Correction fluid for lithographic printing plate

专利摘要:
Selected from the group consisting of a carbonate ester, a compound represented by the following general formula (1), a carboxylic acid fluoride, an alkali hydrogen fluoride compound, an alkali fluoride compound and a group 4 metal hydrofluoric acid (B) A flat plate printing modifier comprising at least one compound. [Wherein, R 1 to R 3 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 (wherein R 3 is not a hydrogen atom when R 1 and R 2 are methyl groups), R 1 ~R 3 may optionally form a ring with two of (where, R 1 or R 2, if R 3 and forms a ring, R 2 or R 1 is not a methyl group each, respectively);
公开号:KR20040012448A
申请号:KR1020030026243
申请日:2003-04-25
公开日:2004-02-11
发明作者:사카모토아츠시；토야마타다오；사사키히데히토；니시오카아키라
申请人:후지 샤신 필름 가부시기가이샤；
IPC主号:

专利说明:

Corrector for flat plate printing {Correction Fluid for Lithographic Printing Plate}
[1] The present invention relates to a modifier for flat printing plates. More specifically, the image portion of a flat plate printing plate manufactured to form an image portion and a non-image portion by developing after photolithography or laser exposure (area designed to receive oily ink by repelling dampening water used in flat printing) ) Is used to modify a modifier used to extinguish).
[2] Japanese Patent Publication No. 51-33442 (British Patent No. 1,408,709) is a modification of a flat printing plate made of a photosensitive flat plate printing plate (called a PS plate) having a photosensitive layer made of an o-quinonediazide compound, Modifiers containing lactones containing 3 to 6 carbon atoms are disclosed. In addition, JP-A-62-27190 discloses ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, lactone, N, N-dimethylformamide, N-methylpyrrolidone as component A. And a combination composition of at least one compound selected from cyclohexane, phosphoric acid and acetic acid as component B, hydrofluoric acid as component C, hydrofluoric acid silicon and the like. In addition, Japanese Patent Application Laid-Open No. 8-324150 discloses a solvent having an ether bond, a solvent having an amide bond, and a combination composition of a metal hexafluoride (IV) acid, a fatty fluoride fatty acid, an alkali dihydrogen fluoride compound, ammonium fluoride, and the like. It is. In addition, Japanese Patent Application Laid-Open No. 7-248631 discloses a carbonate compound such as ethylene carbonate and propylene carbonate and a modifier combining N, N-dimethylformamide, N-methylpyrrolidone, etc. as a solvent for dissolving or swelling the burned portion. It is proposed.
[3] However, these known modifiers have the following drawbacks. That is, in the modifier disclosed in Japanese Patent Application Laid-open No. 51-33442, as a result of the strengthening of the image portion in accordance with the recent high-strength orientation of the flat plate printing plate, the solubility of the image portion with respect to the correction agent decreases, which is necessary for the correction. Significantly increased time, there was a problem in workability. In addition, in the modifier disclosed in Japanese Patent Application Laid-Open No. 62-27190, hydrofluoric acid, silicon hydrofluoric acid and the like are used for the purpose of removing the image component remaining on the roughened support of the flat plate. There was a problem that etching of the support occurred, the roughening support made hydrophilic was destroyed, and the treated erase part was easily contaminated. In addition, it has been pointed out that N, N-dimethylformamide and N-methylpyrrolidone have problems in stability, such as an increase in the possibility of impairing the health of the worker when the modifier is attached to the skin. In addition, in the modifier disclosed in Japanese Patent Application Laid-Open No. 8-324150, there is a problem in that an image portion is apparently removed at the time of engraving, and ink is attached to the portion at the time of printing, which is considered to be erased. The odor of the solvent contained in the modifier could potentially impair worker health. In addition, in the correction agent disclosed in Japanese Patent Laid-Open No. 7-248631, since the vapor of the solvent contained acts on the image portion other than the image portion that requires correction, the necessary image portion adjacent to the unnecessary image portion to be erased is required. Even when there is a problem of easily erasing from the printing plate, and also a problem in safety aspects such as N, N-dimethylformamide and N-methylpyrrolidone, which are listed as solvents, has been pointed out. There was a possibility of impairing the health of the worker.
[4] Japanese Patent Application Laid-Open No. 7-248631 also discloses inorganic acids such as hydrofluoric acid, hydrochloric acid, sulfuric acid, persulfuric acid, nitric acid, permanganic acid, phosphoric acid, hydrofluoric acid, silicon hydrofluoric acid, acetic acid, citric acid, malic acid, lactic acid, It is proposed to contain organic acids such as oxalic acid, trichloroacetic acid, tannic acid, phytic acid, p-toluenesulfonic acid and phosphonic acid. However, the carbonate ester contained in the modifier is decomposed by these acidic components over time, and the scavenging function of the image portion cannot be completed, and the gas generated from deformation or breakage of the modifier container due to the gas generated. Leakage of the contents was not prevented. In addition, when the acidic substance presented is used as a modifying agent, there is a problem such as lack of hydrophilization of the aluminum support of the erased image portion, which is contaminated during printing, or is contaminated during printing because of excessive destruction of the aluminum support. .
[5] Accordingly, an object of the present invention is to provide a flat plate printing plate correcting agent which can erase only the image portion requiring correction and considers the health of the worker without adversely affecting other image portions positioned adjacent to the target image portion. It is. Another object of the present invention is to provide a flat plate printing modifier that can erase an image portion quickly and does not cause contamination in the erase portion. It is still another object of the present invention to provide a modifier capable of stably exhibiting an erasing function over a long period of time, and without deformation and breakage of the container to be preserved or leakage of contents from the container.
[6] MEANS TO SOLVE THE PROBLEM The present inventors reached | attained this invention as a result of earnestly examining in order to achieve the said objective.
[7] That is, the present invention is a group (A) consisting of a carbonate ester and a compound represented by the following general formula (1) and a group consisting of carboxylic acid fluorides, alkali hydrogen fluoride compounds, alkali fluoride compounds and group 4 metal hydrofluoric acid ( It is a flat plate printing modifier characterized by containing 1 or more types of compounds chosen from B).
[8]
[9] [Wherein, R ₁ to R ₃ 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 (wherein R ₃ is not a hydrogen atom when R ₁ and R ₂ are methyl groups), You may form a ring by two of R <_1> -R <_3> (when R <_1> or R <_2> forms a ring with R <_3> , the remaining R <_2> or R <_1> is not a methyl group, respectively).
[10] The modifying agent of the present invention can also be used for a flat printing plate obtained by being plated from any original flat printing plate. In particular, it is suitably used for correcting the flat type printing plate obtained by developing a positive type thermosensitive flat plate printing plate or a thermal polymerization type thermosensitive flat plate printing plate having an image recording layer containing an infrared absorber after image exposure. Moreover, it is used suitably also for correcting the flat printing plate obtained by developing a photopolymerization type photosensitive flat printing plate after image exposure.
[11] The modifying agent of the present invention has a short time required for erasing the image portion of the flat plate, and does not have any effect on the image portion that should not be erased. By the specific action obtained by the combination of the carbonate ester and the compound represented by the formula (1), the support is not broken by the acidic compound, and no contamination is caused in the erasing part. In addition, by using a compound selected from carboxylic acid fluorides, alkali hydrogen fluorides, alkali fluorides, and Group 4 metal hydrofluoric acid, the aluminum support can be prevented from interfering with the hydrophilization of the aluminum support of the eraser. There is no excessive destruction.
[12] The modifiers of the present invention also contain no compounds which are concerned about safety and therefore do not adversely affect the health of the worker. In addition, the modifier of the present invention can exert a scavenging function stably over a long period of time, and also does not cause deformation or breakage of the container for storing the modifier, so that the contents do not leak from the container.
[13] Example
[14] Hereinafter, each component contained in the modifier of this invention is demonstrated in detail.
[15] [1] carbonate ester used in the present invention
[16] The carbonate ester used in the present invention is preferably a compound represented by the following general formula (2) or (3).
[17]
[18] In formula (2), R <_4> and R <_5> may be same or different, and represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, respectively (The said alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group have both a substituent and a substituent. In the formula (3), R ₆ to R ₉ may be the same or different, and each represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group (the alkyl group, cycloalkyl group, alkenyl group and aryl group are substituents). Both of those having no substituent and those having a substituent) may be formed from two of R ₆ to R ₉ .
[19] As an alkyl group of R <_4> , R <_5> and R <_6> -R <_{9>, it} is an alkyl group of 1-8 carbon atoms, specifically, the methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group which may have a substituent, Hexyl group, 2-ethylhexyl group, octyl group, etc. are mentioned preferably. The cycloalkyl group may be monocyclic or polycyclic. Preferably, they are monocyclic and have 3 to 8 carbon atoms, and for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. which may have a substituent may be mentioned. As the alkenyl group, for example, an alkenyl group having 2 to 8 carbon atoms may specifically include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, etc. which may have a substituent. 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 group, naphthyl group, anthryl group or the like which may have a substituent is preferable. Can be enumerated.
[20] As a ring formed by combining two of R <_6> -R <_9> , it is a 5-8 membered ring, Specifically, the cyclopentane ring, the cyclohexane ring, the cycloheptane ring, the cyclooctane ring etc. which may have a substituent are mentioned preferably. Can be. Substituents substituted with these groups include those having active hydrogens such as amide groups, ureido groups and hydroxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms and iodine atoms) and alkoxy groups (methoxy groups and ethoxy groups). , Propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), cyano group, nitro group, etc. are mentioned.
[21] As a specific example of the carbonate ester represented by General formula (2) or (3), dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. are mentioned. As a carbonate ester, you may use individually by 1 type, and may use 2 or more types together. Especially, as a preferable compound, ethylene carbonate and propylene carbonate are used, and together, ethylene carbonate and propylene carbonate are used together for the purpose of improving the solubility of an image part, improving the water washability after image removal, and maintaining a liquid state at normal temperature. It can improve the ability as a modifier. Although the mixing ratio of ethylene carbonate and propylene carbonate in this case is arbitrary, Preferably it is 90: 10-10: 90, More preferably, it is 90: 10-50: 50 by mass ratio.
[22] In the modifier of the present invention, the content of the carbonate ester is suitably 20 to 80% by mass, and preferably 30 to 70% by mass relative to the total mass of the modifier.
[23] [2] Compound of Group (A): Compound represented by General Formula (1)
[24] General formula (1) is as follows.
[25]
[26] In the formula, R ₁ to R ₃ may be the same or different, and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group (wherein R ₃ is not a hydrogen atom when R ₁ and R ₂ are methyl groups), R ₁ ~R ₃ 2 pieces may be formed in a ring (however, when R ₁ or R ₂ is R ₃ to form a ring and, remaining R ₂ or R ₁ is not a methyl group, respectively).
[27] As an alkyl group of R <_1> -R <_{3>, it} is an alkyl group of 1-8 carbon atoms, specifically, the methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethyl which may have a substituent specifically ,. Hexyl group, octyl group, etc. can be mentioned preferably. The cycloalkyl group may be monocyclic or polycyclic. Preferably, they are monocyclic and have 3 to 8 carbon atoms, and for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc. which may have a substituent may be preferably listed. As the alkenyl group, for example, an alkenyl group having 2 to 8 carbon atoms may specifically include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, etc. which may have a substituent. 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 group, naphthyl group, anthryl group or the like which may have a substituent is preferable. Can be enumerated.
[28] Substituents substituted with these groups include active hydrogens such as amide groups, ureido groups and hydroxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms and iodine atoms) and alkoxy groups (methoxy groups and ethoxy). The time period, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group etc.), cyano group, nitro group, etc. are mentioned.
[29] Moreover, as a specific example of the compound of General formula (1), dimethylacetamide, diethylformamide, diethylacetamide, 2-pyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrid Rollidone, N- (2-hydroxyethyl) pyrrolidone and the like.
[30] As a compound of General formula (1), you may use individually by 1 type and may use 2 or more types together in the modifier of this invention. Among them, dimethylacetamide, diethylformamide, and diethylacetamide are preferred from the viewpoint of improving the solubility of the burn portion and the flushing ability after erasing, and the acetamide compound is more preferred, and dimethylacetamide is particularly preferred. Do.
[31] In the modifier of the present invention, the content of the compound of the general formula (1) is preferably 5 to 50% by mass, preferably 10 to 40% by mass.
[32] Although the mixing ratio of carbonate ester and the compound represented by General formula (1) is arbitrary, Preferably the compound of carbonate ester: Formula (1) is 90: 10-10: 90 by weight ratio, More preferably, 80: 20-20 : 80.
[33] In this invention, 40-90 mass% is suitable with respect to the total mass of a carbonate ester and the compound of General formula (1), Preferably it is the range of 60-90 mass%.
[34] [3] compounds of group (B)
[35] (1) fluorinated carboxylic acids
[36] Examples of fluorinated carboxylic acids used in the present invention include fluorinated fatty acids, fluorinated dicarboxylic acids and the like, and more specifically, formula: C _n F _{2n + 1} COOH or HOOCC _n F _2n COOH, wherein n is Is an integer of 1 to 6). Representative examples thereof include trifluoroacetic acid, tetrafluorosuccinic acid, and the like.
[37] (2) Hydrogen fluoride alkali compounds
[38] As examples of the hydrogen fluoride alkaline compounds used in the present invention, the formula: MF · HF (M: an alkali metal or ^{N (R 1) (R 2} ) (R 3) (R 4) (R 1, R 2, R ³ and R <^4> may be same or different, and represent a hydrogen atom or a hydrocarbon group of about 1-6 carbon atoms, respectively). Representative examples thereof include lithium borohydride, potassium hydrogen fluoride, sodium hydrogen fluoride, ammonium hydrogen fluoride and the like.
[39] (3) alkali fluoride compounds
[40] Examples of the alkali fluoride compounds used in the present invention include formulas: MF (M: alkali metal or N (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) (R ¹ , R ² , R ³ and R ⁴ may be the same or different, and each represents a hydrogen atom or a hydrocarbon group having about 1 to 6 carbon atoms. Representative examples thereof include lithium fluoride, potassium fluoride, sodium fluoride, ammonium fluoride and the like.
[41] (4) Group 4 metal hydrofluoric acid
[42] As examples of Group 4 metal hydrofluoric acid used in the present invention, the expression: may be represented by: (Group 4 metal element M) MH ₂ F _6. Representative examples thereof include zirconic hydrofluoric acid and titanium hydrofluoric acid.
[43] In the modifier of the present invention, one type selected from the above (1) to (4) may be used alone, or two or more types may be used in combination. Among them, zirconic hydrofluoric acid and titanium hydrofluoric acid are preferable from the viewpoint of preventing contamination of the erased portion. In particular, preferably zirconic hydrofluoric acid is used. The addition amount of these fluorine compounds is 0.01-20.0 mass% with respect to the total mass of a modifier, More preferably, it is 0.1-10.0 mass%.
[44] The modifying agent of the present invention may contain one or more compounds selected from the group (A) consisting of the compound represented by the general formula (1), or contain one or more compounds selected from the group (B) It may also contain one or more compounds selected from group (A) and one or more compounds selected from group (B).
[45] [4] acidic compounds
[46] The modifier of the present invention may further contain an acidic compound. In particular, suitable acidic compounds include phosphorus-containing acids and fluorine-containing acids.
[47] 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, Water solubility of 2 (2'-phosphonoethyl) pyridine, aminotri (methylenephosphonic acid), vinylphosphonic acid, polyvinylphosphonic acid, 2-phosphonoethane-1-sulfonic acid, vinylphosphonic acid and acrylic acid and / or vinyl acetate The copolymer etc. can be mentioned. Phosphorus containing acid may be used individually by 1 type, and may use 2 or more types together. Among them, phosphoric acid is preferably used from the viewpoint of preventing contamination of the erased portion. As for the addition amount of phosphorus containing acid, 0.1-20.0 mass% is suitable with respect to the total mass of a modifier, More preferably, it is 0.1-10.0 mass%.
[48] Moreover, as a specific example of fluorine-containing acid, hydrofluoric acid of silicon, hydrofluoric acid of boron, etc. can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among them, hydrofluoric acid and boron hydrofluoric acid are preferable from the viewpoint of pollution prevention. The addition amount of fluorine-containing acid is 0.01-20.0 mass% with respect to the total mass of a modifier, More preferably, it is 0.1-10.0 mass%.
[49] The modifying agent of the present invention may contain one of phosphorus-containing acid and fluorine-containing acid, or both may be used.
[50] As other acidic compounds, mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, malic acid, citric acid, tartaric acid, gluconic acid, tannic acid, oxalic acid, acetic acid, lactic acid, p-toluenesulfonic acid, and the like can also be used.
[51] [5] basic compounds
[52] It is also preferable that the modifier of the present invention further contains a basic compound. Such basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, Inorganic alkali agents such as potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium silicate, potassium silicate, lithium silicate, ammonium silicate, potassium citrate, tripotassium citrate, sodium citrate and the like.
[53] In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanol Organic alkalis, such as amine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide, can also be mentioned preferably.
[54] These basic compounds may be used alone or in combination of two or more thereof.
[55] Especially, an organic alkali agent can be used preferably, Especially preferably, it is triethanolamine. As for the usage-amount of a basic compound, 0.01-10.0 mass% is suitable with respect to the total mass of a modifier, Preferably it is 0.1-10.0 mass%.
[56] The pH value of the modifier of the present invention is generally in the range of 1 to 9, and in order to improve the storage stability of the modifier, in particular, the pH range is preferably set to pH 4 to 9. In the range of pH 4-9, decomposition | disassembly of a carbonate ester can be suppressed more effectively, and deformation | transformation, damage, and leakage of a storage container by carbon dioxide generation can be prevented. The pH value of a more preferable range is pH 4-7.
[57] In the modifier of the present invention, either the acidic compound or the basic compound may be used to set the pH of the modifier to the desired range, or both may be simultaneously used to set the desired range by a neutralization reaction. It is more preferable to use both simultaneously from a viewpoint.
[58] [6] water
[59] It is preferable that the modifier of this invention contains water further. When a correction agent made by using water and a carbonate ester solvent is added to a burned portion that needs correction, it is useful in terms of suppressing bleeding (damage of the surrounding burned portion by the fixer). Moreover, water is effective as a dissolution aid of an acidic compound and a basic compound, and the amount of water is suitably in the range of 3 to 20% by mass with respect to the total mass of the modifier, more preferably in the range of 5 to 15% by mass. It is common to dissolve the said carbonate ester, an acidic compound, a basic compound, etc. in water, and to prepare a modifier.
[60] [7] Other Ingredients Used in Modifiers of the Present Invention
[61] (1) solvents
[62] The modifying agent of the present invention may further contain an organic solvent having a boiling point of 120 ° C. or higher that dissolves or swells an image or ink as necessary. Examples thereof include alcohols, ketones, glycol ethers, lactones having 3 to 6 carbon atoms, esters or hydrocarbons.
[63] Specific examples of the alcohol include n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, nonanol, cyclohexanol, 2-methylcyclohexanol, benzyl alcohol, tetrahydrofur Furyl alcohol is listed.
[64] Specific examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl-n-hexyl ketone, di-n-propyl ketone, diacetone alcohol, acetonyl acetone, isophorone, poron, cyclohexanone and methyl Cyclohexanone and acetophenone are listed.
[65] As glycol ether, the compound represented by the following general formula [I] or [II] is mentioned.
[66] R ₀₁ O- (CH ₂ CH (R ₀₂ ) -O) _m -R ₀₃ [I]
[67] R ₀₄ O- (CH ₂ CH ₂ -O) _p -CO-CH ₃ [II]
[68] In the formula, R ₀₁ to R _{04 each} 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 integers of 1 to 20. Specific examples of the compound represented by the formula [I] or [II] include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, and 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 mono Butyl ether, diethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, Propylene glycol dimethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether, dipropylene glycol diethyl ether are exemplified.
[69] Specific examples of lactones having 3 to 12 carbon atoms include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprylolactone, γ-laurolactone, δ-valerolactone, δ-caprolactone, -caprolactone, crotonolactone, -angelicalactone, -angelicalactone, hexanolactone and the like are listed.
[70] Specific examples of the ester or hydrocarbon include amyl acetate, isoamyl acetate, methylisoamyl acetate, 2-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate and acetic acid Benzyl, butyl propionate, isoamyl propionate, butyl butyrate, isobutyl butyrate, isobutyl butyrate, butyl lactate, amyl lactate, isoamyl lactate, toluene, xylene, mesitylene, tetramethylbenzene, ethylbenzene, methylethylbenzene And methylpropyl benzene, diethyl benzene, petroleum products near boiling point 120 degreeC-300 degreeC, methylnaphthalene, etc. are mentioned. Among these, mesitylene, tetramethylbenzene, methylethylbenzene, methylpropylbenzene, methyl isoamyl acetate, cyclohexyl acetate, benzyl acetate, and amyl lactate are preferable.
[71] In addition to the above, cyclohexanone, sulfolane, dioxolane, dimethyl sulfoxide, polyethylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, monomethyl ether, monoethyl ether, monopropyl ether, isopropyl ether, monobutyl ether of these compounds And the like.
[72] These organic solvents may be used individually by 1 type, or may use 2 or more types together. When the organic solvent is contained in the modifier, the amount is suitably 1 to 20% by mass, and preferably 5 to 15% by mass based on the total mass of the modifier.
[73] (2) water-soluble high molecular compound
[74] By incorporating the water-soluble polymer compound in the modifier of the present invention, even better performance, that is, when the modifier is added to the target image on the flat plate using a brush, it is applied well in the target image part (no white streaks are formed). ) And the correction agent can have properties such as prevention of bleeding into adjacent image portions. A water-soluble high molecular compound is excellent in compatibility with a carbonate ester solvent, and is suitable for giving a moderate viscosity to a modifier.
[75] Preferred water-soluble high molecular compounds include, for example, modified cellulose such as methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose and Na salt, gum arabic, stractan, polyvinylpyrrolidone, polyvinyl methyl High molecular compounds, such as an ether, a polyethyleneglycol, a polypropylene glycol, a vinyl methyl ether maleic anhydride copolymer, and a vinyl acetate- maleic anhydride copolymer, are mentioned. Among them, modified cellulose, polyvinylpyrrolidone, vinyl methyl ether maleic anhydride copolymer, stractane and the like are useful. The said water-soluble high molecular compound can be used individually or in combination of 2 or more types. The usage-amount is used in 0.1-10 mass% with respect to the gross mass of a modifier, Most preferably, it is 0.3-5 mass%.
[76] (3) surfactant
[77] By containing surfactant in the modifier of this invention, each component in a modifier can give the performance which permeates better into the image part of a flat plate printing plate. Surfactants are also effective because each component contained in the modifier can be uniformly mixed to form a stable solution. As such surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polytyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid portion Addition of oxyethylene and oxypropylene to esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, oxyethylene-oxypropylene-block copolymers, trimethylolpropane, glycerin, polyoxyethylene sorbitan fatty acid partial esters, polyoxy Ethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide, N, N-bis-2-hydroxy Nonionic surfactants such as alkylamines, polyoxyethylenealkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abietinate salts, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinic acid ester salts, Linear alkylbenzenesulfonate, branched alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylphenoxypolyoxyethylenepropylsulfonate, polyoxyethylenealkylsulfophenylether salt, N-methyl-N-oleyltaurine sodium salt, N Alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated castor oil, sulfated tallow oil, sulfate ester salt of fatty acid alkyl ester, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride Sulfuric acid ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt , Alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partially saponified styrene-maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers, naphthalene sulfonates and formalin Anionic surfactants such as condensates, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, cationic surfactants such as polyethylenepolyamine derivatives, carboxybetaine, aminocarboxylic acids, sulfobetaines, amino Amphoteric surfactants, such as a sulfuric acid ester and imidazoline, a fluorine type or a silicon type surfactant are mentioned. Among the surfactants listed above, polyoxyethylene may be replaced with polyoxyalkylene such as polyoxymethylene, polyoxypropylene, polyoxybutylene and the like.
[78] Among these, nonionic surfactants and anionic surfactants are preferable, and since the components contained in the modifier can be satisfactorily mixed, a surfactant having an HLB of 9 or more is more preferable. In particular, nonionic surfactants are preferably used, from the viewpoint of improving the leak rate and permeability to the burn portion and increasing the rate of correction, such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, oxyethylene-oxypropylene block copolymer. , Polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerol fatty acid partial ester and the like are preferred because they improve the image erasing effect of the modifier.
[79] Some of the nonionic surfactants used in the present invention are represented by the following formula (4).
[80] R ₁₀ 0- (CH ₂ CH ₂ 0) _m (CH (CH ₃ ) CH ₂ O) _n (CH ₂ CH ₂ O) _p -R ₁₁ (4)
[81] 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 to 100 Represents an integer.)
[82] As a specific example represented by Formula (4), there is a compound in which at least one of R ₁₀ and R ₁₁ is a hydrogen atom. 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 Phosphorus compounds. M + p preferably represents an integer of 1 to 240, and n preferably represents an integer of 2 to 100, more preferably 2 to 70.
[83] In addition, the most preferable nonionic surfactant represented by Formula (4) is an oxyethylene-oxypropylene block copolymer in which both R ₁₀ and R ₁₁ are hydrogen atoms.
[84] The nonionic surfactant used in the present invention preferably has a weight average molecular weight in the range of 1200 to 3500 in the polypropylene glycol portion, and is about 40 to 90 mass% of an ethylene oxide content.
[85] These surfactant may be used independently and may be used together 2 or more types, Preferably it is 0.01-40 mass%, More preferably, in the range of 0.1-25 mass% with respect to the gross mass of the modifier of this invention. It is contained.
[86] (4) viscosity modifier
[87] It is preferable that the modifier of this invention contains a viscosity modifier further. They impart improved handwriting properties to the modifiers, and do not cause problems such as the dropping of the modifiers from the brushes when the modifiers of the invention are applied to the image portion of the flat plate using a brush, for example. Is available in point. Although some of the water-soluble high molecular compounds can also function as such viscosity modifiers, fine particles such as silicic acid fine powder, colloidal silica, zeolite and the like exhibit excellent performance, and therefore, it is preferable to contain them as viscosity modifiers. The average particle diameter of these fine powders is preferably in the range of 1 to 200 nm, and more preferably in the range of 5 to 100 nm. When the average particle diameter of a fine powder is in the said range, since affinity with a carbonate ester solvent is favorable and moderate thixotropy property is obtained, it is advantageous.
[88] Specific preferred fine particles include silicon dioxide fine powder, aerosil 130 (primary particle average diameter of about 16 nm), aerosil 200 (primary particle average diameter of about 18 nm), and aerosol 300 (primary particle average diameter of about 7 nm), Aerosil 380 (primary particle average diameter about 7 nm), Aerosil R-972 (primary particle average diameter about 16 nm), Aerosil MOX170 (primary particle average diameter about 15 nm), Aerosol OX50 (primary) Particle average diameter about 40 nm), aerosil TT600 (primary particle average diameter about 40 nm), aerosol MOX80 (primary particle average diameter about 30 nm), silica K320DS (primary particle average diameter about 18 nm), SILTEG AS7 (primary particle) Average diameter about 35 nm), CALSIL (average particle average diameter about 40 nm), silica D17 (primary particle average diameter about 20 nm), and aluminum oxide powder Aluminum Oxide C (primary particle average diameter about 20 nm), titanium oxide powder Titanium Oxide P25 (primary particle average diameter 30nm) or more manufactured by Nihon Aerosil Co., Ltd., Nissan Chemical Co., Ltd. -520 (particle average diameter about 10-20 nm), alumina sol-100 (particle size average 100 nm x 10 nm), alumina sol-200 (particle size average 100 nm x 10 nm), Nissan Kagaku Kogyo Co., Ltd. colloidal silica Snortex 20 (particle diameter 10-20 nm), snortex 30 (particle diameter 10-20 nm), snortex C (particle diameter 10-20 nm), snortex N (particle diameter 10-20 nm), snortex O (particle diameter 10-20 nm), etc. These are listed as preferred examples. Particularly preferred among the fine particles is silicon dioxide fine powder, and particularly preferred particle diameter is 5 to 100 nm.
[89] If the particle size is smaller than 1 nm, the particles tend to aggregate and the viscosity of the modifier is easily changed. If the particle size is larger than 200 nm, proper thixotropy cannot be obtained.
[90] As for the usage-amount of these viscosity modifiers, 1-10 mass% is suitable with respect to the total mass of a modifier, More preferably, it is the range of 3-8 mass%.
[91] (5) Others (colorants, preservatives, rust inhibitors, antifoams)
[92] As other components, a coloring agent, a preservative, a rust preventive agent, an antifoamer, etc. can be further added to the modifier of this invention. Colorants are used to impart the desired color tone to the modifiers of the present invention and add visual contrast and can be selected from a wide variety of dyes. Particularly, as a preferable colorant, an indicator dye having a dark color tone such as blue, purple, yellow, or red color exhibits an excellent effect. Specifically, for example, dyes such as crystal biored, safranin, brilliant blue, malachite green, and acid rhodamine B may be used as inorganic pigments and organic pigments. When using a coloring agent, the usage-amount is about 0.0001 to about 0.10 mass% with respect to the total mass of the modifier of this invention, Preferably it is the range of 0.001 to 0.05 mass%.
[93] Preservatives used in the present invention include, for example, phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoylthiazolin-3-ones, benztriazole derivatives, and amides. Derivatives such as dinguanidine derivatives, quaternary ammonium salts, pyridine, quinoline, guanidine and the like, diazines, triazole derivatives, oxazoles, oxazine derivatives, 2-bromo-2-nitropropane-1,3-diol and the like do. The preferred amount of addition is a quantity that exhibits a stable effect against bacteria, mold, yeast, etc., and also varies depending on the type of bacteria, mold, yeast, but is preferably in the range of 0.01 to 4% by mass based on the total mass of the modifying agent, It is also desirable to use two or more preservatives in combination to protect the fertilizer from various fungi and bacteria.
[94] As an antifoamer, a silicone antifoamer is preferable. Among them, any of an emulsion dispersion type and a solubilization type can be used. As for the usage-amount, the range of 0.001-1.0 mass% is the most preferable with respect to the total mass of a modifier.
[95] Examples of the rust inhibitors include 1H benzotriazole and derivatives thereof, benzimidazole and derivatives thereof, and thiosalicylic acid. Preferable addition amount is 0.0001-0.1 mass% with respect to the total mass of a modifier.
[96] The modifier of the present invention can be applied to flat plate printing plates produced from various flat plate printing plates. Such an original flat plate printing plate is not particularly limited, and for example, an image recording layer such as a photosensitive layer, a thermal layer, and the like illustrated below is provided on a support. Examples of the image recording layer include conventional positive type, conventional negative type, photo polymer type (photopolymerization type), thermal positive type, and thermal negative type (thermal polymerization type and acid crosslinking type). The conventional convention described herein refers to a conventional flat printing plate original plate that is exposed in the form of an image through transparent positive print or transparent negative print. Hereinafter, these image recording layers will be described. Moreover, the developing solution suitable for each original flat plate printing plate is also demonstrated.
[97] <Convention Positive>
[98] As a preferable thing of the conventional positive photosensitive resin composition, the composition containing an o-quinonediazide compound and an alkali-soluble high molecular compound is mentioned. Examples of o-quinone diazide compounds include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and phenol formaldehyde resins or cresol formaldehyde resins, and US Pat. No. 3,635,709. Esters of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride and pyrogallol-acetone resins as described. An alkali-soluble high molecular compound is a copolymer of phenol formaldehyde resin, cresol formaldehyde resin, phenol cresol formaldehyde cocondensation resin, polyhydroxy styrene, N- (4-hydroxyphenyl) methacrylamide, Carboxyl group-containing polymers and the like described in JP-A-7-36184. Moreover, alkali-type resin containing phenolic hydroxyl group as described in Unexamined-Japanese-Patent No. 51-34711, alkali-type resin which has sulfonamide group as described in Unexamined-Japanese-Patent No. 2-866, urethane type resin, etc. Various alkali-soluble high molecular compounds can also be used. In addition, the photosensitive resin composition is a compound such as a sensitivity modifier, a phosphating agent, a dye disclosed in Japanese Patent Laid-Open Nos. 7-92660, and a coating property such as that disclosed in the same publication. It is preferable to add a surfactant for improving the temperature.
[99] The conventional positive type photosensitive flat plate printing plate in which the photosensitive composition containing these o-quinonediazide compound and alkali-soluble high molecular compound is installed on a support body is exposed to image shape using ultraviolet-ray, and is developed by alkaline developing solution. As such a developer, a developer mainly composed of an alkali metal silicate aqueous solution described in Japanese Patent Application Laid-open No. 57-7427 or Japanese Patent No. 3086354, and a non-reducing sugar and base described in Japanese Patent Application Laid-open No. Hei 8-305039. These are listed as preferred examples.
[100] <Conventional negative type>
[101] As a conventional negative photosensitive resin composition, what contains a diazo resin and alkali-soluble or swellable high molecular compound (binder) is mentioned.
[102] Examples of the diazo resins include condensates of active carbonyl group-containing compounds such as aromatic diazonium salts with formaldehyde, and further include condensates of p-diazophenylamines with formaldehyde and hexafluorophosphate or tetrafluoro. The organic solvent soluble diazo resin inorganic salt which is a reaction product of a borate salt is mentioned. In particular, a high molecular weight diazo compound containing 20 mol% or more of the hexamer or more described in JP-A-59-78340 is preferable. Preferred binders include copolymers containing acrylic acid, methacrylic acid, crotonic acid or maleic acid as essential components, such as 2-hydroxyethyl (meth) acrylate as described in Japanese Patent Application Laid-open No. 50-118802, Polyalkyl copolymers of monomers such as meta) acrylonitrile and (meth) acrylic acid, and alkyl acrylates such as those described in JP-A-56-4144, (meth) acrylonitrile, and unsaturated carboxylic acids. The multicomponent copolymer which consists of these can be mentioned. In addition, in the photosensitive resin composition, compounds such as plasticizers and development accelerators, coating properties, for imparting the flexibility and abrasion resistance of the phosphorizing agent, dye, and coating film disclosed in Japanese Patent Application Laid-open No. Hei 7-281425; It is preferable to add surfactant for improving the quality.
[103] As an underlayer of the conventional positive type or negative type photosensitive layer, an intermediate layer containing a high molecular compound having a component having an acid group and a component having an onium group is described in Japanese Patent Application Laid-Open No. 2000-105462. It is desirable to.
[104] The photosensitive flat printing plate using the conventional negative photosensitive resin composition thus produced is exposed to an image shape using ultraviolet rays, and then developed with a developer. As the 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, if necessary, various additives known in the art as needed. An aqueous solution containing is used. Particularly preferred examples include Japanese Patent Publication No. 56-42860, Japanese Patent Publication No. 58-54341, Japanese Patent Application Laid-Open No. 2-37579, Japanese Patent Publication No. 63-200154, and Japanese Patent Publication No. 64 The developer described in the -44445 publication, etc. are mentioned.
[105] <Photopolymer type>
[106] (Photosensitive layer)
[107] The photopolymerizable photosensitive composition of the photopolymer type (hereinafter referred to as "photopolymerizable composition") includes an ethylenically unsaturated bond-containing compound (hereinafter, simply referred to as "ethylenically unsaturated bond-containing compound") capable of addition polymerization, a photopolymerization initiator and a polymer binder. It is contained as an essential component, and various compounds, such as a coloring agent, a plasticizer, and a photoinhibitor, are contained as needed.
[108] The ethylenically unsaturated bond-containing compound contained in the photopolymerizable composition is a compound having an ethylenically unsaturated bond so that addition polymerization, crosslinking and curing are carried out by the action of a photopolymerization initiator when the photopolymerizable composition is subjected to actinic radiation. The ethylenically unsaturated bond-containing compound may optionally be selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds, such as monomers, prepolymers (ie dimers, trimers and oligomers), mixtures thereof And chemical forms such as copolymers thereof. Examples of the monomer include esters of unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds. Moreover, a urethane type addition polymeric compound is also preferable.
[109] As an initiator contained in a photopolymerizable composition, the combination system (photo-clock) of various photoinitiators or 2 or more types of photoinitiators can be selected suitably, and can be used according to the wavelength of the light source to be used, for example, Unexamined-Japanese-Patent No. 2001-22079 [ Initiation systems disclosed in 0021] to [0023] are preferable. Since the polymeric binder contained in the photopolymerizable composition functions not only as a film forming agent of the photopolymerizable composition, but also needs to dissolve the photosensitive layer in an alkaline developer, an organic polymer polymer soluble or swellable in an alkaline developer is used. As the polymer, those disclosed in the same publication [0036] to [0063] are useful. It is also preferable to add the additive (for example, surfactant for improving applicability | paintability) disclosed in the same publication [0079]-[0088] to another photopolymerizable composition.
[110] In addition, it is preferable to form an oxygen barrier protective layer on the photosensitive layer to prevent polymerization by oxygen. As a polymer contained in an oxygen barrier protective layer, polyvinyl alcohol or its copolymer is mentioned. Moreover, it is also preferable to form the intermediate | middle layer or adhesive layer as disclosed by Unexamined-Japanese-Patent No. 2001-228608-[0165] as a lower layer of the photopolymer type photosensitive layer.
[111] The photosensitive flat printing plate using the photopolymer type photopolymerizable photosensitive composition is exposed to an image shape using ultraviolet rays such as high pressure mercury lamp, argon laser and ultraviolet laser, and then developed with a developer. As the preferred developer, an alkali agent, an organic solvent, a surfactant, a water softener, a reducing agent, an organic carboxylic acid, an inorganic salt, an antifoaming agent, or an aqueous solution further containing various additives known in the art as needed may be used. Particularly preferred examples thereof include the developer described in Japanese Patent Application Laid-Open No. 58-54341, Japanese Patent Application Laid-Open No. 8-248643, Japanese Patent Application Laid-Open No. 2002-91015, Japanese Patent Application Laid-Open No. 8-171214, and the like. Listed.
[112] Since the image portion created from the photopolymer type image recording layer as described above forms a mesh structure by a polymerization reaction, there is a problem that the image portion is difficult to dissolve in the solvent and is difficult to be corrected. By using the fixer of this invention here, it is advantageous because the unnecessary image part can be erased in a short time.
[113] <Thermal positive type>
[114] (Thermal layer)
[115] The thermal positive type heat-sensitive layer contains an alkali-soluble high molecular compound and a photothermal conversion material. This alkali-soluble high molecular compound contains the homopolymer which contains an acidic group in a polymer, these copolymers, and mixtures thereof, In particular, what has an acidic group like (1) or (2) from a viewpoint of the solubility to alkaline developing solution is carried out. Preferred: (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 point which is excellent in image formation property in exposure by an infrared laser etc., for example, a phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / novolak resins such as p-mixed cresol formaldehyde resin and phenol / cresol (any of m-, p- and m- / p-mixed) mixed formaldehyde resin; Pyrogallol acetone resins are preferably listed. More specifically, the polymers disclosed in [0023] to [0042] of JP 2001-305722 A are preferably used.
[116] The photothermal conversion material makes it possible to efficiently convert the exposure energy into heat to release the interaction of the exposed portion region of the heat sensitive layer. From the viewpoint of recording sensitivity, a pigment or dye having a light absorption region in the infrared region having a wavelength of 700 to 1200 nm is preferable. Specific examples of the dye include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium pigments, and pyrilium salts. And dyes such as metal thiorate complexes (eg, nickel thiorate complexes) can be used. Especially, cyanine dye is preferable and the cyanine dye represented by General formula (I) of Unexamined-Japanese-Patent No. 2001-305722 is mentioned. In the composition of the thermal positive type, it is preferable to add a compound such as a sensitivity modifier, a phosphating agent, a dye, or a surfactant for improving applicability in the same form as described in the conventional positive type. Preferred are the compounds disclosed in [0053] to [0059] of 2001-305722.
[117] The thermal positive heat-sensitive layer may be a single layer or may be formed as a two-layer structure as described in JP-A-11-218914.
[118] It is preferable to form a subbing layer between the thermal positive thermal layer and the support. As the component contained in the lower layer, various organic compounds disclosed in Japanese Patent Laid-Open No. 2001-305722 are listed.
[119] The thermal positive thermosensitive flat plate printing plate provided with the thermosensitive composition containing these alkali-soluble high molecular compounds and a photothermal conversion material on a support body is exposed to image shape using an infrared laser, and is developed by alkaline developing solution. As such a developing solution, 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 Japan Developers and the like described in Japanese Patent Application Laid-Open No. 2002-72501 are listed as preferred examples.
[120] <Thermal negative type>
[121] (Thermal layer)
[122] The thermal negative thermal layer is a negative thermal layer in which the infrared laser irradiation section cures to form an image portion.
[123] As an example of such a thermal negative type thermally sensitive layer, a polymeric type layer is mentioned preferably. The polymerization layer contains (A) an infrared absorber, (B) a radical generator (radical polymerization initiator), and (C) a radical polymerizable compound and a (D) binder polymer which polymerize and harden | cure by the generated radical.
[124] In the polymerization layer, infrared rays absorbed by the infrared absorber are converted into heat, and radicals such as anionic salts are decomposed by the heat generated at this time, and radicals are generated. The radically polymerizable compound is selected from compounds having terminal ethylenically unsaturated bonds, and polymerization occurs and cures in series by the generated radicals. (A) As the infrared absorber, for example, the above-described thermal conversion material contained in the thermal positive type thermal layer described above is mentioned. Particularly, examples of cyanine dyes include paragraphs [0017] to [0019] of Japanese Patent Application Laid-Open No. 2001-133969. ] Can be listed. Onium salts are listed as a radical generating agent (B), and the thing of Paragraph No. [0030]-[0033] of Unexamined-Japanese-Patent No. 2001-133969 is mentioned as a specific example of the onium salt which can be used suitably. The (C) radically polymerizable compound is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. It is preferable to use a linear organic polymer as the (D) binder polymer, and the linear organic polymer which is soluble or swellable in water or weakly alkaline water is selected. Among these, (meth) acrylic resins having a benzyl group or an allyl group and a carboxyl group in the side chain are suitable because of excellent balance in film strength, sensitivity and developability. Regarding the (C) radically polymerizable compound and the (D) binder polymer, those described in detail in the same publications [0036] to [0060] can be used. As another additive, it is also preferable to add the additive (for example, surfactant for improving applicability | paintability) disclosed in the same publication.
[125] Moreover, as an example of the thermal negative type thermally sensitive layer other than a polymerization type, an acid crosslinking type layer is mentioned preferably. The acid crosslinking layer contains a compound (hereinafter referred to as an "acid generator") that generates an acid by light or heat (hereinafter referred to as an "acid generator") and a compound that crosslinks by (F) generated acid (hereinafter referred to as a "crosslinking agent"). And a (G) alkali-soluble high molecular compound capable of reacting with a crosslinking agent in the presence of an acid. In order to use the energy of an infrared laser with high efficiency, (A) an infrared absorber is mix | blended with an acid bridge layer. Examples of the (E) acid generator include compounds capable of generating an acid by thermal decomposition such as photoinitiators of photopolymerization, photochromic agents of pigments, and acid generators used in micro resists and the like. The (F) 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. Listed. As a (G) alkali-soluble high molecular compound, novolak resin, the polymer which has a hydroxyaryl group in a side chain, etc. are mentioned.
[126] The thermal negative type thermosensitive flat plate printing plate in which these polymerization type and acid crosslinking type thermal negative layer is provided on a support body is exposed to image shape using an infrared laser, and is developed with alkaline developing solution. Examples of such a developer include a developer disclosed in Japanese Patent Application Laid-Open No. 57-7427, Japanese Patent Application Laid-Open Nos. 2001-133969, [0119] to [0123], Japanese Patent Application No. 2002-47985, and Japanese Patent Application No. 2002-59297. And the developer described in US Patent No. 5,766, 826 are listed as particularly preferred examples.
[127] There is a problem that the image portion manufactured from the original plate of the thermal positive type flat plate printing plate having the image recording layer containing the infrared absorber described above, or the image portion produced from the thermal negative type plate of the negative thermal type flat plate printing plate, is relatively weak against various chemicals. have. Therefore, the use of the fixer of the present invention is advantageous because it is unlikely to have an effect of damaging the image around the correction part.
[128] <Support>
[129] An aluminum plate is generally used as a support body of the original flat plate printing plate in which the image recording layer is provided. An aluminum plate is plate-like object, such as aluminum alloy which has pure aluminum or aluminum as a main component, and contains a trace amount of another atom. Atoms for producing the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. Such atoms are suitably contained in an amount of 10% by mass or less of the aluminum alloy composition. Preferred aluminum is pure aluminum, but since pure aluminum is difficult to manufacture due to refining technology, it is preferable not to contain other atoms as much as possible. Moreover, if it is an aluminum alloy containing another atom by the above-mentioned ratio, it can be said that it is a raw material which can be used for this invention. The composition of an aluminum plate is not specifically limited, A conventionally well-known and common material can be used suitably. As preferable materials, aluminum materials of JIS A 1050, JIS A 1100, JIS A 1200, JIS A 3003, JIS A 3103, JIS A 3005 are listed. As for the thickness of the aluminum plate used in this invention, about 0.1 mm-about 0.6 mm are suitable. Before roughening the aluminum plate, a degreasing treatment, for example, with a surfactant or alkaline aqueous solution, is carried out as necessary to remove the rolled oil adhering to the surface.
[130] Subsequently, roughening treatment, anodizing treatment, hydrophilicity treatment, and the like are appropriately performed in combination, and there is a treatment method of a support such as disclosed in, for example, Japanese Patent Laid-Open No. 2001-356494.
[131] An image recording layer is coated on the support thus prepared to obtain an original plate for a flat printing plate. Before laying the image recording layer on the support, an intermediate layer may be formed. As such an intermediate layer, one containing an organic polymer compound is preferably used, for example, those disclosed in Japanese Patent Laid-Open No. 2001-356494.
[132] If necessary, a coating layer (also referred to as a "back coat layer") made of an organic high molecular compound can be provided on the rear surface of the original plate for flat plate printing, in order to prevent damage to the image recording layer when the original plate is overlapped with another original plate.
[133] After developing the original plate for flat plate printing, it is usually possible to obtain a flat plate by performing post-treatment combining water washing, rinsing, desensitizing, and the like. When there is an unnecessary image portion in the flat plate printing plate thus obtained, the modifying agent of the present invention is added to the image portion to erase the image portion. In order to effectively erase the image portion, when the modifying agent of the present invention is added to the image portion of the flat plate printing plate, it is preferable that the flat plate printing plate is sufficiently washed after the development rather than immediately after development. In addition, although the erase speed is slightly slowed, it is also possible to add a modifier to the rubber-coated flat plate. As a specific method of adding the fixer of this invention to the image part of a flatbed printing plate, the method of apply | coating the fixer of this invention to the image part to remove desired, using a brush is common. After application of the correction agent, the image portion is left as it is for about 5 seconds to about 1 minute, and then washed with water to remove the correction agent, the image portion of the portion to which the correction agent is applied is removed cleanly and becomes a non-image portion. After that, it is treated in a conventional manner (for example, rubber coating or the like) and used as a flat printing plate.
[134] Example
[135] Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these. In addition, "part" shall mean "mass part" and "%" shall mean "mass%" unless there is particular notice.
[136] Examples 1-11 and Comparative Examples 1-6
[137] Example 1
[138] The modifier of the present invention was prepared as follows.
[139] [Modifier A]
[140] First, 8.4 parts of propylene carbonate, 33 parts of ethylene carbonate, 27.6 parts of dimethylacetamide, and tetramethylbenzene as a component (Suwazol 1800 made by Maruzen Sekiyu Chemical Co., Ltd.) and 8 parts of pure water are mixed. 1.2 parts of hydroxypropyl cellulose (70 to 95% of hydroxypropyl group) and an oxyethylene-oxypropylene-block copolymer (polymerized with ethylene oxide at both ends of polypropylene glycol having an average molecular weight of 2,000 in a solution. 10,000 parts of ethylene oxide: 80%) was dispersed. 1.0 part of acetic acid, 0.5 part of oxalic acid, and 0.003 part of crystal violet were dissolved and stirred in order to obtain a uniform solution. 4.0 parts of powder silicon dioxide (manufactured by Nippon Aerosol Co., Ltd., silicon dioxide fine powder aerosil 380 (primary particle average particle diameter 7 nm)) was added to disperse to obtain a viscous liquid crystal. The pH of the modifier was 6.0.
[141] In the same manner as in the above-mentioned Modifier A, the modifiers (modifiers B to K) of Examples 2 to 11 and the modifiers (comparative modifiers a to f) of Comparative Examples 1 to 6 were prepared.
[142] The composition (unit: mass part) and pH value of each modifier are shown to the following Tables 1-3.
[143] ExampleOne23456 ModifierABCDEF Propylene carbonate8.39.310.79.39.39.0 Ethylene carbonate33.034.042.734.034.036.0 Dimethylacetamide27.628.626.628.628.623.0 Swasol 1800 ^{* 1} 8.48.4-8.48.48.2 Zirconic Hydrofluoric Acid (40% aqueous solution)-2.02.0--1.7 Hydrofluoric acid silicon (40% aqueous solution)---2.0-- Hydrofluoric acid (40% aqueous solution)----2.0- Titanium hydrofluoric acid (40% aqueous solution)------ Trifluoroacetic acid------ Ammonium bifluoride (40% aqueous solution)------ pure8.07.17.37.17.17.0 Hydroxypropyl Cellulose ^{* 2} 1.2----2.0 Oxyethylene-oxypropylene block copolymer ^{* 3} 8.55.04.95.05.06.0 Polyvinylpyrrolidone ^{* 4} -0.3-0.30.3- Vinyl methyl ether / maleic anhydride (1: 1 molar ratio) copolymer ^{* 5} --1.5--- Fluorine-based Surfactant ^{* 6} --0.5--- Sodium Alkylbenzenesulfonate------ Phosphoric Acid (85%)--0.5--- Acetic acid1.01.00.51.01.0- Oxalic acid0.5----- Triethanolamine-1.01.01.01.00.7 Crystal violet0.0030.0030.0030.0030.0030.003 Powdered Silicon Dioxide ^{* 7} 4.04.04.84.04.06.0 pH6.04.54.04.55.04.5
[144] ^{* 1} Solvent containing tetramethylbenzene of Maruzen Sekiyu Kagaku Co., Ltd. production sale
[145] ^{* 2} 70-95% of hydroxypropyl group
[146] ^{* 3} Polymerized with ethylene oxide at both ends of polypropylene glycol having an average molecular weight of 2,000. Molecular weight: 10,000, Ethylene oxide content: 80%
[147] ^{* 4} K-15 (made by GAF Corporation)
[148] ^{* 5} Intrinsic viscosity at 2.6 degreeC of the solution which 1g of copolymers melt | dissolved in 100g of methyl ethyl ketone is 2.6-3.5
[149] ^{* 6} Mega Pack F-781-F (made by Dainippon Ink, Inc.)
[150] ^{* 7} Silicon dioxide fine powder Aerosol 380 (primary particle average diameter approximately 7nm) (made by Nippon Aerosol Co., Ltd.)
[151] In the following table, ^{* 1- * 7} are the same as the above.
[152] Example7891011 ModifierGHIJK Propylene carbonate9.310.79.39.39.0 Ethylene carbonate34.042.734.034.036.0 Dimethylacetamide28.626.628.628.623.0 Swasol 1800 ^{* 1} 8.4-8.48.48.2 Zirconic Hydrofluoric Acid (40% Aqueous Solution)1.51.5--- Hydrofluoric acid silicon (40% aqueous solution)----- Hydrofluoric acid (40% aqueous solution)----- Titanium hydrofluoric acid (40% aqueous solution)--1.5-- Trifluoroacetic acid---1.5- Ammonium bifluoride (40% aqueous solution)----1.7 pure7.17.37.17.17.0 Hydroxypropyl Cellulose ^{* 2} ----2.0 Oxyethylene-oxypropylene block copolymer ^{* 3} 5.04.95.05.06.0 Polyvinylpyrrolidone ^{* 4} 0.3-0.30.3- Vinyl methyl ether / maleic anhydride (1: 1 molar ratio) copolymer ^{* 5} -1.5--- Fluorine-based Surfactant ^{* 6} -0.5--- Sodium Alkylbenzenesulfonate----- Phosphoric Acid (85%)0.5--0.5- Acetic acid0.5--0.5- Oxalic acid----- Triethanolamine2.71.5-3.00.7 Crystal violet0.0030.0030.0030.0030.003 Powdered Silicon Dioxide ^{* 7} 4.04.84.04.06.0 pH5.05.54.56.56.0
[153] Comparative exampleOne23456 Comparative modifierabcdef Propylene carbonate13.8-9.39.3-- Ethylene carbonate55.1-34.034.0-- Dimethylacetamide-80.0---- Dimethylformamide--28.6--- N-methylpyrrolidone---28.640.040.0 N, N-dimethylformamide----40.0- Dioxolane-----40.0 Swasol 1800 ^{* 1} 8.4-8.48.4-- Zirconic Hydrofluoric Acid (40% aqueous solution)-2.0---2.0 Hydrofluoric acid silicon (40% aqueous solution)---2.0-- Hydrofluoric acid (40% aqueous solution)2.0-2.0-2.0- Titanium hydrofluoric acid (40% aqueous solution)------ Trifluoroacetic acid------ Ammonium bifluoride (40% aqueous solution)------ pure7.07.47.17.17.07.4 Hydroxypropyl Cellulose ^{* 2} 1.2---1.7- Oxyethylene-oxypropylene block copolymer ^{* 3} 8.55.05.05.58.55.5 Polyvinylpyrrolidone ^{* 4} -0.30.30.3-0.3 Vinyl methyl ether / maleic anhydride (1: 1 molar ratio) copolymer ^{* 5} ------ Fluorine-based Surfactant ^{* 6} -- --- Sodium Alkylbenzenesulfonate-0.50.50.5-0.5 Phosphoric Acid (85%)------ Acetic acid0.50.5---- Oxalic acid--0.5--- Triethanolamine------ Crystal violet0.0030.0030.0030.0030.0030.003 Powdered Silicon Dioxide ^{* 7} 4.04.84.54.54.04.8 pH4.04.54.55.05.55.0
[154] Each of the modifiers prepared in Examples 1 to 11 and Comparative Examples 1 to 6 was evaluated for odor generation and safety concerns in the working environment using the same, and is shown in Table 4 below.
[155] ModifierOdor of Work EnvironmentSafety concerns Example 1AAnestheticnone Example 2BAnestheticnone Example 3CAnestheticnone Example 4DAnestheticnone Example 5EAnestheticnone Example 6FAnestheticnone Example 7GAnestheticnone Example 8HAnestheticnone Example 9IAnestheticnone Example 10GAnestheticnone Example 11KAnestheticnone Comparative Example 1ComparisonAnestheticnone Comparative Example 2ComparisonVolatile odornone Comparative Example 3ComparisonVolatile odorhas exist Comparative Example 4ComparisonAnesthetichas exist Comparative Example 5ComparisonVolatile odorhas exist Comparative Example 6Comparisonstinkhas exist
[156] Test 1
[157] The image part formed in the flat printing plate obtained from the conventional positive type original plate was correct | amended using the said various correction agents of Examples 1-11 and Comparative Examples 1-6.
[158] [Production of Flat Printing Plate]
[159] After polishing the aluminum plate having a thickness of 0.3 μm with a brush, and further electrochemically roughening in a nitric acid solution, and washing well, anodization was performed in a sulfuric acid solution to obtain an oxide film having a thickness of 2.5 g / m ² . Formed on the surface. After washing with water and drying, 3 parts of an esterified product of resorcined benzaldehyde resin and naphthoquinone-1,2-diazide-5-sulfonyl chloride synthesized according to the example of Japanese Patent Application Laid-open No. 56-1044 and cresol-formalin A photosensitive solution obtained by dissolving 9 parts of novolak resin and 0.12 parts of Victoria Pure Blue-BOH (manufactured by Hodogaya Chemical Co., Ltd.) in 100 parts of 2-methoxy ethanol was applied and dried on a support using a rotary applicator, and 2.8 g / A positive PS plate having a photosensitive layer of m ² was obtained. A dot phototransparency enhancement was brought in close contact therewith, and the film was exposed for 60 seconds with a metal halide lamp located at a distance of 0.8 m, and developed with the following developer to obtain a flat printing plate.
[160] (developer)
[161] 120 parts of potassium silicate A (SiO ₂ 26%, K ₂ O 13.5%)
[162] 86% Potassium Hydroxide 15.5
[163] 500 parts water
[164] In the flat printing plate obtained in this way, the edge of the said transparent positive film remained thin as an image on the plate surface.
[165] Each of the modifiers was contained in a brush, and the transparent positive film edge on the flat plate was applied to the remaining surface area as an image, left for 5 seconds to 10 minutes for testing, and sprayed with water after each time to remove the modifier. .
[166] Here, the influence (smear) on the periphery of the region where the correction agent is applied (whether or not the periphery of the region where the modification agent is applied is not faded on the printed matter), the application of the correction agent necessary for erasing unnecessary images on the plate After leaving time, as described later, the leaving time after application of the correction agent necessary to prevent the ink from adhering to the erased portion immediately after the printing is started, and the contamination by damage to the support 10 minutes after the application of the correction agent (10 minutes after application of the correction agent) After rinsing off with water afterwards, whether or not ink contamination occurred in the erase section at the start of printing was examined. About printing, the Arabic rubber 14 degree Be aqueous solution was apply | coated on the board | substrate with which correction was completed, and it put into an offset press and printed 10,000 sheets.
[167] These results are shown in Table 5.
[168] The image portion modified with the modifier of the present invention was such that the hydrophilic layer was completely exposed and became slightly white compared with other non-image portions. Since no ghost image remains in the portion where the image is erased, and the printing plate is very easy to inspect after the correction operation, the time for inspecting the printing plate is shortened. In addition, when a printing operation was performed using the printing plate, a clean printed matter was obtained without any contamination in the portion corresponding to the image portion erased from the printing plate using the correction agent. In addition, the correction agent of the present invention has a minimal bleeding of liquid even in the elimination of details, and can be corrected with confidence, and also has high safety in terms of physiology and almost no unpleasant cases.
[169] In addition, the deterioration of the scavenging properties after the storage of the modifier of the present invention for 7 days in 50 ° C./80% RH was examined as a compulsory aging test.
[170] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone1010none Bnone1010none Cnone1010none Dnone1515none Enone1515none Fnone1010none Gnone1010none Hnone1010none Inone1010Slightly Jnone1015Slightly Knone1015Slightly Comparisonnone2020none Comparisonnone55none Comparisonplenty1010none Comparisonplenty1010none Comparisonplenty1040has exist Comparisonplenty1030none
[171] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[172] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[173] *** Contamination due to support damage 10 minutes after application of the modifier
[174] Test 2
[175] The plates obtained by developing a thermal positive original plate (including a substrate treated with silicate and coated with a lower layer) with a silicate developer were modified using various modifiers of Examples 1-11 and Comparative Examples 1-6.
[176] [Production of board]
[177] The aluminum plate (JIS A 1050) with a thickness of 0.3 mm was washed with trichloroethylene and degreased, and then roughened on the surface by using a nylon brush and a 400 mesh water powder suspension, and washed well with water. It was. The aluminum plate was immersed in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds to perform etching. After washing with water, the aluminum plate was further immersed in 20% nitric acid solution for 20 seconds and washed with water. At this time, the etching amount of the roughening surface was about 3 g / m <^2> . Next, the plate was formed with a 7% sulfuric acid solution as an electrolyte, and a 3 g / m ² direct current anodized film at a current density of 15 A / dm ² was washed with water and dried.
[178] This was treated with 30 mass% of sodium silicate aqueous solution at 30 degreeC for 10 second, the following servant liquid was apply | coated, and the coating film was dried at 80 degreeC for 15 second, and the board | substrate was obtained. The coating amount of the coating film after drying was 15 mg / m <^2> .
[179] <Composition of servant liquid>
[180] 0.3 parts of the following copolymer of molecular weight 28,000
[181] 100 parts methanol
[182] 1 part water
[183]
[184] The following coating liquid for photosensitive layer formation was apply | coated to the obtained board | substrate so that application amount might be 1.8 g / m <^2> , and it dried, and obtained the flat printing plate original plate.
[185] <Composition of the Photosensitive Layer Coating Liquid>
[186] M, p-cresol novolac 1.0part
[187] (m / p ratio = 6/4, weight average molecular weight 8,000
[188] 0.5 mass% of unreacted cresol)
[189] 0.1 part cyanine dye A (following structure)
[190] Tetrahydrophthalic anhydride 0.05 part
[191] 0.002 parts of p-toluenesulfonic acid
[192] Counter ion of ethyl violet
[193] 0.02 parts of 6-hydroxy-β-naphthalene sulfonic acid
[194] Fluorine-based surfactant 0.05 part
[195] (Mega pack F-781-F, Dainippon ink Kagaku Kogyo Co., Ltd.)
[196] 12 parts of methyl ethyl ketone
[197]
[198] The original flat plate printing plate was exposed using Creo Corporation's plate setter "Trendsetter 3244F" (rotational speed: 150 rpm), and developed with an alkali liquid (pH about 13) having the following composition to obtain a flat plate.
[199] [Composition of Alkaline Developer]
[200] _{· SiO 2 · K 2 O 4.0} %
[201] (K ₂ O / SiO ₂ = 1.1 (molar ratio))
[202] Citric acid 0.5%
[203] 0.5% polyethylene glycol (weight average molecular weight = 1000)
[204] 95.0% of water
[205] In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image portion was treated in the same manner as Test 1 with the various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6, and erased to printed.
[206] The results are shown in Table 6.
[207] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone1010none Bnone1010none Cnone1010none Dnone1515none Enone1515none Fnone55none Gnone510none Hnone510none Inone510Slightly Jnone515Slightly Knone515Slightly Comparisonnone2020none Comparisonnone55In a little Comparisonplenty1010none Comparisonplenty1010none Comparisonplenty1040has exist Comparisonplenty1540none
[208] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[209] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[210] *** Contamination due to support damage 10 minutes after application of the modifier
[211] Test 3
[212] The plates obtained by developing the thermal positive original plate (including the substrate treated with silicate and coated with the lower layer) with a non-silicate developer were modified using various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6 described above.
[213] The original flat plate obtained in the same manner as in Test 2 was exposed in the same manner, and 1 liter of a potassium salt 45% aqueous solution composed of D-sorbitol / potassium oxide (K ₂ O) in which a non-reducing sugar and a base were combined was used as an amphoteric surfactant. 20 g of pionein C-158G (manufactured by Takemoto Yuji Kagashi Co., Ltd.) and 2.0 g of antifoaming agent "Olphin AK-02" (manufactured by Nisshin Kagaku Co., Ltd.) were added to form a concentrate, and the concentrate was diluted nine times with water. Development was carried out to obtain a flat printing plate.
[214] In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image portion was treated in the same manner as Test 1 with the various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6, and erased to printed.
[215] The results are shown in Table 7.
[216] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone1010none Bnone1010none Cnone1010none Dnone1515none Enone1515none Fnone55none Gnone510none Hnone510none Inone510Slightly Jnone510Slightly Knone515Slightly Comparisonnone2020none Comparisonnone55none Comparisonplenty1515none Comparisonplenty55In a little Comparisonplenty1540has exist Comparisonplenty1530none
[217] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[218] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[219] *** Contamination due to support damage 10 minutes after application of the modifier
[220] Test 4
[221] A plate obtained by developing a thermal positive original plate (including a substrate without silicate treatment and without a lower layer) was developed with a silicate developer, and the plates obtained by modifying the various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6 were used. .
[222] In the same manner as in Test 2, a substrate was obtained from degreasing the aluminum plate to forming the oxide film. The photosensitive liquid was applied and dried in the same manner as in Test 2 and then exposed and developed in the same manner as in Test 2, except that the obtained substrate was not treated with sodium silicate and was not coated with a phosphorus solution. In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image portion was treated in the same manner as Test 1 with the various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6, and erased to printed.
[223] The results are shown in Table 8.
[224] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone1010none Bnone1010none Cnone1010none Dnone1015none Enone1515none Fnone55none Gnone510none Hnone510none Inone510Slightly Jnone515Slightly Knone515Slightly Comparisonnone2020has exist Comparisonnone55has exist Comparisonplenty1515In a little Comparisonplenty1010In a little Comparisonplenty1540has exist Comparisonplenty1530has exist
[225] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[226] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[227] *** Contamination due to support damage 10 minutes after application of the modifier
[228] Test 5
[229] A plate obtained by developing a thermal positive original plate (including a substrate without silicate treatment and without a lower layer) was developed with a non-silicate developer, and the plate obtained was modified with various modification agents.
[230] In the same manner as in Test 4, the photosensitive liquid was applied from degreasing of the aluminum plate and then dried and exposed and developed in the same manner as in Test 3 to obtain a flat printing plate. In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image portion was treated in the same manner as Test 1 with various correction agents, and was performed from erasure to printing.
[231] The results are shown in Table 9.
[232] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone1010none Bnone1010none Cnone1010none Dnone1515none Enone1515none Fnone55none Gnone510none Hnone510none Inone510Slightly Jnone515Slightly Knone515Slightly Comparisonnone2020has exist Comparisonnone55has exist Comparisonplenty1515In a little Comparisonplenty1015In a little Comparisonplenty2040has exist Comparisonplenty2030has exist
[233] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[234] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[235] *** Contamination due to support damage 10 minutes after application of the modifier
[236] Exam 6
[237] The plate produced from the photopolymerizable photosensitive flat plate printing plate was modified using the various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6 above.
[238] An aluminum plate of material 1S having a thickness of 0.30 mm was used with No. 8 nylon blush and 800 mesh permist water suspension, and the surface thereof was roughened, and then washed well with water. It was immersed for 60 seconds at 70 ° C. with 10% aqueous sodium hydroxide solution, and then etched, washed with running water in neutral, neutralized and washed with 20% HNO ₃ solution. This was electrolytically roughened using an alternating waveform current of sinusoidal waveform under the condition of V _A = 12.7V with an electric charge amount of 300 coulombs / dm ² in 1% nitric acid solution. When the surface roughness was measured, it was 0.45 micrometer (Ra display) with the centerline average roughness defined by JIS B 0601. Subsequently, the aluminum plate was immersed in 30% H ₂ SO ₄ aqueous solution, desmuted at 55 ° C. for 2 minutes, and then the negative electrode was placed on the surface roughened in 33 ° C. and 20% H ₂ SO ₄ aqueous solution. And anodized for 50 seconds at a current density of 5 A / dm ² and the thickness was 2.7 g / m ² . The photopolymerizable composition of the following composition was apply | coated on the aluminum plate processed in this way so that dry coating weight might be 1.5 g / m <^2> , and it dried at 100 degreeC for 1 minute, and formed the photosensitive layer.
[239] (Photopolymerizable composition)
[240] 1.5 mass parts of ethylenically unsaturated bond containing compounds (A1)
[241] 2.0 parts by mass of linear organic polymer (B1)
[242] 0.15 mass part of sensitizers (C1)
[243] 0.2 parts by mass of photoinitiator (D1)
[244] 0.02 parts by mass of ε-phthalocyanine (F1) dispersion
[245] Fluorinated nonionic surfactant Megapack F117 0.03 parts by mass
[246] (Dai Nippon ink Kagaku Kogyo KK)
[247] 9.0 parts by mass of methyl ethyl ketone
[248] 7.5 parts by mass of propylene glycol monomethyl ether acetate
[249] Toluene 11.0 parts by mass
[250] Dispersions of the ethylenically unsaturated bond-containing compound (A1), linear organic polymer (B1), sensitizer (C1), photoinitiator (D1), and ε-phthalocyanine (F1) are as follows.
[251]
[252] A 3 mass% aqueous solution of polyvinyl alcohol (saturation degree 98 mol%, polymerization degree 500) was applied on the photosensitive layer so as to have a dry coating weight of 2.5 g / m ² , and dried at 120 ° C. for 3 minutes to obtain a photosensitive flat plate. .
[253] The photosensitive flatbed printing plate was subjected to a FD and YAG laser ("CSI Jet Plate 4" manufactured by CSI) at a exposure dose of 100 µJ / cm ² , beta image and 1 to 99% halftone image at 175 lines / inch at 4000 dpi. After scanning exposure of 1% engraving, an automatic developer (Fuji Shacin film) injected with a developer (pH: 11.5 at 25 ° C., conductivity: 5 mS / cm) and a finishing rubber solution FP-2W (manufactured by Fuji Shashin Film) having the following composition Production process was performed with LP-850P2). In the preheating condition, the plate reach temperature was 100 ° C, the developing temperature was 30 ° C, and the immersion time in the developer was about 15 seconds.
[254] (developer)
[255] 0.15 g of potassium hydroxide
[256] 5.0 g of polyoxyethylene phenyl ether (n = 13)
[257] Killest 400 (chelating agent manufactured by Celest Co., Ltd) 0.1g
[258] 94.75 g of water
[259] In the flat printing plate thus obtained, unnecessary image parts remained due to uneven irradiation of the laser. This unnecessary image portion was treated in the same manner as in Test 1 with the various modifiers of Examples 1 to 11 and Comparative Examples 1 to 6, and erased to printed.
[260] The results are shown in Table 10.
[261] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone2020none Bnone2020none Cnone2020none Dnone3030none Enone3030none Fnone2020none Gnone2020none Hnone2020none Inone2030none Jnone3030none Knone3030none Comparisonnone4040has exist Comparisonnone2020has exist Comparisonplenty4060In a little Comparisonplenty6060In a little Comparisonplenty6090has exist Comparisonplenty5090has exist
[262] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[263] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[264] *** Contamination due to support damage 10 minutes after application of the modifier
[265] Test 7
[266] The plate obtained by making a thermopolymerization type thermosensitive flat plate printing plate was modified using the various modifiers of Examples 1-11 and Comparative Examples 1-6.
[267] JIS A 1050 molten aluminum alloy containing not less than 99.5% of aluminum, 0.30% of Fe, 0.10% of Si, 0.02% of Ti, and 0.013% of Cu was subjected to a cleaning treatment and casting. In the cleaning treatment, in order to remove unnecessary gas such as hydrogen in the molten metal, degassing treatment and ceramic tube filter treatment were performed. Casting was performed by die cast casting. An ingot of a solid plate thickness of 500 mm was smoothed about 10 mm from the surface, and a homogenization treatment was performed at 550 ° C. for 10 hours so as not to coarsen the intermetallic compound. Subsequently, hot rolling was performed at 400 ° C., and annealing was performed at 500 ° C. for 60 seconds in a continuous annealing furnace, followed by cold rolling to obtain an aluminum rolled plate having a plate thickness of 0.30 mm. By suppressing the roughness of a rolling roll, center line average surface roughness Ra defined by JIS B 0601 after cold rolling was controlled to 0.2 micrometer. Then, a tension leveler was applied to improve the planarity.
[268] Subsequently, the aluminum plate was subjected to surface treatment to obtain a flat plate support. First, degreasing treatment was performed at 50 ° C. for 30 seconds with an aqueous 10% sodium aluminate solution to remove the rolling oil on the surface of the aluminum plate, and neutralization and smut removal treatment was performed at 50 ° C. for 30 seconds with an aqueous 30% sulfuric acid solution.
[269] Next, in order to improve the adhesiveness of a support body and a photosensitive layer, and to provide water retention property to a non-image part, the surface of a support body was roughened, ie, the roughening process was performed. An aqueous solution containing 1% nitric acid and 0.5% aluminum nitrate was maintained at 45 ° C., while an aluminum web was flowed in the aqueous solution by an indirect feeding cell, the current density was 20 A / dm ² , and an impact ratio. (duty ratio) Electrolytic roughening was performed by applying an electric charge of 240 C / dm ² to the cathode side in an alternating waveform of 1: 1. Thereafter, an etching treatment was performed at 50 ° C. for 30 seconds with an aqueous 10% sodium aluminate solution, and a neutralization and smut removal treatment was performed at 50 ° C. for 30 seconds with an aqueous 30% sulfuric acid solution.
[270] In addition, in order to improve wear resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. Anodized at 2.5 g / m ² by using an aqueous 20% sulfuric acid solution at 35 ° C. as an electrolyte and carrying an electrolytic treatment with a direct current cell at a direct current of ¹⁴ A / dm ² while transporting the aluminum web through the electrolyte. The film was prepared.
[271] Next, in order to ensure the hydrophilicity of the printing plate non-image part, a silicate process was performed. The treatment was carried out by keeping the 1.5% aqueous sodium silicate 1.5% solution at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and washed with water. The deposition amount of Si was 10 mg / m ² . Thus, Ra (center line surface roughness) of the support body produced was 0.25 micrometer.
[272] Subsequently, the following supporting liquid was applied to this aluminum support with a wire bar, and dried at 90 ° C. for 30 seconds using a warm air drying apparatus. The coating amount after drying was 10 mg / m ² .
[273] (Servant amount)
[274] Of ethyl methacrylate and sodium 2-acrylamide-2-methyl-1-propanesulfonic acid salt
[275] 0.1 g of copolymer with a molar ratio of 75:15
[276] 0.1 g of 2-aminoethylphosphonic acid
[277] Methanol 50 g
[278] 50 g of ion-exchanged water
[279] (Photosensitive layer)
[280] Next, the following solution [P] was prepared, it apply | coated to the aluminum plate provided with said servant layer using the wire bar, and it dried at 115 degreeC for 45 second with the warm air drying apparatus, and obtained the negative plate type negative printing plate. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² .
[281] Solution [P]
[282] Infrared absorber 0.08 g (following [IR-6])
[283] 0.30 g of onium salt (following [OI-6])
[284] Dipentaerythritol hexaacrylate 1.00g
[285] 80:20 molar ratio of allyl methacrylate and methacrylic acid
[286] 1.00 g of copolymer (weight average molecular weight 120,000)
[287] Victoria Pure Blue Naphthalene Sulfonate 0.40g
[288] 0.01 g of fluorine-based surfactant
[289] (Megapack F-176, Dainippon Ink Chemical Industries, Ltd.)
[290] 9.0 g of methyl ethyl ketone
[291] Methanol 10.0 g
[292] 8.0 g of 1-methoxy-2-propanol
[293]
[294] The negative plate of negative type flat plate obtained in this way was exposed under the condition of output of 9W, outer drum rotation speed 210rpm, plate energy 100mJ / cm ² and resolution 2400dpi at "Trendsetter 3244VFS" manufactured by Creo Co., Ltd. equipped with a water-cooled 40W infrared semiconductor laser. It was.
[295] After exposure, it developed using the automatic developing machine "Stablon 900N" by the Fuji Shashin Film Co., Ltd. make. As a developer, a 1: 1 water dilution solution of DN-3C manufactured by Fuji Shashin Film Co., Ltd. was used as well as an injection solution and a supplement solution. The temperature of the developing bath was 30 ° C. In addition, the finisher (finisher) used 1: 1 water dilution liquid of "FN-6" manufactured by Fuji-Shashin Film Co., Ltd ..
[296] In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image portion was treated in the same manner as Test 1 with various correction agents, and was performed from erasure to printing.
[297] The results are shown in Table 11.
[298] ModifierImpact on the periphery (smear)Plate removal time (sec) *Substrate Erase Time (sec) **Pollution of scavengers *** Anone1010none Bnone1010none Cnone1010none Dnone2020none Enone2020none Fnone1010none Gnone1010none Hnone1010none Inone1015none Jnone1020none Knone1020none Comparisonnone2020has exist Comparisonnone2020has exist Comparisonplenty3060In a little Comparisonplenty4060has exist Comparisonplenty6090In a little Comparisonplenty5090has exist
[299] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[300] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[301] *** Contamination due to support damage 10 minutes after application of the modifier
[302] Examples 12-17
[303] Modifiers L to Q of the present invention were prepared by the composition (unit: parts by mass) shown in Table 12.
[304] Example121314151617 ModifierLMNOPQ Propylene carbonate9.39.39.09.39.39.3 Ethylene carbonate34.034.036.034.034.034.0 Dimethylacetamide28.628.623.028.628.628.6 Swasol 1800 ^{* 1} 8.48.48.28.48.48.4 Zirconic Hydrofluoric Acid (40% Aqueous Solution)0.081.5-1.5-0.5 Hydrofluoric acid silicon (40% aqueous solution)--1.7--- Hydrofluoric acid (40% aqueous solution)------ Titanium hydrofluoric acid (40% aqueous solution)------ Trifluoroacetic acid------ Ammonium bifluoride (40% aqueous solution)------ pure7.17.17.07.17.17.1 Hydroxypropyl Cellulose ^{* 2} --2.0--- Oxyethylene-oxypropylene block copolymer ^{* 3} 5.05.06.05.05.05.0 Polyvinylpyrrolidone ^{* 4} 0.30.3-0.30.30.3 Vinyl methyl ether / maleic anhydride (1: 1 molar ratio) copolymer ^{* 5} ------ Fluorine-based Surfactant ^{* 6} ------ Sodium Alkylbenzenesulfonate------ Phosphoric Acid (85%)-0.5---- Acetic acid-0.5---- Oxalic acid------ Triethanolamine-3.70.7--4.0 Crystal violet0.0030.0030.0030.0030.0030.003 Powdered Silicon Dioxide ^{* 7} 4.04.06.04.04.04.0 pH4.58.55.03.07.010.0
[305] In Table 12, ^{* 1- * 7} are the same as that of Table 1.
[306] About 100 g of said polyethylenes F-H and L-Q, 100 g of hard polyethylene containers were filled. Using this, the storage stability of a modifier was investigated by the following test.
[307] Test 8
[308] The storage stability of various modifiers was investigated using a flat printing plate obtained from a conventional positive type disc.
[309] The flat plate printing plate was exposed and developed similarly to the test 1, and the flat plate printing plate was obtained. In the flat printing plate thus obtained, the edge of the positive film remained thin on the plate surface.
[310] The modifier was contained in a brush and applied to the area where the edge of the positive film on the flat plate was left as an image, left for 5 seconds to 10 minutes for testing, and sprayed with water after each time to remove the modifier.
[311] Here, the leaving time after application of the correction agent necessary for erasing the unnecessary image on the plate, the leaving time after application of the correction agent necessary for preventing the ink from adhering to the erasing portion immediately after starting printing, as described below. Contamination by damage to the support after 10 minutes of application (washed off with water 10 minutes after application of the crystal, and whether or not ink contamination occurred in the erase section at the start of printing) was examined. Regarding printing, an Arabic rubber 14 ° Be aqueous solution was applied onto the plate on which the correction was completed, and the sheet was placed in an offset press and printed with 10,000 sheets.
[312] In addition, assuming that the modifier was stored for a long time, the same test as above was carried out after storage at 45 ° C. for 1 month, and the deformation and breakage of the container were also examined.
[313] When the modifying agent of the present invention was used in the correction operation, the modified image part was completely exposed to the hydrophilic layer and became slightly white compared with other non-image parts. Since no ghost image remains in the portion where the image is erased, and the printing plate is very easy to inspect after the correction operation, the time for inspecting the printing plate is shortened. In addition, when a printing operation was performed using the printing plate, a clean printed matter was obtained without any contamination in the portion corresponding to the image portion erased from the printing plate using the correction agent. The result after storage at 45 degreeC for 1 month was also favorable similarly, and the deformation | transformation and damage of the container did not occur. The results are shown in Table 13.
[314] Modifier (pH)Plate Erase Time (sec) *Printout Erase Time (sec) **Pollution of scavengers ***45 ℃, after 1 month storage Plate Erase Time (sec) *Substrate Erase Time (sec) **Pollution of scavengers ***Deformation and damage of container F (4.5)1010none1010nonenone G (5.0)1010none1010nonenone H (5.5)1010none1010nonenone L (4.5)1015none1015nonenone M (8.5)1010none1015noneSlightly deformed N (5.0)1015Slightly1015Slightlynone O (3.0)1010none4060noneSlightly deformed P (7.0)1040none1040nonenone Q (10.0)1010Slightly4060SlightlySlightly deformed
[315] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[316] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[317] *** Contamination due to support damage 10 minutes after application of the modifier
[318] Exam 9
[319] The storage stability of various modifiers F-H and L-Q was investigated using the board obtained by developing the thermal positive original plate (including the board | substrate which did not carry out the silicate process and the lower layer was not laid) with the silicate developer.
[320] [Production of board]
[321] The aluminum plate (JIS A 1050) having a thickness of 0.3 mm was washed with trichloroethylene and degreased, and then the surface was roughened and washed well with water using a nylon blush and a 400 mesh perm powder. The plate was immersed in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds to perform etching. After washing with water, the plate was further immersed in 20% nitric acid solution for 20 seconds and washed with water. At this time, the etching amount of the roughening surface was about 3 g / m <^2> . Next, the plate was formed with 7% sulfuric acid as an electrolytic solution, and a 3 g / m ² DC anodic oxide film was formed at a current density of 15 A / dm ² , followed by washing with water and drying.
[322] The following coating liquid for photosensitive layer formation was apply | coated to the obtained board | substrate so that application amount might be 1.8 g / m <^2> , and it dried, and obtained the flat printing plate original plate.
[323] <Composition of the Photosensitive Layer Coating Liquid>
[324] M, p-cresol novolac 1.0part
[325] (m / p ratio = 6/4, weight average molecular weight 8,000
[326] 0.5 mass% of unreacted cresol)
[327] 0.1 part cyanine dye A (following structure)
[328] Tetrahydrophthalic anhydride 0.05 part
[329] 0.002 parts of p-toluenesulfonic acid
[330] The counterion of ethyl violet
[331] 0.02 parts of 6-hydroxy-β-naphthalenesulfonic acid
[332] Fluorine-based surfactant 0.05 part
[333] (Mega pack F-781-F, Dainippon ink Kagaku Kogyo Kiyaki)
[334] 12 parts of methyl ethyl ketone
[335]
[336] The original flat plate printing plate was exposed using Creo Corp. plate setter "Trendsetter 3244F" (rotational speed: 150 rpm), and developed with alkaline developing solution (pH about 13) of the following composition, and obtained the flat plate.
[337] [Composition of Alkaline Developer]
[338] _{· SiO 2 · K 2 O 4.0} %
[339] (K ₂ O / SiO ₂ = 1.1 (molar ratio))
[340] Citric acid 0.5%
[341] 0.5% polyethylene glycol (weight average molecular weight = 1000)
[342] 95.0% of water
[343] In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image part was processed similarly to the test 8 with each of fixers F-H, L-Q, and the test was performed.
[344] The results are shown in Table 14.
[345] Modifier (pH)Plate Erase Time (sec) *Printout Erase Time (sec) **Pollution of scavengers ***45 ℃, after 1 month storage Plate Erase Time (sec) *Substrate Erase Time (sec) **Pollution of scavengers ***Deformation and damage of container F (4.5)55none55nonenone G (5.0)510none510nonenone H (5.5)510none510nonenone L (4.5)1015none1015nonenone M (8.5)1010none1015noneSlightly deformed N (5.0)1015Slightly1015Slightlynone O (3.0)1010none3060noneSlightly deformed P (7.0)1040none1040nonenone Q (10.0)1010Slightly3060SlightlySlightly deformed
[346] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[347] ** Leave time after application of the correction agent necessary to prevent ink from depositing on the erased portion immediately after starting printing
[348] *** Contamination due to support damage 10 minutes after application of the modifier
[349] Exam 10
[350] The storage stability of various modifiers F to H and L to Q was investigated using a plate obtained by developing a thermal positive original plate (including a substrate treated with silicate and coated with a lower layer) with a non-silicate developer.
[351] [Production of board]
[352] The aluminum plate (JIA S 1050) having a thickness of 0.3 mm was washed with trichloroethylene and degreased, and then, the surface of the surface was roughened and washed well with water using a nylon blush and a 400 mesh perm powder. The plate was immersed in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds to perform etching. After washing with water, the plate was further immersed in 20% nitric acid solution for 20 seconds and washed with water. At this time, the etching amount of the roughening surface was about 3 g / m <^2> . Next, the plate was formed with a 7% sulfuric acid as an electrolytic solution, and a 3 g / m ² direct current anodized film at a current density of 15 A / dm ² was washed with water and dried.
[353] This was processed for 10 seconds at 30 degreeC with 2.5 mass% sodium silicate aqueous solution, the following servant liquid was apply | coated, and the coating film was dried at 80 degreeC for 15 second, and the board | substrate was obtained. The coating amount of the coating film after drying was 15 mg / m <^2> .
[354] <Composition of servant liquid>
[355] 0.3 parts of the following copolymer of molecular weight 28,000
[356] 100 parts methanol
[357] 1 part water
[358]
[359] The following coating liquid for photosensitive layer formation was apply | coated to the obtained board | substrate so that application amount might be 1.8 g / m <^2> , and it dried, and obtained the flat printing plate original plate.
[360] <Composition of the Photosensitive Layer Coating Liquid>
[361] M, p-cresol novolac 1.0part
[362] (m / p ratio = 6/4, weight average molecular weight 8,000
[363] 0.5 mass% of unreacted cresol)
[364] 0.1 part cyanine dye A (following structure)
[365] Tetrahydrophthalic anhydride 0.05 part
[366] 0.002 parts of p-toluenesulfonic acid
[367] The counterion of ethyl violet
[368] 0.02 parts of 6-hydroxy-β-naphthalene sulfonic acid
[369] Fluorine-based surfactant 0.05 part
[370] (Mega pack F-781-F, Dainippon ink Kagaku Kogyo Kiyaki)
[371] 12 parts of methyl ethyl ketone
[372]
[373] The original flat platen plate thus obtained was set-exposed in the same manner as in Test 9, and 1 liter of a potassium salt 45% aqueous solution composed of D-sorbitol / potassium oxide (K ₂ O) containing a combination of non-reducing sugar and base was used as an amphoteric surfactant. 20 g of Nin C-158G (manufactured by Takemoto Yuji Kagashi Co., Ltd.) and 2.0 g of antifoaming agent "Olphin AK-02" (manufactured by Nisshin Kagaku Co., Ltd.) were added to the concentrate, and the concentrate was diluted nine times with water. It developed and obtained the flat printing plate.
[374] In the flat plate obtained in this way, the unnecessary image part by the nonuniform irradiation of the laser remained. This unnecessary image part was processed similarly to the test 8 with each of fixers F-H, L-Q, and the test was performed.
[375] The results are shown in Table 15.
[376] Modifier (pH)Plate removal time (sec) *Printout Erase Time (sec) **Pollution of scavengers ***After storage at 45 ℃ for 1 month Plate Erase Time (sec) *Substrate Erase Time (sec) **Pollution of scavengers ***Deformation and damage of container F (4.5)55none510nonenone G (5.0)510none510nonenone H (5.5)510none510nonenone L (4.5)515none515nonenone M (8.5)510none515noneSlightly deformed N (5.0)515Slightly515Slightlynone O (3.0)510none3050noneSlightly deformed P (7.0)540none540nonenone Q (10.0)510Slightly3050SlightlySlightly deformed
[377] * Leaving time after application of the correction agent necessary to erase unnecessary images on the plate
[378] ** Leave time after application of the correction agent necessary to prevent ink from adhering to the erased portion immediately after starting printing
[379] *** Contamination due to support damage 10 minutes after application of the modifier
[380] The fixer of the present invention has a remarkably fast erase speed of the image portion. Therefore, the erase process is shortened and the efficiency of the plate making operation is improved. In addition, there is an advantage that an image portion requiring correction can be removed without adversely affecting other images adjacent to the target image portion. Therefore, erasing of the image part of the complicated fine part can also be performed easily and completely. In addition, there is no odor during work, and it does not contain a solvent which is concerned about stability, and thus does not impair worker's health. In addition, since the leaving time after application of the correction agent necessary for erasing on the plate and the leaving time after application of the correction agent required to prevent ink from adhering to the erasing portion immediately after the printing is started, the erased time on the plate is eliminated. If it can be confirmed that ink does not adhere to the erase portion at the start of printing, the time for re-erasing during printing is omitted.
[381] The modifier of the present invention is also capable of stably exhibiting a scavenging function over a long period of time, and also prevents leakage of contents due to deformation or breakage of the storage container, and especially when adjusted to a predetermined pH range. Can be exerted more notably.

权利要求:
Claims (22)
[1" claim-type="Currently amended] Selected from the group consisting of a carbonate ester, a compound represented by the following general formula (1), a carboxylic acid fluoride, an alkali hydrogen fluoride compound, an alkali fluoride compound and a group 4 metal hydrofluoric acid (B) A flat plate printing modifier comprising at least one compound.

[Wherein, R ₁ to R ₃ 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 (wherein R ₃ is not a hydrogen atom when R ₁ and R ₂ are methyl groups), You may form a ring by two of R <_1> -R <_3> (when R <_1> or R <_2> forms a ring with R <_3> , the remaining R <_2> or R <_1> is not a methyl group, respectively).
[2" claim-type="Currently amended] The flat panel printing modifier according to claim 1, which contains at least one compound selected from the group (A) consisting of the compound represented by the general formula (1).
[3" claim-type="Currently amended] 2. The flat panel printing plate according to claim 1, comprising at least one compound selected from the group (B) consisting of carboxylic acid fluorides, alkali hydrogen fluoride compounds, alkali fluoride compounds and Group 4 metal hydrofluoric acid. Fixative.
[4" claim-type="Currently amended] The at least one compound selected from the group (A) consisting of the compound represented by the general formula (1), and fluorinated carboxylic acids, alkali hydrogen fluoride compounds, alkali fluoride compounds and group 4 metal fluoride according to claim 1. A flat panel printing modifier comprising at least one compound selected from the group (B) consisting of hydrogen acid.
[5" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 4, wherein the carbonate ester is at least one selected from the compounds represented by the following general formulas (2) or (3).

[In formula (2), R <_4> and R <_5> may be same or different, and represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, respectively (the said alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group has a substituent, and In the formula (3), R ₆ to R ₉ may be the same or different, and each represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group (the alkyl group, cycloalkyl group, alkenyl group and aryl group). And both of those having no substituent and having a substituent), and R ₆ to R ₉ may form a ring] [6" claim-type="Currently amended] The flat panel printing modifier according to any one of claims 1 to 5, which contains 20 to 80 mass% of carbonate ester.
[7" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 6, wherein the carbonate ester is selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.
[8" claim-type="Currently amended] 8. The flat plate printing modifier according to any one of claims 1 to 7, which contains ethylene carbonate and propylene carbonate.
[9" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 8, wherein ethylene carbonate and propylene carbonate are contained in a mass ratio of ethylene carbonate: propylene carbonate = 90: 10 to 10:90.
[10" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 9, wherein ethylene carbonate and propylene carbonate are contained in a mass ratio of ethylene carbonate: propylene carbonate = 90:10 to 50:50.
[11" claim-type="Currently amended] The compound represented by formula (1) according to any one of claims 1 to 10, wherein dimethylacetamide, diethylformamide, diethylacetamide, 2-pyrrolidone, N-ethylpyrrolidone And N-propylpyrrolidone, N-butylpyrrolidone, and N- (2-hydroxyethyl) pyrrolidone.
[12" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 11, wherein the compound represented by the general formula (1) is selected from dimethylacetamide, diethylformamide, and diethylacetamide. .
[13" claim-type="Currently amended] The content of the compound selected from group (A) is 5-50 mass%, The modifier for flat printing plates of any one of Claims 1-12 characterized by the above-mentioned.
[14" claim-type="Currently amended] The compound according to any one of claims 1 to 13, wherein the compound selected from carbonate ester and group (A) is selected from carbonate ester: group (A) in a mass ratio of 90:10 to 10:90. A crystal for flat plate printing, characterized in that it contains.
[15" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 14, wherein the total content of the carbonate ester and the compound selected from the group (A) is 40 to 90 mass%.
[16" claim-type="Currently amended] The compound according to any one of claims 1 to 15, wherein the compound of group (B) is a fluorinated fatty acid, a fluorinated dicarboxylic acid, a formula: MF.HF (M: alkali metal or N (R ¹ ) (R ² ). A compound represented by (R ³ ) (R ⁴ ) (R ¹ , R ² , R ³ and R ⁴ may be the same or different, and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms); M: Alkali metal or N (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) (R ¹ , R ² , R ³ and R ⁴ may be the same or different, respectively, a hydrogen atom or a hydrocarbon of 1 to 6 carbon atoms Group; and a compound represented by the formula: MH ₂ F ₆ (M: Group 4 metal element).
[17" claim-type="Currently amended] The compound according to any one of claims 1 to 16, wherein the compound of Group (B) is trifluoroacetic acid, tetrafluorosuccinic acid, lithium fluoride, potassium hydrogen fluoride, sodium hydrogen fluoride, ammonium bifluoride, lithium fluoride, A flat plate printing modifier, characterized in that it is selected from potassium fluoride, sodium fluoride, ammonium fluoride, zirconic hydrofluoric acid, and titanium hydrofluoric acid.
[18" claim-type="Currently amended] 18. The modifier for flat printing plates according to any one of claims 1 to 17, wherein the content of the compound of the group (B) is 0.01 to 20.0 mass%.
[19" claim-type="Currently amended] The flat plate printing modifier according to any one of claims 1 to 18, further comprising an acidic compound and / or a basic compound.
[20" claim-type="Currently amended] The pH value is in the range of 1.0-9.0, The modifier for flat printing plates of any one of Claims 1-19 characterized by the above-mentioned.
[21" claim-type="Currently amended] The modifier for flat printing plates according to claim 20, wherein the pH value is in the range of 4.0 to 9.0.
[22" claim-type="Currently amended] The modifier for flat printing plates according to claim 21, wherein the pH value is in the range of 4.0 to 7.0.

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同族专利:

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公开号 | 公开日

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AT333378T|2006-08-15|

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EP1356949A1|2003-10-29|

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CN1453647A|2003-11-05|

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DE60306837D1|2006-08-31|

---

CN1308774C|2007-04-04|

---

DE60306837T2|2006-12-07|

---

EP1356949B1|2006-07-19|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-04-25|Priority to JPJP-P-2002-00124166

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2002-04-25|Priority to JP2002124166

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2002-07-12|Priority to JP2002203488

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2002-07-12|Priority to JPJP-P-2002-00203488

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2002-07-24|Priority to JPJP-P-2002-00215279

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2002-07-24|Priority to JP2002215279

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2003-04-25|Application filed by 후지 샤신 필름 가부시기가이샤

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2004-02-11|Publication of KR20040012448A

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2002-00124166|2002-04-25|

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JP2002124166|2002-04-25|

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JP2002203488|2002-07-12|

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JPJP-P-2002-00203488|2002-07-12|

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JP2002215279|2002-07-24|

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JPJP-P-2002-00215279|2002-07-24|