CN100400284C - Lithographic printing method and presensitized plate - Google Patents

Abstract

Disclosed is a presensitized plate composed of a support having thereon an image recording layer which includes: an infrared absorber (A) that is a cyanine dye having at least one fused ring composed of a nitrogen-containing heterocycle in combination with an aromatic ring or a second heterocycle, and having on the aromatic ring or second heterocycle an electron-withdrawing group or a heavy atom-containing group, a radical generator (B), and a radical-polymerizable compound (C), and which is removable with printing ink and/or dampening water. The presensitized of the present invention can be imaged with an infrared light-emitting laser to directly record an image from digital data on a computer or the like and is then subjected to on-machine development without carrying out a development step, which is capable of providing a large number of good impressions with a practical amount of energy.

Description

Lithography and presensitized plate

Technical field

The lithography that the present invention relates to be used for lithographic presensitized plate and use this presensitized plate.More particularly, the present invention relates to a kind of presensitized plate, can directly make lithographic plate by the exposure in the infrared laser of scanning in the data signal of sending based on computer etc. and thereon, the invention still further relates to a kind of lithography, wherein, above-mentioned presensitized plate is chemical development and printing on printing machine, without development step.

Background technology

Lithographic plate generally is made of the hydrophily non-image areas of lipophile image-region that receives printing ink in print job and reception humidification water.Lithographic printing is to utilize between water and the oil-based ink method of repulsion mutually by having as the lipophile image-region of the version that receives inked areas and having as the hydrophily non-image areas that receives aqua region (not receiving the zone of printing ink), thereby make printing ink produce difference, printing ink only is deposited in the lipophile image-region in the lip-deep adhesive capacity of version.Selective deposition is transferred to subsequently at the printing ink on the version and prints on substrate such as the paper.

The presensitized plate that is made of the hydrophily photosensitive resin layer (image recording layer) that is on the hydrophilic carrier is widely used in preparing this lithographic plate.In general, lithographic plate obtains with graphic arts process, wherein, exposes in the light of the master of presensitized plate on seeing through graphic arts film etc.Image recording layer is kept intact in image-region, but in non-image areas with alkaline developer or organic solvent with its dissolving with remove, thereby manifest the surface of hydrophilic carrier.

Make a plate when operation with the presensitized plate of prior art, generally need be after exposure with the developer that is applicable to image recording layer with the non-image areas dissolving and the step of removing.A kind of problem demanding prompt solution is how to simplify or eliminate the wet development that carries out as auxiliary operation.Particularly relevant with the wet-treating processing to waste discharge has become a subject matter industrial, because this is related to the global environment problem, the solution of the problems referred to above is seemed urgent day by day.

A kind ofly be called " developing " at machine for responding the simple plate making method that above-mentioned needs design.This method relates to the use of the image recording layer of the non-image areas that can remove presensitized plate in common printed operation.After the presensitized plate exposure, on printing machine, remove non-image areas, make lithographic plate.

Exemplary comprises at the machine development method: use to have the technology that can dissolve or be dispersed in the presensitized plate of the image recording layer in humidification water, printing ink solvent or humidification water and the ink emulsion; Thereby on printing machine, make image recording layer contact the technology that its machinery is removed with impression cylinder or blanket cylinder; Weaken cohesive force in the image recording layer or the cohesive force between image recording layer and the carrier by infiltration as humidification water or printing ink solvent, thereby make image recording layer contact the technology that its machinery is removed then with impression cylinder or blanket cylinder.

In this manual, unless otherwise indicated, " development step " refers to the following operation of carrying out with the device except that printing machine (generally being automatic processor): the zone of the presensitized plate of not using infrared laser exposure is as yet contacted with liquid (generally being alkaline developer), and be removed, thereby manifest the surface of hydrophilic carrier.Equally, " developing at machine " among the application refers to the following process and operation of carrying out with printing machine: the zone of the presensitized plate of not using infrared laser exposure is as yet contacted with liquid (generally being the humidification water that is used to print), and be removed, thereby manifest the surface of hydrophilic carrier.

But, when in using prior art, utilizing the image recording layer of ultraviolet ray or visible light document image, because even exposure back image recording layer does not have photographic fixing yet, therefore, all must adopt a kind of numerous and diverse method always, for example before the presensitized plate with exposure is installed on the printing machine, it is stored under the complete shading state or under the constant temperature.

In recent years, adopted digital technology in electronics industry, use a computer storage and output information are very general, and for adapting to this digital technology, people bring into use various new images output systems.It should be noted that most that these trend have expedited the emergence of computer forme technology, wherein, digital image data is carried on scanning on the high collected radiation bundle such as laser on the presensitized plate, make its exposure, thereby directly produce lithographic plate, be no longer dependent on the use of graphic arts film.Technical main challenge always is the development of the presensitized plate that is applicable to the computing mechanism platemaking technology.

As mentioned above, at present strong day by day to the needs of the simplification plate-making operation that relates to dry process development or Nonvisualization, these all be because to the concern of global environment and with digitized compatibility.

Suppose and can access cheap height output laser such as semiconductor laser and YAG laser now, then use these high output laser just to demonstrate wide prospect as the method for image recorder, because these technology can be produced lithographic plate by scanning type exposure, this is easy to digitizing technique integrated.

In existing method for platemaking, the image-type of photosensitive presensitized plate exposure is carried out under middle illuminance condition low, the image-type change records image of the physical property that produces by the photochemical reaction in the image recording layer.On the contrary, state in the use in the method for high output laser, will treat the time that the exposure area irradiation is very short with a large amount of luminous energy, luminous energy is converted into heat energy effectively, and heat energy causes the variation of chemical change, phase change and form or structure in image recording layer.These variations are used for document image.Therefore, image information is imported with luminous energy such as laser, but the reacting record that image is usefulness luminous energy and heat energy to be caused.The technology that the heat that utilizes this high power density exposure to produce writes down is commonly referred to as " hot type record ", and luminous energy is commonly referred to as " photo-thermal conversion " to heat energy conversion.

Utilizing the major advantage of the method for platemaking of hot type record is that image recording layer is insensitive to light such as the room light generally measured, and the image of measuring the exposure record by height does not need photographic fixing.That is, the presensitized plate that uses in the hot type record is insensitive to room light before exposure, need be with image fixing after exposure.Thereby can have a kind of print system, wherein, for example make its soluble or soluble image recording layer carry out the image-type exposure by exposure in the light that sends at superpower laser, exposure layer is made lithographic plate subsequently in by the plate-making operation of carrying out of developing at machine.In such system, even when exposing in the indoor light around, exposed images is also unaffected.Therefore, we have certain reason to believe: can obtain being applicable to the presensitized plate that develops at machine by using the hot type record.

Obvious improvement has been arranged in laser technology recently.Particularly, easily obtain launching the small-sized high output semiconductor laser of infrared light of 760-1200nm wavelength and the solid state laser possibility that become.When directly making printed panel by the numerical data on computer etc., such infrared laser is exceedingly useful as recording light source.

But in the reality recording materials the strongest as the light sensitivity of image recording layer, wavelength photoreceptor is in 760nm or the littler visible region at wavelength.Can not use infrared laser document image on this material.Therefore, need the enough infrared lasers of the energy material of document image thereon at present.

Respond this needs, JP2938397B (among the application with term " JPXXXXXXX B " expression " Japan Patent ") has described a kind of presensitized plate, wherein, on hydrophilic carrier, be provided with the image formation layer of forming by the hydrophilic agglomerant that wherein is dispersed with hydrophobic thermoplastic polymer's particle.JP2938397B described with infrared laser subsequently coalescent to form image under heat effect of the exposure of presensitized plate, hydrophobic thermoplastic polymer's particle, also described galley and is then on the cylinder that how to be installed to printing machine and how to carry out developing at machine with humidification water and/or printing ink.

Although it is good in the machine developing performance to utilize hot melt that the coalescent imaging method of granule is had in this way separately, the image intensity of exposed plate (with the adhesiveness of carrier) is very low, and therefore, its printing life-span is short.

JP2002-287334A (among the application with term " JPXX-XXXXXX A " expression " the not Japanese Laid-Open Patent Application of Shening ") has described a kind of presensitized plate that is made of carrier, has been provided with the photosensitive layer that contains infrared absorbent, radical polymerization initiator and polymerizable compound on carrier.

Utilize the method for polymerized/cross-linked reaction to have better image intensity by this way, because very high chemical bond density is arranged in image-region.But, because printing life-span and polymerization efficiency (sensitivity) are not suitable for practical application, so such version does not obtain commercialization so far.

Summary of the invention

Therefore, an object of the present invention is to provide a kind of lithography, wherein, can be used for the direct document image of numerical data from the computer etc. with the presensitized plate of laser instrument imaging of emission infrared light, carry out then developing at machine, and do not carry out development step (using the wet development step of alkaline developer), this method can provide the big measured space of a whole page with the energy of practicality amount.Another object of the present invention provides the presensitized plate that can be used in the lithography.

The present inventor is to being used for the composition further investigation back discovery that lithographic presensitized plate can be used as the negativity image recording materials of image recording layer: the image recording layer that comprises infrared absorbing agents by use can be realized above-mentioned purpose, and this infrared absorbing agents is the cyanine dye with specific part structure.This discovery has caused a first aspect of the present invention.

In the process of these same researchs, the present inventor also finds: the image recording layer that comprises infrared absorbing agents by use can be realized above-mentioned purpose, and this infrared absorbing agents has specific oxidizing potential.This discovery has caused a second aspect of the present invention.

Therefore, the invention provides following presensitized plate (i)-(vi) and lithography (vii)-(ix).

(i) a kind of presensitized plate is made of the carrier that image recording layer is arranged on it, and image recording layer comprises:

Infrared absorbing agents (A), this is a kind of cyanine dye, has by nitrogen heterocyclic ring and aromatic rings or second at least one condensed ring that heterocycle constitutes jointly, and on aromatic rings or second heterocycle, has electron withdraw group or contain the group of heavy atom,

Radical-forming agent (B) and

The compound of free redical polymerization (C),

And this image recording layer can be removed with printing-ink and/or humidification water.

(ii) according to the described presensitized plate in front (i), wherein, infrared absorbing agents (A) is the compound of following formula (1).

(in formula, R ¹And R ²Represent independently of one another carbon number mostly be most 20 can substituted alkyl.Ar ¹And Ar ²Expression can substituted aryl radical or heterocyclic group independently of one another.Y ¹And Y ²Represent independently of one another sulphur atom, oxygen atom, selenium atom, carbon number mostly be most 12 dialkyl group methylene or-the CH=CH-group.Z ¹And Z ²Be respectively the substituting group that is selected from alkyl, oxygen base, electron withdraw group and contains the heavy atom group, Z ¹And Z ²In at least one be electron withdraw group or the group that contains heavy atom.Letter n and m represent 0 or bigger integer separately, and condition is that n and m sum are 1 at least.

Q can be selected from five methines or seven methines that following substituent group replaces: the substituting group of alkoxyl, aryloxy group, alkylthio group, arylthio, dialkyl amido, ammonia diaryl base, halogen atom, alkyl, aralkyl, cycloalkyl, aryl, oxygen, imines alkali (iminium base) and following formula (2); Also can have the cyclohexene, cyclopentene or the cyclobutane ring that contain three continuous methine chains.

(in the formula, R ³And R ⁴Represent the alkyl of hydrogen atom, a 1-8 carbon atom or the aryl of 6-10 carbon atom independently of one another; Y ³Be oxygen atom or sulphur atom.)

X-be in needs and the situation of electric charge under the counter anion that exists.)

(iii) a kind of presensitized plate is made of the carrier that image recording layer is arranged on it, and image recording layer comprises:

Infrared absorbing agents (A), its oxidizing potential are 0.45V (vs.SCE) at the most,

Radical-forming agent (B) and

The compound of free redical polymerization (C),

And this image recording layer can be removed with printing-ink and/or humidification water.

(iv), wherein, the priming coat and the image recording layer that contain the compound that has polymerizable groups on the molecule are arranged successively on the carrier according to the (iii) described presensitized plate in front.

(v) according to the (iv) described presensitized plate in front, wherein, the compound that has polymerizable groups on the molecule also has on molecule OxiraneGroup.

(vi) according to the (iv) described presensitized plate in front, wherein, the compound that has polymerizable groups on the molecule also has the adsorbable group of carrier on molecule.

(vii) according to front (i)-(vi) described arbitrary presensitized plate, wherein, at least some in the compound (C) of infrared absorbing agents (A), radical-forming agent (B) and free redical polymerization are microencapsulations.

(viii) a kind of lithography, it comprises the steps: with infrared laser front (i)-(but arbitrary described presensitized plate with image recording layer of infrared imaging carries out the image-type exposure vii), on the version after the exposure, provide aqueous components and oil-based ink, then printing to remove the unexposed area of image recording layer.

(ix) (viii) described lithography wherein, is installed in presensitized plate on the printing machine carry out the image-type exposure with infrared laser before according to the front.

(x) (viii) described lithography wherein, is installed in presensitized plate on the printing machine before carrying out image-type exposure back with infrared laser and aqueous components and oil-based ink are provided according to the front.

The presensitized plate of the present invention first and second aspects (below abbreviate " presensitized plate of the present invention " as) has the very long printing life-span.

Can be directly during the numerical data document image from computer etc. when using with the presensitized plate of the ultrared laser instrument imaging of emission, the lithography of the present invention first and second aspects (below abbreviate " lithography of the present invention " as) can provide the big measured space of a whole page with the energy of actual amount, the laser imaging version is developed on printing machine, without development step.

We also are not very clear to the mechanism of operating under first aspect present invention.Clearly, when in the image recording layer at presensitized plate with cyanine dye during as infrared absorbing agents with at least one condensed ring that constitutes by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle and on aromatic rings or second heterocycle, have electron withdraw group, the polymerisation that the compound of free redical polymerization causes is carried out fast, form lasting image recording layer, thereby improved the printing life-span of version.This is likely the acceleration polymerization because of the compound of the free redical polymerization that causes owing to following reason.

(1) electron withdraw group has improved the ionization potential of cyanine dye.As a result, except that the normal decomposition of initator that the photo-thermal conversion causes, in the infrared radiation process, also be easy to take place some quick interactions between the dyestuff of excitation state and the initator.

(2) because the reaction of infrared absorbing agents self makes the possibility that produces free radical increase.

Equally, in the image recording layer of presensitized plate, constitute and the cyanine dye that on aromatic rings or second heterocycle, has at least one condensed ring that contains the heavy atom group during as infrared absorbing agents with having by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle, the compound of free redical polymerization obviously makes the polymerisation acceleration, form lasting image recording layer, thereby improved the printing life-span of version.A kind of possible reason is: in the infrared radiation process, infrared absorbing agents is easy to form triplet excited state, and the triplet excited state most probable makes the dissolved oxygen inactivation of the inhibition polymerization that exists in the layer.In addition, the infrared absorbing agents of triplet excited state and radical-forming agent may react in some way, promote the decomposition of radical-forming agent.

We neither be very clear to the mechanism of carrying out the present invention's operation in a second aspect of the present invention.Clearly, use the low infrared absorbing agents of oxidizing potential can promote the decomposition of radical-forming agent, the polymerisation of the compound of free redical polymerization is carried out fast, form lasting image recording layer, thereby improved the printing life-span of version.This is likely because the low infrared absorbing agents of oxidizing potential has the good body performance of giving.Promptly, except that the normal decomposition of radical-forming agent that the photo-thermal conversion causes, infrared absorbing agents improves has obviously promoted forming of the intermediate that is made of infrared absorbing agents and radical-forming agent for the body performance, and can think that this intermediate has been brought into play effect in the decomposition of radical-forming agent.

The specific embodiment

Be described in more detail below the present invention.

Presensitized plate

Image recording layer:

A first aspect of the present invention is a kind of presensitized plate, on carrier, has image recording layer, image recording layer comprises: infrared absorbing agents (A), this is a kind of cyanine dye, it has at least one condensed ring that is made of the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle, and has electron withdraw group or contain the group of heavy atom on aromatic rings or second heterocycle; The compound (C) of radical-forming agent (B) and free redical polymerization, and this image recording layer can be removed with printing-ink and/or humidification water.A second aspect of the present invention is a kind of presensitized plate, has image recording layer on carrier, and image recording layer comprises: infrared absorbing agents (A), its oxidizing potential are 0.45V (vs.SCE) at the most; The compound (C) of radical-forming agent (B) and free redical polymerization, and this image recording layer can be removed with printing-ink and/or humidification water.When shining these presensitized plates with infrared light, solidify the exposure area of image recording layer, forms hydrophobicity (lipophile) zone.When the printing beginning, unexposed area is removed from carrier fast with humidification water, printing ink or humidification water and ink emulsion.That is, image recording layer be can with printing-ink and/or humidification water remove the layer.

Each component of image recording layer is described below.

Infrared absorbing agents (A):

The infrared absorbing agents (A) that is used in the first aspect present invention is a kind of cyanine dye, it has at least one condensed ring that is made of the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle, and has electron withdraw group or contain the group of heavy atom on aromatic rings or second heterocycle.The infrared absorbing agents (A) that is used in the second aspect present invention is that oxidizing potential is the infrared absorbing agents of 0.45V (vs.SCE) at the most.As have by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle constitute and on aromatic rings or second heterocycle, have electron withdraw group or contain the infrared absorbing agents of cyanine dye of at least one condensed ring of heavy atom group and infrared absorbing agents that oxidizing potential is 0.45V (vs.SCE) at the most can be advantageously utilised in of the present invention first and second aspect in.

The infrared absorbing agents that is used in the first aspect present invention is:

Have the cyanine dye (A-1) that constitutes and on aromatic rings or second heterocycle, have at least one condensed ring of electron withdraw group by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle, and/or

Has the cyanine dye (A-2) that constitutes and on aromatic rings or second heterocycle, have at least one condensed ring that contains the heavy atom group by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle.

At first describe and have the cyanine dye (A-1) that constitutes and on aromatic rings or second heterocycle, have at least one condensed ring of electron withdraw group by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle.

Electron withdraw group is Hammett (Hammett) σ constant (σ of contraposition _ParaConstant) preferably being 0.01 at least, more preferably is 0.05 at least, even more preferably is 0.20 at least, further preferably is 0.30 substituting group at least.

σ _ParaConstant is that 0.05 substituent example comprises halogen atom such as fluorine (0.06), chlorine (0.30), bromine (0.27) and iodine (0.30) at least; The carbonyl substituted base as-CHO (0.22) ,-COCH ₃(0.50) ,-COC ₆H ₅(0.46) ,-CONH ₂(0.36) ,-COO-(0.30) ,-COOH (0.41) ,-COOCH ₃(0.39) and-COOC ₂H ₅(0.45); Sulfonyl or sulfinyl substituting group are as-SOCH ₃(0.49) ,-SO ₂CH ₃(0.72) ,-SO ₂C ₆H ₅,-SO ₂CF ₃(0.93) ,-SO ₂NH ₂(0.57) ,-SO ₂OC ₆H ₅,-SO ₃ ^-(0.09) and-SO ₃H (0.50); Nitrogenous substituting group as-CN (0.01) ,-N (CH ₃) ₃ ⁺(0.82) and-N (CF ₃) ₂(0.53); The substituting group that has a halogen is as-CCl ₃,-CH ₂Cl (0.18) ,-CHCl ₂With-CF ₃(0.54).The σ of the numeric representation all cpds in the bracket _ParaConstant.

The preferred example of these electron withdraw groups comprises the substituting group with non-covalent duplet.Substituent example with non-covalent duplet comprises the substituting group, the substituting group that has sulfonyl that have carbonyl, have the substituting group of sulfinyl and have the substituting group of ehter bond.The substituting group that wherein preferably has carbonyl.

The substituent object lesson that has carbonyl comprises acyl group such as acetyl group and benzoyl; Alkoxy carbonyl or aryloxycarbonyl such as methoxycarbonyl and toluyl oxygen base carbonyl; Amide groups such as diethylamino carbonyl; And carboxyl.These substituting groups can be by being at least the divalent linking group binding on the aromatic rings of cyanine dye or second heterocycle.

Describe below and have the cyanine dye (A-2) that constitutes and on aromatic rings or second heterocycle, have at least one condensed ring that contains the heavy atom group by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle.

Contain the substituting group that atomic weight is at least 28 atom with " containing the heavy atom group " expression among the application.The preferred example of such atom comprises silicon (28.09), phosphorus (30.97), sulphur (32.07), chlorine (35.45), germanium (72.61), arsenic (74.92), selenium (78.96), bromine (79.90), tin (118.71), antimony (121.76), tellurium (127.60) and iodine (126.90).The atomic weight of the various atoms of numeric representation in the bracket.In these heavy atoms, from the security of raw material be easy to obtain the aspect and consider preferred silicon, phosphorus and halogen (as chlorine, bromine, iodine).Preferred especially halogen.

These atomic weight are at least 28 atom and combine formation separately or with other atoms and be positioned at the aromatic rings of cyanine dye or the substituting group on second heterocycle.These substituting groups can be by being at least the divalent linking group binding on the aromatic rings of cyanine dye or second heterocycle.

Siliceous substituent example is included in the substituting group that has alkyl or aryl on the silicon atom, for example trimethyl silyl, t-butyldimethylsilyl and 3,5-dimethylphenyl silicyl.Phosphorous substituent example is included in the substituting group that has alkyl or aryl on the phosphorus atoms, as dimethyl phosphino-and diphenylphosphino and phosphono.The substituent example of sulfur-bearing comprises alkyl sulphonyl or aryl sulfonyl such as methyl sulphonyl and phenyl sulfonyl; Alkyl sulphinyl or aryl sulfonyl kia such as ethyl sulfinyl and toluyl sulfinyl; Sulfate such as sulfo group (sulfo), sulfino (sulfino) and time sulfo group (sulfeno) and salt and ester derivant; Alkyl sulfide and artyl sulfo such as methyl sulphur and phenyl sulphur.The example of halogen substituent comprises the alkyl of halogen atom, halogen replacement and the aryl that halogen replaces.

In order to make image recording layer have good imaging performance and suitable absorbing wavelength, in a first aspect of the present invention, particularly preferred cyanine dye is seven methine cyanine dyes with indolenine skeleton, benzo indolenine skeleton, benzothiazole skeleton, benzoxazole skeleton or benzo selenazoles skeleton.The seven methine cyanine dyes that most preferably have indolenine skeleton or benzo indolenine skeleton.The cyanine dye of formula for example, (1) is needs highly.

In formula, R ¹And R ²Represent independently of one another carbon number mostly be most 20 can substituted alkyl.The alkyl of preferred especially 1-4 carbon atom.

Ar ¹And Ar ²Expression independently of one another can have substituent aryl radical or heterocyclic group.The example of aryl radical comprises phenyl ring and naphthalene nucleus.The example of heterocyclic group comprises pyridine ring and pyrazine ring.Wherein preferred phenyl ring and naphthalene nucleus.

Y ¹And Y ²Represent independently of one another sulphur atom, oxygen atom, selenium atom, carbon number mostly be most 12 dialkyl group methylene or-the CH=CH-group.Wherein preferred dialkyl group methylene (as the dimethylated methylene base).

Z ¹And Z ²Be respectively the substituting group that is selected from alkyl, oxygen base, electron withdraw group and contains the heavy atom group, wherein at least one is electron withdraw group or contains the heavy atom group.Electron withdraw group comprises halogen atom, can have substituent carbonyl, can have substituent sulfonyl, thio group, haloalkyl and silicyl with the preferred example that contains the heavy atom group.Wherein preferred halogen atom, alkoxy carbonyl and haloalkyl.

Letter n and m represent 0 or bigger integer separately, and condition is that n and m sum are 1 at least.

Q is five methines or seven methines.From infrared light wavelength applicability and stable aspect are considered preferred seven methines.Q can be selected from following substituent group and be replaced: the substituting group of alkoxyl, aryloxy group, alkyl sulfide, aryl sulphur, dialkyl amido, ammonia diaryl base, halogen atom, alkyl, aralkyl, cycloalkyl, aryl, oxygen, imines alkali (iminium bases) and following formula (2).Wherein preferred ammonia diaryl base (as diphenyl amino) and aryl thio group (as phenyl sulphur).Preferred especially ammonia diaryl base.For good stable is provided, Q preferably includes cyclohexene, cyclopentene or the cyclobutane ring that contains three continuous methine chains.Wherein preferred cyclohexene or cyclopentene ring.

In formula, R ³And R ⁴Represent the alkyl of hydrogen atom, a 1-8 carbon atom or the aryl of 6-10 carbon atom independently of one another.Y ³Be oxygen atom or sulphur atom.

X ^-Be in needs and the situation of electric charge under the counter anion that exists.

At the cyanine dye that all has halogen atom on the aromatic rings at two ends places or all have a carbonyl substituted base on the aromatic rings at place, two ends is preferred.

In order to make the coating fluid that forms image recording layer have excellent storage stability, the preferred example of counter anion comprises halide ion and perchlorate, tetrafluoroborate, hexafluoro-phosphate radical and sulfonate ion.Preferred especially perchlorate and sulfonate ion.

The example of preferred cyanine dye comprises those cyanine dyes of following formula (3).

In formula, R ⁵And R ⁶Represent independently of one another carbon number mostly be most 20 can substituted alkyl.The alkyl of preferred especially 1-4 carbon atom.

Ar ³And Ar ⁴Represent the alkyl of hydrogen atom, a 1-4 carbon atom or the aryl of 6-10 carbon atom independently of one another.Preferred especially phenyl.

Y ⁴And Y ⁵Represent independently of one another sulphur atom, oxygen atom, selenium atom, carbon number mostly be most 12 dialkyl group methylene or-the CH=CH-group.Wherein preferred dialkyl group methylene (as the dimethylated methylene base).

Z ³-Z ¹⁰Be hydrogen atom, electron withdraw group or contain the heavy atom group that wherein at least one is electron withdraw group or contains the heavy atom group respectively.Preferred especially halogen atom and alkoxy carbonyl.

X ^-Identical with in the top formula (1).Preferred CF ₃SO ₃ ^-Ion.

The object lesson of preferred cyanine dye comprises but is not defined as chromophore skeleton and substituent those dyestuffs that have shown in the following table.In the cyanine dye shown in the following table, IR-2, IR-6, IR-8, IR-11 and IR-33 are the compounds of following formula (3) expression, wherein, and X ^-Be CF ₃SO ₃ ^-

Other preferred cyanine dyes of following formula (3) expression comprise Compound I R-36 and IR-37, among the embodiment of these two kinds of compounds with specification in the back.

Chemical formula among the table 1-8

	Z	R	X -
				IR-1	Cl	C 2H 5	ClO 4 -
IR-2	Cl	C 2H 5	CF 3SO 3 -
				IR-3	Br	C 3H 7	ClO 4 -
IR-4	Br	C 6H 13	PF 6 -
				IR-5	I	C 2H 5	ClO 4 -
IR-6	I	C 4H 8	CF 3SO 3 -
				IR-7	CO 2C 2H 5	C 2H 5	ClO 4 -
IR-8	SCF 3	CH 3	CF 3SO 3 -
				IR-9	SO 2CF 3	CH 3	ClO 4 -
IR-10	Cl	CH 3	BF 4 -
				IR-11	CF 3	C 2H 5	CF 3SO 3 -

	Z	R	X -
				IR-22	CO 2CH 3	CH 3	ClO 4 -
IR-23	SO 2OC 2H 5	CH 2C 6H 5	CF 3SO 3 -

	Z	R	X -
				IR-26	Br	C 2H 5	ClO 4 -
IR-27	SO 2OC 2H 5	CH 3	CF 3SO 3 -

	Z	R	Y 1	Y 2	X -
						IR-28	Cl	CH 3	Cl	S	ClO 4 -
IR-29	Br	CH 2(CH 2) 8CH 3	SPh	S	Br -
						IR-30	COCH 3	CH 2CH＝CH 2	Cl	O	SbF 6 -
IR-31	CO 2C 2H 5	CH 3	NPh 2	S	BF 4 -

	Z 1	Z 2	R 1	R 2	X -
						IR-32	Cl	H	C 2H 5	C 2H 5	ClO 4 -
IR-33	Cl	CH 3	C 2H 5	CH 3	CF 3SO 3 -
						IR-34	Cl	C(CH 3) 3	CH 3	CH 3	ClO 4 -
IR-35	I	Cl	C 2H 5	C 2H 5	ClO 4 -

Above-mentioned cyanine dye can use separately, also can two or more be used in combination.

Constitute and the cyanine dye of at least one condensed ring that on aromatic rings or second heterocycle, has electron withdraw group or contain the heavy atom group during with having in the present invention as infrared absorbing agents (A) by the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle, can make presensitized plate have excellent sensitivity, can make by the lithographic plate that obtains that develops at machine to have the excellent printing life-span.Therefore, by after the energy of infrared laser instrument with actual amount exposes to presensitized plate the version after the exposure being carried out developing at machine, the big measured space of a whole page can obtained under the condition of development step with launching.

As long as can reach purpose of the present invention, can also use together is not the infrared absorbing agents of above-mentioned cyanine dye A-1 and A-2.In these cases, in the infrared absorbing agents solid amount, the content of the infrared absorbing agents of non-above-mentioned cyanine dye A-1 and A-2 preferably is not more than 40wt%.

Absorbing wavelength to the infrared absorbing agents that can use jointly is not particularly limited, as long as they are to absorb light ray radiation that is used to write down and the material that can produce heat.But in order with the high output lasers that obtains easily good compatibility to be arranged, maximum absorption wavelength is that infrared absorbing dye and the pigment of 760-1200nm is preferred.

Operable dyestuff comprise be purchased dyestuff and technical literature such as Senryo Binran[Handbookof Dyes] known dye mentioned in (The Society of Systhetic Organic Chemistry, Japan, 1970).Suitable dyestuff comprises azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dyes, cyanine dye, squarylium dyestuff, pyralium salt, metal mercaptide salt complex, oxonol dye, diimine dyestuff, ammonium dyestuff and gram ketone (croconium) dyestuff.

Preferred dyestuff comprises the cyanine dye of mentioning among JP58-125246A, JP59-84356A, JP59-202829A and the JP60-78787A; The methine dyes of mentioning among JP58-173696A, JP58-181690A and the JP58-194595A; The naphthoquinone dyestuff of mentioning among JP58-112793A, JP58-224793A, JP59-48187A, JP59-73996A, JP60-52940A and the JP60-63744A; The squarylium dyestuff of mentioning among the JP58-112792A; The cyanine dye of mentioning among the GB434875B.

Can also advantageously use the near infrared absorption emulsion of mentioning among the US5156938.Preferred other compounds that use by this way comprise substituted aryl benzo (sulfo-) pyralium salt of mentioning among the US3881924; The cyclonite thiapyran salt of mentioning among the JP57-142645A (US4327169); The pyrylium compound of mentioning among JP58-181051A, JP58-220143A, JP59-41363A, JP59-84248A, JP59-84249A, JP59-146063A and the JP59-146061A; The cyanine dye of mentioning among the JP59-216146A; The five methine sulfo-pyralium salts of mentioning among the US4283475; The pyrylium compound of mentioning among JP5-13514B (the Japanese publication of examining with " JP XX-XXXXXX B " expression among the application) and the JP5-19702B.

Also preferably use US4756993 Chinese style (I) and hear-infrared absorption dye (II).

In these dyestuffs, more preferred example comprises cyanine dye, phthalocyanine dye, oxonol dye, squarylium dyestuff, pyralium salt, sulfo-pyralium salt and mercaptan nickel salt complex compound.Consider from the photo-thermal conversion efficiency aspect, even the dyestuff of general formula (a)-(e) more preferably.The cyanine dye of general formula (a) below preferred especially because they can provide high polymerization activity, also has excellent stability and cost effectiveness.

In the superincumbent general formula (a), X ¹Be hydrogen atom, halogen atom ,-NPh ₂The alkyl of (wherein, " Ph " expression phenyl), oxygen atom, sulphur atom, a 1-12 carbon atom, contain the group that heteroatomic alkyl or following formula are represented that contains of heteroatomic aromatic rings, a 1-12 carbon atom.Represent nitrogen-atoms, sulphur or oxygen atom, halogen atom or selenium atom with " hetero atom " among the application.

R ¹And R ²Each is the alkyl of 1-12 carbon atom, binding mutually naturally.In order to make the coating fluid that forms image recording layer have excellent storage stability, R ¹And R ²Preferably have the alkyl of 2 carbon atoms separately at least, more preferably be R ¹And R ²Binding forms 5 or 6 yuan of rings mutually.

Ar ¹And Ar ²Expression can substituted aryl radical independently of one another.Preferred aryl radical comprises phenyl ring and naphthalene nucleus.Preferred substituted comprises that carbon number mostly is 12 alkyl, halogen atom and carbon number most and mostly is most 12 alkoxyl.

Y ¹And Y ²Represent that independently of one another sulphur atom or carbon number mostly are 12 dialkyl group methylene most.

R ³And R ⁴Expression independently of one another can mostly be 20 alkyl most by substituted carbon number.Preferred substituted comprises that carbon number mostly is 12 alkoxyl, carboxyl and sulfo group most.

R ⁵-R ⁸Represent that independently of one another hydrogen atom or carbon number mostly are 12 alkyl most.In order to be easy to obtain raw material, R ⁵-R ⁸It preferably all is hydrogen atom.

Z _a ^-The expression counter anion.But, at R ¹-R ⁸In any one situation about being replaced by sulfo group under, Z _a ^-Be unwanted.In order to make the coating fluid that forms image recording layer have excellent storage stability, Z _a ^-Preferred example comprise halide ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions and sulfonate ion.Wherein, preferred especially perchlorate, hexafluorophosphoricacid acid ions and aryl sulfonic acid radical ion.

The object lesson of the cyanine dye of following formula (a) is shown below.

In the superincumbent general formula (b), L is the methine chain that has 7 covalency carbon at least.Methine chain can have substituting group, and these substituting groups binding mutually become ring structure.

Z _b ⁺It is counter cation.Preferred example comprises ammonium, iodine, sulfonium, phosphine, pyrans and alkali metal cation (Na ⁺, K ⁺, Li ⁺).

R ⁹-R ²⁰Expression is selected from hydrogen, halogen atom, cyanogen, alkyl, aryl, thiazolinyl, alkynyl, carbonyl, thio group, sulfonyl, sulfinyl, oxygen base and amino substituting group or the substituting group of two or three combinations arbitrarily wherein separately.R ⁹-R ²⁰Binding becomes ring structure mutually.

Consider that from being easy to obtain raw material and efficient aspect the dyestuff of top general formula (b) preferably wherein L has 7 covalency carbon and R ⁹-R ²⁰It all is the dyestuff of hydrogen atom.

The object lesson of the dyestuff of top general formula (b) is shown below.

In the superincumbent general formula (c), Y ³And Y ⁴Represent oxygen atom, sulphur atom, selenium atom or tellurium atom independently of one another.

M is the methine chain that has 5 covalency carbon at least.

R ²¹-R ²⁸Represent hydrogen atom, halogen atom, cyanogen, alkyl, aryl, thiazolinyl, alkynyl, carbonyl, thio group, sulfonyl, sulfinyl, oxygen base or amino independently of one another.

Z _a ^-Identical with in the top general formula (a).

The object lesson of the dyestuff of top general formula (c) is shown below.

In the superincumbent general formula (d), R ²⁹-R ³²Represent hydrogen atom, alkyl or aryl independently of one another.R ²⁹And R ³⁰Binding Cheng Huan mutually.Equally, R ³¹And R ³²Binding Cheng Huan mutually.

R ³³And R ³⁴Oxygen base or the halogen atom of representing alkyl, replacement independently of one another.There are a plurality of R ³³With a plurality of R ³⁴Situation under, R ³³Part is binding Cheng Huan, perhaps R mutually ³⁴Part is binding Cheng Huan mutually.

Can also be R ²⁹And/or R ³⁰With R ³³Binding Cheng Huan, R ³¹And/or R ³²With R ³⁴Binding Cheng Huan.

Letter n and m represent the integer of 0-4 independently of one another.

X ²And X ³Represent hydrogen atom, alkyl or aryl independently of one another, condition is X ²And X ³In at least one be hydrogen atom or alkyl.

Q is can substituted cyclonite or five methines, and Q can form ring structure together with divalent organic group.

Z _c ^-Identical with in the top general formula (a).

The object lesson of the dyestuff of top general formula (d) is shown below.

In the superincumbent general formula (e), R ³⁵-R ⁵⁰Represent hydrogen atom, halogen atom or replacement or unsubstituted cyano group, alkyl, aryl, thiazolinyl, alkynyl, hydroxyl, carbonyl, thio group, sulfonyl, sulfinyl, oxygen base or amino or salt structure independently of one another.If R ³⁵-R ⁵⁰Have electric charge, then the dyestuff of general formula (e) can also have counter ion counterionsl gegenions.

M represents two hydrogen atoms, metallic atom, halo metal group or oxygen metal group.Some metallic atoms that can be included among the M are element, transition metal and the lanthanide series that belongs to family 1 (IA family), family 2 (HA family), family 13 (IIIB family) and family 14 (IVB family) in periodic table.Wherein preferably copper, magnesium, iron, zinc, cobalt, aluminium, titanium and vanadium.

The object lesson of the dyestuff of top general formula (e) is shown below.

Operable pigment comprises and is purchased the pigment of mentioning in pigment and the technical literature, the example of these technical literatures has Colour Index, Saishin Ganryo Binran[Latest Handbook ofPigments] (Japan Association of Pigment Technology, 1977), Saishin GanryoOyo Gijutsu[Recent Pigment Application Technology] (CMC Shuppan 1986) and Insatsu Inki Gijutsu[Printing Ink Technology] (CMC Shuppan, 1984).

Suitable pigment comprises black pigment, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, blue pigment, viridine green, fluorescent pigment, metallic powdery pigment and polymer-bound dyestuff.Object lesson comprises soluble AZOpigments, azo lake pigment, concentrates AZOpigments, chelating AZOpigments, phthalocyanine color, anthraquinone pigment, perylene and naphthalenone (perinone) pigment, thioindigo color, Kui acridone pigment, triazine dioxin pigment, isoindolinone pigment, Kui titanium ketone pigment, mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment and carbon black.Wherein preferred carbon black.

Pigment can directly use without surface treatment, also can use after surface treatment.The example of surface treatment method comprises with resin or wax coating surface, surfactant deposition, reactive materials (as: silane coupler, epoxide or PIC) is bonded on the surface of pigments.Operable surface treatment method comprises those methods of describing in the following document: KinzokuSekken no Seishitsu to Oyo[Properties and Applications of MetallicSoaps] (Koshobo), Insatsu Inki Gijutsu[Printing Ink Technology] (CMCShuppan, 1984) and Saishin Ganryo Oyo Gijutsu[Recent Pigment ApplicationsTechnology] (CMC Shuppan 1986).

The oxidizing potential that can be used in the infrared absorbing agents in the second aspect present invention is 0.45V (vs.SCE) at the most.The oxidizing potential of infrared absorbing agents preferably is 0.40V (vs.SCE) at the most, even more preferably is 0.35V (vs.SCE) at the most.

Lower limit to the oxidizing potential of the infrared absorbing agents of preferred use does not have concrete regulation, but when with radical-forming agent (B) when being used in combination, consider from stable aspect, the oxidizing potential of infrared absorbing agents preferably is 0.10V (vs.SCE) at least, even more preferably is 0.15V (vs.SCE) at least.

For the low infrared absorbing agents of such oxidizing potential, the chromophore on the infrared absorbing agents preferably has to electron substituent group.Hammett (Hammett) σ constant (σ that preferably comprises contraposition to electron substituent group _ParaConstant) be-0.10 or littler substituting group.Object lesson comprises methyl, ethyl and propyl group (σ _ParaConstant is about-0.12 to about-0.20); Hydroxyl (σ _ParaConstant is-0.37); Alkoxyl such as methoxyl group, ethyoxyl, propoxyl group and butoxy (σ _ParaConstant is about-0.24 to about-0.45); Aryloxy group such as phenoxy group and toluyl oxygen base (toluyloxy) (σ _ParaConstant is about-0.32); Amino or substituted-amino are as amino, methylamino, ethylamino, butyl amino, dimethylamino, diethylamino, phenyl amino and diphenyl amino (σ _ParaConstant is-0.50 to about-0.35).Wherein, especially preferably give the strong group of Electronic Performance, as alkoxyl and amino or substituted-amino.

Substituting group with the aromatic radical that is connected with hetero atom also is preferred, because they have enlarged chromophoric conjugated system, has reduced oxidizing potential.The heteroatomic example that connects aromatic radical comprises nitrogen, oxygen, phosphorus, sulphur and selenium atom.Especially preferably use sulphur atom as hetero atom.

The example of the aromatic radical that is connected with above-mentioned hetero atom comprises hydro carbons aromatic radical such as phenyl, naphthyl and anthryl; Heterocyclic group such as furyl, thianthrene group, pyrazolyl, triazolyl, indyl and benzothiazolyl.Heterocyclic group is particularly preferred.These aromatic radicals can have substituting group, and substituent preferred example comprises Hammett σ _ParaConstant is-0.10 or littler above-mentioned substituting group.

Consider that from suitable absorbing wavelength, fine solubility, good stable and suitable oxidizing potential aspect the chromophoric example that needs on the infrared absorbing agents comprises polymethine dyestuff such as cyanine dye and (sulfo-) pyrylium dye.Wherein preferred cyanine dye.For suitable absorbing wavelength and suitable oxidizing potential are provided, the cyanine dye that uses among the present invention especially preferably has seven methine cyanine dyes of indolenine skeleton, benzo indolenine skeleton, benzothiazole skeleton, benzoxazole skeleton or benzo selenazoles skeleton.These polymethine dyestuffs generally are the dyes of positive ion that wherein chromophore has positive charge.But in order to reduce oxidizing potential, the betaine type dyestuff that has negative electrical charge in chromophore is preferred.The example of betaine type dyestuff comprises that dyestuff that polymethine chain is wherein replaced by (sulfo-) barbiturates group and squarylium skeleton wherein or croconium skeleton mix the dyestuff in the polymethine chain.

In containing above-mentioned chromophoric various dyestuffs, below those dyestuffs of general formula D 1-D5 be preferred.

In general formula D 1, R ¹And R ²Be hydrogen atom or alkyl independently of one another with 1-12 carbon atom.R ¹And R ²Binding becomes ring structure mutually, and in this case, the ring of formation is 5 or 6 yuan of rings preferably.Ar ¹And Ar ²Can be similar or not similar, they can each naturally can substituted aryl radical.Preferred aryl radical comprises phenyl ring and naphthalene nucleus.Preferred substituted comprises that carbon number mostly is 12 alkyl, halogen atom and carbon number most and mostly is most 12 alkoxyl.Y ¹And Y ²Can be similar or not similar, they represent that separately sulphur atom or carbon number mostly are 12 dialkyl group methylene most.R ³And R ⁴Can be similar or not similar, they are mostly to be 20 alkyl most by substituted carbon number.Preferred substituted comprises that carbon number mostly is 12 alkoxyl, carboxyl and sulfo group most.R ⁵, R ⁶, R ⁷And R ⁸Can be similar or not similar, they are that hydrogen atom or carbon number mostly are 12 alkyl most.In order to be easy to obtain raw material, preferably all be hydrogen atom.R ⁹And R ¹⁰Can be similar or not similar, they are aryl radical that can a substituted 6-10 carbon number, the alkyl or the hydrogen atom of a 1-8 carbon atom.R ⁹And R ¹⁰Also binding becomes the ring of following structure mutually.

Wherein, preferred fragrance alkyl such as phenyl.

X ^-It is counter anion.At R ¹-R ⁸In any one situation about being replaced by sulfo group under, X ^-Be unwanted.In order to make the coating fluid that forms image recording layer have excellent storage stability, X ^-Preferred example comprise halide ion and perchlorate, tetrafluoroborate, hexafluoro-phosphate radical and sulfonate ion.Wherein, preferred especially perchlorate, hexafluoro-phosphate radical and aryl sulfonic acid radical ion.

In general formula D 2, R ¹-R ⁸, Ar ¹, Ar ², Y ¹, Y ²And X ^-All with general formula D 1 in identical.Ar ³Being heterocyclic group, can be monocycle, also can be many rings, and contains in nitrogen, oxygen and the sulphur atom at least one.Preferred heterocyclic group is selected from thiazole, benzothiazole, naphthothiazoles, thianaphtheno-7 ', 6 ', 4,5-thiazole, oxazole, benzoxazole, naphthoxazole, selenazoles, benzo selenazoles, naphthalene selenazoles, thiazoline, 2-quinoline, 4-quinoline, 1-isoquinolin, 3-isoquinolin, benzimidazole, 3,3-dialkyl group benzo indolenine, 2-pyridine, 4-pyridine, 3,3-dialkyl group benzo [e] indoles, tetrazolium, triazole, pyrimidine and thiadiazoles.The heterocyclic group that especially preferably has following structure.

In general formula D 3, R ¹-R ⁸, Ar ¹, Ar ², Y ¹And Y ²All with general formula D 1 in identical.R ¹¹And R ¹²Can be similar or not similar, the alkyl of their expression hydrogen atoms, pi-allyl, cyclohexyl or 1-8 carbon atom.Z is oxygen atom or sulphur atom.

In general formula D 4, R ¹³The group of expression is represented the substituting group of one of them following structure independently of one another, wherein, and R ¹⁴And R ¹⁵The alkyl of representing 1-8 carbon atom independently of one another, Y ³Be oxygen or sulphur atom.

In general formula D 5, R ³, R ⁴, Ar ¹, Ar ², Y ¹And Y ²All with above-mentioned general formula D 1 in identical.

In having above-mentioned chromophoric dyestuff, the dyestuff that preferred formula D1-D3 represents, the dyestuff that special preferred formula D1 represents.

In a second aspect of the present invention, " oxidizing potential " of infrared absorbing agents refers to the value that obtains by the potential measurement method with suitable indicator electrode (as hydrogen electrode, glass electrode or quinhydrone electrode) and suitable reference electrode (as: saturated calomel electrode or silver-silver chloride electrode) here in polar solvent such as acetonitrile or methyl alcohol, and be expressed as current potential with respect to standard calomel electrode (saturated calomel electrode abbreviates " SCE " herein as).

In a second aspect of the present invention, below the non-limitative example (IR-1 to IR-12) that the preferred oxidizing potential that uses is some infrared absorbing agents of 0.45V (vs.SCE) to the maximum is set forth in together with their oxidizing potential.The oxidizing potential of following infrared absorbing agents be with the platinum rotating disc electrode as indicator electrode and with Ag/AgCl (silver-silver chloride) electrode as reference electrode at polar solvent (0.1MEt ₄NClO ₄/ MeCN, wherein, " Et " represents ethyl, " Me " represents methyl) in the current potential measured, then the current potential of measuring is expressed as with respect to value as the standard calomel electrode of reference electrode.

When using the infrared absorbing agents of above-mentioned those suboxides current potentials, to compare with the situation of using the high oxidation potential infrared absorbing agents, the curing performance of image recording layer sharply improves.Though we also are not very clear to its reason, but can infer: infrared absorbing agents that oxidizing potential is low and ion radical-forming agent use the decomposition that can promote radical-forming agent together, polymerisation is carried out fast, thereby cause having the formation of the image-region of excellent in strength.

Only otherwise undermine required effect of the present invention, can use the common infrared absorbing agents of oxidizing potential jointly greater than 0.45V (vs.SCE).But in this case, the consumption of the common infrared absorbing agents that these are shared preferably is no more than the 40wt% of infrared absorbing agents solid amount.Can comprise dyestuff and the pigment of mentioning among JP7-285275A and the JP10-268512A by shared infrared absorbing agents.

In aspect of the present invention first and second, infrared absorbing agents can use separately, also can use together by two or more infrared absorbing agents.

In the solid amount in the image recording layer, the content of above-mentioned infrared absorbing agents (A) and other infrared absorbing agents is 0.01-50wt% preferably, more preferably 0.1-20wt%, further 0.5-10wt% preferably, even more preferably 1-10wt%.In the time of in this scope, the sensitivity of image-region and film-strength are all good especially.

The optical density (OD) at the obtained the maximum absorption place of image recording layer in infrared region is 0.05-3.0 preferably.In the time of in this scope, this layer has very high sensitivity.Because above-mentioned optical density (OD) depends on the content of infrared absorbing agents and the thickness of image recording layer, so can obtain required optical density (OD) by controlling these two parameters.

With commonsense method can the measurement image recording layer optical density (OD).In a suitable method, on transparent or white support, form image recording layer, select the thickness of image recording layer, make dried coating weight in the scope of presensitized plate requirement, measure the optical density (OD) of drying layer then with the conveying type optical densitometer.In another approach, on reflection carrier such as aluminium, form image recording layer, measure reflection density.

In image recording layer, infrared absorbing agents can equally with other components add with in one deck, also can add the different layers that provide respectively as described later in the top coat.

Radical-forming agent (B):

Under the energy of light, heat or two kinds of forms, radical-forming agent produces free radical, thereby causes and quicken the polymerization of the compound (C) of the described free redical polymerization in back.

The radical-forming agent that uses among the present invention (B) for example can be known thermal polymerization or the compound with the little key of bond dissociation energy.The example of radical-forming agent comprises salt, contains the triaizine compounds of trihalomethyl group, peroxide, azo-type polymerization initiator, azide, quinone diazide, Metallocenic compound and organic boronic salt compound.Wherein, salt is preferred especially because of its high sensitivity.

The object lesson of salt comprises diazol, salt compounded of iodine, sulfonium salt, ammonium salt and pyridiniujm.Wherein preferred salt compounded of iodine, diazol and sulfonium salt, more preferably sulfonium salt, even more preferably counter ion counterionsl gegenions are sulfonium salts of carboxylic acid ion.Preferred example comprises the salt described among the JP2001-133969A and the salt of following general formula (III)-(V).When enforcement is of the present invention, need water soluble salt, because they can improve the hydrophilicity of image recording layer, thereby can improve it at the machine developing performance.

In general formula (III), Ar ¹¹And Ar ¹²Be to have substituent carbon number mostly to be 20 aryl most independently of one another.Preferred substituted comprises that halogen atom, nitro, carbon number mostly are 12 alkyl, carbon number most and mostly are most 12 alkoxyl and carbon number and mostly are 12 aryloxy group most.

Z ^11-Be counter ion counterionsl gegenions, be selected from halide ion, perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions and sulfonate ion.Wherein, preferred perchlorate, hexafluorophosphoricacid acid ions, carboxylic acid ion and aryl sulfonic acid radical ion.

In above-mentioned general formula (IV), Ar ²¹Be to have substituent carbon number mostly to be 20 aryl most.Preferred substituted comprises that halogen atom, nitro, carbon number mostly are 12 alkyl, carbon number most and mostly are most 12 alkoxyl, carbon number and mostly are 12 aryloxy group, carbon number most and mostly are most 12 alkyl amino, carbon number and mostly are 12 dialkyl amido, carbon number most and mostly are most 12 arylamino and carbon number and mostly are 12 ammonia diaryl base most.

Z ^21-With the Z in the general formula (III) ^11-Identical.

In general formula (V), R ³¹-R ³³Be to have substituent carbon number mostly to be 20 alkyl most independently of one another.Preferred substituted comprises that halogen atom, nitro, carbon number mostly are 12 alkyl, carbon number most and mostly are most 12 alkoxyl and carbon number and mostly are 12 aryloxy group most.

Z ^31-With the Z in the general formula (III) ^11-Identical.

Provide the object lesson (OS-1 to OS-7) of the salt of the object lesson (ON-1 to ON-5) of salt of object lesson (OI-1 to OI-10), general formula (IV) of the salt of general formula (III) and general formula (V) below.

Other preferred radical-forming agents comprise the specific fragrant sulfonium salt of mentioning among JP2002-148790A, JP2001-343742A and the JP2002-6842A.

Provide the example of some typical compounds that are applicable to other preferred radical-forming agents of the present invention of mentioning among the JP2002-148790A below.

Radical-forming agent can use separately, also can use together by two or more radical-forming agents.

In the present invention, above-mentioned salt is as acid forming agent, but as the ionic initiator of radical polymerization.

Maximum absorption wavelength that can radical-forming agent used in this invention (B) preferably is not more than 400nm, more preferably no more than 330nm, even more preferably no more than 270nm.When making absorbing wavelength drop in the ultraviolet ray range in this way, can under white light, handle image recording material.

In the solid amount in the image recording layer, the content of radical-forming agent (B) is 0.1-50wt% preferably, more preferably 0.5-30wt%, even more preferably 1-20wt%.In the time of in this scope, the sensitivity of image recording layer and during printing the non-image areas of recording layer to avoid the performance of ink pollution good especially.

In image recording layer, radical-forming agent can equally with other components add with in one deck, also can add the different layers that provide respectively as described later in the top coat.

The compound of free redical polymerization (C):

The compound of the free redical polymerization that uses among the present invention (C) is the compound with free redical polymerization of at least one alkene formula unsaturated double-bond, is selected to have at least one, the compound of preferred two or more ends alkene formula unsaturated double-bond.These compounds are widely used in the industrial circle related to the present invention, can be without any particular restriction ground with in the present invention.These compounds have the number of chemical form, comprise monomer and prepolymer (as dimer, trimer and oligomer) and composition thereof and copolymer.

The example of these monomers and copolymer thereof comprises unsaturated carboxylic acid (as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid and maleic acid) and ester and acid amides.Preferred example comprises the ester of unsaturated carboxylic acid and aliph polyols and the acid amides of unsaturated carboxylic acid and fat polyamine.

Also preferred the use has the esters of unsaturated carboxylic acids of nucleophilic displacement of fluorine base such as hydroxyl, amino and sulfydryl or the addition reaction product of acid amides and single function or multi-functional isocyanates or epoxide, perhaps the dehydration condensation product of the esters of unsaturated carboxylic acids of similar replacement or acid amides and single function or multi-functional carboxylic acid.Also preferred the use has the esters of unsaturated carboxylic acids of electrophilic substituent such as isocyanate groups or epoxide group or the addition reaction product of acid amides and single function or multifunctional alcohol, amine or mercaptan; Have the esters of unsaturated carboxylic acids that can remove substituting group such as halogen or tosyl oxygen or the substitution reaction product of acid amides and single function or multifunctional alcohol, amine or mercaptan.In addition, for example, the compound group that can use wherein above-mentioned unsaturated carboxylic acid to be replaced by for example unsaturated phosphoric acid or styrene.

Provide the object lesson of the ester of unsaturated carboxylic acid and aliph polyols below.

Acrylate, comprise glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloyl-oxy propyl group) chlorinated isocyanurates and polyester acrylic ester oligomers.

Methacrylate, comprise butanediol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, 1, the 3-butanediol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two [right-(3-methacryloxypropyl-2-hydroxyl propoxyl group) phenyl]-dimethylmethanes and two [right-(methacryloxypropyl ethyoxyl) phenyl]-dimethylmethane.

Itaconate comprises ethylene glycol bisthioglycolate itaconate, propane diols diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate and D-sorbite four itaconates.

Crotonates comprises ethylene glycol bisthioglycolate crotonates, 1,4-butanediol two crotonates, pentaerythrite two crotonates and D-sorbite four crotonates.

The iso-crotonic acid ester comprises ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters and D-sorbite four iso-crotonic acid esters.

Maleate comprises ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate and D-sorbite four maleates.

The preferred example of the ester that other are suitable comprises the aliphatic alcohol ester of mentioning among JP46-27926B, JP51-47334B and the JP57-196231A; Has the ester of mentioning among the ester of fragrant skeleton such as JP59-5240A, JP59-5241A and the JP2-226149; The ester of mentioning among the JP1-165613 that has amino.

Can comprise methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1 as the object lesson of the acid amides of the unsaturated carboxylic acid of monomer and fat polyamine, 6-hexylidene bisacrylamide, 1, the two Methacrylamides of 6-hexylidene, diethylenetriamines three acrylamides, xylylene bisacrylamide and the two Methacrylamides of xylylene.

Other suitable amide type monomers comprise those monomers with cyclohexylidene structure of mentioning among the JP54-21726B.

Also preferably use isocyanate groups and hydroxyl urethane type addition polymerizable compound by the addition reaction preparation.Object lesson is included in the vinyl urethane compound that contains two or more polymerizable vinyl in the molecule, as described in JP-B-48-41708, its preparation method is: the vinyl monomer that has hydroxyl of following formula (VI) is added in a molecule have on the polyisocyanate compounds of at least two isocyanate groups.

CH ₂＝C(R ⁴¹)COOCH ₂CH(R ⁴²)OH (VI)

(in following formula, R ⁴¹And R ⁴²Independently of one another expression-H or-CH ₃)

Also preferred in addition those urethane acrylates of mentioning among urethane acrylate such as JP51-37193A, JP2-32293B and the JP2-16765B, the urethane compound of mentioning among JP58-49860B, JP56-17654B, JP62-39417B and the JP62-39418 of using with ethylene oxide type skeleton.

Other preferred examples comprise the compound of the free redical polymerization of mentioning among JP63-277653A, JP63-260909A and the JP1-105238 that has amino structure or sulfide structure in molecule.

Other examples comprise multifunctional acrylic ester or methacrylate, comprise the epoxy acrylate that the reaction of polyester acrylate and epoxy resin and (methyl) acrylic acid obtains, as those compounds of mentioning among JP48-64183A, JP49-43191B and the JP52-30490B.

Other examples comprise the vinyl phosphoric acid compound of mentioning among the specific unsaturated compound mentioned among JP46-43946B, JP1-40337B and the JP1-40336B and the JP2-25493.

Need to use the structure of mentioning among the JP61-22048A that contains perfluoroalkyl in some cases.

Can also use Nippon Setchaku Kyoukaishi in addition, Vol.20, No.7, light solidity monomer and the oligomer mentioned among the pp300-308 (1984).

The details of use of the compound of relevant free redical polymerization (C), for example it should have the structure of what type, is to use separately or two or more are used in combination, and its addition can be selected according to the required performance characteristic of recording materials.For example, when selecting, can consider following factor.

In order to obtain good sensitivity, preferably use the high structure of unsaturated group mass contg in each molecule.In most of the cases, its degree of functionality preferably is at least 2.In addition, (that is) intensity, cured film needs 3 or bigger degree of functionality in order to improve image-region.Other methods of effectively regulating intensity are that the compound (as acrylate compounds, methacrylate compound, distyryl compound, vinyl ether compound) that will have the group of the functional group of different numbers or different polymerization degree is used in combination.The selection of the compound of free redical polymerization and using method thereof also are to influence this compound and compatibility and the dispersed key factor thereof of other compositions (as binder polymer, initator, colouring agent) in image recording layer.For example, can improve compatibility by the compound that uses the low-purity compound or be used in combination two or more free redical polymerizations.Can also select ad hoc structure, to improve the caking property of itself and carrier or top coat.

Consider above-mentioned situation, in the solid amount in the image recording layer, the ratio of the compound of free redical polymerization (C) is 5-80wt% preferably usually, more preferably 20-75wt%, even more preferably 25-75wt%.These compounds can use separately, also can two or more be used in combination.As for the occupation mode of the compound (C) of free redical polymerization, can suppress the suitable choice structure of consideration, composition and the addition of resolution ratio, atomizing trend, change of refractive and surface viscosity of degree, the galley needs of polymerization based on oxygen.In some cases, can use the layer structure that comprises priming coat and top coat and corresponding coating process.

Binder polymer (D):

When enforcement is of the present invention,, also need to use binder polymer (D) in order to improve the film properties of image recording layer.Preferably use linear organic polymer as binder polymer.Known linear organic polymer can be used for this purpose.

Although using the main purpose of binding agent as mentioned above is to improve film properties,, add the dispersiveness of unexposed area in printing ink that the lipophile binding agent can also improve image recording layer effectively.The example of this binding agent comprises polyvinyl acetal resin, polyurethane resin, polyamide, epoxy resin, acrylic resin, methacrylic resin, polystyrene resin, varnish-type phenolic resin, carbamide resin, polyimide resin, mylar, synthetic rubber and natural rubber.

These binding agents preferably have crosslinkable.In order to make binding agent have crosslinkable, can on main polymer chain or side chain, introduce crosslinkable functional group such as alkene formula unsaturated double-bond.Crosslinkable functional group can introduce by copolymerization.

It is poly--1 that the example that has the polymer of alkene formula unsaturated double-bond on molecular backbone comprises, 4-butadiene and poly--1,4-isoprene.

The example that has the polymer of alkene formula unsaturated double-bond on molecular side chain comprises the polymer of acrylic or methacrylic acid esters or acid amides, and wherein, ester or amide residues (COOR or-" R " among the CONHR) have alkene formula unsaturated bond.

Example with residue (above-mentioned " R ") of alkene formula unsaturated bond 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) ₂-X (wherein, R ¹-R ³Alkyl, aryl, alkoxyl or the aryloxy group of representing hydrogen atom, a halogen atom or 1-20 carbon atom separately, R ¹Can and R ^{2 or}R ³Binding Cheng Huan; Letter n is the integer of 1-10; X is the dicyclopentadienyl residue).

The object lesson of suitable ester residue comprises-CH ₂CH=CH ₂(described in the JP7-21633B) ,-CH ₂CH ₂O-CH ₂CH=CH ₂,-CH ₂C (CH ₃)=CH ₂,-CH ₂CH=CH-C ₆H ₅,-CH ₂CH ₂OCOCH=CH-C ₆H ₅,-CH ₂CH ₂-NHCOO-CH ₂CH=CH ₂With-CH ₂CH ₂O-X (wherein, X is the dicyclopentadienyl residue).

The object lesson of suitable amide residue comprises-CH ₂CH=CH ₂,-CH ₂CH ₂-Y (wherein, Y is the cyclohexylidene residue) and-CH ₂CH ₂-OCO-CH=CH ₂

For example can solidify: directly between the polymer or utilize on the crosslinkable functionality of polymeric chain at polymer of polymerizable compound and grow free radical (polymerization in the polymerizable compound polymerization process causes free radical or increases base) to carry out addition polymerization with the binder polymer that following method will have a cross-linking properties.Also can solidify: slough atom (as: hydrogen atom or the carbon atom contiguous) on the polymer with crosslinkable functionality with free radical with the binder polymer that following method will have a cross-linking properties, thereby form the free polymer readical of mutual binding, the result forms crosslinked between polymer molecule.

In every gram binder polymer, the content of crosslinkable groups in binder polymer (content of the unsaturated double-bond of the free redical polymerization of measuring with iodimetry) is 0.1-10.0mmol preferably, more preferably 1.0-7.0mmol, even more preferably 2.0-5.5mmol.In the time of in this scope, the storage stability of the coating fluid of the sensitivity of image recording layer and formation image recording layer is good especially.

In order to improve with humidification water but not printing ink, can add hydrophilic polymer to the developing performance of exposed plate.Preferred example comprises the binding agent of possess hydrophilic property group, and the example of hydrophilic radical is hydroxyl, carboxyl, ethoxy, hydroxypropyl, amino, amino-ethyl, aminopropyl, carboxymethyl, sulfo group or phosphono.

The object lesson of these binding agents comprises gum arabic, casein, gel, starch derivatives, carboxymethyl cellulose and sodium salt thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid, styrene-maleic acid copolymer, polyacrylic acid and salt thereof, polymethylacrylic acid and salt thereof, the homopolymers of hydroxyethyl methacrylate and copolymer, the homopolymers of hydroxy-ethyl acrylate and copolymer, the homopolymers of hydroxy propyl methacrylate and copolymer, the homopolymers of hydroxypropyl acrylate and copolymer, the homopolymers of methacrylic acid hydroxy butyl ester and copolymer, the homopolymers of acrylic acid hydroxy butyl ester and copolymer, polyethylene glycol, the hydroxyl acrylic polymers, polyvinyl alcohol, degree of hydrolysis is 60wt% at least, is the hydrolyzed poly vinyl acetate of 80wt% at least preferably, the polyvinyl formal, polyvinyl butyral, PVP, the homopolymers of acrylamide and copolymer, the homopolymers of the homopolymers of Methacrylamide and copolymer and N hydroxymethyl acrylamide and copolymer.

In addition, the example of useful water soluble linear organic polymer comprises PVP and PEO.For example, alcohol soluble nylon or 2, the polyethers of two (4-hydroxyphenyl) propane of 2-is used in combination with chloropropylene oxide and can improves the curing film strength effectively.

Because image recording layer must can receive printing ink, so oil loving water-insoluble binding agent is more preferably as binder polymer (D) than hydrophilic water-soluble binder.

The weight average molecular weight of binder polymer (D) is 5000 at least preferably, is more preferably 10000-300000, and its number-average molecular weight is 1000 at least preferably, is more preferably 2000-250000.Polydispersity index (weight-average molecular weight/number-average molecular weight) is 1.1-10 preferably.

Binder polymer (D) can be atactic polymer, block polymer, graft polymers etc.Preferred atactic polymer.

Can be with method synthetic binder polymer well known in the art (D).The example of operable solvent comprises oxolane, dichloroethanes, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, 2-methoxy ethyl acetic acid esters, diethylene glycol dimethyl ether, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl-acetic acid ester, N between synthesis phase, dinethylformamide, N, N-dimethylacetylamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide (DMSO) and water.These solvents can use separately, also can two or more mix use.

Operable radical polymerization initiator comprises compound known such as azo initiator and peroxide initiator during synthetic binder polymer (D).

Binder polymer (D) can use separately, also can two or more mix use.

In solid amount in the image recording layer, the content of binder polymer (D) preferably is 10wt% at least, more preferably be 20wt% at least, even more preferably be 30wt% at least, preferably be 95wt% at the most, more preferably being 90wt% at the most, even more preferably being 80wt% at the most, further preferably is 70wt% at the most.Content in this scope can make the intensity of image-region and imaging performance good especially.

Compound of free redical polymerization (C) and binder polymer (D) weight ratio in use be 1/9-7/3 preferably.

Surfactant:

In order to promote to begin to print exposed plate at the machine developing performance and improve the coating surface shape, in image recording layer, need to use surfactant.The example of surfactant comprises non-ionic surface active agent, anion surfactant, cationic surfactant, amphoteric surfactant and fluorine-containing surfactant.Surfactant can use separately, also can two or more be used in combination.

Any known non-ionic surface active agent can be with in the present invention, without any special restriction.Object lesson comprises polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, the polystyrene-based phenyl ether of polyoxyethylene, polyoxyethylene polyoxy-propylene, the partial fatty acid ester of glycerine, the partial fatty acid ester of sorbitan, the partial fatty acid ester of pentaerythrite, the fatty-acid monoester of propane diols, the partial fatty acid ester of sucrose, the partial fatty acid ester of polyoxyethylene sorbitan, the partial fatty acid ester of polyoxyethylene sorbitol, the fatty acid ester of polyethylene glycol, the partial fatty acid ester of polyglycereol, polyoxyethylenated castor oil, the partial fatty acid ester of polyoxyethylene glycerine, fatty diglycollic amide, N, N-pair-2-hydroxy alkyl amine, polyoxyethylene alkyl amine, the fatty acid ester of triethanolamine, the trialkylamine oxide, polyethylene glycol, the copolymer of polyethylene glycol and polypropylene glycol.

Any known anion surfactant can be with in the present invention, without any special restriction.Object lesson comprises soap; rosinate; hydroxyalkylated sulfonic acid salt; alkylsulfonate; dialkyl sulfosuccinates; linear alkylbenzene sulfonate (LAS); branch-alkylbenzene sulfonate; alkylnaphthalene sulfonate; alkyl phenoxy polyoxyethylene propyl sulfonic acid salt; polyxyethylated sulfo group phenyl ether salt; N-methyl-N-oleyl sodium taurocholate; the disodium salt of N-alkyl sulfosuccinic acid monoamides; petroleum sulfonate; the sulphation butter; the sulfuric ester of fatty acid alkyl esters; alkyl sulfate; polyoxyethylene alkyl ether sulfate salt; aliphatic acid list glycerine sulfate; polyoxyethylene alkylphenyl ether sulfate salt; polyoxyethylene styryl phenyl ether sulfate; alkylphosphonic; polyoxyethylene alkyl ether phosphate; polyoxyethylene alkyl phenyl ether phosphate; partly-hydrolysed phenylethylene/maleic anhydride copolymer; partly-hydrolysed alkene/copolymer-maleic anhydride and naphthalene sulfonic acids-formaldehyde condensation products.

Any known cationic surfactant can be with in the present invention, without any special restriction.Object lesson comprises alkylamine salt, quaternary ammonium salt, polyoxyethylene alkyl amine salt and polyethylene polyamine derivative.

Any known amphoteric surfactant can be with in the present invention, without any special restriction.Object lesson comprises carboxybetaine, amino carboxylic acid, sulfobetaines, amidosulphuric acid salt and imidazoline.

In above-mentioned surfactant, term " polyoxyethylene " can substitute with more general term " polyoxy alkene ", and other example comprises polyformaldehyde, polyoxypropylene and polyoxy butylene.The surfactant that contains back described polyoxy thiazolinyl group equally can be with in the present invention.

Even preferred surfactant comprises the fluorine-containing surfactant that has perfluoroalkyl on molecule.The example of these fluorine-containing surfactants comprises anion surfactant such as perfluoroalkyl carboxylate, fluorinated alkyl sulfonate and perfluoroalkyl phosphate; Amphoteric surfactant such as perfluoroalkyl betaine; Cationic surfactant such as perfluoroalkyl leptodactyline; With non-ionic surface active agent such as perfluoroalkyl amine oxide, perfluoroalkyl-ethylene oxide adduct, contain perfluoroalkyl and hydrophilic radical oligomer, contain perfluoroalkyl and lipophilic group oligomer, contain perfluoroalkyl, hydrophilic radical and lipophilic group oligomer, contain the urethane of perfluoroalkyl and lipophilic group.Preferred example comprises the fluorine-containing surfactant of mentioning among JP62-170950A, JP62-226143A and the JP60-168144A.

Surfactant can use separately, also can two or more be used in combination.

In solid amount in the image recording layer, surface-active contents is 0.001-10wt% preferably, is more preferably 0.01-5wt%.

Colouring agent:

When enforcement is of the present invention, except that said components, can also add other all cpds as required.For example, can be used in visible region and absorb big dyestuff as the image colouring agent.Object lesson comprises oil yellow #101, oil yellow #103, the red #312 of oil-bound distemper, glossy dark green BG, oil blue BOS, oil blue #603, glossy black BY, glossy black BS and glossy black T-505 (by Orient Chemical Industries, Ltd produces); Also has the dyestuff of mentioning among Victoria's ethereal blue, crystal violet (CI 42555), crystal violet (CI 42535), ethyl violet, rhodamine B (CI 145170B), peacock green (CI 42000), methylene blue (CI 52015) and the JP62-293247A.Also preferably use pigment such as phthalocyanine color, AZOpigments, carbon black and titanium oxide.

They need to add these colouring agents, because can make image-region and non-image areas after the imaging distinguish mutually easily.In solid amount in the image recording layer, its addition generally is 0.01-10wt%.

Developer:

In order to form visual image, can in image recording layer, add the chromophore compound of acid or free radical response.The example that can be effective to these compounds of this purpose comprises diphenyl methane, triphenyl methane, thiazine, oxazine, xanthene, anthraquinone, iminoquinone, azo and azomethine dyes.

Object lesson comprises dyestuff such as bright green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose-red, tropeolin G, thymol blue, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurine 4B, Alpha-Naphthyl is red, Nile blue 2B, Nile blue A, crystal violet, peacock green, paramagenta, Victoria's pure blue B OH (Hodogaya ChemicalCo.Ltd production), oil blue #603 (Orient Chemical Industries, Ltd produces), the red #312 of oil-bound distemper (Orient Chemical Industries), oil red 5B (Orient Chemical Industries), oil scarlet (Orient Chemical Industries), oil red OG (Orient Chemical Industries), oil red RR (Orient Chemical Industries), glossy dark green #502 (Orient ChemicalIndustries), the red BEH class of Spiron (Hodogaya Chemical), the metacresol purple, cresol red, rhodamine B, rhodamine 6G, thiocyanic acid amine B, auramine, 4-is to diethylamino phenylimino naphthoquinones, 2-carboxyl anilino--4-is to diethylamino phenylimino naphthoquinones, the amino 4-of 2-carboxyl stearyl is right-N, and two (ethoxy) aminophenyl imino group naphthoquinones of N-, 1-phenyl-3-methyl-4-to diethylamino phenylimino-5-pyrazolone and 1-betanaphthyl-4-to diethylamino phenylimino-5-pyrazolone; With leuco dye such as p, p ', p "-hexamethyl triaminotriphenyl methylmethane (Leuco CrystalViolet) and the blue SRB (Ciba Geigy) of Pergascript.

Except that above-mentioned dyestuff, can also advantageously use the known leuco dye that is used in temperature-sensitive or the impact paper.Object lesson comprises the crystal violet lactone; the peacock green lactone; the benzoyl leukomethylene; 2-(N-phenyl-N-the methylamino)-amino fluorane of 6-(N-p-methylphenyl-N-ethyl); 2-anilino--3-methyl-6-(the N-ethyl-to toluidino) fluorane; 3; 6-dimethoxy fluorane; 3-(N; the N-diethylamino)-5-methyl-7-(N; the N-diphenyl amino) fluorane; 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluorane; 3-(N; the N-diethylamino)-6-methyl-7-anilino fluorane; 3-(N; the N-diethylamino)-the amino fluorane of 6-methyl-7-dimethylbenzene; 3-(N; the N-diethylamino)-6-methyl-7-chlorine fluorane; 3-(N; the N-diethylamino)-the amino fluorane of 6-methoxyl group-7-; 3-(N; the N-diethylamino)-7-(4-chloroanilino) fluorane; 3-(N; the N-diethylamino)-7-chlorine fluorane; 3-(N; the N-diethylamino)-the amino fluorane of 7-benzyl; 3-(N; the N-diethylamino)-7; 8-benzo fluorane; 3-(N; the N-dibutylamino)-6-methyl-7-anilino fluorane; 3-(N; the N-dibutylamino)-the amino fluorane of 6-methyl-7-dimethylbenzene; 3-piperidyl-6-methyl-7-anilino fluorane; 3-pyridine radicals-6-methyl-7-anilino fluorane; 3; two (1-ethyl-2 methyl indole-3-yl) benzofuranones of 3-; 3; two (1-normal-butyl-2 methyl indole-3-yl) benzofuranones of 3-; 3, two (right-the dimethylaminophenyl)-6-dimethylamino benzofuranones of 3-; 3-(4-diethylamino-2-ethoxyl phenenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine benzofuranone and 3-(4-diethylamino phenyl)-3-(1-ethyl-2 methyl indole-3-yl) benzofuranone.

In solid amount in the image recording layer, the addition of the chromophore compound of acid or free radical response is 0.01-10wt% preferably.

Polymerization inhibitor:

In the production of image recording layer or between the storage life,, need in image recording layer, add the small amount of thermal polymerization inhibitor for unnecessary thermal polymerization takes place the compound (C) that prevents free redical polymerization.

The preferred example of thermal polymerization inhibitor comprises quinhydrones, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2, the aluminium salt of 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol) and N-nitroso-N-phenyl hydroxylamine.

In solid amount in the image recording layer, the preferably about 0.01wt% of the addition of thermal polymerization inhibitor is to about 5wt%.

Advanced higher fatty acid derivative etc.:

In order to prevent the inhibitory action of oxygen to polymerization, can add advanced higher fatty acid derivative like mountain Yu acid or mountain Yu acid acid amides, the layer after coating makes it mainly concentrate on the surface of image recording layer when dry.In solid amount in the image recording layer, preferably about 0.1wt% such as the addition of advanced higher fatty acid derivative etc. is to about 10wt%.

Plasticizer:

In order to improve at the machine developing performance, image recording layer can also contain plasticizer.

The preferred example of plasticizer comprises phthalic acid ester such as repefral, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, phthalic acid octyl group capryl ester, dicyclohexyl phthalate, phthalic acid two (13) ester, phthalic acid butyl phenyl ester, diisooctyl phthalate and diallyl phthalate; Diol ester such as diethylene glycol (DEG) phthalic acid ester, ethyl phthalyl ethohexadiol acid esters, methyl phthalyl ethohexadiol acid esters, butyl phthalyl butyl glycol acid esters and triethylene glycol dieaprylate; Phosphate such as tricresyl phosphate and triphenyl phosphate; Binary fatty acid ester such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl azelate and dibutyl maleate; Polymethyl acid glyceride, triethyl citrate, triacetyl glycerine and butyl laurate.

In solid amount in the image recording layer, the content of plasticizer preferably is no more than about 30wt%.Inorganic particles:

Can contain inorganic particles in the image recording layer.

Preferred example comprises silica, aluminium oxide, magnesia, titanium oxide, magnesium carbonate, calcium alginate of fine pulverizing and composition thereof.Even these inorganic particles can not carry out the photo-thermal conversion, they also can be used for the purpose such as the interface adhesion of reinforced film, raising and superficial makings.

The particle mean size of inorganic particle is 5nm-10 μ m preferably, more preferably 0.5 μ m-3 μ m.In the time of in this scope, they can stably be dispersed in the image recording layer, can make image recording layer keep sufficiently high film-strength, can make the non-image areas of formation have excellent hydrophily, are difficult for by ink pollution during printing.

These inorganic particles are easy to be purchased product as cataloid dispersion liquid and other and obtain.

In solid amount in the image recording layer, the content of these inorganic particles preferably is no more than 20wt%, more preferably no more than 10wt%.

Low-molecular-weight hydrophilic compounds:

For improve presensitized plate at the machine developing performance, image recording layer can contain the low-molecular-weight compound of hydrophily.The example of the suitable low-molecular-weight compound of hydrophily comprises following water-soluble organic compounds: glycol such as ethylene glycol, diethylene glycol (DEG), triethylene glycol, propane diols, DPG and tripropylene glycol and ether thereof or ester derivant; Polyol such as glycerine and pentaerythrite; Organic amine such as triethanolamine, diethanol amine and monoethanolamine and salt thereof; Organic sulfonic acid such as toluenesulfonic acid and benzene sulfonic acid and salt thereof; Organic phospho acid such as phenyl-phosphonic acid and salt thereof; Organic carboxyl acid such as tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid and amino acid and salt thereof.

Can also comprise other additives except that said components in the image recording layer.

Form image recording layer:

When enforcement is of the present invention, can any diverse ways said components be added image recording layer.

A kind of method according to described in the JP2002-287334A is dispersed or dissolved in mentioned component in the solvent, becomes the coating fluid that forms image recording layer.Coating fluid is coated on back drying on the described carrier in back, thereby forms image recording layer.This method provides the molecule dispersion type image recording layer.

The non-limiting example of solvent comprises dichloroethanes, cyclohexanone, methyl ethyl ketone, methyl alcohol, ethanol, propyl alcohol, glycol monomethyl methyl ether, 1-methoxyl group-2-propyl alcohol, 2-methoxy ethyl acetic acid esters, 1-methoxyl group-2-propyl-acetic acid ester, dimethoxy-ethane, methyl lactate, ethyl lactate, N, N-dimethylacetylamide, N, dinethylformamide, tetramethylurea, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), sulfolane, gamma-butyrolacton, toluene, acetone and water.These solvents can use separately, also can two or more mix use.

The solid concentration of the coating fluid of formation image recording layer is 1-50wt% preferably.

In JP2001-277740A and the described another kind of method of JP2001-277742A, image recording layer is to form after being encapsulated in the mentioned component some or all in the microcapsules.This method provides the microcapsule-type image recording layer.The advantage of this image recording layer is can access better at the machine developing performance.Especially preferably with in the compound (C) of infrared absorbing agents (A), radical-forming agent (B) and free redical polymerization at least some with microencapsulated.

In the microcapsule-type image recording layer, above-mentioned various compositions can all carry out microencapsulated, and a part that also can be wherein is in the microcapsules outside.

Can be composition is microencapsulated with known method.The non-limiting example of preparation microcapsules technology comprises the method for using cohesion that relates to described in US2800457 and the US2800458; The method of the dependence interfacial polymerization described in US3287154, JP38-19574B and the JP42-446B; The method that relates to polymer deposition described in US3418250 and the US3660304; The method of the use isocyanates polyalcohol wall material described in the US3796669; The method of the use isocyanates wall material described in the US3914511; The method that US4001140,4087376 becomes wall material with the use ureaformaldehyde described in 4089802 or ureaformaldehyde-resorcinol; The method of the use wall material described in the US4025445 such as melamino-formaldehyde resin and hydroxylated cellulose; The in situ method that relates to monomer polymerization of instructing among JP36-9163B and the JP51-9079B; Spray drying process described in GB930422B and the US3111407; Electrolysis described in GB952807B and the GB967074B disperses cooling method.

The microcapsule wall that the present invention preferably uses is to have three-dimensional cross-linked and the wall dissolvable agents swelling.Therefore, preferably polyureas, polyurethane, polyester, Merlon, polyamide or its mixture of microcapsule wall material.Preferred especially polyureas and polyurethane.Compound can be imported in the microcapsule wall, thereby above-mentioned binder polymer can be imported with crosslinkable functionality such as alkene formula unsaturated bond.

The particle mean size of microcapsules is 0.01-3.0 μ m preferably, more preferably 0.05-2.0 μ m, even more preferably 0.10-1.0 μ m.In the time of in above-mentioned scope, the coating fluid of the formation image recording layer that obtains has good galley resolution ratio and good stability in time.

Coating process:

Though the coating weight (solids content) that is used to form image recording layer is different with application, coating weight is 0.3-3.0g/m preferably generally ²Too little coating weight can cause big apparent sensitivity, but can sacrifice the film properties of image recording layer.

Can use any different coating process.The example of suitable coating process comprises that rod is coated with, spin coating, spraying coating, curtain coating, dip-coating, airblade coating, scraper coating and roller coat.

Can prepare multiple coating fluid, repeat coating and dry, can form image recording layer with this.Priming coat:

In presensitized plate of the present invention, if desired, can between image recording layer and carrier, provide priming coat.The effect of priming coat is as heat insulation layer, can make full use of the heat that infrared laser produces like this, does not make in its diffusion cutter carrier, thereby helps to increase sensitivity.In addition, in non-image areas, priming coat helps separating of image recording layer and carrier, thereby can improve at the machine developing performance.

Priming coat preferably contains the compound that has polymerizable groups on molecule.But concrete preferred example comprises the silane coupler of the two key reactive groups of mentioning among the JP10-282679A of the alkene formula that has addition polymerization and has the phosphorus compound of the two key reactive groups of alkene formula.

The coating weight (solid) that is used to form priming coat is 0.1-100mg/m preferably ², more preferably 3-30mg/m ²

The molecular weight of compound that is used to form priming coat is high more, and its absorption property to carrier is strong more, and therefore, this compound is polymerizable compound preferably.

The compound that also needs in addition to use in the priming coat has the group that can be adsorbed on the carrier, is referred to as " carrier adsorptivity group " below.These groups are through after force handling as anodization or hydrophilicity-imparting treatment, generally can form ionic bond, hydrogen bond, coordinate bond or owing to molecular separating force forms key as metal, metal oxide or hydroxyl on the carrier with being present in.

Carrier adsorptivity group preferably has acidic group or base on molecule.

Acidic group is acid dissociation constant (pK preferably _a) be not more than 7 group.Object lesson comprises-COOH ,-SO ₃H ,-OSO ₃H ,-PO ₃H ₂,-OPO ₃H ₂,-CONHSO ₂-and-SO ₂NHSO ₂-.Wherein, especially preferably-PO ₃H ₂

Group preferably contains the atom that is selected from 15 families (5B) in the periodic table or 16 families (6B).Wherein, the group of preferably nitrogenous, phosphorus or sulphur atom.The group of preferred especially nitrogen atom.

In the compound that uses in priming coat, the example of the polymerizable groups that can comprise comprises polyaddition reaction group such as thiazolinyl and alkynyl.The non-limiting example of thiazolinyl comprises vinyl, acrylic, pi-allyl, cyclobutenyl and dialkyl group maleimide.The non-limiting example of alkynyl comprises acetylene and alkyl acetenyl.

In these groups, more preferred example is vinyl, acrylic, pi-allyl, acrylic acid (derivative of vinyl) and methacrylic acid (derivative of acrylic) group.

The compound that uses in the priming coat preferably has on molecule gives hydrophilic group.The preferred example of giving hydrophilic group comprises the ethylene oxide group of following formula

-(OCH ₂CH ₂) _n-

(wherein, n is the integer of 1-50, preferably the integer of 1-20).

On molecule, need to have ethylene oxide group because it can improve very bigly image recording layer at the machine developing performance.

In the present invention, for example can determine with following method whether this compound has adsorptivity to carrier.

Test compound is dissolved in the strong solvent of solvability, prepares coating fluid with this.Then coating fluid is coated on the carrier, making dried coating weight is 30mg/m ², carry out drying then.With the strong solvent of solvability on it the carrier of coated test compound thoroughly clean, measure then not by the residual volume of the test compound of flush away, calculate the adsorbance of carrier.Can directly measure the surplus of material compound by measuring remaining compound amount on the carrier, also at first quantitative assay is dissolved in the amount of the test compound in the washing lotion, carries out indirect calculation then.The method of quantitative assay compound comprises fluorescent x-ary analysis, reflection spectrometry and liquid chromatography.In the present invention, " compound that carrier is had adsorptivity " carries out carrying out washing treatment still residual 15mg/m at least on carrier as mentioned above even refer to ²Compound.

Compound [A]-[Q] that on carrier, has the concrete non-limiting example of the compound of adsorptivity to enumerate below comprising.

[A]CH ₂＝C(CH ₃)COO(C ₂H ₄O) _nP＝O(OH) ₂

N=1:Phosmer M (Uni-Chemical Co.Ltd production), Kayamer PM-1 (NipponKayaku Co.Ltd), Light-Ester P-M (Kyoeisha Chemical Co.Ltd), NK EsterSA (Shin-Nakamura Chemical Co.Ltd)

n＝2：Phosmer PE2(Uni-Chemical Co.Ltd)

n＝4-5：Phosmer PE(Uni-Chemical Co.Ltd)

n＝8：Phosmer PE8(Uni-Chemical Co.Ltd)

[B] [CH ₂=C (CH ₃) COO (C ₂H ₄O) _n] _mP=O (OH) _3-mThe mixture of the compound of n=1 and m=1 and 2 o'clock: MR-200 (Daihachi Chemical IndustryCo.Ltd)

[C]CH ₂＝CHCOO(C ₂H ₄O) _nP＝O(OH) ₂

N=1:Phosmer A (Uni-Chemical Co.Ltd production), Light-Ester P-A (KyoeishaChemical Co.Ltd.)

[D][CH ₂＝CHCOO(C ₂H ₄O) _n] _mP＝O(OH) _3-m

The mixture of the compound of n=1 and m=1 and 2 o'clock: AR-200 (Daihachi Chemical IndustryCo.Ltd)

[E]CH ₂＝C(CH ₃)COO(C ₂H ₄O) _nP＝O(OC ₄H ₉) ₂

n＝1：MR-204(Daihachi Chemical Industry Co.Ltd)

[F]CH ₂＝CHCOO(C ₂H ₄O) _nP＝O(OC ₄H ₉) ₂

n＝1：AR-204(Daihachi Chemical Industry Co.Ltd)

[G]CH ₂＝C(CH ₃)COO(C ₂H ₄O) _nP＝O(OC ₈H ₁₇) ₂

n＝1：MR-208(Daihachi Chemical Industry Co.Ltd)

[H]CH ₂＝CHCOO(C ₂H ₄O) _nP＝O(OC ₈H ₁₇) ₂

n＝1：AR-208(Daihachi Chemical Industry Co.Ltd)

[I]CH ₂＝C(CH ₃)COO(C ₂H ₄O)P＝O(OH)(ONH ₃C ₂H ₄OH)

n＝1：Phosmer MH(Uni-Chemical Co.Ltd)

[J]CH ₂＝C(CH ₃)COO(C ₂H ₄O) _nP＝O(OH)(ONH(CH ₃) ₂C ₂H ₄OCOC(CH ₃)＝CH ₂)

n＝1：Phosmer DM(Uni-Chemical Co.Ltd)

[K]

CH ₂＝C(CH ₃)COO(C ₂H ₄O) _nP＝O(OH)(ONH(C ₂H ₅) ₂C ₂H ₄OCOC(CH ₃)＝CH ₂)

n＝1：Phosmer DE(Uni-Chemical Co.Ltd)

[L] CH ₂=CHCOO (C ₂H ₄O) _nP=O (O-ph) ₂(wherein, ph represents phenyl ring)

n＝1：AR-260(Daihachi Chemical Industry Co.Ltd)

[M] CH ₂=C (CH ₃) COO (C ₂H ₄O) _nP=O (O-ph) ₂(wherein, ph represents phenyl ring)

n＝1：MR-260(Daihachi Chemical Industry Co.Ltd)

[N][CH ₂＝C(CH ₃)COO(C ₂H ₄O) _n] ₂P＝O(OH)

n＝1：MR-200(Daihachi Chemical Industry Co.Ltd)、Kayamer PM-2(NipponKayaku Co.Ltd)、Kayamer PM-21(Nippon Kayaku Co.Ltd)。

[O][CH ₂＝CHCOO(C ₂H ₄O) _n] ₃P＝O

n＝1：Viscoat 3PA(Osaka Organic Chemical Industry Ltd)

[P][CH ₂＝CHCOO(C ₂H ₄O) _n] ₂P＝O(OC ₄H ₉)

n＝1：PS-A4(Daihachi Chemical Industry Co.Ltd)

Operablely be purchased that product comprises but be not defined as above-claimed cpd.

The same with common acrylic monomers, can be with the Jikken Kagaku K ō za[Lectures in experimental Chemistry of Kiyoshi Kato work] or Shigaisen K ō kaShisutemu[Ultraviolet curing systems] described in mode by the dehydration between acrylic or methacrylic acid and the phosphate cpd or by synthetic these phosphorus compounds that obtains of ester exchange reaction.Phosphorus compound also can be used as the mixture of several compounds of any proper ratio.In the superincumbent chemical formula, the increase of the number of representing along with oxirane chain length n, synthetic net product is more and more difficult; On the contrary, can obtain having the mixture of several compounds of about required chain length.The concrete non-limiting example of chain long number n comprises 0,1,2, about 4-5, about 5-6, about 7-9, about 14, about 23, about 40 and about 50.

Multiple these compounds can mix the back with any suitable ratio to be used.

The formation method of priming coat can be: above-claimed cpd is dissolved in water, organic solvent such as methyl alcohol, ethanol or methyl ethyl ketone or its mixed solvent, forms coating fluid, then coating fluid is coated on the carrier, and dry then.The another kind formation method of priming coat is: above-claimed cpd is dissolved in water, organic solvent such as methyl alcohol, ethanol or methyl ethyl ketone or its mixed solvent, form coating fluid, then carrier is immersed in the coating fluid, compound is adsorbed on the carrier, flush away excess liquid such as water is dry then then.

In preceding a kind of method, can in all sorts of ways as rod be coated with, spin coating, spraying coating and curtain rubbing method be coated with wherein that the concentration of above-claimed cpd is the solution of 0.005-10wt%.

In a kind of method in back, solution concentration is 0.01-20wt% preferably, is more preferably 0.05-5wt%.Preferably 20-90 ℃ of soaking temperature is more preferably 25-50 ℃.Soak time preferably 0.1 second to 20 minutes, more preferably 2 seconds to 1 minute.

Protective layer:

In presensitized plate of the present invention, can randomly on image recording layer, provide protective layer.When enforcement was of the present invention, exposure was carried out under the condition in opening at atmosphere usually.Protective layer can prevent that the oxygen that exists in the atmosphere and micromolecular compound such as alkaline matter from entering image recording layer; otherwise the imaging reaction that can cause exposure forms inhibitory action, thereby can prevent that the imaging reaction that is caused by exposure under to the air open condition is suppressed.Therefore, the permeability that the required performance of protective layer preferably includes oxygen and micromolecular compound is low, the exposure light line propagated good, image recording layer is had excellent caking property, when machine develops, be easy to remove after the exposure.Various protective layers with these performances have obtained research in the prior art, and are described in detail in as among US3458311 and the JP55-49729A.

The material that can be used in the protective layer comprises the water-soluble polymeric compound with better degree of crystallinity, as polyvinyl alcohol, PVP, acid cellulose, gel, gum arabic and polyacrylic acid.Wherein, from key property such as oxygen shielding properties and the aspect of performance of removing protective layer during developing consider that (PVA) can access best effect as key component with polyvinyl alcohol.Can make protective layer have required oxygen shielding properties and water miscible unsubstituted vinyl alcohol units as long as polyvinyl alcohol comprises, some vinyl alcohol units can be replaced by ester, ether or acetal, but protective layer can also comprise other copolymerization components.

Polyvinyl alcohol preferably degree of hydrolysis is that 71-100% and molecular weight are the polyvinyl alcohol of 300-2400.The object lesson of these polyvinyl alcohol comprises the following product of all being produced by Kuraray Co.Ltd.: PVA-105, PVA-110, PVA-117, 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 and L-8.

When the composition of selection appropriate condition such as protective layer (select PVA and use additive etc.), coating weight; not only to consider the oxygen shielding properties and develop during remove performance; and to consider other performances of protective layer to comprise mist formation performance, caking property and anti-scratch property.In general, PVA degree of hydrolysis high more (that is, the content of unsubstituted vinyl alcohol units in protective layer is high more), film thickness is big more, and then the oxygen shielding properties is high more, thereby causes better sensitivity.But when the oxygen shielding properties was too high, the problem that causes was: unnecessary polymerisation, mist formation, image line multiviscosisty and other unwanted effects during image exposure took place between production and storage life.In addition, comprise that other performances with the caking property of image-region and anti-scratch property also are extremely important when handling presensitized plate.That is, when owing to containing the water-soluble polymeric compound and be hydrophilic protective layer and be superimposed upon on the lipophile image recording layer, protective layer can may layering because caking property is not high enough.In the zone of layering, polymerisation produces defective such as the film curing performance is poor owing to oxygen has suppressed.

In order to improve the caking property between image recording layer and the protective layer, people have proposed the whole bag of tricks.For example, mention among JP49-70702A and the GB1303578A: the acrylic emulsion or the water-insoluble vinylpyrrolidone/vinyl acetate copolymer of in the hydrophilic polymer that mainly constitutes, sneaking into 20-60wt% by polyvinyl alcohol, with the mixture that obtains as film-stack on image recording layer, can obtain sufficiently high caking property like this.All these known technologies all can be applied to the present invention for this purpose.The object lesson of the method that is used to be coated with protective layer has been described among US3458311 and the JP55-49729A.

Can also give protective layer in addition with other functions.For example, the infrared light that is used to expose is had excellent propagated and can effectively absorb the colouring agent (as water-soluble dye) of the light of other wavelength by adding, can under the situation of desensitization not, improve the controllability of under safety lamp, handling presensitized plate.

Carrier:

The carrier that uses in presensitized plate of the present invention can be the thin slice or the plate of dimensionally stable, does not have what particular restriction.Its example comprises paper, the paper, metallic plate (as aluminium, zinc, copper), plastic foil (as cellulose diacetate, cellulosic triacetate, cellulose propionate, cellulose butylate, cellulose acetate butyrate, cellulose nitrate, PETG, polyethylene, polystyrene, polypropylene, Merlon, polyvinyl acetal) of (as polyethylene, polypropylene, polystyrene) that be laminated with plastics, stacked or vapour deposition has the plastic foil of above-mentioned metal on it.Preferred carrier comprises polyester film and aluminium sheet.Wherein, preferred especially aluminium sheet is because its dimensionally stable, more cheap.

Aluminium sheet can be a pure aluminum plate, mainly is made of aluminium but contains the alloy sheets of a small amount of other elements or be laminated to plastics on the aluminum or aluminum alloy film.Other elements that may reside in the aluminium alloy comprise silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium etc., and the content of these other elements in alloy preferably is no more than 10wt%.In the present invention, preferred pure aluminum plate.But, also be acceptable so there are a small amount of other elements because be difficult to produce pure aluminium fully with melting technique.Composition for aluminium sheet does not stipulate that public above-mentioned any material known in this field can use.

The thickness of carrier is preferably 0.1mm-0.6mm, more preferably 0.15mm-0.4mm, even more preferably 0.2mm-0.3mm.

Aluminium sheet preferably carries out surface treatment such as roughening processing or anodization before use.Surface treatment can improve hydrophily, is easy to make the good caking property of maintenance between image recording layer and the carrier.Before aluminium sheet being carried out the roughening processing, can remove rolling oil from the surface randomly with as surfactant, organic solvent or alkaline aqueous solution his-and-hers watches emaciated face fat.

Can in all sorts of ways surface of aluminum plate is carried out roughening processing, for example mechanical roughening, electrochemical roughening (wherein, electrochemical dissolution is carried out on the surface) and chemical roughening (wherein, surface selectivity ground chemolysis).

Can use the known roughening method of carrying out, as the roughening of polishing ball, silk brush roughening, sandblast roughening or polishing method.

Suitable electrochemical roughening method is included in the method for carrying out with alternating current or direct current in the electrolyte that contains sour example hydrochloric acid or nitric acid.Other suitable methods are to use mixed acid, the method described in JP54-63902A.

If desired, can carry out alkaline etching to the aluminium sheet through roughening with the aqueous solution as potassium hydroxide or NaOH handles.In addition, the aluminium sheet of alkaline etching can randomly carry out anodization after neutralization, to improve wearability.

To the aluminium sheet anodization time, can use the various electrolyte that can form porous oxide film.General sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or its mixture of using.Set these electrolytical concentration according to electrolytical type.

Though can change the anodization condition according to the particular electrolyte of using, general preferred condition is: electrolyte concentration is 1-80wt% in the solution empirically, solution temperature is 5-70 ℃, and current density is 5-60A/dm ², voltage is 1-100V, electrolysis time is 10 seconds to 5 minutes.The weight of the anodization layer that forms is 1.0-5.0g/m preferably ², be more preferably 1.5-4.0g/m ²

After carrying out anodization, if desired, surface of aluminum plate is carried out hydrophilicity-imparting treatment.A kind of suitable method of hydrophilizing is the alkali silicate method described in US2714066, US3181461, US3280734 and the US3902734.In the method, carrier soaks in as sodium silicate aqueous solution or electrolytic treatments.Other hydrophilicity-imparting treatment comprise the processing of carrying out with Potassium Zirconium Fluoride described in the JP36-22063B, and the processing of carrying out with the polyvinyl phosphonic acids described in US3276868, US4153461 and the US4689272.

Advantageously, the center line average roughness of carrier is 0.10-1.2 μ m.

The color density of the carrier of representing with reflection density is 0.15-0.65 preferably.

Back coating:

After the carrier surface processing or forming priming coat, can randomly on the carrier back side, provide back coating.

The preferred example of back coating is the coating that the metal oxide that is obtained by organo-metallic compound or inorganic metal compound hydrolysis and polycondensation mentioned among the coating that is made of organic polyhydroxyl compound mentioned among the JP5-45885A, the JP6-35174A constitutes.Wherein, silane oxo-compound such as Si (OCH ₃) ₄, Si (OC ₂H ₅) ₄, Si (OC ₃H ₇) ₄Or Si (OC ₄H ₉) ₄Because price is low, raw material is easy to obtain but preferred.

Exposure

In lithography of the present invention, the presensitized plate of the invention described above is carried out the image-type exposure with infrared laser.

Though the infrared laser that uses among the present invention is not particularly limited, solid state laser and the semiconductor laser that can launch the infrared light of 760-1200nm wavelength are preferred.The power output of infrared laser preferably is 100mW at least.In order to shorten the time for exposure, preferably use the multi-beam laser apparatus.

The time for exposure of each pixel preferably is no more than 20 μ s.The energy emission measure is 10-300mJ/cm preferably ²

Printing

As mentioned above, in lithography of the present invention, with infrared laser presensitized plate of the present invention is carried out image-type exposure after, aqueous ingredients and oil-based ink are supplied with exposed plate, directly print without development step independently.

Concrete example comprises following method: with infrared laser presensitized plate is exposed, then exposed plate is installed on the printing machine, directly carry out method of printing without development step; Presensitized plate is installed on the printing machine, on printing machine, exposes, directly carry out method of printing without development step then with infrared laser.

When thereby presensitized plate being carried out image-type exposure back when supplying with aqueous ingredients and oil-based ink and directly printing without development step such as wet development with infrared laser, in the exposure area of image recording layer, the image recording layer that solidifies by exposure forms the zone of accepting oil-based ink with lipophilic surface.Simultaneously, in unexposed area, remove with uncured image recording layer dissolving or after disperseing, manifest the hydrophilic surface of version in these zones with the aqueous components and/or the oil-based ink of supply.

As a result, aqueous components is bonded on the hydrophilic surface of present exposure, and oil-based ink is deposited on the exposure area of image recording layer, begins printing.At first aqueous components or oil-based ink are supplied with the version surface, polluted by image recording layer in the unexposed area of version, preferably at first supply with oil-based ink in order to prevent aqueous components.Aqueous ingredients and oil-based ink generally are humidification water and oil base printing-ink.

On offset press, presensitized plate is developed in this way, directly under this development state, print a large amount of spaces of a whole page then.

In lithography of the present invention, because the presensitized plate to the specific infrared absorbing agents of use of the present invention develops on printing machine, so presensitized plate has excellent sensitivity, lithographic plate has the outstanding printing life-span.

The application requires the priority of Japanese patent application 2003-85166,2003-327659 and 2003-341197, introduces them herein as a reference.In addition, the content of the document of quoting among the application all as a reference.

Embodiment

Provide some embodiment below, but the invention is not restricted to these embodiment.

1-1, manufacturing presensitized plate

(1) produce carrier:

Produce aluminium sheet according to following method.The melt of the JIS Al050 aluminium alloy that will be made of following element carries out casting after the cleaning: 99.5wt% or more aluminium, the iron of 0.30wt%, the silicon of 0.10wt%, the titanium of 0.02wt% and the copper of 0.013wt%, surplus is a unavoidable impurities.Cleaning is handled by the degassing and is formed, and it is to remove unwanted gas such as hydrogen in the melt that the degassing is handled, and carries out earthenware then and filters.Cast with direct cast-in chills method.Thickness is that the curing ingot bar of 500mm is polished, and removes the thick material of 10mm from the surface, carries out 10 hours the processing that homogenizes then under 550 ℃, prevents the intermetallic compound coarse.Then at 400 ℃ of following hot rolling ingot bars, in 60 seconds of intermediate annealing in 500 ℃ continuous annealing furnace, cold rolling then one-tenth thickness is the Rolling Aluminium Plate of 0.30mm.By the roughness of controlling the roll that uses in this method the center line average roughness Ra after cold rolling is controlled to be 0.2 μ m.Make Rolling Aluminium Plate process tension level(l)er to improve flatness then, with following method the aluminium sheet that obtains is carried out surface treatment then.

At first, in order to remove rolling oil from surface of aluminum plate, with the sodium aluminate aqueous solution of 10wt% 50 ℃ of 30 seconds of following ungrease treatment.Neutralize under 50 ℃ with the aqueous sulfuric acid of 30wt% then and remove to wash mud and handled for 30 seconds.

Next, in order to improve the caking property between image recording layer and the carrier,, carry out roughening and handle in order to give non-image areas to keep the performance of water.Specifically, using the electrolysis that is made of following step to carry out electrochemical roughening handles: aluminium sheet is crossed as Netcom contained 1wt% nitric acid and 0.5wt% aqueous solution of aluminum nitrate, this aqueous solution is supplied with non-direct current supply reservoir, simultaneously, applies 240C/dm on the aluminium sheet as anode ²Electric current, current density is 20A/dm ², the duty ratio of AC wave shape is 1/1.

In addition,, neutralize under 50 ℃ with the aqueous sulfuric acid of 30wt% then and remove to wash mud and handled for 30 seconds 35 ℃ of 30 seconds of following etch processes with the sodium hydrate aqueous solution of 10wt%.

Carry out anodization then, to improve the performance of wearability, chemical resistance and reservation water.This processing method is made of following step: as aqueous sulfuric acid (solution temperature is 35 ℃) by the 20wt% of supply in the non-direct current supply reservoir of the aluminium sheet of net the time, be 14A/dm with current density ²Direct current it is carried out electrolytic treatments, thereby on aluminium sheet, form 2.5g/m ²Anodization layer.

Next, in order to guarantee the hydrophily of non-image areas, under 70 ℃, aluminium sheet silicate was handled for 15 seconds with No. 3 sodium silicate aqueous solutions of 1.5wt%.The deposition of silicon is 10mg/m ²Aluminium sheet after the water flushing is handled then obtains refining carrier.The center line average roughness Ra of the carrier that so obtains is 0.25 μ m.

(2) form image recording layer:

Embodiment 1-1

Preparation has the coating fluid A of the formation image recording layer of following composition below.The coating fluid of just having made is coated on the carrier that obtains previously with the coiling rod immediately, uses air drier 115 ℃ of following dry 45 seconds then, thereby form image recording layer, and finished the production of negativity presensitized plate P-1.Dried coating weight is 1.0g/m ²Form the composition of the coating fluid A of image recording layer:

Infrared absorbing agents (IR-2 in the first aspect) 0.05g

Radical-forming agent (OS-7 of front) 0.2g

The monomeric compound 1.3g of following formula

Poly-(allyl methacrylate) (weight average molecular weight is 120000) 0.5g

Victoria's ethereal blue, naphthalene sulfonate 0.02g

The fluorine-containing surfactant 0.1g of following formula

Methyl ethyl ketone 18.0g

Embodiment 1-2 to 1-7

Except that kind, use the method identical to obtain negativity presensitized plate P-2 to P-7 with embodiment 1-1 by infrared absorbing agents that uses among each embodiment of change shown in the table 1 and radical-forming agent.

Embodiment 1-8

Except that the copolymer with allyl methacrylate and Sodium methacrylate (mol ratio is 80: 20) substitutes poly-(allyl methacrylate), use the method identical to obtain negativity presensitized plate P-8 with embodiment 1-1.

Embodiment 1-9

Except that substituting the monomeric compound of following formula, use the method identical to obtain negativity presensitized plate P-9 with embodiment 1-2 with dipentaerythritol acrylate.

Comparative example 1-1

Except that the infrared absorbing agents that will use changes into the IR-786 of following formula, use the method identical to obtain negativity presensitized plate P-10 with embodiment 1-1.

Embodiment 1-10

Preparation has the coating fluid B of the formation image recording layer of following composition.Coating fluid is coated on the carrier that obtains previously with the coiling rod, dry 60 seconds in 70 ℃ baking oven, thus form image recording layer, and finished the production of negativity presensitized plate P-11.Dried coating weight is 1.0g/m ²

Form the composition of the coating fluid B of image recording layer:

Water 95g

Microcapsules liquid (face as follows) 5g

(just amount of solid)

Ethoxylated trimethylolpropane triacrylate (the SR9035 that Nippon Kayaku 0.2gCo.Ltd produces; Oxirane addition molal quantity is 15; Molecular weight is 1000)

Radical-forming agent (OS-7 of front) 0.5g

The infrared absorbing agents IR-36 0.15g of following chemical formulation

Ethylene glycol 0.1g

Fluorine-containing surfactant (Dainippon Ink ﹠amp; Chemicals, Inc produces the Megaface F-171 of 0.1g)

Microcapsules liquid:

Prepare oil phase component with following method: dissolving 10g trimethylolpropane-eylylene diisocyanate addition product (Mitsui Takeda Chemicals in 17g ethyl acetate, the Takenate D-110N that Inc produces), 3.15g pentaerythritol triacrylate (SR444 that Nippon Kayaku Co.Ltd produces), 0.35g have the 3-(N of infrared absorbing agents IR-37, the 1g of following formula, the N-diethylamino)-6-methyl-7-anilino fluorane (Yamamoto Chemicals, the ODB that Inc produces) and 0.1g surfactant (Takemoto Oil ﹠amp; The Pionin A-41C that Fat Co.Ltd produces).Obtain the water component with following method: preparation 40g contains the aqueous solution of 4wt% polyvinyl alcohol (PVA-205 that Kuraray Co.Ltd produces).With homogenizer with the rotating speed of 12000rpm with oil phase component with the water component is mixed and emulsification 10 minutes.The emulsion that obtains is joined in the 25g distilled water, stir this mixture then, at first at room temperature stirred 30 minutes, stirred 3 hours down at 40 ℃ then.Then with distilled water with this mixture diluted, be the microcapsules liquid of 20wt% to form solid concentration.The particle mean size of microcapsules is 0.3 μ m.

1-2. Exposure and printing

With the presensitized plate exposure of the Trendsetter 3244VX that is equipped with water-cooled 40W infrared semiconductor laser (Creo Inc) to obtaining, power output is 9W, and the external drum rotating speed is 210rpm, and resolution ratio is 2400dpi.Line chart is included in the exposure image.Presensitized plate after the exposure does not at first develop and is directly installed on the light sensitive plate cylinder of SOR-M printing machine (Heidelberger Druckmaschinen AG).Use humidification water (EU-3 (etchant that Fuji Photo Film Co.Ltd produces)/water/isopropyl alcohol=1/89/10 (volume ratio)) and TRANS-G (N) tusche (India ink) (Dainippon Ink andChemicals, Inc), at first with humidification water and inking light sensitive plate, then with the print speed printing speed printing of 6000 spaces of a whole page per hour 100 editions.

Test is at the machine developing performance, be characterized by image recording layer unexposed area be developed in the printing paper number of finishing on the printing machine and needing when stopping to be transferred on the printing paper at machine from the printing ink of non-image areas.When using each presensitized plate, the unpolluted space of a whole page of non-image areas is less than 100.

1-3. Estimate

In general, under the situation of negativity presensitized plate, lower exposure dose causes the lower curing degree of image recording layer (photosensitive layer), and higher exposure dose causes higher curing degree.If the curing degree of image recording layer is too low, then the printing life-span of presensitized plate lacks, and the replication performance of point and fine rule is poor.On the contrary, when image recording layer had high curing degree, presensitized plate had the long printing life-span, and good point and fine rule replication performance can be provided.

As following described, printing life-span and the fine rule replication performance of the negativity presensitized plate P-1 to P-11 that obtains in to the embodiment of the invention under exposure dose condition same as described above are estimated.Represent the sensitivity of presensitized plate with these results.That is, space of a whole page number is big more in its printing life-span, and the live width when duplicating fine rule is more little, we can say that the sensitivity of such presensitized plate is high more.

(1) fine rule replication performance

After printing 100 spaces of a whole page and the verified as mentioned above space of a whole page that obtains and in non-image areas, not being subjected to ink pollution, continue other 500 spaces of a whole page of printing.With 25 times of magnifying glasses the line chart (the exposure width is the figure of the fine rule of 10,12,14,16,18,20,25,30,35,40,60,80,100 and 200 μ m) on 600 spaces of a whole page is altogether detected, the fine rule replication performance is carried out classification according to the fine rule width that is replicated in the printing ink without any interrupting.The results are shown in the following table 1.

(2) the printing life-span

After carrying out above-mentioned printing evaluation fine rule replication performance, continue printing again.Along with the increase of space of a whole page number, image recording layer weares and teares gradually, and the printing ink receptivity descends, and causes the ink density on the printing paper to descend.Drop to the space of a whole page number that printed according to ink density (reflection density) at 0.1 o'clock by when beginning printing, estimate the printing life-span.The results are shown in the following table 1.

Can clearly be seen that from table 1: when implementing lithography of the present invention with the presensitized plate (embodiment 1-1 to 1-10) of first aspect present invention, fine rule replication performance and printing life-span be many than presensitized plate (comparative example 1-1) fashion of using prior art all.

Table 1

	Presensitized plate	Infrared absorbing agents	Radical-forming agent	Fine rule replication performance (μ m)	The printing life-span (1000 spaces of a whole page)
						Embodiment 1-1	P-1	IR-2 in the first aspect	OS-7	10	50
Embodiment 1-2	P-2	IR-5 in the first aspect	OS-7	10	50
						Embodiment 1-3	P-3	IR-10 in the first aspect	OS-7	10	50
Embodiment 1-4	P-4	IR-16 in the first aspect	OS-7	20	40
						Embodiment 1-5	P-5	IR-2 in the first aspect	OS-1	16	40
Embodiment 1-6	P-6	IR-2 in the first aspect	OI-5	16	35
						Embodiment 1-7	P-7	IR-2 in the first aspect	ON-1	16	35
Embodiment 1-8	P-8	IR-2 in the first aspect	OS-7	25	20
						Embodiment 1-9	P-9	IR-5 in the first aspect	OS-7	10	35
Comparative example 1-1	P-10	IR-786	OS-7	40	10
						Embodiment 1-10	P-11	IR-36 IR-37	OS-7	16	30

2-1, Make presensitized plate

(1) produce carrier:

With with above-mentioned " 1-1, make presensitized plate " part in " (1) produces carrier " identical method obtain carrier.

(2) form image recording layer:

Embodiment 2-1

The coating fluid (1) that will have the formation image recording layer of following composition is coated on the carrier that obtains previously with the coiling rod, and be 0.7g/m thereby form drying coated amount dry 60 seconds in 80 ℃ baking oven then ²Image recording layer, and finished the production of presensitized plate 1.

Form the composition of the coating fluid (1) of image recording layer:

Infrared absorbing agents (IR-1 in the second aspect present invention)	0.05g
		Radical-forming agent (OS-6 of front)	0.2g
The binder polymer of following formula (1) (mean molecule quantity is 80000)	0.5g
		Polymerisable compound (NK Ester M-315, three (2-ethoxy) chlorinated isocyanurates triacrylate that Shin Nakamura Chemical Co.Ltd produces)	1.0g
Non-ionic surface active agent (Emulgen 147, Kao Corporation)	0.2g
		The fluorine-containing surfactant of following formula (1)	0.1g
Methyl ethyl ketone	18.0g

Fluorine-containing surfactant (1)

Binder polymer (1)

Embodiment 2-2 and 2-3

Change infrared absorbing agents and the radical-forming agent except that pressing shown in the table 2, use the method identical to obtain presensitized plate 2 and 3 with embodiment 2-1.

Embodiment 2-4

The coating fluid (1) that will have the formation priming coat of following composition is coated on the carrier that obtains previously with the coiling rod, and the amount of coating fluid is 7.5mL/m ², 10 seconds of carrier drying after in 80 ℃ baking oven, will being coated with then.Use the method coating identical to form the coating fluid of image recording layer then, thereby form presensitized plate 4 with embodiment 2-3.

Form the composition of the coating fluid (1) of priming coat:

Water	15g
		Methyl alcohol	135g
The compd A of following formula	0.72g

Embodiment 2-5

Except the copolymer with allyl methacrylate and Sodium methacrylate (mol ratio is 80: 20) in image recording layer substitutes the binder polymer (1), with the method identical painting bottom coating and image recording layer successively, thereby obtain presensitized plate 5 with embodiment 2-4.

Embodiment 2-6

The coating fluid (2) that will have the formation image recording layer of following composition is coated on the carrier that obtains previously with the coiling rod, and be 0.3g/m thereby form drying coated amount dry 60 seconds in 80 ℃ baking oven then ²Image recording layer.Have the coating fluid (3) of the formation image recording layer of following composition then with the coating thereon of coiling rod, obtain another coating, dried coating weight is 0.4g/m ², dry 60 seconds in 80 ℃ baking oven then, thus the production of presensitized plate 6 finished.

Form the composition of the coating fluid (2) of image recording layer:

Water

100g

Foregoing microcapsules liquid	5g (solid-based)
		Radical-forming agent (OS-7 of front)	0.5g
Fluorine-containing surfactant recited above (1)	0.2g

Form the composition of the coating fluid (3) of image recording layer:

Infrared absorbing agents (IR-8 in the second aspect present invention)	0.05g
		Radical-forming agent (OS-7 of front)	0.2g
The binder polymer of following formula (1) (mean molecule quantity is 80000)	0.5g
		Polymerisable compound (NK Ester M-315, three (2-ethoxy) chlorinated isocyanurates triacrylate that Shin Nakamura Chemical Co.Ltd produces)	1.0g
Non-ionic surface active agent (Emulgen 147, Kao Corporation)	0.2g
		The fluorine-containing surfactant of following formula (1)	0.1g
Methyl ethyl ketone	18.0g

Embodiment 2-7

The coating fluid (1) that will have the formation image recording layer of above-mentioned composition is coated on the carrier that obtains previously with the coiling rod, and the amount of coating fluid is 7.5mL/m ², dry 10 seconds in 80 ℃ baking oven then.Use the method identical to form another image recording layer thereon then, thereby form presensitized plate 7 with embodiment 2-6.

Embodiment 2-8 and 2-9

Except according to changing shown in the table 2 infrared absorbing agents and radical-forming agent that uses in the coating fluid (3) that forms image recording layer, use the method identical to obtain presensitized plate 8 and 9 with embodiment 2-7.

Comparative example 2-1

Change infrared absorbing agents and the radical-forming agent except that pressing shown in the table 2, use the method identical to obtain contrasting presensitized plate 1 with embodiment 2-1.The oxidizing potential of IR-786 is 0.49V (vs.SCE).

Comparative example 2-2

Except when preparing microcapsules liquid, not using infrared absorbing agents and, using the method identical to obtain contrasting presensitized plate 2 with embodiment 2-7 by changing shown in the table 2 infrared absorbing agents and radical-forming agent that uses in the coating fluid (3) that forms image recording layer.

2-2. Exposure and printing

With the presensitized plate exposure of Trendsetter 3244 VX (Creo Inc) that are equipped with water-cooled 40W infrared semiconductor laser to obtaining, power output is 9W, and the external drum rotating speed is 210rpm, and resolution ratio is 2400dpi.Line chart is included in the exposure image.Presensitized plate after the exposure does not at first develop and is directly installed on the light sensitive plate cylinder of SOR-M printing machine (Heidelberger Druckmaschinen AG).Use humidification water (EU-3 (etchant that Fuji Photo Film Co.Ltd produces)/water/isopropyl alcohol=1/89/10 (volume ratio)) and TRANS-G (N) tusche (India ink) (Dainippon Ink andChemicals, Inc), at first with humidification water and inking light sensitive plate, then with the print speed printing speed printing of 6000 spaces of a whole page per hour 200 editions.

Test is at the machine developing performance, be characterized by image recording layer unexposed area be developed in the printing paper number of finishing on the printing machine and needing when stopping to be transferred on the printing paper at machine from the printing ink of non-image areas.When using each presensitized plate, the unpolluted space of a whole page of non-image areas is less than 200.

2-3. Estimate

After finishing the inspection of developing on the printing machine, continue printing.Along with the increase of printing surface number, image recording layer weares and teares gradually, and the printing ink receptivity descends, and the ink density on the printing paper descends.Drop to the space of a whole page number that printed according to ink density (reflection density) at 0.1 o'clock by when beginning printing, estimate the printing life-span.The results are shown in the following table 2.

Table 2

	Infrared absorbing agents	Radical-forming agent	The printing life-span (1000 spaces of a whole page)
				Embodiment 2-1	IR-1 in the second aspect	OS-6	25
Embodiment 2-2	IR-5 in the second aspect	OI-5	20
				Embodiment 2-3	IR-8 in the second aspect	OS-7	25
Embodiment 2-4	IR-8 in the second aspect	OS-7	35
				Embodiment 2-5	IR-8 in the second aspect	OS-7	15
Embodiment 2-6	IR-8 in the second aspect	OS-7	20
				Embodiment 2-7	IR-8 in the second aspect	OS-7	30
Embodiment 2-8	IR-5 in the second aspect	OI-5	25
				Embodiment 2-9	IR-10 in the second aspect	OS-4	20
Comparative example 2-1	IR-786	OI-5	2
				Comparative example 2-2	IR-786	OS-4	2

Can clearly be seen that from table 2: the presensitized plate of the application of the invention second aspect (embodiment 2-1 to 2-9) can obtain printing outstanding lithographic plate of life-span.

Claims (11)

1. presensitized plate, it comprises carrier, priming coat and image recording layer, and described priming coat has the compound that contains the adsorbable group of carrier, polymerizable groups and ethylene oxide group on the molecule, and described image recording layer comprises:

Infrared absorbing agents (A), this is a kind of cyanine dye, it has at least one condensed ring that is made of the nitrogen heterocyclic ring that combines with aromatic rings or second heterocycle, and has electron withdraw group or contain the group of heavy atom on aromatic rings or second heterocycle,

Radical-forming agent (B) and

The compound of free redical polymerization (C),

And this image recording layer can be removed with printing-ink and/or humidification water.

2. presensitized plate according to claim 1, wherein, infrared absorbing agents (A) is the compound of following formula (1),

In formula, R ¹And R ²Represent independently of one another carbon number mostly be most 20 can substituted alkyl, Ar ¹And Ar ²Expression can substituted aryl radical or heterocyclic group independently of one another, Y ¹And Y ²Represent independently of one another sulphur atom, oxygen atom, selenium atom, carbon number mostly be most 12 dialkyl group methylene or-the CH=CH-group, Z ¹And Z ²Be respectively the substituting group that is selected from alkyl, oxygen base, electron withdraw group and contains the heavy atom group, Z ¹And Z ²In at least one be electron withdraw group or the group that contains heavy atom, alphabetical n and m represent 0 or bigger integer separately, condition is that n and m sum are 1 at least,

Q is five methines or seven methines, and it can be selected from following substituent group and replace: the substituting group of alkoxyl, aryloxy group, alkyl sulfide, aryl sulphur, dialkyl amido, ammonia diaryl base, halogen atom, alkyl, aralkyl, cycloalkyl, aryl, oxygen, imines alkali and following formula (2); It also can have cyclohexene, cyclopentene or the cyclobutane ring that contains three continuous methine chains;

In this formula, R ³And R ⁴Represent the alkyl of hydrogen atom, a 1-8 carbon atom or the aryl of 6-10 carbon atom independently of one another; And Y ³Be oxygen atom or sulphur atom,

X ^-Be in needs and the situation of electric charge under the counter anion that exists.

3. presensitized plate, it comprises carrier, priming coat and image recording layer, and described priming coat has the compound that contains the adsorbable group of carrier, polymerizable groups and ethylene oxide group on the molecule, and described image recording layer comprises:

Infrared absorbing agents (A), its oxidizing potential are 0.45V (vs.SCE) at the most,

Radical-forming agent (B) and

The compound of free redical polymerization (C),

And this image recording layer can be removed with printing-ink and/or humidification water.

4. presensitized plate according to claim 1, wherein, at least some in the compound (C) of infrared absorbing agents (A), radical-forming agent (B) and free redical polymerization are micro-encapsulated.

5. presensitized plate according to claim 3, wherein, at least some in the compound (C) of infrared absorbing agents (A), radical-forming agent (B) and free redical polymerization are micro-encapsulated.

6. lithography, it comprises the steps: with infrared laser but the described presensitized plate with image recording layer of infrared imaging of claim 1 to be carried out the image-type exposure, on the version after the exposure, provide oil-based ink and aqueous components, then printing to remove the unexposed area of image recording layer.

7. lithography, it comprises the steps: with infrared laser but the described presensitized plate with image recording layer of infrared imaging of claim 3 to be carried out the image-type exposure, on the version after the exposure, provide oil-based ink and aqueous components removing the unexposed area of image recording layer, and printing.

8. lithography according to claim 6 wherein, is installed in presensitized plate on the printing machine carry out the image-type exposure with infrared laser before.

9. lithography according to claim 7 wherein, is installed in presensitized plate on the printing machine carry out the image-type exposure with infrared laser before.

10. lithography according to claim 6 wherein, is installed in presensitized plate on the printing machine before carrying out image-type exposure back with infrared laser and oil-based ink and aqueous components are provided.

11. lithography according to claim 7 wherein, is installed in presensitized plate on the printing machine before carrying out image-type exposure back with infrared laser and oil-based ink and aqueous components are provided.