JP2003195520A - Printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a printing original plate having excellent scratch resistance and discrimination property between an image part and a non-image part, and particularly for direct plate making to directly make a plate from digital signals by a computer or the like. <P>SOLUTION: The printing original plate has a multilayer structure having a layer containing an alkali-soluble resin and an image recording layer formed thereon containing an alkali-soluble resin and an IR absorbent and increasing the solubility with an alkali aqueous solution by exposure. In the method for manufacturing the above plate, the image recording layer is applied to the plate while the temperature of the supporting body is controlled to ≥42°C. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing original plate.
Especially from digital signals such as computers
Printing master plate for direct plate making that can be directly made
More specifically, scratch resistance and development latitude
Relates to a wide printing original plate. [0002] 2. Description of the Related Art Recent development of laser
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 the exposed 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 areas are dissolved)
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
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.
Cause damage, reduce scratch resistance,
Have problems such as instability. On the other hand, the unexposed part
If you lower the solubility of the binder resin to strengthen
Degradation is caused. Therefore, the image part and non-image
The range of development conditions that can maintain distinction from the image area (development lattice)
(Tude) is restricted. 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. [0008] However, these are problems to be solved.
Even if the compound is added, the dissolution promoting effect is sufficient.
The effect of improving the distinctiveness, film properties and sensitivity that are fully satisfactory
In a situation where further improvement is necessary
is there. Therefore, the object of the present invention is to use infrared light in particular.
Can make plates directly from digital signals from computers, etc.
As described above for the printing master for direct plate-making
Overcoming the shortcomings of conventional technology and developing
Improves discrimination between images and non-image areas
And presenting means for improving scratch resistance. [0009] The present inventor has found that scratch resistance and current
Is the above-mentioned solution problem represented by distinctiveness in images conventional?
Despite being considered from the viewpoint of materials used,
In view of the fact that the solution has not been sufficiently developed,
After intensive investigation focusing on the manufacturing conditions of the board,
Image film depending on the form of heat application when coating the image recording layer
It was found that the mechanical properties of the
As a result of further examination based on the observation, the invention is completed
It came to. That is, the present invention is as follows. (1) On the support, water-insoluble and alkaline
A layer containing a resoluble resin and a water-insoluble
Infrared laser containing potash-soluble resin and infrared absorber
Exposure to alkaline aqueous solution increases
For the production of printing master plates with a multi-layer structure provided with an image recording layer
At this time, the temperature of the support is controlled to 42 ° C. or higher to display the image.
A method of manufacturing a printing original plate characterized by applying a recording layer
Law. In the application of a printing master plate having a multi-layer structure,
Usually after coating the lower layer or after drying the lower layer, the upper layer
In the present invention, the upper layer, that is, the image recording is applied.
The support temperature at the start of recording layer coating is at least 42 ° C.
The resulting original plate is developed during development.
The solubility of the image area is reduced (decrease in film loss) and the non-image area is dissolved.
Solution is accelerated (decrease in residual film), resulting in development latitude
The feature is that the card has been enlarged and is less likely to be scratched.
It is. At the time of coating in the production of the above printing original plate
The substrate temperature is controlled by the scratch resistance and development latitude of the original printing plate.
Mechanism of unexpected and prominent effects on the card is unknown
However, if the temperature of the support is low and drying proceeds slowly,
After the upper layer is applied, the whole is dried (fixed)
During which time soluble components elute from the lower layer
Although the development resistance (resisting property) of the upper layer is lowered
In contrast, the drying temperature can be shortened by increasing the drying temperature.
This negative effect is alleviated and the lower layer retains soluble components
It is estimated that the loss of solubility is avoided.
Also, the high support temperature means that there is no heat transfer loss to the support.
On the other hand, heat is supplied from the side of the support with a large heat capacity.
Thus, it is considered that rapid drying proceeds after application. Heavy
In the layer printing master, the lower layer is easy to dissolve and the upper layer is lower
A design that is harder to dissolve than the layer ensures identification in development.
In the drying process according to the present invention
So, if the above mechanism is happening,
Such a preferable solubility relationship is established.
The On the other hand, rapid drying improves the development resistance of the photosensitive layer,
The range of conductivity of developers that can form images tends to be wider
is there. This is thought to be due to different binder interactions.
ing. [0013] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
The method for producing a printing original plate of the present invention is water-insoluble and
A layer containing potash-soluble resin, and a water-insoluble
Including infrared-soluble resin and infrared absorber,
Image whose solubility in alkaline aqueous solution is increased by light
When the image recording layer is provided on the support, the temperature of the support is
Is controlled to 42 ° C. or higher, and the image recording layer is applied on the lower layer.
A method for producing a printing master plate having a multilayer structure
It is. First, a multilayer structure to which the manufacturing method of the present invention is applied.
The original printing plate, and then how to make it
Describe. First, the components of the image recording layer
The [Alkali-soluble resin] Next, it is used in the present invention.
Alkali-soluble in the image recording layer of printing masters
The functional resin (polymer compound) will be described. For the present invention
The image recording layer of the printing original plate 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 bonded₂−
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 printing original plate used in 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 printing original plate used in 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. In the printing original plate used in the present invention, the upper layer
The alkali-soluble polymer used in
Cresol formaldehyde resin etc. from the viewpoint of agent solubility
The novolak resin is preferred. High alkali solubility in the lower layer
The molecule is (2) from the viewpoint of developer solubility and coating solvent solubility.
Alkali-soluble polymer compounds with sulfonamide groups
Or alkali-soluble high having active imide group of (3)
A resin having a molecular compound 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 lower layer, preferred
40 to 95% by mass, particularly preferably 50 to 90% by mass
% Added. Addition of alkali-soluble polymer
If the amount is less than 30% by mass, the durability of the lower layer deteriorates.
In addition, if it exceeds 99 mass%, it is preferable for both sensitivity and durability.
It ’s not. [Infrared absorber] Printing raw material used in the present invention
Infrared absorber 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 printing original plate used in the present invention, infrared rays are used.
The absorbent is preferably 0.01 to 50% by mass, based on the total solid content.
0.1 to 50% by mass, particularly preferably 0.1 to 3%.
It can be added at a ratio of 0% by mass. Amount of dye added
If the content is less than 0.01% by mass, the sensitivity tends to be low.
If the amount exceeds 50% by mass, the uniformity of each layer is lost.
The durability of each layer tends to deteriorate. [Solubility Inhibiting Compound] For printing used in the present invention
In order to increase the inhibition (dissolution inhibition) of the original plate,
The image recording layer contains various inhibitors.
Can do. The inhibitor is not particularly limited.
Quaternary ammonium salt, polyethylene glycol type
Compound etc. are mentioned. 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 forming layer.
The solid content is 0.1 to 50% of the total solid content.
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. R¹-{-O- (R^Three-O-)_m-R²}_n (R¹Is a polyhydric alcohol residue or polyhydric phenol
Nord residue, R²Is a hydrogen atom, C₁~_{twenty five}With a substituent of
Alkyl group, alkenyl group, alkynyl group, al
Kiroyl group, aryl group or aryloyl group, R^ThreeIs
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. Addition amount of polyethylene glycol compound
Is 0.1 to 5 solids with respect to the total solid content of the image forming layer
0% is preferable and 1-30% is preferable
More preferable. Less than 0.1% has little inhibitory effect on solubility
It is not preferable. When 50% or more is added, the binder
Polyethylene glycol compounds that cannot interact with
Promotes developer penetration and adversely affects image formation
There is. 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). [0044] [Chemical 1] [0045] [Chemical 2] In general formula (LI) and general formula (L-II)
X¹, X², X^ThreeAnd X^FourIs a ring atom or atom
It is a child group that may be the same or different, each independent
May have a substituent, and in general formula (LI)
X¹, X²And X^ThreeAnd at least one of the general formula (LI
X in I)¹, X², X^ThreeAnd X^FourAt least one of
Are substituted with an electron-withdrawing group or an electron-withdrawing group.
Has a substituent. X¹, X², X^ThreeAnd X^FourRing structure represented by
An adult atom or group of atoms is two single bonds to form a ring
A nonmetallic atom having an atomic group or an atomic group containing the nonmetallic 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, X²And X
^ThreeOr at least one of the general formula (L-II)¹,
X², X^ThreeAnd X^FourAt 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, the 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. [0049] [Chemical 3] [0050] [Formula 4]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 addition, in the printing original plate used in the present invention,
In addition, in a state that is thermally decomposable and does not thermally decompose
Substances that substantially reduce the solubility of alkali-soluble resins
Further increases the difference between the unexposed areas and the exposed areas.
It is preferable from the point. This “pyrolytic and pyrolytic
The solubility of alkali-soluble resins is substantially reduced
There are no particular limitations on the substance to be used, but various types of
Examples thereof include nium salts and quinonediazide compounds. Special
From the viewpoint of thermal decomposition, onium salts are preferred.
Yes. 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
Thus, for example, S. I. 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
Ammonium salt described in the specification of No. 0, D. C. 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, J. V. 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 salts described in the issue, J. V. Crivello et al, Po
lymer J. 17, 73 (1985), J. V. Crivelloeta
l. J. Org. Chem., 43, 3055 (1978), W. R.
 Watt et al, J. Polymer Sci., Polymer Chem. Ed.,
22, 1789 (1984), J. V. Crivelloet al, P
olymer Bull., 14, 279 (1985), J. V. Criv
ello et al, Macromorecules, 14 (5), 1141 (1
981), J. V. 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, J. V. Crivello et al, Macrom
orecules, 10 (6), 1307 (1977), J.V.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 printing original plate used in 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
Benzo as described in Japanese Patent Publication No. 3-28403
Quinone (1,2) -diazide sulfonic acid chloride or
Is naphthoquinone- (1,2) -diazide-5-sulfone
Este of acid 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 addition amount of the non-diazide compound is preferably lower solids
1-50% by mass, more preferably 5-30 quality
% By weight, particularly preferably in the range of 10 to 30% by weight.
These compounds can be used alone, but with several mixtures
May be used. Addition of o-quinonediazide compound
If the amount is less than 1% by mass, the image recordability deteriorates,
If it exceeds 50% by mass, the durability of the image area deteriorates and the sensitivity
Or drop. From the viewpoint of degradability, pyrolyzables
The quality is more preferably an onium salt. This highly decomposable
By using an onium salt, the thermally decomposable material in the exposed area
Disassembly of the quality is further promoted, and the unexposed areas of the exposed areas are separated.
Nation is thought to improve. The printing original plate used in the present invention has 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 thermal decomposability and not pyrolyzing
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 printing original plate used in the present invention, there is a scratch.
Low surface friction coefficient for the purpose of imparting resistance
A compound to be reduced can also be added. In particular,
Long as used in US Pat. No. 6,117,913
Examples include esters of chain alkyl carboxylic acids.
come. Such a compound can be
It can be contained in either the upper layer or the upper layer, but it is more effective
What is included is to be contained in the upper layer. Good addition amount
Preferably, the proportion of the material forming the layer is 0.1
-10 mass%, more preferably 0.5-5 mass%
The If necessary, it has a low molecular weight acidic group.
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 a sulfonic acid group. Specifically
Are 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
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%.
%. Furthermore, in the image recording layer, the exposure is increased.
Print-out agent and image coloring to obtain a visible image immediately after heating
Dyes and pigments as agents can be added. Bake out
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 for 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. 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. Further, a layer having no image recording function is an image recording layer.
And is also provided between the support and this is called 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 printing original plate used in the present invention is 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 lower layer solvent 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. 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
If it behaves like a single layer, the book by having two layers
The effect of the invention may be impaired, which is not preferable. This
Therefore, the solvent used to apply the image recording layer is the lower layer.
It is a poor solvent for alkali-soluble polymers contained in
It is desirable. The above components in the solvent when applying each layer
The concentration of the minute (total solid content including additives) is preferably 1 to
50% by 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 / m²In
The lower layer is 0.3-3.0 g / m²Prefer to be
That's right. Upper layer is 0.05 g / m²If it is less than
The image formability deteriorates and 1.0 g / m²Sensitivity exceeds
There is a possibility of decline. In addition, the total of the two layers
0.5-3.0 g / m²It is preferable that the coating amount
0.5g / m²If it is less than 3, the film properties are deteriorated.
0g / m²If 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
%. 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. Regarding the developability of the printing original plate,
If the drying conditions are severe, the conductivity of the developer that can form an image
If the degree is high (developability is low) and is moderate,
The conductivity of the developer that can form an image is low (high developability)
Tend to). The desired drying conditions are selected by the air temperature.
Temperature, air flow, air flow direction, contact heat medium temperature and material, etc.
This is done by adjusting the conditions. Immediately before application of the image recording layer
It is preferable that the residual solvent in the lower layer injection is small. Preferably
Is 80 mg / m²Or less, more preferably 60 mg / m²
It may be the following. A lower layer and an image recording layer are provided on the support.
When the lower layer is dried, the temperature of the support is once set to the predetermined temperature.
The image recording layer is applied after the temperature is lowered. Of the image recording layer
The temperature of the support during coating has a significant effect on performance.
found. In the present invention, the drying method is any of the above.
However, just before applying the image recording layer coating solution,
The temperature of the support is 42 ℃ when the coating solution comes into contact with the support.
It is necessary that the temperature of the support is
By starting application at a high temperature, scratch resistance and image area
And non-image areas are assured.
Range of conductivity of developer that can be developed with improved developability
Becomes wider. Support temperature control provides this effect
The mechanism is unknown, but the temperature of the support is
If it is low, the time required for drying the image recording layer becomes longer.
Therefore, the soluble components in the lower layer can easily escape and the drying conditions are
When strengthened, the escape rate decreases and the dissolution rate of the lower layer decreases.
It is estimated that this can be prevented. As a method for lowering the temperature of the support, cold air is used.
Spray the refrigerant body inside the roller and
The holder is brought into contact with this roller and the heat from the roller surface
Method of cooling by conduction, passing through low temperature environment such as water
Method, injecting low boiling point liquid and cooling by heat of vaporization
The method of doing is mentioned. Above all, blow cool air
The method is preferred. The temperature of the cold air should be 50 ° C or less.
Good. More preferably, it is 30 ° C. or less, and 10 ° C. or less.
It is particularly preferable to do this. FIG. 1 shows a support for coating an image recording layer.
The method for producing a printing plate according to the present invention having a temperature of 42 ° C. or higher
Although one mode is shown, the image recording layer is supported at the entrance of the coating apparatus.
Use any other drying method as long as body temperature conditions are met
Can do. The coating / drying apparatus according to the present invention is as shown in FIG.
The lower layer coating / drying unit 1 and the image recording layer coating / drying unit 2
Consists of. In FIG. 1, the support P is used for roller conveyance.
Therefore, it is sent to the coating device 12 of the lower layer coating unit 1. Coating equipment
In this embodiment, the device 12 is a dip coating method.
The coating liquid 13 is applied to the support by the application roller 14.
Smeared. The coating thickness depends on the conveyance speed, coating solution temperature, coating
It is controlled by the cloth liquid solids concentration and the coating liquid viscosity. In this embodiment, a dip coating method is used.
However, any of the above mentioned hopper coat methods
You can also take a method. Supports that have finished painting the lower layer
The holder is conveyed to the lower layer drying unit 15. Drying part of this embodiment
Are the first section 16, the second section 17 and the third section.
It consists of three chambers in section 18, each
The chamber has a hot air inlet for drying b and a hot air for drying.
And an exhaust port a.
Intake / exhaust air conditioning near the hot air intake of the intake duct
It is controlled by the device. Intake port b and exhaust port of each chamber
The flow rate of a is inconvenient empty from the dry matter entrance and exit
It is adjusted so that there is no air inflow or exhaust, and the amount of dry air
And the temperature can be changed independently. Finish drying the lower layer
The coated base material coated with the lower layer has a cold air inlet d and a cold air exhaust.
It is conveyed to a cooling section 19 with an outlet c. cooling
The temperature of the wind is preferably 50 ° C. or less. More preferably
30 ° C. or less, most preferable temperature, 10 ° C. or less. Next, the support carrying the lower layer is used for image recording.
It is conveyed to the coating device 22 of the recording layer coating unit 2, and in this embodiment
Again, the image recording layer is applied by dip coating.
It is. The support is applied to the coating liquid 2 by the application roller 24.
3 is smeared. Coating thickness is the conveyance speed and coating solution temperature
Controlled by the coating liquid solids concentration and coating liquid viscosity
The In this embodiment, the image recording layer also uses the dip coating method.
However, another coating method may be used. Application of image recording layer
The support that has been pasted is carried to the image recording layer drying unit 25.
Sent. The drying section of this embodiment is the first section 26, the second
Consisting of section 27 and third section 28, which
Each section has a dry air intake b and dry air
A discharge port a is provided, allowing the amount of dry air and temperature to be controlled independently.
It is possible to change it. Lower layer coating after lower layer drying
The finished support has a cold air inlet d 'and a cold air outlet c'.
To the cooled cooling section 29, where it is cooled and
The plate printing original plate P ′ is completed. Feed from coating / drying equipment
The temperature on the support side of the finished printing original plate is 40 ° C.
It is below, Preferably it is 22-35 degreeC. [Support] For lithographic printing usable in the present invention
As a support for the original plate, it has the required strength and durability.
For example, paper, plastic, etc.
(Eg polyethylene, polypropylene, police
Paper, metal plates (for example, aluminum)
(Luminium, zinc, copper, etc.), plastic film (example)
For example, cellulose diacetate, cellulose triacetate, propio
Cellulose acetate, cellulose butyrate, cellulose acetate butyrate
, Cellulose nitrate, polyethylene terephthalate, polyethylene
Reethylene, polystyrene, polypropylene, polycar
Bonate, polyvinyl acetal, etc.), gold as above
Paper or plastic on which the genus is laminated or vapor-deposited
Includes sticky film. Support of a lithographic printing plate that can be used in the present invention
As a body, polyester film or aluminum plate
Is preferable, among which dimensional stability is good and relatively inexpensive
An aluminum plate is particularly preferred. Suitable alumini
Um plate is mainly composed of pure aluminum plate and aluminum
Alloy plate containing a trace amount of foreign elements, and aluminum
Um-laminated plastic film
Rum may be used. 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 an aluminum plate of a public material 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 anodizing treatment conditions 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 / dm², Voltage 1-100V, Electrolysis time
A range of 10 seconds to 5 minutes is appropriate. Anodized film
Is 1.0 g / m²If 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
As a hydrophilization treatment applied to the support of the original plate related to Ming
U.S. Pat. Nos. 2,714,066 and 3,18.
1,461, 3,280,734 and 3,90
Alkali metal silicon as disclosed in US Pat. No. 2,734
There is a Kate (for example, sodium silicate aqueous solution) method. This
In this method, the support is an aqueous sodium silicate solution.
Soaked or electrolytically treated. In addition, Shoko 36
Zirconic acid disclosed in Japanese Patent No. 22063
Potassium and US Pat. No. 3,276,868, ibid.
Open to 4,153,461 and 4,689,272
Treatment with polyvinylphosphonic acid as indicated
The law is used. The original plate for lithographic printing which can be used in the present invention is a supporting plate.
At least the lower layer and the image recording layer described above were provided on the holder.
If necessary, subbing between the support and the lower layer
A layer can be provided. Various subbing layer components
For example, carboxymethylcellulose
Source, dextrin, gum arabic, 2-aminoethyl
Phosphonic acids with amino groups such as phosphonic acid, substitution
Phenylphosphonic acid, naphthylphospho which may have a group
Acid, alkylphosphonic acid, glycerophosphonic acid, methyl
Organics such as rangephosphonic acid and ethylenediphosphonic acid
Phosphonic acid, optionally substituted phenyl phosphoric acid,
Futyl phosphate, alkyl phosphate, glycerophosphate, etc.
Organophosphoric acid, phenyl phosphite which may have a substituent
Acid, naphthylphosphinic acid, alkylphosphinic acid and
Organic phosphinic acids such as glycerophosphinic acid,
Amino acids such as syn and β-alanine, and trietano
Amine having a hydroxy group, such as hydrochloride of hydrochloride
Or a mixture of two or more types.
Good. 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. [0089] [Chemical formula 5] R¹¹Is a hydrogen atom, halogen atom or alkyl
R group, R¹²And R¹³Each independently
Child, hydroxyl group, halogen atom, alkyl group, substituted alkyl
Group, aryl group, substituted aryl group, -OR¹⁴, -COO
R¹³, -CONHR¹⁶, -COR¹⁷Or -CN
Or R¹²And R¹³May combine to form a ring
R¹⁴~ R¹⁷Each independently represents an alkyl group or
X represents a hydrogen atom, a metal atom, NR¹⁸R¹⁹R
²⁰R^{twenty one}Represents R¹⁸~ R^{twenty one}Each independently
Child, alkyl group, substituted alkyl group, aryl group or
Represents a substituted aryl group or R¹⁸And R¹⁹Combined
A ring may be formed, and m represents an integer of 1 to 3. This subbing 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 / m²Is suitable and preferred
5-100mg / m²It is. The above coating amount is 2m
g / m²If it is less, sufficient printing performance cannot be obtained.
200 mg / m²It is the same even if it is larger. [Plate making / printing] Created as described above
In the original printing plate, a slip sheet is inserted between the printing original plates.
Shipped in packaged and packaged product form
It is a common mode to be transported and stored.
As a typical mode for plate making and printing, auto
A pair of interleaving paper and original paper is automatically loaded by the loader.
Installed at a position where it is secured by the loader, transported, and plate making is performed.
Attached and fixed, after which the slip is removed
There is, but is not limited to this. The position where plate making is done is
In the direct printing system, it is on a printing press. Original strips removed
The plate is subjected to image exposure and development processing. Used for image exposure
As an active light source that emits light from the near infrared to the infrared region,
A light source with a light wavelength is preferable, and it is not necessarily a scanning method.
It may not be necessary, that is, the surface exposure method may be used.
Scanning dew that uses body laser or semiconductor laser
Light is preferred. The emission wavelength is 760 to 1080n.
m is preferred. The present invention is applied to a printing original plate that can be used in the present invention.
A developer having a pH of 9.0 to 14.0
Developer, preferably in the range of 12.0 to 13.5
It is. Developer (hereinafter referred to as developer including replenisher)
Can be used with a conventionally known alkaline aqueous solution.
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.₂And
Lucari metal oxide M₂O ratio (generally [SiO₂] /
[M₂O] in terms of molar ratio) and density
For example, Japanese Patent Laid-Open No. 54-62004
SiO as disclosed in₂/ Na₂O molar ratio
1.0 to 1.5 (ie [SiO₂] / [Na₂O] is
1.0 to 1.5) and SiO₂The content of 1-4
An aqueous solution of mass% sodium silicate, and JP-B-57-7
No. 427, [SiO₂] /
[M] is 0.5 to 0.75 (ie, [SiO₂] / [M
₂O] is 1.0 to 1.5), and SiO₂Concentration 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
When image processing is performed, the surface of the photosensitive layer is not deteriorated.
And maintaining a good thickness of the photosensitive layer.
it can. In addition, lithographic printing plate materials are generally developed
The screen is narrow and the change in the line width etc. due to the developer pH
However, a non-silicate developer can be used to reduce pH fluctuations.
Because non-reducing sugars with impulsive properties are included, silicate
This is advantageous as compared with the case of using a developing solution containing. Further
In addition, non-reducing sugars control liquid activity compared to silicates.
It is hard to pollute conductivity sensors and pH sensors
Therefore, non-silicate developer is also advantageous in this respect.
The Also, the distinction between the image area and the non-image area (discriminator)
Nation) improvement effect is remarkable. This is in the present invention.
Contact with the developer, which is important for maintaining distinctiveness and film properties.
The touch (penetration) becomes mild and the difference between exposed and unexposed areas
This is presumably due to the fact that 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 in the original sugar alcohol, 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. Further, it is 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
Rudehydr (, aldehydes such as pyridine-4-aldehyde (etc.
, Salicylic acid, 3-hydroxy-2-naphthoic acid,
Catechol, gallic acid, sulfosalicylic acid, 3,4-di
Hydroxysulfonic acid, 3,4-dihydroxybenzoic acid
Acid, hydroquinone (11.56), pyrogallol,
Fe, such as o-, m-, p-cresol, resorsonol
Compound having a hydroxyl group, acetoxime, 2-hy
Droxybenzaldehyde oxime, dimethylglyoxy
Shim, ethanediamide dioxime, acetophenone oxy
Oximes such as shims, adenosine, inosine, guani
Nucleic acid functions such as N, cytosine, hypoxanthine and xanthine
In addition to continuous substances, diethylaminomethylphosphonic acid,
Preferred examples include benzimidazole and barbituric acid.
The In the developer and replenisher, development property is promoted.
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 original plate according to the present invention, the image
Expose, develop, rinse and / or rinse and / or gum
Unnecessary image area (for example, lithographic printing plate obtained by drawing)
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
On the lithographic printing plate, or
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 / m²(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. [0112] 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 5 and Comparative Examples 1 to 3 [Preparation of substrate] Aluminum plate with 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 ²Met. Next, this plate
% Sulfuric acid as electrolyte and current density 15A / dm²3g /
m²After 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 / m²Met. [0114] [Undercoat liquid]   ・ The following polymer compound 0.3g   ・ Methanol 100g   ・ Water 1g [0115] [Chemical 6] [Formation of Image Recording Layer] This example is shown in FIG.
Dip coating method for the coating part of printing plate coating and drying equipment
Is shown in Fig. 1 except that the wire bar coating method is changed
This was done in the manner described above. Application apparatus 1 shown in FIG.
In 2, the following lower layer coating solution is wet coated on the substrate
The amount is 19cc / m²After applying with a wire bar, dry
Conveyed by a convection heating system using hot air
It dried with the continuous conveyance drying apparatus (drying oven). 1st section
For 16 seconds at an intake temperature of 140 ° C. for 10 seconds.
The cushion 17 has a first intake temperature of 160 ° C. for 20 seconds.
3 section 18 is dry for 40 seconds with an intake air temperature of 160 ° C.
It is set to dry. The support with the lower layer that has passed through the drying apparatus is cooled.
Is transported to the rejection section 19 and cooled, and the intake port c is discarded
For adjusting the temperature and air volume of the cooling air performed by the outlet d
Therefore, the support temperature at the entrance of the second coating device 22 is expressed.
The temperature was adjusted to the temperature shown in 1. Next
In the coating device 22 of 2, the image recording layer coating solution is formed on the lower layer.
The wet coating amount is 19cc / m²With wire bar
Application was performed. After coating, the original plate sample is transported to the drying device
In the fourth section 26, an intake air temperature of 120 ° C.
1 second at 130 ° C. inspiratory temperature in the fifth section 27
0 sec, 6th section 28 with 150 ° C intake air temperature
Drying is performed for 20 seconds, followed by cooling section 29
Is cooled to room temperature and the original plate sample P ′ for lithographic anti-printing is
Obtained. [0118] [Lower layer coating solution] ・ N- (4-Aminosulfophenyl) methacrylamide / Acrylonitrile / Methacryl Binder of methyl oxalate (36/34/30: mass average molecular weight 5000)                         2.133 g ・ Cyanine dye A (the following structure) 0.109 g ・ 4,4'-Bizhydroxyphenylsulfone 0.126g ・ Tetrahydrophthalic anhydride 0.190g ・ 0.008 g of p-toluenesulfonic acid ・ Change the counter anion of ethyl violet to 6-hydroxynaphthalenesulfonic acid Food 0.100g 3-methoxy-4-diazophenylamine hexafluorophosphate (heat Decomposable compound) 0.03g -Fluorosurfactant (Megafac F176, manufactured by Dainippon Ink Industries, Ltd.)                                                0.035g ・ Methyl ethyl ketone 26.6g 1-methoxy-2-propanol 13.6 g ・ Γ-Butyrolactone 13.8g [0119] [Coating liquid for image recording layer] ・ M, p-cresol novolak (PR54046, manufactured by Sumitomo Deyures)                                                         0.348g ・ Cyanine dye A (the following structure) 0.0192 g ・ Tetraethylammonium bromide 0.030g -Fluorosurfactant (Megafac F176, manufactured by Dainippon Ink & Chemicals, Inc. 0.035g ・ Methyl ethyl ketone 26.6g 1-methoxy-2-propanol 13.6 g [0120] [Chemical 7] [0121] [Table 1] [Evaluation of original plate for lithographic printing]
Developed by Fuji Photo Film Co., Ltd. for each sample on the original plate
Development is performed using liquid DT-1 in the usual manner.
Scratch resistance test, sensitivity and
The electrical conductivity causing film loss was evaluated. Evaluation test
Was conducted after storage for 7 days at 25 ° C
It was. The results are also shown in Table 1. [Scratch resistance test] The resulting lithographic printing of the present invention
For original plates 1-8, use a scratch tester made by HEIDON
Apply a load to the sapphire (1.0 mm)
Scratch, then Developer D from Fuji Photo Film Co., Ltd.
T-1 (Diluted to a conductivity of 45 mS / cm)
And developed, and the load at which scratches were visible was displayed. Numeric value is large
The better the scratch resistance, the better. [Evaluation of Sensitivity] The obtained lithographic printing original plate
Exposure energy with Trend setter manufactured by Creo
Change the-and draw the test pattern in the image
It was. Thereafter, developer DT-1 manufactured by Fuji Photo Film Co., Ltd.
Development with dilution (conductivity 45mS / cm)
The exposure energy that can develop the non-image area with this developer
Was measured as sensitivity. The smaller the value, the higher the sensitivity.
And evaluate. [Conductivity causing film reduction]
Measure the `` conductivity at which the exposed part of the recording layer causes film loss ''.
Set. That is, several types of developers having different conductivities are prepared,
Each conductivity was measured and the imagewise exposure was performed.
The plate printing plate is developed with each developer described above, and unexposed areas
The image density of (image part) is set to GRETAG reflection densitometer D19.
6 (manufactured by GretagMacbeth)
Highest electric conductivity that does not dissolve the light part (non-image part)
The image density of a lithographic printing plate developed with a developer containing
Next, an image that is 0.06 or less less than this image density
Measures the conductivity of the developer with the density image area formed
This is referred to as “conductivity causing film loss” in the present invention.
did. From Table 1 above, the support for coating the image recording layer
Plate printing original plate of the present invention having a body temperature of 42 ° C. or higher (implemented)
In Examples 1 to 5, the support temperature just before coating was 36 to 4
Scratch resistance and film reduction compared to Comparative Examples 1 to 3 applied at 0 ° C
It is excellent in both conductivity and sensitivity
Understand. [0127] The printing original plate of the present invention has the above-mentioned specific properties.
Since the image recording layer contains a compound having a structure, sensitivity
While improving the film strength and film loss.
Yes.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic explanatory diagram of a coating / drying process according to an embodiment of the printing original plate manufacturing method of the present invention. [Explanation of Symbols] P Support P ′ Master 1 Lower layer coating / drying unit 2 Image recording layer coating / drying unit 12 Lower layer coating device 13 Lower layer coating solution 14 Coating roller 15 Lower layer drying device 16 First drying section 17 Second drying Section 18 Third drying section 19 Cooling section 17 Second drying section 22 Upper layer coating device 23 Upper layer coating liquid 24 Coating roller 25 Upper layer drying device 26 Fourth drying section 27 Fifth drying section 28 Sixth drying section 29 Cooling section a, a ′, c, c ′ Exhaust ports b, b ′, d, d ′

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA13 AB03 AC08 AD03 CB17                       CB28 CB41 CB45 CB52 CC20                       DA36 EA04 FA03 FA17                 2H096 AA07 AA08 BA16 BA20 CA05                       CA12 EA04 GA08

Claims (1)

What is claimed is: 1. A water-insoluble and alkali-soluble resin layer is formed on a support, and a water-insoluble and alkali-soluble resin and an infrared absorber are formed thereon. In the production of a multi-layer printing original plate provided with an image recording layer having increased solubility in an aqueous solution, the temperature of the support is controlled to 42 ° C. or higher, and the image recording layer is applied. A manufacturing method of an original plate.