JP2003228164A - Original plate for planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original plate for a planographic printing plate having an image forming layer which has improved in uniformity and in solubility and dispersibility in a developing solution and having a high-contrast image forming property without lowering sensitivity. <P>SOLUTION: The original plate for a planographic printing plate has on a support an image forming layer comprising a fluoroaliphatic group-containing copolymer obtained by copolymerizing at least the following monomers (A) and (B); (A) a (meth)acrylate compound having a specified fluoroalkyl group at the end of a side chain and (B) a polyoxyalkylene-containing ethylenically unsaturated compound. <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Copolymer having an oroaliphatic group (hereinafter referred to as fluorine polymer)
A new lithographic printing plate precursor containing
Uniform coated surface without causing production failure such as foaming
Provides a lithographic printing plate with excellent developability and ink fillability.
The present invention relates to a lithographic printing plate precursor that can be provided. An original plate for a lithographic printing plate forms an image on a substrate.
It has the structure which provided the layer. A typical manufacturing process is suitable.
Supports with surface treatment, undercoating, and back coating
Of images dispersed or dissolved in an organic solvent on the surface of
An image forming layer comprising the composition and, if necessary, a protective layer, etc.
The upper layer is applied and dried. Also typical plate making
The process is a contact or projection method surface through an image mask.
Electromagnetic waves based on exposure and image information from a computer
The image shape on the support is directly exposed by scanning and modulation.
After image-induced physical property change in the composition, non-image
Part of image forming composition (development) and hydrophilic as required
Hydrophilicity is achieved by processing such as sensitization, oil sensitization, and protective film formation.
Non-image area consisting of support surface layer and hydrophobic composition surface layer?
To form a lithographic printing plate having an image portion
The The lithographic printing plate thus obtained is used in typical printing processes.
The hydrophilic non-image area is fountain solution and the lipophilic image area.
Receives the ink and forms an ink image on the surface. Gain
Printed ink image directly or on the desired print media
Printed matter can be obtained by transferring it in contact. As the image forming layer used here, dew
Change from soluble to insoluble as a property change in light
Negative type and positive type that changes from insoluble to soluble,
In addition, those that use photoreaction as the principle of physical property change and
Using a remote mode process or thermal recording
Various techniques are already known. Any image forming layer
Even if you use, a highly useful lithographic printing plate precursor is realized.
There are common technical issues to do. (1) Image
High uniformity of the formation layer, (2) High hydrophobicity of the image area
In addition, the development removability of the non-image area is high. Image form
The uniformity of stratification is technically mainly related to the above manufacturing process.
Although the original is not uniform enough, it is homogeneous with high image quality.
A printing plate that provides a large number of stable prints
To reduce the performance required basically.
It ’s not. In addition, the fact that the image part has high hydrophobicity is
To increase the durability of the developer in the plate process
Better resolution, sufficient in the printing process
Important in terms of obtaining printing durability and ink fillability.
The However, the high degree of hydrophobicity in the image area means that the current use is normal.
Reduced solubility in alkaline aqueous solution.
This can cause development failure in non-image areas or in the developer.
May cause undesirable results such as sludge generation in
The That is, the hydrophobicity of the image area and the removability of the non-image area
These are contradictory properties in 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. example
For example, Japanese Patent Application Laid-Open No. 54-135004 discloses an image forming layer.
The effect of improving the uniformity of the is disclosed.
Also, JP-A-62-170950 and JP-A-8-158.
58, JP 2000-19724 A, etc.
Monomer unit having a uroaliphatic group and a specific functional group
The usefulness of a copolymer containing monomer units having
It is. These techniques simply have a fluoroaliphatic group
The prior art that disclosed the use of high molecular weight compounds
Improved by selection of further substituents on the child compounds
Yes, a polymer with fluoroaliphatic groups is made and printed
Reduces adverse effects on the process or conversely works
It is a technology to utilize. Specifically, JP-A-62-170.
No. 950 discloses a uniform film resulting from an improvement in surface activity.
Further improvement of the function of sex expression, JP-A-8-15858
For the development delay caused by hydrophobicity,
No. 0-19724 uses hydrophobicity and orientation force
High contrast by balancing hydrophobicity of image area and removability of non-image area
The effect of image formation is disclosed. Fluoroaliphatic groups
Among these effects due to the polymer compounds possessed, the uniformity of the film
Regarding the expression, the fluoroaliphatic group-containing polymer compound
Surfactant activity, i.e., the imaging composition in the manufacturing process.
Due to the ability to lower the surface tension of organic solvent dispersions
Conceivable. Polymerization with fluoroaliphatic groups
Another effect of the compound is that the image forming layer of the lithographic printing plate precursor
High content of fluoroaliphatic group-containing polymer compound contained in
Hydrophobicity and orientation, uneven distribution and localization on the surface of the image forming layer
It is thought to be caused by Noh. That is, fluoroaliphatic
Group-containing polymer compound surface distribution in the image forming composition
Since it can be relatively high in the vicinity, the current photosensitive layer as a whole
Maintains image removability while maintaining particularly high hydrophobicity on the surface
It is thought that it can be granted. In addition, full
As a measure to improve polymer compounds having oroaliphatic groups
A method other than the selection of the copolymerization component can also be considered. For example,
JP 2000-187318 A discloses a fluoroaliphatic group.
Polymer compound using monomer units having two or more groups
Depending on the object, the soluble discriminant of the image area and the non-image area
It is disclosed that an image forming material excellent in application can be obtained.
It is. As mentioned above, containing fluoroaliphatic compounds
The image forming layer to be used is an image forming layer for a lithographic printing plate precursor
And a method for achieving the common technical problems (1) and (2)
It is effective. However, on the other hand, the effect is still
It is not enough, and further improvements are desired.
The For example, when using a positive image forming layer,
In order to obtain a printed product, an image obtained after exposure and development can be obtained.
Only the discrimination between the image area and the non-image area is high.
In other words, the image with high gradation (high contrast) is image reproducibility.
It is preferable in terms of scratch resistance and high sensitivity.
Therefore, it is necessary to satisfy the requirements for white light safety and development tolerance.
It is necessary, but technology that can be fully satisfied is still being developed.
Not in. Here, if the image is soft, it means that
Images begin to remain when exposed and developed through edges
The difference between the number of steps and the number of steps where the film remains completely is large.
Means. Also, if the image is hard, the image remains
The difference between the number of steps that starts and the number of steps where the film remains completely is small
It means that Burns are caused by decomposition of the photosensitive material.
The squirrel film is lifted by the gas
This occurs because light cannot be produced.
When the rear sensitivity is the same, the harder the image,
Easy to eliminate blur. White light safety is a printing plate
Of image sensitivity when exposed to white light such as fluorescent light
The higher the brightness of the image, the greater the safety of white light.
Is good. The step wedge is the density of each step.
It is a strip-shaped film that changes by 0.15 and the exposure amount
And the relationship between the amount of film remaining on the photosensitive layer after development after exposure
Used. Clear sensitivity is the image after exposure and development.
Sensitivity at the beginning The development tolerance is
When the developer concentration changes, after exposure and development
This is to see how much the image sensitivity changes, and the sensitivity
The smaller the fluctuation, the better the development tolerance. In addition, light represented as a negative type lithographic printing plate
Including a monomer having a double bond polymerizable with a polymerization initiator
Photopolymerization printing plates, especially laser light in the visible light region
In a laser direct exposure printing plate with high sensitivity to lines
Since the gradation is soft, the printing plate is fixed and mixed.
The inner drum type
When image exposure is performed with the plate setter, scattered light and reflection
It was easy to cause fogging by light. The printing durability of the printing plate
It is necessary to expose with high energy to increase
However, fog caused by scattered light and reflected light will increase more and more.
Therefore, the exposure amount could not be increased. Therefore printing durability
In order to increase the
It is necessary to prevent fogging. That
In order to solve this problem, the gradation can be made hard.
Because image exposure by laser is per dot
Compared to the short exposure of about 1 microsecond order
However, fog caused by scattered or reflected light is extremely sensitive to photosensitive materials.
Photocuring by exposure to weak light for a long time of the order of a few minutes
Therefore, if the gradation of the photosensitive material becomes too high, it will be weak.
In light, the photosensitive material is difficult to photocur and is removed by development.
It is because it is not fogged. Also infrared laser
In thermal lithographic printing plates drawn using
Low discrimination between image and non-image areas.
Image of the part touched with bare hands due to low gradation (soft tone)
Occurrence of omissions and poor stability against trauma
There was a problem. [0009] The present invention provides the technical section.
Achieve titles (1) and (2) at a level exceeding conventional technology
Is to build a technology that can
Has improved uniformity, solubility in developer and dispersibility.
High contrast without reducing sensitivity.
To provide a lithographic printing plate precursor with excellent image forming properties
To do. [0010] The present inventors have made extensive studies.
As a result, a specific fluoropolymer was added to the image forming layer.
It is found that the above purpose is achieved by adding
It was. The present invention relates to the copolysynthesis of certain fluoroaliphatic groups
It is an invention based on the discovery made by examining the details in detail.
The That is, the present invention provides at least the modules (A) and (B).
Fluoropolymer obtained by copolymerizing a nomer (described later)
It has an image forming layer containing a copolymer containing an aliphatic group
A lithographic printing plate precursor characterized by the above-mentioned technical problem
Found and completed (1) and (2)
Is. Such a fluoroaliphatic group-containing copolymer
For example, surface quality due to foaming during production
Gives a uniform coated surface without causing abnormalities and low sensitivity
Good solubility and dispersibility in developer without lowering
It has been found that a positive photosensitive resin composition can be obtained. In addition, a specific hook defined in the present invention.
Negative lithographic printing plate by adding base polymer
In addition to the above improvements in surface quality and developer solubility,
Especially in the case of laser-sensitive photopolymerization printing plates
It is highly sensitive to laser light and is suitable for scattered light and reflected light.
Resulting in a printing plate with good fog and high printing durability.
Turned out to be. In addition, the smell for the heat-sensitive lithographic printing plate
In addition to improving the surface quality and developer solubility,
Nation is large and image intensity is strong, so bare hands
The image touched by the
It has been found that printing plates with improved stability can be obtained. The lithographic printing plate precursor according to the present invention comprises:
Consists of configuration. On the support, at least the following (A) and
And (B) monomers obtained by copolymerizing the monomers.
Has an image-forming layer containing a fluoroaliphatic group-containing copolymer.
(A) a full plate represented by the following general formula (I) or (II):
Oroalkyl (meth) acrylate: ## STR2 ## (Where X ¹ Is —O— or —NR ^Three -Is shown. R ¹ Is
-H or -CH _Three Indicates. R ^Three Is a hydrogen atom or a substituent
An alkyl group having 1 to 12 carbon atoms and a substituent which may have
C3-C12 cycloalkyl group which may have, substitution
An aryl group having 6 to 12 carbon atoms which may have a group, or
An aralkyl group having 6 to 24 carbon atoms which may have a substituent.
Show. R ² Represents H or F. m is an integer from 0 to 10,
n is an integer of 2 or 3, and o and p are each 1 or
Represents an integer of 2), (B) polyoxyalkylene group included
Ethylenically unsaturated monomer. DETAILED DESCRIPTION OF THE INVENTION (Fluoroaliphatic Group-Containing Polymerization)
Compound) Fluoroaliphatic used in the present invention
Polymers having a group in the side chain ("Fluoropolymer")
Will be described in detail. Main departure
The fluorine-based polymer used in the light is described in (A) and (B).
A polymer that meets the requirements. (A) Full represented by the following general formula (I) or (II)
Oroalkyl (meth) acrylate (Where X ¹ Is —O— or —NR ^Three -Is shown. R ¹ Is
-H or -CH _Three Indicates. R ^Three Is a hydrogen atom or a substituent
An alkyl group having 1 to 12 carbon atoms and a substituent which may have
C3-C12 cycloalkyl group which may have, substitution
An aryl group having 6 to 12 carbon atoms which may have a group, or
An aralkyl group having 6 to 24 carbon atoms which may have a substituent.
Show. R ² Represents H or F. m is an integer from 0 to 10,
n is an integer of 2 or 3, and o and p are each 1 or
Represents an integer of 2. As the substituents in the above groups,
Hydroxy group, halogen atom, alkyl group (preferably
An alkyl group having 1 to 12 carbon atoms), an alkoxy group (preferably
Or an alkoxy group having 1 to 12 carbon atoms) or an aryl group (preferably
Preferably an aryl group having 6 to 12 carbon atoms), sulfamoy
Group and carboxyl group. Preferred R ^Three Is water
Elemental atoms, alkyl groups having 1 to 6 carbon atoms, more preferred
Or a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Book
In the specification, an aryl group is a group commonly used in the art.
That means Specifically derived from aromatic compounds
Substituents such as phenyl, tolyl, xylyl,
Biphenylyl group, naphthyl group, anthryl group, phenane
Means a tolyl group and the like. Specific examples of these include the following compounds:
Things. These compounds are Daikin Fine
Chemical, Amax, Hydras Chemical, Central Medicine
Products, Wako Pure Chemicals, etc. are commercially available. Embedded image Next, the fluorine polymer used in the present invention.
-(B) Polyoxyalkylene group-containing ethylenically unsaturated
The sum monomer will be described. In this specification, polyoxy
Silane group-containing ethylenically unsaturated monomer is a molecule
Contains ethylenically unsaturated groups and polyoxyalkylene groups.
Meaning a copolymerizable monomeric compound.
There is no particular limitation as long as it is a compound. An ethylenically unsaturated group
The availability of raw materials, blending in various coating compositions
Of compatibility with materials, and controlling such compatibility
(Meth) acrylic from the viewpoint of ease or polymerization reactivity
Those containing ester groups and related groups are suitable.
The The polyoxyalkylene group is represented by (OR) x.
R is an alkyle having 2 to 4 carbon atoms.
-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ −,
-CH (CH _Three ) CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -
Or -CH (CH _Three ) CH (CH _Three )-Is preferred
That's right. x is a positive integer. Preferably x is 2 to 50
It is an integer, more preferably an integer of 3 to 30.
Oxyalkyles in the above poly (oxyalkylene) groups
Units are the same as in poly (oxypropylene)
It may be composed of only oxyalkylene units.
In addition, oxypropylene units and oxyethylene units
Two or more different oxyalkyles, such as those that are tied
Even if the unit is connected regularly or irregularly
good. Bonded to the end of a poly (oxyalkylene) chain
The atom or group to be formed is a hydrogen atom or any other group
There may be a hydrogen atom, an alkyl group (preferably carbon
Prime number 1-20), allyl group (preferably carbon number 1-2)
0), an aryl group (for example, having 6 to 10 carbon atoms)
Is preferred. The aryl group is an alkyl group (for example, carbon number
1-10), may have a substituent such as a halogen atom
Yes. One or more poly (oxyalkylene) chains
A chain bond (for example, -CONH-Ph-NHCO-,-
S- and the like: Ph represents a phenylene group)
Can be included. Branched oxyalkylene units
3 or more valences at the chain bond site to provide
Can have. Of poly (oxyalkylene) groups
The molecular weight is preferably 250 to 3000 including the chain bond.
Yes. (B) Polyoxy used in the present invention
As an example of an ethylenically unsaturated monomer containing a salkylene group
And monomers represented by the following general formula (III)
The [Chemical formula 5] (Where X ² Is —O— or —NR ⁶ -Is shown. Y is set
An alkylene group having 1 to 5 carbon atoms which may have a substituent is shown.
The R ^Four Is —H or —CH _Three Indicates. R ^Five Is a hydrogen atom
Or an alkyl having 1 to 12 carbon atoms which may have a substituent.
Group, a C3-C12 cycloal which may have a substituent
An aryl having 6 to 12 carbon atoms which may have a kill group or a substituent.
Or an aryl group having 6 to 24 carbon atoms which may have a substituent.
Represents an aralkyl group; R ⁶ May have a hydrogen atom or a substituent
It may have a good alkyl group having 1 to 12 carbon atoms and a substituent.
A C3-C12 cycloalkyl group having a substituent
It may have an aryl group having 6 to 12 carbon atoms or a substituent.
An aralkyl group having 6 to 24 carbon atoms which may be used. q is
Indicates a positive integer. When q is 2 or more, Ys are the same as each other
It may or may not be. ) Substitution in each of the above groups
As the group, a hydroxy group, a halogen atom, an alkyl group
(Preferably an alkyl group having 1 to 12 carbon atoms), alkoxy
Si group (preferably an alkoxy group having 1 to 12 carbon atoms),
A reel group (preferably an aryl group having 6 to 12 carbon atoms),
Examples thereof include a sulfamoyl group and a carboxyl group. Formula II
In I, preferred Y is a linear or branched group having 2 to 4 carbon atoms.
A branched alkylene group, preferably q is 2-50, more
Preferably it is an integer of 3-30. The polyoxyalkylene group-containing ethyl ether of the present invention
Specific examples of the renically unsaturated monomer include poly
(Oxyalkylene) acrylates and methacrylates
Is a commercially available hydroxypoly (oxyalkylene) material,
For example, the product name "Pluronic" [Pluronic (Asahi Denka Kogyo)
Manufactured by Asahi Denka Kogyo Co., Ltd.)
), Carbowax [Carbowax (Glico Product)
), Triton [Toriton (Rohm and Haas)
(Rohm and Haas))] and PEG (Daiichi Kogyo Seiyaku)
A product sold as
Kuryl acid, methacrylic acid, acrylic chloride, methacrylate
Reacting with luchloride or acrylic anhydride
Therefore, it can manufacture. Separately, a poly
It is also possible to use (oxyalkylene) diacrylate, etc.
it can. As a commercially available monomer, Nippon Oil & Fats Co., Ltd.
Company-made hydroxyl-terminated polyalkylene glycol mono (medium
B) Blemmer PE-90, Blemmer P as acrylate
E-200, Blemmer PE-350, Blemmer AE-90, Blemma
ー AE-200 、 Blemmer AE-400 、 Blemmer PP-1000 、
Lemmer PP-500, Bremmer PP-800, Bremmer AP-15
0, Blemmer AP-400, Blemmer AP-550, Blemmer A
P-800, Blemmer 50PEP-300, Blemmer 70PEP-350B,
Blemmer AEP series, Blemmer 55PET-400, Blen
Mar 30PET-800, Blemmer 55PET-800, Blemmer AET
Series, Bremmer 30PPT-800, Bremmer 50PPT-80
0, Bremmer 70PPT-800, Bremmer APT series,
Lemmer 10PPB-500B, Bremer 10APB-500B, etc.
It is done. Similarly, alkyl-terminated poly made by NOF Corporation
As alkylene glycol mono (meth) acrylate
Blemmer PME-100, Blemmer PME-200, Blemmer PM
E-400, Blemmer PME-1000, Blemmer PME-4000,
Lemmer AME-400, Bremmer 50POEP-800B, Bremmer
50AOEP-800B, Blemmer PLE-200, Blemmer ALE-20
0, Blemmer ALE-800, Blemmer PSE-400, Blemma
-PSE-1300, Blemmer ASEP series, Blemmer PKEP
Series, Blemmer AKEP series, Blemmer ANE-30
0, Bremmer ANE-1300, Bremmer PNEP series,
Lemmer PNPE series, Bremmer 43ANEP-500, Blen
MER 70ANEP-550 etc.
Ester MC, light ester 130MA, light ester 041
MA, light acrylate BO-A, light acrylate EC-
A, light acrylate MTG-A, light acrylate 130
A, Light acrylate DPM-A, Light acrylate P-20
0A, light acrylate NP-4EA, light acrylate NP
-8EA etc. It should be noted that the present invention is not limited to the above specific examples.
Of course, it is not specified. Polyoxyal
(B) is one type of ethylenically unsaturated monomer containing a xylene group
You can use only two kinds or more
It doesn't matter. Particularly preferred as the fluoropolymer of the present invention.
A preferred embodiment includes a monomer represented by the general formula (I) and
Poly (oxyethylene) acrylate and / or poly
(Oxyethylene) methacrylate and poly (oxyal)
Xylene) and / or poly (oxyalkyl)
Copolymerization of 3 or more monomers with (len) methacrylate
Polymer. In this case, poly (oxyal)
Xylene) and / or poly (oxyalkyl)
Len) methacrylate is a poly (oxyethylene)
Relate and / or poly (oxyethylene) methacrylate
Poly (oxyalkylene) acrylates other than the rate and
And / or poly (oxyalkylene) methacrylate
is there. In the present invention, the essential component (A)
Monomer represented and (B) polyoxyalkylene group containing
In addition to ethylenically unsaturated monomers, these are copolymerizable with these
It is possible to use a fluoropolymer that has been reacted with a monomer.
it can. Other than the monomers represented by (A) and (B)
The copolymerization ratio of other copolymerizable monomers is
30% by mass or less in the nomer, more preferably 20% by mass
It is as follows. Such monomers include Polymer Hand
book 2nd ed., J. Brandrup, WileyInterscience, (197
5) Use the one described in Chapter 2, Page 1-483
I can do it. For example, acrylic acid, methacrylic acid, acrylic acid
Esters, methacrylates, acrylamide
, Methacrylamides, allyl compounds, vinyl ether
Addition-polymerizable unsaturated compounds selected from
Examples include compounds having at least one sum bond
it can. Specifically, the following monomers can be mentioned:
it can. Acrylic acid esters: methyl acrylate, a
Ethyl crylate, propyl acrylate, chloroethyl acetate
Acrylate, 2-hydroxyethyl acrylate, tri
Methylolpropane monoacrylate, benzyl acrylic
Rate, methoxybenzyl acrylate, furfuryl
Chlorate, tetrahydrofurfuryl acrylate, etc.
Methacrylates: methyl methacrylate, methacrylate
Ethyl laurate, propyl methacrylate, chloroethyl ester
Tacrylate, 2-hydroxyethyl methacrylate,
Trimethylolpropane monomethacrylate, benzyl
Methacrylate, methoxybenzyl methacrylate,
Rufuryl methacrylate, tetrahydrofurfuryl meta
Chryrate, etc. Acrylamide: Acrylamide, N-
Alkylacrylamide (the alkyl group has 1 carbon atom)
~ 3, such as methyl, ethyl, propyl
Group), N, N-dialkylacrylamide (alkyl group)
As those having 1 to 3 carbon atoms), N-hydroxyethyl
-N-methylacrylamide, N-2-acetamido
Chill-N-acetylacrylamide and the like. Methacrylic
Mides: methacrylamide, N-alkyl methacrylic
Mido (the alkyl group has 1 to 3 carbon atoms, for example
Methyl group, ethyl group, propyl group), N, N-dialkyl
Rumethacrylamide (the alkyl group has 1 to 3 carbon atoms)
), N-hydroxyethyl-N-methyl methacrylate
Luamide, N-2-acetamidoethyl-N-acetyl
Such as methacrylamide. Allyl compounds: allyl esters
(Eg allyl acetate, allyl caproate, caprylic acid)
Allyl, allyl laurate, allyl palmitate,
Allyl allate, allyl benzoate, allyl acetoacetate,
Allyl lactate), vinyl such as allyloxyethanol
Ethers: alkyl vinyl ethers (eg hexyl)
Vinyl ether, octyl vinyl ether, decyl vinyl
Ether, ethyl hexyl vinyl ether, methoxy
Ethyl vinyl ether, ethoxy ethyl vinyl ether
, Chloroethyl vinyl ether, 1-methyl-2,2
-Dimethylpropyl vinyl ether, 2-ethylbutyl
Vinyl ether, hydroxyethyl vinyl ether, di
Ethylene glycol vinyl ether, dimethylamino ester
Til vinyl ether, diethylaminoethyl vinyl ether
Tellurium, butylaminoethyl vinyl ether, benzyl vinyl
Nyl ether, tetrahydrofurfuryl vinyl ether
Vinyl esters such as: vinyl vinylate, vinyl iso
Butyrate, vinyl trimethyl acetate, vinyl die
Chill acetate, vinyl valerate, vinyl capro
, Vinyl chloroacetate, vinyl dichloroacetate
, Vinyl methoxyacetate, vinyl butoxyacete
, Vinyl lactate, vinyl-β-phenylbutyrate
And vinyl cyclohexyl carboxylate. Dialkyl itaconates: dimethyl itaconate
Chill, diethyl itaconate, dibutyl itaconate, etc.
Dialkyl esters or monoalkyl esters of fumaric acid
Steal: Dibutyl fumarate and other croton
Acid, itaconic acid, acrylonitrile, methacrylonitrile
Ru, maleonitrile, styrene, etc. It should be noted that the electrolytic hook, which has been favorably used in the past, has been used.
Some of the fluorine-based chemical products manufactured by the raw material method are
It is a substance with low biodegradability and low degradability, and its degree is light
There is concern about having reproductive toxicity and developmental toxicity though it is very small.
It is. More fluorine-based chemical products used in the present invention
It is also industrially advantageous that it is a highly environmentally safe substance.
It can be said that it is a point. In the fluoropolymer used in the present invention,
Amount of fluoroaliphatic group-containing monomer (A) used
Is 5 to 90 mass based on the total amount of the fluoropolymer
%, Preferably 5 to 70% by mass, more preferred
7 to 60% by mass, particularly preferably 40 to 70 quality
The amount is in the range of%. Polyoxyalkylene group-containing ethyl
The amount of the unsaturated unsaturated monomer (B) is the amount of the fluoropolymer.
10 to 95% by weight based on the total weight, preferably
15-70 mass%, more preferably 20-60 quality
%. Preferred fluoropolymers used in the present invention
Preferred weight average molecular weight is 3,000 to 200,000
Is preferred, and 6,000-80,000 is more preferred
Yes. Further, the fluorine-based polymer used in the present invention.
The preferred addition amount is a photosensitive composition for the image forming layer.
0.005-8 quality with respect to product (coating component excluding solvent)
In the range of 0.01% by mass, preferably 0.01-5% by mass.
More preferably in the range of 0.05 to 3% by mass.
is there. Addition amount of fluorine-based polymer is not 0.005% by mass
If full, the effect is insufficient, and more than 8% by mass
If the coating film is not sufficiently dried,
Adversely affects the performance (for example, sensitivity). In this case, the polymerization initiator is known in the art.
For example, benzoic peroxide
, Peroxides such as diacyl peroxide, azobisisobutyro
Azolation of nitrile, phenylazotriphenylmethane, etc.
Compound, Mn (acac) _Three Metal chelate compounds such as
Examples include transition metal catalysts that cause dical polymerization. Further, if necessary, lauryl mercapta
, 2-mercaptoethanol, ethylthioglycol
Chain transfer agents such as acids, octylthioglycolic acid, and more
Cups such as γ-mercaptopropyltrimethoxysilane
Add ring chain-containing thiol compounds and other additives such as chain transfer agents
Can be used. In addition, photosensitivity in the presence of a photosensitizer or photoinitiator
Or polymerization using radiation or heat as an energy source.
However, the fluorine-based random or block used in the present invention
A lock copolymer can be obtained. The polymerization is carried out either in the presence or absence of a solvent.
However, in the presence of solvent from the viewpoint of workability
Is preferred. Solvents include ethanol, isopropyl
Pill alcohol, n-butanol, iso-butanol
, Alcohols such as tert-butanol, aceto
, Methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as tilamyl ketone, methyl acetate, ethyl acetate
Butyl acetate, methyl lactate, ethyl lactate, butyl lactate
Esters such as methyl 2-oxypropionate, 2-
Ethyl oxypropionate, 2-oxypropionate
Lopyl, butyl 2-oxypropionate, 2-methoxy
Methyl propionate, ethyl 2-methoxypropionate
, Propyl 2-methoxypropionate, 2-methoxy
Monocarboxylic acid esters such as butyl propionate, di
Methylformamide, dimethyl sulfoxide, N-methyl
Polar solvent such as lupyrrolidone, methyl cellosolve, celloso
Rub, butyl cellosolve, butyl carbitol, ethyl
Ethers such as cellosolve acetate, propylene glycol
Coal, propylene glycol monomethyl ether, plastic
Lopylene glycol monomethyl ether acetate
Lopylene glycol monoethyl ether acetate
Such as propylene glycol monobutyl ether acetate
Propylene glycols and their esters 1,1,1
-Halogen-based solutions such as trichloroethane and chloroform
Agents, ethers such as tetrahydrofuran and dioxane,
Aromatics such as benzene, toluene, xylene, and more
Fluorooctane, perfluorotri-n-butylamine, etc.
Fluorinated inert liquids, etc.
Either can be used. Depending on the polymerizability of each monomer, the reaction vessel contains
Drop polymerization method that polymerizes while dropping the monomer and initiator
Is also effective for obtaining a polymer having a uniform composition. The
In addition, column filtration and reprecipitation of polymer with a high fluorine content
Repelled by removing it by manufacturing, solvent extraction, etc.
Can be improved. Next, the composition for the image forming layer in the present invention.
Necessary when preparing a photosensitive resin composition as a product
The other components will be described. Fluoropolymer described above
The photosensitive resin composition for an image forming layer containing
In addition to the base polymer, at least the photosensitive compound or
Contains a photothermal conversion agent. (Positive photosensitive resin composition)
As the positive photosensitive resin composition, a photosensitive compound is used.
The solubility or swelling in the developer before and after exposure.
It can be used if it changes, but it is
Preferred examples include o-quinonediazide compounds
It is done. For example, alkali-soluble resin and o-quinonedia
Field of positive photosensitive resin composition containing zido 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-sulfo
Nyl chloride and resorcin-pyrogallol / acetone
Esters with co-condensation resins; Japanese Patent Publication No. 56-45,127
A polymer having a hydroxyl group at the end described in the publication
1,2-Naphthoquinone-2-diazide-5-s in reester
Esterified sulfonyl chloride;
N- (4-hydride) described in Japanese Patent No. 0-24,641
Roxyphenyl) methacrylamide homopolymer or
Are copolymerized with other copolymerizable monomers.
Fluoroquinone-2-diazide-5-sulfonyl chloride
Stylized; Japanese Examined Patent Publication No. 54-29,922
1,2-naphthoquinone-2-diazide-5
-Sulfonyl chloride and bisphenol formal
Esters with dehydr resins; Japanese Examined Patent Publication No. 52-36,043
Homopo of p-hydroxystyrene described in the publication
To copolymer with limer or other copolymerizable monomer
1,2-naphthoquinone-2-diazide-5-sulfonylchloro
Esterified ride; 1,2-naphthoquinone-
2-diazide-5-sulfonyl chloride and polyhydroxy
There are esters with cibenzophenone. In addition, 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.
Can be mentioned in the publications
Yes. The content of the o-quinonediazide compound is
Usually 5 to 60 mass with respect to the total solid content of the photosensitive resin composition
%, More preferably 10 to 40% by mass. Photosensitive compounds other than o-quinonediazide and
A compound in which an alkali-soluble group is protected with an acid-decomposable group
Chemically amplified photosensitive material comprising a combination with a photoacid generator
Can be used. Photoacid generation used in chemical amplification systems
As the crude agent, known ones can be used. For example, SI Schlesinger, Photogr. S
ci. Eng., 18, 387 (1974), TSBalet al, Polymer, 2
1, 423 (1980) and the like diazonium salt, U.S. Pat.
No. 069,055, No. 4,069,056, JP-A-3-140140 etc.
Ammonium salt, DCNecker et al, Macromolecule
s, 17, 2468 (1984), CS Wen et al, Teh, Proc. Con
f.Rad. Curing ASIA, p478 Tokyo, Oct (1988), US
Phosphonium as described in Tomi No. 4,069,055, 4,069,056, etc.
Salt, JV Crivello et al, Macromorecules, 10 (6),
1307 (1977), Chem. & Eng. News, Nov. 28, p31 (198
8), European Patent No. 104,143, US Patent No. 339,049, No.
No. 410,201, JP 2-150848, JP 2-965514, etc.
The described iodonium salt, JV Crivello et al, Polyme
r J. 17, 73 (1985), JV Crivello et al. J. Org. C
hem., 43, 3055 (1978), WR Wattetal, J. Polymer S
ci., Polymer Chem. Ed., 22, 1789 (1984), JV Criv
elloet al, Polymer Bull., 14, 279 (1985), JV Cr
ivello et al, Macromorecules, 14 (5), 1141 (1981),
JV Crivello et al, J. Polymer Sci., Polymer Che
m. Ed., 17, 2877 (1979), European Patent No. 370,693, USA
Patent 3,902,114, European Patent 233,567, 297,443
No. 297,442, U.S. Pat.Nos. 4,933,377, 410,201
No., No. 339,049, No. 4,760,013, No. 4,734,444, No.
2,833,827, Korean Patent No. 2,904,626, 3,604,580
Sulfonium salts described in No. 3,604,581, etc. JV Crivello et al, Macromorecules,
10 (6), 1307 (1977), JV Crivelloet al, J. Polymer
Sci., Polymer Chem. Ed., 17, 1047 (1979), etc.
Selenonium salt, CS Wen et al, Teh, Proc. Conf.
Rad. Curing ASIA, p478 Tokyo, Oct (1988) etc.
Onium salts such as arsonium salts, U.S. Pat.No. 3,905,815
No., JP-B 46-4605, JP-A 48-36281, JP-A 55-32
070, JP 60-239736, JP 61-169835, JP
JP 61-169837, JP 62-58241, JP 62-212401
No., JP-A 63-70243, JP-A 63-298339, etc.
Organohalogen compounds, K. Meier et al, J. Rad. Curing,
13 (4), 26 (1986), TP Gill et al, Inorg.Chem., 1
9, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (1
2), 377 (1896), and organic metals described in JP-A-2-16145
/ Organic halides, S. Hayase et al, J. Polymer Sc
i., 25, 753 (1987), E. Reichmanis et al, J. Pholyme
r Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu
et al, J. Photochem., 36, 85, 39, 317 (1987), B. Am
it et al, Tetrahedron Lett., (24), 2205 (1973), D.
HR Barton et al, J. Chem Soc., 3571 (1965), P.
M. Collins et al, J. Chem. Soc., Perkin I, 1695 (197
5), M. Rudinstein et al, Tetrahedron Lett., (17),
1445 (1975), JW Walker et al J. Am. Chem. Soc.,
110, 7170 (1988), SCBusman et al, J. Imaging Tech
nol., 11 (4), 191 (1985), HMHoulihan et al, Macorm
olecules, 21, 2001 (1988), PMCollins et al, J. Ch
em. Soc., Chem. Commun., 532 (1972), S. Hayase et a
l, Macromolecules, 18, 1799 (1985), E. Reichmanis et
al, J. Electrochem. Soc., Solid State Sci. Techno
l., 130 (6), FMHoulihan et al, Macromolcules, 21,
2001 (1988), European Patent Nos. 0290,750, 046,083,
156,535, 271,851, 0,388,343, U.S. Patent
3,901,710, 4,181,531, JP-A-60-198538, Special
O-Nitrobenzyl-type protecting group described in Kaisho 53-133022 etc.
A photoacid generator having the following: M. TUNOOKA et al, Polymer Preprints Ja
pan, 35 (8), G. Berner et al, J. Rad. Curing, 13
(4), WJ Mijs et al, Coating Technol., 55 (697),
45 (1983), Akzo, H. Adachi et al, Polymer Preprints,
Japan, 37 (3), European Patent Nos. 0199,672, 84515,
199,672, 044,115, 0101,122, U.S. Pat.
618,564, 4,371,605, 4,431,774, JP-A 64-
18143, JP-A-2-245756, Japanese Patent Application 3-140109, etc.
Photolysis, such as the listed iminosulfonate,
Compounds that generate phonic acid, described in JP-A-61-166544
The disulfone compound can be mentioned. By irradiation with these actinic rays or radiation
The amount of the compound that generates acid upon decomposition is determined by the photosensitive resin
Usually based on the total weight of the composition (excluding coating solvent)
Used in the range of 0.001 to 40% by mass, preferably
0.01 to 20% by mass, more preferably 0.1 to 5% by mass
Used in the range of%. Further, the alkali-soluble group is protected with an acid-decomposable group.
As a compound, a —C—O—C— or —C—O—Si— bond is used.
The following examples can be given. (A) at least one orthocarboxylic acid ester and
And those selected from the group of carboxylic acid amide acetals
Therefore, the compound can have polymerizability and
Lutocarboxylic acid ester and carboxylic acid amide aceta
Group may be included as a bridging element in the main chain, and
Is a compound that may be contained in the side chain, (b) in the main chain
Including those selected from the repetitive acetal and ketal groups
Oligomeric or polymeric compound, (c) at least
A kind of enol ester or N-acylaminocarbo
A compound comprising an ate group, (d) a β-ketoester or
a cyclic acetal or ketal of β-ketoamide, (e) a compound containing a silyl ether group,
(F) a compound containing a silyl enol ether group, (g)
The aldehyde or ketone component is 0.
Monoaceter having solubility of 1 to 100 g / liter
Or (h) tertiary alcohol-based esters
-Tel, and (i) tertiary allylic or benzylic positions
Carboxylic esters and carbonates of alcohols. The above-mentioned type (a) that can be cleaved by an acid
The compound is described in German Patent Publication No. 2,610,842 and
No. 2,928,636. type
A mixture containing the compound of (b) is described in German Patent 2,30.
Described in US Pat. Nos. 6,248 and 2,718,254
It is. Compound of type (c) is published in European patent
No. 0,006,626 and 0,006,627
In the issue. The compound of type (d) is European
Patent Publication No. 0,202,196,
The compound used as type (e) is the German Patent Publication No.
3,544,165 and 3,601,264
It is described in. The compound of type (f) is a German patent
Published No. 3,730,785 and No. 3,730,7
83, and the compound of type (g) is
This is described in Japanese Patent Publication No. 3,730,783.
Compound of type (h) is for example US Pat. No. 4,603,603.
The compound of type (i) is described in Example 101
For example, US Pat. No. 4,491,628 and JM Frec
Also in het et al. (J. Imaging Sci. 30, 59-64 (1986))
Has been described. Compounds protected with these acid-decomposable groups
The content of the product is usually based on the total solid content of the photosensitive resin composition
1-60 mass%, more preferably 5-40 mass%
The The photosensitive resin composition contains water insoluble and alkaline.
Synthetic resin soluble in aqueous solution (hereinafter referred to as alkali-soluble resin)
May be added. As alkali-soluble resin
For example, phenol / formaldehyde resin, Crezo
Formaldehyde resin, phenol cresol
・ Formaldehyde co-condensation resin, phenol-modified xyle
Resin, polyhydroxystyrene, polyhalogenated hydride
Loxystyrene, N- (4-hydroxyphenyl) metac
Rylamide copolymer, hydroquinone monomethacrylate
In addition to carbonate copolymers, described in JP-A-7-28244
Sulfonylimide-based polymer, JP-A-7-36184
Examples include carboxyl group-containing polymers described in
It is done. Others disclosed in JP-A-51-34711
Acrylic containing phenolic hydroxyl groups
Resin, sulfonamido described in JP-A-2-866
Acrylic resin having a group, urethane resin, etc.
Various alkali-soluble polymer compounds can also be used.
Yes. These alkali-soluble resins or polymer compounds
Is a number average molecular weight of 500 to 20,000
Those having a weight of 200 to 60,000 are preferred. Take
Is there one kind of alkali-soluble resin or polymer compound?
May be used in combination of two or more types,
It is used in an addition amount of 80% by mass or less of the form. 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 solid content of the composition.
It is used in an addition amount of 90% by mass or less of the form. In the photosensitive resin composition, if necessary, further.
Cyclic acid anhydride to increase sensitivity, possible immediately after exposure
Print-out agent for obtaining visual image, dyeing as image colorant
A charge, other fillers, etc. can be added. In the photosensitive resin composition of the present invention,
In order to increase sensitivity, cyclic acid anhydrides, phenols,
It is preferable to add mechanical acids. As cyclic acid anhydride
Is described in U.S. Pat. No. 4,115,128.
As phthalic anhydride, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride, 3,6-endooxy-Δ
4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride
Phosphoric acid, maleic anhydride, chloromaleic anhydride, α-fluoro
Phenyl maleic anhydride, succinic anhydride, pyromellitic anhydride
There is tonic acid. As phenols, bisphenol
A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydro
Xylbenzophenone, 2,4,4'-trihydroxybenzene
Nzophenone, 4,4 ', 4 "-trihydroxy-trif
Enylmethane, 4,4 ', 3 ", 4" -tetrahydroxy
Si-3,5,3 ', 5'-tetramethyltriphenylmeta
For example. 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,
The proportion of enols and organic acids in the photosensitive resin composition
The total solid content in the composition is 0.05 to 15 mass
% Is preferable, and more preferably 0.1 to 5% by mass.
The Baking 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 that 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 addition amount is 0.3 to 15 with respect to the total solid content of the composition.
A range of mass% is preferred. In the photosensitive resin composition of the present invention,
Photodecomposition products of compounds that generate acid substances upon photolysis
Organic dyes that change their colors by interacting with each other
At least one kind is used. Such organic dyes
As diphenylmethane, triarylmethane
, Thiazine, oxazine, phenazine, xanthine
Ten, anthraquinone, iminonaphthoquinone, a
A zomethine dye can be used. Specifically
It ’s like that. 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 [Hodogaya Chemical Co., Ltd.], [Pure] Pure Blue [Sumitomo Mikuni Chemical
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,
Japanese Utility Model Publication No. 62-293471, Japanese Patent Application No. 4-11284
As a counter anion as shown in the specification No. 4
Those having phonic acid compounds are particularly useful. these
Dyes can be used alone or in combination, and the amount added is
0.3 to 15% by mass relative to the total weight of the photosensitive resin composition
Is preferred. In combination with other dyes and pigments as necessary
The amount used is 70 quality with respect to the total weight of the dye and pigment.
The amount is not more than%, more preferably not more than 50% by mass. (Negative photosensitive resin composition) Next, in the present invention,
The photosensitive resin composition is a negative type printing plate
Used as an image forming layer (photosensitive layer) for photopolymerizable printing plates
The negative photosensitive resin composition will be described. In the present invention
The negative photosensitive resin composition is a photopolymerizable photosensitive resin group.
In the case of a composition, the main component is the fluorine
In addition to polymer-based polymers, addition-polymerizable ethylenic double bonds
Containing compounds, photopolymerization initiators, etc.
A compound such as a combination inhibitor is added. 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 pentaacrean
Dipentaerythritol hexaacrylate, sol
Bitol triacrylate, sorbitol tetraacrylate
Rate, sorbitol pentaacrylate, sorbitol
Lehexaacrylate, tri (acryloyloxyethyl)
L) Isocyanurate, polyester acrylate
There are gomers. 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 pentamethacrylate
Sorbitol trimethacrylate, sorbitol
Tetramethacrylate, bis [p- (3-methacryloxy
Si-2-hydroxypropoxy) phenyl] dimethylmeta
Bis- [p- (methacryloxyethoxy) pheny
E) Dimethylmethane and the like. 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. Isochro
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 (R ⁷ ) COOCH ₂ CH (R ⁸ ) OH (A)
But R ⁷ And R ⁸ Is H or CH _Three Indicates. Also 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
In Japan Adhesion Association Vol. 20, No. 7, 300-30
8 pages (1984)
You can also use what has been introduced as a gomer
The In addition, the usage-amount of the compound containing these double bonds is
5 to 70% by mass, preferably 1 based on the solid content of all components
It is 0-50 mass%. Photopolymerizable photosensitive resin used in the present invention
As the photopolymerization initiator contained in the composition, the light source used
Various photopolymerizations known in patents, literature, etc., depending on the wavelength of
Initiator or a combination system of two or more photopolymerization initiators (light
A polymerization initiation system) can be appropriately selected and used. Example
For example, when light near 400 nm is used as the light source,
Jill, benzoin ether, Michler's ketone, Ant
Laquinone, thioxanthone, acridine, phenazine,
Benzophenone and the like are widely used. Further, visible light of 400 nm or more, Ar light
Laser, second harmonic of semiconductor laser, SHG-YAG
There are various photopolymerization initiation systems when using a laser as a light source.
For example, U.S. Pat. No. 2,850,44.
Certain photoreducible dyes described in No. 5, such as roseben
Gal, eosin, erythrosin, etc. or with dye
Systems in combination with photoinitiators, for example dyes
Amine complex initiation system (Japanese Patent Publication No. 44-20189), f
Oxaarylbiimidazole, radical generator and dye
Combination system (Japanese Patent Publication No. 45-37377), Hexaary
Rubiimidazole and p-dialkylaminobenzylidene
Ketone system (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-Open No. 54-15
5292), dyeing with cyclic cis-α-dicarbonyl compounds
System (JP-A-48-84183), cyclic triazine
And merocyanine dye system (Japanese Patent Laid-Open No. 54-151024)
No.) 3-ketocoumarin and activator system (Japanese Patent Laid-Open No. 52-11)
2681, Japanese Patent Laid-Open No. 58-15503), biimidazo
System of styrene, styrene derivative and thiol (JP 59-1)
40203), a system of organic peroxide and dye (Japanese Patent Laid-Open No. Sho 59)
-1504, JP-A-59-140203, JP-A-59
-189340, Japanese Patent Laid-Open No. 62-174203, Shoko
62-1641, US Pat. No. 4,766,055), dyeing
And a system of active halogen compounds (Japanese Patent Laid-Open No. 63-25890)
3, JP-A-2-63054, etc.), a system of a dye and a borate compound (JP-A 62-62)
143044, JP-A 62-150242, JP
64-13140, JP-A 64-13141, JP-A
64-13142, JP-A 64-13143, JP-A
JP 64-13144, JP-A 64-17048, JP
1-222903, JP-A-1-298348, JP-A-1
1-138204), a dye having a rhodanine ring
And radical generator system (Japanese Patent Laid-Open No. 2-179433,
Kaihei 2-244050), titanocene and 3-ketocumari
Dye systems (Japanese Patent Laid-Open No. 63-221110), titanose
And xanthene dyes, amino groups or urethane groups
Combination of addition-polymerizable ethylenically unsaturated compounds containing
Systems (JP-A-4-221958, JP-A-4-219)
756), a system of titanocene and specific merocyanine dyes
(JP-A-6-295061), titanocene and benzopi
A dye system having a orchid ring (JP-A-8-334897)
Etc. Use of these photoinitiators
The amount is 100 parts by mass of the ethylenically unsaturated compound.
0.05 to 100 parts by mass, preferably 0.1 to 70 parts by mass
Parts, more preferably in the range of 0.2 to 50 parts by weight
be able to. Further, the photopolymerizable photosensitive tree in the present invention.
In the oil composition, in addition to the above basic components, a photosensitive resin
Ethylene that can be polymerized during manufacture or storage of the composition
Low to prevent unwanted thermal polymerization of renically unsaturated compounds
It is desirable to add an amount of thermal polymerization inhibitor. Moderate heat
Polymerization inhibitors include haloid quinone and p-methoxyphene.
Diol, di-t-butyl-p-cresol, pyrogallol,
t-butylcatechol, benzoquinone, 4,4'-thiobi
(3-methyl-6-tert-butylphenol), 2,2'-
Methylene bis (4-methyl-6-tert-butylphenol),
N-nitrosophenylhydroxylamine cerium
Salt, N-nitrosophenylhydroxylamine alumini
Um salt and the like. Addition amount of thermal polymerization inhibitor is composition
About 0.01 to about 5% by mass based on the total solid content of the product is preferred
Yes. If necessary, prevent polymerization inhibition by oxygen
In order to induce higher fatty acids such as behenic acid and behenic acid amide
Add a conductor etc., and in the process of drying after coating,
It may be unevenly distributed on the surface. Amount of higher fatty acid derivative added
Preferably about 0.5 to about 10% by weight of the total solids of the composition
That's right. (Oxygen-blocking protective layer) The photosensitive tree of the present invention
Use a photopolymerizable oil composition as an image forming layer.
The lithographic printing plate precursor has oxygen on the image forming layer.
In order to prevent polymerization inhibition by
Can be provided. Water-soluble in oxygen barrier protective layer
Examples of the functional vinyl polymer include polyvinyl alcohol and
And its partial esters, ethers, and acetals,
Or a substantial amount that makes them necessary water-soluble
Copolymers containing a number of unsubstituted vinyl alcohol units
Is mentioned. As polyvinyl alcohol, 71-
100% hydrolyzed with a polymerization degree of 300-2400
The thing of the surroundings is mentioned. Specifically, PVA-10 manufactured by Kuraray Co., Ltd.
5, PVA-110, PVA-117, PVA-117
H, PVA-120, PVA-124, PVA-124
H, PVA-CS, PVA-CST, PVA-HC, PV
A-203, PVA-204, PVA-205, PVA-2
10, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-217E, PVA-2
20E, PVA-224E, PVA-405, PVA-4
20, PVA-613, L-8 and the like. Above
Polymers include 88-100% hydrolyzed polyvinyl chloride.
Nyl acetate chloroacetate or propionate
, Polyvinyl formal and polyvinyl acetal
And copolymers thereof. Other useful weight
The combination includes polyvinylpyrrolidone, gelatin and
Labia rubber, these are used alone or in combination
It may be used. In the present invention, an oxygen blocking protective layer is applied.
As a solvent to be used, pure water is preferable.
Alcohol, ethanol and other alcohols, acetone,
It is also possible to mix ketones such as ruethyl ketone with pure water.
Yes. And the density | concentration of the solid content in a coating solution is 1-20 mass%
Is appropriate. The oxygen barrier protective layer further improves coatability.
To improve the physical properties of the surfactant and film
A known additive such as a water-soluble plasticizer may be added. water
Examples of soluble plasticizers are propionamide,
Lohexanediol, glycerin, sorbitol, etc.
The In addition, water-soluble (meth) acrylic polymer
It may be added. The coating amount of the oxygen barrier protective layer is
About 0.1 / m by weight ² ~ 15 / m ² The range of is appropriate
The More preferably 1.0 / m ² ~ About 5.0 / m ² In
The (Other lithographic printing plate materials) The present invention is as described above.
Quinonediazide or an acid-decomposable group
Positive-type photosensitive tree using a compound having a Lucari-soluble group
Positive lithographic printing plate having an image forming layer having a fat composition
Original plate (also called positive PS plate), nebula using photopolymerization system
In addition to the ga PS plate, for example, the following types of lithographic printing plates
The material can be used similarly. (1) Negative type using an image forming layer containing a diazo resin
Planographic printing plate material. (2) Negative using an image forming layer containing a photocrosslinking resin
Type lithographic printing plate material. (3) Alkali-soluble binder, acid generator, acid (heat) rack
Negative type laser using image-forming layer containing bridging compound
Direct-drawing lithographic printing material. (4) Photothermal conversion agent, alkali-soluble binder and as required
In the state that is thermally decomposable and does not decompose, the alkali
A substance that substantially reduces the solubility of the soluble binder
In addition, a positive type laser direct drawing type using an image forming layer
Lithographic printing material. (5) Photothermal conversion agent / thermal radical generator / radical polymerizability
Negative type laser using an image forming layer containing a compound
Direct-drawing planographic printing plate. The materials used in each example will be described in detail below.
To do. As the diazo resin used in (1), for example, diazo resin
Condensation of azodiarylamines with active carbonyl compounds.
There are diazo resins typified by salt of products, photosensitivity, water insoluble
And soluble in organic solvents are preferred. Particularly suitable dia
Examples of the zo resin include 4-diazodiphenylamine,
4-diazo-3-methyldiphenylamine, 4-diazo-
4'-methyldiphenylamine, 4-diazo-3'-methyl
Diphenylamine, 4-diazo-4'-methoxydipheny
Ruamine, 4-diazo-3-methyl-4'-ethoxydiphe
Nylamine, 4-diazo-3-methoxydiphenylamine
Etc. and formaldehyde, paraformaldehyde, aceto
Aldehydes, benzaldehydes, 4,4'-bis-methoxy
Organic acid salt of condensate with dimethyl diphenyl ether etc.
Or an inorganic acid salt. As the organic acid at this time, for example, methanes
Sulfonic acid, benzenesulfonic acid, toluenesulfonic acid,
Xylene sulfonic acid, mesitylene sulfonic acid, dodecyl
Benzene sulfonic acid, naphthalene sulfonic acid, propyl
Naphthalenesulfonic acid, 1-naphthol-5-sulfone
Acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzene
Sulfonic acid, 2-hydroxy-4-methoxybenzopheno
-5-sulfonic acid, and the like.
Safluorophosphoric acid, tetrafluoroboric acid, thiocyan
An acid etc. are mentioned. Furthermore, Japanese Patent Laid-Open No. 54-30121
A diazo resin whose main chain is a polyester group;
Carboxylic anhydride described in JP-A-61-273538
Residue polymer and hydroxyl group diazo
Diazo resin obtained by reacting compounds; polyisocyanate
Reacting a compound with a diazo compound having a hydroxyl group
A diazo resin or the like can also be used. The amount of these diazo resins used depends on the composition.
A range of 0 to 40% by mass with respect to the solid content is preferable,
If necessary, two or more diazo resins may be used in combination.
Yes. When preparing a negative photosensitive resin composition,
Usually used with organic polymer binder. Such organic polymer
Examples of the binder include acrylic resin and polyamide resin.
Fat, polyester resin, epoxy resin, polyacetal
Resin, polystyrene resin, novolac resin, etc.
The Furthermore, in order to improve performance, known additives such as
Thermal polymerization inhibitors, dyes, pigments, plasticizers, stability improvers, etc.
Can be added. Suitable dyes include, for example, crystal
Violet, Malachite Green, Victoria Bull
-Methylene blue, ethyl violet, rhodamine
And basic oil-soluble dyes such as B. As a commercial product
For example, "Victoria Pure Blue BOH"
Tsuchiya Chemical Industry Co., Ltd.), “Oil Blue # 603”
(Orient Chemical Industry Co., Ltd.). face
Examples of the material include phthalocyanine blue and phthalose
Anine green, dioxazine violet, quinacrid
Don red and the like can be mentioned. As the plasticizer, for example, diethyl phthalate
, Dibutyl phthalate, dioctyl phthalate, lithium
Tributyl phosphate, Trioctyl phosphate, Tricrete phosphate
Jill, tri (2-chloroethyl) phosphate, tricitrate
Examples include butyl. Furthermore, as a known stability improver
For example, phosphoric acid, phosphorous acid, oxalic acid, tartaric acid,
Ngoic acid, citric acid, dipicolinic acid, polyacrylic acid,
Also use benzene sulfonate, toluene sulfonate, etc.
be able to. The amount of these various additives added is
Generally, the photosensitive resin composition solid
A range of 0 to 30% by mass per minute is preferred. As the photocrosslinking resin used in (2),
Photocrosslinking resin with affinity for aqueous alkaline developer
Is preferable. For example, in Japanese Examined Patent Publication No. 54-15711
Copolymers having cinnamic acid groups and carboxyl groups as described above;
Phenylenedia described in JP-A-60-165646
Polyester tree with crylic acid residue and carboxyl group
Fat: Phenyle described in JP-A-60-203630
Polyacrylic acid residues and polyphenols having phenolic hydroxyl groups
Ester resin; described in JP-B-57-42858
Phenylenediacrylic acid residue and sodium iminodisulfur
Polyester resin having a phonyl group;
An azido group and a carboxyl group on the side chain described in Japanese Patent No. 8552
Polymer having a group, described in JP-A-7-295212
Polymers with maleimide groups in the side chains can be used
The Alkali-soluble binder used in (3)
-The acid generator is the quinonediazide or acid content mentioned above.
A compound having an alkali-soluble group protected with a degradable group
Use the same material used for the positive PS plate used
Can. Acid (thermal) crosslinkable compound is the presence of acid
Refers to compounds that crosslink under, for example, hydroxymethyl
Group, acetoxymethyl group or alkoxymethyl group
Aromatic and heterocyclic compounds polysubstituted with
Among them, as a preferable example,
Compounds obtained by condensing aldehydes and aldehydes under basic conditions
Is mentioned. Preferred among the above compounds
For example, phenol and formaldehyde
Compounds condensed under basic conditions, m
-A compound obtained from cresol and formaldehyde,
Compound obtained from bisphenol A and formaldehyde
From 4,4'-bisphenol and formaldehyde
Obtained compounds and others, GB No. 2,082,339
And compounds disclosed as resole resins
The 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
Monomers and oligomers disclosed in No. 64, melamine
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. Embedded image Where L ₁ ~ L ₈ Are 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 5% of the total solid content of the image forming layer.
~ 80% by weight, preferably 10-75% by weight, particularly preferred
Alternatively, it is used in an addition amount of 20 to 70% by mass. Acid crosslinking
That can be obtained when the addition amount of the functional compound is less than 5% by mass
The durability of the image forming layer of the printing plate material deteriorates, and 80
Exceeding mass% is not preferable in terms of stability during storage. Alkali-soluble binder used in (4)
Is used in the positive PS plate using quinonediazide described above.
The same materials as used can be used. Thermal decomposition
In the state of being soluble and not decomposing,
Substances that substantially reduce the solubility of the
Various onium salts, quinonediazide compounds, etc.
Excellent in reducing the solubility of resoluble binders
And is preferably used. Diazoni as onium salt
Umum salt, ammonium salt, phosphonium salt, iodonium
Salt, sulfonium salt, selenonium salt, arsonium
A salt etc. can be mentioned. As an onium salt used in the present invention
For example, SISchlesinger, P
hotogr. Sci. Eng., 18, 387 (1974), TSBal et al.,
Polymer, 21, 423 (1980), JP-A-5-1823030, etc.
Diazonium salt, U.S. Pat.Nos. 4,069,055, 4,063
No. 9,056, ammonium described in JP-A-3-140140, etc.
Salt, DCNecker et al., Macromolecules, 17, 2468 (19
84), CSWen et al., Teh, Proc. Conf. Rad. Curing
ASIA, p478, Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
Phosphonium salts described in No. 4,069,056, etc., JVCri
vello et al., Macromolecules, 10 (6), 1307 (1977), C
hem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049 and 410,201, JP
Iodonium as described in JP-A-2-150848, JP-A-2-965514, etc.
Salt, [VC] JVCrivello et al., Polymer J. 17, 73
(1985), JVCrivello et al., J. Org. Chem., 43, 30
55 (1978), WRWatt et al., J. Polymer Sci., Polyme
r Chem. Ed., 22, 1789 (1984), JVCrivello et al., P
olymer Bull., 14,279 (1985), JVCrivello et al., M
acromolecules, 14 (5), 1141 (1981), JVCrivello eta
l., J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (19
79), European Patent No. 370,693, US Patent No. 3,902,114,
European Patent Nos. 233,567, 297,443, 297,442, US
National Patent Nos. 4,933,377, 410,201, 339,049,
4,760,013, 4,734,444, 2,833,827, Germany
To permit 2,904,626, 3,604,580, 3,604,581 etc.
The described sulfonium salt, JVCrivello et al., Macromo
lecules, 10 (6), 1307 (1977), JVCrivello et al.,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979)
Selenonium salts described in the above, CSWen et al., Teh, Pro
c. Conf. Rad. Curing ASIA, p478, Tokyo, Oct (1988) etc.
And the arsonium salts described in the above. In the present invention, among these, in particular dia
Zonium salts are preferred. Also particularly suitable diazonium
Examples of the salt include those described in JP-A-5-158230.
Can be mentioned. Suitable quinonediazide compounds
May include o-quinonediazide compounds. O-Quinonediazide used in the present invention
The compound has at least one o-quinonediazide group
This compound increases alkali solubility by thermal decomposition.
Yes, compounds with various structures can be used. Tsuma
O-quinonediazide is soluble in alkali by thermal decomposition
Losing the binder's ability to inhibit dissolution and o-quinonedia
Both Zido itself turns into an alkali-soluble substance
This helps the solubility of the sensitive material system. Used in the present invention
Examples of the o-quinonediazide compound to be obtained include J.
“Wright-Sensitive Systems” by Korser (Joh
n Wiley & Sons. Inc.) pp. 339-352
Compounds can be used, but especially various aromatic polyhydroxys
O-key reacted with compound or aromatic amino compound
Non-diazide sulfonic acid ester or sulfonic acid ester
Mid is preferred. In addition, Japanese Patent Publication No.43-28403
Benzoquinone- (1,2) -di
Azidosulfonic acid chloride or naphthoquinone
(1,2) -Diazide-5-sulfonic acid chloride and pyro
Esters with gallol-acetone resin, US Pat.
Ben described in 6,120, 3,188,210, etc.
Zoquinone- (1,2) -diazide sulfonic acid chloride
Or naphthoquinone- (1,2) -diazide-5-sulfonic acid
Chloride and phenol-formaldehyde resin
Steal is also preferably used. Further, naphthoquinone- (1,2) -diazide
-4-Sulphonic acid chloride and phenol-formalde
With hydride resin or cresol-formaldehyde resin
Esters of naphthoquinone- (1,2) -diazide-4-s
Between sulfonic acid chloride and pyrogallol-acetone resin
Esters are preferably used as well. Other useful o
-As quinonediazide compounds, many patent-related
There are reports in the literature and it is known. For example, JP-A-47-530
No. 3, JP-A 48-63802, JP-A 48-63803, JP-A 48-63
96575, JP-A 49-38701, JP-A 48-13354, JP
Sho 41-11222, Shoko 45-9610, Shoko 49-17481,
U.S. Pat.Nos. 2,797,213, 3,454,400, 3,554,
No.323, No.3,573,917, No.3,674,495, No.3,78
No. 5,825, British Patent No. 1,277,602, No. 1,251,345,
No. 1,267,005, No. 1,329,888, No. 1,330,932
No., German Patent No. 854,890, etc.
You can list what is listed. O-Quinonediazide used in the present invention
The addition amount of the compound is preferably the total solid content of the lithographic printing plate material
1 to 50% by mass, more preferably 5 to 30%
% By weight, particularly preferably in the range of 10 to 30% by weight.
These compounds can be used alone, but several
May be used as a mixture. o-Quinonediazide
If the added amount of the compound is less than 1% by mass, the image recordability is poor.
On the other hand, if it exceeds 50% by mass, the durability of the image area is poor.
Or sensitivity decreases. The counter ion of the onium salt is tetrafluoride.
Boric acid, hexafluorophosphoric acid, triisopropylnaphthalene
Sulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfur
Rufosalicylic acid, 2,5-dimethylbenzenesulfone
Acid, 2,4,6-trimethylbenzenesulfonic acid, 2-ni
Trobenzenesulfonic acid, 3-chlorobenzenesulfone
Acid, 3-bromobenzenesulfonic acid, 2-fluorocapri
Lunaphthalenesulfonic acid, dodecylbenzenesulfone
Acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy
Droxy-5-benzoyl-benzenesulfonic acid, and
Paratoluenesulfonic acid etc. can be mentioned. this
Among them, in particular, hexafluorophosphate, triisopropyl naphthalate
Phthalenesulfonic acid or 2,5-dimethylbenzenesulfone
Alkyl aromatic sulfonic acids such as acids are preferred. o
The addition amount of the above compounds other than the -quinonediazide compound is
Preferably 1-50 with respect to the total solid content of the lithographic printing plate material
% By weight, more preferably 5-30% by weight, particularly preferred
Or in the range of 10 to 30% by mass. As a specific example of the material used in (5)
List the examples listed above as examples of photopolymerization systems
Can do. Many photoinitiators are thermal radical generators and
Even useful. Also, azobis compounds (azobisi
Sobutyronitrile) and diazonium compounds are also thermally polymerized.
Can be used as an initiator. Common compounds for addition polymerization
It is. In addition, the photothermal conversion agent can absorb the light from the exposure light source.
Any material can be used, so photopolymerization
All the dye groups exemplified in the system are applicable. However, in fact
High power laser light for heat mode exposure
The source is mainly a (near) infrared light source of 750 nm or more.
As the photothermal conversion agent is currently the most
Useful are compounds that can absorb (near) infrared light.
A variety of IR absorbers are available.
Also preferably used is heptamethine cyanine dye
And phthalocyanines and carbon black. The photosensitive resin composition used in the present invention.
Some of them are hydrophobic to improve the ink fillability of the image.
Various resins having a group such as octylphenol
Mualdehyde resin, t-butylphenol / formal
Dehydric resin, t-butylphenol benzaldehyde
Resin, rosin modified novolak resin, and modified novo
O-Naphthoquinonediazidesulfonic acid s of rack resin
Tell, etc .; plasticizers to improve the flexibility of the coating, eg
Dibutyl phthalate, dioctyl phthalate, butylglyco
Rate, tricresyl phosphate, dioctyl adipate
Various additives can be added according to various purposes.
The These addition amounts are set to 0. 0 to the total solid content of the composition.
The range of 01-30 mass% is preferable. Furthermore, 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 in the range of 2 to 40% by mass with respect to the total solid content of the composition.
preferable. In the photosensitive resin composition of the present invention,
In order to widen the development latitude, JP-A-62
-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 resin composition in the total solid content of the composition
0.05 to 15% by mass is preferable, and more preferable.
Is 0.1-5 mass%. In the photosensitive resin composition of the present invention,
Is a yellow dye, preferably having an absorbance at 417 nm of 436
Add a yellow dye that has 70% or more of the absorbance at nmm.
be able to. In accordance with the present invention, a fluoropolymer was included.
When obtaining photosensitive materials for planographic printing plates from photosensitive resin compositions
In this case, it is provided as an image forming layer on the support. In the present invention
The photosensitive resin composition containing the fluorine-based polymer in
Dissolve or dissolve in the following organic solvents
Is dispersed, applied to a support and dried. With organic solvent
Any known and conventional ones can be used, but the boiling point
40 ° C to 200 ° C, especially 60 ° C to 160 ° C
Is selected from the advantages in drying. Of course, book
The one that the fluoropolymer of the invention dissolves is selected.
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 mass.
Is appropriate. As a method for applying the composition in the present invention,
For example, roll coating, dip coating
Air knife coating, gravure coating,
Gravure offset coating, hopper coating
, Blade coating, wire doctor coating
After drying, methods such as coating and spray coating are used.
0.3 to 4.0 g / m in weight ² Is preferred. Coating
The smaller the exposure, the smaller the exposure to get an image.
However, the film strength decreases. As the amount of application increases
As a result, the amount of exposure is required, but the photosensitive film becomes stronger.
For example, when used as a printing plate, the number of printable sheets is high (high
A printing plate is obtained. The photosensitive resin composition coated on the support
Drying is usually performed with heated air. Heating
30 ° C to 200 ° C, especially 40 ° C to 140 ° C is preferred
It is. The drying temperature is only kept constant during drying.
Alternatively, a method of increasing in a stepwise manner can be performed. Also dry
In some cases, the wind can be successfully dehumidified.
The The heated air is 0.1 m / second to 3 to the coated surface.
Supply at a rate of 0m / second, especially 0.5m / second to 20m / second
It is preferable to do this. (Matte layer) Provided as described above.
The surface of the image forming layer is subjected to contact exposure using a vacuum printing frame.
To reduce the vacuuming time and prevent burning
Therefore, it is preferable to provide a mat layer. Specifically,
Kaisho 50-125805, Shoko 57-6582, the same
MA as described in each publication of 61-28986
A method for providing a heating layer is disclosed in Japanese Patent Publication No. 62-62337.
Method of heat-sealing solid powder as described
Is mentioned. (Support) Used for photosensitive lithographic printing plate, etc.
The support is a dimensionally stable plate-like material.
Used as a support for, and preferably used
Can. Such supports include paper, plastic.
(Eg polyethylene, polypropylene, police
Paper, such as aluminum.
(Including aluminum alloys), zinc, iron, copper, etc.
Metal plates such as cellulose diacetate, cellulose triacetate
, Cellulose propionate, cellulose butyrate, butyric acid
Cellulose acetate, cellulose nitrate, polyethylene terf
Talate, polyethylene, polystyrene, polypropylene
, Polycarbonate, polyvinyl acetal, etc.
Such as plastic films
Minated or vapor-deposited paper or plastic film
Film is included, but aluminum plate is particularly preferred.
Yes. Aluminum plate is pure aluminum plate and aluminum plate.
Um alloy plates are included. Various aluminum alloys
For example, silicon, copper, manganese, mug
Nesium, chromium, zinc, lead, bismuth, nickel, etc.
Alloys of aluminum and aluminum are used. These pairs
The composition is neglected in addition to some iron and titanium
It also contains a possible amount of impurities. The support is surface-treated as necessary. Example
For example, in the case of a photosensitive lithographic printing plate, the surface of the support is hydrophilic.
Is applied. Also metal, especially aluminum surface
In the case of a support having a graining treatment, sodium silicate
Aqueous solution of potassium, potassium zirconate fluoride, phosphate, etc.
Surface treatment such as immersion treatment or anodizing treatment
It is preferable that it is made. US Pat. No. 2,7
As described in the 14,066 specification,
And then dipped in an aqueous solution of sodium silicate.
Minium plate in US Pat. No. 3,181,461
Anodized aluminum plate as described
And then immersed in an aqueous alkali metal silicate solution.
Are also preferably used. The above anodizing treatment
Inorganic acids such as phosphoric acid, chromic acid, sulfuric acid, boric acid,
Or organic acids such as oxalic acid and sulfamic acid, or these
An aqueous solution or non-aqueous solution of one or more of the above
Current in an electrolyte solution with an aluminum plate as the anode
It is carried out by doing. 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 resin provided on it
In order to prevent harmful reactions with the composition and to adhere to the image forming layer
It is given to improve the properties. aluminum
Roll the surface as needed prior to graining the plate
Remove oil and expose clean aluminum surface
Therefore, pretreatment of the surface may be performed. For the former
For example, a solvent such as trichlene or a surfactant is used.
Yes. For the latter, sodium hydroxide, potassium hydroxide
Widely used methods using alkali etching agents such as um
It has been broken. As the 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
0.3-40g / m per minute ² To be done
Is most preferred, but above or below this
It doesn't matter if it exists. 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 / m ² It 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, smut is generated, so normal
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 nickel 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 mass, and the liquid temperature is 5 to 70.
° C, current density 0.5-60 amps / dm ² , Voltage 1
A range of 100V and electrolysis time of 30 seconds to 50 minutes is appropriate.
The Of these anodizing treatments, the UK patent
In sulfuric acid as described in US Pat. No. 1,412,768
Method of anodizing at high current density and US Pat. No. 3,5
An electrolytic bath containing phosphoric acid described in No. 11,661
The method of anodizing is preferred. Rough surface as above
Anodized and anodized aluminum plate is required
Depending on the case, it may be hydrophilized.
U.S. Pat. Nos. 2,714,066 and 3,18.
Alkali metal silicon as disclosed in US Pat. No. 1,461
Kate, for example, sodium silicate aqueous solution or Shoko 3
Zirconium fluoride disclosed in JP-A-622063
Potassium mumate and U.S. Pat. No. 4,153,461
Treated with polyvinylphosphonic acid as disclosed in the specification.
There is a way to manage. (Organic undercoat layer) Photosensitive lithographic printing plate of the present invention
Before applying the image forming layer, provide an organic subbing layer.
Is preferable for reducing the remaining image forming layer in the non-image area. Or
Examples of organic compounds used in organic undercoat layers
Carboxymethylcellulose, dextrin, ara
Amino groups such as beer gum and 2-aminoethylphosphonic acid
Phosphonic acids having a phenyl group which may have a substituent
Phosphonic acid, naphthylphosphonic acid, alkyl phosphone
Acid, glycerophosphonic acid, methylenediphosphonic acid and
Organic phosphonic acids such as ethylenediphosphonic acid, substituents
Phenyl phosphoric acid, naphthyl phosphoric acid, alkyl
Organophosphates such as luric acid and glycerophosphoric acid, substitution
Phenylphosphinic acid, naphthylphos
Finic acid, alkylphosphinic acid and glycerophosphine
Organic phosphinic acids such as phosphoric acid, glycine and β-arani
And other amino acids, and salts of triethanolamine
Hydrochlorides of amines with hydroxyl groups such as acid salts
However, it may be used as a mixture of two or more. 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 mass of the above 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 mass, preferably 0.05.
-5 mass%, immersion 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. (HO) y-R ⁹ -(COOH) z (a) where R ⁹ Is an optionally substituted substituent having 14 or less carbon atoms.
Represents a rylene group, and y and z 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. ² Is appropriate
Preferably 2 to 70 mg / m ² It is. above
Covering amount is 2mg / m ² If it is less, sufficient printing performance can be obtained.
I can't. 100 mg / m ² Same for larger
It is. (Back coat) Necessary for the back surface of the support.
Depending on the situation, a back coat is provided. Such a backcoat
As an example, the organic organic materials described in JP-A-5-45885
Molecular compounds and those described in JP-A-6-35174
Hydrolysis and polycondensation of organic or inorganic metal compounds
A coating layer made of a metal oxide is preferably used.
It is. Of these coating layers, Si (OCH _Three ) _Four , Si (O
C ₂ H _Five ) _Four , Si (OC _Three H ₇ ) _Four , Si (OC _Four H ₉ ) _Four Kay
Elemental alkoxy compounds are cheap and readily available
The metal oxide coating layer is excellent in anti-developing solution, especially
preferable. (Exposure) Lithographic plate prepared as described above
The printing plate is usually subjected to image exposure and development processing. Image exposure
As an actinic ray light source used for
Lamp, metal halide lamp, xenon lamp, chemical
There are lamps and carbon arc lamps. As radiation,
There are electron beams, X-rays, ion beams, far-infrared rays, and the like. Ma
G-line, i-line, Deep-UV light, high-density energy beam
A laser beam is also used. Laser beam
As helium-neon laser, argon laser
ー 、 Krypton laser 、 Helium ・ Cadmium laser
-KrF excimer laser and the like. Leh
The direct printing type printing plate emits light from the near infrared to the infrared region
Light source with wavelength is preferred, solid state laser, semiconductor laser
Is particularly preferred. (Development) The photosensitive resin composition of the present invention is applied.
Preferred as a developer for use in a coated lithographic printing plate precursor
(A) at least one selected from non-reducing sugars
Containing sugars and (b) at least one base, pH
Is a developer in the range of 9.0 to 13.5. Below
The developer will be described in detail. In this specification,
Unless otherwise noted, development starts with a developer.
It means a liquid (narrowly defined developer) and a development 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 mass, more preferably
Is 1-20 mass%. 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
Described in TS OF ORGANIC ACIDS IN AQUEOUS SOLUTION
For example, 2,2,3,3-te
Trifluoropropanol-1 (PKa 12.74),
Trifluoroethanol (12.37), Trichloro
Alcohols such as ethanol (12.24);
Gin-2-aldehyde (12.68), pyridine-4-a
Aldehydes such as aldehyde (12.05), Salichi
Luric acid (13.0), 3-hydroxy-2-naphthoic acid
(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. Good
Preferred surfactants include anionic, cationic,
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 surfactants, 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
Naphthalenesulfonate 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 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.
0.001-10 mass in the developer
%, More preferably 0.01 to 5% by mass
It is. In the developer, various development stabilizers are used.
be able to. As a preferred example thereof, JP-A-6-
Polysaccharide of sugar alcohol described in Japanese Patent No. 282079
Glycol adduct, tetrabutylammonium hydro
Tetraalkylammonium salts such as xoxide, tetrabu
Phosphonium salts such as tilphosphonium bromide and
Iodonium such as diphenyliodonium chloride
A preferred example is a salt. Furthermore, JP-A-5
Anionic surfactants described in Japanese Patent No. 0-51324
Is an amphoteric surfactant, and JP-A-55-95946
Water-soluble cationic polymer described in JP-A-56-1
Water-soluble amphoteric polymer described in Japanese Patent No. 42528
Mention may be made of electrolytes. Further, a) disclosed in Japanese Patent Laid-Open No. 59-84241.
Organoboron compounds with added ruxylene glycol, special
Polyoxyethylene described in Japanese Laid-Open Patent Application No. 60-111246
Water-soluble field of Len-polyoxypropylene block polymerization type
Surfactant, polyoxy of JP-A-60-129750
Alkyle substituted with polyethylene / polyoxypropylene
Diamine compounds, disclosed in JP-A 61-215554
Polyethyleneglycol having a weight average molecular weight of 300 or more
, A cationic group disclosed in JP-A-63-175858
Fluorine-containing surfactants having the above, JP-A-2-39157
4 mol or more of ethylene oxide in the acid or alcohol of the publication
Addition of water-soluble ethylene oxide obtained by addition of side
Compounds and water-soluble polyalkylene compounds.
The If necessary, an organic solvent is added to the developer.
It is done. Such organic solvents have water solubility.
About 10% by mass or less is suitable, preferably 5 quality
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 organic solvent content is based on the total weight of the liquid used.
0.1 to 5% by mass. The amount of the surfactant used
It is closely related to the amount used, and 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 mass.
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 with 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 mass, the effect is not sufficient, and 1
If it is 0% by mass or more, the effect cannot be improved any further.
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 mass, more preferably 0.5 to 4
% By mass. 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 softening agent is used for its chelation and
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 mass%, more preferably 0.01 to 0.
It is in the range of 5% by mass. 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. A lithographic plate using the photosensitive resin composition of the present invention
As a developing solution for a printing plate precursor, JP-A-6-6
Developers described in Japanese Patent No. 282079 can also be used. this
Is SiO ₂ / M ₂ M of O (M represents an alkali metal)
The alkali metal silicate having a ratio of 0.5 to 2.0 and the hydroxyl group
4 mol or more of sugar alcohol with 5 mol or more of ethylene oxide
Addition of water-soluble ethylene oxide obtained by addition of side
A developer containing a compound. Sugar alcohol is sugar alcohol
Dehydride group and ketone group are reduced to the first and second, respectively.
It is a polyhydric alcohol corresponding to an alcohol group
The Examples of sugar alcohol shells include D, L-Tre
It, Elite, D, L-Arabit, Ribi
, Xyrit, D, L-Sorbit, D, L-Mannic
G, D, L-Exit, D, L-Talit, Zulsit,
Allozulcit, etc., and further condensed with sugar alcohol
Such as di, tri, tetra, penta and hexaglycerin
You can list them. The above water-soluble ethylene oxide addition compound
The product is 5 moles or more of ethylene per mole of the sugar alcohol.
It can be obtained by adding hydroxide. And more
If necessary, the propylene oxide is added to the lenoxide addition compound.
Block copolymerization of xoxide with acceptable solubility
May be. These ethylene oxide adducts alone
Or you may use combining 2 or more types. these
The amount of the water-soluble ethylene oxide addition compound is
0.001 to 5 mass% is suitable for the (use liquid)
More preferably, it is 0.001-2 mass%. This developer further includes development acceleration and present properties.
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 waste water 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 The present invention will be further described with reference to the following examples.
The However, the present invention is limited by these examples.
It is not a thing. Synthesis Example 1 Glass flask equipped with stirrer, condenser and thermometer
Methyl ethyl ketone (hereinafter abbreviated as MEK) 100
Add part by mass, heat to 75 ° C in a hot water bath, nitrogen stream
Lower 2,2,3,3,4,4,4-heptafluorobutyl acetate
Relate (I-1) 50 parts by mass, propylene oxide
Monoacrylate compound in side chain BLEMMER AP-
400 (Nippon Yushi Co., Ltd.) 45 parts by mass, ethylene
Monoacrylate compound with a side chain on the side
5 parts by mass of MER-AE-400 (Nippon Yushi Co., Ltd.)
100 parts by mass of methyl ethyl ketone as a polymerization initiator
V-601 (Wako Pure Chemical Industries, Ltd.) 1 part by weight of mixture
Was dropped by a dropping funnel over 2 hours. After dropping
The mixture was further stirred at 75 ° C. for 2 hours and further at 90 ° C. for 2 hours.
This high permeation chromatography
Measure the weight average molecular weight (polystyrene standard) of molecular compounds
As a result, it was 58,000. (Fluorine polymer
-(A)) Synthesis Example 2 Glass flask equipped with stirrer, condenser and thermometer
Fluorinated alkyl group-containing acrylate monomer (II
-6) 60 parts by mass, ethylene oxide and propylene
Monoacrylate compounds with side-chain copolymers with oxides
40 parts by weight of product and 200 parts by weight of MEK
Heated to 75 ° C under air flow, V-601 quality as initiator
10 parts lauryl mercaptan as part of chain transfer agent
Add a part and stir for 5 hours, then stir at 90 ° C for 2 hours.
It was. Gel permeation chromatography
Weight average molecular weight (polystyrene standard)
Was 8,300. (Fluorine-based poly
Mer (b)) [Synthesis Examples 3 to 6]
1 is synthesized as a fluorine-based polymer (c) to (f).
It was. [Table 1] [Examples 1 to 12, Comparative Examples 1 to 5] (Percentages in the following examples are unless otherwise specified.)
All are mass%. ) JIS A 1050 aluminum plate with a thickness of 0.24mm
A suspension of pamiston and water with an average particle size of about 2.1 μm
While supplying to the aluminum surface, the rotating knife shown below
Brush graining was performed with a Ron brush. First
The brush has a hair length of 100 mm, a hair diameter of 0.95 mm, and a flocking density.
70 / cm ² The second brush has a hair length of 80 mm and a hair diameter
0.295mm, flocking density 670 / cm ² Met. The
The rotation of lasilole was 250 rpm in all cases. The
10% water after rinsing and washing thoroughly
Immerse in sodium oxide at 60 ° C for 25 seconds for etching
Wash with water, neutralize with 20% nitric acid, and wash with water.
It was. These are the sinusoidal crossings under the condition of VA = 12.7V.
160 claw in 1% aqueous nitric acid solution using a waveform current
N / dm ² Electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode.
The surface roughness was measured and found to be 0.79 μm (Ra table
It was Subsequently, 1% sodium hydroxide aqueous solution
After being immersed in the solution at 40 ° C. for 30 seconds, in a 30% sulfuric acid aqueous solution
After soaking and desmutting at 60 ° C. for 40 seconds, 20
In 2% sulfuric acid aqueous solution, current density 2A / dm ² 1.6
g / m ² Anodic oxidation with direct current so that the oxide film weight of
Then, the substrate was adjusted. On the surface of the substrate treated in this way,
The undercoat liquid 1 was applied and dried at 80 ° C. for 30 seconds.
The coating amount after drying is 10 mg / m ² Met. (Undercoat liquid 1) -β-alanine 0.10 g -methanol 40 g -pure water 60 g In this way, a substrate (I) was produced. Then this board
On (I), the following image forming layer coating solution 1 is
At 12ml / m ² Apply and apply at 100 ° C for 1 minute
This was dried to obtain a positive photosensitive lithographic printing plate precursor. After drying
The coating amount of 1.15 g / m ² Met. (Image Forming Layer Coating Solution 1) Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 0.8 g ・ Cresol-formaldehyde novolak resin (meta, para ratio 6: 4, weight average molecular weight 8000): 1.5 g ・ Phenol-formaldehyde resin (weight average molecular weight 15,000): 0 .3 g poly [N- (p-aminosulfonylphenyl) acrylamide-co-normal butyl acrylate-co-diethylene glycol monomethyl ether methacrylate] (molar ratio of each monomer is 40:40:20, weight average molecular weight 40,0 in order) 00, number average molecular weight 20,000): 0.2 g p-normal octie Phenol-formaldehyde resin (described in US Pat. No. 4,123,279): 0.02 g. Naphthoquinone diazide-1,2-diazide-4-sulfonic acid chloride: 0.01 g. Tetrahydrophthalic anhydride: 0.02 g Pyrogallol: 0.05 g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine: 0.07 g-Dye obtained by changing the counter anion of Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.] to 1-naphthalenesulfonic acid: 0.045 g-Fluoropolymer (see Table 2): listed in Table 2 MEK / 1-methoxy-2-propanol: 15 g / 10 g In addition, photosensitive printing produced as described above.
For the plate, visually observe the surface of the image-forming layer application surface.
It was. The surface shape is the number of pinholes per square meter
Expressed as a number. In order to further reduce the vacuum contact time,
Mat as described in Japanese Kokai 61-28986
Layers were formed. Photosensitive lithographic seal created in this way
The printing plate precursor was evaluated by the following method. From solid and halftone dots
3 kW metal from a distance of 1.5 m
Fuji Photo after 1 minute exposure with halide lamp
The following is shown on PS processor 900V made by Film Co., Ltd.
Fuji Photo Film as image liquid 1 and finisher
FP2W (1: 1) manufactured by Mu Co., Ltd., 12 at 30 ° C
Developed for a second to prepare a lithographic printing plate. Then Laurent
Dainippon Ink as the R201 printing machine manufactured by DO
Printing was performed using GEOS-G (N) manufactured by
Until sufficient ink density is obtained in the image area at the start of printing.
The number of meats was examined and the number of meats was determined. The smaller the number
Good lithographic printing plate. In addition, the solid part of the printed material
Prints until smearing starts, and prints begin to smear
The printing durability was evaluated by determining the number. The higher the number of printed sheets, the better
Is a lithographic printing plate. The results are shown in Table 3. (Developer 1)-Pure water 90 wt%-D-sorbite 6 wt%-KOH 2.5 wt% [Table 3] As apparent from Table 3, the present invention is specified.
A lithographic printing plate precursor using a fluoropolymer of
The uniformity of the formed layer was excellent. Also for the lithographic printing plate
The original plate is an excellent lithographic printing plate that is both thick and durable.
Yeah. In contrast, the fluorine-based polymer that is outside the scope of the present invention.
The lithographic printing plate precursors of Comparative Examples 1 and 2 using a
The shape is not uniform, and flatness with poor inking and printing durability
A plate printing plate was given. Moreover, the surface shape of the light-sensitive material of Comparative Example 3 is the entire surface.
Because it was a mottled and non-uniform film, the number of printed sheets and printing durability
The test could not be performed. As above
Ming's lithographic printing plate precursor is a combination of a fluoromonomer and a specific structure.
Fluoropolymer with polymerized monomer selected as image forming layer
Add to the surface to improve the surface of the coating, and increase the thickness and resistance.
It is thought that the printing was expressed. Next, the photosensitive lithographic printing plate precursor is prepared as follows.
The method was evaluated. Sensitivity is manufactured by Fuji Photo Film Co., Ltd.
Through the step wedge (density difference at each stage is 0.15)
1m from a distance of 1m by a 3kW metal halide lamp
After a minute exposure, the PS film manufactured by Fuji Photo Film Co., Ltd.
Using Rosser 900V, S for 12 seconds at 30 ° C
iO ₂ / K ₂ The molar ratio of O is 1.16, SiO ₂ Concentration is 1.
It was developed with a 4% aqueous solution and expressed as the number of clear stages. This
The higher the number of steps, the higher the sensitivity. The gradation is
The difference between the clear plate number and the solid plate number of the sample for which sensitivity was evaluated
Represented. It shows that it is so hard that this value is low. developing
Tolerance is based on the above developer and the pH is raised and lowered.
The same sensitivity as above except that the liquid increased or decreased by 0.2 is used.
Exposure and development are performed, and the change in the number of solids due to pH is indicated.
It was. The smaller this value, the better the development tolerance.
The These results are shown in Table 4. [Table 4] As is apparent from Table 4, the lithographic mark of the present invention
The original plate for printing plates is hardened without degrading sensitivity.
A lithographic printing plate having good development tolerance was obtained (Examples 7 to
12). On the other hand, a fluorine polymer outside the scope of the present invention.
In lithographic printing plate precursors using
In either case, the results are inferior to those of the present invention.
It was a fruit (Comparative Examples 4 and 5). [Examples 13 to 17 and Comparative Examples 6 to 8]
Strip-shaped aluminum with a thickness of 0.3 mm and a width of 1,000 mm
Of sodium triphosphate first kept at 80 ° C.
Degreasing was carried out by passing through a 10% aqueous solution for 1 minute. Next
Nylon brush and 400 mesh pumice-water suspension
The surface was grained using and washed thoroughly with water. This
Plate in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds
Immerse it for etching, wash it with water, and then add 20% glass.
It was immersed in an acid for 20 seconds and washed with water. Grained surface at this time
Etching amount of about 8g / m ² Met. Next, this board
7% sulfuric acid as electrolyte and current density 15A / dm ² 3
g / m ² After providing the direct current anodic oxide film, washing with water and drying,
It led to the coating process. In the coating process, the next image forming layer is coated.
Liquid 2 was prepared. (Image forming layer coating solution 2) Ester compound of naphthoquinone-1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 0.90 g cresol formaldehyde resin (described in US Pat. No. 4,123,279) 2.00 g t-butylphenol formaldehyde resin (US Pat. No. 4,123,279) 0.05 g ・ Naphthoquinone-1,2-diazide-4-sulfonyl chloride 0.03 g ・ Oil Blue # 603 (manufactured by Orient Chemical Co., Ltd.) 0.05 g・ Fluoropolymer (Table 5) 0.015 g ・ Methyl ethyl ketone 8 g ・ Propylene glycol monomethyl ester Ether 25 g [0165] strip the coating solution was grained Arumini
30 g / m continuously on the um ² After coating at the rate of 1
By passing through a hot air drying zone of 00 ° C for 1 minute
And dried to form a photosensitive layer. For obtained lithographic printing plates
For the original, the uniformity of the photosensitive layer, the number of sheets to be printed, and the printing durability
Sex was evaluated as described below. The results are shown in Table 5. Table 5 [0167] Photosensitive layer uniformity Visual observation of the surface of the photosensitive layer of the obtained lithographic printing plate precursor
And evaluated according to the following criteria. A: Uniform and non-uniformity B: Slightly light unevenness C: Unevenness due to dry air, etc. D: Excessive unevenness due to dry air, etc.
In Examples 13 to 17, the uniformity of the film thickness of the photosensitive layer was added.
Compared to the comparative example 8 that was not there
Karu. Fluorine-based surfactants other than those prescribed in the present invention
In Comparative Example 6 using the coating film, the uniformity of the coating film was inferior.
It was. [0168] Incarnation After exposure through the image film, Fuji Photo Film Co., Ltd.
Automatic developer 800U, automatic developer DP-4
(1: 8) for 40 seconds at 25 ° C.
Apply the company's gum (GP) and print one week later
Ink receiving is performed with the number of prints until the ink is completely attached.
I examined the capacity. From Table 5, Comparative Examples 6 and 7 are ink receptivity.
Is inferior. [0169] Printing durability Each photosensitive lithographic printing plate is original
After film and contact exposure, developed with developer, and then
The photosensitive lithographic printing plates of Examples 13 to 17 are sensitive, original patterns.
It turns out that the reproducibility of the turn is excellent.
It was. When printed using this, printing durability, image strength
It was found to be a uniform and excellent one. [Example 18 and Comparative Examples 9 and 10] Thickness
A 0.30mm material 1S aluminum plate No. 8 Nairro
Use a water suspension of brush and 800 mesh pumiston
The surface was grained and washed thoroughly with water. 1
Immerse in 0% sodium hydroxide at 70 ° C for 60 seconds.
20% HNO after washing with running water _Three Neutralized washing with
Purified and washed with water. This is a sine under the condition of VA = 12.7V
300 waves in 1% nitric acid aqueous solution using alternating wave current
-Ron / dm ² Electrolytic surface roughening with the amount of electricity at the anode
It was. The surface roughness measured was 0.45 μm (Ra
Display). Continuously 30% H ₂ SO _Four Aqueous solution
After dipping in and desmutting at 55 ° C. for 2 minutes, 33
℃, 20% H ₂ SO _Four Cathode on grained surface in aqueous solution
Current density 5A / dm ² Positive for 50 seconds
When oxidized, the thickness is 2.7 g / m ² Met. Further, No. 3 sodium silicate (SiO 2 ₂ = 28 ~
30% Na ₂ O = 9-10%, Fe = 0.02% or less
(Lower) 2.5% by mass, pH = 11.2, 70 ° C. aqueous solution
For 13 seconds, followed by washing with water. Silica at that time
10 mg / m ² Met. Measurement is X-ray fluorescence
The amount of Si element was determined by analysis. Next, the SG method is performed according to the following procedure.
A liquid composition (sol solution) was prepared. The following set in a beaker
The composition was weighed and stirred at 25 ° C. for 20 minutes. (Sol solution) ・ Si (OC ₂ H _Five ) _Four 38 g ・ 3-Methacryloxypropyltrimethoxysilane 13 g ・ 85% aqueous phosphoric acid solution 12 g ・ Ion-exchanged water 15 g ・ Methanol 100 g The solution was transferred to a three-necked flask and cooled under reflux.
Attach a three-necked flask to a room temperature oil bath.
It was. Magnetic stirrer for contents of three-necked flask
The mixture was raised to 50 ° C. over 30 minutes with stirring at ˜. bath
While maintaining the temperature at 50 ° C., the mixture is further reacted for 1 hour.
(Sol solution) was obtained. This sol solution is methanol / ethylene
Glycol = 20/1 (weight ratio) 0.5% by mass
Dilute and apply a wheeler to the substrate, and 100 minutes at 100 ° C
Dried. The coating amount at that time is 4 mg / m ² Met.
The amount of Si was also determined by fluorescent X-ray analysis.
Therefore, it was set as the coating amount. Aluminum treated in this way
A highly sensitive photopolymerizable composition having the following composition on a nium plate
The image forming layer coating solution 3 has a dry coating weight of 1.5 g / m. ² When
And then dried at 100 ° C for 1 minute to form an image
A stratification was formed. (Image forming layer coating solution 3 (photopolymerizable composition)) Tetramethylolmethane tetraacrylate 1.5 g Linear organic polymer (B1) (Allyl methacrylate / methacrylic acid copolymer, co-polymer) Polymerization molar ratio 80/20, weight average molecular weight 45,000) 2.0 g Sensitizer (C1) (λmax THF 479 nm, ε = 6.9 × 10 ^Four ) 0.15 g ・ Photopolymerization initiator (D1) 0.2 g ・ IRGACURE907 (E1) (Ciba-Geigy) 0.4 g ・ Fluoropolymer (a) 0.2 g ・ γ-phthalocyanine / ( B1) Dispersion 0.2 g ・ Methyl ethyl ketone 9.0 g ・ Propylene glycol monomethyl ether acetate 7.5 g ・ Toluene 11.0 g The structure of the sensitizer (C1) is shown below. [Chemical 7] The structure of the photopolymerization initiator (D1) is shown below.
The Embedded image On this image forming layer, an oxygen barrier protective layer and
Polyvinyl alcohol (saponification degree 98 mol%, polymerization
The dry coating weight is 2.5%
g / m ² Apply and dry at 120 ° C for 3 minutes
A photopolymerizable lithographic printing plate precursor was obtained. Image forming layer film
The uniformity was good (Example 18). On the other hand, the above picture
Excluding the fluoropolymer (P-9) from the composition of the image forming layer
The film was mottled and uneven (comparative example)
9). The same except for changing P-9 to R-1.
A comparative sensitizing solution was also prepared, but P-9 was added.
In other systems, the foaming property of the photosensitive solution was also suppressed, whereas R
When -1 is added, the foaming property is high, and the film of the image forming layer is
More than 10 pinholes per square meter
It was recognized (Comparative Example 10). Optronic the resulting plate
XLP4000 (Ar laser 75mW, 488
nm), exposure 4000 dpi, 175 lines / inch
1% to 99% in increments of 1%
One exposed. By exposing it to 120 ° C for 20 seconds.
Thereafter, heat treatment was performed. Development is carried out in the following developer 2 at 25 ° C. and 30 minutes.
Dipped for 2 seconds. (Developer 2) 1K potassium silicate 30 g Potassium hydroxide 15 g Water 1000 g Next, GU-7 (Fuji Photo Film Co., Ltd.)
Made) Using a solution of gum solution diluted twice with water,
Processed. 4000 dpi, 175 line / inch condition
The amount of plate surface energy that 1% reproduces
The sensitivity was found to be 0.2 mJ.
I got a good sensitivity. In addition, the dot quality at that exposure
It was good and no unwanted fog or flare was observed. mark
Use a Heidelberg SORKZ as the printing machine
As the tank, Dainippon Ink Kurafu G (N) is used.
When a printing durability test was conducted, it was good for 180,000 sheets or more.
A printed matter could be obtained (Example 18). Furthermore, the photosensitive material was stored at 60 ° C. for 3 days and then the same.
Exposure development and printing in the same way, stable over time by visual evaluation
Sex was evaluated. Immediately after application, printing durability, stain resistance and image quality
It was good with no change in materials. Next, examples of a heat-crosslinking type lithographic printing plate precursor
Show about. [Example 19] Aluminum plate (material) with a thickness of 0.30 mm
1050) washed with trichlorethylene and degreased
After, nylon brush and 400 mesh pumiston-water
Grain the surface using a suspension and wash thoroughly with water.
It was. Put this plate in 45% 25% aqueous sodium hydroxide solution
Immerse for 9 seconds, etch, wash with water, and then 2% H
NO _Three For 20 seconds and washed with water. Graining at this time
Surface etching amount is about 3g / m ² Met. Then this
7% H board ₂ SO _Four Current density 15A / dm
² 3g / m ² After providing a direct current anodic oxide film, washing with water and drying
did. Next, the following undercoat liquid 2 is applied to the aluminum plate.
And dried at 80 ° C. for 30 seconds. The coating amount after drying is 10
mg / m ² Met. (Undercoat liquid 2) β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g Next, the following image forming layer coating liquid 4 was prepared,
Apply this solution to the above primed aluminum plate
And dry for 1 minute at 100 ° C.
Obtained. The coated surface was uniform and good. Coverage after drying
Is 1.5 g / m ² Met. (Image forming layer coating solution 4) Fluoropolymer (b) 0.05 g Acid generator [SH-1] 0.3 g Crosslinking agent [KZ-1] 0.5 g Binder polymer [BP-1] 1.5 g ・ Infrared absorber [IK-1] 0.07 g ・ AIZEN SPILON BLUE C-RH (manufactured by Hodogaya Chemical Co., Ltd.) 0.035 g ・ Methyl ethyl ketone 12 g ・ Methyl alcohol 10 g 1-methoxy-2-propanol 8 g The structure of the crosslinking agent [KZ-1] is shown below. Embedded image The binder polymer [BP-1] is Maruzen
Poly (p-hydroxystyrene) manufactured by Petrochemical Co., Ltd.
Marca Linker MS-4P (trade name) was obtained and [B
P-1]. Used acid generator [SH-1] and infrared
The structure of the line absorber [IK-1] is shown below. Embedded image The surface of the obtained negative type lithographic printing plate precursor
Touch with bare hands, then red with a wavelength of about 820-850nm
Scanning exposure was performed with a semiconductor laser emitting an external line. After exposure,
Heat treatment was performed at 110 ° C. for 30 seconds with a flannel heater.
Later, a developer manufactured by Fuji Photo Film Co., Ltd., DP-4 (1:
8). Touch with bare hands after image formation
It was judged visually whether the image of the part was missing.
However, no image omission occurred. Separately for lithographic printing plates
Original 1m ² Is exposed to 100 ml of developer after exposure
Then, the occurrence of sludge in the developer after processing was observed. F
No drooling was observed and the solubility in the developer was good.
It was confirmed that there was. [Comparative Example 11] Solution used in Example 19
In [G], do not use a fluorine-based polymer (b)?
A solution was prepared in the same manner as in Example 19 except that
It was. This solution was added to the precoated primer used in Example 19.
Apply to a minium plate and dry at 100 ° C for 1 min.
A lithographic printing plate was obtained. The coated surface is mottled and uneven
It was. This lithographic printing plate precursor is the same as in Example 19.
Images were formed by the same operation. The part touched with bare hands after image formation
This is a visual judgment that the minute image is missing.
B) Clear image loss occurred. [Comparative Example 12] Solution used in Example 19
In [G], instead of the fluoropolymer (b)
A solution was obtained in the same manner as in Example 19 except that (g) was used.
Was prepared. This solution was used as an undercoat used in Example 19.
Apply to the aluminum plate and dry at 100 ° C for 1 minute
As a result, a negative lithographic printing plate was obtained. This lithographic printing plate precursor
An image was formed in the same manner as in Example 19. Image formation
After that, if the image of the part touched with bare hands is missing,
As a result of visual judgment, image omission occurred. Separately
Master plate for lithographic printing plate 1m ² Is exposed to the whole surface, and then the developer 10
The amount of sludge generated in the developer after processing with 0 ml
Observed. Obvious sludge formation was observed and
It was inferior in solubility and dispersibility. Next, a thermal positive type lithographic printing plate precursor
Examples will be described. [Example 20] [Preparation of copolymer 1] A stirrer, a cooling pipe and a dropping funnel were added.
Into a 20 ml three-necked flask equipped, N- (p-aminos
(Luphonylphenyl) methacrylamide 4.61 g (.
0192 mol), 2.94 g (0.
0258 mol), 0.80 g of acrylonitrile (0.0
15 mol) and 20 g of N, N-dimethylacetamide.
And stir the mixture while heating to 65 ° C in a hot water bath
did. 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 substrate] Aluminum having a thickness of 0.3 mm
Um plate (material 1050) washed with trichlorethylene
After degreasing, nylon brush and 400 mesh Pami
Grain the surface with a stone-water suspension and rinse with water.
Washed thoroughly. 25% sodium hydroxide at 45 ° C
Etching is performed by dipping in an aqueous solution for 9 seconds.
Furthermore, it was immersed in 20% nitric acid for 20 seconds and washed with water. At this time
The etching amount of the grained surface is about 3 g / m ² Met.
Next, this plate was treated with 7% sulfuric acid as an electrolyte and a current density of 15 A /
dm ² 3g / m ² After providing a direct current anodic oxide coating,
And dry, and then apply the following undercoat liquid 3
Dry at 90 ° C. for 1 minute. The coating amount after drying is 10m
g / m ² Met. (Undercoat liquid 3) β-alanine 0.5 g methanol 95 g water 5 g Further, sodium silicate 2.5% by mass water
Treat with solution at 30 ° C for 10 seconds and apply the following undercoat liquid 4
The coating film was dried at 80 ° C. for 15 seconds to obtain a substrate. Dry
The coating amount of the later coating film is 15 mg / m ² Met. (Undercoat liquid 4) • The following compound 0.3 g • Methanol 100 g • Water 1 g The following image forming layer coating solution 5 was prepared. Up
The coating amount of this photosensitive solution 1 is applied to the substrate obtained as described above.
1.8 g / m ² Apply the coating surface of the image forming layer.
A lithographic printing plate precursor excellent in shape was obtained. (Image forming layer coating solution 5) Fluoropolymer (a) 0.02 g-Copolymer 1 0.75 g-m, p-cresol novolak (m, p ratio = 6/4, weight) Average molecular weight 3,500, containing 0.5% by mass of unreacted cresol) 0.25 g p-toluenesulfonic acid 0.003 g tetrahydrophthalic anhydride 0.03 g cyanine dye (IK-1) 017 g • Dye with Victoria Pure Blue BOH counter ion as 1-naphthalenesulfonic acid anion 0.015 g • γ-butyllactone 10 g • Methyl ethyl ketone 10 g • 1-methoxy-2-propanol 1 g About the original for lithographic printing plate
The development stability against trauma was evaluated by this method. Lithographic seal
The photosensitive material surface of the printing plate precursor is placed on the continuous load type scratch strength tester “S”.
B62 type "(manufactured by Shinto Kagaku Co., Ltd.) and scratch jig plate
Advantech on the square plane part of 1cm square that hits the top
Paste “No. 5C” filter paper made by Toyo Co., Ltd., 100 g
Was loaded and scratched at a speed of 6 cm / sec. Next
Output 500mW, wavelength 830nm, beam diameter 17μ
m (l / e ² ) Main scanning speed 5m
Fuji Photo Film after exposure to 5% halftone dot image / second
Developed for 30 seconds with a developer, DP-4 (1: 8)
did. The obtained image formed good halftone dots and scratched parts.
The image portion of the minute does not dissolve at all, and the lithographic printing plate precursor of the present invention
The development stability of lithographic printing plates produced from
It was found to be good. In addition, the foaming property of the photosensitive solution is
There are few pinholes per square meter on the coated surface
It was as good as 5 or less. Separately, lithographic printing plate precursor 1m
² Is exposed to 100 ml of developer, and then processed.
The state of sludge generation in the developer later was observed. Sludge generation
Is not observed and the solubility in the developer is good.
Was confirmed. [Comparative Example 13] Using fluoropolymer
For lithographic printing plates in the same manner as in Example 20 except that
I got the original version. The film was mottled and had a non-uniform surface. Next
In addition, this lithographic printing plate precursor is the same as in Example 20.
The development stability against trauma was evaluated. Scratched
In the part, the unexposed halftone dot part where the image should originally be is developed.
It has been removed. [Comparative Example 14] (h)
For lithographic printing plates in the same manner as in Example 20 except that
I got the original version. 15 pinholes per square meter
As a result, the surface condition was inferior. Next, this lithographic printing plate
For the original plate, in the same manner as in Example 20, against the trauma
The development stability was evaluated. In the scratched part, the original image
The unexposed halftone dots where the image should have been developed have been removed.
It was. Separately, lithographic printing plate precursor 1m ² After exposing the entire surface,
Processed with 100 ml of developer, and sludge in the developer after processing
The occurrence was observed. Obvious sludge development is observed,
The solubility and dispersibility in the developer were poor. Results of Example 20 and Comparative Examples 13 and 14
In addition, the addition of a specific fluoropolymer improves the surface shape
The image forming layer is in a state before development.
To improve the stability against trauma and
It has excellent solubility and dispersibility and does not cause sludge generation.
Karu. Next, radical polymerization type thermal negative type
Examples of the lithographic printing plate precursor will be described. [Example 21] "Preparation of support" 99.5% or more of aluminum and Fe
0.30%, Si 0.10%, Ti 0.02%, Cu
Wash molten metal of JIS A1050 alloy containing 0.013%
It was cast after being purified. In the cleaning process,
Degassing treatment to remove unnecessary gases such as hydrogen
Lamic tube filter treatment was performed. Casting is DC casting
I went by the manufacturing method. Is the solidified 500nm thick ingot on the surface?
And a rolled aluminum plate of 10 nm. Rolling roll
Centerline average surface after cold rolling by controlling roughness
The roughness Ra was controlled to 0.2 μm. Then improve the flatness
I put it on the tension lever to raise it. Next, a surface treatment for forming a lithographic printing plate support is performed.
I did it. First, remove the rolling oil on the aluminum surface
Therefore, 10% sodium aluminate aqueous solution at 50 ° C for 30 seconds
Performs a neutral degreasing treatment and 30% sulfuric acid aqueous solution at 50 ° C.
Neutralization and smut removal treatment were performed for 2 seconds. Then the support and
Good adhesion of image forming layer and water retention in non-image area
In order to give a rough surface to the support, so-called,
Graining was performed. 1% nitric acid and 0.5% nitric acid
Keep the aqueous solution containing Lumi at 45 ° C
While flowing in aqueous solution, current density 2 by indirect power supply cell
0A / dm ² , With an alternating waveform with a duty ratio of 1: 1
Load side electricity quantity 240C / dm ² Giving electrolytic grain
Standed up. Then with 10% sodium aluminate aqueous solution
Etching is performed at 50 ° C for 30 seconds, 30% sulfuric acid water
Neutralize with solution at 50 ° C for 30 seconds to remove smut
went. Further improved wear resistance, chemical resistance and water retention
To form an oxide film on the support by anodic oxidation
I let you go. Uses 20% sulfuric acid aqueous solution at 35 ° C as electrolyte
Indirect power feeding while carrying the aluminum web through the electrolyte
14 A / dm depending on the cell ² Electrolytic treatment with direct current
2.5g / m ² An anodized film was prepared. "Undercoating" Next, this aluminum support
The following undercoat liquid 5 is dried with a wire bar.
Is 5mg / m ² Apply and use a hot air dryer
And dried at 90 ° C. for 30 seconds. (Undercoat 5) 2-aminoethylphosphonic acid 0.1 g ・ Phenylphosphonic acid 0.1 g ・ Methanol 75 g ・ Water 25 g [0208]
Apply image forming layer coating solution 6 using a wire bar,
In a flat dryer and dry at 115 ° C for 45 seconds
An original plate for printing plate was obtained. The coated surface has excellent uniformity
It is. The coating amount is 1.3 g / m ² Met. (Image forming layer coating solution 6) Photothermal converter (cyanine dye TN-1) 0.10 g Thermal radical generator (sulfonium salt compound TN-2) 0.30 g Addition polymerizable unsaturated compound (Dipentaerythritol hexaacrylate) 1.00 g ・ Alkali-soluble binder polymer (copolymer of allyl methacrylate and methacrylic acid having a copolymer molar ratio of 83 to 17 and a weight average molecular weight of 125,000 1.2 g Colorant (Victoria Pure Blue naphthalene sulfonate) 0.04 g Fluoropolymer (c) 0.005 g Methyl ethyl ketone 10.0 g 1-methoxy-2-propanol 8.0 g (Cyanine Dye TN-1) Structure Structure of (sulfonium salt compound TN-2)
Structure [0212] The obtained negative lithographic printing plate precursor was water-cooled.
Creo Tr equipped with 40W infrared semiconductor laser
Endsetter 3244VFS, output 9W outside
Surface drum rotation speed 210rpm, while energy 100m
J / cm ² , 50% halftone dot with 2400 dpi resolution
The image was exposed. Next, Fuji Photo Film Co., Ltd.
Development was performed using an imager Stavlon 900N. developing
The liquid and replenisher use the following composition, the developing bath temperature is 30 ° C,
As a finisher, Fuji Photo Film's FN-6
A 1: 1 dilution of water (pH = 10.8) was used. (Developer 3)-Potassium hydroxide 3 g-Potassium bicarbonate 1 g-Potassium carbonate 2 g-Sodium sulfite 1 g-Polyethylene glycol mononaphthyl ether 150 g-Dibutyl naphthalene sulfonate sodium salt 50 g-Ethylenediamine 4 Acetic acid tetrasodium salt 8 g-Water 785 g (Replenisher)-Potassium hydroxide 6 g-Potassium carbonate 2 g-Sodium sulfite 1 g-Polyethylene glycol mononaphthyl ether 150 g-Dibutylnaphthalene sulfonic acid sodium salt 50 g -Hydroxyethane diphosphonic acid potassium salt 4 g-Silicon TSA-731 (manufactured by Toshiba Silicone Co., Ltd.) 0.1 g-Water 786.9 g A uniform and good halftone image was obtained. The resulting lithographic printing plate
Printing machine Heidel SOR-M manufactured by Heidelberg
And 110,000 sheets or more of printed matter could be obtained.
In addition, the photosensitive solution of this example has low foaming properties and is required for defoaming.
The time is less than 5 minutes and the surface condition is good (1 square meter
No more than 5 pinholes). Separate lithographic printing
Master 1m for printing ² With 100ml developer
Processed and observed the occurrence of sludge in the developer after processing.
It was. No sludge was observed and the solubility in the developer was
It was confirmed to be good. (Comparative Example 15)
Except for the remmer, the lithographic seal is exactly the same as in Example 21.
An original plate for printing plate was prepared. Image formation layer is not uniform enough
there were. In addition, exposure and development processing was performed as in Example 21.
As a result, the halftone image portion was damaged. (Comparative Example 16) Fluoropolymer from the above photosensitive solution
Except for the change to (g), the lithographic plate is exactly the same as in Example 21.
A printing plate precursor was prepared. High foaming performance, required for defoaming
It takes 30 minutes or more and is inferior in manufacturing suitability.
It was. The image forming layer had insufficient uniformity. Further implementation
When exposure and development processing was performed in the same manner as in Example 21, a halftone dot image was obtained.
The image part was scratched. Separately, lithographic printing plate precursor 1m ² All
After surface exposure, process with 100 ml of developer,
The state of sludge generation in the image liquid was observed. Obvious sludge
Inferior in solubility and dispersibility in developer
It was. From Example 21, Comparative Examples 15 and 16, this
For the use of specific fluoropolymers specified in the invention
Therefore, the surface shape is uniform and the developer resistance of the image area is
An improved thermal negative lithographic printing plate is obtained and further developed
Excellent solution solubility and dispersibility
I understand that The present invention is at least represented by (A) and (B).
Fluoro fat obtained by copolymerizing monomers
Having an image forming layer containing an aliphatic group-containing copolymer
Produces foaming, etc. by using a lithographic printing plate precursor
Gives a uniform coating surface without causing structural failure, developability,
Providing a planographic printing plate with excellent inking ability.

Front page continuation (51) Int.Cl. ⁷ Identification symbol FI Theme code (reference) G03F 7/033 G03F 7/033 F-term (reference) 2H025 AA04 AA18 AB03 AC01 AD01 AD03 CB14 CB41 CC04 2H096 AA06 BA01 BA09 EA02 4J027 AC02 AC03 AC04 AC06 AJ02 BA07 BA14 CB10 CC07 CD10 4J100 AL08P AL08Q AM21P BA08Q BB18P CA04 DA36 JA38

Claims (1)

1. An image forming layer containing a fluoroaliphatic group-containing copolymer obtained by copolymerizing at least the following monomers (A) and (B) on a support: (A) Fluoroalkyl (meth) acrylate represented by the following general formula (I) or (II): embedded image (In the formula, X ¹ represents —O— or —NR ³ —. R ¹ represents —H or —CH _3. R ³ has 1 to 12 carbon atoms which may have a hydrogen atom or a substituent. An alkyl group, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or an optionally substituted carbon group having 6 carbon atoms. Represents an aralkyl group of ˜24, R ² represents H or F. m is an integer of 0 to 10,
n represents an integer of 2 or 3, and o and p each represent an integer of 1 or 2, and (B) a polyoxyalkylene group-containing ethylenically unsaturated monomer.