Planographic printing plate precursor and plate-making method for planographic printing plate

Abstract

Provided are a planographic printing plate precursor including: a support; and an image recording layer provided on the support, in which the image recording layer contains an infrared absorbing agent, a polymerization initiator, a polymerizable compound containing a hydrogen bonding group, and a hard polymer particle containing at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group on the surface of the hard polymer particle, and a number average primary particle diameter of the hard polymer particle is in a range of 0.01 to 1 m; and a plate-making method for a planographic printing plate obtained by using the planographic printing plate precursor.

Claims

1. A planographic printing plate precursor comprising: a support; and an image recording layer provided on the support, wherein the image recording layer contains an infrared absorbing agent, a polymerization initiator, a polymerizable compound containing a hydrogen bonding group, and a hard polymer particle containing at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group on the surface of the hard polymer particle, a number average primary particle diameter of the hard polymer particle is in a range of 0.01 to 1 m, a coating ratio of the at least one group selected from the group consisting of the urethane group, the urea group, the imide group, the amide group, and the sulfonamide group, present on the surface of the hard polymer particle, is in a range of 1% to 99%, the coating ratio being measured by a TOF-SIMS method, a polymer constituting the hard polymer particle comprises a polymer having any one or both of a monomer unit derived from a styrene compound and a monomer unit derived from a (meth)acrylonitrile compound, and the at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group is a group that has been grafted by polymerizing at least one monomer selected from the group consisting of a urethane (meth)acrylate compound, a (meth)acrylate compound containing a urea group, a monomer containing an imide group, a (meth)acrylamide compound, and a monomer containing a sulfonamide group, in a presence of the polymer constituting the hard polymer particle.

2. The planographic printing plate precursor according to claim 1, wherein the polymer comprised in the hard polymer particle further has a monomer unit derived from a poly(ethylene glycol) alkyl ether methacrylate compound.

3. The planographic printing plate precursor according to claim 1, which is used for on-press development.

4. The planographic printing plate precursor according to claim 1, wherein the at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group is a group that has been grafted by polymerizing at least one monomer selected from the group consisting of a urethane (meth)acrylate compound, a (meth)acrylate compound having a urea group, a maleimide compound, a (meth)acrylamide compound, and a (meth)acrylamide compound having a sulfonamide group, in a presence of the polymer constituting the hard polymer particle.

5. A plate-making method for a planographic printing plate comprising, in order: a step of imagewise-exposing the planographic printing plate precursor according to claim 1; and a step of supplying at least one of a printing ink or dampening water and removing an unexposed portion of an image recording layer in the planographic printing plate precursor.

6. A planographic printing plate precursor comprising: a support; and an image recording layer provided on the support, wherein the image recording layer contains an infrared absorbing agent, a polymerization initiator, a polymerizable compound containing a hydrogen bonding group, and a hard polymer particle containing at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group on the surface of the hard polymer particle, a number average primary particle diameter of the hard polymer particle is in a range of 0.01 to 1 m, a coating ratio of the at least one group selected from the group consisting of the urethane group, the urea group, the imide group, the amide group, and the sulfonamide group, present on the surface of the hard polymer particle, is in a range of 1% to 99%, the coating ratio being measured by a TOF-SIMS method, a polymer constituting the hard polymer particle comprises a polymer having any one or both of a monomer unit derived from a styrene compound and a monomer unit derived from a (meth)acrylonitrile compound, and the at least one group selected from the group consisting of a urethane group, a urea group, an imide group, an amide group, and a sulfonamide group is present at a side chain of a polymer present at the surface of the hard polymer particle.

Description

SYNTHESIS EXAMPLES

(1) [Synthesis of Hard Polymer Particles p-1 to p-12]

(2) Synthesis of Hard Polymer Particles p-1

(3) Synthesis was performed according to the following method.

(4) A monomer A represented by the following structural formula was synthesized according to the method described in Chemical Communications, 2007, #9 p. 954 to 956.

(5) ##STR00017##

(6) 10 g of methoxy polyethylene glycol methacrylate (PEGMA, molecular weight of 1,000, average number of repeating units of ethylene glycol: 23), deionized water (75 g), and n-propanol (240 g) were put into a three-neck flask. This flask was gradually heated to 75 C. in a N.sub.2 atmosphere. A solution obtained by mixing styrene (20 g), acrylonitrile (70 g), and AIBN (2,2-azobis(2-methylpropionitrile), 0.7 g) in advance was added to the flask for 2 hours. After 6 hours, a mixture obtained by mixing the monomer A (10 g) and AIBN (0.5 g) in advance was added dropwise thereto for 30 minutes, and the temperature of the resulting solution was increased to 80 C. Next, AIBN (0.35 g) was added to the solution for 6 hours, and the solution was allowed to react for 3 hours, thereby obtaining a dispersion liquid containing hard polymer particles p-1. The solid content in the dispersion liquid was 24.3%. In the particle size distribution of the particles, the number average primary particle diameter was 280 nm.

(7) Synthesis of Hard Polymer Particles p-2

(8) Hard polymer particles p-2 were synthesized in the same manner as that for the hard polymer particles p-1 except that the monomer A was changed to a phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (AH-600, manufactured by KYOEISHA CHEMICAL Co., Ltd.).

(9) Synthesis of Hard Polymer Particles p-3

(10) Hard polymer particles p-3 were synthesized in the same manner as that for the hard polymer particles p-1 except that the monomer A was changed to N-phenylmaleimide.

(11) Synthesis of Hard Polymer Particles p-4

(12) Hard polymer particles p-4 were synthesized in the same manner as that for the hard polymer particles p-1 except that the monomer A was changed to N-phenylmethacrylamide.

(13) Synthesis of Hard Polymer Particles p-5

(14) Hard polymer particles p-5 were synthesized in the same manner as that for the hard polymer particles p-1 except that the monomer A was changed to 4-methacrylamide benzene sulfonamide (manufactured by Fujifilm Fine Chemicals Co., Ltd.).

(15) Synthesis of Hard Polymer Particles p-6

(16) 10 g of methoxy polyethylene glycol methacrylate (PEGMA, molecular weight of 1,000, average number of repeating units of ethylene glycol: 23), deionized water (75 g), and n-propanol (240 g) were put into a three-neck flask. This flask was gradually heated to 75 C. in a N.sub.2 atmosphere. A solution obtained by mixing acrylonitrile (90 g) and AIBN (0.7 g) in advance was added to the flask for 2 hours. After 6 hours, a mixture obtained by mixing the monomer A (10 g) and AIBN (0.5 g) in advance was added dropwise thereto for 30 minutes, and the temperature of the resulting solution was increased to 80 C. Next, AIBN (0.35 g) was added to the solution for 6 hours, and the solution was allowed to react for 3 hours, thereby obtaining a dispersion liquid containing hard polymer particles p-6. The solid content in the dispersion liquid was 24.3%. In the particle size distribution of the particles, the number average primary particle diameter was 320 nm.

(17) Synthesis of Hard Polymer Particles p-7

(18) Deionized water (180 g) in which polyoxyethylene alkyl sulfoammonium (HITENOL 08E, manufactured by DKS Co., Ltd.) (0.1 g) was dissolved was added to a flask provided with a stirrer, an inert gas introduction pipe, a reflux condenser, and a thermometer. A mixture obtained by mixing methyl methacrylate (16 g), the monomer A (2.0 g), trimethylolpropane trimethacrylate (2.0 g), AIBN (0.2 g), and 3,4-dinitrobenzoic acid (0.2 g), which was prepared in advance, was added to the solution, and the solution was stirred using a T. K. homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 8,000 rpm for 5 minutes to obtain a uniform suspension. Next, the suspension was heated to 75 C. while being blown by nitrogen gas and was continuously stirred at this temperature for 5 hours to cause a suspension polymerization reaction. This suspension was transferred to a beaker and heated and stirred in air, and the moisture content was volatilized until the solid content of the dispersion liquid was set to 20%, thereby obtaining a dispersion liquid (solid content of 20%) containing hard polymer particles p-7.

(19) Synthesis of Hard Polymer Particles p-8

(20) Polyoxyethylene alkyl sulfoammonium (HITENOL 08E, manufactured by DKS Co., Ltd.) (5.0 g), deionized water (75 g), and n-propanol (240 g) were put into a three-neck flask. This flask was gradually heated to 75 C. in a N.sub.2 atmosphere. A solution obtained by mixing styrene (20 g), acrylonitrile (60 g), and AIBN (0.7 g) in advance was added to the flask for 2 hours. After 6 hours, a mixture obtained by mixing the monomer A (20 g) and AIBN (0.5 g) in advance was added dropwise thereto for 30 minutes, and the temperature of the resulting solution was increased to 80 C. Next, AIBN (0.35 g) was added to the solution for 6 hours, and the solution was allowed to react for 3 hours, thereby obtaining a dispersion liquid containing hard polymer particles p-8. The solid content in the dispersion liquid was 23.8%. In the particle size distribution of the particles, the number average primary particle diameter was 350 nm.

(21) Synthesis of Hard Polymer Particles p-9

(22) A monomer represented by the following structural formula was synthesized as follows. 20 g of polyethylene glycol monomethacrylate (molecular weight of 350) was added to a flask, 1.42 g of ethyl isocyanate and 0.05 g of NEOSTANN U-600 (manufactured by NITTO KASEI CO., LTD.) were added thereto, and the solution was stirred at 50 C. for 3 hours, thereby synthesizing 21.4 g of a monomer B.

(23) ##STR00018##

(24) The monomer B (20.0 g), deionized water (75 g), and n-propanol (240 g) were put into a three-neck flask. This flask was gradually heated to 75 C. in a N.sub.2 atmosphere. A solution obtained by mixing styrene (20 g), acrylonitrile (60 g), and AIBN (0.7 g) in advance was added to the flask for 2 hours. After 6 hours, AIBN (0.5 g) was added thereto, and the temperature of the resulting solution was increased to 80 C. Next, AIBN (0.35 g) was added to the solution for 6 hours, and the solution was allowed to react for 3 hours, thereby obtaining a dispersion liquid containing hard polymer particles p-9. The solid content in the dispersion liquid was 23.8%. In the particle size distribution of the particles, the number average primary particle diameter was 400 nm.

(25) Synthesis of Hard Polymer Particles p-10

(26) 10 g of methoxy polyethylene glycol methacrylate (PEGMA, molecular weight of 2,000, average number of repeating units of ethylene glycol: 50), deionized water (75 g), and n-propanol (240 g) were put into a three-neck flask. This flask was gradually heated to 75 C. in a N.sub.2 atmosphere. A solution obtained by mixing styrene (20 g), acrylonitrile (70 g), and AIBN (0.7 g) in advance was added to the flask for 2 hours. After 6 hours, AIBN (0.5 g) was added thereto, and the temperature of the resulting solution was increased to 80 C. Next, AIBN (0.35 g) was added to the solution for 6 hours. The polymerization was progressed by 98% or greater at a stage where the solution was allowed to react for 3 hours, thereby obtaining a dispersion liquid containing polymer particles p-10 (for comparison). The solid content in the dispersion liquid was 24.0%. In the particle size distribution of the particles, the number average primary particle diameter was 250 nm.

(27) Synthesis of Hard Polymer Particles p-11

(28) 10 g of methoxy polyethylene glycol methacrylate (PEGMA, molecular weight of 2,000, average number of repeating units of ethylene glycol: 50), deionized water (75 g), and n-propanol (240 g) were put into a three-neck flask. This flask was gradually heated to 75 C. in a N.sub.2 atmosphere. A solution obtained by mixing acrylonitrile (90 g) and AIBN (0.7 g) in advance was added to the flask for 2 hours. After 6 hours, AIBN (0.5 g) was added thereto, and the temperature of the resulting solution was increased to 80 C. Next, AIBN (0.35 g) was added to the solution for 6 hours. The polymerization was progressed by 98% or greater at a stage where the solution was allowed to react for 3 hours, thereby obtaining a dispersion liquid containing polymer particles p-11 (for comparison). The solid content in the dispersion liquid was 24.0%. In the particle size distribution of the particles, the number average primary particle diameter was 280 nm.

(29) Synthesis of Hard Polymer Particles p-12

(30) Deionized water (180 g) in which polyoxyethylene alkyl sulfoammonium (HITENOL 08E, manufactured by DKS Co., Ltd.) (0.1 g) was dissolved was added to a flask provided with a stirrer, an inert gas introduction pipe, a reflux condenser, and a thermometer. A mixture obtained by mixing methyl methacrylate (18 g), trimethylolpropane trimethacrylate (2.0 g), AIBN (0.2 g), and 3,4-dinitrobenzoic acid (0.2 g), which was prepared in advance, was added to the solution, and the solution was stirred using a T. K. homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 8,000 rpm for 5 minutes to obtain a uniform suspension. Next, the suspension was heated to 75 C. while being blown by nitrogen gas and was continuously stirred at this temperature for 5 hours to cause a suspension polymerization reaction. This suspension was transferred to a beaker and heated and stirred in air, and the moisture content was volatilized until the solid content of the dispersion liquid was set to 20%, thereby obtaining a dispersion liquid (for comparison) (solid content of 20%) containing hard polymer particles p-12.

(31) With respect to each of the hard polymer particles p-1 to p-12 prepared in the above-described manner, groups on the surface of the polymer, which constitute the hard polymer, the coating ratio (coating ratio (%)) of the groups on the surface, the number average primary particle diameter (particle diameter (m)), and the Rockwell hardness are listed in Table 1.

(32) The description of the hard polymer particles p-10 to p-12 with the sign of - in the columns for groups on the surface means that the particles do not contain any of the urethane group, the urea group, the imide group, the amide group, and the sulfonamide group on the surface.

(33) The coating ratio of the groups on the surface and the number average primary particle diameter were measured according to the above-described methods.

(34) The Rockwell hardness was measured according to the method described below.

(35) Each hard polymer particle dispersion liquid was dried in an oven at 60 C. for 16 hours to obtain hard polymer particles. A polymer piece having a size of 2 cm2 cm0.6 cm was prepared by press-forming the obtained hard polymer particles at an optional compression forming temperature.

(36) First, a reference load was applied to each polymer piece using a steel ball indenter specified in ASTM D785. Next, a test load was applied thereto and then the reference load was applied again. An M scale was used as the steel ball indenter.

(37) A difference (h) (unit: mm) in the penetration depth of the indenter used for applying the reference load two times before and after was acquired.

(38) The Rockwell hardness was calculated using the following equation.
Rockwell hardness=130500(h)

(39) TABLE-US-00001 TABLE 1 Names of Hard polymer Groups on Coating ratio Particle Rockwell particles the surface (%) diameter hardness Hard polymer Urea Approximately 10 0.28 M75 particles p-1 Hard polymer Urethane Approximately 10 0.25 M75 particles p-2 Hard polymer Imide Approximately 10 0.25 M75 particles p-3 Hard polymer Amide Approximately 10 0.27 M75 particles p-4 Hard polymer Sulfonamide Approximately 10 0.30 M75 particles p-5 Hard polymer Urea Approximately 10 0.32 M80 particles p-6 Hard polymer Urea Approximately 10 0.28 M80 particles p-7 Hard polymer Urea Approximately 50 0.35 M75 particles p-8 Hard polymer Urethane Approximately 50 0.40 M75 particles p-9 Hard polymer 0 0.25 M75 particles p-10 Hard polymer 0 0.28 M80 particles p-11 Hard polymer 0 0.28 M90 particles p-12

(40) [Synthesis of Polymerizable Compounds m-1 to m-9]

(41) Synthesis of Polymerizable Compound m-1

(42) 3.2 g of trimethyl hexamethylene diamine and 32 g of tetrahydrofuran were added to a reaction container, and the reaction container was cooled using ice water. Next, a mixed solution of 9.6 g of 1,1-(bisacryloyloxymethyl)ethyl isocyanate (KARENZ BEI, manufactured by SHOWA DENKO K. K.) and 10 g of tetrahydrofuran was added dropwise thereto for 30 minutes and stirred for 1 hour while being cooled. After the completion of the reaction was confirmed using .sup.1HNMR, the solution was added dropwise to 300 g of water which was being stirred. The deposited solid was filtered and dried using a blast dryer at 40 C. for 12 hours, thereby obtaining 12.0 g of a polymerizable compound m-1.

(43) Synthesis of Polymerizable Compound m-2

(44) A polymerizable compound m-2 was synthesized according to the method described in paragraphs 0089 to 0091 in JP2010-534651A.

(45) Synthesis of Polymerizable Compound m-3

(46) A 80 mass % solution of DESMODUR N100 (an aliphatic polyisocyanate resin containing hexamethylene diisocyanate as a main agent, manufactured by Bayer AG) and urethane acrylate obtained by the reaction between hydroxyethyl acrylate and pentaerythritol triacrylate in 2-butanol was prepared and used as a polymerizable compound m-3.

(47) Synthesis of Polymerizable Compound m-4

(48) A polymerizable compound m-4 was synthesized according to the method described in paragraphs 0049 to 0071 in JP2014-118442A.

(49) Synthesis of Polymerizable Compound m-5

(50) 4.2 g of 2-amino-2-ethyl-1,3-propanediol, 37 g of acetonitrile, and 3.6 g of triethylamine were added to a reaction container, and the reaction container was cooled using ice water. Next, 5.0 g of 4,4-biphenyl sulfonyl chloride was divided and added thereto little by little for 30 minutes, and the solution was stirred for 1 hour while the container was cooled as it was. 200 g of ethyl acetate and 200 g of 1 mol/l hydrochloric acid water were added to the reaction solution to carry out a liquid separation operation, and 200 g of 1 mol/l hydrochloric acid water was added to the organic layer again to carry out a liquid separation operation. 200 g of a 10 mass % NaCl aqueous solution was added to the organic layer for liquid separation, and approximately the half of ethyl acetate in the obtained organic layer was concentrated using an evaporator. Subsequently, 100 g of hexane was added thereto for solidification, and the obtained solid was filtered. The resultant was dried using a blast dryer at 40 C. for 12 hours, 5.1 g of an obtained intermediate was put into the reaction container again, and 30 g of acetonitrile and 5.0 g of methacrylic acid chloride were added to the container. 6.0 g of triethylamine was added dropwise to the solution, which was being stirred at room temperature, for 30 minutes. The resulting solution was allowed to react at room temperature for 5 hours, and the completion of the reaction was confirmed using .sup.1HNMR. The obtained reaction solution was added dropwise to 300 g of water which was being stirred, and then the resulting solution was stirred for 30 minutes. The deposited solid was filtered and dissolved in 30 g of acetonitrile again, and the solution was added dropwise to 300 g of water which was being stirred. The deposited solid was filtered and dried using a blast dryer at 40 C. for 12 hours, thereby obtaining 5.0 g of a polymerizable compound m-5.

(51) Polymerizable Compounds m-6 to m-9

(52) The following commercially available products were used as the polymerizable compounds m-6 to m-9. m-6: DENACOL ACRYLATE DA-314, manufactured by Nagase ChemteX Corporation m-7: 2,2,6,6-tetramethyl-4-piperidyl methacrylate, manufactured by Wako Pure Chemical Industries, Ltd. m-8: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd. m-9: ARONIX M-360, manufactured by Toagosei Co., Ltd.

(53) Hereinafter, the structures of the polymerizable compounds m-1 to m-9 and the hydrogen bonding group contained in each polymerizable compound will be described.

(54) ##STR00019## ##STR00020##

Examples 1 to 34 and Comparative Examples 1 to 3

(55) <Preparation of Planographic Printing Plate Precursor>

(56) 1. Preparation of Support (1)

(57) An aluminum substrate which had been brush-polished, subjected to phosphoric acid anodization, and subjected to a polyacrylic acid (PAA) post-treatment according to the method described in JP2013-47004A was used as a support (1).

(58) 2. Preparation of Image Recording Layer

(59) Respective components listed in Table 2 shown below were mixed to prepare a coating solution (1) for an image recording layer, the support (1) was coated with the coating solution using a wire bar such that the coating amount after drying the coating solution was set to 1.5 g/m.sup.2, and the coating solution was dried at 115 C. for 34 seconds using a hot air dryer to form an image recording layer, thereby preparing CTP-1 to CTP-34 and CTP-1 for comparison to CTP-3 for comparison which are planographic printing plate precursors listed in Table 3.

(60) In Table 2, the content of each active component is listed in the column of part by mass.

(61) TABLE-US-00002 TABLE 2 Components Part by mass Specific hard polymer particles listed in Table 3 13.53 Polymerizable compound containing hydrogen bonding 2.48 group listed in Table 3 Binder polymer b-1 3.97 Irgacure 250 0.42 IR absorbing dye 0.13 Mercapto-3-triazole 0.18 BYK 336 0.6 KLUCEL M 3.31 n-Propanol 61.97 Water 13.41

(62) The details of each component listed in Table 2 are as follows. Binder polymer b-1: copolymer of PEGMA and allyl methacrylate Irgacure 250: 75 mass % solution of (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate in propylene carbonate, manufactured by Ciba Specialty Chemicals IR absorbing dye: IR absorbing dye represented by the following formula (in the following formula, Ph represents a phenyl group) Mercapto-3-triazole: 3-mercapto-1,2,4-triazole, manufactured by PCAS BYK 336: modified dimethyl polysiloxane copolymer in 25% xylene/methoxypropyl acetate solution, manufactured by Byk-Chemie USA Inc. KLUCEL M: 2% aqueous solution (viscosity: 5,000 mPa.Math.s) of hydroxypropyl cellulose, manufactured by Hercules Inc., Aqualon Division

(63) ##STR00021##

(64) In the prepared planographic printing plate precursors CTP-1 to CTP-34 and CTP-1 for comparison to CTP-3 for comparison, the used supports, coating solutions for an image recording layer, hard polymer particles, and polymerizable compounds containing a hydrogen bonding group are listed in Table 3.

(65) TABLE-US-00003 TABLE 3 Coating Polymerizable Planographic solution Specific compound printing for image hard containing plate recording polymer hydrogen bonding precursor Support layer particles group CTP-1 (1) (1) p-1 m-1 CTP-2 (1) (1) p-1 m-2 CTP-3 (1) (1) p-1 m-3 CTP-4 (1) (1) p-1 m-4 CTP-5 (1) (1) p-1 m-5 CTP-6 (1) (1) p-1 m-6 CTP-7 (1) (1) p-1 m-7 CTP-8 (1) (1) p-1 m-8 CTP-9 (1) (1) p-1 m-9 CTP-10 (1) (1) p-2 m-1 CTP-11 (1) (1) p-2 m-2 CTP-12 (1) (1) p-2 m-3 CTP-13 (1) (1) p-2 m-4 CTP-14 (1) (1) p-2 m-5 CTP-15 (1) (1) p-2 m-6 CTP-16 (1) (1) p-2 m-7 CTP-17 (1) (1) p-2 m-8 CTP-18 (1) (1) p-2 m-9 CTP-19 (1) (1) p-3 m-1 CTP-20 (1) (1) p-3 m-3 CTP-21 (1) (1) p-3 m-5 CTP-22 (1) (1) p-3 m-8 CTP-23 (1) (1) p-4 m-1 CTP-24 (1) (1) p-4 m-3 CTP-25 (1) (1) p-4 m-5 CTP-26 (1) (1) p-4 m-8 CTP-27 (1) (1) p-5 m-1 CTP-28 (1) (1) p-5 m-3 CTP-29 (1) (1) p-5 m-5 CTP-30 (1) (1) p-5 m-8 CTP-31 (1) (1) p-6 m-1 CTP-32 (1) (1) p-7 m-1 CTP-33 (1) (1) p-8 m-1 CTP-34 (1) (1) p-9 m-1 CTP-1 for comparison (1) (1) p-10 m-3 CTP-2 for comparison (1) (1) p-11 m-3 CTP-3 for comparison (1) (1) p-12 m-3

(66) (Evaluation of Planographic Printing Plate Precursor)

(67) (1) Evaluation of Printing Durability

(68) The obtained planographic printing plate precursors CTP-1 to CTP-34 and CTP-1 for comparison to CTP-3 for comparison were exposed in Trendsetter 3244VX (manufactured by Creo Co., Ltd.) equipped with a water-cooling type 40 W infrared semiconductor laser under conditions of a resolution of 175 lpi (line per inch, the number of halftone dots per inch, 1 inch is 2.54 cm), an external surface drum rotation speed of 150 rpm, and an output of 0 to 8 W by changing the range of the output by 0.15 log E. Further, the exposure was performed under conditions of a temperature of 25 C. at a relative humidity of 50% RH. The obtained planographic printing plates were printed using a printing press LITHRONE (manufactured by KOMORI Corporation), the printed material of the image area was observed, and the number of sheets (number of printed sheets) where the image started to be blurred was used as an index of the printing durability. The results are listed in Table 4.

(69) (2) Evaluation of Scratch Resistance

(70) The obtained planographic printing plate precursors CTP-1 to CTP-34 and CTP-1 for comparison to CTP-3 for comparison were alternately laminated with inserting paper (F inserting paper, manufactured by Daiichi Container Co., Ltd.) to prepare planographic printing plate precursor laminates. The obtained planographic printing plate precursor laminates were stacked at a height of 1 m and vibrated for 10 minutes (vibration frequency range of 5 to 55 Hz), exposure and development were performed thereon, and the state in which scratches were generated in the image area during the exposure and the development was visually evaluated. The following determination standard was used as the evaluation scale. The evaluation results are listed in Table 4.

(71) 5: No scratches were found.

(72) 4: Scratches were not able to be confirmed with naked eyes, but one scratch was able to be confirmed using a 6 magnifying loupe.

(73) 3: Scratches were not able to be confirmed with naked eyes, but several scratches were able to be confirmed using a 6 magnifying loupe.

(74) 2: Several scratches were able to be confirmed with naked eyes.

(75) 1: Scratches were confirmed from the entire surface.

(76) TABLE-US-00004 TABLE 4 Planographic Evaluation results printing Printing durability Scratch plate precursor (10,000 sheets) resistance Example 1 CTP-l 5.0 5 Example 2 CTP-2 5.0 5 Example 3 CTP-3 5.0 5 Example 4 CTP-4 4.9 5 Example 5 CTP-5 4.9 5 Example 6 CTP-6 4.5 5 Example 7 CTP-7 4.5 4 Example 8 CTP-8 4.0 4 Example 9 CTP-9 4.0 4 Example 10 CTP-10 5.0 5 Example 11 CTP-11 4.9 5 Example 12 CTP-12 4.9 5 Example 13 CTP-13 4.9 5 Example 14 CTP-14 4.9 5 Example 15 CTP-15 4.5 4 Example 16 CTP-16 4.4 4 Example 17 CTP-17 4.0 4 Example 18 CTP-18 3.9 4 Example 19 CTP-19 5.0 5 Example 20 CTP-20 4.9 5 Example 21 CTP-21 4.5 4 Example 22 CTP-22 4.0 4 Example 23 CTP-23 4.9 5 Example 24 CTP-24 4.9 5 Example 25 CTP-25 4.4 4 Example 26 CTP-26 3.9 4 Example 27 CTP-27 4.9 5 Example 28 CTP-28 4.9 5 Example 29 CTP-29 4.4 4 Example 30 CTP-30 3.9 4 Example 31 CTP-31 5.0 5 Example 32 CTP-32 5.0 5 Example 33 CTP-33 5.0 5 Example 34 CTP-34 5.0 5 Comparative CTP-1 for comparison 1.1 1 Example 1 Comparative CTP-2 for comparison 1.1 1 Example 2 Comparative CTP-3 for comparison 1.1 1 Example 3

Example 35 and Comparative Example 4

(77) 1. Preparation of Support (2)

(78) In order to remove rolling oil on a surface of an aluminum plate (Material JIS A 1050) having a thickness of 0.3 mm, a degreasing treatment was performed using a 10 mass % sodium aluminate aqueous solution at 50 C. for 30 seconds, the aluminum surface was grained using three bundle nylon brushes having a diameter of 0.3 mm and a pumice water suspension (specific gravity of 1.1 g/cm.sup.3) having a median diameter of 25 m and then sufficiently washed with water. This aluminum plate was immersed in a 25 mass % sodium hydroxide aqueous solution at 45 C. for 9 seconds, etched, washed with water, and further immersed in 20 mass % nitric acid at 60 C. for 20 seconds, and then washed with water. The etching amount of the grained surface at this time was approximately 3 g/m.sup.2.

(79) Next, an electrochemical roughening treatment was continuously performed using an AC voltage of 60 Hz. As the electrolytic solution, a 1 mass % nitric acid aqueous solution (including 0.5% by mass of aluminum ions) was used at a liquid temperature of 50 C. Using a trapezoidal rectangular waveform AC having a time TP, until the current value reached a peak from zero, of 0.8 msec and the duty ratio of 1:1 as an AC power source waveform, the electrochemical surface-roughening treatment was performed using a carbon electrode as a counter electrode. As an auxiliary anode, ferrite was used. The current density was 30 A/dm.sup.2 as the peak current value, and 5% of the current flowing from the power source was separated to an auxiliary anode. The electric quantity in the nitric acid electrolysis was 175 C/dm.sup.2 in a case where the aluminum plate was an anode. Thereafter, washing with water was performed using a spray.

(80) Next, an electrochemical roughening treatment was performed according to the same method as the method for nitric acid electrolysis under the condition of an electric quantity of 50 C/dm.sup.2 in a case where an aluminum plate is an anode in a 0.5 mass % hydrochloric acid aqueous solution (including 0.5% by mass of aluminum ions) and an electrolytic solution at a liquid temperature of 50 C. Subsequently, washing with water using a spray was performed.

(81) Next, 2.5 g/m.sup.2 of a DC anodized film was provided on this aluminum plate at a current density of 15 A/dm.sup.2 using 15 mass % nitric acid (including 0.5% by mass of aluminum ions) as an electrolytic solution, washed with water, and then dried, thereby preparing a support (2). The center line average roughness (Ra) of this substrate was measured using a needle having a diameter of 2 m, and the value was 0.51 m.

(82) 2. Application of Undercoat Layer

(83) Next, a coating solution (1) for an undercoat layer was prepared by mixing each of the components with the following composition. The support (2) was coated with the coating solution (1) for an undercoat layer such that the drying and coating amount was set to 20 mg/m.sup.2, thereby preparing a support having an undercoat layer.

(84) [Coating Solution (1) for Undercoat Layer]

(85) TABLE-US-00005 Polymer compound A with the following structure 0.05 parts Methanol 27 parts Ion exchange water 3 parts

(86) Further, each numerical value on the lower right side of parentheses representing each constitutional unit in the following polymer compound A indicates the molar ratio.

(87) ##STR00022##

(88) 3. Application of Image Recording Layer

(89) Respective components listed in Table 5 were mixed to prepare a coating solution (2) for an image recording layer, the undercoat layer was coated with the coating solution using a wire bar such that the coating amount after drying the coating solution was set to 0.9 g/m.sup.2, and the coating solution was dried at 115 C. for 34 seconds using a hot air dryer to form an image recording layer.

(90) In Table 5, the content of each active component is listed in the column of part by mass.

(91) TABLE-US-00006 TABLE 5 Component Part by mass Specific hard polymer particles listed in Table 6 4.568 Polymerizable compound containing hydrogen bonding 0.428 group listed in Table 6 Infrared absorbing agent IR-1 0.038 Radical polymerization initiator S-1 0.061 Radical polymerization initiator I-1 0.094 Mercapto compound SH-1 0.015 Polymerizable compound A 0.311 Polymerizable compound B 0.250 Polymerizable compound C 0.062 Auxiliary sensitizer T-1 0.081 Polymerization inhibitor Q-1 0.0012 Copper phthalocyanine pigment dispersion 0.159 Fluorine-based surfactant 0.0081 MEGAFACE F-780-F, manufactured by DIC Corporation 30 mass % methyl isobutyl ketone solution Methyl ethyl ketone 5.886 Methanol 2.733 1-Methoxy-2-propanol 5.886

(92) The details of each component listed in Table 5 are as follows. Infrared absorbing agent IR-1: compound represented by Formula IR-1 Radical polymerization initiator S-1: compound represented by Formula S-1, photopolymerization initiator Radical polymerization initiator I-1: compound represented by Formula I-1, photopolymerization initiator Mercapto compound SH-1: compound represented by Formula SH-1 Auxiliary sensitizer T-1: compound represented by Formula T-1 Polymerization inhibitor Q-1: compound represented by Formula Q-1 Copper phthalocyanine pigment dispersion: dispersion with the following composition Polymerizable compound A: compound represented by Formula B-1 Polymerizable compound B: compound represented by Formula B-2 Polymerizable compound C: compound represented by Formula B-3 In Formulae S-1 and I-1, Me represents a methyl group.

(93) ##STR00023## ##STR00024##

(94) Further, in Formulae B-1 to B-3, each numerical value on the lower right side of parentheses representing each constitutional unit of the polymer indicates the content (molar ratio) of the constitutional unit.

(95) Copper Phthalocyanine Pigment Dispersion

(96) 15 parts by mass of a copper phthalocyanine pigment, 10 parts by mass of an allyl methacrylate/methacrylic acid (80/20) copolymer as a dispersant, and cyclohexanone/methoxypropyl acetate/1-methoxy-2-propanol (15 parts by mass/20 parts by mass/40 parts by mass) as a solvent were mixed to prepare a copper phthalocyanine pigment dispersion.

(97) 4. Application of Protective Layer

(98) [Lower Protective Layer (1)]

(99) The surface of the image recording layer was coated with a mixed aqueous solution (coating solution (1) for a protective layer) obtained by mixing synthetic mica (SOMASIF MEB-3L, manufactured by CO-OP CHEMICAL CO., LTD., 3.2% aqueous dispersion liquid), polyvinyl alcohol (GOHSERAN CKS-50, saponification degree: 99% by mole, degree of polymerization: 300, sulfonic acid-modified polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), a surfactant A (EMALEX 710, manufactured by Nihon Emulsion Co., Ltd.), and a surfactant B (ADEKA PLUONIC P-84, manufactured by ADEKA CORPORATION) using a wire bar and dried at 125 C. for 30 seconds using a hot air dryer.

(100) The content ratio of the synthetic mica (solid content)/polyvinyl alcohol/surfactant A/surfactant B in this mixed aqueous solution (coating solution (1) for a protective layer) was 7.5/89/2/1.5 (% by mass) and the coating amount (coating amount after drying) was 0.5 g/m.sup.2.

(101) [Upper Protective Layer (1)]

(102) The surface of a lower protective layer was coated with a mixed aqueous solution (coating solution (2) for a protective layer) obtained by mixing an organic filler (ART PEARL J-7P, manufactured by Negami Chemical Industrial Co., Ltd.), synthetic mica (SOMASIF MEB-3L, 3.2% aqueous dispersion liquid, manufactured by CO-OP CHEMICAL CO., LTD.), polyvinyl alcohol (L-3266, saponification degree: 87% by mole, degree of polymerization: 300, sulfonic acid-modified polyvinyl alcohol, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), a thickener (CELLOGEN FS-B, manufactured by DKS Co., Ltd.), the polymer compound A, and a surfactant (EMALEX 710, manufactured by Nihon Emulsion Co., Ltd.) using a wire bar and dried at 125 C. for 30 seconds using a hot air dryer to prepare CTP-35 and CTP-4 for comparison which are planographic printing plate precursors listed in Table 6. The content ratio of the organic filler/synthetic mica (solid content)/polyvinyl alcohol/thickener/polymer compound A/surfactant/in this mixed aqueous solution (coating solution (2) for a protective layer) was 4.7/2.8/67.4/18.6/2.3/4.2 (% by mass) and the coating amount (coating amount after drying) was 1.8 g/m.sup.2.

(103) In the prepared planographic printing plate precursors CTP-35 to CTP-4 for comparison, the used supports, coating solutions for an undercoat layer, coating solutions for an image recording layer, hard polymer particles, polymerizable compounds containing a hydrogen bonding group, and coating solutions for a protective layer are listed in Table 6.

(104) TABLE-US-00007 TABLE 6 Planographic Coating solution Coating solution Specific hard Polymerizable compound Coating solution printing plate for undercoat for image polymer containing hydrogen for protective layer precursor Support layer recording layer particles bonding group Upper Lower CTP-35 (2) (1) (2) p-1 m-1 (2) (1) CTP-4 for (2) (1) (2) p-10 m-1 (2) (1) comparison

(105) (Evaluation of Planographic Printing Plate Precursor)

(106) (1) Evaluation of Printing Durability

(107) The obtained planographic printing plate precursors CTP-35 and CTP-4 for comparison were exposed in Trendsetter 3244VX (manufactured by Creo Co., Ltd.) equipped with a water-cooling type 40 W infrared semiconductor laser under conditions of a resolution of 175 lpi, an external surface drum rotation speed of 150 rpm, and an output of 0 to 8 W by changing the range of the output by 0.15 log E. Further, the exposure was performed under conditions of a temperature of 25 C. at a relative humidity of 50% RH. After the exposure, development was performed at 30 C. for 12 seconds using a processor LP-1310 News (manufactured by Fujifilm Corporation). Further, 1:4 water dilution liquid of DH-N (manufactured by Fujifilm Corporation) was used as a developer and a 1:1 water dilution liquid of GN-2K (manufactured by Fujifilm Corporation) was used as a finisher. In addition, the obtained planographic printing plates were printed using a printing press LITHRONE (manufactured by KOMORI Corporation), the printed material of the image area was observed, and the number of sheets (number of printed sheets) where the image started to be blurred was used as an index of the printing durability. The results are listed in Table 7.

(108) (2) Evaluation of Scratch Resistance

(109) The obtained planographic printing plate precursors CTP-35 and CTP-4 for comparison were alternately laminated with inserting paper (F inserting paper, manufactured by Daiichi Container Co., Ltd.) to prepare planographic printing plate precursor laminates. The obtained planographic printing plate precursor laminates were stacked at a height of 1 m and vibrated for 10 minutes (vibration frequency range of 5 to 55 Hz), exposure and development were performed thereon, and the state in which scratches were generated in the image area during the exposure and the development was visually evaluated. The following determination standard was used as the evaluation scale. The evaluation results are listed in Table 7.

(110) 5: No scratches were found.

(111) 4: Scratches were not able to be confirmed with naked eyes, but one scratch was able to be confirmed using a 6 magnifying loupe.

(112) 3: Scratches were not able to be confirmed with naked eyes, but several scratches were able to be confirmed using a 6 magnifying loupe.

(113) 2: Several scratches were able to be confirmed with naked eyes.

(114) 1: Scratches were confirmed from the entire surface.

(115) TABLE-US-00008 TABLE 7 Planographic Evaluation results printing Printing durability Scratch plate precursor (10,000 sheets) resistance Example 35 CTP-35 8.0 5 Comparative CTP-4 for comparison 5.0 5 Example 4