CN1575975A - Lithographic process involving on press development - Google Patents

Lithographic process involving on press development Download PDF

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Publication number
CN1575975A
CN1575975A CN 200410063675 CN200410063675A CN1575975A CN 1575975 A CN1575975 A CN 1575975A CN 200410063675 CN200410063675 CN 200410063675 CN 200410063675 A CN200410063675 A CN 200410063675A CN 1575975 A CN1575975 A CN 1575975A
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polymerization initiator
lithographic
image formation
formation layer
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CN100374296C (en
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大岛康仁
因埜纪文
光本知由
藤牧一广
嵨田和人
牧野直宪
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from JP2003300337A external-priority patent/JP4426795B2/en
Priority claimed from JP2003300336A external-priority patent/JP2005067041A/en
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Abstract

A lithographic printing process comprises the steps of: imagewise exposing to infrared light a presensitized lithographic plate which comprises a hydrophilic support and an image-forming layer containing an infrared absorbing agent, a polymerization initiator and a binder polymer to polymerize the polymerizable compound within the exposed area; removing the image-forming layer within the unexposed area while mounting the lithographic plate on a cylinder of a printing press; and then printing with the lithographic plate while mounting the lithographic plate on the cylinder of the printing press. The polymerization initiator is a salt of an anion with a sulfonium ion. According to the present invention, a specific anion or a specific sulfonium ion is used in the polymerization initiator.

Description

Relate to the lithographic process that develops on the printing machine
Technical field
The present invention relates to a kind of printing machine (press) that relates to and go up the lithographic process that develops.The invention still further relates to a kind of lithographic plate of pre-sensitizing, the image formation layer that it comprises hydrophilic carrier and contains infrared absorbing agents, polymerization initiator, polymerizable compound and binder polymer.
Background technology
Lithographic plate is generally comprised within the hydrophobicity image-region of accepting oily ink in the printing process and the water wettability non-image areas of accepting wetting water.Conventional lithographic process generally includes following step: offscreen film is sheltered pre-sensitizing (PS) version that comprises hydrophilic carrier and hydrophobicity photosensitive resin layer, by lithographic film galley is exposed, the galley of developing then is to remove non-image areas with developing solution.
Now, the processing of computing machine electronics, storage and output image information are numerical data.Preferably with the directly scanning and do not use lithographic film that image recording is formed numerical data of the dynamic rays of high indication such as laser beam.Term computer to version (CTP) is meant the method for not using lithographic film according to Digital Image Data formation galley.
The conventional lithographic process that forms galley has problem for CTP, and promptly the spectral response of the wavelength region may of laser beam and photosensitive resin does not match.
The step (that is development step) of non-image areas need be dissolved and remove to conventional PS version.The galley of developing should be carried out aftertreatment again, as the water cleaning treatment, handles and use the desensitization processing of Arabic gum or starch derivative solution with the rinsing of surfactant solution.Extra wet process is disadvantageous for conventional PS version.Although the early stage step in lithography process (image formation step) is simplified according to digital processing, the step of back (development step) comprises the wet process of this trouble, and promptly this process can not be simplified fully on the whole.
Printing industry and other industry are interested for global environmental protection.Wet process influences global environment inevitably.The preferred reduced wet process is changed into dry-cure with it, or omits from lithographic plate, to protect the global environment.
To there be the method for wet process to be called the printing developing method, it comprises following step: the pre-sensitizing galley of exposure is adhered on the cylindrical shell of printing machine, and rotary barrel is supplied with wetting water and ink to galley, simultaneously to remove non-image areas from galley.After with the presensitized plate exposure, immediately galley is placed in the printing machine.When carrying out common printing treatment, can finish lithography process.
The presensitized lithographic version that is suitable for printing development must have the photosensitive layer that is dissolved in wetting water or ink solvent.Presensitized plate should be handled under room lighting easily, to print development in the printing machine of settling under room lighting.
Conventional PS version can not satisfy requirement recited above.
Jap.P. 2,938,397 (corresponding to European patent 0770494 and United States Patent (USP)s 6,030,750 and 6,096,481) disclose a kind of method for preparing lithographic plate.This method is used a kind of image component (presensitized plate), described image component comprises the water-wetted surface based on the lithographic plate of image formation layer, and described image formation layer comprises can be under the influence of heat coalescent and is scattered in the hydrophobic thermoplastic polymer's particle in the hydrophilic adhesive and light can be converted to the compound of heat.This method comprises the following step: become image ground that image component is exposed; And by the develop image component of the one-tenth image exposure that obtains thus of following method: it is installed on the printing cylindrical shell of printing machine, and supplies with water-based wetting liquid or ink, simultaneously the rotary printing machine drum body to image formation layer.
Can handle image component under room lighting, reason is that this element has susceptibility at region of ultra-red.
In preparing the method for lithographic plate, polymer beads is coalescent under the heat effects that is converted to by light.The image component that contains the particle that is suitable for printing development shows poor galley wearing quality usually.
The open 2000-211262 of Jap.P., 2001-277740,2002-29162,2002-46361,2002-137562 and 2002-326470 disclose the presensitized lithographic version, wherein disperse to contain the microcapsules of polymerizable compound, replace thermoplastic polymer particles.Compare with the image of being made by fusion and aggregated particle, the image that is formed by the polymerizable compound reaction has stronger permanance and gives better galley wearing quality.
Summary of the invention
Summary of the invention
One object of the present invention is to have the development on the printing machine of presensitized lithographic version of hypersensitivity.
Another object of the present invention is to prepare a kind of lithographic plate, and it has the excellent galley wearing quality of improvement by the development on the printing machine.
A further object of the present invention is to use by the lithographic plate that obtains that develops on the printing machine prints.
Of the present invention also have a purpose to be to improve the polymerization initiator that is used for the presensitized lithographic version.
The invention provides a kind of lithographic process, this method comprises following step:
Become image ground to expose the presensitized lithographic version with infrared ray, described presensitized lithographic version comprises hydrophilic carrier and contains the image formation layer of infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is a kind of sulfonium cation and anionic salt, described negative ion is selected from: (1) hydrogen sulfate ion, (2) sulfuric ester ion, (3) contain the polymkeric substance of carboxylic acid ion, (4) contain the polymkeric substance of sulfonate ion, and (5) contain SO 2-N --R 1(wherein, R 1Be carboxyl, formoxyl, aliphatic group, aromatic group, heterocyclic radical ,-O-R ,-S-R,-CO-R,-O-CO-R or-CO-O-R, and wherein R is an aliphatic group, aromatic group or heterocyclic radical) anionic polymkeric substance, (6) contain by acyl group, carbamyl, the carboxylic acid ion of the alpha-carbon atom that the carbamyl of replacement or cyano group replace, (7) contain the carboxylic acid ion of the alpha-carbon atom that is replaced by two or more aromatic groups, (8) contain the carboxylic acid ion of the alpha-carbon atom that is connected with non-metallic atom the hydrogen except carbon, with the described polymerizable compound of polymerization in the exposure area;
In unexposed area, remove image formation layer, on the cylindrical shell of printing machine, lithographic plate is installed simultaneously; Then
Offscreen the version printed images is installed lithographic plate simultaneously on the cylindrical shell of printing machine.
The present invention also provides a kind of presensitized lithographic version, the image formation layer that it comprises hydrophilic carrier and contains infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is a kind of sulfonium cation and anionic salt, described negative ion is selected from: (1) hydrogen sulfate ion, (2) sulfuric ester ion, (3) contain the polymkeric substance of carboxylic acid ion, SO is contained in polymkeric substance and (5) that (4) contain sulfonate ion 2-N --R 1(wherein, R 1Be carboxyl, formoxyl, aliphatic group, aromatic group, heterocyclic radical ,-O-R ,-S-R ,-CO-R ,-O-CO-R or-CO-O-R, and wherein R is an aliphatic group, aromatic group or heterocyclic radical) anionic polymkeric substance.
The present invention also provides a kind of lithographic process, and this method comprises following step:
Become image ground to expose the presensitized lithographic version with infrared ray, described presensitized lithographic version comprises hydrophilic carrier and contains the image formation layer of infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is the salt of a kind of negative ion and sulfonium cation, described sulfonium cation comprises the sulphur atom that is connected with three aromatic groups, at least one aromatic group is replaced by electron-withdrawing group, with the described polymerizable compound of polymerization in the exposure area;
In unexposed area, remove image formation layer, on the cylindrical shell of printing machine, lithographic plate is installed simultaneously; Then
Offscreen the version printed images is installed lithographic plate simultaneously on the cylindrical shell of printing machine.
The present invention also provides a kind of presensitized lithographic version, the image formation layer that it comprises hydrophilic carrier and contains infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is the salt of a kind of negative ion and sulfonium cation, described sulfonium cation comprises the sulphur atom that is connected with three aromatic groups, and at least one aromatic group is replaced by electron-withdrawing group.
The inventor has studied a kind of polymerization initiator, and it can be advantageously used in and relate to the lithography process that develops on the printing machine.
In the lithography process of routine, lithographic plate is developed by alkaline solution.Therefore, selective polymerization initiating agent so is so that polymerization initiator can easily be removed by alkaline solution.
In the lithographic process that on relating to printing machine, develops,, or mechanically develop with the cylindrical shell on the printing machine with lithographic printing plate-use wetting water or oily ink chemical development.In addition, the polymerization initiator that relates to a kind of hypersensitivity of lithographic process needs that develops on the printing machine.Therefore, be advantageously used in the polymerization initiator that relates in the lithographic process that develops on the printing machine and should be different from the conventional polymerization initiator that is used for conventional lithographic process.
The inventor has been noted that and sulfonium cation and anionic salt can be used to relate to the lithographic process that develops on the printing machine aptly.But this salt should further improve for the development that is used on the printing machine.
The inventor finds at last, (1) to the salt of (8) or special sulfonium cation that has special anionic of comprising recited above can be advantageously used in and relate in the lithographic process that develops on the printing machine.Special salt has hypersensitivity, and removes when can be easily developing on printing machine.
Therefore,, have the presensitized lithographic version of hypersensitivity, can carry out the development on the printing machine by use according to the present invention.
Another object of the present invention is to prepare a kind of lithographic plate, and it has the excellent galley wearing quality of improvement by the development on the printing machine.
A further object of the present invention is to use by the lithographic plate that obtains that develops on the printing machine prints.
Detailed Description Of The Invention
[polymerization initiator of first embodiment]
Among the present invention, with the salt of negative ion and sulfonium cation as polymerization initiator.In first embodiment of the present invention, special negative ion is combined with sulfonium cation.
Special negative ion is selected from: (1) hydrogen sulfate ion, and (2) sulfuric ester ion, (3) contain the polymkeric substance of carboxylic acid ion, and (4) contain the polymkeric substance of sulfonate ion, and (5) contain SO 2-N --R 1(wherein, R 1Be carboxyl; formoxyl; aliphatic group; aromatic group; heterocyclic radical;-O-R ,-S-R ,-CO-R;-O-CO-R or-CO-O-R; and wherein R is an aliphatic group, aromatic group or heterocyclic radical) anionic polymkeric substance, (6) are contained by acyl group; carbamyl; the carboxylic acid ion of the alpha-carbon atom that carbamyl that replaces or cyano group replace, (7) contain the carboxylic acid ion of the alpha-carbon atom that is replaced by two or more aromatic groups, contain the carboxylic acid ion of the alpha-carbon atom that is connected with non-metallic atom the hydrogen except carbon with (8).
(sulfonium cation)
Sulfonium cation is by S +R 3Expression, wherein R is hydrogen, aliphatic group, aromatic group or heterocyclic radical.Two or more groups of being represented by R can be in conjunction with forming heterocyclic radical.Preferred R is an aliphatic group, aromatic group or heterocyclic radical, and more preferably aliphatic group or aromatic group, and most preferably be aromatic group.In other words, preferred sulfonate ion comprises and is connected with three aliphatic series, and the sulphur atom of aromatics or heterocyclic group more preferably comprises the sulphur atom that is connected with three aliphatic series or aromatic group, and most preferably comprises the sulphur atom that is connected with three aromatic groups.
In this manual, aliphatic group is meant alkyl, the alkyl of replacement, alkenyl, the alkenyl of replacement, the alkynyl of alkynyl or replacement.Aliphatic group can have ring-type or branched structure.The preferred aliphatic series base contains 1-20 carbon atom.
Substituent example comprise halogen atom (F, Cl, Br, I), cyano group, nitro, aromatic group, heterocyclic radical; hydroxyl, sulfydryl, formoxyl, carboxyl, amino, carbamyl, sulfamoyl ,-O-R;-S-R ,-CO-R ,-CO-O-R ,-O-CO-R ,-NH-R ,-CO-NH-R ,-NH-CO-R ,-SO 2-R ,-NH-SO 2-R ,-SO 2-NH-R and-N=N-R.R is aliphatic group, aromatic group or heterocyclic radical.
In this manual, aromatic group is meant the aryl of aryl or replacement.Preferred aryl groups contains 6 to 20 carbon atoms.
Except the substituting group example of aliphatic group, substituent example also comprises aliphatic group.
In this manual, heterocyclic radical comprises the heterocyclic radical of unsubstituted heterocyclic and replacement.The heteroatoms of preferred heterocyclic radical is nitrogen, oxygen or sulphur.Preferred heterocyclic radical has five yuan or hexa-member heterocycle.Another kind can be encircled (aliphatic ring, aromatic ring or heterocycle) with described heterocyclic fused.Preferred heterocyclic radical contains 1-20 carbon atom.
Except the substituting group example of aromatic group, substituent example also comprise oxo (=O), sulfo-(=S) and imino group (=NH or=N-R, wherein R is an aliphatic group, aromatic group or heterocyclic radical).
Shown below is the example of sulfonium cation (C1-C18).
C1: right-tert-butyl-phenyl diphenyl sulfonium cation
C2: right-tolyl diphenyl sulfonium cation
C3: two (right-anisyl) phenyl sulfonium cation
C4: three (right-anisyl) sulfonium cation
C5: right-hydroxyphenyl diphenyl sulfonium cation
C6: three (right-tolyl) sulfonium cation
C7: three (right-fluorophenyl) sulfonium cation
C8: benzyl diphenyl sulfonium cation
C9: hexyl methyl phenyl sulfonium cation
C10: triphenylsulfonium ion
C11:2,4,6-trimethylphenyl diphenyl sulfonium cation
C12: three (right-tert-butyl-phenyl) sulfonium cation
C13: right-anisyl diphenyl sulfonium cation
C14: two (right-chlorphenyl) phenyl sulfonium cation
C15: two (right-tolyl) phenyl sulfonium cation
C16: two (right-chlorphenyl) tolyl sulfonium cation
C17: methyldiphenyl base sulfonium cation
C18: tributyl sulfonium cation
(hydrogen sulfate ion and sulfuric ester ion)
Hydrogen sulfate ion is a kind of corresponding to by remove the univalent anion of the atomic group that hydrogen atom forms from sulfuric acid molecule.
The sulfuric ester ion is a kind of univalent anion of being made up of mono-substituted sulfuric ester.Preferably sulfuric acid ester ion is represented by following formula (I):
(I)R-O-SO 3 -
In formula (I), R is aliphatic group, aromatic group or heterocyclic radical.
Shown below is the example of hydrogen sulfate ion (A0) and sulfuric ester ion (A1-A95):
n-C 4F 9-(CH 2) 2-O-SO 3
(A8)
Figure A20041006367500122
C 2H 5-O-SO 3
(A12)
(A16)
CH 3-O-SO 3
(A17)
CF 3-O-SO 3
Figure A20041006367500132
(A19)
CCl 3-O-SO 3
(A20)
n-C 4H 9-O-SO 3
(A21)
HO-CH 2-O-SO 3
(A23)
C 15H 31-O-SO 3
Figure A20041006367500134
(A45)
CH 2＝CH-CH 2-O-SO 3
Figure A20041006367500162
Figure A20041006367500171
(A51)
HO-(CH 2) 2-O-SO 3
(A52)
n-C 8H 17-O-SO 3
(A53)
C 12H 25-O-SO 3
Figure A20041006367500172
(A57)
CH 3-S-(CH 2) 2-O-SO 3
(A61)
CH 2＝CH-O-SO 3
Figure A20041006367500182
(A64)
n-C 4F 9-O-SO 3
Figure A20041006367500183
(A67)
C 8F 17-O-SO 3
(A69)
HS-CH 2-O-SO 3
(A70)
CH 3-O-CO-(CH 2) 2-O-SO 3
(A71)
n-C 19H 39-O-SO 3
(A72)
CH 3-SO 2-NH-CH 2-O-SO 3
Figure A20041006367500201
Figure A20041006367500211
(A87)
n-C 3H 7-O-SO 3
(A90)
CHCl 2-O-SO 3
(A91)
n-C 7H 15-O-SO 3
Figure A20041006367500213
Combination for sulfonium cation and bisulfate ion or sulfuric ester ion is not particularly limited.Shown below is the example of the salt of sulfonium cation and hydrogen sulfate ion or sulfuric ester ion.Following example is meant the sequence number of sulfonium cation (C) and hydrogen sulfate ion or sulfuric ester ion (A).For example, (1) C10A16 is meant methane-sulforic acid (A16) triphenylsulfonium ion (C10).
(1) C10·A16 (2) C10·A17 (3) C10·A0
(4) C10·A7 (5) C10·A21 (6) C10·A18
(7) C10·A67 (8) C10·A68 (9) C10·A69
(10) C10·A70 (11) C10·A44 (12) C10·A61
(13) C10·A71 (14) C10·A72 (15) C10·A45
(16) C10·A73 (17) C10·A74 (18) C10·A75
(19) C10·A1 (20) C10·A2 (21) C10·A62
(22) C10·A59 (23) C10·A76 (24) C10·A3
(25) C10·A77 (26) C10·A30 (27) C10·A31
(28) C10·A32 (29) C10·A33 (30) C10·A78
(31) C10·A35 (32) C10·A36 (33) C10·A79
(34) C10·A13 (35) C10·A47 (36) C10·A58
(37) C10·A4 (38) C10·A14 (39) C10·A49
(40) C10·A80 (41) C10·A10 (42) C10·A81
(43) C10·A5 (44) C10·A55 (45) C10·A82
(46) C10·A83 (47) C11·A73 (48) C11·A84
(49) C11·A85 (50) C11·A86 (51) C12·A2
(52) C12·A17 (53) C12·A87 (54) C12·A88
(55) C12·A68 (56) C13·A1 (57) C13·A17
(58) C13·A89 (59) C14·A4 (60) C14·A16
(61) C14·A90 (62) C15·A91 (63) C15·A92
(64) C16·A11 (65) C16·A0 (66) C17·A93
(67) C17·A78 (68) C18·A20 (69) C18·A2
[synthetic embodiment 1]
(sulfonium cation C10's is synthetic))
In the benzene of 800ml, the diphenyl sulfoxide of dissolving 50.9g.In solution, add the ammonium chloride of 200g.Potpourri was refluxed 24 hours.Use ice-cooled reaction mixture, it is little by little poured in 2 liters the water.The concentrated hydrochloric acid that in potpourri, adds 400ml.In 70 ℃ reaction mixture was heated 10 minutes.Wash the aqueous solution that obtains with ethyl acetate, and filter.In filter liquor, be added in the solution of the 200g ammonium iodide in the 400ml water.
Filter out the powder of precipitation, wash with water, with the ethyl acetate washing, and the dry iodate triphenyl sulfonium that obtains 70g.
(synthesizing of salt (1))
In the methyl alcohol of 100ml, the iodate triphenyl sulfonium of dissolving 7.8g.In solution, add the silver oxide of 4.87g.In stirring at room potpourri 4 hours.Filtering solution.In filter liquor, add 2.6g (excessive) sodium methyl mercaptide.In potpourri, add the 2ml concentrated hydrochloric acid, to begin reaction.Concentrated reaction mixture.With ethyl acetate and hexane wash concentrate, vacuum drying obtains viscous oil.
The oil that obtains is dissolved in the chloroform, filters, and concentrate.Repeat this program twice, obtain the salt (1) of 7.1g.
[synthetic embodiment 2]
(synthesizing of salt (3))
In the methyl alcohol of 100ml, the iodate triphenyl sulfonium of dissolving 7.8g preparation in synthetic embodiment 1.The silver oxide that in solution, adds 4.87g.In stirring at room potpourri 4 hours.Filtering solution.In filter liquor, add the 2.20g concentrated sulphuric acid, begin reaction.Concentrated reaction mixture.With ethyl acetate and hexane wash concentrate, vacuum drying obtains solid.
The solid that obtains with ethyl acetate and hexane wash, and vacuum drying once more obtain the salt (3) of 6.48g.
To be similar to the method for synthetic embodiment,, can also prepare other salt by changing raw material and conditioned reaction condition aptly.
The synthetic J.Amer.Chem.Soc. that is described in of sulfonium salt; 91; 1969; Among the 145-150.
The maximum absorption wavelength of the salt of preferred sulfonium cation and hydrogen sulfate ion or sulfuric ester ion is no more than 400nm, and more preferably no more than 360nm.
Total solid content based on image formation layer, the amount as the salt of the sulfonium cation of polymerization initiator and hydrogen sulfate ion or sulfuric ester ion that image formation layer contains is 0.1 to 50 weight %, 0.5 to 30 weight % more preferably, and most preferably be 1 to 20 weight %.
(anionic polymer)
The negative ion extracting mixture contains carboxylic acid ion (COO -), sulfonate ion (SO 3 -) or-SO 2-N --R 1Negative ion.Optimization acid's radical ion, and the carboxylic acid ion of α-ketone (containing the alpha-carbon atom that is connected with carbonyl) most preferably.
R 1Be carboxyl, formoxyl, aliphatic group, aromatic group, heterocyclic radical ,-O-R ,-S-R ,-CO-R ,-O-CO-R or-CO-O-R.R is aliphatic group, aromatic group or heterocyclic radical.
Preferred anionic is present in the side chain of polymkeric substance.
The main chain of preferred polymers is a hydrocarbon, polyurethane, polyureas, polyester, polyamide, polyethers, phenolics, norbornene resin or its multipolymer.Preferred hydrocarbons, polyurethane and polyureas, and hydrocarbon most preferably.
Preferred polymers comprises the repetitive by following formula (II) expression:
Figure A20041006367500241
In formula (II), R 2Be hydrogen, halogen atom, hydroxyl, carboxyl, formoxyl; amino, carbamyl, urea groups, sulfo group; sulfamoyl, aliphatic group, aromatic group, heterocyclic radical;-O-R ,-S-R ,-CO-R ,-O-CO-R;-CO-O-R ,-NH-R ,-NH-CO-R ,-CO-NH-R;-NH-CO-NH-R ,-NH-CO-O-R ,-O-CO-NH-R ,-SO 2-R ,-NH-SO 2-R or-SO 2-NH-R.R is aliphatic group, aromatic group or heterocyclic radical.Preferred R 2Be hydrogen, carbamyl, aliphatic group ,-O-CO-R or-CO-O-R.
In formula (II), L 1Be singly-bound or divalent linker.Preferred divalent linker is the divalent aliphatic base, divalent aromatic base, divalent heterocycle ,-O-,-S-,-CO-,-NH-,-NR-,-SO 2-or its combination.R is aliphatic group, aromatic group or heterocyclic radical.
In this manual, the divalent aliphatic base is meant alkylidene, the alkylidene of replacement, alkenylene, the alkenylene of replacement, alkynylene, or the alkynylene that replaces.The divalent aliphatic base can have ring-type or branched structure.Preferred divalent aliphatic base contains 1-20 carbon atom.Substituent example is identical with the substituent example of aliphatic group.
In this manual, the divalent aromatic base is meant the arlydene of arlydene or replacement.Preferred divalent aromatic base contains 6 to 20 carbon atoms.Substituent example is identical with the substituent example of aromatic group.
In this manual, divalent heterocycle comprises the divalent heterocycle of unsubstituted divalent heterocycle and replacement.The heteroatoms of preferred divalent heterocycle is nitrogen, oxygen or sulphur.Preferred divalent heterocycle is five yuan or hexa-member heterocycle.Another can be encircled (aliphatic ring, aromatic ring or heterocycle) with described heterocyclic fused.Preferred divalent heterocycle contains 1-20 carbon atom.Substituent example is identical with the substituent example of heterocyclic radical.
In formula (II), Z is-COO--SO 3-or-SO 2-N --R 1, R wherein 1Be carboxyl, formoxyl, aliphatic group, aromatic group, heterocyclic radical ,-O-R ,-S-R ,-CO-R ,-O-CO-R or-CO-O-R.R is an aliphatic group, aromatic group or heterocyclic radical.
In formula (II), M is a sulfonium cation.
Shown below is example by the repetitive of formula (II) expression:
Figure A20041006367500271
Figure A20041006367500291
Figure A20041006367500301
Polymkeric substance can be by the homopolymer that contains anion base and form as the repetitive of the sulfonium cation of its counter ion.Polymkeric substance can also be to comprise two or more to contain anion base and as the multipolymer of the different repeat units of the sulfonium cation of its counter ion.Polymkeric substance can also be to comprise to contain anion base and as the repetitive of the sulfonium cation of its counter ion and the multipolymer of other repetitive.
Preferably other repetitive is represented by following formula (III):
Figure A20041006367500322
In the formula (III), R 3Be hydrogen, halogen atom, carboxyl, aliphatic group ,-O-CO-R or-CO-O-R.
R is aliphatic group, aromatic group or heterocyclic radical.Preferred R 3Be hydrogen or aliphatic group, hydrogen or contain the alkyl of 1 to 6 carbon atom more preferably, and most preferably be hydrogen or methyl.
In formula (III), L 2Be singly-bound or divalent linker.Preferred divalent linker is the divalent aliphatic base, divalent aromatic base, divalent heterocycle ,-O-,-S-,-CO-,-NH-,-NR-,-SO 2-or its combination.R is aliphatic group, aromatic group or heterocyclic radical.
In formula (III), R 4Be aliphatic group, aromatic group or heterocyclic radical.
Shown below is the example of other repetitive:
Figure A20041006367500341
(III-9)
-CO-NH-(CH 2) 6-NH-CO-
Shown belowly contain anion base and as the example of the multipolymer of the repetitive (II) of the sulfonium cation of its counter ion and other repetitive (III) for relating to.The ratio of repetitive is meant a mole %.
CP1： -(II-2) 50- -(III-1) 50-
CP2： -(II-5) 40- -(III-1) 60-
CP3： -(II-10) 60- -(III-3) 40-
CP4： -(II-13) 50- -(III-4) 50-
CP5： -(II-15) 40- -(III-6) 30- -(III-7) 30-
CP6： -(II-18) 40- -(III-8) 40- -(III-9) 10-
-(III-10) 10-
CP7： -(II-19) 50- -(III-11) 30- -(III-12) 10-
-(III-13) 10-
CP8： -(II-22) 30- -(III-6) 70-
CP9： -(II-23) 50- -(III-15) 50-
CP10： -(II-24) 50- -(III-1) 50-
[synthetic embodiment 3]
(4-hydroxyl-3,5-dimethyl ethyl benzoylformate synthetic)
With the nitrobenzene of 350ml, mix with the aluminum chloride of 133g in room temperature.Potpourri is remained in 0 to 10 ℃.In potpourri, the chloro ethyl formate of in 0 to 10 ℃ of dropping 136.5g 15 minutes.Potpourri was stirred 15 minutes.
In the nitrobenzene of 150ml, dissolving 2,6-xylenol.Solution is remained in 0 to 10 ℃, and it was dropped in the potpourri for preparing above 30 minutes.In 0 to 10 ℃ stirred the mixture 2 hours, and in stirring at room 1 hour.
With 2 liters of ice-cooled water, mix the concentrated hydrochloric acid of 60ml.The reaction mixture for preparing is above poured in the hydrochloric acid of dilution quietly.Ethyl acetate extraction potpourri with 500ml.With dried over sodium sulfate and concentrated organic phase.Under reduced pressure remove nitrobenzene, obtain solid.With the slurried again solid that obtains of 300ml diisopropyl ether, filter the 4-hydroxyl-3 that obtains 149g, 5-dimethyl ethyl benzoylformate (yield: 66.8%).
(4-(right-the vinyl benzene sulfonyloxy)-3,5-dimethyl ethyl benzoylformate synthetic)
In the pyridine of 80g, the 4-hydroxyl-3 of dissolving 111g, 5-dimethyl ethyl benzoylformate.Solution is cooled to 0 to 10 ℃.In solution, drip right-styrene sulfonic acid chloride of 152g.In 0 to 10 ℃ stirred the mixture 2 hours, and in stirring at room 2 hours.
With 2 liters of ice-cooled water, mix the concentrated hydrochloric acid of 80ml.The reaction mixture for preparing above with acetone diluted, and pour into quietly in the hydrochloric acid of dilution, with precipitated solid.The solid that filtration obtains, and with the slurried again filter liquor of the methyl alcohol of 300ml, obtain the 4-(right-the vinyl benzene sulfonyloxy)-3 of 151g, 5-dimethyl ethyl benzoylformate (yield: 77.5%).
(poly-(4-(right-the vinyl benzene sulfonyloxy)-3,5-dimethyl benzoyl formic acid synthetic))
In the methyl ethyl ketone of 64g, the 4-(right-the vinyl benzene sulfonyloxy)-3 of dissolving 31.07g, 5-dimethyl ethyl benzoylformate.Under nitrogen atmosphere, stir the mixture in 70 ℃.In potpourri, add 0.64g polymerization initiator (V-65, Wako Pure Chemical Industries Ltd.).Stirred the mixture 2 hours.In potpourri, add the 0.32g polymerization initiator.Stirred the mixture 2 hours.In potpourri, add the 0.16g polymerization initiator.Stirred the mixture 2 hours.Potpourri is cooled to room temperature, and pours in the hexane solution of the 1kg that contains 5% 2-propyl alcohol, obtain the polymkeric substance of 27g.
In 1-methoxyl-2-propyl alcohol of the dimethyl acetic acid of 30ml and 70ml, the polymkeric substance that dissolving 7g obtains.In solution, drip the potassium hydroxide solution of the 1.02g in 70ml water in room temperature.Stirred the mixture 2 hours, and pour in the potpourri of concentrated hydrochloric acid of ice-cooled water of 500ml and 20ml, with the solid of precipitation carboxylic acid.Filter this solid, and dry, gathered (4-(right-the vinyl benzene sulfonyloxy)-3,5-dimethyl benzoyl formic acid.
(homopolymer of forming by repetitive (II-1) synthetic)
In the methyl alcohol of 50ml, two (right-chlorphenyl) of dissolving 1.42g are right-tolyl sulfonium iodide.The silver oxide that in this solution, adds 0.72g.In stirring at room potpourri 4 hours.Filter stirred mixture, and further with the filtrator filtration filter liquor of 0.1 μ m.
To gather that (4-(right-the vinyl benzene sulfonyloxy)-3,5-dimethyl benzoyl formic acid are dissolved in the methyl alcohol of the acetone of 50ml and 10ml.
To gather that (4-(right-the vinyl benzene sulfonyloxy)-3, the drips of solution of 5-dimethyl benzoyl formic acid adds in the filter liquor for preparing above.Enriched mixture is to precipitate semisolid.Wash this semisolid with ethyl acetate and Di Iso Propyl Ether, obtain the homopolymer of forming by repetitive (II-1).Its weight-average molecular weight is 6,300.
Total solid content based on image formation layer, the amount as the anionic polymer of polymerization initiator that the preferred image cambium layer contains is 0.1 to 50 weight %, 0.5 to 50 weight % more preferably, 3 to 30 weight % more preferably again, and most preferably be 5 to 20 weight %.
(carboxylic acid ion)
Carboxylic acid ion can contain by acyl group, carbamyl, the alpha-carbon atom that carbamyl or cyano group replaced of replacement (carbon atom in the 2-position).
Carboxylic acid ion can have ring texture.Ring texture can contain the carbonyl of acyl group or the acylamino-key of (replacement) carbamyl.
Acyl group is meant-CO-R that wherein R is aliphatic group, aromatic group or heterocyclic radical.
The substituting group example of the carbamyl that replaces comprises aliphatic group, aromatic group or heterocyclic radical.
Shown below for containing by acyl group, carbamyl, the carboxylic acid ion example of the alpha-carbon atom that carbamyl or cyano group replaced of replacement:
A101: benzoyl acetate ion
A102:2-benzoyl propionate ion
A103: acetoacetate radical ion
A104: cyanoacetic acid radical ion
A105:2-cyano group cinnamate ion
A106:2-cyanopropionic acid radical ion
A107:5-(3,4,5-trimethyl-6-oxo-8-hydroxyl-3,4,5, the heterochromatic alkene of 6-tetrahydrochysene) carboxylic acid ion
A108:4-(3-oxo-7,7-dimethyl dicyclo [2.2.1] heptane) carboxylic acid ion
Carboxylic acid ion can also contain the alpha-carbon atom (carbon atom in the 2-position) that is replaced by two or more aromatic groups.
Shown below for containing the carboxylic acid ion example of the alpha-carbon atom that is replaced by two or more aromatic groups:
A201: ethylmercapto group diphenyl acetic acid radical ion
A202: hydroxy diphenyl acetate ion
A203: hydroxyl (1-naphthyl) phenylacetic acid radical ion
A204: sulfydryl diphenyl acetic acid radical ion
A205: methoxyl diphenyl acetic acid radical ion
A206: cyano group diphenyl acetic acid radical ion
A207: triphenylacetic acid radical ion
A208:3,3,3-three fluoro-2,2-diphenylprop acid ion
A209: two (right-chlorphenyl) acetate ions of hydroxyl
A210: two (right-tolyl) acetate ions of hydroxyl
A211:2,2-diphenylprop acid ion
A212: hydroxyphenyl (right-nitrobenzophenone) acetate ion
A213: chloro diphenyl acetic acid radical ion
A214:2,2-two (1-naphthyl) propionate ion
A215: three (4-chlorphenyl) acetate ion
A216:2,2-diphenyl butyric acid radical ion
A217: diphenyl acetic acid radical ion
Carboxylic acid ion can also contain the alpha-carbon atom (carbon atom in the 2-position) that non-metallic atom direct and outside de-carbon and the hydrogen is connected.Other non-metallic atom comprise halogen atom (F, Cl, Br, I), O, S, N, Si and P.Preferred halogen atom O, S and N.
Carboxylic acid ion can have ring texture.Ring texture can contain de-carbon and three kinds of outer non-metallic atoms of hydrogen.
Non-metallic atom can directly be connected with alpha-carbon atom as divalence or the substituting group of multivalence (for example: oxo, sulfo-, imino group) more.
Shown below for containing directly the carboxylic acid ion example of the alpha-carbon atom that is connected with de-carbon and hydrogen non-metallic atom outward:
A301: benzoyl formic acid radical ion
A302: pyruvic acid radical ion
A303: right-the methoxybenzoyl formate ion
A304: mercaptopyruvate radical ion
A305:3-methyl-2-ketobutyric acid radical ion
A306:3-o-nitrophenyl-2-oxo propionate ion
A307:3-phenyl-2-oxo propionate ion
A308: right-the chlorobenzoyl formate ion
A309: glyoxalic acid radical ion
A310:1-naphthalene formyl formate ion
A311:N-phenyl amino formyl formate ion
A312:3-indolcarbonyl formate ion
A313:2-ketobutyric acid radical ion
A314: right-acetylbenzene formyl formate ion
A315: trifluoroacetone acid ion
A316: phenyl-pentafluoride formyl formate ion
A317:2-oxopentanoic acid radical ion
A318:3-is right-chlorphenyl-2-oxo propionate ion
A319:3,5-dimethyl benzene formyl formate ion
A320: benzenesulfonyl acetate ion
A321:3, two (trifluoromethyl) benzenesulfonyl acetate ions of 5-
A322:2-benzenesulfonyl propionate ion
A323: right-methoxybenzene sulfonyl acetate ion
A324: fourth sulfonyl acetate ion
A325: mesyl acetate ion
A326:1-naphthalene sulfonyl guanidine-acetic acid radical ion
A327:2-(1, the 3-dioxolanes) carboxylic acid ion
A328: dimethoxy acetate ion
A329: methoxyacetic acid radical ion
A330:2-phenoxy propionic acid radical ion
A331: diethyl phosphonyl acetate ion
A332:2-hydroxyl-2-phenylpropionic acid radical ion
A333:3,3,3-three fluoro-2-phenyl-2-methoxy propyl acid ion
A334: thiophenyl acetate ion
A335: benzylthio acetate ion
A336: acetoxyl group phenylacetic acid radical ion
A337:2-thiophene carboxylic acid radical ion
A338:1-oxoisoindoline diindyl-2-guanidine-acetic acid radical ion
A339: anilinoacetic acid radical ion
A340:2-acetyl group acylamino-propionate ion
A341:2-anilino-propionate ion
A342:2-dimethylamino propionate ion
A343: acetyl group acylamino-acetate ion
A344: dimaleoyl imino acetate ion
A345: right-the toluidine acetate ion
A346: right-methoxybenzene glycine radical ion
A347:2-(5-methylthiophene) carboxylic acid ion
A348: t-butyldiphenylsilyl acetate ion
A349: phenyl seleno acetate ion
A350: trifluoroacetyl oxygen base phenylacetic acid radical ion
A351: right-the methyl benzoyl formate ion
A352:2,4,6-trimethylbenzoyl formate ion
A353:4-fluoro benzoyl formate ion
A354: neighbour-chlorobenzene formacyl formate ion
A355:3,5-dichloro-benzoyl base formate ion
A356: right-the amino benzoyl formate ion
A357:5-indolcarbonyl formate ion
A358:3-furans carbonyl formate ion
A359:2-thiophene carbonyl formate ion
A360:2-oxo-5-(pyridin-3-yl)-4-amylene carboxylic acid ion
A361: bromo acetone acid radical ion
A362:2-oxygen base butyrate ion
A363:2-oxygen base valerate ion
A364: cyclohexane carbonyl formate ion
A365:3-nitrobenzene formyl formate ion
A366:3, two (trifluoromethyl) benzoyl formic acid radical ions of 5-
A367: acetone trichloride acid ion
A368: right-the (2-hydroxybenzoyl) formate ion
A369: methylmercaptan ethyl acid ion
A370: right-chlorobenzene ethyl thioglycollic acid radical ion
A371: butyl benzene aminoacetic acid radical ion
A372:3-(1,2,3, the 4-tetrahydroisoquinoline) carboxylic acid ion
A373:2-benzyloxycarbonyl alanine radical ion
A374:2-benzyloxycarbonyl amino-3 Methylbutanoic acid radical ion
A375: triphen methylamino acetate ion
A376:2-(1-benzyloxycarbonyl pyrrolidine) carboxylic acid ion
A377: nitro-acetic acid radical ion
A378:2-(2,4, the 5-Trichlorophenoxy) propionate ion
A379: phenoxyacetic acid radical ion
A380:2-naphthoxy acetic acid radical ion
A381:2-isopropyl-5-methyl cyclohexane ethoxyacetic acid radical ion
The A382:2-oxolane carboxylic acid ion
A383:3,3,3-three chloro-2,2-dihydroxypropionic acid radical ion
A384: dimaleoyl imino ethoxyacetic acid radical ion
A385:2-(1-methylpyrrole) carboxylic acid ion
A386:2-pyrroles's carboxylic acid ion
A387:2-(5-bromine furans) carboxylic acid ion
A388:4-imidazolyl carboxylic acid radical ion
A389:2-(5-methoxyl indoles) carboxylic acid ion
A390: glycolic acid radical ion
A391: trichloroacetic acid ion
A392: perfluoro-pelargonic acid radical ion
A393: trifluoroacetic acid radical ion
A394:2,4-dioxo tetrahydro-thiazoles-3-guanidine-acetic acid radical ion
A395:2-chloropropionic acid radical ion
A396: chloroacetate root ion
A397: perfluoro decanoate radical ion
A398: bromobenzene guanidine-acetic acid radical ion
A399: phenyl methoxyacetic acid radical ion
A400: trifluoromethyl methoxyacetic acid radical ion
A401: hydroxyphenyl acetate ion
A402:2-(4-oxo-4H-chromene) carboxylic acid ion
A403: t-butoxycarbonyl amino acetate ion
A404:5-(2-Pyrrolidone) carboxylic acid ion
A405:4-(2-oxoimidazolinium) carboxylic acid ion
A406:4-(2-oxo tetrahydro-thiazoles) carboxylic acid ion
A407: right-Methyl benzenesulfonyl guanidine-acetic acid radical ion
A408: phenyl-pentafluoride sulfonyl acetate ion
A409: right-methoxybenzene ethoxyacetic acid radical ion
A410:2-furancarboxylic acid radical ion
A411: mercaptoacetic acid radical ion
Combination for sulfonium cation and carboxylic acid ion is not particularly limited.Shown below is the salt example of sulfonium cation and carboxylic acid ion.Following example is meant the sequence number of sulfonium cation (C) and carboxylic acid ion (A).For example, (101) C10A301 is meant benzoyl formic acid (A301) triphenyl sulfonium (C10).
(101)C10·A301 (102)C10·A302 (103)C10·A303
(104)C10·A304 (105)C10·A305 (106)C10·A306
(107)C1·A307 (108)C1·A308 (109)C14·A309
(110)C14·A310 (111)C14·A311 (112)C12·A301
(113)C12·A312 (114)C17·A313 (115)C17·A314
(116)C15·A301 (117)C14·A301 (118)C10·A320
(119)C10·A407 (120)C10·A408 (121)C12·A325
(122)C12·A320 (123)C12·A321 (124)C12·A322
(125)C13·A323 (126)C10·A101 (127)C10·A102
(128)C10·A103 (129)C10·A104 (130)C2·A327
(131)C2·A328 (132)C10·A329 (133)C10·A330
(134)C10·A105 (135)C3·A331 (136)C5·A332
(137)C10·A333 (138)C10·A334 (139)C10·A335
(140)C10·A336 (141)C10·A409 (142)C6·A204
(143)C6·A337 (144)C10·A338 (145)C10·A339
(146)C10·A340 (147)C7·A341 (148)C8·A342
(149)C10·A201 (150)C10·A202 (151)C10·A203
(152)C10·A204 (153)C11·A205 (154)C11·A207
(155)C11·A208 (156)C11·A209 (157)C11·A210
(158)C11·A211 (159)C10·A339 (160)C10·A379
(161)C10·A390 (162)C10·A392 (163)C10·A411
(164)C10·A393 (165)C10·A395 (166)C10·A107
(167)C18·A391 (168)C18·A382 (169)C10·A337
(170)C10·A410 (171)C10·A336
The salt of sulfonium cation and carboxylic acid ion and synthetic method are described in Jap.P. and disclose among 2001-343742 and the 2002-148790 temporarily.
Salt solubleness in 25 ℃ in water of preferred sulfonium cation and carboxylic acid ion is not less than 5 weight %, more preferably is not less than 10 weight %, more preferably is not less than 20 weight % again, further preferably is not less than 30 weight %, and most preferably is not less than 40 weight %.Solubleness is that salt is dissolved in the amount (g) in the 100g water.
Total solid content based on image formation layer, the salt amount that image formation layer contains as the sulfonium cation of polymerization initiator and carboxylic acid ion is preferably 0.1 to 50 weight %, 0.1 to 30 weight % more preferably, 0.5 to 25 weight % more preferably, 1 to 20 weight % more preferably again, and most preferably be 5 to 15 weight %.
Can be used in combination two or more polymerization initiators of first embodiment.The polymerization initiator of first embodiment can be used in combination with the polymerization initiator (following) of second embodiment.The polymerization initiator of first and second embodiments can be used in combination with other polymerization initiator.Other polymerization initiator comprises known triaizine compounds, borate compound, azo-compound, peroxide compound, lophine dimer (dimeres) and acylphosphanes compound.Under the situation that the polymerization initiator and other the polymerization initiator of first and second embodiments is used in combination, based on the total amount of polymerization initiator, preferably the amount of other polymerization initiator is lower than 30 weight %, and more preferably less than 10 weight %.
[polymerization initiator of second embodiment]
Among the present invention, with the salt of negative ion and sulfonium cation as polymerization initiator.In second embodiment of the present invention, special sulfonium cation and negative ion combination are used.
Special sulfonium cation comprises the sulphur atom that is connected with three aromatic groups, and at least one in the aromatic group replaced by electron-withdrawing group.
Triaryl matte ion and anionic salt are known as polymerization initiator, for example, are described in J.Amer.Chem.Soc.Vol.112 (16), 1990, the 6004-6015 pages or leaves; J.Org.Chem.1988, the 5571-5573 page or leaf, international publication number 02/081,439 is in the European patent 1113005.
Preferred aromatic group is a phenyl, the phenyl of replacement, the naphthyl of naphthyl or replacement, and the phenyl of phenyl or replacement more preferably.
In the aromatic group at least one replaced by electron-withdrawing group.
Contain at sulfonium cation under the situation of an electron-withdrawing group, the Hammett substituent constant of preferred electron-withdrawing group is greater than 0.46, more preferably greater than 0.50, and most preferably greater than 0.60.Preferred Hammett substituent constant is more preferably less than 3.5, most preferably less than 3.0 less than 4.0.
Contain at sulfonium cation under the situation of two or more electron-withdrawing groups, the Hammett substituent constant sum of preferred electron-withdrawing group is greater than 0.46, more preferably greater than 0.50, and most preferably greater than 0.60.Preferred Hammett substituent constant sum is more preferably less than 3.5, most preferably less than 3.0 less than 4.0.
The Hammett substituent constant is described in various files (for example, Naoki Inamoto, Seminar ofChemistry Vol.10, Hammett ' s rule-structure and reactivity (1983), Maruzen, Japanese).
Electron-withdrawing group comprises halogen atom, haloalkyl, acyl group, acyloxy, alkyl sulfinyl, cyano group, acylamino-and carboxyl.
Halogen atom comprise fluorine (at the Hammett substituent constant of a position (m): 0.34, at the Hammett substituent constant of contraposition (p): 0.06), chlorine (m:0.37, p:0.23), bromine (m:0.39, p:0.23) and iodine (m:0.35, p:0.18).At the ortho position Hammett substituent constant of (o) with at the constant of contraposition (p) much at one.
The examples of alkyl of halo comprise trifluoromethyl (m:0.43, p:0.54).
The example of acyl group comprise acetyl group (m:0.37, p:0.45) and formoxyl (m:0.36, p:0.43).
The example of alkyl sulfinyl comprise methanesulfinyl (m:0.52, p:0.45).
The Hammett substituent constant of cyano group is 0.56 (m) and 0.66 (p).
The example of acylamino-comprise acetylamino (m:0.21, p:0.00).
The Hammett substituent constant of carboxyl is 0.37 (m) and 0.45 (p).
Preferred electron-withdrawing group is halogen atom or haloalkyl, fluorine more preferably, and chlorine, bromine or trifluoromethyl most preferably are chlorine.
Two or more aromatic groups can be replaced by electron-withdrawing group.Preferred three aromatic groups are replaced by halogen atom, and are more preferably replaced by the chlorine atom.
Shown below for comprising the specific sulfonium cation example of the sulphur atom that is connected with three aromatic groups.
C101: three (-fluorophenyl) sulfonium cation
C102: three (-chlorphenyl) sulfonium cation
C103: two (right-bromophenyl) right-the chlorphenyl sulfonium cation
C104: two (right-fluorophenyl) right-the trifluorophenyl sulfonium cation
C105: two (right-chlorphenyl) 4-acetoxy-3,5-3,5-dimethylphenyl sulfonium cation
C106: two (3, the 5-dichlorophenyl) phenyl sulfonium cation
C107: three (3-chloro-4-fluorophenyl) sulfonium cation
C108: two (3, the 5-difluorophenyl) are right-the tolyl sulfonium cation
C109: two (right-trifluoromethyl) right-the tolyl sulfonium cation
C110: two (pentafluorophenyl group) phenyl sulfonium cation
C111: three (m-trifluoromethyl phenyl) sulfonium cation
C112: two (pentafluorophenyl groups) right-the methoxyphenyl sulfonium cation
C113: two (right-chlorphenyl) right-the fluorophenyl sulfonium cation
C114: two (right-trifluoromethyl) phenyl sulfonium cation
C115: three (3, the 4-difluorophenyl) sulfonium cation
C116: three (-chlorphenyl) sulfonium cation
C117: two (m-trifluoromethyl phenyl) phenyl sulfonium cation
In second embodiment, anionic example comprises sulfonate ion, sulfinic acid radical ion, carboxylic acid ion (for example benzoyl formic acid radical ion), borate ion, halogen ion (F -, Cl -, Br -, I -), sulfate ion (SO 3 2-), hydrogen sulfate ion (HSO 3 -), hexafluorophosphoricacid acid ions (PF 6 -), tetrafluoroborate ion (BF 4 -) or perchlorate (ClO 4 -).Preferred sulfonate ion and benzoyl formic acid radical ion, and sulfonate ion most preferably.
Shown below is anionic example:
A501: trifluoromethayl sulfonic acid radical ion
A502: right-the toluenesulfonic acid radical ion
A503: tetrafluoroborate ion
A504: hexafluorophosphoricacid acid ions
A505: benzoate anion ion
A506:2,4,6-tri-methyl p-toluenesulfonate radical ion
A507: pyruvic acid radical ion
A508: benzene sulfonic acid radical ion
A509: benzoyl formic acid radical ion
A510: neighbour-sulfo group benzimide negative ion
A511: benzenesulfinic acid radical ion
A512:1-naphthalene sulfonic acids radical ion
A513: phenyl-pentafluoride sulfonate ion
A514: perfluorinated butane sulfonate ion
A515: perchlorate
A516: trifluoroacetic acid radical ion
A517: thiophenyl sulfonate ion
A518: right-the acetylbenzoic acid radical ion
A519: bromide ion
A520: right-the hydroxy benzene sulfonic acid radical ion
A521: diphenyl glycolic acid radical ion
A522:2,4,6-triisopropylbenzene sulfonate ion
A523: hydrogen sulfate ion
A524: trichloroacetic acid ion
A525: adjacent carboxyl benzene sulfonic acid radical ion
A526: dicyclo [2,2,1] heptane-2-carboxylic acid ion
A527: Loprazolam radical ion
A528: right-methylthio phenyl formoxyl formate ion
A529: right-the toluenesulfinic acid radical ion
A530: two (benzenesulfonyl) amine negative ion
The A531:Parmitate ion
A532: right-the chlorobenzenesulfonic acid radical ion
A533: right-the trifluoromethylbenzoic acid radical ion
A534:2-naphthalene sulfonic acids radical ion
A535:1,2-dioxo-1,2-dihydronaphthalene-4-sulfonate ion
A536: benzenesulfonyl mesyl amine negative ion
A537:7,7-dimethyl-2-oxo dicyclo [2,2,1] heptan-1-base methanesulfonate ion
A538: dichloro-acetate ion
Be not particularly limited for sulfonium cation and anionic combination.Shown below is sulfonium cation and anionic salt example.Following example is meant the sequence number of sulfonium cation (C) and carboxylic acid ion (A).For example, (201) C101A501 is meant trifluoromethanesulfonic acid (A501) three (-fluorophenyl) sulfonium (C101).
(201)C101·A501 (202)C101·A502 (203)C101·A503
(204)C101·A504 (205)C101·A505 (206)C101·A506
(207)C101·A507 (208)C101·A508 (209)C102·A501
(210)C102·A502 (211)C102·A503 (212)C102·A504
(213)C102·A509 (214)C102·A510 (215)C102·A511
(216)C102·A512 (217)C102·A506 (218)C102·A513
(219)C102·A514 (220)C102·A515 (221)C102·A516
(222)C102·A517 (223)C102·A518 (224)C102·A519
(225)C103·A520 (226)C103·A504 (227)C103·A521
(228)C103·A522 (229)C103·A523 (230)C103·A524
(231)C104·A501 (232)C104·A502 (233)C104·A503
(234)C104·A504 (235)C104·A518 (236)C104·A525
(237)C104·A526 (238)C104·A527 (239)C105·A501
(240)C105·A508 (241)C105·A503 (242)C105·A515
(243)C105·A528 (244)C105·A510 (245)C105·A529
(246)C105·A512 (247)C105·A530 (248)C105·A513
(249)C105·A514 (250)C105·A531 (251)C106·A502
(252)C106·A504 (253)C106·A521 (254)C106·A522
(255)C106·A501 (256)C106·A524 (257)C107·A501
(258)C107·A532 (259)C107·A503 (260)C107·A504
(261)C107·A533 (262)C107·A534 (263)C107·A535
(264)C108·A501 (265)C108·A502 (266)C108·A504
(267)C108·A515 (268)C108·A528 (269)C108·A510
(270)C108·A529 (271)C108·A512 (272)C108·A536
(273)C108·A513 (274)C108·A537 (275)C104·A521
(276)C104·A522 (277)C104·A538 (278)C109·A501
(279)C109·A502 (280)C109·A503 (281)C109·A504
(282)C109·A533 (283)C109·A534 (284)C109·A513
(285)C109·A522 (286)C110·A501 (287)C110·A502
(288)C111·A501 (289)C112·A527 (290)C113·A501
(291)C113·A502 (292)C113·A503 (293)C114·A514
(294)C114·A502 (295)C114·A504
Anion base can be contained in the polymkeric substance.The main chain of preferred polymers is a hydrocarbon.
Preferred polymers comprises the repetitive by following formula (IV) expression:
Figure A20041006367500481
In the formula (IV), R 4For hydrogen or contain the alkyl of 1 to 6 carbon atom, L 3Be singly-bound or divalent linker, and A 1It is anion base.
Preferred T 4Be hydrogen or methyl.
Preferred L 3For singly-bound or be selected from-CO--O-,-NH-, arlydene, the divalent linker of alkylidene and combination thereof.
Preferred A 1For being selected from sulfonate ion, sulfinic acid radical ion, carboxylic acid ion, the anion base of borate ion and halide ion.
Shown below is example by the repetitive of formula (IV) expression:
Figure A20041006367500482
Combination for sulfonium cation and repetitive is not particularly limited.Shown below is the example that contains the repetitive of sulfonium salt.Following example is meant the sequence number of sulfonium cation (C) and repetitive (IV):
IV-1·C107 IV-1·C108 IV-1·C106 IV-1·C101 IV-1·C102
IV-1·C103 IV-1·C113 IV-2·C104 IV-2·C105 IV-3·C102
IV-3·C101 IV-4·C115 IV-4·C116 IV-4·C102 IV-4·C117
The homopolymer that polymkeric substance can be made up of the repetitive that contains sulfonium salt.Polymkeric substance can also be the multipolymer that comprises two or more different repeat units that contain sulfonium salt.Polymkeric substance can also be the multipolymer that comprises the repetitive that contains sulfonium salt and other repetitive.
Preferred other repetitive is by formula (III) expression of first embodiment recited above.
Example for the multipolymer that relates to the repetitive (IV) that contains sulfonium salt and other repetitive (III) shown below:
CP101：-(IV-3·C102)- -(III-2)-
CP102：-(IV-3·C101)- -(III-2)-
CP103：-(IV-1·C102)- -(III-1)-
CP104：-(IV-1·C101)- -(III-1)-
Based on the total solid content of image formation layer, the amount that image formation layer contains as the salt of the sulfonium cation of polymerization initiator and carboxylic acid ion is preferably 0-1 to 50 weight %, 0.5 to 30 weight % more preferably, and most preferably be 1 to 20 weight %.
Can be used in combination two or more polymerization initiators of second embodiment.The polymerization initiator of second embodiment can be used in combination with the polymerization initiator of (above-mentioned) first embodiment.The polymerization initiator of first and second embodiments can be used in combination with other polymerization initiator (first embodiment is described).Under the situation that the polymerization initiator and other the polymerization initiator of first and second embodiments is used in combination, based on the total amount of polymerization initiator, preferably the amount of other polymerization initiator is lower than 30 weight %, and more preferably less than 10 weight %.
[infrared absorbing agents]
By being 760 to 1 with wavelength, the infrared laser beam of 200nm scanning galley and with the lithographic printing plate-use infrared ray exposure of pre-sensitizing.Thereby it is 760 to 1 that preferred infrared absorbing agents has absorbing wavelength, the function of the infrared laser beam of 200nm.
Infrared absorbing agents also can have the function that light is converted to heat.The heat energy that forms can decompose polymerization initiator (free radical precursor) to generate free radical, and it further causes polyreaction.
Infrared absorbing agents also has other function as infrared sensitizer, and it can convert light to chemical energy, and it excites polymerization initiator, to cause polyreaction.
Infrared absorbing agents can have two or more functions recited above.
Preferred infrared absorbing agents is an infrared absorbing dye.Infrared absorbing agents can be purchased.Infrared absorbing dye is described in " Handbook of Dyes (Japanese) ", and 1970, edit by Association of OrganicSynthetic Chemistry.
The example of infrared absorbing dye comprises azo dyes, the bimetallic salt complex azo dyes, the pyrazolone azo dyes, naphthoquinone dyestuff (is described in Jap.P. and discloses 58 (1983)-112793 temporarily, 58 (1983)-224793,59 (1984)-48187,59 (1984)-73996,60 (1985)-52940 and 60 (1985)-63744), anthraquinone dye, phthalocyanine dye (be described in Jap.P. and disclose 11 (1999)-235883) temporarily, squarilium dyestuff (be described in Jap.P. and disclose 58 (1983)-112792) temporarily, pyrylium dyestuff (United States Patent (USP) 3,881,924,4,283,475, Jap.P. discloses 57 (1982) 142645 temporarily, and 58 (1983)-181051,58 (1983)-220143,59 (1984)-41363,59 (1984)-84248,59 (1984)-84249,59 (1984)-146063,59 (1984)-146061, Jap.P. discloses 5 (1993)-13514 and 5 (1993)-19702), carbonium dye, quinoneimine dye and methine dyes (be described in Jap.P. and disclose 58 (1983)-173696,58 (1983)-181690 and 58 (1983)-194595) temporarily.
Preferred methine dyes.More preferably cyanine dye (be described in BrP 434,875, United States Patent (USP) 4,973,572, Jap.P. disclose 58 (1983)-125246 temporarily, 59 (1984)-84356,59 (1984)-216146 and 60 (1985)-78787).
Define cyanine dye by following formula:
(cyanine dye)
Bo-Lo＝Bs
In the formula, Bs is an alkalescence nuclear, and Bo is the alkalescence nuclear of form, and the methine chain be made up of the odd number methine of Lo.
In the infrared absorption methine dyes, preferred Lo is the methine chain of being made up of 7 methines.
Methine placed in the middle (in-position) can contain substituting group.Substituent example comprises halogen atom, diphenylamino ,-O-R ,-S-R ,-NH-R and 1-pyridinio base.
R is aliphatic group (preferably containing 1 to 12 carbon atom), aromatic group (preferably containing 6 to 12 carbon atoms) and heterocyclic radical (preferably containing 1 to 12 carbon atom).
The 1-pyridinio base can contain substituting group or phase pair anion.Substituent example comprises alkyl, aryl, amino, the amino of replacement and halogen atom.Opposite anionic example comprises halide ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions and aryl sulfonic acid radical ion.
With the methine of centre (in-position) adjacent two methines can contain substituting group, as contain hydrocarbon (aliphatic series or the aromatics) base of 1 to 12 carbon atom.Two substituting groups be can merge and five-membered ring or hexatomic ring formed.
Other methine of methine chain can contain substituting group, as contains hydrocarbon (aliphatic series or the aromatics) base of 1 to 12 carbon atom.But preferably other methine does not have substituting group.
Preferred two alkalescence nuclears have the five-ring heterocycles that contains at least one nitrogen-atoms.Preferred hydrocarbons (aliphatic series or aromatics) base is connected with nitrogen-atoms.Alkyl can contain substituting group.Substituent example comprises alkoxy, carboxyl and the sulfo group that contains 1 to 12 carbon atom.
The five-ring heterocycles (wherein nitrogen-atoms is in the 1-position) that preferably contains at least one nitrogen-atoms is connected with the 1-position of methine chain at heterocycle.The five-ring heterocycles that preferably contains at least one nitrogen-atoms contains sulphur atom or is contained the carbon atom of two alkyl (dimethylated methylene base) of 1 to 12 carbon atom in the replacement of 3-position.Preferably contain the five-ring heterocycles of at least one nitrogen-atoms and aromatic ring (for example phenyl ring, naphthalene nucleus) condensation.Preferred condensation aromatic ring between pentacyclic 4-position and 5-position.Aromatic ring can contain substituting group.Substituent example comprises hydrocarbon (aliphatic series or aromatics) base, and halogen atom contains the alkoxy of 1 to 12 carbon atom, acyl group and contain the haloalkyl of 1 to 12 carbon atom.
Cyanine dye can have the phase pair anion.The molecular structure of cyanine dye can contain anion base and replace the phase pair anion as substituting group.Opposite anionic example comprises halide ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions and sulfonate ion.Preferred perchlorate, hexafluorophosphoricacid acid ions and aryl sulfonic acid radical ion.
Shown below is the example of cyanine dye:
Figure A20041006367500521
Figure A20041006367500531
Can be with infrared absorption pigment as infrared absorbing agents.
Pigment is described in " Handbook of Color Index (CI) ", " Latest Handbook ofpigments (Japan) ", 1977, edit " Latest Application Technology of Pigment (Japanese) ", 1986 by Japan Association of Pigment Technology, publish by CMC, " Technology of Printing Ink (Japanese) ", 1984, publish by CMC.
Pigment comprises mineral black, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, blue pigment, viridine green, fluorescent pigment, metallic powdery pigment, combination of polymers pigment, azo lake pigment, condensed azo pigment, chelating AZO pigments, phthalocyanine color, anthraquinone pigment ， perylene dye, perinone pigment, thioindigo color, quinacridone pigment ， triazine dioxin pigment, isoindolinone pigment, quinolinone pigment, dyeing mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, inorganic pigment and carbon black.Carbon black is most preferred infrared absorption pigment.
Infrared absorption pigment can carry out surface treatment.The surface-treated example comprises the disposal route with resin or wax coating surface, to the method for surface adhesion surfactant, with the method for reactive material (for example, silane coupling agent, epoxy compound, polyisocyanate) in conjunction with surface of pigments.Surface treatment is described in " Characteristics and Applications of Metal Soap (Japanese) ", edit by Saiwai Shobo, " Technology of Printing Ink (Japanese) ", 1984, publish by CMC, " LatestApplication Technology of Pigment (Japanese) ", 1986, publish by CMC.
The average particle size particle size of preferred pigments is 0.01 to 10 μ m, 0.05 to 1 μ m more preferably, and most preferably be 0.1 to 1 μ m.Regulate average particle size particle size, to improve stability or the formation uniform layer of granules of pigments in coating solution.
Can pass through known process for dispersing dispersed color, described method is generally used for the preparation of ink or toner.Dispersion machine comprises ultrasonic dispersing machine, sand mill, attitor, pearl mill, super grinding machine, bowl mill, homo-mixer, dispersion machine, KD mill, colloid mill, Dai Nuomo, triple-roller mill and pressure kneader (needer).Process for dispersing is described in " Latest Application Technology ofPigment (Japanese) ", and 1986, publish by CMC.
Based on the total amount of image formation layer, the amount of the infrared absorbing agents that the preferred image cambium layer contains is 0.1 to 20 weight %, and 1 to 10 weight % more preferably.
Image formation layer can comprise two-layer or multilayer, and one deck wherein can contain infrared absorbing agents, and other the layer can contain other component, as polymerization initiator, polymerizable compound and binder polymer.
Preferably will be adjusted to 0.3 to 1.2 according to the absorbance log that method for reflection records at maximum absorption wavelength (760 to 1, the wavelength region may of 200nm in), and more preferably 0.4 to 1.1.Regulate absorbance log, to carry out uniform polyreaction at image formation layer along thickness direction, it improves the film strength of image-region and the bounding force between carrier and the image-region.
The amount by regulating infrared absorbing agents and the thickness of image formation layer, can control chart as cambial absorbance log.Can determine absorbance log according to conventional methods.For example, can determine absorbance log by following method: go up at reflectivity carrier (as aluminium sheet) and form image formation layer (having the thickness that is adjusted to the dried thickness that requires in the lithographic plate); With measure reflection density by opacimeter.Can also measure absorbance log according to the method for reflection that uses integrating sphere by spectrophotometer.
[polymerizable compound]
Preferred polymerizable compound is an alkene formula unsaturated polymerizable compound, and it contains at least one alkene formula unsaturated double-bond.Alkene formula unsaturated double-bond can cause addition polymerization.Preferred polymerizable compound contains two or more alkene formula unsaturated links.Preferred alkene formula unsaturated double-bond is present in the end of polymerizable compound molecular structure.
Polymerizable compound can be the form of oligomer (dimer, tripolymer, the tetramer) or performed polymer.
Preferred polymerizable compounds is unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid), its ester or its acid amides.More preferably polymerizable compound is the ester of polyvalent alcohol and unsaturated carboxylic acid or the acid amides of aliphatic polyamine and unsaturated carboxylic acid.
Unsaturated carboxylic acid can contain substituting group, as nucleophilic group (for example, hydroxyl, amino, sulfydryl), or cancellation group (as halogen atom, tosyloxy).
The addition reaction product of isocyanates or epoxy compound and unsaturated carboxylic acid can also be used as polymerizable compound.Can also be with unsaturated carboxylic acid anhydrides as polymerizable compound.The reaction product of passing through to use undersaturated phosphoric acid, styrene or vinyl ether to replace unsaturated carboxylic acid to form can also be used as polymerizable compound.
The example of acrylate comprises ethylene glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, the diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, isocyanic acid three (acryloxy second) ester and polyacrylic acid ester oligomer.
The example of methacrylate comprises: dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triethyleneglycol ester, the dimethacrylate DOPCP, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, Ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, dimethacrylate hexanediol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, two [right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethanes and two [right-(3-methacryloxy ethoxy) phenyl] dimethylmethane.
The example of itaconate comprises two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acid 1,3 butylene glycol esters, two itaconic acids 1,4-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid pentaerythritol esters and four itaconic acid sorbitol esters.
The example of crotonates comprises two crotonic acid glycol esters, two crotonic acids 1,4-butanediol ester, two crotonic acid pentaerythritol esters and four crotonic acid sorbitol esters.
The example of iso-crotonic acid ester comprises two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters and four iso-crotonic acid sorbitol esters.
The example of maleate comprises two maleic acid glycol esters, two maleic acid triethyleneglycol ester, two maleic acid pentaerythritol esters and four maleic acid sorbitol esters.
Other polymerizable ester is described in Jap.P. and discloses 46 (1971)-27926, and 51 (1976)-47334, Jap.P. discloses 57 (1982)-196231 temporarily, and 59 (1984)-5240,59 (1984)-5241,1 (1989)-165613 and 2 (1990)-226149.
The example of acid amides comprises di-2-ethylhexylphosphine oxide (acrylamide), di-2-ethylhexylphosphine oxide (Methacrylamide), 1,6-hexa-methylene two (acrylamide), 1,6-hexa-methylene two (Methacrylamide), Diethylenetriamine four (acrylamide), xylylene two (acrylamide) and xylylene two (Methacrylamide).
Other polymerizable acid amides is described in Jap.P. and discloses 54 (1979)-21726.
Can also will contain the carbamate compounds of alkene formula unsaturated link as the polymerizable compounds.Polymerisable carbamate compounds is described in Jap.P. and discloses 48 (1973)-41708.By in its molecule, contain the polyisocyanate compounds of two or more isocyanate group with by CH 2=CRCOOCH 2The addition reaction of the unsaturated alcohol of CHROH (wherein R is hydrogen or methyl) expression can be synthesized the carbamate compounds that contains two or more alkene formula unsaturated groups.
Polymerizable compound comprises that further the urethanes acrylate (is described in the interim patent disclosure 51 (1976)-37193 of Japan, Jap.P. discloses 2 (1991)-16765,2 (1991)-32293), the carbamate compounds that contains ethylene oxide unit (is described in Jap.P. and discloses 56 (1981)-17654,58 (1983)-49860,62 (1987)-39417,62 (1987)-39418), the polymerizable compound that is used for addition polymerization that contains amino or sulfide structure (is described in the interim patent disclosure 63 (1988)-260909 of Japan, 63 (1988)-277653,1 (1990)-105238).
Polymerizable compound also comprises polyacrylate, (be described in the interim patent disclosure 48 (1973)-64183 of Jap.P. by epoxy resin and the epoxy acrylate that the reaction of (methyl) acrylic acid forms, Jap.P. discloses 49 (1974)-43191,52 (1977)-30490), vinyl phosphonate ester compounds (being described in the interim patent disclosure 2 (1990)-25493 of Jap.P.).Perfluoroalkyl compound (being described in the interim patent disclosure 61 (1886)-22048 of Jap.P.)).
Other polymerizable compound is described in Jap.P. and discloses 46 (1971)-43946, and 1 (1990)-40336 and 1 (1990)-40337.
Polymerizable compound may further include and is described in Journal of Japan Adhesive Society, Vol.20, No.7, photocurable monomer and oligomer in the 300-308 page or leaf (1984).
Can be used in combination two or more polymerizable compounds.
Preferred polymerizable compound contains two or more unsaturated groups in a molecule, to improve susceptibility.Preferred polymerizable compound contains three or above unsaturated group, to improve the intensity in image (i.e. sclerosis) zone.Can be used in combination two or more polymerizable compounds, to regulate susceptibility and intensity.
According to dissolving or cambial other component of distributed image generation (for example, modified polyvinyl alcohol, infrared absorbing agents, polymerization initiator), select polymerizable compound.Sometimes the polymerizable compound of low-purity or two or more polymerizable compounds are dissolving or are disperseing to have advantage aspect other component.
Specific molecular structure can be introduced in the polymerizable compound, to improve for example bounding force between carrier or the overlayer of image formation layer and other layer.
Polymerizable compound is preferably with the amount of 5 to 80 weight %, and more preferably is contained in the image formation layer with the amount of 25 to 75 weight %.
[binder polymer]
The preferred adhesive polymkeric substance is linear organic polymer, and it can form coated film.
The example of polymkeric substance comprises poly-(methyl) acrylic acid, poly-(methyl) acrylate, poly-(ethene butyral), polyurethane, polyamide, polyethers (epoxy resin), polystyrene and line style varnish polyphenyl.
The preferred adhesive polymkeric substance is crosslinkable, to strengthen coated film.Binder polymer can contain crosslinkable groups (for example, alkene formula unsaturated link) in its main chain or side chain.Can crosslinkable groups be introduced binder polymer by copolymerization.
It is poly--1 that the examples of polymer that contains crosslinkable groups in main chain comprises, the 4-butadiene is poly--1,4-isoprene, natural or synthetic rubber.
The polymkeric substance that preferably contains crosslinkable groups in side chain is the polymkeric substance of acrylic or methacrylic acid esters or acid amides, and wherein the residue of ester or acid amides (COOR or-R of CONHR) contains alkene formula unsaturated link.
The example that contains the residue (corresponding to R recited above) of alkene formula unsaturated link comprises-(CH 2) nCR 1=CR 2R 3,-(CH 2O) nCH 2CR 1=CR 2R 3,-(CH 2CH 2O) nCH 2CR 1=CR 2R 3,-(CH 2) nNH-CO-O-CH 2CR 1=CR 2R 3,-(CH 2) n-O-CO-CR 1=CR 2R 3With-(CH 2CH 2O) n-X (wherein, R 1, R 2And R 3Be hydrogen independently of one another, halogen atom contains the alkyl of 1 to 20 carbon atom, aryl, alkoxy or aryloxy group, R 1And R 2Or R 3Can be in conjunction with forming ring, n is 1 to 10 integer, X is the cyclopentadienyl group residue).
The example of ester residue comprises-CH 2CH=CH 2(be described in Jap.P. and disclose 7 (1995)-21633) ,-CH 2CH 2O-CH 2CH=CH 2,-CH 2C (CH 3)=CH 2,-CH 2CH=CH-C 6H 5,-CH 2CH 2-NHCOO-CH 2CH=CH 2With-CH 2CH 2O-X (wherein X is the cyclopentadienyl group residue).
The example of amide residues comprises-CH 2CH=CH 2,-CH 2CH 2O-X (wherein X is the cyclopentadienyl group residue) and-CH 2CH 2-OCO-CH=CH 2
Crosslinkable binder polymer can be by forming crosslinked the sclerosis between polymkeric substance.Crosslinked can formation by addition polymerization, addition polymerization is to add free radical (the growth free radical in the polyreaction of polymerization initiator free radical or polymerizable compound) by the crosslinkable groups to binder polymer, directly between polymkeric substance, cause, or in the polyreaction of polymerizable compound, cause.Crosslinked can also and formation between polymer molecule by free polymer readical reaction, described free polymer readical are to be removed an atom (for example, the hydrogen on the carbon atom adjacent with crosslinkable groups) and formed by polymkeric substance.
Based on the binder polymer of 1g, the amount of the crosslinkable groups that the preferred adhesive polymkeric substance contains is 0.1 to 10.0 mM, 1.0 to 7.0 mMs more preferably, and most preferably be 2.0 to 5.5 mMs.Can pass through iodometric titration, measure the amount of crosslinkable groups (unsaturated double-bond that for example, is used for Raolical polymerizable).Regulate the amount of crosslinkable groups, with the susceptibility and the stability of the lithographic plate of control pre-sensitizing.
The preferred adhesive polymer dissolution or be scattered in ink or wetting water in, developed image cambium layer (removing unexposed area) when on printing machine, developing.The preferred adhesive polymkeric substance is hydrophobic, to be dissolved or dispersed in the ink.The preferred adhesive polymkeric substance is a water wettability, to be dissolved or dispersed in the wetting water.Can be used in combination hydrophilic adhesive polymkeric substance and hydrophobic adhesive polymkeric substance among the present invention.
Hydrophilic adhesive polymkeric substance possess hydrophilic property group.The example of hydrophilic radical comprises hydroxyl, carboxyl, carboxylic acid ester groups, hydroxyethyl, polyoxyethylene groups, hydroxypropyl, polyoxypropylene base, amino, aminoethyl, aminopropyl, ammonium, acylamino-, ethyloic, sulfo group and phospho-.
The example of hydrophilic polymer comprises polysaccharide (for example, Arabic gum, starch derivative, carboxymethyl cellulose, its sodium salt, cellulose acetate, mosanom), protein (for example, casein, gelatin), polyvinyl acetate, poly, polystyrene, poly hydroxy ethyl acrylate, Poly(Hydroxyethyl Methacrylate), the polymethylacrylic acid hydroxypropyl acrylate, polyacrylic acid hydroxypropyl acrylate, polymethylacrylic acid hydroxy butyl ester, the polyacrylic acid hydroxy butyl ester, polyglycol, poly-hydroxyl propylene, polyvinyl alcohol (PVA), partially hydratedly (preferably be not less than 60 weight %, more preferably be not less than 80 weight %) polyvinyl acetate, polyvinyl formal, poly-(vinyl butyral), polyvinylpyrrolidone, polyacrylamide, PMAm, poly-(N hydroxymethyl acrylamide), be dissolved in the nylon in the alcohol, 2, the polyethers of 2-two (hydroxyphenyl) propane and chloropropylene oxide, and multipolymer.The example of multipolymer comprises vinyl acetate-maleic acid, styrene-maleic acid copolymer.
The weight-average molecular weight of preferred adhesive polymkeric substance is not less than 5,000, and more preferably 10,000 to 300,000.The number-average molecular weight of preferred adhesive polymkeric substance is not less than 1,000, and more preferably 2,000 to 250,000.The polydispersity index of preferred polymers (ratio of weight-average molecular weight and number-average molecular weight) is 1.0 to 10.
At binder polymer is under the situation of multipolymer, and multipolymer can be atactic polymers, block polymer or graft polymer.Preferred copolymer is an atactic polymers.
Can come the composite adhesives polymkeric substance according to known method.In the synthetic method of polymkeric substance, use solvent usually.The example of solvent comprises ether (for example, tetrahydrofuran), and halogenated hydrocarbons (for example, ethylene dichloride), ketone (for example, cyclohexanone, methyl ethyl ketone, acetone), alcohol is (for example, methyl alcohol, ethanol, 1-methoxyl-2-propyl alcohol), ether (for example, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether), ester (for example, acetate 2-methoxyl ethyl ester, acetate 1-methoxyl-2-propyl ester, ethyl acetate, methyl lactate, ethyl lactate), acid amides (for example, dimethyl formamide, N,N-dimethylacetamide), hydrocarbon (for example, toluene), sulfoxide (for example, dimethyl sulfoxide) and water.Can be used in combination two or more solvents.
Known polymerization initiator such as azo initiator or peroxide initiator can be used for the synthetic of binder polymer.
Can be used in combination two or more binder polymers.
Based on the total solid content of image formation layer, the amount of the binder polymer that contains in the preferred image cambium layer is 10 to 90 weight %, 20 to 80 weight % more preferably, and most preferably be 30 to 70 weight %.Regulate the amount of binder polymer, with the intensity of improving image and the formation that promotes image.
The weight ratio of preferred polymerizable compound and binder polymer is 1/9 to 7/3.
[microcapsules]
Preferred polymerizable compound is contained in the microcapsules, and the preferred adhesive polymkeric substance is placed in the outside of microcapsules.
The image formation layer that contains microcapsules is described in Jap.P. and discloses 2001-277740 and 2001-277742 temporarily.
Can prepare microcapsules according to following method: condensing method (is described in United States Patent (USP) 2,800,457,2,800,458), interfacial polymerization method is described in United States Patent (USP) 3,287,154, Jap.P. discloses 38 (1963)-19574, and 42 (1967)-446), the polymer deposition method (is described in United States Patent (USP) 3,418,250,3,660,304), use isocyanates-polyol (to be described in United States Patent (USP) 3 as the method for wall material, 796,669), use isocyanates (to be described in United States Patent (USP) 3,914 as the method for wall material, 511), use urea-formaldehyde or urea-formaldehyde-resorcinol (to be described in United States Patent (USP) 4,001,140 as the method for wall material, 4,087,376,4,089,802), use melamine formaldehyde resin or hydroxylated cellulose (to be described in United States Patent (USP) 4,025 as the method for wall material, 445), the method of monomer in-situ polymerization (be described in Jap.P. and disclose 36 (1961)-9163,51 (1976)-9079), the jet drying method (is described in BrP 930,422, United States Patent (USP) 3,111,407), disperse cooling means (to be described in BrP 952 with electrophoresis, 807,967,074).
The housing of preferred microcapsules has three-dimensional crosslinking structure, and it can use solvent swell.The housing of preferred microcapsules comprises polyureas, polyurethane, polyester, polycarbonate, polyamide, its multipolymer or its potpourri.More preferably housing comprises polyureas, polyurethane, its multipolymer or its potpourri.Alkene formula unsaturated link can be introduced in the polymkeric substance of microcapsules housing.
The average particle size particle size of preferred microcapsules is 0.01 to 3.0 μ m, 0.05 to 2.0 μ m more preferably, and most preferably be 0.10 to 1.0 μ m.Regulate average particle size particle size, with the sharpness of raising image and the stability of microcapsules.
Can melt microcapsules with heat.In preparation presensitized lithographic version, the content in the microcapsules can leak out or enter the housing of microcapsules.Content in the microcapsules can react with the hydrophilic resin or the low molecular weight compound that are contained in the image formation layer.Can in image formation layer, contain two or more different microcapsules.Have at different microcapsules under the situation of different thermal response functional groups, microcapsules can react each other.Preferably carry out the reaction of microcapsules, to melt microcapsules, it can form stable image.
Based on the total solid content of image formation layer, preferred microcapsules are to be not less than 50 weight %, and more preferably the amount with 60 to 95 weight % is contained in the image formation layer.Regulate the amount of microcapsules, print on the printing machine carrying out, to improve susceptibility and to improve printability resistance.
In the preparation of microcapsules, in the dispersion of microcapsules, add solvent.The content of the housing of preferred solvent swelling microcapsules and dissolving microcapsules.Solvent with swelling microcapsules housing function can promote content to diffuse into the outside of microcapsules.Solvent with swelling microcapsules housing function is according to the dispersion medium of microcapsules, the housing polymkeric substance of microcapsules, and the thickness of housing and the content of microcapsules are determined.Have the housing of crosslinked urea or polyurethane at microcapsules and be scattered under the situation in the water, preferably with following material as solvent: alcohol (for example, methyl alcohol, ethanol, propyl alcohol, the tert-butyl alcohol), ether (for example, tetrahydrofuran, propylene glycol monomethyl ether, ethylene glycol diethyl ether, glycol monoethyl ether), acetal, ester (for example, methyl lactate, lactic acid acetate, gamma-butyrolacton), ketone (for example, methyl ethyl ketone), dibasic alcohol, polyol, acid amides (for example, dimethyl formamide, N, the N-dimethyl acetamide), amine or fatty acid.These solvents can be purchased.Can be used in combination two or more solvents.Solvent can with a kind of liquid mixing (precondition is that the potpourri of liquid and solvent can be dissolved in the dispersion of microcapsules) that is insoluble to dispersion of microcapsules.
Preferred solvent is with the amount of 5 to 95 weight %, more preferably with the amount of 10 to 90 weight %, and most preferably is contained in the coating solution of image formation layer with the amount of 15 to 85 weight %.
[surfactant]
Image formation layer can contain surfactant.Surfactant has the function (the particularly incipient stage of development) of developing on the promotion printing machine.Surfactant has the other function of improving the coating surface condition.Surfactant is categorized as non-ionic surfactant, anionic surfactant, cationic surfactant, zwitterionic surfactant and fluorinated surfactant.
The example of non-ionic surfactant comprises polyoxyalkylene alkyl, the polyoxyalkylene alkyl phenyl ether, the polystyrene-based phenyl ether of polyoxyalkylene, polyoxyalkylene polyoxypropylene alkyl ether, the partial ester of glycerine and fatty acid, the partial ester of anhydro sorbitol and fatty acid, the partial ester of pentaerythrite and fatty acid, the monoesters of propylene glycol and fatty acid, the partial ester of sucrose and fatty acid, the partial ester of polyoxyalkylene sorbitan and fatty acid, the partial ester of polyoxyalkylene D-sorbite and fatty acid, the ester of polyglycol and fatty acid, the partial ester of polyglycerol and fatty acid, castor oil with the polyoxyalkylene reaction, the partial ester of polyoxyalkylene glycerine and fatty acid, the aliphatic series diglycollic amide, N, N-two (2-hydroxyalkyl) amine, the polyoxyalkylene alkyl amine, the ester of triethanolamine and fatty acid, the trialkylamine oxide, polyglycol and 1,2 ethylene glycol/propylene glycol copolymers.Preferred polyoxyalkylene recited above is a polyoxymethylene, polyoxyethylene, polyoxypropylene or polyoxy butylene.
The example of anionic surfactant comprises the salt of fatty acid; abietate; the hydroxyl paraffin sulfonate; paraffin sulfonate; the salt of dialkyl sulfosuccinate succinate; linear alkylbenzene sulfonate; branch-alkylbenzene sulfonate; alkylnaphthalene sulfonate; alkyl phenoxy polyoxygenated allylsulfonate; the salt of polyoxyalkylene alkyl sulfo group phenyl ether; the sodium salt of N-methyl-N-oil base taurine; the disodium salt of N-alkyl sulfosuccinic acid monoamides; mahogany sulfonate; tallow sulfate; the sulfuric acid of fatty acid alkyl esters; the salt of alkyl sodium sulfate ester; the salt of the sulfuric ester of polyoxyalkylene alkyl; the salt of the sulfuric ester of glycerine monofatty ester; the salt of the sulfuric ester of polyoxyalkylene alkyl phenyl ether; the salt of the sulfuric ester of polyoxyalkylene styryl phenyl ether; the salt of alkylphosphonate; the salt of the phosphate of polyoxyethylene alkyl ether; the salt of the phosphate of polyoxyalkylene alkyl phenyl ether; the partly-hydrolysed product of phenylethylene/maleic anhydride copolymer; the partly-hydrolysed product of alkene/copolymer-maleic anhydride and the condensation product of naphthalene sulfonate and formalin.Preferred polyoxyalkylene recited above is a polyoxymethylene, polyoxyethylene, polyoxypropylene or polyoxy butylene.
The example of cationic surfactant comprises the derivant of alkylamine salt, quaternary ammonium salt, polyoxyalkylene alkylamine salt, polyethylenepolyamine.
Examples of amphoteric surfactants comprises carboxybetaine, amino carboxylic acid, sulfobetaine, amidosulphuric acid ester and imidazoline.
The example of fluorinated surfactant comprises: anionics (as perfluoroalkyl carboxylate, fluorinated alkyl sulfonate and perfluoroalkyl phosphate), cationics (as the perfluoroalkyl leptodactyline), (as the ethylene oxide adduct of perfluoroalkyl amine oxide, perfluoroalkyl, contain perfluoroalkyl and lipophilic group oligomer, contain the carbamate of perfluoroalkyl and lipophilic group).Fluorinated surfactant is described in Jap.P. and discloses 60 (1985)-168144,62 (1977)-170950,62 (1977)-226143 temporarily.
Can be used in combination two or more surfactants.
Based on the total solid content of image formation layer, preferred surfactant is with the amount of 0.001 to 10 weight %, and more preferably is contained in the image formation layer with the amount of 0.01 to 5 weight %.
[colorant]
Image formation layer can contain colorant, with the image that confirms that the development back forms.Preferred colorant is the dyestuff that big absorbance log is arranged in visible wavelength region.
The example of these dyestuffs comprises oil yellow #101, oil yellow #103, oil-bound distemper #312, glossy dark green BG, oil blue BOS, oil blue #603, glossy black BS, (it is commercially available in Orient ChemicalIndustries for glossy black T-505, Ltd.), Victoria's ethereal blue, crystal violet (C.I.:42,555), methyl violet (C.I.:42,535), ethyl violet, rhodamine B (C.I.:145,170B), peacock green (C.I.:42,000), methylene blue (C.I.:52,015).The dyestuff that is used as colorant is described in Jap.P. and discloses 62 (1987)-293247 temporarily.
Based on the total solid content of image formation layer, preferred colorant is contained in the image formation layer with the amount of 0.01 to 10 weight %.
[printing off reagent]
Image formation layer can contain and prints off reagent, with the image that confirms to form behind the development prior exposure.Preferably printing off reagent is a kind of compound that can cause change color with acid or free radical.Preferably printing off reagent is diphenylmethane dye, triphenhlmethane dye, thiazine dye ， oxazine dye, xanthene dye, anthraquinone dye, iminoquinone dyestuff, azo dyes and azomethine dyes.
Comprise as the dyestuff example that prints off reagent: bright green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose-red, soap (Metanil) Huang, thymol blue, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurine 4B, Alpha-Naphthyl is red, Nile blue 2B, Nile blue A, methyl violet, peacock green, paramagenta, and Victoria's pure blue B OH (HodogayaChemical Co., Ltd.), oil blue #603 (Orient Chemical Industries, Ltd.), and the red #312 of oil-bound distemper (Orient Chemical Industries, Ltd.), oil red 5B (Orient Chemical Industries), the scarlet #308 of oil (Orient Chemical Industries, Ltd.), oil red OG (Orient ChemicalIndustries, Ltd.), oil red RR (Orient Chemical Industries, Ltd.), glossy dark green #502 (Orient Chemical Industries, Ltd.), the red BEH Special of Spiron (HodogayaChemical Co., Ltd.) ,-cresol-purple, cresol red, rhodamine B, rhodamine 6G, sulfo group rhodamine B, the Chinese scholartree Huang, leuco crystal violet, the blue SRB (Cuba) of Pargascript, crystal violet lactone, the peacock green lactone, Bengoyl Leuco Methylene Blue.
As the examples of compounds of printing off reagent comprise 4-right-lignocaine phenyl imino group naphthoquinones, 2-carboxyl anilino--4-is right-lignocaine phenyl imino group naphthoquinones, 2-carboxyl stearyl amino-4-is right-N, N-two (hydroxyethyl) aminophenyl imino group naphthoquinones, 1-phenyl-3-methyl-4-is right-lignocaine phenyl imino group-5-pyrrolinone, 1-betanaphthyl-4-is right-lignocaine phenyl imino group-5-pyrrolinone, P, P '; P "-hexamethyl triaminotriphenyl methylmethane (leuco crystal violet), the amino fluorane of 2-(N-phenyl-N-methylamino)-6-(N-right-tolyl-N-ethyl), 2-anilino--3-methyl-6-(N-ethyl-right-toluidino) fluorane, 3,6-dimethoxy fluorane, 3-(N, the N-lignocaine)-5-methyl-7-(N, N-dibenzyl amino) fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluorane, 3-(N, the N-lignocaine)-6-methyl-7-xylidino fluorane, 3-(N, the N-lignocaine)-6-methyl-7-chlorine fluorane, 3-(N, the N-lignocaine)-the amino fluorane of 6-methoxyl-7-, 3-(N, the N-lignocaine)-7-(4-chloroanilino) fluorane, 3-(N, the N-lignocaine)-7-chlorine fluorane, 3-(N, the N-lignocaine)-7-benzyl fluorane, 3-(N, the N-lignocaine)-7,8-benzo fluorane, 3-(N, the N-dibutylamino)-6-methyl-7-xylidino fluorane, 3-piperidino-6-methyl-7-anilino fluorane, 3-pyloridio-6-methyl-7-anilino fluorane, 3, two (1-ethyl-2 methyl indole-3-yl) 2-benzo [c] furanones of 3-, 3, two (1-butyl-2 methyl indole-3-yl) 2-benzo [c] furanones of 3-, 3, two (right-dimethylamino phenyl)-6-dimethylamino 2-benzo [c] furanones of 3-, 3-(4-lignocaine-2-ethoxyl phenenyl)-3-(1-ethyl-2 methyl indole-3-yl) 4-azepine benzo [c] furanone, 3-(4-lignocaine phenyl)-3-(1-ethyl-2 methyl indole-3-yl) 2-benzo [c] furanone.
Based on the total solid content of image formation layer, preferably print off reagent and be contained in the image formation layer with the amount of 0.01 to 10 weight %.
[polymerization inhibitor]
Image formation layer can contain a spot of polymerization inhibitor, to stop polymerization after the preparation presensitized lithographic and before using presensitized lithographic.
The example of polymerization inhibitor comprises quinhydrones, right-metoxyphenol, two-tert-butyl group-p-Cresol, 1,2,3,-thrihydroxy-benzene (pyrogarol), tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), the aluminium salt of N-nitroso--N-phenylhydroxylamine.
Based on the total solid content of image formation layer, preferred polymerization inhibitor is contained in the image formation layer with the amount of 0.01 to 5 weight %.
[higher fatty acid and acid amides thereof]
Image formation layer can contain higher fatty acid or its acid amides, to stop the influence of airborne oxygen to polyreaction.Oxygen has the function that stops polyreaction.Behind the coating image formation layer, during dry image formation layer, higher fatty acid or its acid amides tend to move to the surface (interface between layer and air) of image formation layer.
Based on the total solid content of image formation layer, preferred higher fatty acid or its acid amides are contained in the image formation layer with the amount of 0.1 to 10 weight %.
[plastifier]
Image formation layer can contain plastifier, develops to improve on the printing machine.
The example of plastifier comprises: phthalic ester (as, repefral, diethyl phthalate; dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate; phthalic acid octyl group capryl ester, dicyclohexyl phthalate, phthalic acid two (tridecyl) ester; butyl benzyl phthalate; diisooctyl phthalate, diallyl phthalate), glycol ester is (for example; dimethyl glycol phthalate; ethyl phthalyl ethyl glycollate, the sweet acetoacetic ester of methyl phthalyl, the sweet acid butyl ester of butyl phthalyl; triethylene glycol dieaprylate); phosphate (for example, tricresyl phosphate, triphenyl phosphate); the binary fatty acid ester (for example; diisobutyl adipate, dioctyl adipate, dimethyl sebacate; dibutyl sebacate; dioctyl azelate, dibutyl maleate), the many ethylene oxidic esters of methacrylic acid; triethyl citrate, glyceryl triacetate and butyl laurate.
Based on the total solid content of image formation layer, preferred plasticizer is contained in the image formation layer with the amount that is no more than 30 weight %.
[inorganic particle]
Image formation layer can contain inorganic particle, to improve the sclerosis film strength in the image-region and to improve on the printing machine in the non-image areas and develop.
The dead matter of particle comprise silicon dioxide, aluminium oxide, magnesium oxide, titania, magnesium carbonate and composition thereof.Particle such as the cataloid dispersion that is purchased can be used as inorganic particle.
The average particle size particle size of preferred inorganic particle is 5nm to 10 μ m, and 0.5 to 3 μ m more preferably.Regulate average particle size particle size, with even and stably discrete particles in image formation layer.Evenly and the particle of stable dispersion can strengthen sclerosis film strength in the image-region, and easily remove non-image areas can on printing machine, develop the time.
Based on the total solid content of image formation layer, preferred inorganic particle to be being no more than the amount of 20 weight %, and more preferably is contained in the image formation layer with the amount that is no more than 10 weight %.
[organic granular]
Image formation layer can contain organic granular (as the calcium alginate particle) and replace inorganic particle recited above.
[low-molecular-weight hydrophilic compounds]
Image formation layer can contain low-molecular-weight hydrophilic compounds, to improve the development on the printing machine.Preferred low-molecular-weight hydrophilic compounds is water miscible organic compound.
The example of water miscible organic compound comprise dibasic alcohol (as, 1,2 ethylene glycol, diglycol, triethylene glycol, propylene glycol, dipropylene glycol, 3 third glycol), its ether, its ester, polyvalent alcohol (as, glycerine, pentaerythrite), amine (as, triethanolamine, diethanolamine, monoethanolamine), its salt, sulfonic acid (as, toluenesulfonic acid, benzene sulfonic acid), its salt, phosphonic acids (as, phenyl-phosphonic acid), its salt, carboxylic acid (as, tartrate, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, amino acid), its salt.
[formation of image formation layer]
Content that can be by dissolving, dispersion or emulsion layer is in solvent, and preparation coating solution and coating prepared solution form image formation layer.
The example of solvent comprises halogenated hydrocarbons (for example, ethylene dichloride), ketone (cyclohexanone for example, methyl ethyl ketone), alcohol (for example, methyl alcohol, ethanol, propyl alcohol, 1-methoxyl-2-propyl alcohol), ether (for example, dimethoxy-ethane, glycol monoethyl ether), ester (for example, acetate (2-methoxyl second) ester, acetate (1-methoxyl-2-third) ester, methyl lactate, ethyl lactate), acid amides is (for example, N,N-dimethylacetamide, dimethyl formamide), tetramethylurea, N-Methyl pyrrolidone, dimethyl sulfoxide, sulfolane, gamma-butyrolacton, toluene and water.
Solid content in the preferred coating solution is 1 to 50 weight %.
Can form image formation layer by being coated with two or more coating solutions that differ from one another.
After the image formation layer drying, the cambial coating weight of preferred image (solid content) is 0.3 to 3.0g/m 2Regulate coating weight, to control the susceptibility and the characteristic of the layer that forms.
Can be coated with method, spin-coating method, spraying process, curtain coating method, dip coating, air knife knife coating, scraper plate rubbing method or rolling method according to rod, the coating image formation layer.
[hydrophilic carrier]
The preferred hydrophilic carrier is the film of dimensionally stable, thin plate or sheet material.
The example of carrier comprises: paper, with polymkeric substance (tygon for example, polypropylene, polystyrene) paper of film laminating, metal is (as aluminium, zinc, copper) plate, polymkeric substance is (as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose-acetate propionate, cellulose acetate-butyrate, cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, polyvinyl acetal) film, the paper of lamination metal, the thin polymer film of lamination metal, carry out the paper of vapor deposited metal, carry out the thin polymer film of vapor deposited metal.Preferred polymer films and sheet metal, more preferably mylar and aluminium sheet, and aluminium sheet most preferably.
Especially preferably carried out the aluminium sheet of anodized.
Aluminium sheet is a kind of pure aluminum plate or alloy sheets, and described alloy sheets comprises key component aluminium and a spot of other metal.The example of other metal comprises Si, Fe, Mn, Co, Mg, Cr, Zn, Bi, Ni and Ti.The amount of preferred these metals is no more than 10 weight %.Be difficult to prepare fine aluminium on the melting technique.Therefore, in fact use the aluminium alloy plate that comprises a small amount of other metal.
The thickness of preferred aluminium sheet is 0.1 to 0.6mm, and more preferably 0.15 to 0.4mm, and most preferably is 0.2 to 0.3mm.
Preferably surface treatment is carried out on the surface of aluminium sheet, as roughened and anodized.Surface treatment has the surface of making and has more hydrophilic function.Surface treatment also has the function of improving the bounding force between carrier and image formation layer.
Can before carrying out surface treatment, carry out ungrease treatment to aluminium sheet.By using surfactant, organic solvent or alkaline aqueous solution carry out ungrease treatment, to remove lip-deep machine oil.
Roughened comprises mechanically roughened processing, electrochemical roughening processing (the electrochemical dissolution surface is to form rough surface) and chemical roughened (the chemical dissolution surface is to form rough surface).
The example of mechanically roughened processing comprises ball grinding method, brushing method, gas mill method and polishing mill method.
The electrochemical roughening processing for example is, in the electrolytic solution that contains sour example hydrochloric acid or nitric acid, adopts the process that plate is applied direct current or alternating current.The electrochemical roughening processing can be used acid mixture, discloses described in 54 (1979)-63902 as Jap.P. temporarily.
After the roughened, can carry out alkali etching to aluminium sheet and handle.Preferred alkaline etch solution is the aqueous solution of potassium hydroxide or NaOH.Alkali etching can carry out neutralisation treatment after handling, and preferably carries out anodized, to improve the wearing quality of carrier after neutralisation treatment.
Electrolyte is used for anodized, to form the porous oxide film.Electrolytical example comprises sulfuric acid, hydrochloric acid, oxalic acid, chromic acid and composition thereof.
Usually under concrete condition, carry out anodized.For example, the concentration of electrolyte solution is that the temperature of 1 to 80 weight %, solution is that 5 to 70 ℃, current density are 5 to 60A/dm 2, voltage is that 1 to 100 volt and electrolysis time are 10 seconds to 5 minutes.
Preferably the thickness of the oxidation film that is formed by anodic oxidation is 1.0 to 5.0g/m 2, and more preferably 1.5 to 4.0g/m 2Regulate thickness, to improve wearing quality.
After the anodized, aluminium sheet further can be carried out hydrophilic treatment.Preferred hydrophilic treatment is that alkali silicate is handled (being described in U.S. Patent Publication 2,714,066,3,181,461,3,280,734 and 3,902,734).In alkali silicate is handled, aluminium sheet be impregnated in the aqueous solution of alkali silicate (for example sodium silicate) or carry out electrolysis therein.Can also carry out hydrophilic treatment by using potassium fluorozirconate (be described in Jap.P. and disclose 36 (1961)-22063) and polyphosphoric acid vinyl acetate (being described in United States Patent (USP) 3,276,868,4,153,461,4,689,272).
The center surface roughness (Ra) of preferred vector is 0.10 to 1.2 μ m.
The color density of preferred vector is 0.15 to 0.65, and it is measured according to reflection density.
[back coating]
Can on the back side of carrier, form back coating.Preferably after carrier carries out surface treatment or forms undercoat, form back coating by coating.
Preferred back coating is a kind of coating (be described in Jap.P. and disclose 5 (1993)-45885) that contains organic polymer temporarily.Back coating can be a kind of coating that comprises metal oxide, and its hydrolysis or polycondensation by the organic or inorganic metallic compound forms (be described in Jap.P. and disclose 6 (1994)-35174) temporarily.Preferred organometallics is an alkoxy-silicon compound, as Si (OCH 3) 4, Si (OC 2H 5) 4, Si (OC 3H 7) 4, Si (OC 4H 9) 4
[undercoat]
Can between carrier and image formation layer or back coating, form undercoat.
Undercoat has the function of thermal barrier.Thermal barrier can prevent that heat (forming by the conversion infrared light) from diffusing to carrier from image formation layer.Therefore, thermal barrier has the function of the thermal efficiency that improves the presensitized lithographic version.In other words, can be by improve the susceptibility of presensitized lithographic version as the thermal barrier of undercoat.
Undercoat also has another kind and improves the function of developing on the printing machine, wherein removes image formation layer in the unexposed area from carrier.
Can form undercoat (be described in Jap.P. and disclose 10 (1998)-282679) by the phosphorus compound that uses reaction to cause the silane coupling agent of addition polymerization or to contain alkene formula unsaturated double-bond temporarily.
The coating weight of preferred undercoat (solid content) is 0.1 to 100mg/m 2, and more preferably 3 to 30mg/m 2
[protective seam]
Can on image formation layer, form protective seam.Protective seam can have the surface function of not swiped of protection image formation layer.Protective seam also has another kind and prevents that oxygen from infiltrating through the function of image formation layer.With the laser beam flying presensitized lithographic version of high illumination the time, protective seam can further have the not frayed effect of protection image formation layer.
The presensitized lithographic version is exposed with infrared ray in air usually, and air contains the oxygen with prevention polyreaction function.Preferred protective seam has and prevents that oxygen or low-molecular-weight alkaline matter from infiltrating through the function of image formation layer.Preferred protective seam has low-permeability for low molecular weight substance.Also preferred protective seam is transparent for infrared ray.Protective seam also has good bounding force for image formation layer.Remove when in addition, preferred protective seam develops on printing machine easily.Protective seam is described in United States Patent (USP) 3,458,311 and Jap.P. disclose 55 (1980)-49729 temporarily.
Preferred protective seam comprise can crystallization water-soluble polymers.The example of water-soluble polymers comprises polyvinyl alcohol (PVA), polyvinylpyrrolidone, acid cellulose derivant, gelatin, Arabic gum and polyacrylic acid.Special preferably polyethylene alcohol (PVA).Polyvinyl alcohol (PVA) has the excellent oxygen that prevents and infiltrates through the function of image formation layer.When can developing on printing machine easily, removes polyvinyl alcohol (PVA).These functions are to be given by the unsubstituted vinyl alcohol units that contains in polyvinyl alcohol (PVA).Alcoholic hydroxyl in the polyvinyl alcohol (PVA) can be replaced by ester bond, ehter bond or acetal bonds, as long as there is the alcoholic hydroxyl of a great deal of to remain in the polyvinyl alcohol (PVA).Polyvinyl alcohol (PVA) can be the multipolymer of vinyl alcohol units and other repetitive.
The saponification degree of preferably polyethylene alcohol is 71 to 100%.The degree of polymerization of preferably polyethylene alcohol is 300 to 2,400.Polyvinyl alcohol (PVA) (for example, PVA-105, PVA-105, PVA-110, the PVA-117 that can be purchased by use, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, L-8, Kuraray Co. Ltd.) forms external coating.
Have the polyvinyl alcohol (PVA) of high saponification degree (the wherein ratio height of unsubstituted vinyl alcohol units) or thick protective seam and have the excellent oxygen that prevents and infiltrate through the function of image formation layer, to improve susceptibility.But, be unnecessary to the extremely low permeability of oxygen.Under normal pressure, preferably to the permeability (cc/m of oxygen in 25 ℃ 2My god) be 0.2 to 20.
Protective seam can contain polyvalent alcohol (as glycerine, dipropylene glycol), and is flexible to improve.Based on the amount of water-soluble polymers, preferred protective seam contains polyvalent alcohol with the amount of 1 to 10 weight %.
Protective seam can contain anionic surfactant (as sodium alkyl sulfate, alkyl sodium sulfonate), amphoteric surfactant (as the salt of alkyl amino carboxylate, the salt of alkyl amino dicarboxylic ester) or non-ionic surfactant (as polyoxyethylene alkyl phenyl ether).Based on the amount of water-soluble polymers, preferred protective seam contains surfactant with the amount of 1 to 10 weight %.。
The thickness of preferred protective seam is 0.1 to 5 μ m, and 0.2 to 2 μ m more preferably.
The protective seam that comprises water-soluble polymers, it is a hydrophilic layer, tends to peel off with image formation layer.If protective seam and image formation layer are peeled off, do not protect image formation layer not to be subjected to the influence of oxygen.Protective seam can further contain acrylic emulsion or insoluble polymer (as vinylpyrrolidone/vinyl acetate copolymer); its amount is 20 to 60 weight % based on water-soluble polymers; to improve the bounding force between protective seam and image formation layer; as Jap.P. disclose temporarily 49 (1974)-70702 and BrP disclose 1; 303,578 is described.The coating protective seam method be described in United States Patent (USP) 3,458,311 and Jap.P. disclose 55 (1980)-49729 temporarily.
Protective seam can have the function as color filter layer.For example, protective seam can contain colorant (preferred water miscible dyestuff), and it is transparent and absorbs other light for infrared ray (being used for image forms).Colorant has reduction not to be reduced ultrared susceptibility for the susceptibility of safety light.
[becoming the step of image exposure]
Become image ground to expose the presensitized lithographic version with infrared ray.Preferably with infrared laser beam scanning presensitized lithographic version.
Preferred ultrared wavelength is 760 to 1,200nm.
The light source of preferred infrared laser beam is solid state laser or semiconductor laser.The power of preferred infrared laser is not less than 100mW.Can use the multiple laser device, to shorten the time shutter.
The time shutter of a preferred pixel is shorter than 20 microseconds.Preferred exposure energy is 10 to 300mJ/cm 2
In the time of on the cylindrical shell that lithographic plate is placed in printing machine, the presensitized lithographic version can become image ground to expose with infrared ray.
Ultrared luminous energy is passed to polymerization initiator by infrared absorbing agents.Infrared absorbing agents as the situation of reagent that light is converted to heat under, give polymerization initiator with the thermal energy transfer of conversion as thermal polymerization.Under the situation of infrared absorbing agents as infrared sensitizing dyestuff, luminous energy is changed into chemical energy, and chemical energy is delivered to the polymerization initiator as Photoepolymerizationinitiater initiater.Infrared absorbing agents can have two or more functions recited above.
Polymerization initiator causes the polyreaction of polymerizable compound in the exposure area.
[step of developing on the printing machine]
After exposure presensitized lithographic version, remove the image formation layer in the unexposed area, lithographic plate is placed on the cylindrical shell of printing machine simultaneously.
On printing machine, in the step of developing, wetting water and oily ink are supplied with to lithographic plate.
Can pass through chemical action, the image formation layer in unexposed area is removed in mechanical force or its combination.Chemical action is given by water (in the wetting water) or oil (in the oily ink).That is, image formation layer is dissolved or dispersed in water or the oil.Mechanical force is given by the cylindrical shell of printing machine.
Behind the image formation layer in removing unexposed area, exposed the hydrophilic surface of carrier, it forms water wettability (non-image) zone.On the other hand, in the exposure area, image formation layer is retained on the hydrophilic carrier, and it is corresponding to hydrophobicity (image) zone.
[print steps]
After developing on the printing machine, in the time of on the cylindrical shell that lithographic plate is placed in printing machine, version printed images offscreen.Thereby, can carry out step of developing and print steps on the printing machine continuously.
In print steps, supply with wetting water and oily ink to lithographic plate.Wetting water adheres to water wettability non-image areas (not exposing with infrared ray), and oily ink adheres to hydrophobicity image-region (exposing with infrared ray).Preferably at first oily ink is supplied with to lithographic plate, polluted the content of the image formation layer in the unexposed area to prevent wetting water.
As mentioned above, in the time of on the cylindrical shell that lithographic plate is placed in printing machine, lithographic plate is developed, and carried out printing process.
Embodiment
Embodiment 1
(preparation of alumina supporter)
The melt of cleaning and casting JIS-A-1050 alloy, it contains Al (99.5 weight % or more than), Fe (0.30 weight %), Si (0.10 weight %), Ti (0.02 weight %), Cu (0.013 weight %) and unavoidable impurities (surplus).In order to clean this melt, melt is outgased, to remove contamination gas (as hydrogen), filter by the ceramic pipe filtrator then.For the melt of casting, carry out the DC casting.The casting metals that solidifies is thick board-like of 500mm.Plate is dug 10mm, carry out homogeneous in 550 ℃ then and handled 10 hours, so that intermetallic compound can not be assembled.After 400 ℃ of hot rolling systems, in annealing furnace, annealed 60 seconds in 500 ℃.Then this plate is carried out cold rolling, obtain the thick aluminium sheet of 0.30mm.The surface of prior controlled rolling machine, so that such roughness that aluminium sheet has, promptly center surface roughness (Ra) is 0.2 μ m.Then aluminium sheet is placed in the tension level(l)er, to improve flatness.
The aluminium sheet that obtains is carried out following surface treatment, to form the carrier of lithographic plate.
Pressure roller oil is removed on the slave plate surface, in 50 ℃ aluminium sheet is carried out oil removal treatment 30 seconds with the sodium aluminate aqueous solution of 10 weight %.Then with the aqueous sulfuric acid of 30 weight % in 50 ℃ are carried out aluminium sheet and 30 seconds, and remove stain.
Then, roughened (being called the sand roughening) is carried out on the surface of aluminium sheet, to improve the bounding force between carrier and the image formation layer and to make non-image areas keep enough water.Be that aluminium sheet carries out electrolysis sand roughened in 45 ℃ the aqueous solution that contains nitric acid (1 weight %) and aluminium nitrate (0.5 weight %).In processing, when being positioned over solution, supply with the alternating current that exchanges ripple under the indirect battery condition below: current density is 20A/dm with aluminium net (web) 2, duty ratio is that 1: 1 and anode electric weight are 240C/dm 2After the processing, in 50 ℃ aluminium sheet was carried out etch processes 30 seconds with the sodium aluminate aqueous solution of 10 weight %.Use 30 weight % aqueous sulfuric acids in 50 ℃ and aluminium sheet 30 seconds then, and remove stain.
And, needing wearing quality in order to improve, chemical resistance and water-retaining property form oxidation film by anodic oxidation on carrier.In film formed, when 20% the aqueous sulfuric acid that the aluminium net is positioned over 35 ℃, indirect battery was supplied with 14A/dm 2Direct current carry out electrolysis, be used to form 2.5g/m 2Oxidation film.
Aluminium sheet is carried out silicate handle, so that non-image areas has more water wettability.In processing, make aluminium sheet contact 15 seconds, and water clean with aluminium net in 70 ℃ 1.5 weight % sodium silicate (No. 3) aqueous solution.The silicon amount that adheres to is 10mg/m 2The center surface roughness (Ra) of Zhi Bei carrier is 0.25 μ m thus.
(preparation of dispersion of microcapsules)
In the ethyl acetate of 17g, adduct (the Takenate D-110N of dissolving 9.5g trimethylolpropane and XDI (diisocianate), Mistui-Takeda Chemicals, Inc.), 0.5g isocyanic acid (2-methacryloxy second) ester, 3.15g pentaerythritol triacrylate, the surfactant of the infrared absorbing agents of 0.35g (4) and 0.1g (Pionine A-41C, Takemoto oil ﹠amp; FatCo., Ltd.), with the preparation oil phase.
In addition, (aqueous solution Ltd.) is as water for PVA-205, Kuraray Co. for the 4 weight % polyvinyl alcohol (PVA) of preparation 40g.
Mix oil phase and water, and with homogenizer in 12,000rpm emulsification 10 minutes.In the emulsion that obtains, add the distilled water of 25g.In stirring at room potpourri 30 minutes, and stirred the preparation dispersion of microcapsules again 3 hours in 40 ℃.Use the distilled water diluting dispersion of microcapsules, regulating solid content is 20 weight %.The average particle size particle size of microcapsules is 0.32 μ m.
(formation of image formation layer)
By using wire bar applicator, the coating solution on alumina supporter below the coating, and in 70 ℃ baking oven drying 60 seconds, forming dry-coated amount is 0.8g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Water 100g
Dispersion of microcapsules (solid content) 5g
Polymerization initiator (1) 0.5g
Following fluorochemical surfactant 0.2g
(polymerization initiator (1))
(fluorochemical surfactant)
Figure A20041006367500742
(method)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 17W, the external drum revolution is 133rpm, and resolution is 2,400dpi.Exposure image contains the fine rule chart.
(assessment of developing on the printing machine)
Do not carry out development treatment, the plate that exposed is placed in immediately on the cylindrical shell of printing machine (Heidelberg SOR-M).For wetting water, supply with etching solution (EU-3, Fuji Photo Film Co., Ltd.)/water/isopropyl alcohol [by volume, 1/89/10]) potpourri.When resupplying black ink (TRANS-G (N), Dainippon Ink ﹠amp; Chemicals is in the time of Inc.), with 100 paper of speed printing of 6,000 per hour.
When the unexposed area of image formation layer is removed, when developing, do not transfer on the paper at the ink on the unexposed area to finish printing on the printing machine.To when finishing the printing development, having printed what paper count, and assess the suitability that develops on the printing machine thus.
The results are shown in the table 1.
(repeatability of fine rule chart)
Behind 100 paper of printing, confirm not transfer on the paper at the ink on the unexposed area.And then print 500 paper.Magnifier by 25 times is observed the fine rule chart (exposure 10,12,14,16,18 of printing on 600 paper altogether then, 20,25,30,35,40,60,80,100 and the fine rule of 200 μ m), with the fine rule of finding under the condition that not have interruption, to duplicate, assess the repeatability of fine rule thus.The line that duplicates is thin more, and the susceptibility of pre-sensitizing plate is high more.
The results are shown in the table 1.
(plate wearability)
After the printing of carrying out above-mentioned assessment line reproducibility, continue printing again.Paper number increase along with printing grinds off image formation layer gradually, and less receives ink, so reduced the ink density on the printing paper.During based on the printing beginning,, printed what paper and counted, thus the evaluation board wearability fading 0.1 o'clock up to ink density (reflection density).
The results are shown in the table 1.
Embodiment 2
Except using polymerization initiator (3) to replace repeating the program of embodiment 1 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 1.
(polymerization initiator (3))
Embodiment 3
Except using polymerization initiator (60) to replace repeating the program of embodiment 1 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 1.
(polymerization initiator (60))
Comparative example 1
Except using polymerization initiator (X1) to replace repeating the program of embodiment 1 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 1.
(polymerization initiator (X1))
Comparative example 2
Except using polymerization initiator (X2) to replace repeating the program of embodiment 1 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 1.
(polymerization initiator (X2))
Table 1
Show line reproducibility plate wearability on the pre-sensitizing plate polymerization initiator printing machine
The suitability of shadow
5,500 of 1 (1) 20 20 μ m of embodiment
4,500 of 2 (3) 20 20 μ m of embodiment
4,800 of 3 (60) 20 20 μ m of embodiment
2,300 of 20 30 μ m of comparative example 1 (X1)
2,000 of 20 30 μ m of comparative example 2 (X2)
Embodiment 4
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 1 preparation below the coating, and in 100 ℃ baking oven drying 60 seconds, forming dry-coated amount is 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Infrared absorbing agents (3) 0.05g
Polymerization initiator (1) 0.2g
Following binder polymer (mean molecular weight: 80,000) 0.5g
Triacrylate (NK Ester 1.0g with the sex change of oxirane isocyanuric acid ester
M-315，Shin?Nakamura?Chemical?Industries，Ltd.)
The fluorochemical surfactant 0.1g that uses among the embodiment 1
Water 100g
Methyl ethyl ketone 18.0g
(binder polymer)
Figure A20041006367500771
(method and assessment)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 9W, the external drum revolution is 210rpm, and resolution is 2,400dpi.Exposure image contains the fine rule chart.
In the mode identical finished lithographic plate is assessed with embodiment 1.The results are shown in table 2.
Embodiment 5
Except using polymerization initiator (3) to replace repeating the program of embodiment 4 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 2.
Embodiment 6
Except using polymerization initiator (60) to replace repeating the program of embodiment 4 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 2.
Comparative example 3
Except using polymerization initiator (X1) to replace repeating the program of embodiment 4 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 2.
Comparative example 4
Except using polymerization initiator (X2) to replace repeating the program of embodiment 4 polymerization initiator (1), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 2.
Table 2
Show line reproducibility plate wearability on the pre-sensitizing plate polymerization initiator printing machine
The suitability of shadow
4,500 of 4 (1) 40 30 μ m of embodiment
4,500 of 5 (3) 42 30 μ m of embodiment
4,800 of 6 (60) 41 30 μ m of embodiment
2,300 of 41 40 μ m of comparative example 3 (X1)
2,500 of 43 40 μ m of comparative example 4 (X2)
Embodiment 7
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 1 preparation below the coating, and in 70 ℃ baking oven drying 60 seconds, forming dry-coated amount is 0.8g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Water 100g
Dispersion of microcapsules (solid content) 5g of preparation among the embodiment 1
The homopolymer 0.5g that forms by repetitive (II-21)
The fluorochemical surfactant 0.2g that uses among the embodiment 1
(method and assessment)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 17W, the external drum revolution is 133rpm, and resolution is 2,400dpi.Exposure image contains the fine rule chart.
In the mode identical finished lithographic plate is assessed with embodiment 1.The results are shown in table 3.
Embodiment 8
The homopolymer that the homopolymer of being made up of repetitive (II-9) except use replaces being made up of repetitive (II-21), repeat the program of embodiment 7, with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 3.
Embodiment 9
The homopolymer that the homopolymer of being made up of repetitive (II-25) except use replaces being made up of repetitive (II-21), repeat the program of embodiment 4, with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 3.
Table 3
Show line reproducibility plate wearability on the pre-sensitizing plate polymerization initiator printing machine
The suitability of shadow
5,000 of 20 20 μ m of embodiment 7 (II-21)
4,700 of 20 20 μ m of embodiment 8 (II-9)
4,200 of 20 20 μ m of embodiment 9 (II-25)
2,300 of 20 30 μ m of comparative example 1 (X1)
2,000 of 20 30 μ m of comparative example 2 (X2)
Embodiment 10
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 1 preparation below the coating, and in 100 ℃ baking oven drying 60 seconds, forming dry-coated amount is 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Infrared absorbing agents (3) 0.05g
The homopolymer 0.2g that forms by repetitive (II-1)
The binder polymer 0.5g that uses among the embodiment 4
Triacrylate (NK 1.0g with the sex change of oxirane isocyanuric acid ester
Ester?M-315，Shin?Nakamura?Chemical?Industries，
Ltd.)
The fluorochemical surfactant 0.1g that uses among the embodiment 1
Methyl ethyl ketone 18.0g
(method and assessment)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 9W, the external drum revolution is 210rpm, and resolution is 2,400dpi.Exposure image contains the fine rule chart.
In the mode identical finished lithographic plate is assessed with embodiment 1.The results are shown in table 4.
Embodiment 11
The homopolymer that the homopolymer of being made up of repetitive (II-3) except use replaces being made up of repetitive (II-1), repeat the program of embodiment 10, with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 4.
Embodiment 12
The homopolymer that the homopolymer of being made up of repetitive (II-17) except use replaces being made up of repetitive (II-1), repeat the program of embodiment 10, with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 4.
Embodiment 13
The homopolymer that the homopolymer of being made up of repetitive (II-21) except use replaces being made up of repetitive (II-1), repeat the program of embodiment 10, with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 4.
Table 4
Show line reproducibility plate wearability on the pre-sensitizing plate polymerization initiator printing machine
The suitability of shadow
5,200 of 40 30 μ m of embodiment 10 (II-1)
4,700 of 40 30 μ m of embodiment 11 (II-3)
4,600 of 42 30 μ m of embodiment 12 (II-17)
4,600 of 42 30 μ m of embodiment 13 (II-21)
2,300 of 41 40 μ m of comparative example 3 (X1)
2,500 of 43 40 μ m of comparative example 4 (X2)
Embodiment 14
(preparation of alumina supporter)
(thickness: aluminium sheet 0.3mm) carries out following processing (a) to (k), the preparation alumina supporter with JIS-A-1050.
(a) mechanically roughened processing
When supply with proportion to the surface of aluminium sheet is the suspending liquid of 1.12 the lapping compound in water (silica sand) during as the lapping compound slurries, by using the rotation nylon bruss, surface of aluminum plate is carried out mechanically roughened processing.The average particle size particle size of lapping compound is that 8 μ m and the largest particles diameter are 50 μ m.Nylon bruss is made by 6.10 nylon.The length of bristle is 50mm, and bristle diameter is 0.3mm.Be to bore aperture on the stainless-steel tube of 300mm by diameter, and bristle is planted thick and fast in the hole, form nylon bruss.Use three rotating brush.With diameter is the bottom that two support roller of 200mm are placed in brush.Distance between two support roller is 300mm.Under such pressure, support roller is squeezed to aluminium sheet with brush roll, though the CD-ROM drive motor of brush rotation load on load difference before and after the extruding brush roll be 7kW or more than.The sense of rotation of brush is identical with the throughput direction of aluminium sheet.The revolution of brush is 200rpm.
(b) alkali etching is handled
By spray the NaOH aqueous solution (aluminium ion that contains 6.5 weight % amount) of 70 ℃ 26 weight % to aluminium sheet, aluminium sheet is carried out etch processes.(6g/m partly 2) the dissolving aluminium sheet.By cleaning aluminium sheet to aluminium sheet spray well water.
(c) decontamination point is handled
By spray the aqueous solution of nitric acid (aluminium ion that contains 0.5 weight % amount) of 30 ℃ 1 weight % to aluminium sheet, aluminium sheet is carried out decontamination point handle.By cleaning aluminium sheet to the aluminium sheet shower water.Aqueous solution of nitric acid is to use the waste liquid after aqueous solution of nitric acid carries out the electrochemical roughening processing.
(d) electrochemical roughening processing
Aluminium sheet is carried out the electrochemical roughening processing.Handle continuously.In processing, use the alternating current of 60Hz.Electrolytic solution is 50 ℃ the aqueous solution of nitric acid that contains the aluminum ions 10.5g/L of 5g/L.In AC wave shape, it is that 0.8 millisecond and duty factor are 1: 1 that current value reaches the required time T P of peak value from zero.The waveform of alternating current is trapezoidal.Counter electrode is made by carbon.Impressed current anode is to be made by ferrite.Electrolytic tank is the radiant type electrolytic bath type.Current density during peak value is 30A/dm 2When anode was aluminium sheet, total electricity was 220C/dm 25% electric current is branched to impressed current anode.
By cleaning aluminium sheet to aluminium sheet spray well water.
(e) alkali etching is handled
By to the NaOH that contains 26 weight % of 32 ℃ of aluminium sheet sprays and the aluminum ions solution of 6.5 weight %, aluminium sheet is carried out alkali etching handle.(0.20g/m partly 2) the dissolving aluminium sheet.And remove stain on the aluminium sheet from aluminium sheet, it is included in the aluminium hydroxide that electrochemical roughening processing place forms.In addition, be partly dissolved the edge of the depression of generation, obtain smooth edges.
By cleaning aluminium sheet to aluminium sheet spray well water.
Etch quantity is 3.5g/m 2
(f) decontamination point is handled
15 weight % aqueous solution of nitric acid (aluminium ion that contains 4.5 weight % amount) by to 30 ℃ of aluminium sheet sprays come that aluminium sheet is carried out decontamination point and handle.By cleaning aluminium sheet to the aluminium sheet shower water.Aqueous solution of nitric acid is to use the waste liquid after aqueous solution of nitric acid carries out the electrochemical roughening processing.
(g) electrochemical roughening processing
Aluminium sheet is carried out the electrochemical roughening processing.Handle continuously.In processing, use the alternating current of 60Hz.Electrolytic solution is 35 ℃ the aqueous hydrochloric acid solution that contains the aluminum ions 7.5g/L of 5g/L.The waveform of alternating current is a rectangle.Counter electrode is made by carbon.Impressed current anode is to be made by ferrite.Electrolytic tank is the radiant type electrolytic bath type.Current density during peak value is 25A/dm 2When anode was aluminium sheet, total electricity was 50C/dm 2
By cleaning aluminium sheet to aluminium sheet spray well water.
(h) alkaline etching is handled
By to the NaOH that contains 26 weight % of 32 ℃ of aluminium sheet sprays and the aluminum ions solution of 6.5 weight %, aluminium sheet is carried out alkali etching handle.(0.10g/m partly 2) the dissolving aluminium sheet.Remove stain on the aluminium sheet from aluminium sheet, it is included in the aluminium hydroxide that electrochemical roughening processing place forms.In addition, be partly dissolved the edge of the depression of generation, obtain smooth edges.
By cleaning aluminium sheet to aluminium sheet spray well water.
(i) decontamination point is handled
By spray the aqueous sulfuric acid (aluminium ion that contains 0.5 weight % amount) of 60 ℃ 25 weight % to aluminium sheet, aluminium sheet is carried out decontamination point handle.By cleaning aluminium sheet to the aluminium sheet shower water.
(j) anodized
Aluminium sheet is carried out anodization.Electrolytic solution is the aqueous solution that contains the aluminum ions 170g/L sulfuric acid of 0.5 weight %.Temperature of reaction is 43 ℃.Current density is about 30A/dm 2The oxidation film that forms is 2.7g/m 2By cleaning aluminium sheet to the aluminium sheet shower water.
(k) silicate is handled
By aluminium sheet being impregnated in 30 ℃ 1.5 weight % silicate (No. 3) aqueous solution 10 seconds, aluminium sheet is carried out silicate handle.The silicate amount that adheres to is 3.6mg/m 2By cleaning aluminium sheet to the aluminium sheet shower water.
(formation of image formation layer)
By using wire bar applicator, the coating solution on alumina supporter below the coating, and 120 ℃ of dryings 60 seconds, forming dry-coated amount was 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Infrared absorbing agents (5) 2 weight portions
Polymerization initiator (101) (solubleness in the water: 40 weight % or more than) 10 weight portions
Six acrylic acid dipentaerythritol ester (NK Ester A-DPH, 55 weight portions
Shin?Nakamura?Chemical?Industries，Ltd.)
Polyvinyl acetal resin (Elex B BM-S, 37 weight portions
Sekisui?Chemical?Industries，Ltd.)
Fluorochemical surfactant 6 weight portions that use among the embodiment 1
Methyl ethyl ketone 900 weight portions
(polymerization initiator (101))
Figure A20041006367500851
(method and assessment)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 10.2W, and the external drum revolution is 150rpm.Exposure image contains the fine rule chart.
In the mode identical finished lithographic plate is assessed with embodiment 1.The results are shown in table 5.
Embodiment 15
(preparation of alumina supporter)
With JIS-A-1050 (thickness: the processing (a) that aluminium sheet 0.3mm) carries out carrying out among the embodiment 14 is to (f), (j) and (k), the preparation alumina supporter.In other words, except not handling (g), (h) and (i) outside, with embodiment 14 in identical mode prepare alumina supporter.
(method and assessment)
Except using the alumina supporter for preparing above, prepare and assess the presensitized lithographic version in the mode identical with embodiment 14.The results are shown in the table 5.
Embodiment 16
(preparation of alumina supporter)
With JIS-A-1050 (thickness: the processing (b) that aluminium sheet 0.3mm) carries out carrying out among the embodiment 14 is to (f), (j) and (k), the preparation alumina supporter.In other words, except not handling (a), (g), (h) and (i) outside, with embodiment 14 in identical mode prepare alumina supporter.
(method and assessment)
Except using the alumina supporter for preparing above, prepare and assess the presensitized lithographic version in the mode identical with embodiment 14.The results are shown in the table 5.
Embodiment 17
(preparation of alumina supporter)
With JIS-A-1050 (thickness: aluminium sheet 0.3mm) carries out the processing (b) carried out among the embodiment 14, (c), (g) to (k), the preparation alumina supporter.In other words, except not handling (a), (d), (e) and (f) outside, with embodiment 14 in identical mode prepare alumina supporter.In addition, the total electric weight that will handle (g) is changed into 450C/dm 2
(method and assessment)
Except using the alumina supporter for preparing above, prepare and assess the presensitized lithographic version in the mode identical with embodiment 14.The results are shown in the table 5.
Embodiment 18
(preparation of alumina supporter)
With JIS-A-1050 (thickness: aluminium sheet 0.3mm) carries out the processing (b) carried out among the embodiment 14, (c), (g) to (j), the preparation alumina supporter.In other words, except not handling (a), (d), (e), (f) and (k) outside, with embodiment 14 in identical mode prepare alumina supporter.In addition, the total electric weight that will handle (g) is changed into 450C/dm 2And, after handling (j), carry out following primary coat and handle.
(1) primary coat is handled
By the following coating solution of coating on aluminium sheet, aluminium sheet is carried out primary coat handle.Coating weight is counted about 0.05g/m by phosphorus 2In 100 ℃ of dry coatings 1 minute.
The coating solution of undercoat
Phenyl phosphate 2 weight portions
Methyl alcohol 800 weight portions
Water 50 weight portions
(method and assessment)
Except using the alumina supporter for preparing above, prepare and assess the presensitized lithographic version in the mode identical with embodiment 14.The results are shown in the table 5.
Comparative example 5-9
Except using polymerization initiator (X3) to replace repeating the program of embodiment 14-18 the polymerization initiator (101), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 5.
(polymerization initiator (X3))
Table 5
Pre-sensitizing plate alumina supporter locate on the polymerization initiator printing machine to show the plate wearability
The suitability of reason shadow
(101) 30 8,000 of embodiment 14 a-k
Embodiment 15 a-f, j, (101) 50 12,000 of k
Embodiment 16 b-f, j, (101) 45 10,000 of k
Embodiment 17 b-c, (101) 50 12,600 of g-k
Embodiment 18 b-c, g-j, (101) 35 7,000 of l
80 1,000 of comparative example 5 a-k (X3)
Comparative example 6 a-f, j, 200 2,000 of k (X3)
Comparative example 7 b-f, j, 150 1,000 of k (X3)
Comparative example 8 b-c, 120 1,000 of g-k (X3)
Comparative example 9 b-c, g-j, 100 1,000 of l (X3)
Embodiment 19
(formation of protective seam)
By using the blade coating device, the coating solution on the image formation layer of embodiment 14 preparations below the coating, and 125 ℃ of dryings 75 seconds, forming dry-coated amount was 0.5g/m 2Protective seam.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of protective seam
Polyvinyl alcohol (PVA) (saponification degree: 98%, the degree of polymerization: 500) 95 weight portions
Polyvinylpyrrolidone//vinyl acetate copolymers 4 weight portions
Non-ionic surfactant (EMALEX 710,1 weight portions
Japan Emulsion Co., Ltd.)
Pure water 3,000 weight portions
(method and assessment)
Assess the presensitized lithographic version in the mode identical with embodiment 1.The results are shown in the table 6.
Comparative example 10
Except using polymerization initiator (X3) to replace repeating the program of embodiment 19 polymerization initiator (101), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 6.
Table 6
The plate wearability of developing on the pre-sensitizing plate polymerization initiator printing machine
Suitability
19 (101) 60 16,000 of embodiment
300 2,000 of comparative examples 10 (X3)
Embodiment 20
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 14 preparations below the coating, and 120 ℃ of dryings 60 seconds, forming dry-coated amount was 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Infrared absorbing agents (5) 2 weight portions that use among the embodiment 1
Polymerization initiator (101) (solubleness in the water: 40 weight % or more than) 10 weight portions
Following polymerizable compound 65 weight portions
Following binder polymer (weight-average molecular weight: 6,500) 47 weight portions
Fluorochemical surfactant 6 weight portions that use among the embodiment 1
Methyl ethyl ketone 900 weight portions
(polymerizable compound)
Figure A20041006367500891
(binder polymer)
(method and assessment)
Assess the presensitized lithographic version in the mode identical with embodiment 1.The results are shown in the table 7.
Comparative example 11
Except using polymerization initiator (X3) to replace repeating the program of embodiment 20 polymerization initiator (101), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 7.
Table 7
The plate wearability of developing on the pre-sensitizing plate polymerization initiator printing machine
Suitability
20 (101) 45 13,000 of embodiment
80 2,000 of comparative examples 11 (X3)
Embodiment 21
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 14 preparations below the coating, and 120 ℃ of dryings 60 seconds, forming dry-coated amount was 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Infrared absorbing agents (5) 2 weight portions that use among the embodiment 1
Polymerization initiator (101) (solubleness in the water: 40 weight % or more than) 10 weight portions
Following polymerizable compound 65 weight portions
Following binder polymer (weight-average molecular weight: 11,000) 47 weight portions
Fluorochemical surfactant 6 weight portions that use among the embodiment 1
Methyl ethyl ketone 900 weight portions
(polymerizable compound)
Figure A20041006367500901
(binder polymer)
(method and assessment)
Assess the presensitized lithographic version in the mode identical with embodiment 1.The results are shown in the table 8.
Comparative example 12
Except using polymerization initiator (X3) to replace repeating the program of embodiment 21 polymerization initiator (101), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 8.
Table 8
The plate wearability of developing on the pre-sensitizing plate polymerization initiator printing machine
Suitability
21 (101) 50 16,000 of embodiment
60 3,000 of comparative examples 12 (X3)
Embodiment 22
(preparation of dispersion of microcapsules)
In the ethyl acetate of 17.7 weight portions, dissolve the adduct (TakenateD-110N that 6 weight portions contain the XDI of 1 mole trimethylolpropane of 25 weight % ethyl acetate and 3 moles, Mistui-Takeda Chemicals, Inc.), 7.5 five acrylic acid dipentaerythritol ester (SR-399E of weight portion, Nihon Kayaku Co., Ltd.), 1.5 the surfactant of infrared absorbing agents of weight portion (6) and 0.1 weight portion (Pionine A-41C, Takemoto oil ﹠amp; Fat Co., Ltd.), with the preparation oil phase.
In addition, (aqueous solution Ltd.) is as water for PVA-205, Kuraray Co. to prepare 4 weight % polyvinyl alcohol (PVA) of 37.5 weight portions.
Mix oil phase and water, and with homogenizer with 12, the rotating speed emulsification of 000rpm 10 minutes.The distilled water that in the emulsion that obtains, adds 2.45 weight portions.In stirring at room potpourri 30 minutes, and stirred the preparation dispersion of microcapsules again 3 hours in 40 ℃.Use the distilled water diluting dispersion of microcapsules, regulating solid content is 20.0 weight %.The average particle size particle size of microcapsules is 0.36 μ m.
(formation of image formation layer)
In embodiment 14 preparation alumina supporter on the coating below coating solution, and in 70 ℃ baking oven the drying 90 seconds, forming dry-coated amount is 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Water 100 weight portions
Dispersion of microcapsules (solid content) 45 weight portions
Polymerization initiator (101) 1 weight portions
Fluorochemical surfactant (Megaface F-171,0.1 weight portion
Dainippon?Ink?Chemicals，Ltd.)
(method and assessment)
Assess the presensitized lithographic version in the mode identical with embodiment 1.The results are shown in the table 9.
Comparative example 13
Except using polymerization initiator (X3) to replace repeating the program of embodiment 22 polymerization initiator (101), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 9.
Table 9
The plate wearability of developing on the pre-sensitizing plate polymerization initiator printing machine
Suitability
22 (101) 25 4,000 of embodiment
50 500 of comparative examples 13 (X3)
Embodiment 23-29
Except using polymerization initiator (114), (129), (132), (138), (145), (150), (164) to replace repeating the program of embodiment 17 polymerization initiator (101), with preparation presensitized lithographic version.
Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 10.
(polymerization initiator (114))
(polymerization initiator (129))
(polymerization initiator (132))
(polymerization initiator (138))
(polymerization initiator (145))
Figure A20041006367500935
(polymerization initiator (150))
(polymerization initiator (164))
Table 10
The plate wearability of developing on the pre-sensitizing plate polymerization initiator printing machine
Suitability
23 (114) 90 4,000 of embodiment
24 (129) 75 5,000 of embodiment
25 (132) 65 6,000 of embodiment
26 (138) 70 9,000 of embodiment
27 (145) 70 8,000 of embodiment
28 (150) 90 7,000 of embodiment
29 (164) 65 9,000 of embodiment
Embodiment 30-36
Except using polymerization initiator (114), (129), (132), (138), (145), (150), (164) to replace repeating the program of embodiment 22 polymerization initiator (101), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 11.
Table 11
The plate wearability of developing on the pre-sensitizing plate polymerization initiator printing machine
Suitability
30 (114) 55 5,000 of embodiment
31 (129) 75 5,000 of embodiment
32 (132) 75 5,000 of embodiment
33 (138) 70 8,000 of embodiment
34 (145) 60 6,000 of embodiment
35 (150) 70 5,000 of embodiment
36 (164) 60 7,000 of embodiment
Embodiment 37
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 1 preparation below the coating, and 70 ℃ oven drying 60 seconds, forming dry-coated amount was 0.8g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Water 100g
Dispersion of microcapsules (solid content) 5g of preparation among the embodiment 1
Polymerization initiator (201) 0.5g
The fluorochemical surfactant 0.2g that uses among the embodiment 1
(polymerization initiator (201))
Figure A20041006367500951
Hammett substituent constant: 1.02
(method and assessment)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 17W, the external drum revolution is 133rpm, and resolution is 2,400dpi.Exposure image contains the fine rule chart.
In the mode identical finished lithographic plate is assessed with embodiment 1.The results are shown in table 12.
Embodiment 38
Except using polymerization initiator (209) to replace repeating the program of embodiment 37 polymerization initiator (201), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 12.
(polymerization initiator (209))
Hammett substituent constant: 0.69
Embodiment 39
Except using polymerization initiator (213) to replace repeating the program of embodiment 37 polymerization initiator (201), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 12.
(polymerization initiator (213))
Figure A20041006367500962
Hammett substituent constant: 0.69
Embodiment 40
Except using polymerization initiator (290) to replace repeating the program of embodiment 37 polymerization initiator (201), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 12.
(polymerization initiator (290))
Hammett substituent constant: 0.52
Comparative example 14
Except using polymerization initiator (X4) to replace repeating the program of embodiment 37 polymerization initiator (201), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 12.
(polymerization initiator (X4))
Hammett substituent constant :-0.81
Comparative example 15
Except using polymerization initiator (X5) to replace repeating the program of embodiment 37 polymerization initiator (201), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 12.
(polymerization initiator (X5))
Hammett substituent constant: 0
Table 12
Show line reproducibility plate wearability on the pre-sensitizing plate polymerization initiator printing machine
The suitability of shadow
4,800 of 37 (201) 20 20 μ m of embodiment
4,500 of 38 (209) 20 20 μ m of embodiment
4,700 of 39 (213) 20 20 μ m of embodiment
4,600 of 40 (290) 20 20 μ m of embodiment
1,000 of 20 30 μ m of comparative example 14 (X5)
1,200 of 20 30 μ m of comparative example 15 (X6)
Embodiment 41
(formation of image formation layer)
By using wire bar applicator, the coating solution on the alumina supporter of embodiment 1 preparation below the coating, and in 100 ℃ baking oven drying 60 seconds, forming dry-coated amount is 1.0g/m 2Image formation layer.Thus, the lithographic plate that has prepared pre-sensitizing.
The coating solution of image formation layer
Infrared absorbing agents (3) 0.05g
Polymerization initiator (204) 0.2g
The binder polymer 0.5g that uses among the embodiment 4
Triacrylate 1.0g with the sex change of oxirane isocyanuric acid ester
(NK?Ester?M-315，Shin?Nakamura?Chemical
Industries，Ltd.)
The fluorochemical surfactant 0.1g that uses among the embodiment 1
Methyl ethyl ketone 18.0g
(polymerization initiator (204))
Figure A20041006367500991
Hammett substituent constant: 1.02
(method and assessment)
The image exposure machine (Trendsetter3244VX is from Creo) of the water-cooling semiconductor infrared laser by being equipped with 40W becomes the exposure of image ground with the presensitized lithographic version for preparing above.Regulate conditions of exposure, so that be output as 9W, the external drum revolution is 210rpm, and resolution is 2,400dpi.Exposure image contains the fine rule chart.
In the mode identical finished lithographic plate is assessed with embodiment 1.The results are shown in table 13.
Embodiment 42
Except using polymerization initiator (209) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
Embodiment 43
Except using polymerization initiator (244) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
(polymerization initiator (244))
Figure A20041006367501001
Hammett substituent constant: 0.63
Embodiment 44
Except using polymerization initiator (252) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
(polymerization initiator (252))
Hammett substituent constant: 1.48
Embodiment 45
Except using polymerization initiator (291) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
(polymerization initiator (291))
Figure A20041006367501003
Hammett substituent constant: 0.52
Embodiment 46
Except using polymerization initiator (292) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
(polymerization initiator (292))
Figure A20041006367501011
Hammett substituent constant: 0.52
Embodiment 47
Except the homopolymer that uses repetitive IV-1C101 replaces repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
(repetitive IV-1C101)
Figure A20041006367501012
Comparative example 16
Except using polymerization initiator (X4) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
Comparative example 17
Except using polymerization initiator (X5) to replace repeating the program of embodiment 41 polymerization initiator (204), with preparation presensitized lithographic version.Assess the galley of preparation in the mode identical with embodiment 1.The results are shown in the table 13.
Table 13
Show line reproducibility plate wearability on the pre-sensitizing plate polymerization initiator printing machine
The suitability of shadow
5,500 of 41 (204) 40 30 μ m of embodiment
5,500 of 42 (209) 40 20 μ m of embodiment
4,500 of 43 (244) 45 30 μ m of embodiment
5,000 of 44 (252) 40 20 μ m of embodiment
4,500 of 45 (291) 40 30 μ m of embodiment
4,500 of 46 (292) 40 30 μ m of embodiment
5,000 of 43 20 μ m of embodiment 47 (IV-1C101)
1,500 of 47 50 μ m of comparative example 16 (X4)
2,000 of 40 50 μ m of comparative example 17 (X5)

Claims (19)

1. lithographic process, this method comprises following step:
Become image ground to expose the presensitized lithographic version with infrared ray, described presensitized lithographic version comprises hydrophilic carrier and contains the image formation layer of infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is a kind of sulfonium cation and anionic salt, described negative ion is selected from: (1) hydrogen sulfate ion, (2) sulfuric ester ion, (3) contain the polymkeric substance of carboxylic acid ion, (4) contain the polymkeric substance of sulfonate ion, and (5) are contained-SO 2-N --R 1(wherein, R 1Be carboxyl, formoxyl, aliphatic group, aromatic group, heterocyclic radical ,-O-R ,-S-R,-CO-R,-O-CO-R or-CO-O-R, and wherein R is an aliphatic group, aromatic group or heterocyclic radical) anionic polymkeric substance, (6) contain by acyl group, carbamyl, the carboxylic acid ion of the alpha-carbon atom that the carbamyl of replacement or cyano group replace, (7) contain the carboxylic acid ion of the alpha-carbon atom that is replaced by two or more aromatic groups, (8) contain the carboxylic acid ion of the alpha-carbon atom that is connected with non-metallic atom the hydrogen except carbon, with the described polymerizable compound of polymerization in the exposure area;
In unexposed area, remove image formation layer, on the cylindrical shell of printing machine, lithographic plate is installed simultaneously; Then
Offscreen the version printed images is installed lithographic plate simultaneously on the cylindrical shell of printing machine.
2. lithographic process according to claim 1, wherein said sulfonate ion comprises the sulphur atom that is connected with three aliphatic groups, aromatic group or heterocyclic radicals.
3. lithographic process according to claim 2, wherein said sulfonate ion comprises the sulphur atom that is connected with three aromatic groups.
4. lithographic process according to claim 1, wherein said polymerization initiator are a kind of sulfonium cations and salt by the sulfuric ester ion of following formula (I) expression:
(I)R-O-SO 3 -
Wherein, R is aliphatic group, aromatic group or heterocyclic radical.
5. lithographic process according to claim 1, wherein said polymerization initiator are a kind of polymkeric substance that comprises by the repetitive of following formula (II) expression:
Wherein, R 2Be hydrogen, halogen atom, hydroxyl, carboxyl, formoxyl; amino, carbamyl, urea groups, sulfo group; sulfamoyl, aliphatic group, aromatic group, heterocyclic radical;-O-R ,-S-R ,-CO-R ,-O-CO-R;-CO-O-R ,-NH-R ,-NH-CO-R ,-CO-NH-R;-NH-CO-NH-R ,-NH-CO-O-R ,-O-CO-NH-R ,-SO 2-R ,-NH-SO 2-R or-SO 2-NH-R, wherein R is an aliphatic group, aromatic group or heterocyclic radical; L 1Be singly-bound or divalent linker; X is-COO--SO 3-or-SO 2-N --R 1, R wherein 1Be carboxyl, formoxyl, aliphatic group, aromatic group, heterocyclic radical ,-O-R ,-S-R ,-CO-R ,-O-CO-R or-CO-O-R, and wherein R is an aliphatic group, aromatic group or heterocyclic radical; And M is a sulfonium cation.
6. lithographic process according to claim 1, wherein based on the total solid content of image formation layer, the amount of the polymerization initiator that image formation layer contains is 0.1 to 50 weight %.
7. lithographic process according to claim 1, wherein said polymerizable compound is contained in the microcapsules, and it is scattered in the image formation layer, and binder polymer is placed in the outside of microcapsules.
8. lithographic process according to claim 1, wherein said presensitized lithographic version is exposed with infrared ray by forming image ground with infrared laser beam scanning galley.
9. lithographic process according to claim 1, in the time of wherein on the cylindrical shell that lithographic plate is placed in printing machine, described presensitized lithographic version becomes image ground to expose with infrared ray.
10. presensitized lithographic version, the image formation layer that it comprises hydrophilic carrier and contains infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is a kind of sulfonium cation and anionic salt, described negative ion is selected from: (1) hydrogen sulfate ion, (2) sulfuric ester ion, (3) contain the polymkeric substance of carboxylic acid ion, polymkeric substance and (5) that (4) contain sulfonate ion are contained-SO 2-N --R 1(wherein, R 1Be carboxyl, formoxyl, aliphatic group; aromatic group, heterocyclic radical ,-O-R;-S-R;-CO-R ,-O-CO-R or-CO-O-R, and wherein R is an aliphatic group; aromatic group or heterocyclic radical) anionic polymkeric substance; wherein said polymerizable compound is contained in the microcapsules, and it is scattered in the image formation layer, and binder polymer is placed in the outside of microcapsules.
11. a lithographic process, this method comprises following step:
Become image ground to expose the presensitized lithographic version with infrared ray, described presensitized lithographic version comprises hydrophilic carrier and contains the image formation layer of infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is the salt of a kind of negative ion and sulfonium cation, described sulfonium cation comprises the sulphur atom that is connected with three aromatic groups, at least one aromatic group is replaced by electron-withdrawing group, with the described polymerizable compound of polymerization in the exposure area;
In unexposed area, remove image formation layer, on the cylindrical shell of printing machine, lithographic plate is installed simultaneously; Then
Offscreen the version printed images is installed lithographic plate simultaneously on the cylindrical shell of printing machine.
12. lithographic process according to claim 11, wherein said negative ion are sulfonate ion, sulfinic acid radical ion, carboxylic acid ion, borate ion, halide ion, sulfate ion, hydrogen sulfate ion, hexafluorophosphoricacid acid ions, tetrafluoroborate ion, or perchlorate.
13. lithographic process according to claim 11, wherein said sulfonium cation contain a Hammett substituent constant greater than 0.46 electron-withdrawing group.
14. lithographic process according to claim 11, wherein said sulfonium cation contains two or more electron-withdrawing groups, and the Hammett substituent constant sum of described electron-withdrawing group is greater than 0.46.
15. lithographic process according to claim 11, wherein based on the total solid content of image formation layer, the amount of the polymerization initiator that image formation layer contains is 0.1 to 50 weight %.
16. lithographic process according to claim 11, wherein said polymerizable compound is contained in the microcapsules, and it is scattered in the image formation layer, and binder polymer is placed in the outside of microcapsules.
17. lithographic process according to claim 11, wherein said presensitized lithographic version is exposed with infrared ray by forming image ground with infrared laser beam scanning galley.
18. lithographic process according to claim 11, in the time of wherein on the cylindrical shell that lithographic plate is placed in printing machine, described presensitized lithographic version becomes image ground to expose with infrared ray.
19. presensitized lithographic version, the image formation layer that it comprises hydrophilic carrier and contains infrared absorbing agents, polymerization initiator and binder polymer, described polymerization initiator is the salt of a kind of negative ion and sulfonium cation, described sulfonium cation comprises the sulphur atom that is connected with three aromatic groups, at least one aromatic group is replaced by electron-withdrawing group, wherein said polymerizable compound is contained in the microcapsules, it is scattered in the image formation layer, and binder polymer is placed in the outside of microcapsules.
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CN104703809A (en) * 2012-09-26 2015-06-10 富士胶片株式会社 Lithographic printing original plate and plate making method

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WO1998029258A1 (en) * 1996-12-26 1998-07-09 Asahi Kasei Kogyo Kabushiki Kaisha Plate for direct thermal lithography and process for producing the same
BR9915407A (en) * 1998-11-16 2001-07-24 Mitsubishi Chem Corp Photosensitive positive lithographic printing plate sensitive to near infrared rays; production method and method to form a positive image
US6576401B2 (en) * 2001-09-14 2003-06-10 Gary Ganghui Teng On-press developable thermosensitive lithographic plates utilizing an onium or borate salt initiator
JP2003076010A (en) * 2001-09-04 2003-03-14 Fuji Photo Film Co Ltd Original plate of planographic printing plate
JP4645789B2 (en) * 2001-06-18 2011-03-09 Ｊｓｒ株式会社 Negative radiation sensitive resin composition

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CN103842185A (en) * 2011-09-30 2014-06-04 富士胶片株式会社 Printing method using on press development lithograph printing plate precursor
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