JP2003215803A - Ir sensitive photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an IR sensitive photosensitive composition for direct plate making having such properties that when the composition is used as an image forming layer of a lithographic printing original plate, the layer shows a stable state before development, is superior from the economical viewpoint and has a preferable coating surface state, the layer is hardly dissolved in an unexposed part even when a developer liquid having strong developer activity is used, the layer shows excellent depositing property for printing ink, and thereby, the discrimination of an image is improved and favorable latitude for development is obtained. <P>SOLUTION: The IR sensitive photosensitive composition comprises (A) a resin insoluble with water and soluble with an alkali aqueous solution, (B) a photothermal converting agent, (C) a fluorine-containing polymer having a (meth)acrylate monomer having 2 or 3 specified perfluoroalkyl groups in the molecule as the polymerization component, (D) a fluorine-containing polymer having at least specified three kinds of monomers as the copolymerization component and (E) a specified copolymer. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
It relates to an image recording material that can be used as a star.
In particular, directly from digital signals from computers, etc.
Infrared sensitivity for so-called direct planographic printing plates
The present invention relates to a light-sensitive composition. [0002] 2. Description of the Related Art An original for a lithographic printing plate forms an image on a substrate.
It has the structure which provided the composition. The typical manufacturing process is
Coating and drying the image forming composition on the surface of the support
It is. Also, the typical plate making process is exposure, image formation
Image-forming layer in non-image area after causing physical property change in the layer
By carrying out treatment such as removal (development) of the hydrophilic support surface
Image consisting of non-image area consisting of face layer and surface layer of hydrophobic composition
A lithographic printing plate having an image portion is formed. Kakushi
In the typical printing process, the lithographic printing plate obtained is
Water-based non-image area is dampening water, and lipophilic image area is ink.
Receiving and forming an ink image on the surface. Inn obtained
Transfer images directly or indirectly to the desired print media
By doing so, printed matter can be obtained. Highly useful as the above lithographic printing plate precursor
1) High uniformity of image forming layer
2) The hydrophobicity of the image area is high and the non-image area is developed.
There is a technical problem of high removability. The uniformity of the image area is
Technically, it is mainly related to the above manufacturing process.
Master plates with insufficient uniformity are stable in high-quality, uniform prints.
It is not preferable because a large number of sheets cannot be provided. Ma
In addition, the high hydrophobicity of the image area means that in the plate making process.
By improving the durability against developer,
Obtaining resolving power, sufficient printing durability and printing in the printing process
This is important from the standpoint of obtaining solid meat. However,
The high hydrophobicity of the image area means that the developer, which is a commonly used developer, is used.
May cause reduced solubility in aqueous solution of Lucari
Development defects in the non-image area and sludge formation in the developer.
Unfavorable results such as minute generation can occur. That is,
The hydrophobicity of the image area and the removability of the non-image area are simply contradictory.
Is required for the image forming layer, and these are compatible
The development of possible technologies is a difficult and important issue. In response to such technical problems, an image forming composition is used.
Containing a polymer compound having a fluoroaliphatic group as
It is known that the use of various compositions is useful. Concrete
In particular, it is a machine for expressing the uniformity of the film due to the improvement of the surface activity.
Solution for development delay due to hydrophobicity
Hydrophobicity and non-image of the image area by utilizing the erasing, hydrophobicity and orientation force
Disclosed the effect of high-contrast image formation through compatibility of image area removability
Has been. For example, in Japanese Patent Laid-Open No. 11-288093
Is a hook containing three specific monomers as copolymerization components.
Due to the element-containing polymer, the state before development is stable.
It is disclosed that an image forming material excellent in handleability can be obtained.
ing. Japanese Patent Laid-Open No. 2000-187318 is full.
A monomer unit having two or more oroaliphatic groups was used.
The solubility of the image area and non-image area is reduced by the polymer compound.
It is possible to obtain an image forming material excellent in scripting.
Are disclosed. As mentioned above, containing fluoroaliphatic compounds
The image forming layer to be used as the image forming layer of the lithographic printing plate precursor
Effective as a method to achieve the common technical problems 1) and 2)
It is effective. However, on the other hand, the effect is still sufficient.
For example, for coating surface defects and developer sensitivity fluctuations
Insufficient image state fluctuation, stability over time, and inking properties
The actual situation is that further improvements are desired. [0006] SUMMARY OF THE INVENTION The present invention provides the above-described conventional technique.
More specific, trying to overcome the drawbacks of the technology
As an example, it is used as an image forming layer of an original plate for lithographic printing.
The state before development is stable and excellent over time.
A developer with good coating surface and strong developer activity
Even if it is used, it is difficult to dissolve the non-exposed part, and ink inking property is improved.
Excellent, thus improving image discrimination,
Infrared sensitive for direct plate making with good development latitude
It is intended to provide a photosensitive composition. [0007] [Means for Solving the Problems] The present inventors have conducted intensive research.
As a result of, for example, the image forming layer of the lithographic printing plate precursor
Specific to infrared sensitive compositions that can be used in
By adding three types of fluoropolymers,
I found that the goal was achieved. That is, the present invention is as follows.
This is achieved by the above configuration. <1> (A) Water-insoluble alkaline water-soluble tree
Fat, (B) photothermal conversion agent, (C) 3 to 20 carbon atoms in the molecule
Having 2 or 3 perfluoroalkyl groups (meth)
A polymer comprising an acrylate monomer as a polymerization component, (D)
At least the following (1) to (3) are included as copolymerization components
Fluorine-containing polymer, (1) The hydrogen atom on the carbon atom is
Fluoroaliphatic groups substituted with nitrogen atoms in the side chain
Addition-polymerizable fluorine-containing monomer, (2)
Monomers represented by structures [1] to [4]; [0009] [Chemical 2] [Wherein A¹ Is a hydrogen atom, halogen atom or
Represents an alkyl group, W is oxygen, or -NR¹-
R¹ Represents a hydrogen atom, an alkyl group, an aryl group,
R² Is an optionally substituted alkyl group or substituent.
Represents an aryl group which may have, R_ThreeIs alkyl
Group represents an aryl group, U represents cyano group, aryl group,
Lucoxy group, aryloxy group, acyloxymethyl
Group, a heterocycle containing a nitrogen atom, or -CH₂OCO
R_Three (R_Three  Represents the same as above) (3) It has an acidic hydrogen atom, and the acidic hydrogen atom is a nitrogen atom
An addition-polymerizable monomer having an acidic group bonded to
And (E) (i) having 3 to 20 carbon atoms and 40 layers
Contains at least 3% fluorine and at least 3 charcoal at the end
Fluoroaliphatic groups in which the elementary atoms are fully fluorinated
(Rf group) -containing (meth) acrylate and (ii) poly
Copolymerization with (oxyalkylene) (meth) acrylate
Rf group-containing (meth) acrylate monomer
The unit is 25 to 70% by weight based on the weight of the copolymer
Infrared sensation characterized by containing a copolymer of
Photogenic composition. Hereinafter, preferred embodiments will be described. <2> The polymer in (C) is
Polymerization component and (meth) acrylate having OH group
<1 which is a copolymer with a monomer
> The infrared-sensitive composition according to the above. <3> Molecular weight of copolymer in (E)
Is 2,500 to 100,000
The infrared sensitive photosensitive composition according to <1>. <4> The copolymer is an Rf group-containing acrylate and a polymer.
Including ri (oxyalkylene) acrylate monomer unit
The infrared sensitive infrared ray as described in <3> above, wherein
Photosensitive composition. [0013] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
To do. [(C) Fluorine-containing polymer] (C)
Fluorine-containing polymers have 3 to 20 carbon atoms in their molecules.
(Meth) acrylic having 2 or 3 fluoroalkyl groups
Rate monomer (hereinafter, “(C) fluorine-containing monomer”
Is used as a polymerization component.
Is a perfluoroalkyl group having 3 to 20 carbon atoms.
3 are tetravalent with acryloyl group or methacryloyl group
As long as it is a monomer bonded with a linking group of
It is not something. In the present invention, perfluoroal
Those containing only one kill group,
If the rualkyl group has less than 3 carbon atoms,
In some cases, the limitation may not be improved.
If the number of carbon atoms exceeds 20, the sensitivity may decrease. The (C) fluorine-containing polymer includes the following ones:
A fluorine-containing monomer represented by the general formula (I) is used as a polymerization component.
It is preferable to do. Formula (I) [0016] [Chemical Formula 3] In the general formula (I), R¹ Has 3-20 carbon atoms
Represents a perfluoroalkyl group. R¹The carbon
May represent a perfluoroalkenyl group of 3 to 20
Yes. These can be linear, branched, cyclic, or a combination
Any of the above can be used.
What the child intervened, eg (CF_Three)₂ CFOCF₂ C
F₂ -Etc. may be sufficient. Z¹ Is-(CH₂) N-(where n is 1
Represents an integer of ~ 6. ) Or a group represented by the following formula
(However, R²Is a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
Represents a ru group. ). Here, in general formula (I), 2 or 3
Z included¹Are two or three different connections
It may be a group. [0019] [Formula 4] Z² Is-(CH₂ ) M-(where m is 2
Represents an integer of ~ 6. ) Or a group represented by the following formula. [0021] [Chemical formula 5] R is a hydrogen atom, a methyl group, or a halogen
Represents an atom (Cl, Br, etc.). X is represented by the following formula:
Represents a divalent linking group (provided that Y represents a carbon number of 15 or less.
And the weight ratio in the X group is 35 to 65%.
A certain divalent linking group is represented. ). [0023] [Chemical 6] Here, representative of the divalent linking group represented by Y
Examples of typical ones include the following. [0025] [Chemical 7] [0026] [Chemical 8] P and q are integers satisfying p + q = 4
(Where p is 2 or 3). A is represented by the following formula.
Represents a tetravalent linking group. [0028] [Chemical 9]The (C) fluorine-containing monomer is described below.
Although a specific example is given, this invention is not limited to these at all.
It is not a thing. [0030] Embedded image [0031] Embedded image[0032] Embedded image [0033] Embedded image[0034] Embedded image [0035] Embedded image[0036] Embedded image [0037] Embedded image [0038] Embedded image[0039] Embedded image The fluorine-containing polymer (C) is
2 perfluoroalkyl groups having 3 to 20 carbon atoms in the molecule
Or three (meth) acrylate monomers and carbonized
It is a copolymer with hydrogen (meth) acrylate monomer
May be. The hydrocarbon (meth) acrylate monomer
Those having an OH group are preferred. Also hydrocarbon type
You may use together with an acrylate. Examples of the hydrocarbon acrylate include:
It has one or two acryloyl groups.
Known in the industry (for example, “Kuyo Sato, Shoji Nakahara” U
34, 35 in "Introduction to V-curing technology" (Polymer Publications)
Table 10 on page, Table 16 on page 46-48, Table 20 on page 57,
From the compounds described in Table 60 on pages 170 to 172) as appropriate
For example, the following (B-1 to B
-8). Of these, B-2 is particularly preferred
Can be mentioned. [0042] Embedded image(C) Molecular weight of fluorine-containing polymer
Is not particularly limited, but the weight average molecular weight is
Those of 3,000 to 200,000 are preferred, and 4,0
The thing of 00-100,000 is more preferable. Also before
The amount of fluorine-containing polymer added is the total amount of photosensitive composition
The content is preferably 0.01 to 10% by weight, and 0.1%.
More preferred is ˜5% by weight. Next, the (D) fluorine-containing polymer of the present invention.
-(Hereinafter referred to as “(D) fluorine-containing polymer”)
Will be described. [(D) Fluorine-containing polymer] used in the present invention
(D) The fluorine-containing polymer is at least the above (1) to
(3) is included as a copolymerization component. Charcoal, component (1)
Full hydrogen atoms on the atoms are replaced by fluorine atoms
Oroaliphatic groups are usually saturated and generally monovalent and divalent
Is an aliphatic group. This is linear, branched, and cyclic
Including Fluoroaliphatic radicals are well
3 to 20, preferably 6
All of the fluorine-containing monomers having ~ 12 carbon atoms
40% by weight or more based on the amount, preferably 50
It has at least wt% fluorine bonded to carbon atoms. Good
Suitable fluoroaliphatic groups are C_nF_{2n + 1}-(N is 1 or more)
An integer greater than or equal to 3).
Perfluorinated aliphatic group (hereinafter referred to as Rf)
(Also abbreviated as a group). Water on carbon atom shown as component (1)
Fluoroaliphatic radicals in which the elementary atoms are replaced by fluorine atoms
Addition-polymerizable part in addition-polymerizable monomer having
As radically polymerizable vinyls having unsaturated groups and
Its derivatives are used. Preferred among addition polymerizable parts
Acrylate, methacrylate, acrylic
, Methacrylamide, styrene, vinyl and these
Is a derivative. Acrylates with fluoroaliphatic groups attached
Specific examples of G and methacrylate include, for example, Rf-
R'-OOC-C (R ") = CH₂(Where R 'is an example
For example, single bond, alkylene, sulfonamide alkyle
Or carbonamidoalkylene and R ″ is water
Elementary atom, methyl group, halogen atom, or perfluoro
And an aliphatic group). Specific examples thereof include, for example, US Pat.
No. 2803615, No. 2642416, No. 282
No. 6564, No. 3102103, No. 328290
No. 5 and No. 3304278, JP-A-6-2562
89, JP-A-62-1116, JP-A-62-487
72, JP 63-77574, JP 62-36
No. 657 and the Chemical Society of Japan Journal 1985 (No.
10) Examples include those described on pages 1884 to 1888.
it can. Also, these fluoroaliphatic group-bonded monomers
In addition, ReportsRes. Lab.Asahi Glass Co. Ltd., 3
Volume 4, pp. 27-34, 1984.
Combined macromers can be used advantageously. Also fluo
As the aliphatic group-bonded monomer, the following structural formula is used.
-Mixtures with different lengths of fluoroalkyl groups may also be used.
You can. [0047] Embedded image (D) Fluorine-containing poly used in the present invention
These fluoroaliphatic group-containing monomers used in the
The amount of mer is 3 to 70 weights based on the weight of the polymer
%, Preferably in the range of 7-40% by weight. The monomer used as component (2) is:
It is shown by the following structures [1] to [4]. [0050] Embedded image Where A¹ Is a hydrogen atom, a halogen atom or
Represents an alkyl group, W is oxygen, or -NR¹−
R¹ Represents a hydrogen atom, an alkyl group, or an aryl group. R²
Has an alkyl group which may have a substituent, and a substituent.
An aryl group optionally represented by R^Three Is an alkyl group
Represents a reel group, U represents a cyano group, an aryl group, an alkoxy group
Si group, aryloxy group, acyloxymethyl group, nitrogen
Heterocycle containing atoms, or -CH₂OCOR^Three (R^Three
 Represents the same as above. Represented by structures [1]-[4]
As a preferable range of the monomer, A¹Is a hydrogen atom,
A halogen atom or an alkyl group having 1 to 4 carbon atoms;
Is oxygen or -NR¹ -And R¹ Is a hydrogen atom, carbon
An alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms
Represents. R²May have a substituent and has 1 to 8 carbon atoms
An aryl group optionally having an alkyl group or a substituent
Group, R^Three Is an alkyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
Represents an aryl group of 0; U is a cyano group, aryl group, a
Lucoxy group, aryloxy group, acyloxymethyl
Group, a heterocycle containing a nitrogen atom, or -CH₂OCO
R^Three (R^ThreeRepresents the same as above. R² Optionally substituted alkyl
Group, the substituents are fluorine, chloro, bromo
Halogen atoms such as hydroxyl group, methoxy, ethoxy, etc.
An alkoxy group, an aryloxy group such as phenoxy,
Cyano group, amide group such as acetamide, ethoxycal
List alkoxycarbonyl groups such as bonyl groups
be able to. R²May optionally have a substituent
In addition to the above, a methyl group is included as a substituent when
I can make it. Preferred specific compounds of component (2) are as follows:
Shown in For example, methyl (meth) acrylate, ethyl
(Meth) acrylate, propyl (meth) acrylate
, Butyl (meth) acrylate, amyl (meth) acrylate
Relate, 2-ethylhexyl (meth) acrylate,
Octyl (meth) acrylate, 2-chloroethyl (meth)
Ta) acrylate, cyclohexyl (meth) acrelane
2-hydroxyethyl (meth) acrylate, 2-
Hydroxylpropyl (meth) acrylate, 2-hydride
Roxybutyl (meth) acrylate, diethyleneglycol
Mono (meth) acrylate, 2-hydroxy-3-
Phenoxypropyl (meth) acrylate, glycidyl
(Meth) acrylate, diethylaminoethyl (meth)
Acrylate, furfuryl (meth) acrylate, Tet
Lahydrofuryl (meth) acrylate, phenyl (meth
Ta) acrylate, hydroxyphenyl (meth) acryl
Rate, cresyl (meth) acrylate, naphthyl (me
) Acrylate, benzyl (meth) acrylate,
(Meth) actyl such as toxibenzyl (meth) acrylate
Rylates; (meth) acrylamide, N-eth
Le (meth) acrylamide, N-propyl (meth) acrylic
Rilamide, N-butyl (meth) acrylamide, N-
Hexyl (meth) acrylamide, N-octyl (me
) Acrylamide, N-cyclohexyl (meth) aqua
Rilamide, N-methylol (meth) acrylamide,
N-hydroxyethyl (meth) acrylamide, N-be
Nyl (meth) acrylamide, N-phenyl (meth)
Acrylamide, N-nitrophenyl (meth) acrylic
Amide, N-tolyl (meth) acrylamide, N-hydride
Roxyphenyl (meth) acrylamide, N, N-dimethyl
Til (meth) acrylamide, N, N-diethyl
) Acrylamide, N, N-dicyclohexyl (me
T) (Meth) acrylamides such as acrylamide; N
-Methylmaleimide, N-ethylmaleimide, N-pro
Pyrmaleimide, N-butylmaleimide, N-pentyl
Maleimide, Nn-hexylmaleimide, N-lauri
Rumaleimide, N-stearylmaleimide, N-cyclo
Hexylmaleimide, N-phenylmaleimide, N-c
Lolophenylmaleimide, N-tolylmaleimide, N-
N such as hydroxymaleimide and N-benzylmaleimide
-Substituted maleimides; allyl acetate, allyl caproate,
Ants such as allyl stearate and allyloxyethanol
Compound: ethyl vinyl ether, propyl vinyl ether
Tellurium, butyl vinyl ether, octyl vinyl ether
, Methoxyethyl vinyl ether, ethoxyethyl vinyl
Nyl ether, 2-chloroethyl vinyl ether, hydride
Roxyethyl vinyl ether, benzyl vinyl ether
, Tetrahydrofurfuryl vinyl ether, phenyl
Vinyl ether, tolyl vinyl ether, diethylamino
Vinyl ethers such as noethyl vinyl ether: Vinyl
Acetate, vinyl butyrate, vinyl caproate,
Vinyl chloroacetate, vinyl methoxyacetate,
Vinyl phenyl acetate, vinyl acetoacetate,
Vinyl es such as vinyl benzoate and vinyl chlorobenzoate
Tellurium; styrene, α-methylstyrene, methylstyrene
, Dimethylstyrene, chloromethylstyrene, etoxy
Simethylstyrene, hydroxystyrene, chlorostyrene
Styrenes such as styrene and bromostyrene; N-vinyl pyrrole
Don, N-vinylpyridine, acrylonitrile, etc.
It is done. Particularly preferred among these components (2)
It is a monomer represented by the structure [1] or [3]. Component (3), which has an acidic hydrogen atom,
As the acidic group in which the acidic hydrogen atom is bonded to the nitrogen atom,
Any acidic group known in the literature can be used. Acidic
Known documents of the group include J.A. Dean ed., Lange's Handbo
ok of Chemistry 3rd. ed. 1985 McGraw-Hill Book Co.
Can be mentioned. Of these acidic groups, acidic hydrogen
Concrete structure of acidic group with atom bonded to nitrogen atom
Examples include those represented by the following [A] to [G].
Rukoto can. -SO₂ NH₂[A] -SO₂ NH- [B] -CONHSO₂-[C] -CONHCO- [D] -SO₂ NHSO₂-[E] -CONHSO₂NH- [F] -NHCONHSO₂ -[G] In addition to these structures, JP-A-7-248628
Nitrogen-containing heterocyclic structures having a coupler structure
Is also included. Examples of these nitrogen-containing heterocyclic structures
Can include those represented by [H] and [I] below.
Yes. [0055] Embedded image The acidic hydrogen atom shown as component (3)
And has an acidic group in which the acidic hydrogen atom is bonded to a nitrogen atom.
As an addition polymerizable part in the addition polymerizable monomer
And vinyls having unsaturated groups capable of radical polymerization and their
Derivatives are used. Preferred addition polymerization part
Acrylate, methacrylate, acrylamide,
Tacrylamide, styrene, vinyl and their derivatives
It is. It has an acidic hydrogen atom, and the acidic hydrogen atom
Examples of preferred structures of acidic group-containing monomers bonded to the
Is represented by the following general formula [5], [6] or [7].
And monomers having structural units
The [0057] Embedded image Where A² Is a hydrogen atom, halogen atom or
Represents an alkyl group having 1 to 4 carbon atoms. B is an arylene group
Represents. X is -CO- or -SO₂-Represents. X is
-SO₂When-, Y is a hydrogen atom, an alkyl group, an aryl
Group, -CO-R^FourOr -SO₂-R^FourRepresents. Also
When X is —CO—, Y is —CO—R.^FourOr -SO₂−
R^FourRepresents. Z is —NH—, —NR^Four-Represents -O-.
E represents an arylene group or an alkylene group. R^FiveIs
A hydrogen atom, an alkyl group, or an aryl group is represented. m and s
Represents 0 or 1, but both m and s are 0
There is no. R^FourRepresents an alkyl group or an aryl group. B
And Y, or E and R are connected to each other to form a nonmetallic atom
A ring may be formed. [0059] Embedded imageF and G are a phenylene group or an alkylene group.
Represents. T is -O-CO-, -CO-, or -SO
₂-Represents. p, p ', q, q' represents 0 or 1
However, q and q ′ are not 0 at the same time. General
In the formulas [5] and [6], A²Preferred of
Is a hydrogen atom or a methyl group. Y, R^FourAlso
Or R^FivePreferred alkyl groups represented by
C 1-20 Al, such as ru, ethyl, isopropyl
There is a kill group, Y, R^FourOr R^FivePreferred represented by
The aryl group has 6 carbon atoms such as phenyl and naphthyl.
There are ˜18 aryl groups. Preferred represented by B or E
Preferred arylene groups are phenylene and naphthylene.
Which can be mentioned, the preferred alkyl represented by E
Len group has 1-2 carbon atoms such as methylene and ethylene
There are zero alkylene groups. Y, R^FourOr R^FiveAlkyl represented by
Group, aryl group, and aryl represented by B or E
The len group and the alkylene group may have a substituent.
Substituting groups include halogen atoms such as fluorine, chloro and bromo.
Child, alkoxy group such as methoxy, ethoxy, pheno
Aryloxy groups such as xy, cyano group, acetamide
Such as amide group, ethoxycarbonyl group etc.
C1-C20 alkyl other than xyloxy group
Groups and aryl groups having 6 to 18 carbon atoms.
Yes. In the general formula [7], preferred examples of F and G
Is the same as that used in B or E.
I can make it. The general formulas [5] to [7]
Of these, the monomers [5] and [6] are more preferred.
Used in fluorine-containing polymer used in the present invention
The amount of these acidic group-containing monomers is determined by the weight of the polymer.
5 to 80% by weight, preferably 10 to 7
It is in the range of 0% by weight. Next, acidic water used in the present invention
Specific examples of monomers containing acidic groups in which an elementary atom is bonded to a nitrogen atom
An example of a typical structure is shown below. [0062] Embedded image [0063] Embedded image[0064] Embedded image[0065] Embedded image[0066] Embedded imageThe fluorine-containing polymer (D) of the present invention is known.
It can be produced by a conventional method. For example, fluoro fat
(Meth) acrylates having aliphatic groups, aliphatic groups or
Is (meth) acrylate having an aromatic group and acidic water
Acid group-containing vinyl monomer in which an elementary atom is bonded to a nitrogen atom
Add a general-purpose radical polymerization initiator in an organic solvent
And can be produced by thermal polymerization. Or if
Add other addition-polymerizable unsaturated compounds with
It can be produced by the same method as described above. Other additional weights used depending on circumstances
Polyunsaturated compounds include PolymerHandbook 2nd ed.,
J. Brandrup, Wiley Interscience (1975) Chapter 2 Pag
e 1-483 can be used. These examples
For example, methyl (meth) acrylate,
Chill (meth) acrylate, 2-chloroethyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate
(Eg, glycidyl (meth) acrylate)
) Acrylates, (meth) acrylamide, N-E
Chill (meth) acrylamide, N-propyl (meth) a
Kurylamide, N-methylol (meth) acrylami
N, N-dimethyl (meth) acrylamide, N-hy
Droxyethyl (meth) acrylamide, N- (p-hy
Such as droxyphenyl) -meta-acrylamide
T) Acrylamides, allyl acetate, caproate ants
And allyl compounds such as allyloxyethanol; ethyl
Vinyl ether, propyl vinyl ether, butyl vinyl
Ether, octyl vinyl ether, methoxyethylene
Ruvinyl ether, ethoxyethyl vinyl ether, 2
-Chloroethyl vinyl ether, hydroxyethyl vinyl
Luether, benzyl vinyl ether, tetrahydroph
Rufuryl vinyl ether, phenyl vinyl ether,
Ril vinyl ether, diethylaminoethyl vinyl ether
Vinyl ethers such as tellurium; vinyl acetate, vinyl
Butyrate, vinyl caproate, vinyl chloroacete
, Vinyl methoxyacetate, vinyl phenylacetate
Tate, vinyl acetoacetate, vinyl benzoate,
Vinyl esters such as vinyl lorbenzoate; styrene,
α-methylstyrene, methylstyrene, dimethylstyrene
Chloromethylstyrene, ethoxymethylstyrene,
Hydroxystyrene, chlorostyrene, bromostyrene
Styrenes such as methyl vinyl ketone, ethyl vinyl ketone
T, propyl vinyl ketone, phenyl vinyl ketone, etc.
Vinyl ketones; isobutylene, butadiene, isoprene
Olefins such as len; other, butyl crotonate, a
Dimethyl taconate, diethyl itaconate, di maleate
Methyl, diethyl fumarate, N-vinylpyrrolidone, N
-Vinyl pyridine, acrylonitrile, etc. are mentioned. In addition to these monomers, JP-A-62-2
226143, described in JP-A-3-17249
Using polyoxyalkylene (meth) acrylate
You can. Hereinafter, the fluorine-containing polymer of the present invention
An example of a specific structure is shown. The numbers in the formula are the monomers
The molar ratio of components is shown. [0070] Embedded image [0071] Embedded image[0072] Embedded image[0073] Embedded image[0074] Embedded image (D) Fluorine-containing polymer used in the present invention
The molecular weight range is 3000 to 200 as the average molecular weight,
Up to 000, preferably 6,000 to 10
Those up to 10,000 can be used. Also this departure
The amount of fluorine-containing polymer used in the light is excluded from the solvent
It is in the range of 0.001 to 10% by weight with respect to the total composition.
More preferably, it is in the range of 0.01 to 5% by weight. Next, the (E) fluorine-containing polymer of the present invention.
-(Hereinafter referred to as “(E) fluorine-containing polymer”)
Will be described. [(E) Fluorine-containing polymer] used in the present invention
(E) Fluorine-containing polymer is (i) carbon source of 3-20
And containing 40% by weight or more of fluorine
Contains at least three fully fluorinated carbon atoms
Contains fluoroaliphatic groups (hereinafter referred to as Rf groups)
An acrylate or methacrylate, and (ii)
Poly (oxyalkylene) acrylate or poly (o
Is a copolymer with xylene) methacrylate
Rf group-containing acrylate or Rf group-containing methacrylate
Rate monomer units are 2 based on the weight of the copolymer.
It is characterized by being 5 to 70% by weight. The fluoroaliphatic radical Rf is saturated and general
Are monovalent aliphatic groups. This is branched and large enough
In the case of a threshold, a ring or a combination thereof (e.g.
Lucycloaliphatic group). Fluoroaliphatic backbone is charcoal
Chain oxygen and / or trivalent nitrogen bound only to elementary atoms
It can contain elementary heteroatoms, which are
Provides a stable bond between orocarbon groups and inactive Rf groups
Does not interfere with sexual characteristics. Rf group exerts sufficient effect
For this purpose, 3 to 20, preferably 6 to 12 carbon atoms are used.
And 40% by weight or more, preferably 50% by weight or more
Having fluorine bonded to a carbon atom. R
At least three carbon atoms at the end of the f group are fully fluorinated
Has been. The end of the Rf group is, for example, CF_ThreeCF₂CF₂
-And the preferred Rf group is C_nF_{2n + 1}(N is 3 or more
Integer)) is virtually fully or fully fluorinated
Alkyl group. When the Rf group fluorine content is less than 40% by weight
The object of the present invention is not fully achieved. Fluorine atom is Rf
It is more effective to localize at the end of the group. Rf group
Increase the fluorine content even if the number of carbon atoms is 2 or less
Although the total number of fluorine atoms becomes insufficient,
weak. Fully fluorinated Rf with 2 or fewer carbon atoms
Increasing the ratio of group-containing monomer to copolymer
Even if the fluorine content in the copolymer is increased by
Since nitrogen atoms are not localized, a sufficient effect can be obtained.
Absent. On the other hand, the Rf group has 21 or more carbon atoms.
Is not suitable for the solvent of the copolymer obtained when the fluorine content is high.
If the solubility is low and the fluorine content is low,
Nitrogen atoms are not sufficiently localized and a sufficient effect is obtained.
I can't. The solubilized portion in the copolymer is poly (oxya).
(Alkylene) group, (OR ') x, where R' is 2-4.
An alkylene group having a carbon atom, for example -CH₂CH
₂-, -CH₂CH₂CH₂-, -CH (CH_Three) CH₂-
Or -CH (CH_Three) CH (CH_Three)-Is preferred
Yes. Oxyal in the above poly (oxyalkylene) group
As in the poly (oxypropylene) unit
Two or more different types that may be the same or different from each other
It may be an irregular distribution of xyalkylene
Straight or branched oxypropylene and oxy
Ethylene units or linear or branched
Block of oxypropylene units and oxyethylene
It may exist like a unit block.
One or more poly (oxyalkylene) chains
The following chain bonds [0081] Embedded image Can be mediated by or include
The The linkage of the chain has three or more valences
In some cases this gives a branched oxyalkylene unit.
Provide a means for The copolymer is also used as a photosensitive composition.
In order to obtain the desired solubility when added to
The molecular weight of the (oxyalkylene) group is 250 to 2500
Is appropriate. The above copolymer used in the present invention is, for example,
For example, fluoroaliphatic group-containing acrylate or fluoro
Aliphatic group-containing methacrylate and poly (oxyalkylene)
) Acrylate or poly (oxyalkylene) meta
Acrylates, such as monoacrylates or diacrylates
Produced by free radical initiated copolymerization with
I can build it. The molecular weight of the polyacrylate oligomer is
Initiator concentration and activity, monomer concentration and polymerization reaction temperature
The chain transfer agent, e.g.
Add all, eg n-octyl mercaptan.
And can be adjusted by. As an example, a fluoroaliphatic group
Containing acrylate, Rf-R'-O₂C-CH = CH
₂(Where R ′ is, for example, sulfonamidoalkylene,
Carbonamidoalkylene, or alkylene
E.g. C₈F₁₇SO₂N (C_FourH₉) CH₂CH₂O₂
CCH = CH for poly (oxyalkylene) monoacrylate
Tote CH₂= CHC (O) (OR ') xOCH_ThreeCopolymerized with
Then, a copolymer having the following repeating unit is obtained. [0084] Embedded image The fluoroaliphatic group-containing acrylate is
U.S. Pat. Nos. 2,803,615 and 2,642,4
16, No. 2,826,564, No. 3,102,
No. 103, No. 3,282,905 and No. 3,3
04,278. Production of the above copolymer
Poly (oxyalkylene) acrylate used in
And other acrylates useful for this purpose are commercially available
Hydroxypoly (oxyalkylene) materials such as quotients
Product name “Pluronic” [Pluronic (Asahi Denka Kogyo Co., Ltd.)
Manufactured by Asahi Denka Kogyo Co., Ltd.)
"Carbowax" (Carbowax)
(Glyco Products) Co.)], "Triton"
(Rohm and Hass Co.)
And P.E.G. (Daiichi Kogyo Seiyaku Co., Ltd.)
Acrylic acid, methacrylic acid,
React with acrylic chloride or acrylic anhydride.
And can be manufactured by Separately, the pox produced by a known method
Li (oxyalkylene) diacrylate, CH₂= CH
CO₂(R'O) xCOCH = CH₂, Eg CH₂= CH
CO₂(C₂H_FourO)_Ten(C_ThreeH₆O)_{twenty two}(C₂H_FourO)_TenCOCH
= CH₂A fluoroaliphatic group-containing acrylate
When copolymerized, a polyacrylic resin having the following repeating units:
A rate copolymer is obtained. [0086] Embedded image The copolymer used in the present invention is produced
Other fluoroaliphatic group-containing terminal ethylene unsaturated
Sum monomers are disclosed in U.S. Pat. No. 2,592,069,
No. 2,995,542, No. 3,078,245,
No. 3,081,274, No. 3,291,843
And 3,325,163, the above-mentioned
Manufacture terminal ethylenically unsaturated monomers containing fluoroaliphatic groups
An ethylenically unsaturated material suitable for manufacturing is US Pat.
No. 3,574,791. The copolymer used in the present invention is a fluoro fat.
Aliphatic group-containing acrylate or fluoroaliphatic group-containing
Tacrylate and poly (oxyalkylene) acrylate
Or with poly (oxyalkylene) methacrylate
A polymer comprising a fluoroaliphatic group-containing monomer unit.
Containing 25 to 70% by weight based on the weight of the oligomer
Yes. 25% by weight of fluoroaliphatic group-containing monomer unit
If it is less, the effect is not sufficient, and conversely, it is more than 70% by weight.
If so, the solubility in the solvent is too low. Main departure
The molecular weight of the copolymer used is 2,500-10.
If it is less than 2,500, it is effective.
Not enough, if it is greater than 100,000,
Since solubility falls, it is unpreferable. The copolymer used in the present invention is fluoro.
As aliphatic group-containing monomer, fluoroaliphatic group-containing monomer
Acrylate to fluoroaliphatic group-containing monomer units
50-100% by weight and poly (oxyalkyl)
Len) acrylate monomer units to the total weight of the copolymer
In contrast, those obtained by using more than 15% by weight are preferred.
Fluoroaliphatic group-containing acrylate and poly (oxy
Especially preferred are copolymers with (alkylene) acrylates.
Yes. Fluoroaliphatic group-containing methacrylate
50% by weight or more based on the aliphatic group-containing monomer unit
And solvent solubility decreases. Poly (oxyalkylene)
) Acrylate monomer with respect to the total weight of the copolymer
If it is less than 15% by weight, pinholes are likely to occur in the coating film.
Become. (E) Fluorine-based surface activity used in the present invention
The preferred use range of the light-sensitive agent is the photosensitive composition (excluding the solvent).
Coating component) is in the range of 0.01 to 5% by weight.
More preferred range of use is 0.05 to 3% by weight.
It is. 0.01% by weight of fluorosurfactant
Less than 5% by weight, the effect is insufficient.
If this happens, the coating will not dry sufficiently,
It adversely affects the performance as a material (for example, developability). The infrared-sensitive photosensitive composition of the present invention includes
(A) Water-insoluble alkaline water-soluble resin (hereinafter referred to as “(A)
"Lucali-soluble resin"). Alkali soluble
Examples of functional resins include phenol and formaldehyde
Resin, Cresol / Formaldehyde resin, Phenol
・ Cresol-formaldehyde co-condensation resin, pheno
Modified xylene resin, polyhydroxystyrene, poly
Rogenated hydroxystyrene, N- (4-hydroxyphene
Nyl) methacrylamide copolymer, hydroquinone
In addition to a non-methacrylate copolymer, JP-A-7-28244
Sulfonylimide-based polymer described in JP-A-7-
A carboxyl group-containing polymer described in Japanese Patent No. 36184
And so on. Other JP-A-51-34711
Containing phenolic hydroxyl groups as disclosed in
Acrylic resin, sulfone described in JP-A-2-866
Acrylic resin with amide group or urethane resin
Use various alkali-soluble polymer compounds such as
Can do. These alkali-soluble polymer compounds are heavy
The number average molecular weight is 500 to 20,000, and the number average molecular weight is
Those of 200 to 10,000 are preferred. Such arca
One or more resoluble polymer compounds
May be used in combination, up to 80% by weight of the total composition
Used in addition amount. Furthermore, US Pat. No. 4,123,279
As described in the booklet, t-butylphenol phosphate
Lumaldehyde resin, octylphenol formaldehyde
Alkyl group having 3 to 8 carbon atoms such as hydride resin as a substituent
Condensation product of phenol and formaldehyde
Is preferred to improve the oil sensitivity of the image.
Yes. Such an alkali-soluble resin is usually the total weight of the composition.
In an amount of 90% by weight or less. In the present invention, other alkali-soluble resins
Especially preferably, (a-1) phenolic hydroxide
Group, (a-2) sulfonamide group, (a-3) active imi
Polymer compound having any functional group in the group
Examples thereof include the following. (A-1) High having a phenolic hydroxyl group
As a molecular compound, it has a phenolic hydroxyl group in the side chain.
High molecular compounds can be used. Phenol on side chain
Examples of the polymer compound having a rutile hydroxyl group include phenol
Each has one or more polymerizable unsaturated bonds
Homopolymerizing a polymerizable monomer comprising a low molecular weight compound,
Alternatively, another monomer can be copolymerized with the monomer
The polymer compound obtained by the above can be mentioned. Feno
Examples of polymerizable monomers having a hydroxyl group include phenol.
Acrylamide having a hydroxyl group, methacrylamido
, Acrylic acid ester, methacrylic acid ester,
Examples include hydroxystyrene. Specifically, N
-(2-hydroxyphenyl) acrylamide, N-
(3-hydroxyphenyl) acrylamide, N- (4
-Hydroxyphenyl) acrylamide, N- (2-H
Droxyphenyl) methacrylamide, N- (3-hydride)
Roxyphenyl) methacrylamide, N- (4-hydro
Xylphenyl) methacrylamide, o-hydroxyphene
Nyl acrylate, m-hydroxyphenyl acrylate
P-hydroxyphenyl acrylate, o-hydro
Xiphenyl methacrylate, m-hydroxyphenyl
Methacrylate, p-hydroxyphenyl methacrylate
, O-hydroxystyrene, m-hydroxystyrene
, P-hydroxystyrene, 2- (2-hydroxyphenyl)
Enyl) ethyl acrylate, 2- (3-hydroxyphenyl)
Enyl) ethyl acrylate, 2- (4-hydroxyphenyl)
Enyl) ethyl acrylate, 2- (2-hydroxyphenyl)
Enyl) ethyl methacrylate, 2- (3-hydroxy
Phenyl) ethyl methacrylate, 2- (4-hydroxy)
Siphenyl) ethyl methacrylate and the like are preferably used.
be able to. Resin having such a phenolic hydroxyl group
Use one or more or a combination of two or more
May be. (A-2) High content having a sulfonamide group
Examples of the child compound include a polymerizable module having a sulfonamide group.
Homopolymerization of the monomer, or other polymerizable monomers
List polymer compounds obtained by copolymerization of mer
Can do. A polymerizable monomer having a sulfonamide group;
At least one water on a nitrogen atom in one molecule
Sulfonamide group bonded with elementary atoms -NH-SO₂−
And low with at least one polymerizable unsaturated bond
Examples thereof include polymerizable monomers composed of molecular compounds. That
Among them, acryloyl group, allyl group, or vinyloxy
A group and a substituted or monosubstituted aminosulfonyl group or
Low molecular weight compounds having a substituted sulfonylimino group are preferred.
That's right. Examples of such compounds include the following general formula:
The compounds represented by (a) to (e) can be mentioned.
In the light, it is not limited to these. [0096] Embedded image Where X¹, X²Each independently
Child or NR⁷Represents. R¹, R^FourAre each independently hydrogen
Atom or CH_ThreeRepresents. R², R^Five, R⁹, R¹², R¹⁶Is
1 to 1 carbon atoms that may each independently have a substituent
2 alkylene group, cycloalkylene group, arylene group
Or represents an aralkylene group. R^Three, R⁷, R¹³Is that
Independently, a hydrogen atom and optionally having 1 substituent
~ 12 alkyl groups, cycloalkyl groups, aryl groups or
Represents an aralkyl group. R⁶, R¹⁷Each
Alkyl having 1 to 12 carbon atoms which may have a substituent
Group, cycloalkyl group, aryl group, aralkyl group
Represent. R⁸, R^Ten, R¹⁴Are independently hydrogen atoms or
Is CH_ThreeRepresents. R¹¹, R¹⁵Are each independently a single bond
Or an alkyl having 1 to 12 carbon atoms which may have a substituent.
Rene group, cycloalkylene group, arylene group or arral
Represents a xylene group. Y¹, Y²Are each independently a single bond or
Represents CO. Among them, m-aminosulfonylphenyl group
Tacrylate, N- (p-aminosulfonylphenyl)
Methacrylamide, N- (p-aminosulfonylphen
) Methacrylamide, N- (p-aminosulfonyl)
Enyl) acrylamide etc. can be preferably used
The (A-3) Polymerization having an active imide group
The compound has an active imide group represented by the following formula in the molecule.
As this polymer compound, in one molecule
Are polymerizable with an active imino group represented by the following formula:
From low molecular weight compounds each having one or more unsaturated bonds
Homopolymerization of a polymerizable monomer or other
Polymer compound obtained by copolymerization of polymerizable monomers
Can be mentioned. [0100] Embedded image As such a compound, specifically,
N- (p-toluenesulfonyl) methacrylamide, N
-(P-toluenesulfonyl) acrylamide and the like are preferable
Can be used for Furthermore, as other alkali-soluble resins
Is a polymerizable monomer having the phenolic hydroxyl group,
A polymerizable monomer having a sulfonamide group and an active monomer;
Polymerizes two or more of polymerizable monomers having a mid group
Polymer compounds or polymerizability of two or more of them
Obtained by copolymerizing monomers with other polymerizable monomers
Polymeric compounds can be used. Phenolic water
A polymerizable monomer having an acid group has a sulfonamide group.
With polymerizable monomers and / or active imide groups
When copolymerizing monomers,
The total weight ratio should be in the range of 50:50 to 5:95
Preferably in the range of 40:60 to 10:90
Is particularly preferred. Another alkali-soluble resin is the phenol.
Polymerizable monomer having a functional hydroxyl group, sulfonamide group
Polymerizable monomer having an active imide group
Is a copolymer of a polymerizable monomer and another polymerizable monomer
In some cases, the monomer that imparts alkali solubility is 10 moles.
Preferably contained at least 20% by mole
Is more preferable. Less than 10 mol% copolymerization component
And alkali solubility is likely to be insufficient, and development latitude
The effect of improving the speed may not be sufficiently achieved. Polymerizable module having phenolic hydroxyl group
A polymerizable monomer having a monomer, a sulfonamide group,
Is copolymerized with a polymerizable monomer having an active imide group
Examples of the monomer component include the following (1) to (12).
The monomers listed in
Is not to be done. (1) For example, 2-hydroxyethyl acetate
Relate or 2-hydroxyethyl methacrylate
Acrylic esters having an aliphatic hydroxyl group, and
Methacrylic acid esters. (2) Methyl acrylate, ethyl acrylate, acrylic
Propyl butyl, butyl acrylate, amyl acrylate, amyl
Hexyl acrylate, octyl acrylate, acrylic acid base
Nylyl, 2-chloroethyl acrylate, glycidyl
Chlorate, N-dimethylaminoethyl acrylate, etc.
Alkyl acrylates. (3) Methyl methacrylate, ethyl methacrylate, meta
Propyl crylate, butyl methacrylate, methacrylic acid
Amyl, hexyl methacrylate, cyclohexyl methacrylate
Xylyl, benzyl methacrylate, 2-methacrylic acid
Loroethyl, glycidyl methacrylate, N-dimethyl
Alkyl methacrylate such as aminoethyl methacrylate
G. (4) Acrylamide, methacrylamide, N-methylo
Acrylamide, N-ethylacrylamide, N-
Hexyl methacrylamide, N-cyclohexyl acrylic
Luamide, N-hydroxyethylacrylamide, N-
Phenylacrylamide, N-nitrophenyl acrylic
Amide, N-ethyl-N-phenylacrylamide, etc.
Acrylamide or methacrylamide. (5) Ethyl vinyl ether, 2-chloroethyl vinyl
Ether, hydroxyethyl vinyl ether, propyl
Vinyl ether, butyl vinyl ether, octyl buni
Vinyl ethers such as ruether and phenyl vinyl ether
Le. (6) Vinyl acetate, vinyl chloroa
Vinylates such as cetate, vinyl butyrate, vinyl benzoate
Ruesters. (7) Styrene, α-methylstyrene, methylstyrene
And styrenes such as chloromethylstyrene. (8) Methyl vinyl ketone, ethyl vinyl ketone, professional
Vinyl ketones such as pill vinyl ketone and phenyl vinyl ketone
Tons. (9) Ethylene, propylene, isobutylene, butadiene
And olefins such as isoprene. (10) N-vinyl pyrrolidone, N-vinyl carbazo
, 4-vinylpyridine, acrylonitrile, methacrylate
Ronitrile etc. (11) Maleimide, N-acryloylacrylami
, N-acetylmethacrylamide, N-propionyl
Methacrylamide, N- (p-chlorobenzoyl) meta
Unsaturated imides such as chloramide. (12) Acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid. Another alkali-soluble resin is the phenol
Polymerizable monomer having a hydroxyl group, sulfonamide group
A polymerizable monomer having
In the case of homopolymers or copolymers of compatible monomers,
The weight average molecular weight is 2000 or more, the number average molecular weight is 500 or more
The above is preferred. More preferably, the weight average molecule
The number average molecular weight is 800 to 300,000 and 800
~ 250,000, dispersity (weight average molecular weight / several
The average molecular weight) is 1.1-10. The infrared-sensitive photosensitive composition of the present invention includes
(B) a photothermal conversion agent (hereinafter also referred to as “component (B)”)
Added. (B) Photothermal conversion used in the present invention
The agent is particularly effective if it absorbs infrared light and generates heat.
There is no limit, in addition to infrared absorbing dyes, infrared absorbing pigments
Various known pigments or infrared rays other than those exemplified
Absorbing dyes can be used. As a pigment, commercially available
Pigment and Color Index (CI) Handbook, “Latest
Pigment Handbook "(edited by the Japan Pigment Technology Association, published in 1977),
“Latest Pigment Application Technology” (CMC Publishing, 1986),
Described in “Printing Ink Technology” published by CMC, published in 1984)
Available pigments can be used. As the types of pigments, black pigment, yellow face
, Orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Examples include polymer-bound dyes. Specifically, insoluble
Zo pigment, azo lake pigment, condensed azo pigment, chelate azo
Pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, key
Nacridone pigments, dioxazine pigments, isoindole
Non-based pigments, quinophthalone pigments, dyed lake pigments,
Azine pigment, nitroso pigment, nitro pigment, natural pigment, firefly
Light pigments, inorganic pigments, carbon black, etc. can be used. These pigments may be used without surface treatment.
Alternatively, a surface treatment may be applied. Surface treatment
Methods include surface coating with resin and wax, surface activity
Methods of attaching agents, reactive substances (eg silane
(Pulling agents, epoxy compounds, polyisocyanates, etc.)
For example, a method of binding the pigment to the pigment surface can be considered. Above table
The surface treatment method is "Characteristics and application of metal soap" (Shoshobo),
“Printing Ink Technology” (CMC Publishing, 1984) and
To "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Has been described. The particle size of the pigment ranges from 0.01 μm to 10 μm.
Preferably in the range of 0.05 μm to 1 μm
More preferably, it is particularly 0.1 μm to 1 μm.
It is preferable that it exists in the range. The pigment particle size is 0.01μ
If it is less than m, the stability of the dispersion in the recording layer coating solution
It is not preferable, and if it exceeds 10 μm, the recording layer is uniform.
It is not preferable in terms of uniformity. As a method of dispersing pigment
Is a known dispersion used in ink production, toner production, etc.
Technology can be used. Dispersers include ultrasonic dispersers and supporters.
Wind mill, attritor, pearl mill, super mill,
Ball mill, impeller, disperser, KD mill, co
Lloyd mill, Dynatron, 3-roll mill, pressure knee
And the like. For details, see “Latest Pigment Application Technology”.
(CMC Publishing, published in 1986). As the dye, commercially available dyes and literature (for example,
“Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970
The well-known thing described in can be utilized. Specifically
Azo dyes, metal complex azo dyes, pyrazolone azo dyes
Material, anthraquinone dye, phthalocyanine dye, carbo
Nium dye, quinoneimine dye, methine dye, cyanine
And dyes such as dyes. In the present invention, these
Infrared light or near infrared light
That absorbs light emits infrared light or near infrared light
This is particularly preferable because it is suitable for use with a laser. Absorb such infrared light or near infrared light.
Carbon black is preferably used as the pigment
The In addition, dyes that absorb infrared light or near infrared light
For example, JP-A-58-125246, JP-A-5
9-84356, JP 59-202829, JP
Cyanine dyeing described in Sho 60-78787
, JP-A-58-173696, JP-A-58-181
690, JP-A-58-194595, etc.
Methine dyes, JP-A 58-112793, JP-A
58-224793, JP-A-59-48187,
No. 59-73996, JP-A-60-52940,
Naftoki described in JP-A-60-63744
Non-dyes, described in JP-A-58-112792, etc.
Squaryllium dye, British Patent 434,875
Listed cyanine dyes. Further, as dyes, US Pat. No. 5,156,
The near infrared absorption sensitizer described in No. 938 is also preferably used.
Substituted in U.S. Pat. No. 3,881,924
Arylbenzo (thio) pyrylium salt, JP-A-57-1
42645 (U.S. Pat. No. 4,327,169)
Trimethine thiapyrylium salt, JP-A 58-1810
51, 58-220143, 59-41363
No. 59-84248 No. 59-84249 No.
Described in 59-146063 and 59-146061
Pyryllium-based compounds, JP 59-2161
46, a cyanine dye described in U.S. Pat. No. 4,283,4
No. 75 pentamethine thiopyrylium salt, etc.
Disclosure in Japanese Patent Laid-Open Nos. 5-13514 and 5-19702
As a commercially available product, an epoxy
Epolight III-178, Epoli manufactured by Phosphorus
ght III-130, Epolight III-125, etc.
Is particularly preferably used. Another example that is particularly preferable as a dye is shown below.
In U.S. Pat. No. 4,756,993.
Near-infrared absorbing dyes described as (I) and (II)
Can be mentioned. These pigments or dyes are all
0.01 to 50% by weight, preferably 0.1%, based on solids
-10% by weight, particularly preferably in the case of dyes 0.5-10
% By weight, particularly preferably in the case of pigments, 3.1 to 10% by weight
Can be added at a ratio of [0117] The amount of pigment or dye added is 0.01 wt.
If it is less than 50%, the sensitivity will be low, and will exceed 50% by weight.
In this case, the uniformity of the image forming layer is lost and the durability of the image forming layer is lost.
Becomes worse. These dyes or pigments are the same as other ingredients.
It can be added to one layer or another layer can be added
May be. Next, a composition for an image forming layer according to the present invention and
To be added in preparing the photosensitive composition
Other components that can be produced will be described. Positive photosensitive composition
For example, before or after exposure.
It can be used as long as its moisture content changes, but it is included in it.
Preferred examples include o-quinonediazide compounds
Is mentioned. For example, alkali-soluble resin and o-kino
Of a positive photosensitive composition containing a diazide compound
The o-quinonediazide compound comprises at least one o-quinone
A compound having a quinonediazide group, which is
Those that increase the solubility in an aqueous solution of Lucari are preferred. Such a thing has various structures.
For example, “Light-Sensitive” by J. KOSAR
 Systems '' (John Wiley & Sons, Inc, 1965) P.33
6 to P.352 for details. Positive photosensitive resin group
As the photosensitive compound of the composition, various hydroxyl groups are used.
Compound and o-benzoquinonediazide or o-naphtho
Nondiazide sulfonate esters are preferred. O-quinonediazide compounds as described above and
For example, 1,2-naphthoquinone-2-diazide-5
-Sulfonyl chloride and phenol formaldehyde
Resin and cresol / formaldehyde resin
Steal; described in US Pat. No. 3,635,709
1,2-naphthoquinone-2-diazide-5-sulfur
Ethyl chloride and pyrogallol / acetone resin
Steal; described in Japanese Examined Patent Publication No. 63-13,528
1,2-naphthoquinone-2-diazide-5-sulfonyl
Chloride and resorcin-benzaldehyde resin
Steal; described in Japanese Examined Patent Publication No. 62-44,257
1,2-naphthoquinone-2-diazide-5-sulfonyl
Chloride and resorcin-pyrogallol / acetone co-condensation
Ester with compound resin; As described in Japanese Patent Publication No. 56-45,127.
A polyester having a hydroxyl group at its terminal
1,2-naphthoquinone-2-diazide-5-sulfonylchloro
Esterified ride; Japanese Patent Publication No. 50-24,6
N- (4-hydroxypheny) described in Japanese Patent No. 41
E) Methacrylamide homopolymer or other copolymerization
1,2-naphthoquinone-2 as a copolymer with a possible monomer
-Diazide-5-sulfonyl chloride esterified
Described in Japanese Patent Publication No. 54-29,922
1,2-naphthoquinone-2-diazide-5-sulfonyl
With chloride and bisphenol-formaldehyde resin
Esters described in Japanese Patent Publication No. 52-36,043
P-hydroxystyrene homopolymer or
1,2-naphtha as a copolymer with other copolymerizable monomers
Toquinone-2-diazide-5-sulfonyl chloride
1,2-naphthoquinone-2-diazide-
5-sulfonyl chloride and polyhydroxybenzofe
There is an ester with non. Other known o-keys that can be used in the present invention.
Non-diazide compounds include those disclosed in JP-A-63-80,25.
4, JP-A-58-5,737, JP-A-57-111,
530, JP 57-111,531, JP 57-
114,138, JP-A-57-142,635, Special
Kaisho 51-36, 129, Shoko 62-3,411,
Shoko Sho 62-51,459, Shoko Sho 51-483, etc.
You can raise things listed in each specification of
it can. The content of the o-quinonediazide compound is
Usually 5 to 60% by weight based on the total solid content of the photosensitive composition
More preferably, it is 10 to 40% by weight. In the photosensitive composition, if necessary,
Cyclic anhydride for increased sensitivity, visible image immediately after exposure
Baking agent to obtain a dye, dye as an image colorant,
Other fillers can be added. In the photosensitive composition of the present invention, sensitivity is included.
To increase cyclic anhydrides, phenols, organic acids
It is preferable to add a kind. Rice as a cyclic acid anhydride
It is described in Japanese Patent No. 4,115,128.
Phthalic anhydride, tetrahydrophthalic anhydride, hex
Sahydrophthalic anhydride, 3,6-endooxy ~ Δ4 ~ te
Trahydrophthalic anhydride, tetrachlorophthalic anhydride,
Maleic anhydride, chloromaleic anhydride, α-phenyl
Maleic anhydride, succinic anhydride, pyromellitic anhydride, etc.
There is. As phenols, bisphenol A, p
-Nitrophenol, p-ethoxyphenol, 2,3
4-trihydroxybenzophenone, 4-hydroxyben
Zophenone, 2,4,4'-trihydroxybenzofe
Non 4,4 ', 4 "-trihydroxy-triphenylme
Tan, 4,4 ', 3 ", 4" -tetrahydroxy-3
5,3 ', 5'-tetramethyltriphenylmethane, etc.
Is mentioned. Examples of organic acids include JP-A-60-8894.
2 and JP-A-2-96755.
Sulfonic acids, sulfinic acids, alkyl sulfuric acid
, Phosphonic acids, phosphinic acids, phosphate esters
, Carboxylic acids, etc., specifically p-tolue
Sulfonic acid, dodecylbenzene sulfonic acid, p-tolu
Enesulfinic acid, ethyl sulfate, phenylphosphonic acid,
Phenylphosphinic acid, phenyl phosphate, diphosphate phosphate
Nyl, benzoic acid, isophthalic acid, adipic acid, p-tolu
Iric acid, 3,4-dimethoxybenzoic acid, phthalic acid, tele
Phthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid
Acid, erucic acid, lauric acid, n-undecanoic acid, Asco
Examples include rubic acid. The above cyclic acid anhydrides,
Ratio of enols and organic acids in the photosensitive composition
Is preferably 0.05 to 15% by weight, more preferably
Is 0.1 to 5% by weight. Printout to obtain a visible image immediately after exposure
As a rusting agent, a photosensitive compound that releases an acid upon exposure
And organic dyes that change color by forming salts with acids
Can be mentioned. A photosensitive compound which releases an acid upon exposure;
For example, it is described in JP-A-50-36,209.
O-Naphthoquinonediazide-4-sulfonic acid listed
Halogenide; described in JP-A-53-36223
Trihalomethyl-2-bilon and trihalomethyl-s-
Triazine; described in JP-A-55-62444
Various o-naphthoquinonediazide compounds;
2-Trihalomes described in Japanese Patent No. 55-77742
Tyl-5-aryl-1,3,4-oxadiazole compound
A diazonium salt and the like. these
These compounds can be used alone or in combination,
The added amount is 0.3 to 15 wt. With respect to the total weight of the composition.
% Range is preferred. In the present invention, the photosensitive composition contains light.
Photolysis products and phases of compounds that decompose to generate acidic substances
Fewer organic dyes that change their color by interacting
At least one type is used. With such organic dyes
For example, diphenylmethane, triarylmethane,
Thiazine, oxazine, phenazine, xanthene
, Anthraquinone, iminonaphthoquinone, azome
A tin-based pigment can be used. Specifically:
It is a thing. Brilliant green, eosin, ethyl
Violet, erythrosine B, methyl green, chestnut
Star violet, basic fuchsin, phenol
Phthalein, 1,3-diphenyltriazine, Alizari
N Red S, Thymolphthalein, Methyl Violet
2B, Kinardine Red, Rose Bengal, Timors
Lufophthalein, xylenol blue, methyl orene
Di, orange IV, diphenylthiocarbazone, 2,7-
Dichlorofluorescein, paramethyl red, Congo
Red, benzopurpurin 4B, α-naphthyl red,
Nile Blue 2B, Nile Blue A, Phenacetalin,
Methyl violet, malachite green, parafukushi
Oil Blue # 603 [Orient Chemical Co., Ltd.
Made], Oil Pink # 312 [Orient Chemical
Co., Ltd.], Oil Red 5B [Orient Chemical Industry
Co., Ltd.], Oil Scarlet # 308 [Orient
Chemical Industry Co., Ltd.], Oil Red OG [Orientation
Gaku Kogyo Co., Ltd.], Oil Red RR [Orient Chemical
Kogyo Co., Ltd.], Oil Green # 502 [Orient
Chemical Industry Co., Ltd.], Spiron Red BEH Special
[Hodogaya Chemical Co., Ltd.], Victoria Pureble
-BOH [made by Hodogaya Chemical Co., Ltd.] Patent Pure-Blue [Sumitomo Sangoku Chemical Co., Ltd.
Industry Co., Ltd.], Sudan Blue II (BASF), m
-Cresol purple, cresol red, rhodamine
B, Rhodamine 6G, First Acid Violet
R, sulforhodamine B, auramine, 4-p-diethyl
Aminophenyliminonaphthoquinone, 2-carboxya
Nilino-4-p-diethylaminophenyliminonaphtho
Non, 2-carbostearylamino-4-p-dihydrooxy
Cyethyl-amino-phenyliminonaphthoquinone, p-me
Toxibenzoyl-p'-diethylamino-o'-methyl
Enyliminoacetanilide, cyano-p-diethylamino
Nophenyliminoacetanilide, 1-phenyl-3-me
Tyl-4-p-diethylaminophenylimino-5-pyrazo
Ron, 1-β-naphthyl-4-p-diethylaminopheny
Louisino-5-pyrazolone etc. Particularly preferred organic dyes are triaryl dyes.
Tan dye. For triarylmethane dyes,
No. 62-293471, Japanese Patent No. 296902
Sulfo as a counter anion as shown in No. 1 publication
Those having acid compounds are particularly useful. These dyes
The materials can be used alone or in combination.
0.3 to 15% by weight based on the total weight of the light composition is preferred
That's right. If necessary, it can be used in combination with other dyes and pigments.
The amount used is 70% by weight or more based on the total weight of the dye and pigment.
Below, more preferably 50% by weight or less. The present invention provides the above-described positive type lithographic printing plate precursor.
In addition to (also called positive PS plate), for example, the following tie
The same can be used for lithographic printing plate materials. (1) Alkali-soluble binder, acid generator, acid (heat)
Negative-type laser direct-drawing planographic printing material containing a crosslinkable compound
Fee. (2) Photothermal conversion agent / thermal radical generator / radical polymerizability
Negative type laser direct drawing lithographic printing plate containing compound Alkali-soluble binder used in (1)
Is the same as described above, and the acid generator is a conventionally known one.
Can be used. What is an acid (thermal) crosslinkable compound?
A compound that crosslinks in the presence of an acid, e.g.
Simethyl group, acetoxymethyl group, or alkoxy
Aromatic compounds and heterocycles polysubstituted by methyl groups
Among them, preferred examples include
Condensation of phenols and aldehydes under basic conditions
Compounds. Preferred among the above compounds
For example, phenol and formaldehyde
Compounds condensed under basic conditions as described above, as well
Obtained from m-cresol and formaldehyde
Obtained from the compound, bisphenol A and formaldehyde
4,4'-bisphenol and formaldehyde
Compounds obtained from hydride, etc., GB 2,082,
No. 339 includes compounds disclosed as resole resins.
I can get lost. These acid crosslinkable compounds have a weight average molecular weight.
The amount is 500-100,000 and the number average molecular weight is 200-
50,000 is preferred. As another preferred example
Is disclosed in EP-A 0,212,482
Substituted with alkoxymethyl or oxiranylmethyl groups
Aromatic compounds, EP-A 0,133,216, D
EA 3,634,671, DE 3,711,2
Monomer and oligomer melamine disclosed in No. 64
Formaldehyde condensates and urea-formaldehyde
Condensate, disclosed in EP-A 0,212,482
Examples include alkoxy-substituted compounds. Yet another preferred example
For example, at least two free N-hydroxymethyls
N-alkoxymethyl or N-acyloxymethyl group
It is a melamine-formaldehyde derivative having This
Of these, N-alkoxymethyl derivatives are particularly preferred.
Yes. Also low molecular weight or oligomeric silanols
Can be used as a silicon-containing crosslinking agent. These examples
Dimethyl- and diphenyl-silanediol, and
Oligomers already precondensed and containing these units
For example, in EP-A 0,377,155
The disclosed one can be used. The alkoxymethyl group
Among the substituted aromatic compounds and heterocyclic compounds
In the position adjacent to the hydroxyl group
And an alkoxy group of the alkoxymethyl group
Are preferable examples of compounds having 18 or less carbon atoms.
As a particularly preferred example, the following general formula (B) to
The compound of (E) can be mentioned. [0136] Embedded image Where L₁~ L₈Are the same but different
Like methoxymethyl, ethoxymethyl, etc.
Alkoxy substituted with an alkoxy group having 18 or less carbon atoms
A dimethyl group is shown. These have high crosslinking efficiency and improve printing durability.
This is preferable in that it can be improved. Due to the above heat
Only one type of cross-linking compound may be used, or 2
A combination of more than one type may be used. Used in the present invention
The acid crosslinkable compound is the total solid content of the lithographic printing plate material.
Among them, 5 to 80% by weight, preferably 10 to 75% by weight,
Preferably, it is used in an addition amount of 20 to 70% by weight.
It is obtained when the amount of the acid-crosslinking compound added is less than 5% by weight.
The durability of the photosensitive layer of the lithographic printing plate material deteriorated, and
If it exceeds 0% by weight, it is preferable in terms of stability during storage.
Yes. As a specific example of the material used in (2)
Is the main component of the ethylenic diisocyanate that can be addition-polymerized.
Compounds containing heavy bonds, thermal radical generators, photothermal conversion agents, etc.
Is included. The compound containing a double bond capable of addition polymerization is
At least one terminal ethylenically unsaturated bond, preferably
Can be arbitrarily selected from compounds having two or more
it can. For example, monomer, prepolymer, ie 2 quantities
, Trimers and oligomers, or mixtures thereof
It has a chemical form such as their copolymer
is there. Examples of monomers and copolymers thereof are
Japanese carboxylic acids (for example, acrylic acid, methacrylic acid,
Such as taconic acid, crotonic acid, isocrotonic acid, maleic acid
And esters of aliphatic polyhydric alcohol compounds
Amides of Japanese carboxylic acids and aliphatic polyvalent amine compounds
can give. Aliphatic polyhydric alcohol compound and unsaturated cal
Specific examples of monomers of esters with boric acid include
Ethyl glycol diacrylate
, Triethylene glycol diacrylate, 1,3
-Butanediol diacrylate, tetramethylene glycol
Cold diacrylate, propylene glycol diacryl
Rate, neopentyl glycol diacrylate, tri
Methylolpropane triacrylate, trimethylol
Propanetri (acryloyloxypropyl) ate
, Trimethylolethane triacrylate, hexane
Diol diacrylate, 1,4-cyclohexanedio
Diacrylate, tetraethylene glycol diac
Relate, pentaerythritol diacrylate, pen
Taerythritol triacrylate, pentaerythritol
Tetraacrylate, dipentaerythritol dia
Chryrate, dipentaerythritol-pentaacrylate
Dipentaerythritol hexaacrylate, sol
Bitol triacrylate, sorbitol tetraacrylate
Rate, sorbitol pentaacrylate, sorbitol
Lehexaacrylate, tri (acryloyloxyethyl)
L) Isocyanurate, polyester acrylate
There are gomers. Examples of methacrylic acid esters include tetrameth
Tylene glycol dimethacrylate, triethylene glycol
Cold dimethacrylate, neopentyl glycol dimethyl
Tacrylate, trimethylolpropane trimethacrylate
, Trimethylolethane trimethacrylate, ethyl
Lenglycol dimethacrylate, 1,3-butanedio
Dimethacrylate, hexanediol dimethacrylate
, Pentaerythritol dimethacrylate, penta
Erythritol trimethacrylate, pentaerythrito
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, dipentaerythritol rupentamethacryle
Sorbitol trimethacrylate, sorbitol
Toramethacrylate, bis [p- (3-methacryloxy
-2-hydroxypropoxy) phenyl] dimethylmeta
Bis- [p- (methacryloxyethoxy) pheny
E) Dimethylmethane and the like. Examples of itaconic acid esters include ethylene glycol.
Recall Diitaconate, Propylene Glycol Diita
Conate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethyle
Glycol diitaconate, pentaerythritol di
Itaconate, sorbitol tetritaconate, etc.
The Examples of crotonic acid esters include ethylene glycol.
Recall dicrotonate, tetramethylene glycol di
Crotonate, pentaerythritol dicrotonate,
Examples include sorbitol tetradicrotonate. Isochrome
Tonic acid esters include ethylene glycol diisocyanate.
Rotonate, pentaerythritol diisocrotonate
And sorbitol tetraisocrotonate. Ma
As the acrylate, ethylene glycol dimale
, Triethylene glycol dimaleate, pentaerythrate
Thritol dimaleate, sorbitol tetramaleate, etc.
There is. In addition, there are mixtures of the aforementioned ester monomers.
I can make it. In addition, an aliphatic polyvalent amine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylate
Imide, 1,6-hexamethylenebis-acrylamide,
1,6-hexamethylenebis-methacrylamide, diethyl
Rentriamine Trisacrylamide, Xylylenebis
Acrylamide, xylylene bismethacrylamide, etc.
is there. As another example, Japanese Patent Publication No. 48-41708
2 or more isocyanes per molecule described in the publication
To the polyisocyanate compound having an ate group,
Vinyl monomer containing a hydroxyl group represented by the general formula (A)
Two or more polymerizable vinyl groups in one molecule to which-is added
And vinyl urethane compounds containing. CH
₂= C (R5) COOCH₂CH (R6) OH (A)
(However, R5 and R6 are H or CH._ThreeIndicates. ) Further, as described in JP-A-51-37193.
Urethane acrylates such as those disclosed in JP-A 48-
64183, Shoko 49-43191, Shoko 52-
Polyester as described in each publication No. 30490
Acrylates, epoxy resins and (meth) acrylic acid
Multifunctional actives such as epoxy acrylates reacted with
Relates and methacrylates can be mentioned. More
Japan Adhesion Association Vol.20, No.7, 300-308 pages
(1984), photocurable monomers and oligomers.
The ones introduced as-can also be used.
The amount of the compound containing these double bonds is
5 to 70% by weight (hereinafter abbreviated as%), preferably
Preferably it is 10 to 50%. As the thermal radical generator, conventionally known light can be used.
Many used as polymerization initiators are useful
The Also, azobis compounds (azobisisobutyronitrile)
And diazonium compounds are also used as thermal polymerization initiators.
it can. The photothermal conversion agent is the same as described above.
The In addition, in the composition of the present invention, image in-
Various trees with hydrophobic groups for improving ki
Fats such as octylphenol formaldehyde tree
Fat, t-butylphenol-formaldehyde resin, t-
Butylphenol benzaldehyde resin, rosin modified
Novolak resins, and o-of these modified novolak resins
Naphthoquinone diazide sulfonate, etc.
Plasticizers for improving flexibility, for example dibutyphthalate
, Dioctyl phthalate, butyl glycolate, phosphoric acid
For various purposes such as tricresyl and dioctyl adipate
Various additives can be added accordingly. These additions
The amount ranges from 0.01 to 30% by weight relative to the total weight of the composition.
An enclosure is preferred. Further, in these compositions, the abrasion resistance of the coating is included.
A known resin for further improving the properties can be added. This
Examples of these resins include polyvinyl acetal resin.
Fat, polyurethane resin, epoxy resin, vinyl chloride tree
Such as grease, nylon, polyester resin, acrylic resin, etc.
Can be used alone or in combination. Addition amount
Is preferably in the range of 2 to 40% by weight relative to the total weight of the composition.
That's right. In the photosensitive composition of the present invention,
In order to widen the development latitude,
No. 251740 and JP-A-4-68355
Nonionic surfactants as described, JP-A-5
9-121044 and JP-A-4-13149.
Adding amphoteric surfactants as described
it can. Specific examples of nonionic surfactants include sol
Vitan tristearate, sorbitan monopalmitate
, Sorbitan trioleate, monoglyceride stearate
Lido, polyoxyethylene sorbitan monooleate, poly
Such as reoxyethylene nonylphenyl ether
Specific examples of amphoteric surfactants include alkyl di (a
Minoethyl) glycine, alkylpolyaminoethylglycine
Syn hydrochloride, Amorgen K (trade name, Daiichi Kogyo Seiyaku)
(N-tetradecyl-N, N-betaine type), 2-
Alkyl-N-carboxyethyl-N-hydroxyethyl ester
Midazolinium betaine, Levon 15 (trade name, Sanyo)
Seiken Co., Ltd., alkyl imidazoline series)
The Photosensitivity of the above nonionic surfactants and amphoteric surfactants
The proportion of the composition is preferably 0.05 to 15% by weight.
More preferably, it is 0.1 to 5% by weight. In the photosensitive composition of the present invention, yellow is included.
Color dye, preferably 417 nm absorbance at 436 nm
It is possible to add a yellow dye having an absorbance of 70% or more
it can. Photosensitivity containing fluoropolymer of the present invention
When obtaining a lithographic printing plate photosensitive material from the resin composition,
First it is provided as an image-forming layer on a suitable support.
The Photosensitive resin composition containing fluoropolymer of the present invention
Are dissolved in the following organic solvents alone or in combination.
Dissolved or dispersed, applied to a support and dried. Organic
Any known solvent can be used as the solvent.
In the range of boiling point 40 ° C to 200 ° C, especially 60 ° C to 160 ° C.
The surroundings are selected for their advantages in drying.
Of course, select the one that dissolves the surfactant of the present invention.
Is good. Examples of the organic solvent include methyl alcohol.
, Ethyl alcohol, n- or iso-propyl alcohol
N- or iso-butyl alcohol, diacetone alcohol
Alcohols such as alcohol, acetone, methyl ethyl ketone
T, methyl propyl ketone, methyl butyl ketone,
Tyramyl ketone, methyl hexyl ketone, diethyl ketone
T, diisobutyl ketone, cyclohexanone, methyl
Ketones such as cyclohexanone and acetylacetone,
Zen, toluene, xylene, cyclohexane, methoxy
Hydrocarbons such as sibenzene, ethyl acetate, n-ma
Or iso-propyl acetate, n- or iso-butyl
Acetate, ethyl butyl acetate, hexyl acetate
Acetate, methylene dichloride, ethyl
Halogenation of range chloride, monochlorobenzene, etc.
, Isopropyl ether, n-butyl ether, geo
Xanthan, dimethyldioxane, tetrahydrofuran, etc.
Ethers, Ethylene glycol, methyl cellosolve,
Methyl cellosolve acetate, ethyl cellosolve, die
Tilcellosolve, cellosolve acetate, butyl celloso
Rub, butyl cellosolve acetate, methoxymethoxy
Ethanol, diethylene glycol monomethyl ether
, Diethylene glycol dimethyl ether, polyethylene
Glycol methyl ethyl ether, diethylene glycol
Diethyl ether, propylene glycol, propylene
Lenglycol monomethyl ether, propylene glycol
Monomethyl ether acetate, propylene glycol
Monoethyl ether, propylene glycol monoe
Tyl ether acetate, propylene glycol monob
Tilether, 3-methyl-3-methoxybutanol, etc.
Polyhydric alcohols and their derivatives, dimethyl sulfoxide,
Special solvent such as N, N-dimethylformamide alone
Or it mixes and is used suitably. And apply
The solid content in the composition should be 2 to 50% by weight.
Is appropriate. As a coating method of the composition of the present invention, for example,
Roll coating, dip coating, air na
IF coating, gravure coating, gravure
Faceted coating, hopper coating, brace
Coating, wire doctor coating, spray
-A method such as coating is used to make the weight after drying.
0.3-4.0 g / m²Is preferred. Small application amount
As it gets smaller, the amount of exposure required to obtain an image is smaller.
However, the film strength decreases. As the amount applied increases,
Light quantity is required, but the photosensitive film becomes stronger. For example, printing plates
When used as a high-printing (high durability) mark
A printing plate is obtained. Drying of the photosensitive composition coated on the support
Is usually performed by heated air. 30 heating
℃ ～ 200 ℃ Especially, the range of 40 ℃ ～ 140 ℃ is suitable
The The temperature of drying is not only a way to keep it constant during drying
A stepwise increase method can also be implemented. Also, the dry wind
Good results may be obtained by dehumidification. Addition
The heated air is 0.1 m / second to 30 m / second with respect to the coated surface.
Supply at a rate of seconds, especially 0.5m / second to 20m / second
Is preferred. Matt layer; feeling provided as described above
The surface of the optical layer is not exposed to true exposure during contact exposure using a vacuum baking frame.
To reduce emptying time and prevent burning,
It is preferable to provide a layer. Specifically, JP-A-50
-125805, JP-B 57-6582, 61-2
A mat layer as described in each publication of No. 8986
The method of providing is described in Japanese Examined Patent Publication No. 62-62337.
Such as a method of heat-sealing solid powders
It is. Support for use in photosensitive lithographic printing plate and the like
Is a dimensionally stable plate-like material that has supported printing plates so far.
It is used as a body and should be used appropriately
Can do. Such supports include paper, plastics
(Eg polyethylene, polypropylene, polystyrene
Etc.) laminated paper such as aluminum (A)
Gold, such as zinc, iron, copper, etc.)
Genus plates such as cellulose diacetate, cellulose triacetate,
Cellulose propionate, cellulose butyrate, acetic acid butyrate
Rulose, cellulose nitrate, polyethylene terephthalate
Polyethylene, polystyrene, polypropylene, polyethylene
Such as polycarbonate, polyvinyl acetal, etc.
Rustyx film, the above metals are laminates
Or vapor-deposited paper or plastic film
In particular, an aluminum plate is preferable. A
Luminium plates include pure aluminum plates and aluminum composites.
A metal plate is included. Various aluminum alloys
For example, silicon, copper, manganese, magnesium
Metals such as chromium, chromium, zinc, lead, bismuth and nickel
An aluminum alloy is used. These compositions
Is negligible in addition to some iron and titanium
It also contains a certain amount of impurities. The support is surface-treated as necessary.
For example, in the case of a photosensitive lithographic printing plate, on the surface of the support,
Hydrophilic treatment is performed. Also of metal, especially aluminum
In the case of a support having a surface, graining treatment, silicic acid
Water such as soda, potassium fluoride zirconate, phosphate
Surface treatment such as immersion in solution or anodic oxidation
It is preferable that the reason is made. US Patent No.
As described in US Pat. No. 2,714,066,
After graining, it is immersed in an aqueous sodium silicate solution.
Aluminum plate, US Pat. No. 3,181,461
Anodizing the aluminum plate as described in the booklet
Immerse in an aqueous solution of alkali metal silicate after treatment
Those treated are also preferably used. Anodizing treatment
Is, for example, inorganic such as phosphoric acid, chromic acid, sulfuric acid, boric acid
Acids, or organic acids such as oxalic acid, sulfamic acid,
Is an aqueous solution or non-aqueous solution of these salts, alone or in combination
Aluminum plate as the anode in the electrolyte solution combined with
This is done by passing a current. Also, US Pat. No. 3,658,662
Silicate electrodeposition as described in the booklet is also effective.
The These hydrophilization treatments make the surface of the support hydrophilic.
In addition to being applied to the photosensitive composition provided on it
To prevent harmful reactions with objects and improve adhesion to the photosensitive layer
It is given to make it. Grained aluminum plate
Remove surface rolling oil as needed prior to standing
To expose and clean aluminum surface
The surface may be pretreated. For the former,
Solvents such as lickle and surfactants are used.
For the latter, sodium hydroxide, potassium hydroxide
A method using an alkali / etching agent such as
ing. As a graining method, mechanical and chemical methods are used.
Both of the electrochemical method and the electrochemical method are effective. Machine
Mechanical methods include ball polishing, blast polishing,
Nylon brush for water-dispersed slurry of stone-like abrasive
There is a brush polishing method to rub, etc., as a chemical method
Is described in JP-A-54-31187.
Method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid
The electrochemical method is hydrochloric acid, nitric acid or
AC electrolysis in acidic electrolytes like these combinations
The method is preferred. Among such roughening methods, in particular,
A machine as described in Japanese Patent Publication No. 55-137993
Roughening method combining mechanical and electrochemical roughening
Is preferred because it has a strong adhesion to the support of the oil-sensitive image.
Yes. Graining using the method described above is an aluminum plate.
The center line surface roughness (Ra) of the surface of 0.3 to 1.0 μm
It is preferable to apply in such a range. like this
The grained aluminum plate is watered as needed.
Washed and chemically etched. The etching solution is usually aluminum.
It is selected from an aqueous solution of a base or acid that dissolves. This place
If the surface of the etched surface is
A film that does not form a coating different from the conductive aluminum
Must. Examples of preferred etchants
Examples of basic substances include sodium hydroxide and potassium hydroxide.
, Trisodium phosphate, disodium phosphate, phosphorus
Tripotassium acid, dipotassium phosphate, etc .;
Sulfuric acid, persulfuric acid, phosphoric acid, hydrochloric acid and its salts, etc.
Metals that have a lower ionization tendency than luminium, such as zinc and copper
Lom, cobalt, nickel, copper and other salts are etched surfaces
This is not preferable because an unnecessary film is formed. These
Etching agent should be used in setting the concentration and temperature.
The dissolution rate of aluminum or alloy
0.3g to 40g / m per minute²It ’s going to be
Most preferably, but above or below this
Even if it is a thing. Etching is performed by adding aluminum to the above etchant.
Um plate is dipped or etching solution into the aluminum plate
The etching amount is 0.5.
-10g / m²It is preferable to be processed so that
Good. As the etching agent, the etching speed
It is possible to use an aqueous solution of a base because of its quickness
desirable. In this case, a smut is generated,
Smut processed. Acid used for desmutting
Nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoride
Hydrohydric acid or the like is used. Etched aluminum
The nium plate is washed with water and anodized as necessary. anode
Oxidation is performed in a conventional manner in this field.
I can. Specifically, sulfuric acid, phosphoric acid, chromium
Acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc.
Or an aqueous solution or a combination of two or more of them
Direct current or alternating current to aluminum in aqueous solution
And forming an anodized film on the surface of the aluminum support.
Can. The treatment conditions for anodization depend on the electrolyte used.
Therefore, it cannot be generally determined because of various changes.
Specifically, the concentration of the electrolytic solution is 1 to 80% by weight, and the liquid temperature is 5 to 70.
° C, current density 0.5-60 amps / dm², Voltage 1-1
A range of 00 V and an electrolysis time of 30 seconds to 50 minutes is appropriate.
Among these anodizing treatments, in particular British Patent No. 1,
No. 412,768 in sulfuric acid described in the specification
Method of anodizing at flow density and US Pat. No. 3,51
Phosphoric acid described in US Pat. No. 1,661 is used as an electrolytic bath.
And anodizing is preferred. Roughening as above
Further anodized aluminum plate is needed
Depending on the case, it may be hydrophilized.
U.S. Pat. Nos. 2,714,066 and 3,181,
Alkali metal silicate as disclosed in 461
Such as an aqueous solution of sodium silicate or
Fluorozirconic acid disclosed in 22063
Potassium and US Pat. No. 4,153,461
Treated with polyvinylphosphonic acid as disclosed in
There is a way. Organic subbing layer; for the photosensitive lithographic printing plate of the present invention
It is not possible to provide an organic subbing layer before coating the photosensitive layer.
This is preferable for reducing the remaining photosensitive layer in the image area. Under such organic
Examples of organic compounds used in the coating layer include
Cymethylcellulose, dextrin, gum arabic, 2
-Phosphorus having an amino group such as aminoethylphosphonic acid
Phonic acids, optionally substituted phenylphosphonic acid,
Naphthylphosphonic acid, alkylphosphonic acid, glycerophor
Sulfonic acid, methylenediphosphonic acid and ethylenediphos
Organic phosphonic acids such as phonic acid, and optionally substituted phosphonic acids
Phenyl phosphate, naphthyl phosphate, alkyl phosphate and
Organic phosphoric acid such as glycerophosphoric acid, may have a substituent
Phenylphosphinic acid, naphthylphosphinic acid, al
Such as kill phosphinic acid and glycerophosphinic acid
Amino such as phosphinic acid, glycine and β-alanine
Acids and hydrides such as triethanolamine hydrochloride
Selected from the hydrochloride of amines having a roxyl group
However, you may use it in mixture of 2 or more types. Other poly (p-vinylbenzoic acid) etc.
A group of polymer compounds having a representative structural unit in the molecule.
Using at least one compound selected from the group consisting of
it can. More specifically, p-vinylbenzoic acid and vinylben
Copolymer with zirtriethylammonium salt, p-vinyl
Benzoic acid and vinylbenzyltrimethylammonium chloride
And a copolymer with Lido. This organic undercoat layer is provided by the following method.
be able to. Water or methanol, ethanol
Or organic solvents such as methyl ethyl ketone
A solution of the above organic compound in a mixed solvent of
A method of coating and drying on a minium plate and water or
Presence of methanol, ethanol, methyl ethyl ketone, etc.
Add the above organic compounds to the organic solvent or mixed solvent
Immerse the aluminum plate in the dissolved solution and add the above organic
The compound is adsorbed and then washed with water and dried.
This is a method of providing an organic undercoat layer by drying. In the former way
Is a concentration of 0.005 to 10% by weight of the organic compound
The solution can be applied in various ways. For example, bar coater
-Coating, spin coating, spray coating, curtain coating, etc.
A deviation method may be used. In the latter method,
The concentration of the liquid is 0.01 to 20% by weight, preferably 0.05.
-5% by weight, soaking temperature is 20-90 ° C, preferably
Is 25 to 50 ° C., and the immersion time is 0.1 second to 20 minutes,
Preferably, it is 2 seconds to 1 minute. The solution used for this is ammonia, trie.
Basic substances such as tilamine and potassium hydroxide, and salts
PH is adjusted with acidic substances such as acid and phosphoric acid, pH 1
It can also be used in the range of -12. In addition, photosensitive
Add yellow dye to improve tone reproducibility of printing plate
You can also Furthermore, this solution contains the following general formula (a):
A compound represented by can also be added. Formula (a) (HO) x-R^Five-(COOH) y However, R^FiveIs an optionally substituted substituent having 14 or less carbon atoms.
Represents a rylene group, x and y independently represent an integer of 1 to 3;
Represent. Specific examples of the compound represented by the general formula (a)
As 3-hydroxybenzoic acid, 4-hydroxybenzoic acid
Acid, salicylic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy
Droxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid
Acid, 2,4-dihydroxybenzoic acid, 10-hydroxy-
Examples include 9-anthracene carboxylic acid. Under organic
The coating amount after drying of the coating layer is 1 to 100 mg / m.²Is appropriate
Preferably 2 to 70 mg / m²It is. above
Covering amount is 2mg / m²If it is less, sufficient printing performance is obtained.
I can't. 100 mg / m²Same for larger
It is. Back coat; on the back surface of the support, if necessary
A back coat is provided accordingly. Such back coat
As an organic polymer described in JP-A-5-45885
Compounds and organic compounds described in JP-A-6-35174.
Or obtained by hydrolysis and polycondensation of inorganic metal compounds.
A coating layer made of a metal oxide is preferably used.
Of these coating layers, Si (OCH_Three)_Four, Si (OC₂H_Five)
_Four, Si (OC_ThreeH₇)_Four, Si (OC_FourH₉)_FourSilicon
Lucoxy compounds are inexpensive and readily available
The metal oxide coating layer is particularly preferred because of its excellent developer resistance.
Yes. A lithographic printing plate prepared as described above
In general, image exposure and development are performed. Used for image exposure
As an active light source,
A light source having an emission wavelength is preferable, and a solid-state laser, a semiconductor laser
The user is particularly preferred. Lithographic printing using the photosensitive resin composition of the present invention
Preferred as a developer for a printing plate is (a) a non-reducing sugar
At least one saccharide selected from (b) at least
Also contains a kind of base and has a pH in the range of 9.0 to 13.5
Developer. The following explains this developer in detail.
Light up. In this specification, there is no special notice.
As long as it is a developer, a developer starter (a developer in a narrow sense) and development
Means replenisher. This developer is mainly composed of non-reducing sugars.
And at least one compound selected from
And the pH of the liquid is in the range of 9.0 to 13.5.
Preferably there is. Such non-reducing sugars are free alcohols.
It is a saccharide that does not have a dehydride group or ketone group and does not exhibit reducing properties.
Yes, trehalose-type oligosaccharides and sugars with reducing groups
Hydrogenated glycosides and saccharides in which a reducing group is bound to a non-saccharide
Classified into sugar alcohols that have been reduced by addition, all suitable
Used for. Trehalose-type oligosaccharides include saccharo
And trehalose.
Examples include glycosides, phenolic glycosides, mustard oil glycosides, etc.
It is. As sugar alcohol, D, L-Arabit,
Rebit, Xylit, D, L-Sorbit, D, L-Ma
Nnit, D, L-Exit, D, L-Talit, Zurishi
And allozulcit. Disaccharide
Of maltitol and oligosaccharides obtained by hydrogenation
The reductant obtained by hydrogenation (reduced water candy) is preferably used.
It is done. Among these, particularly preferred non-reducing sugars are sugar alcohols.
And saccharose, especially D-Sorbit and Saccharose
Callose and reduced water candy have a buffering effect in a moderate pH range.
And low cost. These non-reducing sugars may be used alone or in combination of two or more.
Can be used in combination with the above, occupy in their developer
The proportion is preferably 0.1 to 30% by weight, more preferably
Is 1 to 20% by weight. Less than this range
Impact is not obtained, and at concentrations above this range, high concentrations
It is difficult to shrink, and there is a problem of cost increase. Return
Brown over time when used in combination with base sugar
Discoloration, and the pH gradually decreases, and thus developability decreases.
There is a problem that. Conventional bases to be combined with non-reducing sugars
More known alkaline agents can be used. For example, water
Sodium oxide, potassium hydroxide, lithium hydroxide, lithium
Trisodium phosphate, tripotassium phosphate, triammonic phosphate
Ni, disodium phosphate, dipotassium phosphate, phosphorus
Diammonium acid, sodium carbonate, potassium carbonate, charcoal
Ammonium acid, sodium bicarbonate, potassium hydrogen carbonate
, Ammonium bicarbonate, sodium borate, boric acid
Inorganic alkaline agents such as potassium and ammonium borate
Can be mentioned. Monomethylamine, dimethylamino
, Trimethylamine, monoethylamine, diethylamine
Min, triethylamine, monoisopropylamine, di
Isopropylamine, triisopropylamine, n-butyl
Tylamine, monoethanolamine, diethanolamine
, Triethanolamine, monoisopropanolamine
, Diisopropanolamine, ethyleneimine, ethyl
Organic alkali agents such as range amine and pyridine are also used.
It is. These alkali agents may be used alone or in combination of two or more.
Used in combination with the above. Preferred among these
Is sodium hydroxide, potassium hydroxide, why
By adjusting these amounts for non-reducing sugars
This is because the pH can be adjusted in a wide pH range. Ma
Trisodium phosphate, tripotassium phosphate, sodium carbonate
Lium, potassium carbonate, etc. have their own buffering effect
Therefore, it is preferable. These alkaline agents control the pH of the developer.
It is added so that it is in the range of 9.0 to 13.5.
The amount to be added depends on the desired pH, type of non-reducing sugar and amount added.
A more preferable pH range is 10.0 to 13.
2. The developer further contains weak acids and strong bases other than sugars.
An alkaline buffer solution consisting of can be used in combination. Such buffer
As a weak acid used as a dissociation constant (pKa)
The thing of 10.0-13.2 is preferable. Such a weak acid
As an IONISATION CONSTAN published by Pergamon Press
TS OFORGANIC ACIDS IN AQUEOUS SOLUTION
For example, 2,2,3,3-teto
Rafluoropropanol-1 (PKa 12.74), G
Lifluoroethanol (12.37), trichloroe
Alcohols such as tanol (12.24), pyridi
-2-aldehyde (12.68), pyridine-4-al
Aldehydes such as dehydr (12.05), salicyl
Acid (13.0), 3-hydroxy-2-naphthoic acid (13.0)
12.84), catechol (12.6), gallic acid
(12.4), sulfosalicylic acid (11.7),
3,4-dihydroxysulfonic acid (12.2), 3,
4-dihydroxybenzoic acid (11.94), 1,2,
4-Trihydroxybenzene (11.82), Hyde
Loquinone (same as 11.56), pyrogallol (same as 11.3)
4), o-cresol (10.33), resorcino
(11.27) and p-cresol (10.2)
7), pheno such as m-cresol (10.09)
A compound having a rutile hydroxyl group, 2-butanone oxime (12.45),
Acetoxime (12.42), 1,2-cyclohepta
Dione dioxime (12.3) and 2-hydroxybenzene
Zunsaldehyde oxime (12.10), Dimethyl
Lioxime (11.9), ethanediamide dioxime
(Id. 11.37), acetophenone oxime (Id. 11.
35) oximes, adenosine (12.5
6), inosine (12.5), guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1) Nucleic acid-related substances such as xanthine (11.9)
In addition, diethylaminomethylphosphonic acid (12.
32) 1-amino-3,3,3-trifluorobenzoic acid
(12.29), isopropylidenediphosphonic acid (same as above)
12.10), 1,1-ethylidene diphosphonic acid (same as 1
1.54), 1,1-ethylidene diphosphonic acid 1-hydro
Xy (11.52), benzimidazole (12.
86), thiobenzamide (12.8), picolinchi
Oamide (12.55), barbituric acid (12.
And weak acids such as 5). Of these weak acids, sulfo is preferred.
Salicylic acid and salicylic acid. Combined with these weak acids
The bases that can be used are sodium hydroxide and ammonia
, Potassium and lithium are preferably used.
These alkaline agents are used alone or in combination of two or more.
Used. The above-mentioned various alkali agents have concentrations and combinations.
Adjust the pH within the preferred range by combining
It is. The developer contains development acceleration and development residue.
Necessary for the purpose of improving the ink-philicity of the scattering and printing plate image area
Depending on the conditions, various surfactants and organic solvents can be added. Like
New surfactants include anionic, cationic, and non-ionic surfactants.
Nonionic and amphoteric surfactants can be mentioned. Preferred examples of the surfactant include polio
Xylethylene alkyl ethers, polyoxyethylene
Alkylphenyl ethers, polyoxyethylene poly
Styryl phenyl ethers, polyoxyethylene poly
Oxypropylene alkyl ethers, glycerin fat
Acid partial esters, sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial esters, propire
Glycol monofatty acid esters, sucrose fatty acid part
Esters, polyoxyethylene sorbitan fatty acid part
Esters, polyoxyethylene sorbitol fatty acid part
Esters, polyethylene glycol fatty acid esters
, Polyglycerol fatty acid partial esters, polyoxy
Ethyleneated castor oil, polyoxyethylene glycerin
Fatty acid partial esters, fatty acid diethanolamides,
N, N-bis-2-hydroxyalkylamines, polio
Xylethylene alkylamine, triethanolamine fat
Non-ionics such as fatty acid esters and trialkylamine oxides
On-active surfactant, Fatty acid salts, abietic acid salts, hydroxy
Sialkane sulfonates, alkane sulfonates,
Dialkylsulfosuccinic acid ester salts, linear alkyl bases
Sulfonates, branched alkylbenzene sulfone
Phosphates, alkylnaphthalene sulfonates, alkyls
Ruphenoxy polyoxyethylene propyl sulfonate
Polyoxyethylene alkyl sulfophenyl ether
Salt, sodium N-methyl-N-oleyl taurate
Salt, N-alkylsulfosuccinic acid monoamide disodium
Salt, petroleum sulfonate, sulfated beef oil, fatty acid alkyl
Sulfates of alkyl esters, alkyl sulfates
Salts, polyoxyethylene alkyl ether sulfate ester
Salt, fatty acid monoglyceride sulfate, poly
Oxyethylene alkyl phenyl ether sulfate
Salts, polyoxyethylene styryl phenyl ether sulfate
Acid ester salts, alkyl phosphate ester salts, polio
Xylethylene alkyl ether phosphates
Reoxyethylene alkylphenyl ether phosphate
Tellurium salt, styrene / maleic anhydride copolymer partially saponified
And partial saponification of olefin / maleic anhydride copolymer
Chemicals, Naphthalene sulfonate formalin condensate
Anionic surfactants, alkylamine salts,
Quaternary ammonia such as trabutylammonium bromide
Salts, polyoxyethylene alkylamine salts, poly
Cationic surface activity such as ethylene polyamine derivatives
Agents, carboxybetaines, aminocarboxylic acids, sulfur
Hobetaines, amino sulfates, imidazolines
And amphoteric surfactants. The surface activities listed above
Among the sexual agents, polyoxyethylene is a polyoxyethylene.
Simethylene, polyoxypropylene, polyoxybutyrate
It can also be read as polyoxyalkylene such as
These surfactants are also included. A more preferred surfactant is a perfume in the molecule.
A fluorosurfactant containing a fluoroalkyl group
The Such fluorosurfactants include perfluoro
Alkyl carboxylates, perfluoroalkyl sulfones
Acids such as acid salts and perfluoroalkyl phosphates
ON type, amphoteric type such as perfluoroalkylbetaine,
Such as perfluoroalkyltrimethylammonium salt
Cationic and perfluoroalkylamine oxides
Perfluoroalkylethylene oxide adduct,
An oligomer containing a fluoroalkyl group and a hydrophilic group,
Perfluoroalkyl group and lipophilic group-containing oligomer
-Perfluoroalkyl group, hydrophilic group and lipophilic group
Containing oligomer, perfluoroalkyl group and lipophilicity
Nonionic types such as group-containing urethanes can be mentioned. above
Surfactants can be used alone or in combination of two or more.
0.001 to 10 weight in the developer
%, More preferably in the range of 0.01 to 5% by weight
It is. In the developer, various development stabilizers are used.
be able to. As preferred examples thereof, Japanese Patent Laid-Open No. Hei 6-
Polyethylene of sugar alcohol described in Japanese Patent No. 282079
Glycol adduct, tetrabutylammonium hydroxide
Tetraalkylammonium salts such as Cid, Tetrabuty
Phosphonium salts such as ruphosphonium bromide and
Iodonium such as diphenyliodonium chloride
A salt is a preferred example. Furthermore, JP-A-50
Anionic surfactant described in JP-A-51324 or both
Surfactants and also described in JP-A-55-95946
Water-soluble cationic polymer, JP 56-1425
Water-soluble amphoteric polymer electrolyte described in Japanese Patent No. 28
Can be mentioned. Furthermore, a) disclosed in Japanese Patent Application Laid-Open No. 59-84241.
Organoboron compounds with added ruxylene glycol, special
Polyoxyethylene described in Japanese Utility Model Publication No. 60-111246
Polyoxypropylene block polymerization type water-soluble interface
Activator, polyoxy of JP-A-60-129750
Alkylene substituted with ethylene / polyoxypropylene
Diamine compound, described in JP-A 61-215554
Polyethylene glycol having a weight average molecular weight of 300 or more
The cationic group disclosed in JP-A-63-175858
Fluorine-containing surfactant having, Japanese Patent Laid-Open No. 2-39157
4 mol or more of ethyleneoxy in the acid or alcohol
Water-soluble ethylene oxide addition compound
And water-soluble polyalkylene compounds. If necessary, an organic solvent is added to the developer.
It is done. Such organic solvents have water solubility.
About 10% by weight or less is suitable, preferably 5 layers
It is selected from those having an amount of less than%. For example, 1-phenyl ether
Tanol, 2-phenylethanol, 3-phenyl-1-propyl
Lopanol, 4-phenyl-1-butanol, 4-phenyl
-2-butanol, 2-phenyl-1-butanol, 2-Fe
Noxyethanol, 2-benzyloxyethanol, o-
Methoxybenzyl alcohol, m-methoxybenzyl alcohol
Lucol, p-methoxybenzyl alcohol, benzyl
Alcohol, cyclohexanol, 2-methylcyclohexane
Xanol, 3-methylcyclohexanol and 4-me
Tylcyclohexanol, N-phenylethanolamine
And N-phenyldiethanolamine
be able to. The content of organic solvent is relative to the total weight of the liquid used.
0.1 to 5% by weight. The amount used is a surfactant.
As the amount of organic solvent increases
The amount of the surfactant is preferably increased. this
Uses a small amount of surfactant and a large amount of organic solvent
And organic solvents are not completely dissolved, and therefore have good developability
This is because it cannot be expected. A reducing agent can be further added to the developer.
The This is to prevent stains on the printing plate.
Negative photosensitive lithographic printing containing a light-sensitive diazonium salt compound
As a preferred organic reducing agent that is effective in developing a plate
Thiosalicylic acid, hydroquinone, metol, meso
Toxiquinone, resorcin, 2-methylresorcin, etc.
Phenol compounds, phenylenediamine, phenyl
Examples thereof include amine compounds such as drazine. More preferred
Examples of inorganic reducing agents include sulfurous acid, bisulfite, and sulfite.
Acid, hydrophosphite, dihydrogen phosphite, thiosulfate
And sodium salts of inorganic acids such as dithionite and potassium
And ammonium salts. this
Of these reducing agents,
Sulfate. These reducing agents are used against the developer during use.
Preferably, it is contained in the range of 0.05 to 5% by weight.
The An organic carboxylic acid is further added to the developer.
You can also. Preferred organic carboxylic acids have 6 to 6 carbon atoms.
20 aliphatic carboxylic acids and aromatic carboxylic acids
The Specific examples of aliphatic carboxylic acids include capron
Acid, enanthylic acid, caprylic acid, lauric acid, myristic
Acid, palmitic acid and stearic acid.
Preferred is an alkanoic acid having 8 to 12 carbon atoms. Ma
Even unsaturated fatty acids with double bonds in the carbon chain
It may be of a carbon chain. As aromatic carboxylic acid
Benzene ring, naphthalene ring, anthracene ring, etc.
A compound in which a carboxyl group is substituted, specifically, o
-Chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxy
Benzoic acid, p-hydroxybenzoic acid, o-aminobenzoic acid
Acid, p-aminobenzoic acid, 2,4-dihydrobenzoic acid,
2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid
Benzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydride
Loxybenzoic acid, gallic acid, 1-hydroxy-2-naphtho
Ethic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-
1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid, etc.
Although hydroxy naphthoic acid is particularly effective. The above aliphatic and aromatic carboxylic acids are water-soluble.
Sodium or potassium salt or an
It is preferably used as a monium salt. Used in the present invention
There is no particular limitation on the content of organic carboxylic acid in the developer
However, if it is lower than 0.1% by weight, the effect is not sufficient, and 1
If it is 0% by weight or more, the effect cannot be improved any more
However, dissolution may be hindered when other additives are used in combination.
The Therefore, the preferred addition amount is relative to the developer at the time of use.
0.1 to 10% by weight, more preferably 0.5 to 4
% By weight. In the developer, a preservative, if necessary,
Contains colorants, thickeners, antifoaming agents, water softeners, etc.
It can also be made. Examples of water softeners include poly
Acid and its sodium, potassium and ammo
Nium salt, ethylenediaminetetraacetic acid, diethyleneto
Riaminepentaacetic acid, triethylenetetraminehexavine
Acid, hydroxyethylethylenediaminetriacetic acid, nito
Lilotriacetic acid, 1,2-diaminocyclohexanetetra
Acetic acid and 1,3-diamino-2-propanoltetraacetic acid
Aminopolycarboxylic acids such as acids and their sodium
Salts, potassium and ammonium salts, aminotri
(Methylenephosphonic acid), ethylenediaminetetra (me
Tylenephosphonic acid), diethylenetriaminepenta
Tylene phosphonic acid), triethylenetetramine hexa
(Methylenephosphonic acid), hydroxyethylethylenedi
Amine tri (methylenephosphonic acid) and 1-hydroxy
Citaene-1,1-diphosphonic acid and their sodium
Salt, potassium salt and ammonium salt
Yes. Such a water softener is a chelating agent.
The optimum value depends on the hardness and amount of hard water used.
It changes, but if you show the general usage amount, the developer at the time of use
0.01 to 5% by weight, more preferably 0.01 to 0.
It is in the range of 5% by weight. In addition amounts less than this range
The intended purpose is not fully achieved, and the amount added is within this range.
If there are many, there will be an adverse effect on the image area such as color loss.
The The remaining component of the developer is water. Developer is in use
Use as a concentrate with less water content than
Sometimes it is advantageous for transportation to dilute with water
The The degree of concentration in this case is the separation or precipitation of each component.
No degree is appropriate. Lithographic printing plate using the photosensitive composition of the present invention
As a developing solution for this, JP-A-6-282079
The developer described in the report can also be used. This is SiO₂/ M₂O
The molar ratio (M represents an alkali metal) is 0.5 to 2.0.
Alkali metal silicate and sugar alcohol having 4 or more hydroxyl groups
Obtained by adding more than 5 moles of ethylene oxide to coal
Development containing a water-soluble ethylene oxide addition compound
It is a liquid. Sugar alcohols are sugar aldehyde groups and keto
Reduced to the primary and secondary alcohol groups, respectively.
It is a polyhydric alcohol corresponding to the above. Sugar alcohol
Examples of shells are D, L-Trait, Eritreit
D, L-arabit, rebit, xylit, D,
L-Sorbit, D, L-Mannit, D, L-Ijid
D, L-Tallit, Zulsit, Allozulsit
Di-, tri-, and teto condensed with sugar alcohol
Also included are la, penta and hexaglycerin.
The water-soluble ethylene oxide adduct is a sugar alcohol.
Add 5 mol or more of ethylene oxide to 1 mol of
Can be obtained. Addition of ethylene oxide
The compound is soluble in propylene oxide if necessary
Block copolymerization may be performed within an allowable range. these
These ethylene oxide adducts may be used alone or in combination of two or more
May be used in combination. These water-soluble ethylene
The amount of oxide addition compound added to the developer (working solution)
0.001 to 5% by weight is suitable, more preferably
0.001 to 2% by weight. [0192] This developer further promotes developability and presents.
Increases dispersion of image residue and ink affinity of printing plate image area
As necessary for the purpose, the above-mentioned various surfactants and organic solvents are used.
An agent can be added. PS developed with a developer having such a composition
The plate is washed with water, rinse solution containing surfactant, etc.
Finishers mainly composed of agum and starch derivatives
It is post-treated with a protective gum solution. Post processing of the PS plate of the present invention
In fact, these processes can be used in various combinations.
Yes. In recent years, the plate making work has been rationalized in the stencil and printing industries.
Automatic processing machine for PS plate is widely used for standardization and standardization
It is said. This automatic processor generally has a developing unit and a post-treatment.
It consists of a science department, a PS plate transport device, and each treatment liquid tank
And spray device to horizontally expose the exposed PS plate
Spray each treatment liquid pumped up while transporting
Development and post-processing by spraying from nozzle
The In addition, recently, in the processing liquid tank filled with the processing liquid,
Develop by immersing PS plate with guide rolls
The processing method and a small amount of water for washing on the plate after development
Supply and wash with water, and use the wastewater as dilution water for the developer stock solution.
A method of reusing is also known. In such automatic processing, each processing solution
Each replenisher is replenished according to the processing amount and operating time.
Can be processed. Also virtually unused
The so-called disposable treatment method that treats with the treatment liquid of
Yes. The lithographic printing plate obtained by such treatment is
It is hung on a press machine and used for printing many sheets.
The [0196] The following examples further illustrate the present invention.
The However, the present invention is limited by these examples.
It is not something. <(C) Synthesis of fluorine-containing polymer> Synthesis Example 1 Synthesis of fluorine-containing polymer C-1 Three 500ml bottles equipped with a stirrer, condenser, and dropping funnel
Place 117 g of methyl isobutyl ketone in a hot water bath.
To 75 [deg.] C. and in the above [Chemical Formula 21] under a nitrogen stream.
36.0 g of fluorine-containing monomer (A-31) indicated, 2
-12.0 g of hydroxyethyl methacrylate, methyl
25.0 g of methacrylate, 27.0 of the following compound (I)
g, 117 g of methyl isobutyl ketone, V-601 (sum
A drop of 1.15 g of a mixture of Koyo Pure Chemical Co., Ltd. over 2 hours
It was dripped from the lower funnel. 75 hours at 75 ° C after completion of dropping
Thereafter, the mixture was stirred at 90 ° C. for 2 hours. This allows fluorine-containing polymers
-(C-1) was obtained. By GPC, this compound is
It was a polymer compound having a weight average molecular weight of 35,000. [0198] Embedded image Synthesis Example 2 Synthesis of fluorine-containing polymer C-2
Completion The fluorine-containing monomer (A-1) shown in the above [Chemical Formula 16]
Same as fluorine-containing polymer C-1 except for 5)
To obtain a fluorine-containing polymer C-2. Mn =
It was 9,000. <(D) Synthesis of fluorine-containing polymer> Synthesis Example 1 Synthesis of fluorine-containing polymer D-1 26.4 g of (M-32) shown in [Chemical 26],
Product (II) 25.6 g, lauryl methacrylate 20.4
g and 160 g of dimethylacetamide in 500 ml of 3
Take to a neck flask and stir under nitrogen flow to 65 ° C
Kept. 2,2-azobis (2,4-dimethylvaleroni
2.30 g of (tolyl) was added and stirring was continued. 4 hours later 75
The temperature was raised to 0 ° C. and kept for 1 hour. After the reaction is complete, cool to room temperature
The reaction solution was poured into 400 ml of water. Precipitated solid
The body was collected by filtration and dried. Fluorine-containing poly in a yield of 68.4g
Mer (D-1) was obtained. By GPC, this solid is
It was a polymer compound having a weight average molecular weight of 40,000. [0201] Embedded image Synthesis Example 2 Fluorine-containing polymers D-2 to D
Of -4 A polymer was synthesized in the same manner as in Synthesis Example 1. Composition
Structure, composition ratio, and weight average molecule of the fluorine-containing polymer
The amount (Mw) is shown below. The composition ratio is a molar ratio. [0203] Embedded image<(E) Synthesis of fluorine-containing polymer>
(C) Fluorine-containing polymer, (D) Fluorine-containing polymer
In the same manner as above, polymers E-1 to E-4 were synthesized.
It was. Structure, composition ratio, weight of synthesized fluorine-containing polymer
The average molecular weight (Mw) is shown below. The composition ratio is molar ratio.
It is. [0205] Embedded image<Synthesis of specific copolymer> Stirrer, cooling pipe
And a 500 ml three-necked flask equipped with a dropping funnel.
Tacric acid 31.0 g (0.36 mol), chloroformate
39.1 g (0.36 mol) of chill and acetonitrile 2
Put 00ml and stir the mixture while cooling in an ice water bath
It was. To this mixture was added 36.4 g (0.3
6 mol) was added dropwise using a dropping funnel over about 1 hour.
After dropping, remove the ice-water bath and mix for 30 minutes at room temperature
The thing was stirred. To this reaction mixture, p-aminobenzene was added.
Add 51.7 g (0.30 mol) of lufonamide, oil bath
The mixture was stirred for 1 hour while warming to 70 ° C. reaction
When finished, do not stir the mixture into 1 liter of water.
The resulting mixture was stirred for 30 minutes. this
The mixture was filtered to remove the precipitate, which was then added to 500 m of water.
l. After slurrying with l, the slurry is filtered to obtain
The solid was dried to give N- (p-aminosulfonate
Ruphenyl) methacrylamide white solid was obtained
(Yield 46.9 g). Next, a stirrer, a cooling pipe and a dropping funnel are provided.
Into a 20 ml three-necked flask, N- (p-aminosulfo
Nylphenyl) methacrylamide 4.61 g (0.01
92 mol), 2.94 g of ethyl methacrylate (0.02
58 mol), acrylonitrile 0.80 g (0.015
Mol) and 20 g of N, N-dimethylacetamide
Stirring the mixture while heating to 65 ° C in a hot water bath
It was. To this mixture, “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.)
Add 0.15g and keep at 65 ° C for 2 hours under nitrogen flow
The mixture was stirred. The reaction mixture is further subjected to N- (p-
Aminosulfonylphenyl) methacrylamide 4.61
g, ethyl methacrylate 2.94 g, acrylonitrile
0.80 g, N, N-dimethylacetamide and “V—
65 ”0.15 g of mixture into the dropping funnel over 2 hours
More dripped. After completion of dropping, it was obtained at 65 ° C for 2 hours.
The mixture was stirred. After the reaction, 40g of methanol was mixed
Add to mixture, cool, and mix the resulting mixture to 2 liters of water
The water was added with stirring, and the mixture was stirred for 30 minutes.
After that, the precipitate is removed by filtration and dried.
15 g of a white solid was obtained. Gel permeation chroma
The weight average content of this specific copolymer 1 by
The molecular weight (polystyrene standard) was measured to be 53,000.
0. <Preparation of lithographic printing plate support> (Aluminum plate) Si: 0.06 mass%, Fe: 0.30 trade volume%, Cu:
0.005 mass%, Mn: 0.001 mass%, Mg:
0.001% by mass, Zn: 0.001% by mass, Ti:
0.03% by mass, the balance being Al and inevitable impurities
A molten metal is prepared using an aluminum alloy.
And filtered, thickness 500mm, width 1200m
An ingot of m was prepared by a DC casting method. Average surface 10m
After cutting off with a chamfering machine at a thickness of m, about 550 ° C,
When the temperature is kept constant for 5 hours and the temperature falls to 400 ° C,
A hot rolled mill was used to obtain a rolled plate having a thickness of 2.7 mm. Further
In addition, after performing heat treatment at 500 ° C. using a continuous annealing machine,
Cold rolled to a thickness of 0.30 mm, JIS 10
50 aluminum plates were obtained. This aluminum plate
After making the width 1030 mm, it was subjected to the following surface treatment
It was. Using the aluminum plate shown above,
The surface treatment shown was given and the support body was created. (Production method of support A)
It is made by performing the process continuously in the order of (a) to (h).
Made. In addition, nip roller after each treatment and water washing
The liquid was drained. (A) Mechanical roughening treatment Polishing suspension of polishing agent (pumice) with specific gravity of 1.12 and water
While supplying the slurry liquid to the surface of the aluminum plate
And a mechanically rough surface by a rotating roller nylon brush
The treatment was performed. The average particle size of the abrasive is 40μm, the largest particle
The diameter was 100 μm. The material of the nylon brush is 6.
10 nylon, hair length is 50 mm, hair diameter is 0.3 mm
The thing of was used. Φ300 with nylon brush
Three stainless steel rotating rolls were used. bra
The distance between the two support rollers (φ200mm) at the bottom of the shi is 3
It was 00 mm. Brush roller rotates the brush
The load of the drive motor causes the brush roller to become an aluminum plate.
Until it becomes 7kW plus against the load before pressing
I pressed it down. The rotation direction of the brush is the transfer of the aluminum plate.
The direction of movement was the same. Brush speed is 250rpm
The surface roughness (Ra) of the obtained substrate is 0.55 μm.
there were. (B) Alkali etching treatment The aluminum plate obtained above has a concentration of 2.6% by mass,
Na with a ruminium ion concentration of 6.5% by mass and a temperature of 72 ° C.
An etching process is performed by spraying OH aqueous solution.
Minium plate 10g / m²Dissolved. Then spray
Washed with water. (C) Desmut processing Aqueous solution with a nitric acid concentration of 10.4 g / l at a temperature of 30 ° C. (aluminum
Contains 4.5 g / l of nium ions. )
And then rinse with water.
It was. Nitric acid aqueous solution used for desmut treatment is nitric acid aqueous solution
The process of electrochemical surface roughening using alternating current
The liquid was used. (D) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. The electrolytic solution at this time was 10.4 g of nitric acid.
/ L aqueous solution (4.5 g / l aluminum ion,
Containing 0.007% by mass of monium ions), liquid temperature 50 ° C.
Met. Time to reach the peak from zero
TP is 0.8msec, duty ratio is 1: 1, trapezoidal rectangle
Using wave alternating current, electrochemical with carbon electrode as counter electrode
Roughening treatment was performed. Ferrite on the auxiliary anode
Using. The electrolytic cell used was a radial cell type.
used. The current density is 30 A / d at the peak current value.
m²The amount of electricity is the sum of the amount of electricity when the aluminum plate is the anode.
220C / dm²Met. The auxiliary anode is powered from the power source.
5% of the generated current was shunted. Then by spray
Washed with water. (E) Alkali etching treatment Caustic soda concentration 2.6% by mass, aluminum ion concentration
Etch by spraying using 6.5% by mass aqueous solution
Treatment is performed at 61 ° C. and an aluminum plate is 0.9 g /
m²Dissolved and produced by previous electrochemical roughening treatment
Smut component and vinyl oxide
Melt the edges of the base to smooth the edges
It was. Then, water washing by spraying was performed. (F) Desmut processing A sulfuric acid concentration 170 g / l aqueous solution with a temperature of 30 ° C. (aluminum
Contains 4.5% by mass of muons. )
A smut treatment was performed, followed by washing with water by spraying. De
The sulfuric acid aqueous solution used for the smut treatment is positive in the sulfuric acid aqueous solution.
The waste liquid from the step of performing the extreme oxidation treatment was used. (G) Anodizing treatment Sulfuric acid was used as the electrolytic solution. All electrolytes are
Sulfuric acid concentration 170g / L (0.5% aluminum ion
Including amount%. ), The temperature was 43 ° C. Then spray
Washed with water. The final oxide film amount is 2.6 g /
m²Met. (H) Hydrophilization treatment Treatment tank of 1 mass% aqueous solution of No. 3 sodium silicate at a temperature of 30 ° C
Hydrophilic treatment (alkali silicate) by soaking in for 10 seconds
Treatment). (Production method of support B) Surface shown above
It is performed continuously in the order of (b) to (h) among the processing steps.
Created by. However, the liquid temperature for step (b)
Is performed at 68 ° C., and the amount of dissolved aluminum is 5.5 g / m.
²(E) The liquid temperature is changed for step (e).
The temperature is 38 ° C., and the amount of aluminum dissolved is 0.25 g / m.
²It changed so that it might become. Each process and
After washing with water, the liquid was removed with a nip roller. Next, the back of the support [A] and the support [B]
Apply the following sol-gel reaction diluent on the surface with a bar coater.
And dry at 100 ° C. for 1 minute. The coating amount after drying is 60 m.
g / m²The backcoat layer was provided. [0221] Sol-gel reaction solution   Tetraethyl silicate 50.0 parts by weight   86.4 parts by weight of water   10.8 parts by weight of methanol   Phosphoric acid (85%) 0.08 parts by weight When the above ingredients are mixed and stirred, the reaction takes about 35 minutes.
Heated. After reacting with stirring for 40 minutes, the following dilute
The backcoat coating solution was prepared by mixing with the solution. [0223] Diluted solution   Pyrogallol acetone condensation resin 15.0 parts by weight   Dibutyl maleate 5.0 parts by weight   Methanol silica sol Nissan Chemical Co., Ltd. 70.0 parts by weight   MegaFuck F-177 Dai Nippon Ink Chemical Co., Ltd. 0.1 parts by weight   650 parts by weight of methanol   200 parts by weight of 1-methoxy-2-propanol Next, a support [A] provided with a back coat.
And an organic intermediate layer coating solution having the following composition on the surface of the support [B]
Is applied with a bar coater, dried at 100 ° C. for 10 seconds,
Plate printing plate supports [A] and [B] were obtained. Organic after drying
The coating amount of the intermediate layer is 15 mg / m²Met. [0225] Organic intermediate layer coating solution composition   Compound A 0.2 parts by weight   Methanol 100.0 parts by weight   1.0 part by weight of water [0226] Embedded image Example 1 <Formation of recording layer> Support provided with the obtained organic intermediate layer
[A] and the surface of the support [B] (on the organic intermediate layer)
The following coating solutions were applied with a bar coater at 140 ° C.
Dry for 60 seconds to form a photosensitive layer (recording layer), and lithographic printing
An original version for the plate was obtained. The coating amount of the coating solution after drying is 1.05 g
/ M²Met. [0228] Coating liquid   0.02 part by weight of fluorine-containing polymer C-1   Fluorine-containing polymer D-1 0.04 part by weight   Fluorine-containing polymer E-1 0.002 parts by weight   Specific copolymer 1 2.00 parts by weight   m, p-cresol novolak 0.50 parts by weight (M, p ratio = 6/4, weight average molecular weight 3500, unreacted cresol 0.5% by weight Contains)   0.01 parts by weight of p-toluenesulfonic acid   Tetrahydroxyphthalic anhydride 0.20 parts by weight   Bishydroxyphenylsulfone 0.15 parts by weight   3-methoxy-4-diazodiphenylamine 0.03 parts by weight   Cyanine dye A (the following structural formula) 0.17 parts by weight   Additive B (the following structural formula) 0.02 parts by weight   Additive C (the following structural formula) 0.04 parts by weight   The counter ion of Victoria Pure Blue BOH is 1-naphthalenesulfonic acid anio 0.10 parts by weight of dye   γ-Butyllactone 10 parts by weight   20 parts by weight of methyl ethyl ketone   1-methoxy-2-propanol 10 parts by weight [0229] Embedded imageExamples 2 to 13 and Comparative Examples 1 to 6 Fluorine
Except for using polymers contained in Table 1
A lithographic printing plate was obtained in the same manner as in Example 1. The resulting lithographic stamp
The printing plate was evaluated in the same manner as in Example 1. Evaluation results
Table 1 shows. The obtained lithographic printing plate was evaluated as follows:
The test was conducted. The evaluation results are shown in Table 1. The above organic
The support [A] and the support [B] provided with an intermediate layer were used.
There was no difference in performance. <Development stability against trauma> Obtained flat plate
Printing plate, output 500mW, wavelength 830nm, beam diameter
Main scanning speed using a 17 μm (1 / e2) semiconductor laser
After exposure at a rate of 5 m / sec, continuous load type scratch strength tester
Using "SB62 type" (manufactured by Shinto Kagaku Co., Ltd.), scratching jig
Advante on a 1 cm square square plane that hits the plate
A “No. 5C” filter paper made by Tokusha Co., Ltd.
A load of 0 g was applied and scratched at a speed of 6 cm / sec.
Shishi Photo Film Co., Ltd. developer, DT-1 (1: 8)
Developed for 30 seconds. Evaluation was performed according to the following criteria. When the scratched photosensitive film is completely dissolved; × When the scratched photosensitive film is partially dissolved; △ When the scratched photosensitive film is not dissolved at all; ○ <Developable dilution ratio range> Plate mark obtained
Printing plate, output 500mW, wavelength 830nm, beam diameter 1
Main scanning speed using 7μm (1 / e2) semiconductor laser
After exposure at 5m / sec, Fuji Photo Film Co., Ltd.
Change the ratio of image liquid, DT-1 and water from 1: 5 to 1:10
Then, development was performed for 30 seconds with each of the solutions prepared in the above. Fully exposed area
Elution and dilution with unexposed area density of 90% or more before development
The range of the rate was defined as a dilutable range where development was possible. The wider range
Is good. <Stability over time> The obtained lithographic printing plate was used as a slip sheet.
After heating 10 sheets at 45 ° C for 3 days
In addition, the development stability against trauma was evaluated. Things without change
◯, something that changes a little, △, something that changes a lot
did. <Coating surface quality> Photosensitive layer of the obtained lithographic printing plate
If there is unevenness or pinholes on the surface, ×
The evaluation was evaluated as Δ, and the evaluation was not. <Thickness> The obtained lithographic printing plate was output 50.
0 mW, wavelength 830 nm, beam diameter 17 μm (1 / e
Dew at a main scanning speed of 5 m / sec using the semiconductor laser of 2)
After the light, a developer manufactured by Fuji Photo Film Co., Ltd., DT-1
Developed at 1: 8 for 30 seconds, Fuji Photo Film Co., Ltd.
Apply the gum-making liquid FP-2W (1: 1) and dry it.
Got. This printing plate is a remanufactured by Komori Corporation.
DIC-G made by Dainippon Ink & Chemicals, Inc.
Print with EOS (N) ink and print normally
Ink all areas where there is an image on the printing plate
Necessary to eliminate missing parts on printed materials.
The required number of printed sheets was evaluated as the inking property. The number is small
Good. [0237] [Table 1][0238] According to the present invention, the image form of an original plate for lithographic printing can be obtained.
When used as a stratification, the state before development is stable and time-dependent
The coated surface of the layer is good and the developer activity is excellent.
Even if a strong developer is used, the non-exposed part is hardly dissolved,
Excellent inking quality of printing ink.
Nation is improved and development latitude is good.
It is possible to provide an infrared-sensitive photosensitive composition for EC plate making.
Yes.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AB03 AC08 AD01 AD03                       BC32 BC42 CA00 CA23 CA25                       CB17 CB29 CB52 CC04 CC20                       FA03 FA17                 2H096 AA07 AA08 BA01 BA09 BA16                       BA20 EA04 GA08

Claims (1)

What is claimed is: (A) a water-insoluble alkaline water-soluble resin;
(B) a photothermal conversion agent, (C) a fluorine-containing polymer having a polymerization component of a (meth) acrylate monomer having 2 or 3 C3-20 perfluoroalkyl groups in the molecule, (D) at least the following (1 ) To (3) as a copolymer component, a fluorine-containing polymer, (1) an addition-polymerizable fluorine-containing monomer having in the side chain a fluoroaliphatic group in which a hydrogen atom on a carbon atom is substituted with a fluorine atom,
(2) monomers represented by the following structures [1] to [4]: [Wherein, A ¹ represents a hydrogen atom, a halogen atom or an alkyl group, W represents oxygen or —NR ¹ —, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ² represents a substituent. An alkyl group which may have an aryl group which may have a substituent; R ³ represents an alkyl group or an aryl group; U represents a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group; A methyl group, a heterocycle containing a nitrogen atom, or —CH ₂ OCOR ³ (R ³ is as defined above)] (3) having an acidic hydrogen atom, and having an acidic group in which the acidic hydrogen atom is bonded to the nitrogen atom (E) (i) fluoroaliphatic having 3 to 20 carbon atoms and containing 40% by weight or more of fluorine, and at least three terminal carbon atoms are sufficiently fluorinated Group (R
f group) -containing (meth) acrylate and (ii) poly (oxyalkylene) (meth) acrylate copolymer, wherein the Rf group-containing (meth) acrylate monomer unit is based on the weight of the copolymer An infrared-sensitive composition, comprising a copolymer of 25 to 70% by weight.