JP2003195490A - Lithographic printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithographic printing original plate in which the proofing property can be improved without decreasing the developing property of an exposed part by using a specified compound as a visible light absorbing dye. <P>SOLUTION: The lithographic printing original plate has a heat-sensitive layer containing an IR ray absorbing substance, a water-insoluble and alkali- soluble resin and a visible light absorbing dye on a supporting body. The visible light absorbing dye is a compound having an acidic group even after exposure. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a lithographic printing plate precursor.
In particular, it has excellent developability and plate inspection.
Alkaline possible by photothermal conversion of laser light, which can be improved
Concerning positive type lithographic printing plate precursors having a light-sensitive photosensitive layer
The [0002] In recent years, with the development of image forming technology,
A laser beam with a focused beam is scanned over the plate surface,
Originals, image originals, etc. are formed directly on the plate surface,
It became possible to make the plate directly without using the manuscript. But
Checking whether the completed version is the same as the manuscript
Work is necessary as with a plate using a conventional film manuscript.
is there. Conventionally, the image section has been used as a measure of ease of plate inspection.
And the contrast of the non-image area is called plate inspection.
In order to choose the type of coloring dye
Research is being conducted. Photothermal conversion in the recording layer by laser light irradiation
Causes alkali solubilization of the recording layer
The so-called thermal positive type that forms positive images
In order to improve the plate inspection of lithographic printing plate precursors
For this reason, the conventional UV exposure lithographic printing plate precursor
Color dyes are used, but the commonly used triphenyl
In the case of rumethane-based colored dyes, the amount should be high enough.
If added, the solubility of the exposed area will be reduced.
There is a problem that the image is not able to be produced.
It was. [0004] Accordingly, the present invention provides the present invention.
Laser light with excellent image quality and improved plate inspection
Positive having a photosensitive layer solubilized by alkali by heat conversion
The object is to provide a lithographic printing plate precursor. [0005] The present inventor has achieved the above object.
As a result of intensive studies to achieve this,
By using a compound having an acidic group even after light
Therefore, plate inspection can be achieved without degrading the developability of the exposed area.
And the present invention has been completed.
It was. This also allows conventional UV-sensitive lithographic printing plates
Absorbed at 350-450 nm, which was difficult to use
It has also been found that colored dyes having the above can be used. That is, the above problem is that a photosensitive layer is provided on a support.
A digitized lithographic printing plate precursor, wherein the photosensitive layer is a photothermal conversion product
Quality, water-insoluble and alkali-soluble resin, and exposure
Contains a visible light absorbing dye having an acidic group even after
To be solved by a lithographic printing plate precursor characterized by
Was found. Conventionally, visible light absorption having an acidic group is also performed.
As a dye-collecting dye, JP-A-11-190903 discloses an acid.
In Japanese Patent Application Laid-Open No. 11-143076
Is a dye that develops color with a base. However,
In the case of the former dye, the acidic group of the dye in the exposed area has a cyclic structure.
And the acidic group disappears in the alkaline developer.
Therefore, as with conventional dyes, if a large amount is added, development of the exposed area
The nature will decline. In the case of the latter dye, development
Occasionally there are acidic groups, so even if a large amount is added, developability will decrease.
Although there is no absorption, the dye in the unexposed area has no absorption, so it is colored
The effect is low and the plate inspection is not improved. In contrast to this
Bright visible light absorbing dye can be applied to both unexposed and exposed areas.
However, it also has an acidic group, so the developability of the exposed area is reduced.
In addition, the unexposed area is highly colored (a visible light absorbing dye).
Therefore, plate inspection is also good. [0008] DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below.
The The photosensitive layer in the lithographic printing plate precursor according to the present invention has few photosensitive layers.
Both are photothermal conversion substances, water-insoluble and alkali-soluble
Resin and visible light absorption with acidic groups even after exposure
Contains dyes and, if necessary, contains other ingredients
May be. The photosensitive layer of the present invention may be a single layer.
As described in JP-A-11-218914
It may be composed of more than one layer (hereinafter referred to in this specification).
If there are two or more photosensitive layers,
May be distinguished from each other). Photosensitive layer
In the case of two or more layers, each of the above three components is two or more layers.
As long as it is contained in at least one of the photosensitive layers
In addition, it may be contained in two or more layers. Preferably
It is preferably not contained in the upper layer but contained in the lower layer. In the present invention, the photosensitive layer is a single layer.
Even if the
The solution is higher than the solubility on the surface side
With a different structure, that is, the surface hardly soluble layer is separated into layers
The aspect formed in the upper part of this is also included. In such a case
Would be able to get a bigger descrimation
There are advantages. [Visible light absorbing dye] contained in the photosensitive layer of the present invention
Visible light absorbing dyes have acidic groups, even after exposure
If it is a compound having an acidic group, it is particularly limited.
There is no. Even after exposure, the visible light absorbing dye of the present invention
It has an acidic group, and the acidic group is cyclic in the exposed area.
It does not form a leuco body with a structure. Acidic groups form a cyclic structure
As a result, alkali solubility decreases and developability decreases.
However, when the visible light absorbing dye of the present invention is used,
Since it remains an acidic group without forming a cyclic structure after light,
While maintaining the properties of a visible light absorbing dye,
The developability of the resin is not deteriorated. Also used in the present invention
Visible light absorbing dyes are colored even in unexposed areas
Therefore, it is possible to improve the plate inspection property of a lithographic printing plate
Is. Included in visible light absorbing dyes used in the present invention
Examples of the acidic group include a carboxylic acid group, a sulfonic acid group,
Phenolic hydroxyl group, sulfonamide group, substituted sulfone
Amido acid groups and their sodium salts and potassium
And salt. In particular, a sulfonic acid group is preferable. These visible light absorbing dyes having acidic groups
However, it is not limited, and visible light conventionally used
An acidic group as described above is substituted at any position of the absorbing dye.
It only has to be. For example, Ar-N = N-Ar structure (Ar is
The aryl group is at least one acid
And a visible light absorbing dye having a functional group. In the following, visible light absorption that can be used in the present invention.
Specific examples of the dye will be given, but the present invention is limited to these.
It is not a thing. [0015] [Chemical 1] [0016] [Chemical 2] [0017] [Chemical 3][0018] [Formula 4][Water-insoluble and alkaline water-soluble resin]
In the light, water-insoluble and alkaline used in the photosensitive layer
Water-soluble resin (hereinafter referred to as alkali-soluble polymer as appropriate)
Is an acidic group on the main chain and / or side chain in the resin.
Homopolymers containing these, their copolymers or these
A mixture of Therefore, the photosensitive layer of the present invention has an
It has the property of dissolving when contacted with a caustic developer.
is there. Among these, the acids listed in the following (1) to (6)
Having a functional group in the main chain and / or side chain of the polymer
Is preferable from the viewpoint of solubility in an alkaline developer. (1) Phenolic hydroxyl group (-Ar-O
H) (2) Sulfonamide group (—SO₂NH-R) (3) Substituted sulfoamide acid group (hereinafter referred to as “active imide”
It is called "base". ) [-SO₂NHCOR, -SO₂NHSO₂R, -CON
HSO₂R] (4) Carboxylic acid group (—CO₂H) (5) Sulfonic acid group (-SO_ThreeH) (6) Phosphate group (-OPO_ThreeH₂) In the above (1) to (6), Ar has a substituent.
Represents a divalent aryl linking group which may be
The hydrocarbon group which may have a substituent is represented. An acidic group selected from the above (1) to (6)
Among the alkaline water-soluble polymers that have (1) pheno
Group, (2) sulfonamide group and (3) active imi
Alkali water-soluble polymers having a group are preferred,
(1) a phenol group or (2) a sulfonamide group
Alkaline water-soluble polymer having an alkaline developer
Most preferable from the standpoint of ensuring sufficient solubility and film strength.
Good. Next, these alkaline water soluble polymers
A typical example of the polymerization component will be described. (1) Polymerizability having a phenolic hydroxyl group
Monomers that can be polymerized with phenolic hydroxyl groups
From low molecular weight compounds each having one or more saturated bonds
For example, phenolic monomers
Acrylamide having a hydroxyl group, methacrylamide,
Krylate ester, methacrylate ester or hydroxy
Examples include styrene. Specifically, for example, N-
(2-hydroxyphenyl) acrylamide, N- (3
-Hydroxyphenyl) acrylamide, N- (4-H
Droxyphenyl) acrylamide, N- (2-hydro)
Xylphenyl) methacrylamide, N- (3-hydroxy
Cyphenyl) methacrylamide, N- (4-hydroxy
Phenyl) methacrylamide, o-hydroxyphenyl
Acrylate, m-hydroxyphenyl acrylate,
p-hydroxyphenyl acrylate, o-hydroxy
Phenyl methacrylate, m-hydroxyphenyl meta
Acrylate, p-hydroxyphenyl methacrylate,
o-hydroxystyrene, m-hydroxystyrene, p
-Hydroxystyrene, 2- (2-hydroxypheny)
E) Ethyl acrylate, 2- (3-hydroxypheny)
E) Ethyl acrylate, 2- (4-hydroxypheny)
E) ethyl acrylate, 2- (2-hydroxypheny)
E) Ethyl methacrylate, 2- (3-hydroxyphene)
Nyl) ethyl methacrylate, 2- (4-hydroxyphenyl)
Nenyl) ethyl methacrylate and the like. these
Two or more types of monomers having phenolic hydroxyl groups
You may use it in combination. (2) Polymerizable module having a sulfonamide group
Nomers include at least one nitrogen atom in one molecule.
Sulfone amide group (—NH—SO
₂-) And at least one polymerizable unsaturated bond
Polymerizable monomers composed of low molecular weight compounds
For example, an acryloyl group, an allyl group, or vinyloxy
A substituted or monosubstituted aminosulfonyl group or a
Low molecular weight compounds having a substituted sulfonylimino group are preferred.
Yes. Examples of such compounds include the following general formula:
Examples include compounds represented by (I) to (V). [0026] [Chemical formula 5] Where X¹And X²Are respectively -O-ma
Or -NR⁷-Is shown. R¹And R ^FourAre each hydrogen
Atom or -CH_ThreeRepresents. R², R^Five, R⁹, R¹²and
R¹⁶Each have 1 to 1 carbon atoms which may have a substituent.
12 alkylene groups, cycloalkylene groups, arylenes
Represents a group or an aralkylene group. R^Three, R⁷And R
¹³Each may have a hydrogen atom or a substituent.
An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an
Represents a reel group or an aralkyl group. R⁶and
R¹⁷Each have 1 to 1 carbon atoms which may have a substituent.
12 alkyl groups, cycloalkyl groups, aryl groups or
Represents an aralkyl group. R⁸, R^TenAnd R^{1 Four}Is hydrogen
Atom or -CH_ThreeRepresents. R¹¹And R¹⁵Is that
A single bond or optionally having 1 to 1 carbon atoms
12 alkylene groups, cycloalkylene groups, arylenes
Represents a group or an aralkylene group. Y¹And Y²The
Each represents a single bond or -CO-. Polymerizable monomer having a sulfonamide group
Specifically, m-aminosulfonylphenyl meta
Acrylate, N- (p-aminosulfonylphenyl)
Tacrylamide, N- (p-aminosulfonylpheny
E) Acrylamide and the like can be preferably used. (3) Alkali-soluble with an active imide group
The active polymer compound has an active imide group represented by the following formula:
What is contained in the child is preferable, and as this polymer compound
Is an active imide group represented by the following formula,
Low molecular weight with one or more unsaturated bonds that can be combined
A polymerizable monomer composed of a compound is homopolymerized, or
Obtained by copolymerizing this monomer with another polymerizable monomer
High molecular compounds. [0030] [Chemical 6] A polymerizable monomer having an active imide group
Specifically, N- (p-toluenesulfonyl)
Tacrylamide, N- (p-toluenesulfonyl) actyl
Rilamide and the like can be preferably used. (4) Alkaline water having a carboxylic acid group
Examples of the soluble polymer include a carboxylic acid group and a polymerizable polymer.
Compounds having one or more active unsaturated groups in the molecule
A polymer whose main constituent is the smallest constituent unit derived from
Can be mentioned. (5) an alkaline water-soluble polymer having a sulfonic acid group;
For example, a sulfonic acid group and a polymerizable unsaturated group
Derived from a compound having 1 or more in the molecule
Examples include polymers with small constituent units as the main constituent
it can. (6) As an alkaline water-soluble polymer having a phosphate group
For example, a molecule comprising a phosphate group and a polymerizable unsaturated group
The smallest component derived from a compound having one or more of each
And polymers having a main component as a main component. Arca used in the lithographic printing plate precursor according to the present invention
From the above (1) to (6) constituting a water-soluble polymer
The smallest structural unit with an acidic group chosen is in particular one kind of
It is not necessary to have a simple structure with the same acidic group.
Minimum constituent unit having two or more kinds of positions or different acidic groups
It is also possible to use those obtained by copolymerizing two or more kinds of positions. Conventionally known copolymerization methods are known.
Graft copolymerization method, block copolymerization method, random copolymerization
A polymerization method or the like can be used. In addition, phenolic hydroxide
A polymerizable monomer having a group has a sulfonamide group
Having polymerizable monomers and / or active imide groups
When copolymerizing polymerizable monomers, these components
The blending mass ratio is in the range of 50:50 to 5:95.
Preferably, it is in the range of 40:60 to 10:90
More preferred. The copolymer is copolymerized (1) to (1) to
The compound having an acidic group selected from (6) is in the copolymer
Are preferably contained in an amount of 10 mol% or more,
More preferably, it is contained in an amount of at least 1%. 10 mol%
If it is less than 1, development latitude can be improved sufficiently.
There is a tendency not to be able to. In the present invention, a copolymer is obtained by copolymerizing a compound.
In the case of forming the compound, the compound (1) to (1) to
It is also possible to use other compounds that do not contain acidic groups in (6).
Yes. (1) to (6) of other compounds not containing an acidic group
Examples include the compounds listed in the following (m1) to (m12)
Can be exemplified, but is not limited to these.
There is no. (M1) 2-hydroxyethyl acrylate
Or aliphatic such as 2-hydroxyethyl methacrylate
Acrylic acid ester having a hydroxyl group and methacryl
Acid esters. (M2) Methyl acrylate, ethyl acrylate, acrylic
Propyl lurate, butyl acrylate, amyl acrylate,
Hexyl acrylate, octyl acrylate, acrylic acid
Benzyl, 2-chloroethyl acrylate, glycidyl
Alkyl acrylates such as acrylates; (M3) methyl methacrylate, ethyl methacrylate, me
Propyl tacrylate, butyl methacrylate, methacryl
Amyl acid, hexyl methacrylate, cyclomethacrylate
Hexyl, benzyl methacrylate, methacrylic acid-2-
Alkyl such as chloroethyl and glycidyl methacrylate
Methacrylate. (M4) Acrylamide, Methacrylami
, N-methylolacrylamide, N-ethylacryl
Luamide, N-hexyl methacrylamide, N-cyclo
Hexylacrylamide, N-hydroxyethyl acrylate
Luamide, N-phenylacrylamide, N-nitrof
Phenyl acrylamide, N-ethyl-N-phenyl acrylate
Acrylamide such as rilamide or methacrylamid
De. (M5) Ethyl vinyl ether, 2-chrome
Roethyl vinyl ether, hydroxyethyl vinyl ether
Tellurium, propyl vinyl ether, butyl vinyl ether
, Octyl vinyl ether, phenyl vinyl ether
Vinyl ethers such as (M6) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate
Kind. (M7) Styrene, α-methylstyrene, methylstyrene
And styrenes such as chloromethylstyrene. (M8) Methyl vinyl ketone, ethyl vinyl ketone, plastic
Vinyl such as propyl vinyl ketone and phenyl vinyl ketone
Ketones. (M9) Ethylene, propylene, isobuty
Olefins such as len, butadiene and isoprene. (M10) N-vinylpyrrolidone, acrylonitrile,
Methacrylonitrile and the like. (M11) Maleimide, N-acryloylacrylami
, N-acetylmethacrylamide, N-propionyl
Methacrylamide, N- (p-chlorobenzoyl) meta
Unsaturated imides such as chloramide. (M12) Acrylic acid, methacrylic acid, maleic anhydride
Unsaturated carboxylic acids such as acids and itaconic acids. Examples of the alkaline water soluble polymer include infrared rays.
In terms of excellent image formability during exposure with a laser, etc.
It preferably has an enolic hydroxyl group, for example
Enol formaldehyde resin, m-cresol form
Aldehyde resin, p-cresol formaldehyde tree
Fat, m- / p-mixed cresol formaldehyde resin,
Phenol / cresol (m-, p-, or m- / p-
Any of mixing) such as mixed formaldehyde resin
Novolac resin and pyrogallol acetone resin are preferred
Can be mentioned. In addition, an alkenyl having a phenolic hydroxyl group
Examples of the water-soluble polymer further include US Pat. No. 4,12.
As described in US Pat. No. 3,279, t-butyl
Ruphenol formaldehyde resin, octylpheno
3-8 carbon atoms such as ruformaldehyde resin
Phenol and formaldehyde having a kill group as a substituent
A condensation polymer with a hydride is mentioned. The alkali-soluble polymer has a weight average content.
It is preferable that the amount is 500 or more, 1,000 to
More preferably, it is 700,000. Also that
The number average molecular weight is preferably 500 or more, and 75
More preferably, it is 0-650,000. Degree of dispersion
(Weight average molecular weight / number average molecular weight) is 1.1-10
It is preferable. In the present invention, the alkali-soluble high content
The polymerizable compound has a phenolic hydroxyl group as described above.
A polymerizable monomer having a monomer, a sulfonamide group,
Or a homopolymer of a polymerizable monomer having an active imide group
Or in the case of a copolymer, the weight average molecular weight is 2,000.
Those having a number average molecular weight of 500 or more
preferable. More preferably, the weight average molecular weight is 5,000.
0 to 300,000 and a number average molecular weight of 800 to 2
50,000, dispersity (weight average molecular weight / number average
Molecular weight) is 1.1-10. In addition, this departure
In the morning, the alkali-soluble polymer
Trees such as lumaldehyde resin and cresol aldehyde resin
In the case of fat, the weight average molecular weight is 500 to 20,000.
00 and the number average molecular weight is 200 to 10,000.
Those are preferred. In the case of having two or more photosensitive layers,
The alkali-soluble polymer used in the layer is acrylic.
The main resin consists of an organic compound with a buffering action and a base.
Improved solubility of the lower layer in alkaline developer
This is preferable from the viewpoint of image formation during development.
Yes. Furthermore, as this acrylic resin, sulfonamide group
Particularly preferred are those having Also used in photosensitive layer
As an alkali-soluble polymer, strong water is used in unexposed areas.
In the exposed area, some hydrogen bonds are generated.
Is easily released, the difference between the unexposed area and the exposed area
Because of its large image quality, image formation is improved.
A resin having a rutile hydroxyl group is desirable. More preferably
Borac resin. One alkali-soluble polymer
Or two or more types may be used together, the total content
However, in the total solid content of the heat-sensitive layer, 1 to 90% by mass is preferable,
2 to 70% by mass is more preferable, and 2 to 5% by mass is particularly preferable.
Good. When the content is less than 1% by mass, durability
Tends to get worse and over 90% by mass
Is preferred because of its tendency to decrease sensitivity and image formability.
It ’s not good. [Photothermal Conversion Material] Photothermal used in the present invention
The conversion substance is a substance that generates heat by absorbing light. Photothermal change
The conversion material converts the exposure energy into heat to expose the photosensitive layer.
It is possible to efficiently cancel the interaction of subregions
The The photothermal conversion substance in the present invention is used for recording.
If it has a function to absorb light and convert it into heat,
Although not limited to this, from the viewpoint of recording sensitivity, a wavelength of 700 to
A pigment or dye having a light absorption range in the infrared region of 1200 nm
preferable. As the pigment, commercially available pigments or color pigments can be used.
Ndex (C.I.) Handbook, "Latest Pigment Handbook" (Japanese Pigment)
(Technical Association, published in 1977), "Latest Pigment Applied Technology"
(CMC Publishing, 1986) and “Printing Ink Techniques”
The face described in "Jutsu" (CMC Publishing, 1984)
Fees are available. Examples of the pigment include black face
Materials, yellow pigments, orange pigments, brown pigments, red pigments,
Purple pigment, blue pigment, green pigment, fluorescent pigment, metal powder face
And polymer-bound dyes. Specifically, insoluble
Azo pigments, azo lake pigments, condensed azo pigments, chelates
Azo pigment, phthalocyanine pigment, anthraquinone face
, Perylene and perinone pigments, thioindigo face
Materials, quinacridone pigments, dioxazine pigments, isoi
Ndrinon pigments, quinophthalone pigments, dyed lakes
Pigment, azine pigment, nitroso pigment, nitro pigment, natural face
Use of pigments, fluorescent pigments, inorganic pigments, carbon black
You can. These pigments can be used without surface treatment.
The surface treatment may be applied. Surface treatment method
For surface coating with resin or wax, surfactant
Method of adhering, reactive substances (eg silane cups)
Face ring agent, epoxy compound, polyisocyanate)
And a method of bonding to the surface of the material. Above surface treatment
The reasoning methods are “Characteristics and Applications of Metal Soap” (Yokoshobo), “Ink
Printing ink technology "(CMC Publishing, 1984) and
To "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Has been described. The pigment has a particle size of 0.01 to 10 μm.
Is preferably in the range, and in the range of 0.05 to 1 μm.
More preferably, it is in the range of 0.1 to 1 μm.
Particularly preferred. When the pigment particle size is less than 0.01 μm
It is preferable in terms of stability of the dispersion in the photosensitive layer coating solution.
Also, if it exceeds 10 μm, it is favorable in terms of the uniformity of the photosensitive layer.
It ’s not good. As a method for dispersing the pigment, ink may be used.
Uses well-known dispersion techniques used in manufacturing and toner manufacturing
it can. Examples of dispersers include ultrasonic dispersers and sun
Domill, Attritor, Pearl Mill, Super Mill, Bo
Roll mill, impeller, disperser, KD mill, roller
Idmill, Dynatron, 3-roll mill, pressure kneader
-Etc. are mentioned. For details, see “Latest Pigment Application Technology” (C
MC Publishing, published in 1986). As the dye, commercially available dyes and literature (examples)
For example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, 1970
The publicly known thing described in the publication) can be used. concrete
Metal complex salt azo dyes, pyrazolone azo dyes, naphtho
Quinone dye, anthraquinone dye, phthalocyanine dye
Materials, carbonium dyes, quinone imine dyes, methine dyes
Materials, cyanine dyes, squarylium pigments, pyrylium
Salt, metal thiolate complex (eg nickel thiolate)
A dye such as a complex) can be used. In the present invention, an object that absorbs near infrared light
Quality can also be used. Such infrared light or near
Carbon black is the preferred pigment to absorb infrared light
Used for. Also absorbs infrared light or near infrared light
Examples of the dye include those disclosed in JP-A-58-125246.
, JP 59-84356, JP 59-20
2829, JP-A-60-78787, etc.
Cyanine dyes described in JP-A-58-173696
JP, 58-181690, JP 58
Methine dyes described in JP-A 194595
JP-A-58-112793, JP-A-58-224
793, JP 59-48187, JP
No. 59-73996, JP-A-60-52940
Information, JP-A-60-63744, etc.
Naphthoquinone dyes, JP-A-58-112792, etc.
Squaryllium dye described in British Patent No. 43
Cyanine dye described in US Pat. No. 4,875, US Pat.
Dihydroperimidi as described in US Pat. No. 5,380,635
Non-squarylium dyes. Further, as the dye, US Pat. No. 5,15
The near-infrared absorption sensitizer described in US Pat. No. 6,938 is also suitable.
U.S. Pat. No. 3,881,924
Substituted arylbenzo (thio) pyrilyu
Salt, JP-A-57-142645 (US Patent No.
4,327,169))
Pyrylium salt, Japanese Patent Application Laid-Open No. 58-181051, Japanese Patent Application Laid-Open No. 58-181051
JP 58-2220143, JP 59-41363
JP, 59-84248, 59-84248
No. 84249, JP-A-59-146063,
Japanese Patent Application Laid-Open No. 59-146061
Lium compound, described in JP 59-216146 A
Cyanine dyes described in US Pat. No. 4,283,475
Pentamethine thiopyrylium salt, etc. described in the booklet
No. 5-13514 and Japanese Patent Publication No. 5-19702
Disclosed pyrylium compounds; Epolight III-178,
Epolight III-130, Epolight III-125, Epolight IV-62
A (both manufactured by Eporin) etc. are particularly preferably used
The Another example which is particularly preferable as the dye is described above.
In U.S. Pat. No. 4,756,993.
Near-infrared absorbing dyes described as (I) or (II)
You can list the fee. Further, the above-mentioned heat decomposable state does not decompose.
The solubility of the alkaline water-soluble polymer compound is substantially reduced
Instead of substances that degrade, it is thermally decomposable and does not decompose.
The solubility of the alkaline water-soluble polymer compound
A function that lowers the quality and a function that generates heat by absorbing light.
One compound having both may be used. like that
As a compound, it represents with the following general formula (Z), for example.
Things. [0058] [Chemical 7] In the general formula (Z), R^{twenty one}~ R^{twenty four}It
Each independently may have a hydrogen atom or a substituent
1 to 12 alkyl groups, alkenyl groups, alkoxy groups,
Represents a cycloalkyl group or an aryl group, R^{twenty one}And R
^{twenty two}, R^{twenty three}And R^{twenty four}Are bonded together to form a ring structure.
May be. Where R^{twenty one}~ R^{twenty four}Specifically, as
Hydrogen atom, methyl group, ethyl group, phenyl group, dodecyl
Group, naphthyl group, vinyl group, allyl group, cyclohexyl
Groups and the like. Moreover, these groups have a substituent.
In this case, the substituent includes a halogen atom, carbonyl
Group, nitro group, nitrile group, sulfonyl group, carboxy
Group, carboxylic acid ester, sulfonic acid ester, etc.
I can get lost. R^{twenty five}~ R³⁰Each independently has a substituent.
Represents an alkyl group having 1 to 12 carbon atoms,
And R^{twenty five}~ R³⁰Specifically, methyl group, ethyl
Group, phenyl group, dodecyl group, naphthyl group, vinyl
Group, allyl group, cyclohexyl group and the like. Ma
In addition, when these groups have a substituent,
Are halogen atoms, carbonyl groups, nitro groups,
Group, sulfonyl group, carboxyl group, carboxylic acid ester
And sulfonic acid esters. R³¹~ R³³Are each independently a hydrogen atom,
1 to 8 carbon atoms which may have a halogen atom or a substituent
Wherein R represents³²Is R³¹Or R³³
And may form a ring structure, if m> 2
Is a plurality of R₁₂Even if they are bonded together to form a ring structure
Good. R³¹~ R³³Specifically, chlorine atoms,
Chlohexyl group, R³²Cyclopenti made by bonding together
Ring, cyclohexyl ring and the like. Also these
In the case where the group in the above has a substituent, the substituent is halo.
Gen atom, carbonyl group, nitro group, nitrile group, sulfur
Phonyl group, carboxyl group, carboxylic acid ester, sulfo
Examples include phosphonic acid esters. M is an integer from 1 to 8.
Represents a number, preferably 1-3. R³⁴And R³⁵Each independently
1 carbon atom which may have a child, a halogen atom or a substituent
Represents an alkyl group of ~ 8, R³⁴Is R³⁵Combined with ring structure
And when m> 2, a plurality of R³⁴same
May combine to form a ring structure. R³⁴and
R³⁵Specifically, as a chlorine atom, cyclohexyl
Group, R³⁴Cyclopentyl ring formed by bonding together, cyclo
Examples include a hexyl ring. In addition, these groups are substituted
As a substituent, a halogen atom,
Rubonyl, nitro, nitrile, sulfonyl,
Ruboxyl group, carboxylic acid ester, sulfonic acid ester
And the like. M represents an integer of 1 to 8,
Preferably it is 1-3. In the general formula (Z), Z^-Is Anio
Represents Specific examples of the anion compound include excess
Chloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropyl
Lopylnaphthalenesulfonic acid, 5-nitro-o-tolue
Sulfonic acid, 5-sulfosalicylic acid, 2,5-dimethyl
Rubenzenesulfonic acid, 2,4,6-trimethylbenze
Sulfonic acid, 2-nitrobenzenesulfonic acid, 3-
Lolobenzenesulfonic acid, 3-bromobenzenesulfone
Acid, 2-fluorocapryl naphthalene sulfonic acid, dode
Silbenzene sulfonic acid, 1-naphthol-5-sulfo
Acid, 2-methoxy-4-hydroxy-5-benzoyl
-Benzenesulfonic acid, p-toluenesulfonic acid
It is done. Among these, especially hexafluorophosphoric acid, trii
Sopropyl naphthalene sulfonic acid or 2,5-dimethyl
Alkyl aromatic sulfonic acids such as benzene sulfonic acid are preferred.
It is used well. The compound represented by the general formula (Z) is
It is a compound commonly called cyanine dye, specifically
The following compounds are preferably used, but the present invention
It is not limited by this specific example. [0065] [Chemical 8] These compounds absorb light and generate heat.
In the infrared region of 700-1200 nm
It has an absorption range and is also compatible with alkali-soluble polymer compounds.
It has good solubility and is a basic dye.
Alkali-soluble polymer compounds such as nium and iminium groups
In order to have a group that interacts with an object,
It can interact and control its alkali solubility
Can be suitably used in the present invention. These pigments or dyes are used in the entire solid layer of the photosensitive layer.
Preferably from 0.01 to 50% by weight, based on the shape
Preferably it is 0.01-30 mass%, More preferably, it is 0.00.
1 to 10% by mass, particularly preferably 0.5 to
In the case of 10% by mass and pigment, particularly preferably 1 to 10% by mass
% Can be added to the photosensitive composition.
The Addition amount of pigment or dye is less than 0.01% by mass
The sensitivity will be low, and if it exceeds 50% by mass,
The uniformity of the layer is lost, and the durability of the photosensitive layer is deteriorated. [Other components] Photosensitive layer of the present invention
(Including the case of two or more layers), if necessary,
Various additives can be added. These additives
If there are two or more photosensitive layers,
It may be contained only in one layer or in two or more layers
Also good. Below, the example of an additive is given and demonstrated. As an additive, for example, it is thermally decomposable,
In the state that does not decompose, the dissolution of the alkaline water soluble polymer compound
Examples include substances that substantially reduce the solutionability. This substance
Can be used to improve the dissolution inhibition of the image area in the developer.
This is preferable because it can be achieved. Such a substance
For example, onium salts, quinonediazides, aromatics
Sulfone compounds and aromatic sulfonate compounds
I can get lost. Examples of onium salts include diazonium.
Salt, ammonium salt, phosphonium salt, iodonium
Salt, sulfonium salt, selenonium salt, arsonium salt
Is mentioned. Among them, preferable examples include S.
I. Schlesinger, Photogr. Sci. Eng., 18,387 (1974),
T.S.Bal et al, Polymer, 21, 423 (1980) and JP-A-5
Diazonium described in Japanese Patent No. 158230
Salt, U.S. Pat. No. 4,069,055, 4,0
No. 69,056 and JP-A-3-140140
Ammonium salts described in the publication, D.C.Necker et
al, Macromolecules, 17,2468 (1984), C.S.Wen et al,
Teh, Proc.Conf.Rad.Curing ASIA, p.478, Tokyo, Oct
(1988), U.S. Pat. No. 4,069,055 and
Phospho described in US Pat. No. 4,069,056
Ni salt, J.V.Crivello et al, Macromorecules, 10
(6), 1307 (1977), Chem. & Amp, Eng. News, Nov. 28, p31
(1988), European Patent No. 104,143, US Patent
Nos. 339,049 and 410,201
, JP-A-2-150848 and JP-A-2-2-2.
No. 96514, iodonium salt, J.
V. Crivello et al, Polymer J. 17, 73 (1985), J.V. Criv
ello et al. J. Org. Chem., 43, 3055 (1978), W.R.Watt
etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), J.V. Crivello et al, Polymer Bull., 14, 279 (1
985), J.V. Crivello et al, Macromorecules, 14 (5), 1
141 (1981), J.V.Crivello et al, J.Polymer Sci., Pol
ymer Chem. Ed., 17, 2877 (1979), European Patent 370,
693, 233,567, 29
7,443, 297,442, United States
Patent No. 4,933,377, No. 3,902,1
No. 14, No. 410, 201 No., No. 339,
No. 049, No. 4,760,013, No.
No. 4,734,444, No. 2,833,827
Description, German Patent 2,904,626, the same
3,604,580 and 3,604,58
The sulfonium salt described in No. 1 specification, J.V.Criv
ello et al, Macromorecules, 10 (6), 1307 (1977) and
J.V.Crivello et al, J.Polymer Sci., Polymer Chem.E
d., 17, 1047 (1979) described in selenonium salt,
C.S.Wen et al, Teh, Proc. Conf. Rad. Curing ASIA,
p.478, Tokyo, Oct (1988)
Salt. Among the onium salts, diazonium
Particularly preferred is the salt. Also particularly suitable diazonium salts
As described in JP-A-5-158230.
I can get lost. As a counter ion of an onium salt, for example,
Tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylna
Phthalenesulfonic acid, 5-nitro-o-toluenesulfo
Acid, 5-sulfosalicylic acid, 2,5-dimethylbenze
Sulfonic acid, 2,4,6-trimethylbenzenesulfone
Acid, 2-nitrobenzenesulfonic acid, 3-chloroben
Zensulfonic acid, 3-bromobenzenesulfonic acid, 2-
Fluorocapryl naphthalene sulfonic acid, dodecylben
Zensulfonic acid, 1-naphthol-5-sulfonic acid, 2
-Methoxy-4-hydroxy-5-benzoyl-benze
Sulfonic acid and paratoluenesulfonic acid.
Among them, hexafluorophosphoric acid; triisopropylnaphthalene
Such as sulfonic acid, 2,5-dimethylbenzenesulfonic acid, etc.
Alkyl aromatic sulfonic acids are preferred. Suitable quinonediazides include o-quino.
And diazide compounds. Used in the present invention
The o-quinonediazide compound obtained is at least one
It is a compound having o-quinonediazide group.
Compounds with various structures that increase alkali solubility
Can be used. That is, o-quinonediazide is
Losing the ability to inhibit the dissolution of the binder by thermal decomposition;
Non-diazide itself turns into an alkali-soluble substance.
Helps the solubility of the sensitive material system by both effects. The present invention
Examples of o-quinonediazide compounds used in
J. Korser, “Light-sensitive system
(John Wiley & Sons. Inc.) pp. 339-352
The compounds listed above can be used, but in particular various aromatic polyhydrides
Reacted with roxy compounds or aromatic amino compounds
o-Quinonediazide sulfonate or sulfone
Acid amides are preferred. Also, Japanese Patent Publication No. 43-28403
Benzoquinone (1,2) as described in
-Diazide sulfonic acid chloride or naphthoquinone-
(1,2) -Diazide-5-sulfonic acid chloride and pic
Rogalol-ester with acetone resin, US Patent No.
No. 3,046,120 and No. 3,188,210
Benzoquinone- (1,2) -diazidos described
Sulfonic acid chloride or naphthoquinone- (1,2) -di
Azido-5-sulfonic acid chloride and phenol-form
Esters with a mualdehyde resin are also preferably used. Further, naphthoquinone- (1,2) -diazi
Do-4-sulfonic acid chloride and phenol formal
With aldehyde resin or cresol formaldehyde resin
Ester, naphthoquinone- (1,2) -diazide-4
-Sulfonic acid chloride and pyrogallol-acetone resin
Similarly, the esters are also preferably used. Other useful
As an o-quinonediazide compound, many patents
Reported and known. For example, JP-A 47-5303
No. 4, JP-A-48-63802, JP-A-48-6380
3, JP-A-48-96575, JP-A-49-387
01, JP-A-48-13354, JP-B-41-11
222, Shoko 45-9610, Shoko 49-17
481, U.S. Pat. No. 2,797,213, No. 3,
No. 454,400, No. 3,544,323, No.
3,573,917, 3,674,495,
No. 3,785,825, British Patent No. 1,227,60
No. 2, No. 1,251,345, No. 1,267,0
05, 1,329,888, 1,330,
932, German Patent No. 854,890, etc.
What is described in the book can be mentioned. Onium salts and o-quinonediazide compounds
The addition amount is preferably 1 to 50 with respect to the total solid content of the recording layer.
% By weight, more preferably 5-30% by weight, particularly preferably
Is in the range of 10-30% by mass. These compounds are simply
Can be used as one, but it can be used as a mixture of several kinds.
Yes. In addition, image discrimination (sparse
(Water / hydrophilic discrimination) and resistance to surface scratches
For the purpose of strengthening the drag, JP 2000-187318 A
3-20 carbon atoms in the molecule as described in the publication
Having 2 or 3 perfluoroalkyl groups (meth)
Use a polymer containing an acrylate monomer as a polymerization component
be able to. The amount of such a compound added is
A proportion of 0.1 to 10% by mass in the heat layer material is preferred.
More preferably, it is 0.5-5 mass%. In the photosensitive layer of the present invention, resistance to scratches is present.
To reduce surface static friction coefficient for the purpose of imparting
A compound can also be added. Specifically, US611
Long chain alkyls, such as those used in publication No. 7913
Examples thereof include esters of carboxylic acid. this
The preferred amount of such a compound is to form a layer.
It is more preferable that the proportion in the material is 0.1 to 10% by mass.
It is 0.5-5 mass%. In the photosensitive layer of the present invention, if necessary,
And a compound having a low molecular weight acidic group. acid
Examples of functional groups include sulfonic acid, carboxylic acid, and phosphoric acid groups
Rukoto can. Among them, compounds having sulfonic acid groups
preferable. Specifically, p-toluenesulfonic acid, naphth
Aromatic sulfonic acids such as tarene sulfonic acid and aliphatic sulfur
Mention may be made of phonic acids. Addition of such compounds
The preferred amount is in the material forming the layer.
The ratio is 0.05 to 5% by mass. More preferably 0.1-3
% By mass. If it exceeds 5%, the solubility of each layer in the developer
The solution is increased, which is not preferable. In the present invention, the solubility of the photosensitive layer is also determined.
Various dissolution inhibitors may be included for the purpose of adjusting the pH. Melting
As an anti-solution agent, it is disclosed in JP-A-11-119418.
Disulfone compounds or sulfone compounds are preferred.
As a specific example, 4,4'-bishydroxyl
Siphenylsulfone is preferably used. like this
These compounds may be included in either the lower layer or the heat-sensitive layer.
Yes. Preferably, the amount of addition constitutes each layer
The proportion in the material is 0.05-20% by mass, more preferred
It is 0.5 to 10% by mass. Further, the photosensitive layer has an eye for further improving the sensitivity.
Contains cyclic acid anhydrides, phenols, and organic acids
You can also Examples of cyclic acid anhydrides include:
Described in US Pat. No. 4,115,128
Phthalic anhydride, tetrahydrophthalic anhydride, hexahi
Drophthalic anhydride, 3,6-endooxy-Δ4-teto
Lahydrophthalic anhydride, tetrachlorophthalic anhydride, none
Water maleic acid, chloromaleic anhydride, no α-phenyl
Examples include maleic anhydride, succinic anhydride, and pyromellitic anhydride.
I can get lost. Examples of phenols include bisphenol.
Nord A, p-nitrophenol, p-ethoxypheno
2,4,4'-trihydroxybenzophenone,
2,3,4-trihydroxybenzophenone, 4-hydride
Roxybenzophenone, 4,4 ', 4 "-trihydroxy
Citriphenylmethane, 4,4 ', 3 ", 4" -tetra
Hydroxy-3,5,3 ', 5'-tetramethyltrif
One example is phenylmethane. Examples of organic acids include, for example, JP-A-60-
Described in U.S. Pat. No. 88942, JP-A-2-96755, etc.
Sulfonic acids, sulfinic acids, alkylsulfuric acids
Acids, phosphonic acids, phosphate esters, carboxylic acids
Is mentioned. Specifically, for example, p-toluenesulfur
Phosphonic acid, dodecylbenzenesulfonic acid, p-toluene
Rufinic acid, ethyl sulfate, phenylphosphonic acid, pheny
Ruphosphinic acid, phenyl phosphate, diphenyl phosphate,
Benzoic acid, isophthalic acid, adipic acid, p-toluyl
Acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalate
Formic acid, 4-cyclohexene-1,2-dicarboxylic acid,
Lucaic acid, lauric acid, n-undecanoic acid, ascorbine
Examples include acids. The above cyclic acid anhydrides, phenols and
The amount of organic acids added is based on the total solid content of the added layer.
0.05 to 20% by mass is preferable, 0.1
More preferably, it is -15 mass%, 0.1-10 quality
Particularly preferred is an amount%. In addition, the photosensitive layer can be processed for development conditions.
In order to expand stability, Japanese Patent Application Laid-Open No. 62-251740
And JP-A-3-208514.
Nonionic surfactants such as those disclosed in JP-A-59-121044.
And Japanese Patent Application Laid-Open No. 4-13149.
Amphoteric surfactants, such as EP 95
Siloxanes as described in 0,517
Compounds, described in JP-A-11-288093
Containing a fluorine-containing monomer copolymer
be able to. Specific examples of nonionic surfactants include so
Rubitan tristearate, sorbitan monopalmitate
, Sorbitan trioleate, monoglyceride stearate
Lido and polyoxyethylene nonylphenyl ether
I can get lost. Specific examples of amphoteric surfactants include alkyl
Di (aminoethyl) glycine, alkylpolyaminoethyl
Luglycine hydrochloride, 2-alkyl-N-carboxyethyl
Ru-N-hydroxyethyl imidazolinium betaine,
N-tetradecyl-N, N-betaine type (for example, merchandise
The name “Amorgen K”, manufactured by Daiichi Kogyo Co., Ltd.). Up
Addition amount of nonionic surfactant and amphoteric surfactant
Is 0. 0% for the total solids of the added layer, respectively.
It is preferable that it is 05-15 mass%, 0.1-5 mass
% Is more preferred. Further, siloxane compounds include dimethyl compounds.
Block copolymer of tilsiloxane and polyalkylene oxide
A polymer is preferable, and as a specific example, manufactured by Chisso Corporation,
DBE-224, DBE-621, DBE-712, D
BP-732, DBP-534, Tego, Germany, Te
polyalkylene oxide modification such as go Glide 100
Can be mentioned. The photosensitive layer of the present invention is heated by exposure.
Print-out agent and image colorant to obtain a visible image immediately afterwards
As a dye or a pigment. Bake out
As an agent, a compound that releases acid by heating by exposure.
Of organic dyes capable of forming salts with organic acid (photoacid releasing agent)
Is illustrated. Specifically, JP-A-50-3620
No. 9 and JP-A-53-8128.
O-Naphthoquinonediazide-4-sulfonic acid halogeni
Combination of a salt and a salt-forming organic dye, or JP-A-53-3
JP 6223, JP 54-74728, JP
Sho 60-3626, JP 61-143748
Gazettes, Japanese Patent Laid-Open Nos. 61-151644 and 6
Trihalomethyl described in Japanese Patent No. 3-58440
A combination of a compound and a salt-forming organic dye.
The Such trihalomethyl compounds include oxazols.
And triazine compounds, both of which
Excellent temporal stability and gives clear printout image. As the image colorant, the dye of the present invention or the above-mentioned
Other dyes can be used in addition to other salt-forming organic dyes
The Oil-soluble as suitable dyes, including salt-forming organic dyes
And basic dyes. Specifically, for example
Oil yellow # 101, oil yellow # 10
3, Oil Pink # 312, Oil Green BG, Oy
Le Blue BOS, Oil Blue # 603, Oil Black
BY, Oil Black BS, Oil Black T-50
5 (above orient chemical industry), Victoria Pure
Blue, Crystal Violet (C.I. 4255
5) Methyl violet (C.I. 42535), Eth
Le violet, rhodamine B (C.I. 145170
B), Malachite Green (C.I. 42000), Mechi
Ren blue (C.I. 52015) may be mentioned. Also,
JP-A-62-293247 and JP-A-5-31
The dyes described in Japanese Patent No. 3359 are particularly preferred.
The amount of these dyes added is relative to the total solid content of the layer being added.
And 0.01 to 10% by mass is preferable.
It is more preferable that it is 1-3 mass%. In addition, the photosensitive layer imparts flexibility and the like of the coating film.
In order to contain plasticizer, if necessary
The For example, butyl phthalyl, polyethylene glycol
, Tributyl citrate, diethyl phthalate, phthalic acid
Dibutyl, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trio phosphate
Cutyl, tetrahydrofurfuryl oleate, acrylic
Used for acid and methacrylic acid oligomers and polymers
I can. [Support] Used for the lithographic printing plate precursor of the present invention
As a support, the dimensions with the required strength and durability
For example, paper, plastic, etc.
(Eg polyethylene, polypropylene, police
Paper, metal plates (for example, aluminum)
(Luminium, zinc, copper, etc.), plastic film (example)
For example, cellulose diacetate, cellulose triacetate, propio
Cellulose acetate, cellulose butyrate, cellulose acetate butyrate
, Cellulose nitrate, polyethylene terephthalate, polyethylene
Reethylene, polystyrene, polypropylene, polycar
Bonate, polyvinyl acetal, etc.), gold as above
Paper or plastic on which the genus is laminated or vapor-deposited
Includes sticky film. In the present invention, the support is a polyester.
Tellurium film or aluminum plate is preferred, among them
Aluminum plate with good dimensional stability and relatively inexpensive
Is particularly preferred. The preferred aluminum plate is pure aluminum
Umum plate and aluminum as main components, and trace amounts of foreign elements
Alloy plate, and aluminum is laminated.
Alternatively, a vapor-deposited plastic film may be used. Aluminum
The foreign elements contained in the alloy are silicon, iron, manga
Copper, magnesium, chromium, zinc, bismuth, nickel
There are Kell and Titanium. High content of foreign elements in the alloy
10% by mass or less. Particularly suitable for the present invention.
Luminium is pure aluminum but completely pure
Aluminum is difficult to manufacture due to refining technology.
May contain a different element. Thus, in the present invention
The applied aluminum plate is specified for its composition.
Rather than conventional aluminum plates of publicly known materials
Can be used as appropriate. Used in the present invention
The thickness of the ruminium plate is about 0.1mm to 0.6mm
Degree, preferably 0.15mm to 0.4mm, especially preferred
Or 0.2 mm to 0.3 mm. In the present invention, an aluminum plate is used.
In that case, the aluminum plate may be roughened. Armini
When roughing the Um plate, prior to roughening,
For example, surface activity for removing surface rolling oil
Degreasing treatment with an agent, organic solvent or alkaline aqueous solution
Is done. The roughening treatment of the surface of the aluminum plate
For example, the surface is mechanically roughened.
Method for electrochemically dissolving and roughening the surface
It is carried out by a method in which the surface is selectively dissolved. machine
Typical methods include ball polishing, brush polishing, and brass
It is possible to use a known method such as a polishing method or a buffing method.
it can. As an electrochemical roughening method, hydrochloric acid or
There is a method of performing alternating current or direct current in a nitric acid electrolyte. Ma
It is disclosed in JP-A-54-63902.
In other words, a method in which both are combined can also be used.
The roughened aluminum plate can be used as needed.
After alkali etching treatment and neutralization treatment, as desired
Anodizing treatment to improve surface water retention and wear resistance
Reason is given. Used for anodizing of aluminum plates
As the electrolyte to be used, various types of porous oxide films are formed.
Electrolytes can be used, generally sulfuric acid, phosphoric acid, soot
Acid, chromic acid or a mixed acid thereof is used. It
The concentration of these electrolytes is appropriately determined according to the type of electrolyte.
The The anodic oxidation treatment conditions depend on the electrolyte used.
However, in general, it cannot be specified.
Solution concentration is 1-80% by mass solution, liquid temperature is 5-70 ° C.,
Current density 5-60A / dm², Voltage 1-100V, electrolysis
A time range of 10 seconds to 5 minutes is appropriate. anodization
The amount of film is 1.0 g / m²If it is less, the printing durability is insufficient.
Or scratches on the non-image area of the lithographic printing plate
The so-called `` scratch that ink adheres to the scratched part during printing
Dirt "tends to occur. After anodizing,
The ruminium surface is subjected to a hydrophilic treatment if necessary. Book
As the hydrophilization treatment used in the invention, US Pat.
No. 714,066, No. 3,181,461, No. 3,
Disclosed in 280,734 and 3,902,734.
Alkali metal silicates such as silica
Sodium aqueous solution) method. In this method,
The holder is soaked with an aqueous sodium silicate solution, or
Electrolytically treated. In addition, in Japanese Patent Publication No. 36-22063
Disclosed potassium fluoride zirconate and US patents
No. 3,276,868, No. 4,153,461,
Poly as disclosed in US Pat. No. 4,689,272
A method of treating with vinylphosphonic acid is used. [Undercoating] In the lithographic printing plate of the present invention,
If necessary, the support can be subbed.
Various organic compounds are used as the primer component.
Carboxymethylcellulose, dextrin, ara
Amino groups such as beer gum and 2-aminoethylphosphonic acid
Phosphonic acids having a phenyl group which may have a substituent
Phosphonic acid, naphthylphosphonic acid, alkyl phosphone
Acid, glycerophosphonic acid, methylenediphosphonic acid and ether
Organic phosphonic acids such as tylenediphosphonic acid, with substituents
Phenyl phosphate, naphthyl phosphate, alkyl
Organophosphoric acid such as phosphoric acid and glycerophosphoric acid, substituents
Phenylphosphinic acid, naphthylphosphite
Acids, alkylphosphinic acids and glycerophosphinic acids
Organic phosphinic acids such as glycine and β-alanine
Amino acids, and triethanolamine hydrochloride
Selected from hydrochlorides of amines having various hydroxy groups
However, you may use it in mixture of 2 or more types. A more preferred embodiment for the undercoat is described below.
The The primer is not particularly limited as long as it is an alkali-soluble layer.
Not containing a polymer with monomers having acid groups
Monomers having an acid group and onium
It is better to contain a polymer having a monomer having a group
preferable. Hereinafter, the polymer contained in the primer is described in detail.
I will explain. The polymer contained in the primer is at least an acid
It is a compound formed by polymerizing a monomer having a group and is preferred.
Or a monomer having an acid group and an onium group
It is a compound obtained by polymerizing a monomer. Where acid group
As an acid group, an acid dissociation index (pKa) of 7 or less is preferred.
More preferably -COOH, -SO_ThreeH, -OS
O_ThreeH, -PO_ThreeH₂, -OPO_ThreeH₂, -CONHSO
₂-, -SO₂NHSO₂-, Particularly preferably -C
OOH. Also preferred as an onium group
Is group 15 (Group VA) or Group 16 (Group IV) of the Periodic Table
An onium group containing atoms of Group A), more preferred
Or oxygen atoms containing nitrogen, phosphorus or sulfur atoms.
A nitrogen group, particularly preferably an oxygen group containing a nitrogen atom.
It is a nium group. The polymer used in the present invention is preferably
The main chain structure is acrylic resin, methacrylic resin or police
Vinyl polymer such as Tylene, urethane resin, poly
Polymerization characterized by being an ester or a polyamide
Body compound. More preferably, the main chain structure of the polymer
Made of acrylic resin, methacrylic resin or polystyrene
Polymerization characterized by being a vinyl polymer
It is a compound. Particularly preferably, the monomer having an acid group is
It is represented by the following general formula (M1) or general formula (M2)
A compound having an onium group
In general formula (M3), general formula (M4) or general formula (M5)
A polymer compound characterized by being represented by
is there. [0097] [Chemical 9] In the formula, A represents a divalent linking group. B is aromatic
Represents a group or a substituted aromatic group. D and E are
Independently represents a divalent linking group. G represents a trivalent linking group
The Q and Q ′ are each independently pKa of 7 or less
Acid group or alkali metal salt or ammonium salt thereof
Represents. R⁴¹Is a hydrogen atom, alkyl group or halogen atom
Represents a child. a, b, d and e are each independently 0
Or 1 is represented. t is an integer of 1 to 3. More preferable among monomers having an acid group
Represents A—COO— or —CONH—, and B represents F
An enylene group or a substituted phenylene group, and the substituent
Is a hydroxyl group, a halogen atom or an alkyl group. D
And E are each independently an alkylene group or a molecular formula
C_nH_2nO, C_nH_2nS or C_nH_{2n + 1}2 represented by N
Represents a valent linking group. G has the molecular formula C_nH_2n-1, C_nH_2n-1
O, C_nH_2n-1S or C_nH_2nTrivalent linkage represented by N
Represents a group. Here, n represents an integer of 1 to 12.
The Q and Q ′ are each independently carboxylic acid, sulfo
Phosphonic acid, phosphonic acid, sulfuric monoester or phosphoric acid
Represents no ester. R⁴¹Is a hydrogen atom or an alkyl group
Represent. a, b, d and e are each independently 0 or
Represents 1, but a and b are not 0 at the same time. Has an acid group
Among the monomers, a compound represented by the general formula (M1) is particularly preferable.
B is a phenylene group or substituted phenylene group
The substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms.
Kill group. D and E each independently have 1 carbon
1 to 2 carbon atoms linked by an alkylene group of ˜2 or an oxygen atom
Represents an alkylene group of ~ 2. R⁴¹Is a hydrogen atom or al
Represents a kill group. Q represents a carboxylic acid group. a is 0
B is 1. Specific examples of the monomer having an acid group are shown below.
The However, the present invention is not limited to this specific example.
Absent. (Specific examples of monomers having acid groups) Acrylic acid, methacrylate
Rylic acid, crotonic acid, isocrotonic acid, itaconic acid, male
Rain acid, maleic anhydride [0101] Embedded image [0102] Embedded image[0103] Embedded imageNext, there is a monomer having an onium group.
Represented by the following general formula (M3), (M4) or (M5)
The polymer used will be described. [0105] Embedded image In the formula, J represents a divalent linking group. K is aromatic
Represents a group or a substituted aromatic group. M is independently
Represents a divalent linking group. T₁Is Periodic Table 15 (Group VA
Group) and T₂Is periodic table group 16 (Group VIA
Group) atom. W^-Represents a counter anion. R⁴²Is water
Represents an elementary atom, an alkyl group or a halogen atom. R⁴³,
R⁴⁴, R⁴⁵And R⁴⁷Are independently hydrogen atoms or
Is optionally substituted alkyl
Represents a group, aromatic group or aralkyl group, R⁴⁶Is al
Represents a kyridine group or a substituted alkylidine, R⁴³And R
⁴⁴Or R⁴⁶And R⁴⁷Can combine to form a ring.
Good. j, k and m are each independently 0 or 1
Represent. u represents an integer of 1 to 3. Among monomers having an onium group, it is more preferable.
Preferably, J represents -COO- or -CONH-
K represents a phenylene group or a substituted phenylene group,
The substituent is a hydroxyl group, a halogen atom or an alkyl group.
The M is an alkylene group or the molecular formula is C_nH_2nO, C_nH
_2nS or C_nH_{2n + 1}A divalent linking group represented by N is represented.
The However, n represents the integer of 1-12 here. T₁
Represents a nitrogen atom or a phosphorus atom, and T₂Is a sulfur atom
Represent. W^-Is halogen ion, PF₆ ^-, BF_Four ^-Or R
⁴⁸SO_Three ^-Represents. R⁴²Represents a hydrogen atom or an alkyl group
The R⁴³, R⁴⁴, R ⁴⁵And R⁴⁷Are each independently water
Elemental atoms or, optionally, substituents may be bonded
C1-C10 alkyl group, aromatic group or arral
Represents a kill group, R⁴⁶Is an alkylidine group having 1 to 10 carbon atoms
Or a substituted alkylidine, R ⁴³And R⁴⁴,and
R⁴⁶And R⁴⁷May be bonded to each other to form a ring.
j, k and m each independently represent 0 or 1
However, j and k are not 0 at the same time. R ⁴⁸Has a substituent
An alkyl group having 1 to 10 carbon atoms, an aromatic group, or
Represents an aralkyl group. Among monomers having an onium group, particularly preferred
Preferably, K is a phenylene group or a substituted phenylene group.
The substituent is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Kill group. M is an alkylene group having 1 to 2 carbon atoms or
Represents a C 1-2 alkylene group linked by an oxygen atom
The Z^-Is chloride ion or R⁴⁸SO_Three ^-Represents. R⁴²Is
Represents a hydrogen atom or a methyl group. j is 0 and k is 1.
It is. R⁴⁸Represents an alkyl group having 1 to 3 carbon atoms. Specific examples of the monomer having an onium group are as follows.
Shown below. However, the present invention is not limited to this specific example.
Not. (Specific examples of monomers having an onium group) [0110] Embedded image [0111] Embedded image[0112] Embedded image Even if the monomer having an acid group is used alone,
Two or more types may be used in combination, or an onium group
Monomers having a combination of two or more, even if used alone
May be used. Further, the polymer used in the present invention
Are two types with different monomers, composition ratio or molecular weight
You may mix and use the above. At this time, the mono group having an acid group
A polymer having a polymer as a polymerization component is a polymer having an acid group.
It is preferable to contain 1 mol% or more of nomer, preferably 5 mol% or more.
It is more preferable that the monovalent compound has an onium group.
A polymer having a polymer as a polymerization component has an onium group.
Preferably 1 mol% or more of the monomer to be
It is more preferable that the content is at least%. Further, these polymers include the following (1) to (1):
(14) at least selected from the polymerizable monomers
One kind may be included as a copolymerization component. (1) N- (4-hydroxyphenyl) acrylamide
Or N- (4-hydroxyphenyl) methacrylami
, O-, m- or p-hydroxystyrene, o-ma
Or m-bromo-p-hydroxystyrene, o- or
m-chloro-p-hydroxystyrene, o-, m- or
Is p-hydroxyphenyl acrylate or methacrylate
Acrylamides having aromatic hydroxyl groups such as
Tacrylamides, acrylic esters, methacryl
Acid esters and bidoxystyrenes, (2)
Rylic acid, methacrylic acid, maleic acid, maleic anhydride
And its half esters, itaconic acid, itaconic anhydride
And unsaturated carboxylic acids such as half esters thereof, (3) N- (o-aminosulfonylphenyl)
) Acrylamide, N- (m-aminosulfonylphenol)
Nyl) acrylamide, N- (p-aminosulfonyl)
Enyl) acrylamide, N- [1- (3-aminosulfuryl)
Phonyl) naphthyl] acrylamide, N- (2-amino)
Acrylamides such as sulfonylethyl) acrylamide
N- (o-aminosulfonylphenyl) methacryl
Amides, N- (m-aminosulfonylphenyl) metac
Rilamide, N- (p-aminosulfonylphenyl) methyl
Tacrylamide, N- [1- (3-aminosulfonyl)
Naphthyl] methacrylamide, N- (2-aminosulfo
Nylethyl) methacrylamide such as methacrylamide
And o-aminosulfonylphenyl acrylate
, M-aminosulfonylphenyl acrylate, p-
Aminosulfonylphenyl acrylate, 1- (3-A
Aminosulfonylphenylnaphthyl) acrylate
Unsaturated sulfonamides such as crylates, o-a
Minosulfonylphenyl methacrylate, m-aminos
Sulfonylphenyl methacrylate, p-aminosulfonate
Ruphenyl methacrylate, 1- (3-aminosulfone
Methacrylic acid such as ruphenylnaphthyl) methacrylate
Unsaturated sulfonamides such as esters, (4) Substitution like tosylacrylamide
Phenylsulfonylacrylamide, which may have groups
And substituents like tosylmethacrylamide
Good phenylsulfonylmethacrylamide, (5) Fat
Acrylic acid esters and methacrylates having an aliphatic hydroxyl group
Rylate esters such as 2-hydroxyethyl acetate
Relate or 2-hydroxyethyl methacrylate, (6) Methyl acrylate, Ethyl acrylate
, Propyl acrylate, butyl acrylate, acrylic
Amyl acid, Hexyl acrylate, Cyclohexyl acrylate
Sil, octyl acrylate, phenyl acrylate, acrylic
Benzyl yllate, 2-chloroethyl acrylate,
4-hydroxybutyl toluate, glycidyl acrylate
, N-dimethylaminoethyl acrylate, etc.
Replacement) acrylic acid ester, (7) methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, methacrylate
Butyl phosphate, amyl methacrylate, hexyl methacrylate
, Cyclohexyl methacrylate, octyl methacrylate
, Phenyl methacrylate, benzyl methacrylate,
2-chloroethyl tacrylate, 4-hydride methacrylate
Roxybutyl, glycidyl methacrylate, N-dimethyl
(Substituted) methacryl such as ruaminoethyl methacrylate
Acid esters, (8) Acrylamide and methacrylamid
N-methylolacrylamide, N-methylolme
Tacrylamide, N-ethylacrylamide, N-eth
Methacrylamide, N-hexylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl aqua
Rilamide, N-cyclohexylmethacrylamide, N
-Hydroxyethylacrylamide, N-hydroxye
Tylacrylamide, N-phenylacrylamide, N
-Phenylmethacrylamide, N-benzylacrylic
Mido, N-benzylmethacrylamide, N-nitrofe
Nylacrylamide, N-nitrophenyl methacrylate
, N-ethyl-N-phenylacrylamide and
Acrylics such as N-ethyl-N-phenylmethacrylamide
Luamide or methacrylamide, (9) ethyl vinyl
Ether, 2-chloroethyl vinyl ether, hydroxy
Siethyl vinyl ether, propyl vinyl ether,
Til vinyl ether, octyl vinyl ether, pheny
Vinyl ethers such as ruvinyl ether, (10) Vinyl acetate, vinyl chloro
Vinyl acetate, vinyl butyrate, vinyl benzoate, etc.
Nyl esters, (11) Styrene, α-methylstyrene
Styrene, methylstyrene, chloromethylstyrene, etc.
(12) methyl vinyl ketone, ethyl vinyl keto
Propyl vinyl ketone, phenyl vinyl ketone, etc.
Vinyl ketones, (13) ethylene, propylene, iso
Olefins such as butylene, butadiene, isoprene,
(14) N-vinyl pyrrolidone, N-vinyl carbazo
, 4-vinylpyridine, acrylonitrile, methacrylate
Ronitrile etc. The polymer used here has an acid group.
Preferably 1 mol% or more of the monomer to be
% Or more is preferable, and has an onium group.
It is preferable that 1 mol% or more of the monomer is contained. 5 mol%
It is more preferable to include the above. Furthermore, monomers having acid groups
-When 20 mol% or more is included, dissolution during alkali development
Removal is further promoted, and the monomer having an onium group is 1
When it is contained in mol% or more, the adhesiveness is improved due to the synergistic effect with the acid group.
It is further improved. Moreover, the component which has an acid group is independent
May be used in combination of two or more,
Even if the monomer having an onium group is used alone,
A combination of the above may also be used. Further, it is used in the present invention.
Polymers with different monomers, composition ratios or molecular weights
Two or more of these may be mixed and used. Next, in the present invention
The typical example of the polymer used is shown below. In addition,
The composition ratio of the limer structure represents a mole percentage. [0121] Embedded image[0122] Embedded image[0123] Embedded image[0124] Embedded image[0125] Embedded image[0126] Embedded image[0127] Embedded image[0128] Embedded image[0129] Embedded imageThe polymer used in the present invention is generally a polymer.
It can be produced using the dical chain polymerization method ("T
extbook of Polymer Science
e "3rd ed. (1984) FW Billme
yer, A Wiley-Interscience
Publication). The molecular weight of the polymer used in the present invention has a wide range.
It may be a range, but when measured using the light scattering method,
Weight average molecular weight (Mw) is 500 to 2,000,000
Preferably in the range of 1,000 to 600,000.
More preferably, it is a circle. In NMR measurement
Number average calculated from integral intensity of terminal group and side chain functional group
The molecular weight (Mn) is preferably 300 to 500,000.
More preferably, it is in the range of 500 to 100,000.
preferable. When the molecular weight is smaller than the above range,
The adhesive strength of the paper becomes weak and printing durability may deteriorate.
The On the other hand, when the molecular weight increases beyond the above range,
The adhesion to the support becomes too strong, leaving the heat-sensitive layer in the non-image area.
In some cases, the residue cannot be removed sufficiently. Ma
In addition, the amount of unreacted monomer contained in this polymer varies widely.
However, it is preferably 20% by mass or less.
More preferably, it is 10% by mass or less. Polymers having a molecular weight in the above range are compatible.
Polymerization monomer and chain transfer
It can be obtained by adjusting the addition amount in combination with a moving agent.
Yes. The chain transfer agent is a chain transfer in the polymerization reaction.
A substance that moves the active site of a reaction by dynamic reaction.
Good, the ease of the transfer reaction is the chain transfer constant C
It is represented by s. Chain transfer of chain transfer agent used in the present invention
Dynamic constant Cs × 10^Four(60 ° C.) is 0.01 or more
And more preferably 0.1 or more.
The above is particularly preferable. As a polymerization initiator,
Peroxide, azo, which is commonly used during dical polymerization
Compounds and redox initiators can be used as they are
Yes. Of these, azo compounds are particularly preferred. Specific examples of the chain transfer agent include carbon tetrachloride.
Element, halogen compounds such as carbon tetrabromide, isopropyl alcohol
Alcohols such as coal and isobutyl alcohol, 2-
Methyl-1-butene, 2,4-diphenyl-4-methyl
-1-olefins such as pentene, ethanethiol,
Tanthiol, Dodecanethiol, Mercaptoethanol
, Mercaptopropanol, mercaptopropionic acid
Methyl, ethyl mercaptopropionate, mercaptop
Lopionic acid, thioglycolic acid, ethyl disulfide,
sec-Butyl disulfide, 2-hydroxyethyl disulfide
Sulfide, thiosalicylic acid, thiophenol, thioc
Resole, benzyl mercaptan, phenethyl mercap
Sulfur-containing compounds such as tan
Is not to be done. More preferably, ethanethio
, Butanethiol, dodecanethiol, mercaptoe
Tanol, mercaptopropanol, mercaptopropi
Methyl onate, ethyl mercaptopropionate, merca
Ptopropionic acid, thioglycolic acid, ethyl disulfate
, Sec-butyl disulfide, 2-hydroxy ether
Til disulfide, thiosalicylic acid, thiophenol,
Thiocresol, benzyl mercaptan, phenethylme
Lucaptane, particularly preferably ethanethiol,
Butanethiol, Dodecanethiol, Mercaptoethanol
, Mercaptopropanol, mercaptopropion
Methyl acetate, ethyl mercaptopropionate, mercapto
Propionic acid, thioglycolic acid, ethyl disulfide
, Sec-butyl disulfide, 2-hydroxyethyl
Rudisulfide. Further, the unreacted mono carboxylic acid contained in this polymer.
The mer amount may be in a wide range, but is 20% by mass or less.
Preferably, it is 10% by mass or less.
Is preferred. Next, the synthesis of the polymer used in the present invention.
An example is shown. [Synthesis Example 1] Synthesis of polymer (No. 1). 50.4 g of p-vinylbenzoic acid (made by Hokuko Chemical Co., Ltd.)
Triethyl (p-vinylbenzyl) ammonium chloride
15.2 g, 1.9 g mercaptoethanol and
Take 153.1 g of ethanol into a 2 L three-necked flask.
While stirring under a nitrogen stream, heat and keep at 60 ° C.
It was. To this solution was added 2,2'-azobis (isobutyric acid) dimethyl.
2.8 g was added and stirring was continued for 30 minutes. So
Thereafter, p-vinylbenzoic acid 201.5 was added to the reaction solution.
g, triethyl (p-vinylbenzyl) ammonium chloride
60.9 g of Lolide, 7.5 g of mercaptoethanol and
2,2'-azobis (isobutyric acid) dimethyl 11.1 g
For 2 hours.
Dripped. After completion of dropping, the temperature is raised to 65 ° C. and nitrogen
Stirring was continued for 10 hours under a stream of air. Release to room temperature after the reaction is complete.
When cooled, the yield of this reaction is 1132 g,
The solid content concentration was 30.5% by mass. Furthermore, obtained
The number average molecular weight (Mn) of the product¹³C-NMR spectrum
As a result, the value was 2100. [Synthesis Example 2] Synthesis of polymer (No. 2). Triethyl (p-vinylbenzyl) ammonium chloride
Instead of triethyl (vinylbenzyl) ammoni
Using a m / p (2/1) mixture of um chloride,
Mercaptopropionate instead of captoethanol
Except for using chill, the same operation as in Synthesis Example 1 was performed.
A polymer having an average molecular weight (Mn) of 4,800 was obtained. [Synthesis Example 3] Synthesis of polymer (No. 25)
Naru. p-Vinylbenzoic acid (Hokuko Chemical Co., Ltd.) 146.9g
(0.99 mol), vinylbenzyltrimethylammo
44.2 g (0.21 mol) of nium chloride and 2
-446 g of methoxyethanol was added to a 1 L three-necked flask
Heat to 75 ° C while stirring under a nitrogen stream.
Kept. Next, 2,2-azobis (isobutyric acid) dimethyl
Add 2.76 g (12 mmol) of chill and continue stirring.
I did it. After 2 hours, 2,2-azobis (isobutyric acid) dimethyl
2.76 g (12 mmol) was added. 2 o'clock
After a while, 2,2-azobis (isobutyric acid) dimethyl 2.76
g (12 mmol) was added. After stirring for 2 hours, the chamber
Allowed to cool to temperature. The reaction mixture was stirred with 12 L of acetic acid.
Poured into the chill. The precipitated solid was collected by filtration and dried. So
The yield of was 189.5 g. The resulting solid is light scattering
As a result of measuring the molecular weight by the method, the weight average molecular weight (Mw)
Was 32,000. The same applies to other polymers used in the present invention.
Synthesized by the method. In addition, for the undercoating of the planographic printing plate precursor of the present invention
Is a compound represented by the following general formula (X) in addition to the polymer:
A compound can also be added. [0140] Embedded image (Wherein R⁵¹Is an aryle of 6 to 14 carbon atoms
X and y independently represent an integer of 1 to 3.
The ) Regarding the compound represented by the above general formula (X)
This will be described below. R⁵¹Arylene-based charcoal represented by
The prime number is preferably 6 to 14, and 6 to 10
Is more preferable. R⁵¹As an arylene group represented by
Physically, for example, phenylene group, naphthyl group, anth
Examples include a ryl group and a phenathryl group. R⁵¹Represented by
The arylene group is an alkyl group having 1 to 10 carbon atoms, carbon
Alkenyl group having 2 to 10 carbon atoms, alkini having 2 to 10 carbon atoms
Group, aryl group having 6 to 10 carbon atoms, carboxylic acid ester
Group, alkoxy group, phenoxy group, sulfonic acid ester
Group, phosphonic acid ester group, sulfonylamide group,
Toro group, nitrile group, amino group, hydroxy group, halogen
Atom, ethylene oxide group, propylene oxide
Group, triethylammonium chloride group, etc.
It may be. Specific examples of the compound represented by formula (X)
Examples include 3-hydroxybenzoic acid, 4-hydroxy
Droxybenzoic acid, salicylic acid, 1-hydroxy-2-
Naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy
Doroskiy 3-naphthoic acid, 2,4-dihydroxybenzoate
Perfume acid, 10-hydroxy-9-anthracenecarboxylic acid
Is mentioned. However, it is limited to the above specific example
is not. In addition, the compound represented by the general formula (X) alone
It may be used in a mixture of two or more. The above-mentioned undercoating should be performed by the following method.
Can do. That is, water or methanol, ethanol, methyl
Organic solvents such as ruethyl ketone or mixed solutions
A solution prepared by dissolving the above organic compound in the agent is aluminum.
Applying and drying on a plate, water or methanol,
Organic solvents such as
Solutions in which the above organic compounds are dissolved in these mixed solvents
In order to adsorb the above compound by immersing the aluminum plate,
Thereafter, the substrate is washed and dried with water or the like. former
In the method, 0.005 to 10 mass of the above organic compound
% Concentration of solution can be applied in various ways. The latter
In the method, the concentration of the solution is preferably 0.01-20% by mass
Or 0.05 to 5% by mass, and the immersion temperature is 20 to 90%.
° C, preferably 25 to 50 ° C, and the immersion time is 0.1
Second to 20 minutes, preferably 2 seconds to 1 minute. Used for this
Solution containing ammonia, triethylamine, potassium hydroxide
Basic substances such as um, and acidic substances such as hydrochloric acid and phosphoric acid
The pH can be adjusted in the range of 1-12. Ma
In order to improve the tone reproducibility of image recording materials, yellow dyes are used.
It can also be added. In addition, for improving tone reproducibility of planographic printing plates
Add substances that absorb ultraviolet light, visible light, infrared light, etc.
You can also. The coating amount of the undercoat is 2 to 200 mg / m²Is suitable
Preferably 5 to 100 mg / m²It is. above
Covering amount is 2mg / m²If it is less, sufficient printing performance can be obtained.
I can't. 200mg / m²It is the same even if it is larger
The The lithographic printing plate precursor according to the invention is usually as described above.
Dissolve each of the above components constituting the photosensitive layer described in a solvent.
By coating on a suitable support as described above.
Can be. The solvent used here is ethylene.
Dichloride, cyclohexanone, methyl ethyl keto
, Methanol, ethanol, propanol, ethylene
Glycol monomethyl ether, 1-methoxy-2-propyl
Lopanol, 2-methoxyethyl acetate, 1-meth
X-2-propyl acetate, dimethoxyethane, milk
Methyl acid, ethyl lactate, N, N-dimethylacetami
N, N-dimethylformamide, tetramethylurea
A, N-methylpyrrolidone, dimethyl sulfoxide,
Mention of ruphoran, γ-butyrolactone, toluene, etc.
However, it is not limited to this. these
These solvents are used alone or in combination. In addition, the heat-sensitive layer is formed of an upper layer and a lower layer.
In the case of a structure, the solvent used for coating is heat sensitive.
Alkali-soluble polymer used for the layer and alkali used for the lower layer
Choose different solubility for resoluble polymers
Is preferred. That is, after applying the lower layer,
When applying the upper heat-sensitive layer,
A solvent that can dissolve the underlying alkali-soluble polymer
If used, mixing at the layer interface is not negligible.
In some cases, it may become a uniform single layer instead of multiple layers.
is there. In this way, mixing occurs at the interface between two adjacent layers.
Or when they are compatible with each other and behave like a uniform layer,
There is a possibility that the effect of the present invention by having two layers may be impaired.
Yes, not preferred. For this reason, apply the upper thermal layer.
The solvent used for
A poor solvent for the molecule is desirable. The above components in the solvent when each layer is applied
The concentration of (total solid content including additives) is preferably 1-5
0% by mass. Feel on support obtained after coating and drying
The coating amount (solid content) of the optical layer varies depending on the application, but
In the case of a layer configuration, the upper layer is 0.05 to 1.0 g / m.²so
Yes, when providing a lower layer, 0.3 to 3.0 g / m²so
Preferably there is. Upper layer is 0.05 g / m²Is less than
The image formability is reduced, and 1.0 g / m²More than
The sensitivity may be reduced. Also, the lower layer
If the coating amount is out of the above range, it may be too small.
Even in the case of a gap, the image formability tends to decrease. Also,
The total of photosensitive layers (including one layer and two or more layers) is 0.5 to
3.0g / m²The coating amount is preferably 0.5.
g / m²If it is less than 3, the film properties are lowered, and 3.0 g / m²
If it exceeds, the sensitivity tends to decrease. Less application amount
As the apparent sensitivity increases, the skin of the photosensitive film increases.
The membrane properties are degraded. As a coating method, various methods are used.
For example, bar coater coating, spin coating
Cloth, spray coating, curtain coating, dip coating, air
-Knife coating, blade coating, roll coating, etc.
You can. Apparent feel as the application amount decreases
However, the film characteristics of the recording layer film deteriorate. Main departure
In the bright recording layer, there is an interface for improving the coating properties.
Activators, for example, described in JP-A-62-170950
It is possible to add a fluorosurfactant like
it can. A preferred addition amount is 0.01% in the total solid content of the recording layer.
To 1% by mass, more preferably 0.05 to 0.5% by mass.
It is. For the planographic printing plate prepared as described above
The original is usually subjected to image exposure and development. For image exposure
The active light source used is from near infrared to infrared.
A light source with an emission wavelength in the range is preferred, a solid-state laser, a semiconductor
A body laser is preferred. The emission wavelength is 760 to 85.
0 nm is preferable. The lithographic printing plate precursor according to the invention corresponds to the heat sensitive layer.
By various processing methods, it is made a lithographic printing plate.
Free of alkaline and substantially organic solvents
A lithographic printing plate by developing with a developing solution
And preferably substantially alkali metal silicate.
Lithographic printing by developing with a developer that does not contain
A plate is more preferable. About this method
Is described in detail in JP-A-11-109637.
In the present invention, the contents described in the publication
Similar methods can be used. Exposure In this method, image exposure is performed before development processing. image
As an actinic ray light source used for exposure, for example,
-Bon arc lamp, mercury lamp, metal halide lamp, kin
Non-lamp, tungsten lamp, chemical lamp
I can get lost. Examples of radiation include electron beams, X-rays, and ions.
On-beam, far-infrared, g-line, i-line, Deep-UV
Light, high density energy beam (laser beam)
It is. Examples of laser beams include helium and neo
Laser (He-Ne laser), argon laser, chestnut
Puton laser, helium cadmium laser, KrF
Ximer laser, semiconductor laser, YAG laser
It is. Development Alkali substantially free of organic solvent after exposure
The aqueous solution is preferable. However, if necessary
An organic solvent may be contained. Also substantially alkali metal
In the case of a developer containing no silicate, it contains saccharides
It is preferable. For example, from non-reducing sugar as the main component
At least one compound selected and at least one kind
And a developer having a pH of 9.0 to 13.5
Can be mentioned. In addition, the developer can be used to promote developability and develop waste.
Dispersion of ink and improvement of ink affinity in the image area of planographic printing plates
For the purpose, it contains various surfactants as necessary.
You can. In the present invention, anionic surface activity
Agent, cationic surfactant, nonionic surfactant and
Any of the amphoteric surfactants can be used. Ma
The developer may contain various development stabilizers.
Yes. In addition, the developer is used to prevent stains on the lithographic printing plate.
And can contain a reducing agent. Developer
Can contain organic carboxylic acids. [0154] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. Examples 1 to 20 <Production of substrate> Si: 0.06 mass%, Fe: 0.30
Mass%, Cu: 0.014 mass%, Mn: 0.001 quality
%, Mg: 0.001% by mass, Zn: 0.001% by mass
%, Ti: 0.03% by mass, the balance cannot be Al
Prepare molten metal using an aluminum alloy as an impurity to avoid
After hot water treatment and filtration, thickness 500mm, width 1
A 200 mm ingot was created by DC casting. Average surface
550 ° C after scraping with a face mill at a thickness of 10mm
And kept soaking for about 5 hours and the temperature dropped to 400 ° C.
B) Use a hot rolling mill to make a 2.7 mm thick rolled plate.
It was. Furthermore, heat treatment was performed at 500 ° C. using a continuous annealing machine.
And then cold-rolled to an aluminum plate with a thickness of 0.24 mm
Finished. This aluminum plate is 1030mm wide
Thereafter, the following surface treatment was continuously performed. (A) Mechanical roughening treatment Polishing suspension of abrasive (silica sand) with specific gravity of 1.12 and water
While supplying the slurry liquid to the surface of the aluminum plate
And a mechanical roller rough nylon brush
Surfaced. The average particle size of the abrasive is 8μm and the maximum particle size is
It was 50 μm. The material of nylon brush is 6 · 10
Iron, hair length is 50mm, hair diameter is 0.3mm
It was. Nylon brush is a 300mm stainless steel tube
The hair was planted so as to be dense with a hole. 3 rotating brushes
Used this book. Two support rollers at the bottom of the brush (φ200
mm) was 300 mm. Brush roller
The load of the drive motor that rotates the brush
7 kW against the load before pressing against the aluminum plate
Pressed until it was positive. The direction of brush rotation is
The direction of movement of the ruminium plate was the same. Brush rotation
The number was 200 rpm. (B) Etching treatment with alkali agent The aluminum plate after the mechanical surface roughening treatment obtained above
Caustic soda concentration 2.6% by mass, aluminum ion concentration
Etching by spray at a temperature of 6.5 mass% and a temperature of 70 ° C
The aluminum plate 6g / m² Dissolved.
Then, water washing by spraying was performed. (C) Desmut processing 1% by mass aqueous solution of nitric acid with a temperature of 30 ° C.
Contains 0.5% by mass of ON. )
And then washed with water by spraying. Said de
The aqueous nitric acid solution used for the smut is exchanged in the aqueous nitric acid solution.
The waste liquid from the process of electrochemical surface roughening was used. (D) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. The electrolytic solution at this time is nitric acid 10 g / L
Aqueous solution (aluminum ion 5g / L, ammonium
It contains 0.007% by mass of ions. ) The temperature is 80 ° C
It was. The current density is 30 A / dm at the peak current value.² ,Electricity
The amount is 130C as the total amount of electricity when the aluminum plate is anode.
/ Dm² Met. The auxiliary anode has a current flowing from the power source.
5% was diverted. Then wash with water
It was. (E) Alkali etching treatment Aluminum plate with caustic soda concentration of 26% by mass, aluminum
Etching by spray at a concentration of 6.5% by mass
Processing at 32 ° C. and 0.20 g of aluminum plate
/ M² Dissolve and electrochemical roughening using the previous stage alternating current
Mainly made of aluminum hydroxide produced when
The smut component is removed and the generated pit edge is removed.
The edge portion was melted to smooth the edge portion. after that,
Water washing by spraying was performed. (F) Desmut processing Sulfuric acid concentration 25 mass% aqueous solution (aluminum at 60 ° C.
Contains 0.5% by mass of ions. ) And spray death
Perform mat treatment, then wash with water
It was. (G) Anodizing treatment Two-stage feed electrolytic treatment anodic oxidation equipment (first and second electric
Dissolving section length 6m each, first and second feeding section length 3m each, first
And second feed electrode length 2.4m)
Went. As the electrolyte supplied to the first and second electrolysis parts
In this case, sulfuric acid was used. Both electrolytes have a sulfuric acid concentration of 1
70 g / L (containing 0.5% by mass of aluminum ions
Mu ), The temperature was 43 ° C. Then by spray
Washed with water. The final oxide film amount is 2.7 g / m² so
there were. (H) Alkali metal silicate treatment The temperature of the aluminum support obtained by anodizing treatment
In the treatment layer of 1 mass% aqueous solution of No. 3 sodium silicate at 30 ° C
To alkali metal silicate by soaking for 10 seconds
Processing (silicate processing) was performed. Then on the spray
Washed with water. <Undercoat> Al obtained as described above
On the aluminum support after potassium metal silicate treatment,
Apply undercoat liquid 1 of the composition and dry at 80 ° C. for 15 seconds.
It was. The coating amount after drying is 10 mg / m²Met. (Undercoat liquid 1 composition) ・ The following polymer compound (H) 0.2g ・ Methanol 100g ・ Water 1g [0166] Embedded image <Formation of photosensitive layer> Further, a photosensitive layer having the following composition:
Coating solution 1 was prepared (however, the dyes used are listed in Table 1)
To the base for a lithographic printing plate,
The coating amount after drying the photosensitive layer coating solution 1 (photosensitive layer coating amount) is
1.7 g / m²Apply and dry to form a photosensitive layer
And lithographic printing plate precursors 1 to 20 were obtained. [0168] (Composition of photosensitive layer coating solution 1) ・ Novolak resin (m-cresol / p-cresol = 60/40, weight average)   7,000, containing 0.5% by mass of unreacted cresol) 1.0 g -Dye of the present invention (described in Table 1) 0.01 g -Cyanine dye A 0.1 g represented by the following structural formula ・ Tetrahydrophthalic anhydride 0.05g ・ 0.002 g of p-toluenesulfonic acid 6-Hydroxy-β-naphthalenesulfonic acid as the counterion of ethyl violet     0.02g ・ Fluorine surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.)                                                               0.05g ・ Methyl ethyl ketone 12g [0169] Embedded image Example 21 <Undercoat> Alkali metal silicate treatment obtained in Example 1
Undercoat liquid 2 having the following composition on the treated aluminum support
Was applied and dried at 80 ° C. for 15 seconds. Coverage after drying
Is 15 mg / m²Met. (Undercoat liquid 2 composition) ・ 0.3 g of the above polymer compound (H) ・ Methanol 100g ・ Water 1g <Formation of photosensitive layer> Further, a photosensitive layer having the following composition:
The coating liquid 2 was prepared and applied to the undercoated lithographic printing plate support.
Coating amount after drying this photosensitive layer coating liquid 2 (photosensitive layer coating amount)
1.2g / m²Apply to dry and dry the photosensitive layer
The lithographic printing plate precursor 21 was obtained. [0173] (Photosensitive layer coating solution 2) ・ Fluorine-containing polymer (Megafac MCF-312 (30%), Dainippon Ink Kogyo Co., Ltd.) 0.03g Copolymer (1) {N- (4-aminosulfonylphenyl) methacrylamide / Acrylonitrile / methyl methacrylate (36/34/30: weight average molecular weight 50000, acid 2.65)} 0.75g Novolak resin (weight average molecular weight 4,500, unreacted cresol 0.4% by mass 0.25g ・ 0.003 g of p-toluenesulfonic acid ・ Tetrahydrophthalic anhydride 0.03g -Dye (D-17) of the present invention 0.01 g ・ Cyanine dye A 0.017g ・ The counter ion of Victoria Pure Blue BOH is 1-naphthalenesulfonic acid anio     0.015 g dye ・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate                                                               0.02g WAX agent (dimyristyl 3,3'-thiodipropionate) 0.06 g ・ Fluorine surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) ) 0.05g ・ Γ-Butyllactone 10g ・ Methyl ethyl ketone 10g ・ 8g of 1-methoxy-2-propanol Example 22 <Undercoat> Alkali metal silicate treatment obtained in Example 1
On the treated aluminum support, an undercoat liquid 3 having the following composition
a was applied and dried at 80 ° C. for 15 seconds. Coating after drying
The amount is 15mg / m²Met. (Undercoat 3) ・ 0.3 g of the above polymer compound (H) ・ Methanol 100g ・ Water 1g <Formation of photosensitive layer> Further, for the lower layer having the following composition
The coating amount of the photosensitive layer coating solution 3a is 0.85 g / m.²It becomes
After coating, TABAI, PERFECT O
Set Wind Control to 7 at VEN pH200 and set 1
Dry at 40 degrees for 50 seconds, and then upper layer photosensitive layer coating solution
The coating amount of 3b is 0.15 g / m²I applied so that
After drying at 120 degrees for 1 minute, a lithographic printing plate precursor 22 is obtained.
It was. [0177] (Lower photosensitive layer coating solution 3a) ・ The above copolymer (1) 2.133 g ・ Dye (D-17) of the present invention 0.01 g ・ Cyanine dye A 0.109g ・ 4,4'-bishydroxyphenylsulfone 0.126g ・ Tetrahydrophthalic anhydride 0.190g ・ 0.008 g of p-toluenesulfonic acid ・ 3-Methoxy-4-diazodiphenylamine hexafluorophosphate                                                         0.030g ・ The counter ion of ethyl violet was changed to 6-hydroxynaphthalene sulfone.     0.10g ・ Coated surface modified fluorine-based surfactant (Megafac F-176, Dainippon Ink Industries, Ltd.) 0.035g ・ Methyl ethyl ketone 25.38g ・ 13.0 g of 1-methoxy-2-propanol ・ Γ-butyrolactone 13.2 g [0178] (Upper photosensitive layer coating solution 3b) M, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 4500     0.20.846 g, 0.8 mass% of unreacted cresol) ・ Cyanine dye A 0.075g ・ Behenamide 0.060g ・ Surface improving surfactant (Megafac F-176 (20%), Dainippon Ink & Chemicals, 0.022g) ・ Improved image forming fluorosurfactant (Megafac MCF-312 (30%), Dainichi 0.120g made by Ink Industry Co., Ltd. ・ Methyl ethyl ketone 15.1g -1-methoxy-2-propanol 7.7g Comparative Examples 1 to 3 Dye of the present invention used in the photosensitive layer coating solution 1 of Example 1 above
(D-6) Instead of 0.01 g, a dye having the following structure (C
D-1) Same as Example 1 except that 0.01 g was used
Thus, a comparative lithographic printing plate precursor 1 was prepared. Comparative Example 2 Dye of the present invention used in the photosensitive layer coating solution 1 of Example 1 above
Instead of 0.01 g, a dye having the following structure (CD-2)
The ratio was the same as in Example 1 except that 0.01 g was used.
A comparative lithographic printing plate precursor 2 was prepared. Comparative Example 3 In the photosensitive layer coating solution 1 of Example 1, the dye of the present invention
Same as Example 1 except 0.01 g was not added.
In this manner, a comparative planographic printing plate precursor 3 was prepared. [0182] Embedded image (Evaluation of developability and plate inspection) Obtained as described above.
Produced lithographic printing plate precursors 1 to 22 and comparative lithographic printing plate precursors
Versions 1 to 3, respectively, Trendsett made by Creo
er beam intensity 9w, drum rotation speed 150rpm
I drew the test pattern in the image. That
After that, when any one of developer A to C shown below is shown in Table 1
PS processor made by Fuji Photo Film Co., Ltd.
Using -900H, the liquid temperature was kept at 30 degrees and developed.
At this time, the image area is not eluted and the heat-sensitive layer is poorly developed.
Good development without stains and coloring caused by residual film
Sensory evaluation was performed on the product as having good developability. In addition,
Plate inspection by visually judging the contrast between the image area and the non-image area
Rated good and bad. The results are shown in Table 1. [0184] (Developer A) ・ Pure water 464.58g -Potassium hydroxide 7.12g -Potassium silicate 28.3g Pionein D-1107 (manufactured by Takemoto Yushi Co., Ltd., nonionic surfactant: polyethylene Oxide derivatives) 500ppm ・ Amorgen K (Daiichi Kogyo Seiyaku Co., Ltd., double-sided surfactant: betaine type compound)                                                       1000ppm [0185] (Developer B) ・ Pure water 950g ・ D-sorbite / potassium oxide (K₂50 g of potassium salt consisting of O) Pionein D-1107 (manufactured by Takemoto Yushi Co., Ltd., nonionic surfactant: polyethylene Oxide derivatives) 2g ・ Pionine D-158G (manufactured by Takemoto Yushi Co., Ltd., double-sided surfactant) 2g ・ Olfin AK-02 (Nisshin Chemical Co., Ltd., antifoaming agent) 0.2g (Developer C) PS plate developer DT-1 (rich)
Made by Shishi Photo Film Co., Ltd., substantially alkali metal silicic acid
It is a developer that does not contain salt and contains saccharides)
9 times diluted water (developer 1 plus water 8) [0187] [Table 1] From the results shown in Table 1, the present visible light absorbing dye is
By using the dye of the invention, the developability of the exposed area is reduced.
It can be seen that the plate inspection can be improved without lowering. [0189] The lithographic printing plate precursor according to the present invention is sufficiently developed.
And has excellent plate inspection.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AB03 AC08 AD03 CB17                       CB28 CB52 CC13 CC20 FA03                       FA17                 2H096 AA07 AA08 BA11 BA16 BA20                       EA04 GA08                 2H114 AA04 AA22 AA24 BA01 DA52                       DA53 EA01 EA05 GA03 GA06                       GA09 GA27 GA34 GA38

Claims (1)

What is claimed is: 1. A lithographic printing plate precursor having a photosensitive layer provided on a support, the photosensitive layer comprising a photothermal conversion substance, a water-insoluble and alkali-soluble resin, and after exposure. A lithographic printing plate precursor comprising a visible light absorbing dye having an acidic group.