.

  When the fluoroaliphatic group-containing polymer compound is the above-mentioned copolymer, the amount of the monomer (ii) corresponding to the repeating unit represented by the general formula (7) is determined based on each monomer of the copolymer. It may be 5 mol% or more based on the total amount of, preferably in the range of 5 to 70 mol%, more preferably in the range of 20 to 70 mol%. The amount of the monomer (iii) corresponding to the repeating unit represented by the general formula (8) can be 5 mol% or more based on the total amount of each monomer of the copolymer, preferably 5 It is the range of -70 mol%, More preferably, it is the range of 20-70 mol%.

The molecular weight range of the fluoroaliphatic group-containing polymer compound used in the present invention is usually from 3000 to 200,000 as the weight average molecular weight, preferably from 6,000 to 100,000. Can be used. These molecular weights can be determined by, for example, the GPC method using a polystyrene standard substance.
The correction agent for lithographic printing plates of the present invention can contain one or more selected from the above-described fluoroaliphatic group-containing polymer compounds.
The content of the fluoroaliphatic group-containing polymer compound in the lithographic printing plate correction agent of the present invention is 0.001 to 5.0% by mass from the viewpoint of suppressing bleeding of the correction agent and imparting appropriate wettability. It is suitable, Preferably it is 0.005-3.0 mass%, More preferably, it is 0.01-1.0 mass%.

  The fluoroaliphatic group-containing polymer compound used in the present invention can be produced by a known and conventional method. Moreover, the fluoro aliphatic compound which is a monomer component can be synthesized by, for example, the telomerization method or the oligomerization method disclosed in JP-A-2002-72474.

  The fluoroaliphatic group-containing polymer compound used in the present invention can be further reacted with a copolymerizable monomer other than the monomer component. A preferable copolymerization ratio of such a copolymerizable monomer is 20 mol% or less, more preferably 10 mol% or less in all monomers.

Examples of such a monomer include a monomer having an acidic hydrogen atom.
As the group having an acidic hydrogen atom, for example, any of a carboxyl group and a known acidic group in addition to a phenolic hydroxyl group can be used. As a known literature of acidic groups, JADean ed., Lange's Handbook of Chemistry 3rd. Ed. 1985 McGraw-Hill Book Co. can be mentioned.
Moreover, what is represented by following (A1)-(A7) can be mention | raise | lifted as a concrete thing of the partial structure of the acidic group which the acidic hydrogen atom couple | bonded with the nitrogen atom among these acidic groups.

—SO ₂ NH ₂ (A1)
—SO ₂ NH— (A2)
-CONHSO _2- (A3)
-CONHCO- (A4)
—SO ₂ NH—SO ₂ — (A5)
-CONHSO ₂ NH- (A6)
—NHCONHSO ₂ — (A7)

  In addition, acidic groups described in JP-A-8-15858 are also useful. A nitrogen atom-containing heterocyclic structure having a coupler structure described in JP-A-7-248628 is also included. Examples of these nitrogen-containing heterocyclic structures include those represented by the following (H) and (I).

Similarly, an acidic group having a hydrogen atom bonded to a carbon atom adjacent to the electron withdrawing group described in JP-A-2000-19724 is also useful.
In addition, JP-A-11-326881, JP-A-11-327142, JP-A-11-327131, JP-A-11-327126, JP-A-10-339948, JP-A-10-207052, JP-A-10-186642 Application to the copolymers described in JP-A-10-161303 is also suitable.

  As the monomer having an acidic hydrogen atom, a vinyl monomer having an unsaturated group capable of radical polymerization is used. Among these vinyl monomers, preferred are acrylate, methacrylate, acrylamide, methacrylamide, styrene, and vinyl. Examples of preferred structures include compounds described in JP-A-10-142778.

Further, as other copolymerization component, a monomer having a bridge bond described in JP-A-4-222805, an aliphatic group having 9 or more carbon atoms described in JP-A-10-142778, or Copolymerization with acrylate, methacrylate, acrylamide, or methacrylamide monomers having an aromatic group in the side chain substituted with an aliphatic group having two or more carbon atoms is also suitable.
Furthermore, application to urethane polymer technologies described in JP-A-10-186640, JP-A-10-186661, JP-A-2000-3032, JP-A-2000-3040, etc., and JP-A-11- Application to polycondensation and polyaddition type polymers as disclosed in US Pat. No. 327129 is also possible. Furthermore, a (meth) acrylate monomer having 2 to 3 perfluoroalkyl groups of 3 to 20 in the molecule described in JP-A No. 2000-187318 can also be applied.

  Such a fluorine-type polymer can be manufactured by a well-known and usual method. For example, (meth) acrylate having a fluoroaliphatic group, (meth) acrylate having a polyoxyalkylene group, and an acidic group-containing vinyl monomer bonded to an acidic hydrogen atom or nitrogen atom in an organic solvent for general-purpose radical polymerization It can manufacture by adding an initiator and carrying out thermal polymerization. Alternatively, other addition-polymerizable unsaturated compounds can be added in some cases and produced in the same manner as described above.

Further, other addition polymerization unsaturated compounds used in some cases include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley lnterscience (1975) Chapter 2 Pages 1-483 can be used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.

Specifically, the following monomers can be mentioned.
Acrylic esters:
Methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.
Methacrylic acid esters:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.

Acrylamides:
Acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (alkyl group having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.
Methacrylamide:
Methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl groups), N, N-dialkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms) ), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.
Allyl compounds:
Allyl esters (eg allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc.

Vinyl ethers:
Alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. Vinyl esters:
Vinyl bitylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenyl Butyrate, vinyl cyclohexyl carboxylate, etc.

Dialkyl itaconates:
Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.
Dialkyl or monoalkyl esters of fumaric acid:
Dibutyl fumarate, etc. Others such as crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene.

(7) Others (colorants, antiseptics, rust inhibitors, antifoaming agents)
As other components, a colorant, an antiseptic, a rust inhibitor, an antifoaming agent, and the like can be further added to the correction agent of the present invention. The colorant is used to impart a desired color tone to the correction agent of the present invention to give visual contrast, and can be selected from a wide range of dyes. As a particularly preferred colorant, an indicator dye having a deep dyeing such as blue, purple, or red exhibits an excellent effect. Specific examples include dyes such as crystal violet, safranin, brilliant blue, malachite green, and acid rhodamine B, as well as inorganic pigments and organic pigments. When a colorant is used, the amount used is about 0.0001 to about 0.10% by weight, preferably 0.001 to 0.05% by weight, based on the total weight of the correction agent of the present invention. is there.
Examples of the preservative used in the present invention include phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzisothiazolin-3-one, benztriazole derivatives, amiding anidine derivatives, four Examples include quaternary ammonium salts, derivatives such as pyridine, quinoline, and guanidine, diazines, triazole derivatives, oxazoles, oxazine derivatives, 2-bromo-2-nitropropane-1,3-diol, and the like. A preferable addition amount is an amount that stably exerts an effect on bacteria, fungi, yeast, etc., and varies depending on the type of bacteria, fungi, yeast, but 0.01 to The range of 4% by mass is preferable, and it is preferable to use two or more kinds of preservatives together so as to be effective against various molds and sterilization.

As the antifoaming agent, a silicon antifoaming agent is preferable. Among them, an emulsified dispersion type and a solubilized type can be used. The amount used is optimally in the range of 0.001 to 1.0 mass% with respect to the total mass of the correction agent.
Examples of the rust inhibitor include 1H benzotriazole and derivatives thereof, benzimidazole and derivatives thereof, and thiosalicylic acid. A preferable addition amount is 0.0001 to 0.1% by mass with respect to the total mass of the correction agent.

  The correction agent for lithographic printing plates of the present invention can be stored in various containers. Examples of such container materials are polypropylene, polyethylene, polyethylene terephthalate, polyurethane, polystyrene, polycarbonate, polyvinyl chloride, ABS resin, phenol resin, cresol resin, nylon resin, polybutylene terephthalate, polyester, polyacetal, polyamideimide, polyimide. , Melamine resin, acrylic resin, vinylidene chloride resin, unsaturated polyester, and the like. Among these, a polyethylene container is preferably used.

[Correction pen for lithographic printing plate]
A lithographic printing plate correction pen can be made by filling a lithographic printing plate correction agent into a pen-shaped container.
The pen-type container that can be used in the present invention is not particularly limited. Examples of the pen-type container include a so-called felt pen type such as a felt pen, a sign pen, a marking pen, a marker, or a brush pen, and a type in which a tank or a cartridge in the container is directly filled with a correction agent. .
As an example of the felt pen type, there is a type in which cotton or felt for filling is used in a tank portion in a container and this is impregnated and filled with a correction agent. Further, as an example of a tank type pen type, there is a knock type type in which a correction agent is directly filled in a hollow tank and the flow rate is adjusted by opening and closing a valve. Further, a structure in which a correction agent is applied by bringing the pen tip into contact with the plate surface may be used. In addition, a cartridge-type correction pen container as disclosed in Japanese Patent Laid-Open No. 11-258822 and a filter made of a substance having liquid absorbency as disclosed in Japanese Patent Laid-Open No. 11-78377 are used. A pen-shaped container or the like can be used.
Examples of pen-type container materials include polypropylene, polyethylene, polyethylene terephthalate, polyurethane, polystyrene, polycarbonate, polyvinyl chloride, ABS resin, phenol resin, cresol resin, nylon resin, polybutylene terephthalate, polyester, polyacetal, polyamideimide, polyimide , Melamine resin, acrylic resin, vinylidene chloride resin, unsaturated polyester, and the like. Of these, a polypropylene pen-type container is preferably used.

[Version to which correction agent is applied]
The correction agent of the present invention can be applied to lithographic printing plates made from various lithographic printing plate precursors. Such a lithographic printing plate precursor is not limited. For example, an image recording layer such as a photosensitive layer and a heat-sensitive layer exemplified below is provided on a support. Suitable examples of the image recording layer include a conventional positive type, a conventional negative type, a photopolymer type (photopolymerization type), a thermal positive type, and a thermal negative type (thermal polymerization type and acid crosslinking type). The term "conventional" as used herein refers to a conventional lithographic printing plate precursor that performs imagewise exposure through a transparent positive image or a transparent negative image. Hereinafter, these image recording layers will be described. In addition, a developer suitable for each lithographic printing plate precursor will be described.

<Conventional positive type>
A preferable example of a conventional positive photosensitive resin composition is a composition containing an o-quinonediazide compound and an alkali-soluble polymer compound. Examples of o-quinonediazide compounds include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and phenol-formaldehyde resin or cresol-formaldehyde resin, and US Pat. No. 3,635,709. There are esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and pyrogallol acetone resin as described. Examples of the alkali-soluble polymer compound include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde co-condensation resin, polyhydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, Examples thereof include carboxy group-containing polymers described in Japanese Patent No. 36184. Also, acrylic resins containing phenolic hydroxy groups as described in JP-A-51-34711, acrylic resins having sulfonamide groups as described in JP-A-2-866, and urethane Various alkali-soluble polymer compounds such as resins can also be used. Further, the photosensitive resin composition includes compounds such as sensitivity modifiers, printing agents, dyes and the like disclosed in JP-A-7-92660 [0024] to [0027] and those disclosed in the same publication [0031]. It is preferable to add a surfactant for improving the coatability.
A conventional positive photosensitive lithographic printing plate precursor provided with a photosensitive composition containing an o-quinonediazide compound and an alkali-soluble polymer compound on a support is imagewise exposed using ultraviolet rays, and then an alkaline developer. Developed with Examples of such developers include alkali metal silicate aqueous solutions described in Japanese Patent Publication No. 57-7427 and Japanese Patent No. 3086354, and developers containing non-reducing sugars and bases as described in JP-A-8-305039. A preferred example is given.

<Conventional negative type>
Examples of conventional negative photosensitive resin compositions include those containing a diazo resin and an alkali-soluble or swellable polymer compound (binder).
Examples of the diazo resin include a condensate of an aromatic diazonium salt and an active carbonyl group-containing compound such as formaldehyde. Further, for example, a condensate of p-diazophenylamines and formaldehyde and hexafluorophosphate or An organic solvent-soluble diazo resin inorganic salt that is a reaction product with tetrafluoroborate is exemplified. In particular, a high molecular weight diazo compound containing 20 mol% or more of a hexamer described in JP-A-59-78340 is preferable. Suitable binders include copolymers containing acrylic acid, methacrylic acid, crotonic acid or maleic acid as essential components, for example, 2-hydroxyethyl (meta) as described in JP-A-50-118802. ) Acrylate, (meth) acrylonitrile, multi-component copolymers of monomers such as (meth) acrylic acid, alkyl acrylate, (meth) acrylonitrile, and unsaturated as described in JP-A-56-4144 Mention may be made of multi-component copolymers composed of carboxylic acids. Further, the photosensitive resin composition is a plasticizer for imparting the flexibility and wear resistance of the baking agent, dye, and coating film disclosed in JP-A-7-281425 [0014] to [0015]. It is preferable to add a compound such as a development accelerator and a surfactant for improving the coating property.

As a lower layer of the above-mentioned conventional type positive type or negative type photosensitive layer, a polymer compound having a component having an acid group and a component having an onium group described in JP-A-2000-105462 is used. It is preferable to provide an intermediate layer to be contained.
The photosensitive lithographic printing plate using the conventional negative photosensitive resin composition thus prepared is imagewise exposed using ultraviolet rays and then developed with a developer. As a developer for such a conventional negative photosensitive resin composition, an alkali agent, an organic solvent, a surfactant, a water softener, a reducing agent, an organic carboxylic acid, an inorganic salt, an antifoaming agent, and further as necessary. Aqueous solutions containing various additives known in the art are used. Particularly preferable examples include those described in JP-B-56-42860, JP-B-58-54341, JP-B-2-37579, JP-A-62-200154, and JP-A-64-44445. Examples include a developer.

<Photopolymer type>
(Photosensitive layer)
A photopolymer-type photopolymerizable photosensitive composition (hereinafter referred to as “photopolymerizable composition”) is an addition-polymerizable ethylenically unsaturated bond-containing compound (hereinafter simply referred to as “ethylenically unsaturated bond-containing compound”). And a photopolymerization initiator and a polymer binder as essential components, and if necessary, various compounds such as a colorant, a plasticizer, a thermal polymerization inhibitor and the like.
The ethylenically unsaturated bond-containing compound contained in the photopolymerizable composition is such that, when the photopolymerizable composition is irradiated with actinic rays, it undergoes addition polymerization by the action of the photopolymerization initiator, crosslinks and cures. It is a compound having an ethylenically unsaturated bond. The ethylenically unsaturated bond-containing compound can be arbitrarily selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, such as monomers, prepolymers (ie, dimers). Trimers and oligomers), mixtures thereof, and copolymers thereof. Examples of monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and aliphatic polyhydric compounds. And amides with a polyvalent amine compound. Urethane addition polymerizable compounds are also suitable.

As the initiator contained in the photopolymerizable composition, various photopolymerization initiators or a combination system (photoinitiation system) of two or more photopolymerization initiators are appropriately selected and used depending on the wavelength of the light source used. For example, the initiation system shown in JP-A-2001-22079 [0021] to [0023] is preferred. The polymer binder contained in the photopolymerizable composition not only functions as a film-forming agent for the photopolymerizable composition, but also needs to dissolve the photosensitive layer in an alkali developer. An organic high molecular weight polymer that is swellable is used. As the polymer, those shown in the publications [0036] to [0063] are useful. In addition, it is also preferable to add an additive (for example, a surfactant for improving the coating property) shown in the publications [0079] to [0088] to the photopolymerizable composition.
Further, it is preferable to provide an oxygen-blocking protective layer on the photosensitive layer in order to prevent the oxygen polymerization inhibiting action. Examples of the polymer contained in the oxygen barrier protective layer include polyvinyl alcohol or a copolymer thereof. Further, it is preferable to provide an intermediate layer or an adhesive layer as disclosed in JP-A-2001-228608 [0124] to [0165] as the lower layer of the photopolymer type photosensitive layer.
A photosensitive lithographic printing plate using such a photopolymer type photopolymerizable photosensitive composition is imagewise exposed using ultraviolet rays such as a high-pressure mercury lamp, an argon laser and an ultraviolet laser, and then developed with a developer. Preferred developers include alkali agents, organic solvents, surfactants, hard water softeners, reducing agents, organic carboxylic acids, inorganic salts, antifoaming agents, and various other types known in the art as necessary. An aqueous solution containing an additive is used. Particularly preferred examples include the developers described in JP-B-58-54341, JP-A-8-248643, JP-A-2002-91015, and JP-A-8-171214.
The image portion made from the photopolymer type image recording layer as described above has a problem that it is difficult to be corrected and difficult to dissolve in a solvent because it forms a network structure by polymerization reaction. Here, by applying the correction agent of the present invention, unnecessary image portions can be erased in a short time, which is advantageous.

<Thermal positive type>
(Thermosensitive layer)
The thermal positive type heat-sensitive layer contains an alkali-soluble polymer compound and a photothermal conversion substance. This alkali-soluble polymer compound includes a homopolymer containing an acidic group in the polymer, a copolymer thereof, and a mixture thereof. In particular, an acidic group such as the following (1) or (2) is included. It is preferable from the viewpoint of solubility in an alkali developer: (1) phenolic hydroxy group (—Ar—OH), (2) sulfonamide group (—SO ₂ NH—R). In particular, it is preferable to have a phenolic hydroxy group from the viewpoint of excellent image formability upon exposure with an infrared laser or the like, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m− / p−. Preferable examples include mixed cresol formaldehyde resin, phenol / cresol (any of m-, p- and m- / p-mixed) mixed formaldehyde resin and the like, and pyrogallol acetone resin. More specifically, the polymers shown in [0023] to [0042] of JP-A No. 2001-305722 are preferably used.

  The photothermal conversion substance converts exposure energy into heat and can efficiently cancel the interaction of the exposed area of the heat sensitive layer. From the viewpoint of recording sensitivity, a pigment or dye having a light absorption region in the infrared region with a wavelength of 700 to 1200 nm is preferable. As a dye. Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes (for example, A dye such as a nickel thiolate complex) can be used. Among these, cyanine dyes are preferable, and examples thereof include cyanine dyes represented by general formula (I) in JP-A No. 2001-305722. In the composition of the thermal positive type, it is preferable to add a sensitivity control agent, a printing agent, a compound such as a dye similar to those described for the conventional positive type, and a surfactant for improving the coating property. Specifically, the compounds shown in [0053] to [0059] of JP-A No. 2001-305722 are preferable.

The thermal positive type heat-sensitive layer may be a single layer or may be provided as a two-layer structure as described in JP-A-11-218914.
An undercoat layer is preferably provided between the thermal positive type heat-sensitive layer and the support. Examples of components contained in the undercoat layer include various organic compounds disclosed in JP-A-2001-305722, [0068] and [0081].
A thermal positive type heat-sensitive lithographic printing plate precursor provided with a heat-sensitive composition containing these alkali-soluble polymer compound and a photothermal conversion substance on a support is imagewise exposed using an infrared laser, and then an alkaline developer. Developed with Examples of such a developing solution include Japanese Patent Publication No. 57-7427, Japanese Patent No. 3086354, Japanese Patent Application Laid-Open No. 11-216962, Japanese Patent Application Laid-Open No. 2001-51406, Japanese Patent Application Laid-Open No. 2001-174981, and Japanese Patent Application Laid-Open No. 2002-72501. A preferred example is a developing solution described in Japanese Patent Publication No. JP-A.

<Thermal negative type>
(Thermosensitive layer)
The thermal negative-type heat-sensitive layer is a negative-type heat-sensitive layer in which the infrared laser irradiation part is cured to form an image part.
As one of such thermal negative type heat-sensitive layers, a polymerization type layer is preferably exemplified. The polymerization layer comprises (A) an infrared absorber, (B) a radical generator (radical polymerization initiator), a curing reaction caused by the generated radical (C) a radical polymerizable compound, and (D) a binder. Containing polymer.
In the polymerization layer, the infrared rays absorbed by the infrared absorber are converted into heat, and the generated heat decomposes radical polymerization initiators such as onium salts to generate radicals. The radically polymerizable compound is selected from compounds having a terminal ethylenically unsaturated bond, and a polymerization reaction is caused in a chain by the generated radicals and is cured. Examples of the infrared absorber (A) include the photothermal conversion substance contained in the above-described thermal positive type heat-sensitive layer. In particular, as a specific example of the cyanine dye, paragraph number of JP-A No. 2001-133969 [0017] to [0019] may be mentioned. (B) Examples of the radical generator include onium salts. Specific examples of onium salts that can be suitably used are described in paragraphs [0030] to [0033] of JP-A No. 2001-133969. Things can be mentioned. (C) The radically polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. (D) It is preferable to use a linear organic polymer as the binder polymer, and a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected. Of these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxy group in the side chain is particularly preferable because of its excellent balance of film strength, sensitivity, and developability. With respect to (C) the radical polymerizable compound and (D) the binder polymer, those described in detail in the publications [0036] to [0060] can be used. As other additives, it is also preferable to add an additive (for example, a surfactant for improving the coating property) shown in the publications [0061] to [0068].

In addition to the polymerization type, an acid-crosslinking type layer is preferably used as one of the thermal negative type heat-sensitive layers. The acid cross-linking layer comprises (E) a compound that generates an acid by light or heat (hereinafter referred to as “acid generator”) and (F) a compound that cross-links by the generated acid (hereinafter referred to as “cross-linking agent”). And (G) an alkali-soluble polymer compound that can react with a crosslinking agent in the presence of an acid. In order to efficiently use the energy of the infrared laser, (A) an infrared absorber is blended in the acid crosslinking layer. Examples of the acid generator (E) include compounds capable of generating an acid upon thermal decomposition, such as a photoinitiator for photopolymerization, a photochromic agent for dyes, and an acid generator used for a microresist. . (F) The crosslinking agent includes (i) an aromatic compound substituted with a hydroxymethyl group or an alkoxymethyl group, (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, Or (iii) an epoxy compound is mentioned. (G) Examples of the alkali-soluble polymer compound include novolak resins and polymers having a hydroxyaryl group in the side chain.
The thermal negative lithographic printing plate precursor provided with the polymerization type and acid cross-linked thermal negative type thermosensitive layer on the support is imagewise exposed using an infrared laser and then developed with an alkaline developer. Examples of such a developer include Japanese Patent Publication No. 57-7427, Japanese Patent Application Laid-Open No. 2001-133969 [0119] to [0123], Japanese Patent Application Laid-Open No. 2003-302770, Japanese Patent Application Laid-Open No. 2003-255561, And a developer described in U.S. Pat. No. 5,766,826 is a particularly preferable example.
An image part made from a thermal positive type lithographic printing plate precursor having an image recording layer containing the above-mentioned infrared absorber, or an image part made from a thermal polymerization type thermal negative lithographic printing plate precursor is suitable for various chemicals. There is a problem that it is relatively weak. The use of the correction agent of the present invention is advantageous because it is less likely to cause image damage around the correction portion.

<Support>
As a support for a lithographic printing plate precursor provided with the image recording layer, an aluminum plate is generally used. The aluminum plate is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a small amount of foreign atoms. Such heteroatoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium, and the like. As the alloy composition, a foreign atom content of 10% by mass or less is appropriate. The preferred aluminum is pure aluminum. However, since completely pure aluminum is difficult to manufacture by refining technology, it should be free of foreign atoms as much as possible. Moreover, it can be said that it is a raw material which can be used for this invention if it is an aluminum alloy of the foreign atom content rate of the extent mentioned above. The composition of the aluminum plate is not particularly limited, and conventionally known and publicly available materials can be used as appropriate. Preferred materials include JIS A 1050, 1100, 1200, 3003, 3103, and 3005. The thickness of the aluminum plate used in the present invention is suitably about 0.1 mm to 0.6 mm. Prior to roughening the aluminum plate, a degreasing treatment for removing the rolling oil on the surface, for example, with a surfactant or an alkaline aqueous solution is performed as necessary.
Next, roughening treatment, anodic oxidation treatment, hydrophilic treatment and the like are performed in an appropriate combination. For example, there is a support treatment method as disclosed in JP-A-2001-356494.
An image recording layer is coated on such a support to obtain a lithographic printing plate precursor, but an intermediate layer may be provided before coating the image recording layer. A material containing an organic polymer compound is often used as such an intermediate layer, for example, one disclosed in JP-A-2001-356494.
A coating layer made of an organic polymer compound (also referred to as a “back coat layer”) is provided on the back surface of the lithographic printing plate precursor as necessary in order to prevent the image recording layer from being scratched when stacked. Can be provided.

After the development of the lithographic printing plate precursor, usually a combination of washing, rinsing, desensitizing treatment, and the like is performed to obtain a lithographic printing plate. When the lithographic printing plate obtained in this way has an unnecessary image portion, the image portion is erased by applying the correction agent of the present invention on the image portion. When the correction agent of the present invention is applied to the image portion of a lithographic printing plate, it is preferable to apply the lithographic printing plate after development after thoroughly washing it, rather than immediately after development. Further, although the erasing speed is slightly reduced, a correction agent can be applied to the lithographic printing plate that has been gummed.
As a specific method of applying the correction agent of the present invention to the image portion of a lithographic printing plate, a method of including the correction agent of the present invention in a brush and applying it to the desired image portion to be erased is common. Or it can apply | coat to the image part to erase | eliminate by the usage method according to the various forms of the correction pen for lithographic printing plates.
The applied correction agent is left as it is for about 10 seconds to about 1 minute, and then washed with water and the correction agent is washed away, whereby the image portion where the correction agent is applied is removed cleanly and becomes a non-image portion. Thereafter, it is treated by a usual method (for example, gumming) and used as a lithographic printing plate.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these. Unless otherwise specified, “part” means mass part, and “%” means “mass%”.
[Examples 1-7 and Comparative Examples 1-7]
Example 1
The correction agent of the present invention was prepared as follows.
[Correction agent A]
First, 15 parts of propylene carbonate, 60 parts of ethylene carbonate, 7.4 parts of a solvent containing tetramethylbenzene (Swazole 1800 sold by Maruzen Petrochemical Co., Ltd.) and 7 parts of pure water were mixed in a solution containing hydroxypropyl cellulose ( 1.2 parts of hydroxypropoxy group (70 to 95%), oxyethyleneoxypropylene block copolymer (polymerized with ethylene oxide on both ends of polypropylene glycol having an average molecular weight of 2,000. Molecular weight: 10,000, ethylene oxide content: 80 %) 5.4 parts were dispersed. 0.2 parts of triethanolamine and 0.003 parts of crystal violet were sequentially dissolved and stirred to obtain a uniform solution. To this was added 3.8 parts of powdered silicon dioxide (manufactured by Nippon Aerosil Co., Ltd., silicon dioxide fine powder Aerosil 380 (average primary particle diameter: about 7 nm)) and dispersed to obtain a viscous correction agent. Its pH was 7.0.

In the same manner as the correction agent A, correction agents of Examples 2 to 7 (correction agents B to G) and correction agents of Comparative Examples 1 to 7 (comparison correction agents a to g) were prepared. The correction agent G is a pen-type correction agent in which the felt is impregnated with the correction agent C and the felt is stored inside a polypropylene pen container. The comparative correction agent g is a pen type correction agent in which a felt is impregnated with the comparative correction agent b and the felt is stored in a polypropylene pen container.
Tables 1 and 2 below show the composition (unit: part by mass) and pH value of each correction agent.

^{* 1} Solvents containing tetramethylbenzene sold by Maruzen Petrochemical Co., Ltd.
^{* 2} Hydroxypropoxy group 70-95%
^{* 3} Ethylene oxide polymerized on both ends of polypropylene glycol with an average molecular weight of 2,000. Molecular weight: 10,000, ethylene oxide content: 80%
^{* 4} The intrinsic viscosity at 25 ° C of a solution of 1g in 100g of methyl ethyl ketone is 2.6-3.5.
^{* 5} K-15 (manufactured by GAF)
^{* 6} Mega Fuck F-781-F (Dainippon Ink Co., Ltd.)
^{* 7} Silicon dioxide fine powder Aerosil 380 (average primary particle diameter of about 7 nm) (Nippon Aerosil Co., Ltd.)
In Table 2 below, ^{* 1} to ^{* 7} are synonymous.

[Test 1]
The lithographic printing plate obtained from the conventional positive type original plate was corrected with various correction agents.
<Preparation of lithographic printing plate>
An aluminum plate with a thickness of 0.3 mm was polished with a brush, then electrochemically roughened in a nitric acid solution, washed thoroughly, and then anodized in a sulfuric acid solution to give a 2.5 g / m ² oxide film. Was formed on the surface of the aluminum plate. After washing with water and drying, 3 parts of an esterified product of resorcinbenzaldehyde resin and naphthoquinone-1,2-diazide-5-sulfonyl chloride synthesized according to the examples of JP-A-56-1044, 9 parts of cresol formalin novolak resin, A photosensitive solution in which 0.12 part of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) was dissolved in 100 parts of 2-methoxyethanol was applied and dried on the support using a rotary coater, and 2.8 g. A positive PS plate having a photosensitive layer of / m ² was obtained. A halftone dot photographic transparency was brought into close contact therewith, exposed with a metal halide lamp from a distance of 0.8 m for 60 seconds, and developed with the following developer to obtain a lithographic printing plate.
(Developer)
Potassium silicate A (SiO ₂ 26%, K ₂ O 13.5%) 120 parts 86% Potassium hydroxide 15.5 parts Water 500 parts In the lithographic printing plate thus obtained, the edge of the positive film is thinned as an image on the plate surface. It remained.

Each of the above correction agents is included in a brush or applied as a pen-type correction agent (correction agent G and comparative correction agent g) to the area where the film edge on the lithographic printing plate remains as an image for testing. It was allowed to stand for 5 seconds to 10 minutes, and after each time, water was sprayed and washed away.
Here, the influence (bleeding) on the peripheral portion of the area where the correction agent is applied (whether the peripheral portion of the area where the correction agent is applied is not blurred on the printed matter), and an unnecessary image is printed. The time required to leave the correction agent required for erasing above (the erasure time on the plate), and the correction agent required to prevent the ink from depositing on the erased portion immediately after starting printing as described later. Standing time after application (erasing time on printed matter) and stains due to destruction of support 10 minutes after applying correction agent (washing with water after 10 minutes after applying correction agent, and ink stains occur in the erased area when printing is started) Whether or not).
Assuming that the correction agents are stored for a long period of time, the correction tests A to F and the comparison correction agents a to f are the same tests and containers as described above after being stored in a polyethylene container at 45 ° C. for one month. The presence or absence of deformation or damage was examined. Further, the correction agent G and the comparative correction agent g, which are pen-type correction agents, were tested in the same manner as described above after being stored at 45 ° C. for one month, and the polypropylene pen-type container was deformed, damaged or sealed. The cap was checked for looseness.

In the image area corrected by the above method, the hydrophilic layer was completely exposed, and it was slightly white compared with other non-image areas. There was no ghost-like afterimage of the erased trace, and the plate inspection time was shortened because it was very easy to perform plate inspection. In this way, the corrected version was gummed with a 14 ° Be aqueous solution of gum arabic and attached to an offset printing machine to print 10,000 sheets. Obtained. The correction agent of the present invention was able to perform the correction work with peace of mind due to minimal liquid bleeding even in the elimination of details. The correction agent after storing at 45 ° C. for 1 month also showed the same result, and neither deformation nor breakage of the container nor loosening of the cap was observed.
The results are shown in Table 3.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

[Test 2]
A plate obtained by developing a thermal positive type original plate (including a substrate on which a silicate treatment and an undercoat layer were coated) with a silicate developer was corrected with various correction agents.
[Production of substrate]
An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene and degreased, and then a nylon brush and a 400 mesh Pamisu water suspension were used to make the surface grainy and washed thoroughly with water. This plate was etched by being immersed in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, further immersed in 20% nitric acid for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² . Next, the plate was provided with a direct current anodic oxide film having a current density of 15 A / dm ² and 3 g / m ² using 7% sulfuric acid as an electrolytic solution, then washed with water and dried.
This was treated with a 2.5% by mass aqueous solution of sodium silicate at 30 ° C. for 10 seconds, the following undercoat solution was applied, and the coating film was dried at 80 ° C. for 15 seconds to obtain a substrate. The coating amount of the coating film after drying was 15 mg / m ² .
<Composition of undercoat liquid>
-0.3 parts of the following copolymer with a molecular weight of 28,000 0.3, 100 parts of methanol, 1 part of water

The following photosensitive layer forming coating solution was applied to the obtained substrate so that the coating amount was 1.8 g / m ² and dried to obtain a planographic printing plate precursor.
<Composition of photosensitive layer coating solution>
-1.0 part of m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 8000,
Contains 0.5% by mass of unreacted cresol)
・ Cyanine dye A (the following structure) 0.1 part ・ Tetrahydrophthalic anhydride 0.05 part ・ p-toluenesulfuric acid 0.002 part ・ Ethyl violet counter ion was changed to 6-hydroxy-β-naphthalenesulfonic acid 0.02 part of thing, Fluorosurfactant 0.05 part (Megafac F-781-F, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 12 parts

The lithographic printing plate precursor was exposed using a Creo plate setter Trendsetter 3244F (rotation speed: 150 rpm) and developed with an alkali developing solution (pH about 13) having the following composition to obtain a lithographic printing plate.
[Composition of alkali developer]
・ SiO ₂・ K ₂ O 4.0%
(K ₂ O / SiO ₂ = 1.1 (molar ratio))
・ Citric acid 0.5%
・ Polyethylene glycol (weight average molecular weight = 1000) 0.5%
・ Water 95.0%
In the lithographic printing plate obtained in this way, unnecessary image portions due to uneven drawing of the laser remained.
This unnecessary image area was treated with various correction agents in the same manner as in Test 1, and everything from erasing to printing was performed. The results are shown in Table 4.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

[Test 3]
A plate obtained by developing a thermal positive type original plate (including a substrate on which a silicate treatment and an undercoat layer were coated) with a non-silicate developer was corrected with various correction agents.
A lithographic printing plate precursor obtained in the same manner as in Test 2 is similarly setter exposed to 1 liter of a 45% aqueous solution of potassium salt composed of D-sorbite / potassium oxide (K ₂ O), which is a combination of a non-reducing sugar and a base. , 20 g of amphoteric surfactant Pionein C-158G (manufactured by Takemoto Yushi Co., Ltd.) and 2.0 g of antifoaming agent Olphine AK-02 (manufactured by Nissin Chemical Co., Ltd.) to obtain a concentrated solution. The plate was developed with a developer diluted 9 times with water to obtain a lithographic printing plate.
In the lithographic printing plate obtained in this way, unnecessary image portions due to uneven drawing of the laser remained. This unnecessary image area was treated with various correction agents in the same manner as in Test 1, and everything from erasing to printing was performed. The results are shown in Table 5.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

[Test 4]
A plate obtained by developing a thermal positive type original plate (including a substrate not subjected to a silicate treatment and an undercoat layer coating) with a silicate developer was corrected with various correction agents.
In the same manner as in Test 2, a substrate was obtained from degreasing the aluminum plate to providing an oxide film. The resulting substrate was coated with the same sensitizing solution as in Test 2 except that it was not treated with sodium silicate and undercoated, dried, exposed and developed in the same manner as in Test 2 to obtain a lithographic printing plate. In the lithographic printing plate obtained in this way, unnecessary image portions due to uneven drawing of the laser remained. This unnecessary image area was treated with various correction agents in the same manner as in Test 1, and everything from erasing to printing was performed.
The results are shown in Table 6.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

[Test 5]
A plate obtained by developing a thermal positive type original plate (including a substrate not subjected to a silicate treatment and an undercoat layer coating) with a non-silicate developer was corrected with various correction agents.
In the same manner as in Test 4, a photosensitive solution was applied from the degreasing of the aluminum plate, dried, and exposed and developed in the same manner as in Test 3 to obtain a lithographic printing plate. In the lithographic printing plate obtained in this way, unnecessary image portions due to uneven drawing of the laser remained. This unnecessary image area was treated with various correction agents in the same manner as in Test 1, and everything from erasing to printing was performed. The results are shown in Table 7.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

[Test 6]
A plate made from a photopolymerization type photosensitive lithographic printing plate was corrected with various correction agents.
<Preparation of plate>
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 galvanostatic quantity of 300 coulomb / dm ² using a sinusoidal alternating current under the condition of V _A = 12.7V. When the surface roughness was measured, it was 0.45 μm (Ra indication). Next, 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 33 ° C., 20% H ₂ SO ₄ aqueous solution to obtain a current density. When anodized at 5 A / dm ² for 50 seconds, the thickness was 2.7 g / m ² . On the aluminum plate thus treated, a photopolymerizable composition having the following composition was applied so that the dry coating weight was 1.5 g / m ² and dried at 100 ° C. for 1 minute to form a photosensitive layer. .

(Photopolymerizable composition)
Ethylenically unsaturated bond-containing compound (A1) 1.5 parts by mass linear organic polymer (B1) 2.0 parts by mass sensitizer (C1) 0.15 parts by mass photoinitiator (D1) 0.2 Mass part ε-phthalocyanine (F1) dispersion 0.02 part by mass Fluorine nonionic surfactant Megafac F117 0.03 part by mass (Dainippon Ink Chemical Co., Ltd.)
Methyl ethyl ketone 9.0 parts by mass Propylene glycol monomethyl ether acetate 7.5 parts by mass Toluene 11.0 parts by mass

On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 500) was applied so that the dry coating weight was 2.5 g / m ² and dried at 120 ° C. for 3 minutes. A photosensitive lithographic printing plate was obtained.
This photosensitive lithographic printing plate was printed with a solid image and 1-99% halftone dot under the condition of 175 lines / inch at 4000 dpi with an exposure of 100 μJ / cm ² using an FD • YAG laser (Plate Jet 4 manufactured by CSI). After scanning and exposing the image (in 1% increments), a developer having the following composition (pH: 11.5 at 25 ° C., conductivity: 5 mS / cm) and finishing gum solution FP-2W (manufactured by Fuji Photo Film) were charged. Standard processing was performed with an automatic processor (LP-850P2 manufactured by Fuji Photo Film). The preheating conditions were a plate surface temperature of 100 ° C., a developer temperature of 30 ° C., and an immersion time in the developer of about 15 seconds.
(Developer)
Potassium hydroxide 0.15g
Polyoxyethylene phenyl ether (n = 13) 5.0 g
Kirest 400 0.1g
94.75 g of water
In the lithographic printing plate obtained in this way, unnecessary image portions due to uneven drawing of the laser remained. This unnecessary image portion was treated with various correction agents in the same manner as in Test 1, and from erase to printing was performed in the same manner as in Test 1. The results are shown in Table 8.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

[Test 7]
A plate obtained by making a thermal polymerization type heat-sensitive lithographic printing plate was corrected with various correction agents.
<Preparation of plate>
A molten metal of JIS A1050 alloy containing 99.5% or more of aluminum and Fe 0.30%, Si 0.10%, Ti 0.02% and Cu 0.013% was subjected to cleaning treatment and cast. In the cleaning process, a degassing process was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter process was performed. The casting method was a DC casting method. The solidified 500 mm thick ingot was chamfered 10 mm from the surface and homogenized at 550 ° C. for 10 hours so as not to coarsen the intermetallic compound. Next, after hot rolling at 400 ° C. and intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain an aluminum rolled plate having a plate thickness of 0.30 mm. By controlling the roughness of the rolling roll, the centerline average surface roughness Ra after cold rolling was controlled to 0.2 μm. Then, it applied to the tension leveler in order to improve planarity.

Next, the surface treatment for making a lithographic printing plate support was performed. First, in order to remove the rolling oil on the surface of the aluminum plate, degreasing treatment was carried out with a 10% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal treatment were carried out with a 30% sulfuric acid aqueous solution at 50 ° C. for 30 seconds.
Subsequently, in order to improve the adhesion between the support and the photosensitive layer and to provide water retention to the non-image area, a so-called graining treatment was performed to roughen the surface of the support. While maintaining an aqueous solution containing 1% nitric acid and 0.5% aluminum nitrate at 45 ° C. and flowing an aluminum web through the aqueous solution, an alternating waveform with a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell Then, electrolytic graining was performed by giving an anode side electric quantity of 240 C / dm ² . Thereafter, an etching treatment was performed with a 10% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and a 30% sulfuric acid aqueous solution was subjected to neutralization and smut removal treatment at 50 ° C. for 30 lines.

Furthermore, in order to improve wear resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodized film of 2.5 g / m ² by using a 20% sulfuric acid aqueous solution as an electrolyte at 35 ° C. and carrying out an electrolytic treatment with a direct current of 14 A / dm ² by an indirect power feeding cell while carrying an aluminum web into the electrolyte. It was created.
Thereafter, a silicate treatment was performed to ensure hydrophilicity as a non-image portion of the printing plate. The treatment was carried with a 1.5% aqueous solution of sodium silicate 3 maintained at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washed with water. The adhesion amount of Si was 10 mg / m ² . Ra (center line surface roughness) of the support prepared as described above was 0.25 μm.
Next, the following undercoat liquid was applied to this aluminum support with a wire bar, and dried at 90 ° C. for 30 seconds using a hot air drying apparatus. The coating amount after drying was 10 mg / m ² .
(Undercoat liquid)
・ Ethyl methacrylate and 2-acrylamido-2-methyl-1-
0.1 g of propanesulfonic acid sodium salt with a molar ratio of 75:15
・ 2-aminoethylphosphonic acid 0.1g
・ Methanol 50g
・ Ion exchange water 50g

(Photosensitive layer)
Next, the following solution [P] is prepared, applied to the undercoated aluminum plate using a wire bar, and dried at 115 ° C. for 45 seconds in a hot air dryer to obtain a negative lithographic printing plate precursor. Obtained. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² .
Solution [P]
・ Infrared absorber ([IR-6] below) 0.08g
・ Onium salt ([OI-6] below) 0.30g
・ Dipentaerythritol hexaacrylate 1.00g
-Copolymer with a molar ratio of allyl methacrylate and methacrylic acid of 80:20 (weight average molecular weight 120,000) 1.00 g
・ Victoria Pure Blue Naphthalenesulfonate 0.40g
・ Fluorine-based surfactant 0.01g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ Methanol 10.0g
1-methoxy-2-propanol 8.0g

The negative lithographic printing plate precursor thus obtained is exposed with a Trend setter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 9 W, an outer drum rotating speed of 210 rpm, a plate surface energy of 100 mJ / cm ² , and a resolution of 2400 dpi. did.
After the exposure, the film was developed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developing solution, a 1: 1 water dilution of DN-3C manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenishing solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.
In the lithographic printing plate obtained in this way, unnecessary image portions due to uneven drawing of the laser remained. This unnecessary image portion was treated with various correction agents in the same manner as in Test 1, and from erase to printing was performed in the same manner as in Test 1. The results are shown in Table 9.

* 不必要な画像を版上で消去するのに要した修正剤の塗布後放置時間
** 印刷を開始した直後から消去部分にインキが着肉しないために要した修正剤の塗布後放置時間
*** 修正剤塗布１０分後の支持体破壊による汚れ

* Left time after applying the correction agent required to erase unnecessary images on the plate
** Immediately after printing is started, the ink is left on the erased area after applying the corrective agent, so that the ink does not adhere to the erased area.
*** Dirt due to destruction of the support 10 minutes after applying the correction agent

As described above, the correction agent of the present invention exhibits good erasability in various lithographic printing plates. On the other hand, the comparative correction agent is a lithographic printing plate from a thermal positive plate using a styrene resin for the undercoat layer, a photopolymerization type using an acrylic resin for the binder of the image forming layer, and a bond between the undercoat layer and the image forming layer. It clearly shows inferior erasability with respect to a lithographic printing plate from a thermal polymerization type original plate using an acrylic resin as an agent.
Further, as a result of investigating the erasability after storing for 1 month at 45 ° C., assuming that the correction agent was stored for a long time, the erasability of the correction agent of the present invention was not deteriorated. Further, the deformation and breakage of the container and the pen-type correction agent were further examined for the presence or absence of cap loosening, but none of the correction agent of the present invention was found to be deformed or broken or loosening the cap. On the other hand, deformation was observed in the comparative correction agents a, b and g (pH 2.5, 2.1).

Claims (4)

  A lithographic printing plate correcting agent comprising a carbonate and a basic compound. Furthermore, the correction agent for lithographic printing plates of Claim 1 containing the compound shown by following General formula (1).

(Wherein R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ₁ and R ₂ together represent a ring; May be formed.) Furthermore, the correction agent for lithographic printing plates of Claim 1 or 2 containing an acidic compound. A lithographic printing plate correction pen, wherein the lithographic printing plate correction agent according to any one of claims 1 to 3 is filled in a pen-type container.