JP2003255520A - Planographic printing original plate precursor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a planographic printing original plate for direct plate making excellent in scratch resistance, development resistance and printing resistance and capable of direct plate making particularly from digital signals of a computer or the like. <P>SOLUTION: The planographic printing original plate is obtained by disposing on a support an image recording layer comprising a water-insoluble and alkali- soluble resin and an IR absorbent, wherein the water content of the image recording layer is ≥1.0 wt.%. <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor.
In particular, digital signals such as computers
Flat plate for so-called direct plate making that can be made directly from the issue
For printing plate precursors, more details on scratch resistance and development resistance
And a lithographic printing plate precursor having excellent printing durability. [0002] The development of lasers in recent years has been remarkable.
In particular, a solid-state laser with a light emitting region from near infrared to infrared
Semiconductor lasers are easily available in high output and small size
It is like that. Output from a computer, etc.
This is an exposure light source for making plates directly from digital data.
These lasers are very useful. Infrared laser lithographic printing for direct plate making
The plate material is an alkaline aqueous soluble binder resin,
Infrared absorber that absorbs light and generates heat (hereinafter IR dye)
Etc.) as essential components, IR dyes, etc.
However, in the unexposed area (image area),
The solubility of the binder resin is substantially reduced by the action.
It acts as a dissolution inhibitor, and in exposed areas (non-image areas)
Interaction between IR dyes and binder resin due to generated heat
The image area is image-like because it is weakened and dissolved in an alkaline developer.
A lithographic printing plate distributed on the surface is formed. However, for such infrared lasers
For lithographic printing plate materials, unexposed areas under various operating conditions
Dissolution resistance of the (image area) to the developer and exposure area (non-image area)
The difference between the solubility of the image part) is still not enough and it is used
Over-development due to changes in conditions
Film thinning phenomenon) and poor development (non-image area dissolves)
The remaining film phenomenon that remains uncut is likely to occur.
It was. In addition, the image layer is low in strength, so it can be applied to the surface during handling.
Surface condition such as fine scratches caused by touch etc.
Are prone to fluctuating, such fine scratches and slight surface changes
If there is motion, the solubility of the surrounding area will increase.
During development, unexposed areas (image areas) dissolve and become scratched.
Problem that causes deterioration of printing durability and poor wearability
was there. Such a problem is caused by lithographic printing for infrared lasers.
A printing plate material and a lithographic printing plate material that is made by UV exposure
This stems from the essential differences in the plate-making mechanism. That is,
In lithographic printing plate materials made by UV exposure, alkali
Aqueous binder binder resin, onium salt and quinone
It contains diazide compounds as essential ingredients.
Salts and quinonediazide compounds are not exposed (image area)
Acts as a dissolution inhibitor due to interaction with binder resin
In addition, the exposed area (non-image area) is separated by light.
It generates two acids and acts as a dissolution promoter.
It plays a role. In contrast, lithographic printing plate materials for infrared lasers
IR dyes in the coating material are used to prevent dissolution of unexposed areas (image areas).
Promotes dissolution of exposed areas (non-image areas) only by acting as a stopper
It does not advance. Therefore, lithographic printing for infrared lasers
In the plate material, the difference in solubility between the unexposed and exposed areas
As a binder resin,
If a developer with high solubility is used, the film will be reduced.
(Deterioration of development resistance) or scratch resistance was reduced.
Have problems such as unstable state before development.
The On the other hand, in order to strengthen the unexposed area,
Lowering the solution will cause a decrease in sensitivity. But
Therefore, it is possible to maintain the distinction between the image portion and the non-image portion.
The range (called development latitude) is limited. For this reason, there is no suppression of dissolution in the exposed area.
In other words, selective dissolution is maintained in unexposed areas.
Various solubilization inhibitors have been studied,
Japanese Patent Application Laid-Open No. 7-285275 discloses an infrared laser diode.
Photothermal conversion agent and thermal decomposition on the recording layer of dilithographic lithographic printing plate material
Alkali-soluble resin in a state that is soluble and not thermally decomposed
Adding a substance that substantially reduces the solubility of
Therefore, while inhibiting the solubility of the layer and improving the scratch resistance,
In the exposed area, the heat converted by the photothermal conversion agent
The substance is decomposed to prevent dissolution of the alkali-soluble resin.
Techniques that can lose use and improve sensitivity are disclosed. However, these are problems to be solved.
Even if the compound is added, the dissolution promoting effect is sufficient.
Film properties that are fully satisfactory (scratch resistance, development resistance, printing durability)
Improvement effect) has not yet been achieved, and further improvement
Is in a necessary situation. The object of the present invention is thus
Directly from a digital signal such as a computer using line light
For lithographic printing plates for so-called direct plate making that can be plate-making
Overcoming the above-mentioned drawbacks associated with the original technology
Presents means to improve printability, development resistance and printing durability.
It is in. [0009] The present inventor has provided scratch resistance,
Are the above-mentioned solutions, represented by developability and printing durability, conventional?
Despite being considered from the viewpoint of materials used,
In view of the fact that the solution has not been sufficiently solved, lithographic printing
Focusing on the physical properties of the image recording layer of the original plate,
As a result, the water content in the image recording layer is controlled to a certain level or more.
This significantly affects the mechanical properties of the image film.
Based on this discovery, further investigation will be made
As a result, the present invention has been completed. That is, the present invention
Is as follows. (1) Water-insoluble and alkali-soluble resins and
A lithographic plate provided with an image recording layer containing an infrared absorber on a support.
An original plate for a printing plate, wherein the water content of the image recording layer is 1.0
A lithographic printing plate precursor that is at least% by weight. The water content control in the image recording layer is a lithographic mark.
Unexpected effects on scratch resistance, development resistance and printing durability of printing plate precursors
The mechanism of the remarkable effect is unknown, but
The mechanism is estimated. When applying and drying the image recording layer
In this case, the image recording layer dries while the solvent is removed, so
A steady state, i.e., a state where there is little interaction between the binder and
It has become. At this time, the water content in the image recording layer is at a certain level.
If it is present above, moisture will be mutually added to the binder in the image recording layer.
Interaction increases by mediating the increase in action. This
Therefore, the scratch resistance, development resistance and printing durability of the image recording layer are improved.
It is thought that it goes up. The present invention will be described in detail below.
The lithographic printing plate precursor according to the present invention is water-insoluble and alkali-soluble.
An image recording layer containing an adhesive resin and an infrared absorber on a support
A lithographic printing plate precursor provided, comprising the water content of the image recording layer
The rate is 1.0% by weight or more. The lithographic plate of the present invention
The moisture content of the image recording layer of the printing plate precursor is 1.0% by weight or less.
Although it will not specifically limit if it is on, 1.0 to 15 weight% of
Range is preferable, and smoothness of slip sheet is maintained (no wrinkles)
Is more preferably in the range of 1.0 to 12% by weight.
In the range of 1.1 to 10% by weight due to the stability of sensitivity over time
Further preferred. Image recording layer of lithographic printing plate precursor according to the invention
As a method to control the moisture content of the water to 1.0% by weight or more
Although not particularly limited, the image recording layer is applied and formed.
A method of adding water to the coating solution of the image recording layer when
For example, a method of spraying steam after forming the recording layer
The Among them, a method of adding water to the coating solution for the image recording layer
Is preferred. Next, each essential part of the lithographic printing plate precursor according to the present invention is described.
The section is described. First of all, the structure of the image recording layer
Let's start with the ingredients. [Alkali-soluble resin] Next, the plain of the present invention is used.
Alkali-soluble in the image recording layer of a printing plate precursor
The functional resin (polymer compound) will be described. The flat of the present invention
The image recording layer of the plate printing plate precursor is water-insoluble and
Water-soluble polymer compound (hereinafter, appropriately alkali-soluble
Contains polymer or alkali-soluble resin)
It is. The alkali-soluble polymer is a main chain in the polymer.
And / or a homopolymer containing an acidic group in the side chain,
These copolymers or mixtures thereof. Follow
The image recording layer according to the present invention is in contact with an alkaline developer.
It has the property of dissolving when touched. Conventionally known alkali-soluble polymers
(1) Phenolic
Hydroxyl group, (2) sulfonamide group, (3) active imide group
A polymer compound having any functional group of
It is preferable. Examples include the following,
It is not limited to these. (1) Polymer having phenolic hydroxyl group
Examples of the compound include phenol formaldehyde
Resin, m-cresol formaldehyde resin, p-cres
Zole formaldehyde resin, xylenol formal
Dehydric resin, m- / p-mixed cresol formaldehyde
Resin, phenol / cresol (m-, p-, or m
Any of-/ p-mixed) mixed formaldehyde
Novolac resin such as resin and pyrogallol acetone resin
Can be mentioned. Polymer compound having phenolic hydroxyl group
In addition to this, it has a phenolic hydroxyl group in the side chain.
It is preferable to use a polymer compound. Phenol on side chain
Examples of the polymer compound having a rutile hydroxyl group include phenol
Each has at least one polymerizable unsaturated bond
Homopolymerizing a polymerizable monomer comprising a low molecular weight compound,
Alternatively, the monomer is copolymerized with another polymerizable monomer.
Examples thereof include a polymer compound obtained. Polymerizable monomer having a phenolic hydroxyl group
-As an acrylic amine having a phenolic hydroxyl group
, Methacrylamide, acrylic ester, methacrylate
Examples include oxalic acid ester or hydroxystyrene.
The Specifically, N- (2-hydroxyphenyl) ac
Rilamide, N- (3-hydroxyphenyl) acryl
Amide, N- (4-hydroxyphenyl) acrylami
N- (2-hydroxyphenyl) methacrylamido
N- (3-hydroxyphenyl) methacrylamido
N- (4-hydroxyphenyl) methacrylamido
, O-hydroxyphenyl acrylate, m-hydro
Xiphenyl acrylate, p-hydroxyphenyla
Acrylate, o-hydroxyphenyl methacrylate,
m-hydroxyphenyl methacrylate, p-hydroxy
Siphenyl methacrylate, o-hydroxystyrene,
m-hydroxystyrene, p-hydroxystyrene, 2
-(2-hydroxyphenyl) ethyl acrylate, 2
-(3-hydroxyphenyl) ethyl acrylate, 2
-(4-hydroxyphenyl) ethyl acrylate, 2
-(2-hydroxyphenyl) ethyl methacrylate,
2- (3-Hydroxyphenyl) ethyl methacrylate
2- (4-hydroxyphenyl) ethyl methacrylate
And the like can be suitably used. Such pheno
Resin having a rutile hydroxyl group is a combination of two or more
May be used. Further, U.S. Pat. No. 4,123,279.
T-butylphenol as described in the specification
Formaldehyde resin, octylphenol formaldehyde
Place an alkyl group with 3 to 8 carbon atoms such as aldehyde resin.
Condensation of phenol and formaldehyde as a substituent
A polymer may be used in combination. (2) Alkali having a sulfonamide group
The soluble polymer compound has a sulfonamide group
A polymerizable monomer that is homopolymerized, or other monomers
A polymer compound obtained by copolymerizing a polymerizable monomer is
Can be mentioned. Polymerizable monomer having a sulfonamide group
At least one on a nitrogen atom in one molecule
Sulfonamide group -NH-SO to which a hydrogen atom is bonded ₂ −
And low with at least one polymerizable unsaturated bond
Examples thereof include polymerizable monomers composed of molecular compounds. That
Among them, acryloyl group, allyl group, or vinyloxy group
A substituted or monosubstituted aminosulfonyl group or substituted
A low molecular compound having a sulfonylimino group is preferred. (3) Alkali-soluble with an active imide group
Functional polymer compounds with active imide groups in the molecule
The polymer compound is preferably active in one molecule.
One or more polymerizable imide groups and one or more polymerizable unsaturated bonds
Single polymerizable polymer monomer consisting of low molecular weight compounds
Or other polymerizable monomer is copolymerized with the monomer.
The polymer compound obtained by doing this. As such a compound, specifically,
N- (p-toluenesulfonyl) methacrylamide, N
-(P-toluenesulfonyl) acrylamide and the like are preferable
Can be used for Furthermore, as an alkali-soluble polymer compound
Is a polymerizable monomer having the phenolic hydroxyl group,
A polymerizable monomer having a sulfonamide group and an active monomer;
Polymerizes two or more of polymerizable monomers having a mid group
Polymer compounds, or two or more of these polymerizable compounds
Highly obtained by copolymerizing the monomer with other polymerizable monomers
It is preferred to use molecular compounds. Phenolic water
A polymerizable monomer having an acid group has a sulfonamide group.
With polymerizable monomers and / or active imide groups
When copolymerizing monomers,
The total mass ratio can be in the range of 50:50 to 5:95
Preferably in the range of 40:60 to 10:90
Is particularly preferred. In the lithographic printing plate precursor according to the present invention,
Potassium-soluble polymer having the phenolic hydroxyl group
Polymerizable monomer, polymerizable monomer having sulfonamide group
-Or polymerizable monomer having an active imide group and other
In the case of a copolymer with a polymerizable monomer, an alkali
The monomer that imparts solubility should contain 10 mol% or more
Preferably, it contains 20 mol% or more. A
Monomer component that gives lukali solubility from 10 mol%
If it is less, alkali solubility tends to be insufficient, and development
The effect of improving latitude may not be achieved sufficiently.
The Polymerizable module having the phenolic hydroxyl group
A polymerizable monomer having a monomer, a sulfonamide group,
Is copolymerized with a polymerizable monomer having an active imide group
Other monomer components that can be used include the following (m1)
The compounds listed in (m12) can be exemplified.
However, it is not limited to these. Alkaline water
Conventionally known methods for copolymerization of soluble polymer compounds are known.
Graft copolymerization method, block copolymerization method, run
A dam copolymerization method or the like can be used. (M1) 2-hydroxyethyl acrylate
Or aliphatic such as 2-hydroxyethyl methacrylate
Acrylic acid ester having a hydroxyl group and methacryl
Acid esters. (M2) Methyl acrylate, ethyl acrylate, acrylic
Propyl lurate, butyl acrylate, amyl acrylate,
Hexyl acrylate, octyl acrylate, acrylic acid
Benzyl, 2-chloroethyl acrylate, glycidyl
Alkyl acrylates such as acrylates; (M3) methyl methacrylate, ethyl methacrylate, me
Propyl tacrylate, butyl methacrylate, methacryl
Amyl acid, hexyl methacrylate, cyclomethacrylate
Hexyl, benzyl methacrylate, methacrylic acid-2-
Alkyl such as chloroethyl and glycidyl methacrylate
Methacrylate. (M4) Acrylamide, methacrylamide, N-methyl
Roll acrylamide, N-ethyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl aqua
Rilamide, N-hydroxyethylacrylamide, N
-Phenylacrylamide, N-nitrophenyl acrylic
Luamide, N-ethyl-N-phenylacrylamide, etc.
Acrylamide or methacrylamide. (M5) Ethyl vinyl ether, 2-chrome
Roethyl vinyl ether, hydroxyethyl vinyl ether
Tellurium, propyl vinyl ether, butyl vinyl ether
, Octyl vinyl ether, phenyl vinyl ether
Vinyl ethers such as (M6) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate
Kind. (M7) Styrene, α-methylstyrene, methylstyrene
And styrenes such as chloromethylstyrene. (M8) Methyl vinyl ketone, ethyl vinyl ketone, plastic
Vinyl such as propyl vinyl ketone and phenyl vinyl ketone
Ketones. (M9) Ethylene, propylene, isobutylene, butadi
Olefins such as ene and isoprene. (M10) N-vinylpyrrolidone, acrylonitrile,
Methacrylonitrile and the like. (M11) Maleimide, N-acryloylacrylami
, N-acetylmethacrylamide, N-propionyl
Methacrylamide, N- (p-chlorobenzoyl) meta
Unsaturated imides such as chloramide. (M12) Acrylic acid, methacrylic acid, maleic anhydride
Unsaturated carboxylic acids such as acids and itaconic acids. In the lithographic printing plate precursor according to the present invention,
The re-soluble polymer is a heavy polymer having the phenolic hydroxyl group.
Polymerizable monomer, polymerizable monomer having sulfonamide group
-Or single weight of polymerizable monomer having an active imide group
In the case of a polymer or copolymer, the mass average molecular weight is 2,000.
Those having 0 or more and a number average molecular weight of 500 or more are preferred.
More preferably, the weight average molecular weight is 5,000-30.
A number average molecular weight of 800 to 250,000
And the degree of dispersion (mass average molecular weight / number average molecular weight) is
1.1-10. Also, alkali-soluble high content
Child is phenol formaldehyde resin, cresol al
In the case of a resin such as a hydride resin, the mass average molecular weight is
500 to 20,000, and the number average molecular weight is 200 to
10,000 is preferred. These alkali-soluble polymer compounds are
Use one or a combination of two or more
30 to 99% by mass in the total solid content of the image recording layer,
Preferably it is 40-95 mass%, Most preferably, it is 50-9
Used in an addition amount of 0% by weight. Alkali-soluble polymer
If the added amount is less than 30% by mass, the durability of the image recording layer
In addition, when it exceeds 99% by mass, sensitivity and durability are deteriorated.
Unfavorable on both sides. [Infrared absorber] The lithographic printing plate precursor of the present invention
Infrared absorbing agent contained in the plate (hereinafter referred to as infrared absorbing dye)
Sometimes called. ) Dye that absorbs infrared light and generates heat
It is not particularly limited as long as it is a dye.
Various dyes known as materials can be used. As the infrared absorbing dye according to the present invention,
Commercial dyes and literature (eg “Dye Handbook” Synthetic Organic Chemistry Cooperation)
The publicly-known ones described in the association editing, published in 1970
Available. Specifically, azo dyes, metal complex azo dyes
Material, pyrazolone azo dye, anthraquinone dye, phthalo
Cyanine dye, carbonium dye, quinone imine dye,
Examples thereof include methine dyes and cyanine dyes. Book
In the invention, among these dyes, infrared light or near
Those that absorb infrared light emit infrared light or near infrared light.
It is particularly preferable in that it is suitable for use with a laser that emits light. Absorbs such infrared light or near infrared light.
Examples of dyes to be collected include, for example, JP-A-58-125246.
JP, 59-84356, JP 59-2028
29, JP-A-60-78787, etc.
Cyanine dyes, JP-A-58-173696, JP-A-5
No. 8-181690, Japanese Patent Laid-Open No. 58-194595, etc.
The methine dyes described, JP 58-112793
JP, 58-224793, JP 59-482
87, JP 59-73996, JP 60-52
940, JP-A-60-63744, etc.
Naphthoquinone dyes, JP-A-58-112792, etc.
Squaryllium dye described in British Patent 43
And cyanine dyes described in No. 4,875.
The Also, as a dye, US Pat. No. 5,156,
The near infrared absorption sensitizer described in No. 938 is also preferably used.
Substituted in U.S. Pat. No. 3,881,924
Arylbenzo (thio) pyrylium salt, JP-A-57-1
42645 (U.S. Pat. No. 4,327,169)
Trimethine thiapyrylium salt, JP-A 58-1810
51, 58-220143, 59-41363
No. 59-84248 No. 59-84249 No.
Described in 59-146063 and 59-146061
Pyryllium-based compounds, JP 59-2161
46, a cyanine dye described in U.S. Pat. No. 4,283,4
No. 75 pentamethine thiopyrylium salt, etc.
Disclosure in Japanese Patent Laid-Open Nos. 5-13514 and 5-19702
As a commercially available product, an epoxy
Epolight III-178, Epoli manufactured by Phosphorus
ght III-130, Epolight III-125, etc.
Is particularly preferably used. Also particularly preferred as a dye.
Another example is US Pat. No. 4,756,993.
Near-infrared as described in formulas (I) and (II)
Absorbing dyes can be mentioned. In the lithographic printing plate precursor according to the present invention, infrared rays are used.
The absorber is 0.01 to 50 based on the total solid content of the image recording layer.
% By weight, preferably 0.1-50% by weight, particularly preferred
Can be added at a ratio of 0.1 to 30% by mass.
When the added amount of the dye is less than 0.01% by mass, the sensitivity is low.
In addition, when it exceeds 50% by mass, each layer is uniform.
Tend to lose the durability of each layer. [Solubility-inhibiting compound] For lithographic printing plate of the present invention
The original version is an eye to increase its inhibition (solubility inhibition)
Therefore, the image recording layer contains various inhibitors.
Can. The inhibitor is particularly limited
No quaternary ammonium salt, polyethylene glycol
System compounds and the like. The quaternary ammonium salt is not particularly limited.
Tetraalkylammonium salt, trialkyl
Ruaryl ammonium salt, dialkyl diaryl an
Monium salt, alkyltriarylammonium salt,
Traaryl ammonium salt, cyclic ammonium salt, di
Examples include cyclic ammonium salts. Specifically, Tetra
Butylammonium bromide, tetrapentylammoni
Umbromide, tetrahexylammonium bromide,
Tetraoctylammonium bromide, tetralauryl
Ammonium bromide, tetraphenylammonium bromide
Lomid, tetranaphthyl ammonium bromide, tetra
Butylammonium chloride, tetrabutylammonium
Muzide, tetrastearyl ammonium bromide,
Lauryltrimethylammonium bromide, stearyl
Trimethylammonium bromide, behenyltrimethyl
Ammonium bromide, lauryltriethylammonium
Mubromide, phenyltrimethylammonium bromide
3-trifluoromethylphenyltrimethylammo
Nitrobromide, benzyltrimethylammonium bromide
, Dibenzyldimethylammonium bromide, dis
Tearyldimethylammonium bromide, Tristeari
Rumethylammonium bromide, benzyltriethyla
Ammonium bromide, hydroxyphenyltrimethyla
Numonium bromide, N-methylpyridinium bromide
Etc. The amount of quaternary ammonium salt added is the image recording layer.
The solid content is 0.1 to 50% of the total solid content of
And preferably 1-30%.
Yes. Less than 0.1% is preferable because it has less inhibitory effect on solubility.
It ’s not good. If 50% or more is added, the binder
This may adversely affect the film-forming property. As the polyethylene glycol compound,
Although it does not specifically limit, the thing of the following structure is mentioned. R ¹ -{-O- (R ^Three -O-) _m -R ² } _n (R ¹ Is a polyhydric alcohol residue or polyhydric phenol
Nord residue, R ² Is a hydrogen atom, C ₁ ~ _{twenty five} With a substituent of
Alkyl group, alkenyl group, alkynyl group, al
Kiroyl group, aryl group or aryloyl group, R ^Three Is
The alkylene residue which may have a substituent is shown. m is average
10 or more and n is an integer of 1 or more and 4 or less. ) Polyethylene glycol compound having the above structure
Examples of these are polyethylene glycols, polypropylene.
Len glycols, polyethylene glycol alkyl ester
Ethers, polypropylene glycol alkyl ethers
, Polyethylene glycol aryl ethers, poly
Propylene glycol aryl ethers, polyethylene
Glycol alkyl aryl ethers, polypropylene
Lenglycol alkylaryl ethers, polyethylene
Lenglycol glycerol ester, polypropylene
Recall glycerin esters, polyethylene sorbite
Ester, polypropylene glycol sorbitol
Esters, polyethylene glycol fatty acid esters
, Polypropylene glycol fatty acid esters, poly
Ethylene glycolated ethylenediamines, polypropylene
Lenglycolated ethylenediamines, polyethylene glycols
Recalled diethylenetriamines, polypropylene
Examples include recalled diethylenetriamines. Specific examples of these are as follows.
Recall 1000, Polyethylene glycol 2000,
Polyethylene glycol 4000, polyethylene glycol
10000, polyethylene glycol 20000,
Polyethylene glycol 5000, polyethylene glycol
100000, polyethylene glycol 20000
0, Polyethylene glycol 500000, Polypropylene
Lenglycol 1500, polypropylene glycol 3
000, polypropylene glycol 4000, polyethylene
Lenglycol methyl ether, polyethylene glycol
Ruethyl ether, polyethylene glycol phenyl ether
Ether, polyethylene glycol dimethyl ether, polyethylene
Liethylene glycol diethyl ether, polyethylene
Glycol diphenyl ether, polyethylene glycol
Lulauryl ether, polyethylene glycol dilauri
Ether, polyethylene glycol nonyl ether,
Polyethylene glycol cetyl ether, polyethylene
Glycol stearyl ether, polyethylene glycol
Rudistearyl ether, polyethylene glycol behehe
Nyl ether, polyethylene glycol dibehenyl A
Tellurium, polypropylene glycol methyl ether, poly
Propylene glycol ethyl ether, polypropylene
Glycol phenyl ether, polypropylene glycol
Dimethyl ether, polypropylene glycol diethyl
Luether, Polypropylene glycol diphenyl A
Tellurium, polypropylene glycol lauryl ether, poly
Ripropylene glycol dilauryl ether, polypro
Pyrene glycol nonyl ether, polyethylene glycol
Acetyl ester, polyethylene glycol diace
Chill esters, polyethylene glycol benzoate
Polyethylene glycol lauryl ester, polyester
Tylene glycol dilauryl ester, polyethylene glycol
Recall nonyl acid ester, polyethylene glycol ester
Tyrates, polyethylene glycol stearoyl
Ester, polyethylene glycol distearoyl s
Tellurium, polyethylene glycol behenate, poly
Ethylene glycol dibehenate, polypropylene
Glycol acetyl ester, polypropylene glycol
Diacetyl ester, polypropylene glycol
Benzoic acid ester, polypropylene glycol dibenzoic acid
Esters, polypropylene glycol lauric acid esthetics
, Polypropylene glycol dilaurate,
Polypropylene glycol nonylate, polyethylene
Lenglycol glycerol ether, polypropylene
Recall glycerin ether, polyethylene glycol
Sorbitol ether, polypropylene glycol sol
Bitol ether, polyethylene glycolated ethylene
Diamine, polypropylene glycolated ethylene diamine
Polyethylene glycolated diethylenetriamine,
Polypropylene glycolated diethylenetriamine, poly
Reethylene glycolated pentamethylenehexamine
I can get lost. Amount of polyethylene glycol compound added
Is 0.1 to 5 solids with respect to the total solid content of the image recording layer
0% is preferable, and 1-30%
More preferable. Less than 0.1% has little solubility-inhibiting effect
It is not preferable. When an amount exceeding 50% is added,
Polyethylene glycol that cannot interact with binder
Compound promotes penetration of developer and adversely affects image formation
May give. In addition, the above inhibition (solubility inhibition)
When improvement measures are taken, the sensitivity decreases.
In this case, it is effective to add a lactone compound.
When this lactone compound penetrates into the exposed area,
The developer and the lactone compound react to produce a new carboxylic acid
A compound is generated, contributing to dissolution of the exposed area and improving sensitivity.
It is considered a thing. Lactone compounds are particularly limited
The following general formula (LI) and general formula (LI
Examples thereof include compounds represented by I). ## STR1 ## Embedded image In general formula (LI) and general formula (L-II)
X ¹ , X ² , X ^Three And X ^Four Is a ring atom or atom
It is a child group that may be the same or different and independent
May have a substituent, and in general formula (LI)
X ¹ , X ² And X ^Three And at least one of the general formula (LI
X in I) ¹ , X ² , X ^Three And X ^Four At least one of
Are substituted with an electron-withdrawing group or an electron-withdrawing group.
Has a substituent. X ¹ , X ² , X ^Three And X ^Four Ring structure represented by
An adult atom or group of atoms is two single bonds to form a ring
A non-metallic atom or an atomic group containing the non-metallic atom
The Preferred non-metallic atoms or non-metallic atomic groups are methylene
Group, sulfinyl group, carbonyl group, thiocarbonyl
Group, sulfonyl group, sulfur atom, oxygen atom and selenium
An atom or atomic group selected from atoms, more preferred
Or from methylene, carbonyl and sulfonyl groups
The atomic group to be selected. X in the general formula (LI) ¹ , X ² And X
^Three Or at least one of the general formula (L-II) ¹ ,
X ² , X ^Three And X ^Four At least one of the electron withdrawing groups
Have. In this specification, an electron-withdrawing substituent is a hammet.
The substituent constant [sigma] p is a group having a positive valence. Hammett
For the substituent constants of the Journal of Medicinal Chem
Refer to istry, 1973, Vol. 16, No. 11, 1207-1216, etc.
You can. Hammett's substituent constant σp takes a positive value
Examples of electron-withdrawing groups include halogen atoms (fluorine atoms).
Child (σp value: 0.06), chlorine atom (σp value: 0.2)
3), bromine atom (σp value: 0.23), iodine atom (σ
p value: 0.18)), trihaloalkyl group (tribromo)
Methyl (σp value: 0.29), trichloromethyl (σp
Value: 0.33), trifluoromethyl (σp value: 0.5)
4)), cyano group (σp value: 0.66), nitro group (σ
p value: 0.78), aliphatic, aryl or heterocyclic
A sulfonyl group (for example, methanesulfonyl (σp value: 0.
72)), aliphatic / aryl or heterocyclic acyl groups
(For example, acetyl (σp value: 0.50), benzoyl
(Σp value: 0.43)), an alkynyl group (for example, C≡
CH (σp value: 0.23)), aliphatic / aryl or
Is a heterocyclic oxycarbonyl group (for example, methoxycarbo
Nyl (σp value: 0.45), phenoxycarbonyl (σ
p value: 0.44)), carbamoyl group (σp value: 0.3
6), sulfamoyl group (σp value: 0.57), sulfo
Examples include xoxide groups, heterocyclic groups, oxo groups, and phosphoryl groups.
I can get lost. Preferred electron withdrawing groups are amide groups and azo groups.
Group, nitro group, fluoroalkyl group having 1 to 5 carbon atoms,
Tolyl group, C1-C5 alkoxycarbonyl group, charcoal
Prime number 1-5 acyl group, carbon number 1-9 alkyl sulfo
Nyl group, C6-C9 arylsulfonyl group, carbon number
1-9 alkylsulfinyl groups, 6-9 carbon atoms
Sulsulfinyl group, arylcarboni having 6 to 9 carbon atoms
Group, thiocarbonyl group, fluorine-containing alkyl having 1 to 9 carbon atoms
Kill group, fluorinated aryl group having 6 to 9 carbon atoms, 3 carbon atoms
~ 9 fluorine-containing allyl group, oxo group and halogen element?
Is a group selected from More preferably, nitro group, carbon
Number 1-5 fluoroalkyl group, nitrile group, carbon number 1
-5 alkoxycarbonyl group, C1-5 acyl
Group, arylsulfonyl group having 6 to 9 carbon atoms, 6 to carbon atoms
9 arylcarbonyl groups, oxo groups and halogen elements
Is a group selected from In the following, general formula (LI) and
Shows specific examples of the compound represented by formula (L-II)
However, the present invention is not limited to these compounds.
Yes. Embedded image Embedded image In general formula (LI) and general formula (L-II)
The amount of the compound represented is the total solid content of the image recording layer.
The solid content is preferably 0.1 to 50%, preferably 1 to 30%.
% Is more preferable. Less than 0.1% has little effect, 5
When 0% or more is added, the image formability is poor. In addition, this
Since the compound reacts with the developer, the developer is contacted selectively.
It is desirable to do. This lactone compound is either
One type may be used or may be used together. Also two or more types
A compound of general formula (LI), or two or more general formulas (L
-II) The total addition amount of the compound is within the above range, and an arbitrary ratio
You may use together. In the lithographic printing plate precursor according to the invention,
Is further decomposable in the state of being pyrolyzable and not pyrolyzing.
Contains substances that substantially reduce the solubility of potash-soluble resin
Is having the point of further expanding the difference between the unexposed areas and exposed areas?
Is preferable. This “pyrolytic and non-pyrolytic state”
In the state, the solubility of the alkali-soluble resin is substantially reduced.
There are no particular restrictions on the substance, but various onions
And quinonediazide compounds. Especially heat
From the viewpoint of decomposability, an onium salt is preferable. Onium salts include diazonium salts, a
Ammonium salt, phosphonium salt, iodonium salt, sulfur
Listed include honium salts, selenonium salts, arsonium salts, etc.
You can Onium salts used in the present invention
For example, SI Schlesinge
r, Photogr. Sci. Eng., 18, 387 (1974), T.
S. Bal et al, Polymer, 21, 423 (1980),
Diazonium described in JP-A-5-158230
Salt, U.S. Pat. Nos. 4,069,055 and 4,069,0
56, Re 27,992, No. 3-14014
The ammonium salt described in the specification of No. 0, DC Necker e
t al, Macromolecules, 17, 2468 (1984), C.I.
S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p
478 Tokyo, Oct (1988), US Pat. No. 4,069,
Phosphoniums described in Nos. 055 and 4,069,056
Salt, JV Crivello et al, Macromorecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov.
28, p31 (1988), European Patent No. 104,143
U.S. Pat.Nos. 339,049 and 410,201.
No. 1, JP-A-2-150848, JP-A-2-296514
Iodonium salt, JV Crivello et al, Po
lymer J. 17, 73 (1985), JV Crivelloeta
l. J. Org. Chem., 43, 3055 (1978), WR
Watt et al, J. Polymer Sci., Polymer Chem. Ed.,
22, 1789 (1984), JV Crivelloet al, P
olymer Bull., 14, 279 (1985), JV Criv
ello et al, Macromorecules, 14 (5), 1141 (1
981), JV Crivello et al, J. Polymer Sci., Po
lymer Chem. Ed., 17, 2877 (1979), Europe
Patent Nos. 370,693, 3,902,114,
233,567, 297,443, 297,4
42, U.S. Pat.No. 4,933,377, 161,
811, 410,201, 339,049
No. 4,760,013, No. 4,734,444,
No. 2,833,827, German Patent No. 2,904,626
No., No. 3,604,580, No. 3,604,581
The sulfonium salt described, JV Crivello et al, Macrom
orecules, 10 (6), 1307 (1977), JV Criv
ello etal, J. Polymer Sci., Polymer Chem. Ed., 1
7, 1047 (1979), selenonium salt, C.I.
S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA,
p478 Arsonium salt described in Tokyo, Oct (1988)
Etc. In the lithographic printing plate precursor of the present invention,
Diazonium salts are particularly preferred. Also particularly suitable dia
Zonium salts described in JP-A-5-158230
Can be mentioned. The counter ion of the onium salt is tetrafluoride.
Boric acid, hexafluorophosphoric acid, triisopropylnaphthalene
Sulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfo
Acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfuric acid
Phosphonic acid, 3-bromobenzenesulfonic acid, 2-fluoro
Capryl naphthalene sulfonic acid, dodecyl benzene sul
Phosphonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy
Ci-4-hydroxy-5-benzoyl-benzenesulfo
Acid and p-toluenesulfonic acid
The Among these, especially hexafluorophosphoric acid and triisopro
Pyrnaphthalene sulfonic acid or 2,5-dimethylbenzene
Alkyl aromatic sulfonic acids such as sulfonic acids are preferred.
is there. The amount of the above substance added is preferably 0.1-50
% By weight, more preferably 0.1 to 30% by weight, particularly preferred
Or 0.3 to 30% by mass. Suitable quinonediazides include o-quino.
And diazide compounds. Used in the present invention
The o-quinonediazide compound obtained is at least one
It is a compound having o-quinonediazide group.
Compounds with various structures that increase alkali solubility
Can be used. That is, o-quinonediazide is
Loss of ability to inhibit dissolution of alkali-soluble resin by thermal decomposition
And o-quinonediazide itself is an alkali-soluble substance
Helps lower layer solubility by both effects of changing to
The As an o-quinonediazide compound used in the present invention
For example, J. et al. By Korser “Light-sensitive”
・ Systems ”(John Wiley & Sons. Inc.) 339-
The compounds described on page 352 can be used.
Aromatic polyhydroxy compounds or aromatic amino compounds
Sulfonate ester of o-quinonediazide reacted with
Alternatively, sulfonic acid amide is preferable. Also, Shoko 4
Benzoxy as described in Japanese Patent Publication No. 3-28403
Non (1,2) -diazide sulfonic acid chloride or
Naphthoquinone- (1,2) -diazide-5-sulfonic acid
Este of chloride and pyrogallol-acetone resin
U.S. Pat. Nos. 3,046,120 and 3,18.
Benzoquinone- (1,
2) -Diazide sulfonic acid chloride or naphthoquino
-(1,2) -diazide-5-sulfonic acid chloride
And esters of phenol-formaldehyde resin are also preferred
Used properly. Further, naphthoquinone- (1,2) -diazi
Do-4-sulfonic acid chloride and phenol formal
Dehydric resin or cresol-formaldehyde resin
And naphthoquinone- (1,2) -diazide-
4-sulfonic acid chloride and pyrogallol-acetone tree
Ester with fat is also preferably used. Other existence
Numerous patents for o-quinonediazide compounds
Reported and known. For example, JP-A 47-5303
No. 4, JP-A-48-63802, JP-A-48-6380
3, JP-A-48-96575, JP-A-49-387
01, JP-A-48-13354, JP-B-41-11
222, Shoko 45-9610, Shoko 49-17
481, U.S. Pat. Nos. 2,797,213, 3,4
54,400, 3,544,323, 3,57
3,917, 3,674,495, 3,783
No. 5,825, British Patent No. 1,227,602, No. 1,
No. 251,345, No. 1,267,005, No. 1,3
No. 29,888, No. 1,330,932, German patent
It is described in each specification such as No. 854,890
Things can be mentioned. O-key used in the present invention
The amount of the non-diazide compound added is preferably an image recording layer
1 to 50% by mass, more preferably 5 to 5%, based on the total solid content
30 mass%, particularly preferably in the range of 10-30 mass%
is there. These compounds can be used singly, but several
It may be used as a compound. o-Quinonediazide compounds
When the amount of addition is less than 1% by mass, the image recording property deteriorates,
In addition, when it exceeds 50% by mass, the durability of the image portion deteriorated.
Sensitivity is reduced. From the viewpoint of degradability, heat content
The desolvable substance is more preferably an onium salt. This pyrolytic property
By using a high onium salt,
It further promotes the decomposition of the decomposable substance, so that
It is thought that it is improving the crime. The lithographic printing plate precursor according to the present invention comprises the above-described composition.
An image-recording layer containing a component as an essential component is provided on the support.
These image recording layers are at least
Also, a multilayer structure of two or more layers may be used (for convenience, the upper
The case of two layers consisting of a side layer and a lower layer will be described). That
If the upper layer and lower layer constitute an alkali-soluble resin
Apply the alkali-soluble resin described above
The upper layer is more resistant to alkali than the lower layer.
It is preferable that the solubility is low. Infrared absorption
The collector may be a different infrared absorber in each layer.
In addition, an infrared absorber consisting of multiple compounds is used for each layer.
May be. As an amount to be included, it is used for any layer
As described above, the total solid content of the layer to be added
0.01 to 50 mass%, preferably 0.1 to 50 mass
% By weight, particularly preferably 0.1 to 30% by weight
can do. Addition amount when adding to multiple layers
It is preferable to add so that the total
Yes. The above-mentioned heat decomposable and not pyrolyzed
In the state, the solubility of the alkali-soluble resin is substantially reduced.
The substance to be decomposed may be partially decomposed over time
When the image recording layer has a multilayer structure, it is contained in the lower layer.
Is effective, but in any layer,
Both layers may be sufficient. As an amount to be contained, as described above
Street. When adding to multiple layers, add the total amount
Is preferably added in such a range. Ma
In the case of a multi-layer structure, the lactone compound is added to the upper layer.
It is effective to contain, but in any layer
Or both layers. [Other components] The image recording layer is formed.
In addition to the above essential components, the effects of the present invention
As long as it is not damaged, various accessories
Additives can be added. Examples of additives are given below.
Explain. For example, the distinction between the image portion and the non-image portion (decoding
Resistance against strengthening and surface scratches
For the purpose of strengthening the drag, JP 2000-187318 A
3 to 20 carbon atoms in the molecule as described in
-(Meth) actyl having 2 or 3 fluoroalkyl groups
Using a polymer containing a relate monomer as a polymerization component
preferable. Such compounds can be
It may be contained in either the layer or the lower layer, but it is more effective
What is included is to be contained in the upper layer. As addition amount
Is preferably 0.1 to 10% by mass in the layer material
More preferably, it is 0.5 to 5% by mass. In the image recording layer of the lithographic printing plate precursor of the present invention
In order to provide resistance to scratches,
Compounds that reduce the coefficient of friction can also be added.
Specifically, it is used in US Pat. No. 6,117,913.
Such as esters of long-chain alkyl carboxylic acids.
I can make it. Such compounds are
May be included in either the lower layer or the upper layer,
It is more effective to contain it in the upper layer. Addition
The preferred amount is the percentage of the material forming the layer.
0.1 to 10% by mass, more preferably 0.5 to 5%
%. If necessary, it has low molecular weight acidic groups.
It may contain the compound to do. Sulfone as acidic group
Examples include acid, carboxylic acid, and phosphoric acid groups. Inside
Also preferred are compounds having sulfonic acid groups. Specifically
Is p-toluenesulfonic acid, naphthalenesulfonic acid, etc.
List of aromatic sulfonic acids and aliphatic sulfonic acids
You can. Such a compound can be
It may be contained in either the layer or the upper layer. As addition amount
Preferably, the proportion of the material forming the layer is 0.
05-5 mass%, more preferably 0.1-3 mass%
The If it exceeds 5%, the solubility of each layer in the developer increases.
This is not preferable. In the present invention, the solubility is adjusted.
For this purpose, various dissolution inhibitors may be included. Dissolution inhibitor
As shown in Japanese Patent Laid-Open No. 11-119418
Such disulfone compounds or sulfone compounds are preferably used.
As a specific example, 4,4′-bishydroxyphene
It is preferable to use nylsulfone. Such a compound
In the case of multiple layers, the product is contained in either the lower layer or the upper layer.
It may be allowed. The preferred addition amount is that each layer is
The proportion of the constituent material is 0.05 to 20% by mass,
More preferably, it is 0.5-10 mass%. Further, in order to further improve the sensitivity, an annular shape is used.
Use of acid anhydrides, phenols, and organic acids in combination
it can. US Pat. No. 4,115,1 as a cyclic acid anhydride
Phthalic anhydride, tetrahydro
Drophthalic anhydride, hexahydrophthalic anhydride, 3,6
-Endooxy-Δ4-tetrahydrophthalic anhydride,
Tetrachlorophthalic anhydride, maleic anhydride, no chloro
Maleic anhydride, α-phenylmaleic anhydride, succinic anhydride
Succinic acid, pyromellitic anhydride, etc. can be used. Fenault
Bisphenol A, p-nitrophenol
, P-ethoxyphenol, 2,4,4'-trihydride
Roxybenzophenone, 2,3,4-trihydroxybenzene
Nzophenone, 4-hydroxybenzophenone, 4,
4 ', 4 "-trihydroxytriphenylmethane, 4,
4 ', 3 ", 4"-tetrahydroxy-3,5,3',
And 5'-tetramethyltriphenylmethane.
The Further, as organic acids, JP-A-60-88942
No., Japanese Patent Laid-Open No. 2-96755, etc.
Sulfonic acids, sulfinic acids, alkyl sulfates,
Phosphonic acids, phosphate esters and carboxylic acids
Specifically, p-toluenesulfonic acid, dodecy
Rubenzenesulfonic acid, p-toluenesulfinic acid,
Til sulfuric acid, phenylphosphonic acid, phenylphosphine
Acid, phenyl phosphate, diphenyl phosphate, benzoic acid,
Sophthalic acid, adipic acid, p-toluic acid, 3,4-di
Methoxybenzoic acid, phthalic acid, terephthalic acid, 4-cycl
Lohexene-1,2-dicarboxylic acid, erucic acid, lauric
Acid, n-undecanoic acid, ascorbic acid, etc.
It is. The above cyclic acid anhydrides, phenols and organic acids
The proportion of the material constituting the layer is 0.05 to 20
% By mass is preferred, more preferably 0.1 to 15 mass.
%, Particularly preferably 0.1 to 10% by mass. In the image recording layer coating solution, the development conditions are
In order to broaden the stability of the treatment against
1740 and JP-A-3-208514
Nonionic surfactants such as those described in JP-A-59-1
No. 21044, JP-A-4-13149
Amphoteric surfactants, such as EP950517
Siloxane compounds as described in
A hook such as that described in Japanese Patent No. 11-288093.
A monomer-containing monomer copolymer can be added. This
If the image recording layer has a multilayer structure, either
It can be used for one or both. Specific examples of nonionic surfactants include so
Rubitan tristearate, sorbitan monopalmitate
, Sorbitan trioleate, monoglyceride stearate
Lido, polyoxyethylene nonylphenyl ether, etc.
Can be mentioned. Specific examples of amphoteric surfactants include
Rudi (aminoethyl) glycine, alkylpolyamino ester
Tilglycine hydrochloride, 2-alkyl-N-carboxyl
Tyl-N-hydroxyethylimidazolinium betaine
And N-tetradecyl-N, N-betaine type (for example, quotient
Product name “Amorgen K” (Daiichi Kogyo Co., Ltd.)
It is. Examples of siloxane compounds include dimethylsilane.
Block copolymer of loxane and polyalkylene oxide
As a specific example, DBE-2 manufactured by Chisso Corporation
24, DBE-621, DBE-712, DBP-73
2, DBP-534, Tego Gli manufactured by Tego, Germany
Polyalkylene oxide modified silicone such as de100
Can be mentioned. Nonionic surfactant and both
The proportion of the surfactant in the coating solution material is 0.05.
˜15% by mass is preferable, and more preferably 0.1 to 5%.
%. Further, in the image recording layer, the exposure is increased.
Print-out agent to obtain a visible image immediately after heating, and image coloring
Dyes and pigments as agents can be added. Bakeout
As an agent, a compound that releases acid by heating by exposure.
Combination of organic dyes that can form salts with products (photoacid releasing agents)
Can be cited as a representative. Specifically, JP-A-5
Described in each publication of 0-36209 and 53-8128
O-Naphthoquinonediazide-4-sulfonic acid
Combinations of halogenides and salt-forming organic dyes;
-36223, 54-74728, 60-36
No. 26, No. 61-143748, No. 61-15164
No. 4 and 63-58440
A combination of trihalomethyl compounds and salt-forming organic dyes
Can be mentioned. Such trihalomethyl compounds
The oxazole compound and the triazine compound
Yes, both have excellent temporal stability and clear printout images
give. As the colorant of the image, the above-mentioned salt forming property is present.
Other dyes can be used in addition to the machine dye. Salt formation
Oil-soluble dyes and bases as suitable dyes, including organic dyes
Can be mentioned. Specifically, oil yellow
-# 101, Oil Yellow # 103, Oil Pink #
312, Oil Green BG, Oil Blue BOS, Oh
Ilblue # 603, Oil Black BY, Oil Bra
BS, Oil Black T-505 (orientated
Chemical Industry Co., Ltd.), Victoria Pure Blue, Chris
Tal violet (CI42555), methyl violet
(CI42535), ethyl violet, loader
Min B (CI145170B), Malachite Green
(CI42000), methylene blue (CI5201)
5). JP-A 62-2
The dyes described in Japanese Patent No. 93247 are particularly preferred
Yes. These dyes are in an amount of 0.
01 to 10% by mass, preferably 0.1 to 3% by mass
Can be added to the printing plate material. These are pictures
If the image recording layer has a multilayer structure, either one or both
Can be used. Further, in the printing plate material of the present invention, if necessary.
Plasticizers are added to provide flexibility, etc.
The For example, butyl phthalyl, polyethylene glycol
, Tributyl citrate, diethyl phthalate, phthalic acid
Dibutyl, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trio phosphate
Cutyl, tetrahydrofurfuryl oleate, acrylic
Used by oligomers and polymers of acid or methacrylic acid
It is done. The composition described above is a moisture content control of the image recording layer.
From the viewpoint of control, those having a low water content are preferred. Especially 0.
It is preferably 1% or less. In the present specification, the lower layer is a multilayer on the support.
It refers to the layer close to the support of the layer provided in the configuration. Shi
Therefore, it includes that the lower layer of the image recording layer is the lower layer.
It is out. Further, a layer having no image recording function is an image recording layer.
It is also provided between the support and the lower layer
is there. In the former case, if there is no risk of misunderstanding,
The upper layer is simply called the image recording layer and the lower layer is called the lower layer.
Sometimes. The latter lower layer does not contain an infrared absorber.
As a component of the image recording layer,
Each component described above can be contained, and its content
As an addition amount to the solid component constituting the image recording layer
It can be made to contain in the content range described. However,
Is it the viewpoint of setting the solubility of the lower layer higher than the upper layer?
Et al., Solubility-inhibiting compounds, solubility-accelerating compounds, development sensitivity
Adjustment of the amount of compound with an improving effect and new addition
Be made. The lithographic printing plate precursor according to the present invention comprises an image recording layer.
Alternatively, the above components constituting the lower layer are dissolved in a solvent,
It can be formed by coating on a suitable support
Yes. The composition of the image recording layer and the solvent in the lower layer is the
It can be selected depending on the component. Image recording layer
In the lower layer, each component is dissolved separately in a solvent.
And forming by sequentially coating on the support
Can do. The solvent used here is ethylenediamine.
Rholide, cyclohexanone, methyl ethyl ketone,
Tanol, ethanol, propanol, ethylene glyco
Monomethyl ether, 1-methoxy-2-propano
, 2-methoxyethyl acetate, 1-methoxy-
2-propyl acetate, dimethoxyethane, lactic acid methyl
, Ethyl lactate, N, N-dimethylacetamide, N,
N-dimethylformamide, tetramethylurea, N-
Methyl pyrrolidone, dimethyl sulfoxide, sulfora
Γ-butyrolactone, toluene, etc.
However, it is not limited to this. These solvents are
Used alone or in combination. Used for coating
The solvent to be used preferably has a water content of 0.1% or less. After applying the lower layer, the image recording is adjacent to it.
When applying the recording layer, the lower layer alkali is used as the coating solvent.
Using a solvent that can dissolve soluble polymers,
Mixing cannot be ignored.
Sometimes it becomes a single layer. Thus, adjacent
Mixing occurs at the interface between the two layers
When it behaves like one layer, the effect of having two layers
The fruit may be damaged, which is not preferable. For this reason,
The solvent used to apply the image recording layer is contained in the lower layer.
Hope to be a poor solvent for alkali-soluble polymers
Good. The above components (additions) in the solvent when applying each layer
The concentration of the total solid content including the agent is preferably 1 to 50 mass
%. When the image recording layer has a multilayer structure,
The coating amount (solid content) of the upper and lower layers depends on the application.
But the upper layer is 0.05-1.0 g / m ² In
The lower layer is 0.3-3.0 g / m ² Prefer to be
That's right. Upper layer is 0.05 g / m ² If it is less than
The image formability deteriorates and 1.0 g / m ² Sensitivity exceeds
There is a possibility of decline. In addition, the total of the two layers
0.5-3.0 g / m ² It is preferable that the coating amount
0.5g / m ² If it is less than 3, the film properties are deteriorated.
0g / m ² If it exceeds, the sensitivity tends to decrease. Coating
As the amount decreases, the apparent sensitivity increases,
The film properties of the upper and lower layers are reduced. Apply the lower layer and the image recording layer on the support.
Various methods can be used as the method to
For example, bar coater coating, spin coating, spray coating,
Curtain coating, dip coating, air knife coating, blurring
For example, it can be applied by a method such as a cord coating or a roll coating. The present invention
In the image recording layer, the surface activity is improved to improve the coatability.
Agents, for example, described in JP-A-62-170950
Fluorosurfactant can be added
The A preferable addition amount is 0.0 in the total solid content of the layer to be added.
1-1% by mass, more preferably 0.05-0.5% by mass
%. As described above, the lithographic printing plate of the present invention
The water content of the image recording layer of the original plate is 1.0% by weight or more
In order to achieve this, an appropriate amount of water is added to the image recording layer coating solution.
It is preferable to do. After the lower layer is coated on the support, and image
After the recording layer is coated on it, each is dried
It is. As a drying method, using a known general method
Done. For example, hot air is applied to the coated substrate
Convection heating method by spraying and drying, JP-A-60-149871
Radiation from heating plates placed above and below the support described in the publication
Radiation heating method for drying by heat, JP-A-60-21334
Roller described in Japanese Patent Laid-Open No. 60-62778
Conduct the heat medium inside and contact the support with this roller.
Heat transfer to dry by heat conduction from the roller surface
A thermal method or the like can be used. Even in the above method,
Convection drying with hot air is preferred. Meanwhile, image recording
From the point of controlling the moisture content in the bed, the moisture content of the hot air is 0.0
07 kg / kg or less is preferable, and 0.05 kg / kg is more preferable.
Kg or less is preferable. Regarding the developability of the lithographic printing plate precursor,
If these drying conditions are harsh, image forming developer
The conductivity of the film becomes high (developability becomes low) and is moderate.
If so, the conductivity of the developer capable of forming an image is lowered (development
Tend to be higher). The selection of the desired drying conditions is
Air temperature, air volume, air flow direction, contact heat medium temperature and material
This is done by adjusting the conditions. Image recording layer coating
It is preferable that the residual solvent in the immediately preceding lower layer is small. Like
Or 80 mg / m ² Or less, more preferably 60 mg
/ M ² It may be the following. [Support] Used for the lithographic printing plate precursor of the present invention.
As a support that can be used, it has the necessary strength and durability.
Examples include dimensionally stable plates, such as paper, plus
Tic (eg polyethylene, polypropylene, poly
Paper, metal plates (for example, styrene)
Aluminum, zinc, copper, etc.), plastic film
(For example, cellulose diacetate, cellulose triacetate, pro
Cellulose pionate, cellulose butyrate, cellulose acetate butyrate
Cellulose, cellulose nitrate, polyethylene terephthalate,
Polyethylene, polystyrene, polypropylene, polycarbonate
-Bonate, polyvinyl acetal, etc.)
Metal or laminated paper or plastic
For example, a plastic film is included. Supports that can be used in the lithographic printing plate precursor of the present invention
As the holder, polyester film or aluminum
A plate is preferred, among which dimensional stability is good and relatively low.
An aluminum plate which is a valence is particularly preferred. Suitable aluminum
The nickel plate is made of pure aluminum plate and aluminum.
It is an alloy plate containing minute amounts of foreign elements, and aluminum
Plastic film laminated or vapor-deposited with nitrogen
It may be a film. For different elements contained in aluminum alloys
Are silicon, iron, manganese, copper, magnesium, black
, Zinc, bismuth, nickel, titanium, etc. Together
The content of foreign elements in gold is at most 10% by mass. Book
Particularly suitable aluminum in the invention is pure aluminum.
However, completely pure aluminum is manufactured by refining technology.
Because it is difficult to manufacture, even those that contain slightly different elements
Good. Thus, the aluminum plate applied to the present invention
The composition is not specified and is conventionally known
It is possible to use aluminum plates made of public materials as appropriate
Yes. The thickness of the aluminum plate used in the present invention is
About 0.1 mm to 0.6 mm, preferably 0.15 m
m to 0.4 mm, particularly preferably 0.2 mm to 0.3 m
m. Prior to roughening the aluminum plate,
If desired, for example, the surface activity to remove surface rolling oil
Degreasing treatment with an organic agent, organic solvent or alkaline aqueous solution
Is done. The roughening treatment of the surface of the aluminum plate
This can be done in various ways, for example mechanically roughening
A method for electrochemically dissolving and roughening a surface; and
It is carried out by a method of selectively dissolving the surface chemically. Machine
Mechanical methods include ball polishing, brush polishing, and bra
Use known methods such as strike polishing and buff polishing
Can do. As an electrochemical surface roughening method, hydrochloric acid or
There is a method of performing AC or DC in nitric acid electrolyte.
Moreover, it is disclosed by Unexamined-Japanese-Patent No. 54-63902.
You can also use a method that combines both
The The roughened aluminum plate can be used as needed.
After the alkaline etching treatment and neutralization treatment,
Anodic acid to increase surface water retention and wear resistance as desired
Is applied. For anodizing of aluminum plates
The electrolyte that can be used is a species that forms a porous oxide film.
Various electrolytes can be used, generally sulfuric acid, phosphoric acid,
Succinic acid, chromic acid or a mixed acid thereof is used. So
The concentration of these electrolytes is determined appropriately according to the type of electrolyte.
It is. The treatment conditions for anodization depend on the electrolyte used.
Since it varies, it is not possible to specify it in general, but in general electrolytes
The solution has a concentration of 1 to 80% by mass, the liquid temperature is 5 to 70 ° C., and the current
Density 5-60A / dm ² , Voltage 1-100V, Electrolysis time
A range of 10 seconds to 5 minutes is appropriate. Anodized film
Is 1.0 g / m ² If it is less, the printing durability is insufficient.
Or the non-image part of the planographic printing plate is easily scratched,
Ink adheres to the scratched part during printing.
This is likely to occur. After anodizing,
If necessary, the surface of the minium is subjected to a hydrophilic treatment. Main departure
Hydrophilization applied to the support of the lithographic printing plate precursor related to Ming
As processing, US Pat. No. 2,714,066,
No. 3,181,461, No. 3,280,734 and No.
Alkalis as disclosed in US Pat. No. 3,902,734
Metal silicate (for example, sodium silicate aqueous solution) method
is there. In this method, the support is sodium silicate
It is immersed in an aqueous solution or electrolytically treated. Other special
Difluoride disclosed in Japanese Patent Publication No. 36-22063
Potassium luconate and US Pat. No. 3,276,868
No. 4,153,461 No. 4,689,27
Treated with polyvinylphosphonic acid as disclosed in No. 2
Or the like. The lithographic printing plate precursor of the present invention is formed on a support.
At least the image recording layer described above is provided,
If necessary, provide an undercoat layer between the support and the image recording layer
Can. Various organic compounds as undercoat layer components
For example, carboxymethylcellulose,
Cistrin, gum arabic, 2-aminoethylphosphone
Phosphonic acids with amino groups such as acids, with substituents
Phenylphosphonic acid, naphthylphosphonic acid,
Rualkylphosphonic acid, glycerophosphonic acid, methylenediphos
Organic phosphones such as sulfonic acid and ethylenediphosphonic acid
Acid, phenylphosphoric acid optionally substituted, naphthyl
Organic acids such as acid, alkyl phosphate and glycerophosphate
Acid, phenylphosphinic acid optionally having substituent,
Futylphosphinic acid, alkylphosphinic acid and glyce
Organic phosphinic acids such as lophosphinic acid, glycine and β
-Amino acids such as alanine, and triethanolamine
Hydrochlorides of amines having a hydroxy group, such as hydrochlorides of amines
It is selected from the above, but two or more may be used in combination. Furthermore, it has a structural unit represented by the following formula:
At least one compound selected from the group of organic polymer compounds
An undercoat layer containing a material is also preferred. Embedded image R ¹¹ Is a hydrogen atom, halogen atom or alkyl
R group, R ¹² And R ¹³ Each independently
Child, hydroxyl group, halogen atom, alkyl group, substituted alkyl
Group, aryl group, substituted aryl group, -OR ¹⁴ , -COO
R ¹³ , -CONHR ¹⁶ , -COR ¹⁷ Or -CN
Or R ¹² And R ¹³ May combine to form a ring
R ¹⁴ ~ R ¹⁷ Each independently represents an alkyl group or
X represents a hydrogen atom, a metal atom, NR ¹⁸ R ¹⁹ R
²⁰ R ^{twenty one} Represents R ¹⁸ ~ R ^{twenty one} Each independently
Child, alkyl group, substituted alkyl group, aryl group or
Represents a substituted aryl group or R ¹⁸ And R ¹⁹ Combined
A ring may be formed, and m represents an integer of 1 to 3. This undercoat layer is provided by the following method.
Can do. That is, water or methanol, ethanol, methyl
Organic solvents such as ruethyl ketone or mixed solutions
A solution prepared by dissolving the above organic compound in the agent is aluminum.
Applying and drying on a plate, water or methanol
Organic solvents such as water, ethanol and methyl ethyl ketone
Alternatively, the above organic compound is dissolved in the mixed solvent.
The above compound is adsorbed by immersing an aluminum plate in the solution.
Then wash and dry with water, etc.
It is a method to make. In the former method, the above organic compound
Apply a solution with a concentration of 0.005 to 10% by mass by various methods.
Can be clothed. In the latter method, the concentration of the solution is 0.01
-20% by weight, preferably 0.05-5% by weight,
The immersion temperature is 20 to 90 ° C, preferably 25 to 50 ° C.
The immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1
Minutes. The solution used for this is ammonia, triethyl.
Basic substances such as ruamine and potassium hydroxide, hydrochloric acid,
Adjust to pH 1-12 with acidic substances such as phosphoric acid
You can also In addition, the tone reproducibility of image recording materials has been improved.
A yellow dye may be added for good. Undercoat
The coating amount is 2 to 200 mg / m ² Is suitable and preferred
5-100mg / m ² It is. The above coating amount is 2m
g / m ² If it is less, sufficient printing performance cannot be obtained.
200 mg / m ² It is the same even if it is larger. [Plate making / printing] Created as described above
The lithographic printing plate precursor has a slip sheet between the printing plate precursors.
In the form of products stacked and packaged in the inserted state
Shipped, transported and stored in a general manner
is there. As a typical aspect in plate making and printing,
The autoloader creates a pair of interleaving paper and original plate.
Secured by the autoloader, transported, and plate making
Attached and fixed to the table, then the slip is removed
Although it is an aspect, it is not limited to this. The place where plate making is done
The apparatus is on a printing press in the direct printing plate system. Is slip paper removed?
The exposed original is subjected to image exposure and development. For image exposure
The active light source used is from near infrared to infrared.
A light source with a light emission wavelength in the region is preferable, and scanning is not always necessary
It may not be a method, that is, a surface exposure method may be used.
Scanning method using solid laser or semiconductor laser
The formula exposure is preferred. The emission wavelength is 760-10.
80 nm is preferable. Application to the lithographic printing plate precursor of the present invention
The developer that can be used has a pH in the range of 9.0 to 14.0.
The developer is preferably in the range of 12.0 to 13.5.
The For developer (hereinafter referred to as developer including replenisher)
The conventionally known alkaline aqueous solution can be used.
The For example, sodium silicate, potassium, tertiary phosphorus
Sodium, potassium, ammonium, secondary phosphorus
Sodium, potassium, ammonium, sodium carbonate
Lithium, potassium, ammonium, sodium bicarbonate
Um, potassium, ammonium, sodium borate
, Potassium, ammonium, sodium hydroxide,
No ammonium, potassium or lithium
Examples include alkali salts. Monomethylamine,
Dimethylamine, trimethylamine, monoethylamine
, Diethylamine, triethylamine, monoisopropyl
Pyramine, diisopropylamine, triisopropyl
Amine, n-butylamine, monoethanolamine, di
Ethanolamine, triethanolamine, monoisotop
Ropanolamine, diisopropanolamine, ethyl
Organic imines such as nimine, ethylenediamine, pyridine
A potash agent is mentioned. These alkaline aqueous solutions are one kind.
You may use independently and may use 2 or more types together. Of the above alkaline aqueous solutions, according to the present invention.
One effective developer is silicate acid as a base.
Contains potassium or mixes a base with a silicon compound.
So-called “silicate” containing alkali oxalate
An aqueous solution with a pH of 12 or higher
A more preferred developer does not contain alkali silicate,
Contains non-reducing sugar (organic compound with buffering action) and base
It is a so-called “non-silicate developer”. In the former, the alkali metal silicate
The aqueous solution is silicon oxide SiO which is a component of silicate. ₂ And
Lucari metal oxide M ₂ O ratio (generally [SiO ₂ ] /
[M ₂ O] in terms of molar ratio) and density
For example, Japanese Patent Laid-Open No. 54-62004
SiO as disclosed in ₂ / Na ₂ O molar ratio
1.0 to 1.5 (ie [SiO ₂ ] / [Na ₂ O] is
1.0 to 1.5) and SiO ₂ The content of 1-4
An aqueous solution of mass% sodium silicate, and JP-B-57-7
No. 427, [SiO ₂ ] /
[M] is 0.5 to 0.75 (ie, [SiO ₂ ] / [M
₂ O] is 1.0 to 1.5), and SiO ₂ Concentration of 1
~ 4% by weight and all the developer is present in it
At least 20 based on gram atoms of alkali metal
% Of alkali metal silicate containing potassium
An aqueous solution is preferably used. Also, it does not contain alkali silicate and is not reduced
So-called “non-silicate developer” containing sugar and base
However, it is not suitable for the development of the planographic printing plate material of the present invention.
Layer preferred. Using this developer, lithographic printing plate material
Image processing can deteriorate the surface of the image recording layer.
And keep the image recording layer in good condition
be able to. In addition, lithographic printing plate materials are generally developed
Narrow latitude and changes in line width etc. due to developer pH
However, the non-silicate developer suppresses pH fluctuations.
Because it contains non-reducing sugars that have buffering properties,
Compared to the case of using a developing solution containing a Kate
The Furthermore, non-reducing sugars have a higher liquid activity than silicates.
Contamination of conductivity sensor and pH sensor for control
In this respect, the non-silicate developer is advantageous.
It is. In addition, the discriminability between the image area and the non-image area (disc
The effect of improving the (limitation) is remarkable. This is the departure
Important developer for maintaining distinctiveness and film properties
Contact (penetration) becomes mild and exposed and unexposed areas
It is presumed that the difference is easily generated. The non-reducing sugar is a free aldehyde group or
It is a saccharide that has no ketone group and does not show reducibility.
Trehalose-type oligosaccharides in which groups are bonded to each other, reducing groups of sugars
Glycosides with saccharides and non-saccharides, and saccharides returned by hydrogenation
Classified into the original sugar alcohols, both in the present invention
It can be used suitably. In the present invention,
Non-reducing sugars described in JP-A-8-305039
It can be preferably used. Examples of the trehalose-type oligosaccharide include
Examples thereof include saccharose and trehalose. Above
Examples of glycosides include alkyl glycosides and phenols.
Examples include glycosides and mustard oil glycosides. Sugar Arco
For example, D, L-arabit, rebit
G, Xyrit, D, L-Sorbit, D, L-Manni
, D, L-exit, D, L-talit, slippery
And allozulcit. In addition, the disaccharide matrix
Maltitol hydrogenated to lactose, oligosaccharide hydrogen
Preferred examples include reduced form obtained by addition (reduced water candy).
It is. Among these non-reducing sugars, trehalose-type oligosaccharides
And sugar alcohols are preferred, and among them, D-sorby
PH range where salt, sucrose, reduced water candy, etc. are moderate
Is preferable in that it has a buffering action and is inexpensive. These non-reducing sugars can be used alone.
Alternatively, two or more kinds may be used in combination. Of the non-reducing sugar
As the content in the non-silicate developer,
0.1-30 mass% is preferable, and 1-20 mass% is more
preferable. When the content is less than 0.1% by mass,
There is a tendency that a sufficient buffer action cannot be obtained, 30% by mass
It is difficult to achieve high concentration and the cost tends to increase.
is there. Also used in combination with the non-reducing sugar
Examples of the base to be used include conventionally known alkali agents such as
Examples thereof include inorganic alkali agents and organic alkali agents.
Examples of the inorganic alkaline agent include sodium hydroxide,
Potassium hydroxide, lithium hydroxide, trisodium phosphate
, Tripotassium phosphate, triammonium phosphate, phosphoric acid
Disodium, dipotassium phosphate, diammonium phosphate
Sodium carbonate, potassium carbonate, ammonium carbonate
, Sodium bicarbonate, potassium bicarbonate, bicarbonate
Ammonium, sodium borate, potassium borate, boric acid
And ammonium. As the organic alkali agent, for example, monomer
Tylamine, dimethylamine, trimethylamine, mono
Ethylamine, diethylamine, triethylamine,
Noisopropylamine, diisopropylamine, trii
Sopropylamine, n-butylamine, monoethanol
Amine, diethanolamine, triethanolamine,
Monoisopropanolamine, diisopropanolamine
, Ethyleneimine, ethylenediamine, pyridine, etc.
Can be mentioned. The above bases may be used alone.
Two or more kinds may be used in combination. Among these bases
Also preferred are sodium hydroxide and potassium hydroxide. Ma
In the present invention, the non-silicate developer is used.
Instead of using a non-reducing sugar and a base together,
What has a potassium metal salt as a main component can also be used. In addition, the non-silicate developer contains
Alkaline buffer consisting of weak acids and strong bases other than non-reducing sugars
A liquid can be used in combination. As the weak acid, dissociation constant
The number (pKa) is preferably 10.0 to 13.2.
For example, Ionization Constants published by Pergmon Press
of Organic Acidsin Aqueous Solution etc.
You can choose from what you have. Specifically, 2,2,3,3-tetrafur
Oropropanol-1, trifluoroethanol, tri
Alcohols such as chloroethanol, pyridine-2-a
Aldehydes such as aldehyde and pyridine-4-aldehyde
, Salicylic acid, 3-hydroxy-2-naphthoic acid, potassium
Tecole, gallic acid, sulfosalicylic acid, 3,4-dihy
Droxysulfonic acid, 3,4-dihydroxybenzoic acid,
Hydroquinone (11.56), pyrogallol, o
Pheno such as-, m-, p-cresol, resorsonol
Compounds having a hydroxyl group, acetoxime, 2-hydride
Roxybenzaldehyde oxime, dimethylglyoxy
, Ethanediamide dioxime, acetophenoneoxy
Oximes such as mucin, adenosine, inosine, guanine,
Nucleic acid-related substances such as cytosine, hypoxanthine, xanthine
Quality, and others, diethylaminomethylphosphonic acid,
Preferred examples include diimidazole and barbituric acid. The developer and the replenisher have an increase in developability.
Suppression, dispersion of development residue, or parent ink of printing plate image area
For the purpose of enhancing the properties, various surfactants and
Organic solvents can be added. Examples of the surfactant include an anion.
On, cationic, nonionic and amphoteric surfactants
Is preferred. Furthermore, the developer and replenisher are necessary.
Depending on hydroquinone, resorcin, sulfurous acid, sulfurous acid
Return of sodium salt, potassium salt, etc. of inorganic acids such as hydrogen acid
Add base agent, organic carboxylic acid, antifoaming agent, water softener, etc.
I can. Development processing is performed using the developer and the replenisher.
The formed image forming material contains washing water, a surfactant and the like.
Rinse solution, desensitizing solution containing gum arabic and starch derivatives
It is post-processed with. Using the image forming material as a printing plate
As a post-process, you can combine these processes in various combinations.
Can be used together. In recent years, the plate making work has been rationalized in the plate making / printing industry.
Automatic processing machines for printing are widely used for
It is. This automatic developing machine generally has a developing unit and a post-processing unit.
Comprising a printing plate transporting device, each processing liquid tank and spatter
Contain the exposed printing plate horizontally.
Each process liquid pumped up by the pump is spray nozzle.
And developing. In addition, recently
In the treatment liquid tank filled with the chemical solution
Therefore, there is also a known method for processing by immersing and transporting the printing plate.
Yes. In such automatic processing, each processing solution is processed.
Process while replenishing replenisher according to volume and operating time
be able to. Also, treat with a virtually unused processing solution.
A so-called disposable processing method can also be applied. In the printing plate precursor according to the present invention, an image is printed.
Image exposure, development, water washing and / or rinsing and / or gas
Unnecessary image areas (for example, lithographic printing plates obtained by
If there is a film edge mark of the original film)
The unnecessary image portion is erased. like this
Such erasure is described in, for example, Japanese Patent Publication No. 2-13293.
Apply an erasing solution like that on the unnecessary image area.
Or leave it for a predetermined time and then wash it with water.
The method is preferred, but in Japanese Patent Application Laid-Open No. 59-174842
Guided with optical fiber as described
For development after irradiating unwanted image area with active actinic ray
Can also be used. The printing plate obtained as described above is desired.
After applying more desensitized gum, use it in the printing process
However, a lithographic printing plate with even higher printing durability
If not, a burning process is performed. Planographic printing plate
In the case of burning, before the burning, JP 61-2
518, 55-28062, JP-A 62-318
59, 61-159655 described in each publication
It is preferable to treat with a surface conditioning liquid. That way
As a sponge or absorbent cotton soaked with the surface conditioning liquid
Applied on the planographic printing plate or filled with surface-adjusting liquid.
A method of immersing a printing plate in a coating and applying an automatic coater
Application by, for example, is applied. Also, after application,
Squeegee or squeegee roller
Making it one gives a more favorable result. The coating amount of the surface conditioning liquid is generally 0.03 to 0.8.
g / m ² (Dry mass) is appropriate. The surface-adjusting solution is applied
If necessary, the planographic printing plate is dried and then burned.
Processor (for example, Fuji Photo Film Co., Ltd.)
Burning processor on sale: “BP-130
0 ") or the like. In this case, the heating temperature and
Depending on the type of ingredients that form the image,
The range of 1 to 20 minutes is preferable in the range of 180 to 300 ° C.
Yes. A lithographic printing plate that has been burned is necessary.
Depending on the conventional method, washing with water, gumming, etc.
Water-soluble polymer compound that can be treated
If a surface-conditioning liquid containing etc. is used, gumming etc.
The so-called desensitizing treatment can be omitted. this
Planographic printing plates obtained by various processes are offset printing
It is used for printing a large number of sheets. The present invention will be described below with reference to examples.
The scope of the present invention is not limited to these examples. Examples 1 to 12 and Comparative Examples 1 to 9 [Production of Substrate] Aluminum plate having a thickness of 0.3 mm (material)
1050) was washed with trichlorethylene and degreased
After, nylon brush and 400 mesh pumice-water suspension
The surface was grained with a liquid and washed thoroughly with water. This
Plate in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds
Immerse and etch, rinse with water, and then add 20% nitric acid
For 20 seconds and washed with water. Of the grained surface at this time
Etching amount is about 3g / m ² Met. Next, this plate
% Sulfuric acid as electrolyte and current density 15A / dm ² 3g /
m ² After providing the direct current anodic oxide coating, it is washed with water, dried,
Furthermore, the sodium silicate 2.5 mass% aqueous solution at 30 ° C.
Treat for 10 seconds, apply the following undercoat liquid, and coat the film at 80 ° C
The substrate was obtained by drying for 15 seconds. The coating amount after drying is 1
5mg / m ² Met. [Undercoat liquid] 0.3 g of the following polymer compound 100 g of methanol 1 g of water [Formation of image recording layer]
On the other substrate, image recording layers 1 to 3 having the following prescription were provided. Image recording layer 1 An image recording layer prescription 1 coating liquid having the following composition is applied in a wet coating amount.
19cc / m ² Apply with a wire bar and dry.
A lithographic printing plate precursor was obtained. (Image Recording Layer Formulation 1 Coating Solution) N- (4-aminosulfonylphenyl) methacrylamide / 2.370 g acrylonitrile / methyl methacrylate (35/30/35: weight average molecular weight 50000) m, p -Cresol novolak 0.474 g (PR54046, manufactured by Sumitomo Deyures)-Cyanine dye A (the following structure) 0.109 g-4,4'-bis (hydroxyphenyl) sulfone 0.126 g-Tetrahydrophthalic anhydride 0.190 g-p-toluenesulfonic acid 0.008 g-ethyl violet counter anion changed to 0.100 g 6-hydroxynaphthalenesulfonic acid-dimystyryl 3,3'-thiodipropionate 0.030 g-3, 3'-thiodipropionate di-n-dodecyl 0.030 g ・ Fluorine-based surfactant (medium Fax F-176, 0.035 g, manufactured by Dainippon Ink Industries, Ltd.) Fluorosurfactant (Defenser MCF-312 0.035 g, manufactured by Dainippon Ink Industries, Ltd.) Methyl ethyl ketone 26.6 g 1-methoxy-2-propanol 13.6 g γ-butyrolactone 13.8 g Image recording layer 2 Image recording layer formulation 2 coating solution having the following composition: 1.8 g / m ² of
After applying with a wire bar so that the application amount is reached, dry
Thus, an original plate for a lithographic printing plate was obtained. (Image recording layer prescription 2 coating solution) m, p-cresol novolak 1.000 g (PR54020, manufactured by Sumitomo Deyures) Copolymer 1 below 0.100 g Cyanine dye A (above structure) 0. 100 g · 4,4'-bis (hydroxyphenyl) sulfone 0.050 g · tetrahydrophthalic anhydride 0.050 g · p-toluenesulfonic acid 0.002 g · the counter anion of ethyl violet is 0.020 g 6 Changed to hydroxynaphthalenesulfonic acid ・ Dimystyryl 3,3′-thiodipropionate 0.010 g ・ Di-n-dodecyl 3,3′-thiodipropionate 0.010 g ・ Fluorine-based surfactant (Mega Fax F-176, 0.015 g Dainippon Ink & Chemicals, Inc.) Fluorosurfactant (Defenser MCF-3 12 0.035 g (manufactured by Dainippon Ink & Chemicals, Inc.) Methyl ethyl ketone 12.0 g (Synthesis of copolymer 1) Stirrer, cooling tube and
In a 20 ml three-necked flask equipped with a dropping funnel,
6.39 g (0.045 mol) of n-propyl laurate,
1.29 g (0.015 mol) of tacrylic acid and 1-meth
Put 20 g of xyl-2-propanol, 6 in a hot water bath
The mixture was stirred while heating to 5 ° C. To this mixture
Add "V-601" (Wako Pure Chemical Industries, Ltd.) 0.15g
Stir the mixture for 2 hours under nitrogen flow while keeping at 70 ° C.
It was. The reaction mixture is further mixed with n-propyl methacrylate.
6.39 g (0.045 mol), 1.29 methacrylic acid
g (0.015 mol), 1-methoxy-2-propano
2 g of a mixture of 20 g of water and 0.15 g of “V-601”
It dropped by the dropping funnel over the period. After the addition
The resulting mixture was stirred at 90 ° C. for 2 hours. After the reaction
Add 40 g of methanol to the mixture, cool and mix.
The mixture is poured into 2 liters of water while stirring the water.
After stirring the mixture for 0 minutes, the precipitate was removed by filtration
And dried to give 15 g of copolymer 1 as a white solid
Got in. By gel permeation chromatography
The weight average molecular weight of the copolymer 1 (polystyrene standard)
Quasi) was 53,000. Image recording layer 3 A lower coating solution having the following composition was applied in a wet amount of 19 cc / m.
² After applying with a wire bar, it was dried. Then the
Wet the image recording layer prescription 3 coating solution of the following composition on the lower layer.
G coating amount is 19cc / m ² Apply and dry with a wire bar
To obtain an original plate for a lithographic printing plate. (Lower layer coating solution) N- (4-aminosulfophenyl) methacrylamide / 2.133 g Binder of acrylonitrile / methyl methacrylate (36/34/30: weight average molecular weight 5000) Cyanine dye A (above Structure) 0.109 g ・ 4,4′-bizhydroxyphenylsulfone 0.126 g ・ tetrahydrophthalic anhydride 0.190 g ・ p-toluenesulfonic acid 0.008 g ・ the counter anion of ethyl violet is 0.100 g Changed to 6-hydroxynaphthalenesulfonic acid ・ 3-methoxy-4-diazophenylamine 0.03 g hexafluorophosphate (thermally decomposable compound) ・ Fluorosurfactant (Megafac F176, 0.035 g Dainippon Ink Industry Co., Ltd.) ・ Methyl ethyl ketone 26.6 g ・ 1-Met Cy-2-propanol 13.6 g ・ γ-butyrolactone 13.8 g (Image recording layer prescription 3 coating solution) m, p-cresol novolak 0.348 g (PR54046, manufactured by Sumitomo Deyures) ・ Cyanine dye A (above structure) 0.0192 g ・ Tetraethylammonium bromide 0.030 g ・ Fluorosurfactant (Megafac F176, 0.035 g manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 26.6 g ・ 1- Methoxy-2-propanol 13.6 g In the image recording layers 1 and 2,
The image recording layer after formation is shown in the table below for the formulation 1 and 2 coating solutions.
A predetermined amount of water was appropriately added so as to obtain a water content. Ma
In the image recording layer 3, it is formed in the lower layer coating solution.
The moisture content of the lower and upper layers will be as shown in the table below
Thus, a predetermined amount of water was appropriately added. In addition, coating with the above composition
Before adding water, the cloth liquid composition should be completely dried.
The water content (including the solvent) was 0.1% or less. this
The water content of the solvent sometimes used was as follows. Mechi
Ruethyl ketone 0.092%, 1-methoxy-2-propyl
Lopanol 0.063%, γ-butyrolactone 0.
026%. The image recording layer is dried at 160 ° C.
This was done by blowing hot air for 50 seconds. In addition,
The moisture content of the hot air at this time was 0.05 kg / kg. [Measurement of moisture content of image recording layer]
The original plate for printing plates with a size of 50 x 60 cm
Dimethylformamide 15 whose moisture content has already been measured
Soaked in 0 cc, hydrated dimethylformamide after soaking
The moisture content of dimethylformamide before and after immersion
From the difference, the water content of the image recording layer was calculated. Dimethyl
The water content of the formamide is measured by Karl Fischer water.
Performed using a subtotal MKC-210 (Kyoto Electronics Industry Co., Ltd.)
It was. Coulomat, a measurement solution for ketones
AK (generated liquid), Coulomat CK (counter electrode liquid) (both
Kist Co.) was used. [Evaluation of lithographic printing plate precursor] Print obtained
Scratch resistance test and film loss occurred for each sample of the original plate
The electrical conductivity (development resistance) and the printing durability were evaluated.
The results are listed in the following table. In each evaluation test
As the developer used, the image recording layers 1 and 3 are provided.
For the product, DT- from Fuji Photo Film Co., Ltd.
1 and having an image recording layer 2
The resulting alkaline developer A was used. <Alkali Developer A Composition> SiO ₂ ・ K ₂ O (K ₂ O / SiO ₂ = 1/1 (molar ratio)) 4.0 mass% Citric acid 0.5 mass% Polyethylene glycol lauryl ether 0.6 mass% (weight average molecular weight 1,000) Water 50.0 mass% [Scratch resistance test] The obtained lithographic printing plate precursor
Sapphire using a scratch tester made by HEIDON
(1.0 mm) is applied to scratch the plate and
After that, the developer (diluted, DT-1 has a conductivity of 45 mS /
cm, Developer A has a conductivity of 75 mS / cm)
The developed load was displayed so that scratches could be visually recognized. Large numbers
It is evaluated that the scratch resistance is excellent. [Conductivity that causes film loss (development resistance)]
The produced lithographic printing plate precursor is a Trendo manufactured by Creo
Exposure energy at tter 90mJ / cm ² And Tess
The pattern was drawn in the form of an image. Different conductivity
Prepare several types of developer, measure the conductivity of each,
The lithographic printing plate subjected to the imagewise exposure is treated with each of the above-described developers.
To develop the image density of the unexposed area (image area)
ETAG reflection densitometer D196 (GretagMacbe
measured by (th), the exposed part (non-image part) is dissolved
Developed with a developer with the highest conductivity of no limit
Measure the image density of the lithographic printing plate and then determine whether this image density
An image portion having an image density of 0.06 or less is formed.
The electrical conductivity of the developer was measured, and this was determined as “film” in the present invention.
"Conductivity causing a decrease". [Evaluation of printing durability] Tren manufactured by Creo
Exposure energy at dsetter 90mJ / cm
² Then, the lithographic plate in which the test pattern was drawn in the form of an image
The printing plate precursor is diluted with a developer (diluted, DT-1 is conductivity
45 mS / cm, Developer A has a conductivity of 75 mS / cm
Using a lithographic printing plate developed using
High-quality paper by the printing device Heidel KOR-D manufactured by Ruberg
Printed on. Cleaner liquid (Fuji Photocopy) every 5000 prints
Plate made by Shin Film Co., Ltd., plate cleaner CL2)
Printing was performed while wiping the surface. Lower the final number of prints for each
Shown in the table. Here, the final number of printed sheets is the planographic printing plate
Image recording layer The image area is thinned and ink is partially absorbed.
It is the number of sheets until the so-called version skip occurs.
The [Table 1] From the above table, the water content in the image recording layer is 1.
The lithographic printing plate precursor of the present invention having a content of 0% by weight or more (Examples)
1-12) are scratch resistant and development resistant to Comparative Examples 1-9
That it is excellent in both printing performance and printing durability
The The lithographic printing plate precursor according to the present invention is used for image recording.
When the moisture content of the layer is 1.0% by weight or more,
While maintaining the degree, development latitude, etc.
Image property and printing durability The film strength can be improved.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AA12 AA13 AB03 AC08                       AD03 CB42 CC11 FA17                 2H096 AA06 BA06 EA04 GA08

Claims (1)

1. A lithographic printing plate precursor comprising an image recording layer containing a water-insoluble and alkali-soluble resin and an infrared absorber on a support, wherein the water content of the image recording layer is A lithographic printing plate precursor having a content of 1.0% by weight or more.