JP2003345037A - Developer liquid for lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer liquid for a lithographic printing original plate, the liquid free from scum derived from silicates in a developing bath and free from scum or contamination derived from dissolved aluminum in a washing bath and a finisher bath and excellent in printing durability. <P>SOLUTION: The lithographic printing plate developer contains a glycoside and a base. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to development for a lithographic printing plate.
Regarding liquids. [0002] In conventional lithographic printing plates, o-quinonedia
Having a photosensitive layer comprising a photosensitive composition using a zido compound
Lithographic printing plate precursor (hereinafter referred to as photosensitive lithographic printing plate)
U) is exposed to UV through a plate-making film, and then a developer.
Thus, it is created by removing the exposed portion (non-image portion). Also recently
With the advance of computer image processing technology,
No image information is output to the silver halide mask film.
In addition, the laser beam or thermal head
Form a resist image and remove the exposed area (non-image area) with a developer.
The method of creating it is also used. These lithographic signs
In the developing solution for making a printing plate, alkali metal silicate
And developers that use non-reducing agents as buffer agents
Yes. In the case of developer using alkali metal silicate,
There is a problem that debris due to silicate is generated in the image bath. one
On the other hand, JP-A-9-274324 and JP-A-11-21
As disclosed in the 6962 publication,
In the case of developing solution using non-reducing sugar,
No silicate-derived residue is generated and discriminating
Although it has the effect of improving
In order to elute part of the Minium support,
Waste is generated in the nischer bath. Prevent this
In order to achieve this, if the aluminum support is subjected to elution prevention treatment,
Good, lithographic printing plate by aluminum elution prevention treatment
There arises a problem of deteriorating the printing durability. For this reason,
In all of the development bath, washing bath and finisher bath
It is possible to obtain a lithographic printing plate with little occurrence and good printing durability.
A developing solution capable of [0003] The present invention is based on the above-described conventional technique.
In view of the technology, silicic acid in the developing bath
Salt-induced residue and elution in water and finisher baths
There is little residue and dirt caused by aluminum and excellent printing durability
To provide a developer for a lithographic printing plate precursor
To do. [0004] [Means for Solving the Problems] (1) Specially containing a glycoside and a base
Developer for lithographic printing plate precursor. As a preferred embodiment
(2) contains non-reducing sugars, glycosides and bases
A developing solution for a lithographic printing plate precursor. [0006] BEST MODE FOR CARRYING OUT THE INVENTION The developer of the present invention will be described below.
explain. The developer for a lithographic printing plate precursor according to the present invention contains little
A developer containing at least a glycoside and a base. The present invention
Glycosides used in the developer are not particularly limited
However, as an example of a preferred glycoside, a compound of the following general formula (I)
You can list things. [0008] [Chemical 1] Wherein R is a straight chain having 1 to 20 carbon atoms.
Or a branched alkyl group, alkenyl group, alkynyl group
Represent. ) A 1-20 carbon atom represented by R in the above general formula (I)
Examples of the alkyl group include methyl, ethyl, propyl,
Isopropyl, butyl, pentyl, hexyl, heptyl
Octyl, nonyl, decyl, undecyl, dodecy
, Tridecyl, tetradecyl, pentadecyl, hexa
Decyl, heptadecyl, octadecyl, nonadecyl, et
Icosyl group, etc.
Alternatively, it may be branched or a cyclic alkyl group. A
Examples of the lucenyl group include allyl and 2-butenyl groups.
However, examples of the alkynyl group include a 1-pentynyl group.
I can get lost. Specific compounds represented by the above general formula (I)
For example, methyl glucoside, ethyl glucosi
Propyl glucoside, isopropyl glucoside,
Tyl glucoside, isobutyl glucoside, n-hexyl
Lucoside, octyl glucoside, capryl glucoside,
Decyl glucoside, 2-ethylhexyl glucoside, 2-pe
Ntynonyl glucoside, 2-hexyldecyl glucosi
Lauryl glucoside, myristyl glucoside,
Allyl glucoside, cyclohexyl glucoside, 2-buty
Nilglucoside. These compounds are glycosylated
Glucoxide, a type of body, and glucose hemiaceta
The hydroxyl group is a combination of other compounds in ether form.
Yes, for example, a public reaction to react glucose with alcohols
It can be obtained by known methods. These alkyl groups
A part of lycoside is Henkel in Germany
(GLUCOPON) and is used in the present invention.
Can be used. As another example of a preferred glycoside,
Saponins, rutin trihydrate, hesperidin
Til chalcone, hesperidin, narizine hydrate,
Phenol-β-D-glucopyranoside, salicin, 3 ', 5,
Mention may be made of 7-methoxy-7-rutinoside. In the present invention, one or two of the above glycosides are used.
The above can be used together. Glycosides in developer
The concentration of is preferably 0.01 to 20% by weight.
More preferably, it is 0.05 to 5% by weight. 0.01
If it is less than% by weight, the effect of improving dirtiness may not be achieved.
On the other hand, if it exceeds 20% by weight, developability will be reduced.
Sometimes The developer of the present invention comprises an alkali metal silicate and
And / or non-reducing sugars. Alkali metal
Examples of silicates include sodium silicate and potassium silicate.
Can be used. Use alkali metal silicate alone
Or two or more of them may be used in combination. The developer of the present invention further contains non-reducing substances other than glycosides.
More preferably, it contains sugar. As this non-reducing sugar
Does not have a free aldehyde group or ketone group,
It is a saccharide not shown and trehalo with reducing groups attached to each other
Sucrose oligosaccharides and sugar alcohols reduced by hydrogenation of sugars
All of these are suitable for use in the present invention.
You can. In the present invention, JP-A-8-30
The non-reducing sugar described in Japanese Patent No. 5039 is preferably used
be able to. Examples of the trehalose-type oligosaccharide include
For example, saccharose, trehalose and the like can be mentioned. Previous
Examples of sugar alcohols include D, L-arabit.
, Rebit, xylit, D, L-Sorbit, D,
L-man knit, D, L-exit, D, L-talit
, Zulsicit, Allozulcit and the like. Further
Maltitol hydrogenated to the disaccharide maltose,
Reducts obtained by hydrogenation of oligosaccharides (reduced water candy), etc.
Are preferable. Among these non-reducing sugars,
Halose-type oligosaccharides and sugar alcohols are preferred, among them
D-Sorbit, Saccharose, Reduced water candy, etc.
It is favorable in that it has a buffering effect in an appropriate pH range and is inexpensive.
Good. In the present invention, these non-reducing sugars are
Species may be used alone or in combination of two or more
Yes. In addition, when reducing sugar is used in combination with a base described later, browning
However, since the pH also gradually decreases and developability decreases,
Not used in the morning. Examples of the base include 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
Potassium is also used. The developer of the present invention contains a development inhibitor.
Are preferred. The following are development inhibitors, especially surfactants.
And explain. Specific examples of cationic surfactants
For example, lauryltrimethylammonium chlora
Id, cetyltrimethylammonium chloride,
Allyltrimethylammonium chloride, behenyl
Limethylammonium chloride, distearyl dimethyl
Ruammonium chloride, perfluorotrimethyla
Numonium chloride, laurylpyridinium chloride
Quaternary ammonium salts such as 2-octadecyl
Induction of imidazoline such as droxyethyl-2-imidazoline
Conductors, N, N-diethyl-stearamide-methyla
Min hydrochloride, polyoxyethylene stearylamine, etc.
Examples include amine salts. Further, as anionic surfactants, lau
Sodium phosphate, sodium stearate, olein
Higher fatty acid salts such as sodium acid, sodium lauryl sulfate
Almum sulfate esthetics such as sodium and sodium stearyl sulfate
Salts, sodium octyl alcohol sulfate,
Sodium lauryl alcohol sulfate, lauryl
High grade alcohol such as ammonium alcohol sulfate ester
Sulfate esters, acetyl alcohol sulfate
Aliphatic alcohol sulfates such as sodium,
Alkylbens such as sodium decylbenzenesulfonate
Zen sulfonates, isopropyl naphthalene sulfone
Alkyl naphthalene sulfonates such as sodium acid,
Sodium alkyldiphenyl ether disulfonate, etc.
Alkyl diphenyl ether disulfonates, laur
Sodium ril phosphate, sodium stearyl phosphate, etc.
Rukyll phosphates, sodium lauryl ether sulfate
Um polyethylene oxide adduct, lauryl ether
Polyethylene oxide adduct of ammonium sulfate
Polyethylene of lauryl ether sulfate triethanolamine
Polyalkylene sulfate adducts such as lenoxide adducts
Liethylene oxide adducts, nonylphenyl ether
Sodium disulfate polyethylene oxide adduct, etc.
Polyethylene oxalate of alkyl phenyl ether sulfate
Id adducts, poly (sodium lauryl ether)
Alkyl ether phosphates such as ethylene oxide adducts
Polyethylene oxide adducts, nonylphenyl ether
-Sodium oxide phosphate adduct with polyethylene oxide
Alkyl phenyl ether phosphate polyethylene
Xide adducts and the like can be mentioned. In addition, as the nonionic surfactant, poly
Ethylene glycol, polyethylene glycol polypro
Polyethylene such as pyrene glycol block copolymer
Glycols, polyethylene glycol cetylate
Polyethylene glycol stearyl ether, poly
Ethylene glycol oleyl ether, polyethylene group
Polyethylene glycol such as recall behenyl ether
Alkyl ethers, polyethylene glycol polypro
Pyrene glycol cetyl ether, polyethylene glycol
Polypropylene glycol decyl tetradecyl A
Polyethylene glycol polypropylene glyco such as Tell
Alkyl ethers, polyethylene glycol oct
Tylphenyl ether, polyethylene glycol nonyl
Polyethylene glycol alkyl such as phenyl ether
Phenyl ethers, ethylene glycol monostearate
, Ethylene glycol distearate, stearin
Diethylene glycol acid, polyethylene distearate
Glycol, polyethylene glycol monolaurate,
Polyethylene glycol monostearate, mono olei
Polyethylene glycol such as polyethylene glycolate
Fatty acid esters, glyceryl monomyristate,
Glyceryl nostearate, glyceryl monoisostearate
Seryl, glyceryl distearate, monooleate
Glycerin fats such as lyseryl and glyceryl dioleate
Acid esters and their polyethylene oxide adducts
Sorbitan monopalmitate, sodium monostearate
Rubitan, sorbitan tristearate, monoolein
Sorbitan such as sorbitan acid and sorbitan trioleate
Fatty acid esters and polyethylene oxide thereof
Additives, sorbitol monolaurate, tetrasteary
Acid sorbite, hexastearate sorbite, tet
Sorbit fatty acid esters such as sorbite laoleate
, And its polyethylene oxide adducts, castor
Examples include polyethylene oxide adducts of oil.
it can. Further, as the amphoteric surfactant, N-lauri is used.
Ru-N, N-dimethyl-N-carboxymethylammoni
, N-stearyl-N, N-dimethyl-N-carbo
Ximethylammonium, N-lauryl-N, N-dihi
Droxyethyl-N-carboxymethylammonium,
N-lauryl-N, N, N-tris (carboxymethyl)
E) Betaine-type compounds such as ammonium, 2-alkyl
Ru-N-carboxymethyl-N-hydroxyethylimi
Imidazolium salts such as dazolium, imidazoline-N
-Sodium ethyl sulfonate, imidazoline-N-
Imidazolines such as sodium ethyl sulfate
Can be mentioned. Among the above surfactants, used in the present invention.
In the developer, the above-mentioned cationic surfactant is used.
Quaternary ammonium salts as nonionic surfactants
The various polyethylene glycol derivatives,
Polyethylene such as various polyethylene oxide adducts
Oxide derivatives, betaines as amphoteric surfactants
Type compounds are preferred. Further, when developing using an automatic processor.
Is an aqueous solution (replenisher) with higher alkali strength than the developer.
In the developer tank for a long time by adding
A large amount of lithographic printing plates can be processed without changing the developer.
It is known that This replenishment method is also used in the present invention.
Is preferably applied. Developer and replenisher include developer
Promotion and suppression, dispersion of development residue, and printing plate image area
In order to improve the ink affinity, various surface activity
Sexual agents and organic solvents can be added. In addition, the developer and replenisher include
In addition to the surfactant and surfactant, if necessary, hydroquino
Of inorganic acids such as hydrogen, resorcin, sulfurous acid and bisulfite
Reducing agents such as sodium salt and potassium salt, and organic carbo
Contains additives such as acid, antifoam, water softener, pH adjuster, etc.
You can have it. These additives are alkaline
In the image liquid, preferably 0.001 to 5% by mass, particularly preferred
Alternatively, it may be contained at a concentration of 0.005 to 3% by mass.
it can. Development is immersion development, spray development, brush
Usually, preferably 10 to 5 by development, ultrasonic development, etc.
At a temperature of about 0 ° C, particularly preferably about 20-40 ° C.
Is done. Next, a lithographic stamp to which the developer of the present invention can be applied.
The printing plate precursor will be described. By applying to the developer of the present invention
The lithographic printing plate precursor is water-insoluble and alkali-soluble.
A photosensitive layer comprising a photosensitive composition using a polymer compound of
It is necessary to have. For example, water insoluble and alkaline water
Cresol novolac resin as a functional polymer
O-naphthoquinonediazide compounds as photosensitive materials
And alkalis having phenolic hydroxyl groups
Has a photosensitive layer containing a soluble resin and a photothermal conversion substance
And the like. Water-insoluble and alkaline used for the photosensitive layer
Water-soluble polymer compound (hereinafter referred to as alkali soluble high
The term "molecule" means that the main chain and / or side in the polymer
Homopolymers containing acidic groups in the chain, and copolymers of these
Or a mixture thereof. Therefore, according to the present invention
The photosensitive layer containing the polymer is in contact with an alkaline developer.
Then, it has a property of dissolving. Used for the photosensitive layer
The alkali-soluble polymer to be used is a conventionally known polymer.
(1) phenolic hydroxyl group,
(2) Sulfonamide group, (3) Active imide group, (4)
High molecular weight with any functional group of carboxylic acid group
A child compound is preferable. For example:
Although shown, 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, m- / p-mixed creso
Ruformaldehyde resin, phenol / cresol (m
-, P-, or m- / p-mixed)
Novolac resins such as formaldehyde resin and pillow gallows
Examples include luacetone resin. Has phenolic hydroxyl group
In addition to this, as a polymer compound
It is preferable to use a polymer compound having a functional hydroxyl group
Yes. A polymer compound having a phenolic hydroxyl group in the side chain;
Therefore, an unsaturated bond polymerizable with a phenolic hydroxyl group
Polymerizable module consisting of low molecular weight compounds each having one or more
Homopolymerization of the monomer, or other polymerizable monomers
Polymer compounds obtained by copolymerization of
The 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 having 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. Like this
As a compound, specifically, N- (p-toluenesulfo
Nyl) methacrylamide, N- (p-toluenesulfoni
E) Acrylamide and the like can be preferably used. (4) The alkali-soluble polymer having a carboxylic acid group is
Those having a carboxylic acid group in the molecule are preferred.
Molecular compounds can be polymerized with carboxylic acid groups in one molecule.
Low molecular weight compounds each having one or more active unsaturated bonds
Homopolymerizing a polymerizable monomer comprising, or the monomer
Polymerization obtained by copolymerizing with other polymerizable monomers
Compound may be mentioned. Specific examples of such compounds include
Methacrylic acid, acrylic acid, itaconic acid, maleic
An acid etc. can be used conveniently. Furthermore, the alkali-soluble polymer compound of the present invention.
As a product, a polymerizable compound having a phenolic hydroxyl group is used.
A monomer having a sulfonamide group, and
And two or more of polymerizable monomers having an active imide group
Polymer compound polymerized above, or two or more of these
Obtained by copolymerizing polymerizable monomers with other polymerizable monomers
It is preferable to use a polymer compound obtained. Feno
A polymerizable monomer having a hydroxyl group,
A polymerizable monomer having an alkyl group and / or an active imide group
When copolymerizing polymerizable monomers having
The weight ratio of the components is in the range of 50:50 to 5:95
Preferably in the range of 40:60 to 10:90
It is particularly preferred. The alkali-soluble polymer is phenolic
A polymerizable monomer having a hydroxyl group, having a sulfonamide group
Polymerizable monomer having an active imide group
When the monomer is a copolymer of other polymerizable monomers
In this case, the monomer that imparts alkali solubility is 10 moles.
% Or more, preferably those containing 20 mol% or more
More preferred. When the copolymerization component is less than 10 mol%,
Alkali solubility tends to be insufficient, and development latitude
May not be sufficiently achieved. 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
The monomer components are listed in (m1) to (m12) below.
Examples of such compounds include, but are not limited to,
Is not something (M1) 2-Hydroxyethyl acrylate or 2-H
Has an aliphatic hydroxyl group such as droxyethyl methacrylate
Acrylic esters and methacrylic esters
Kind. (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-
Alkyls such as chloroethyl and glycidyl methacrylate
Lemethacrylate. (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. As the alkaline water-soluble polymer compound,
Excellent image formability when exposed to infrared lasers, etc.
And preferably have a phenolic hydroxyl group, for example
Phenol formaldehyde resin, m-cresol
Formaldehyde resin, p-cresol formaldehyde
Resin, m- / p-mixed cresol formaldehyde tree
Fat, phenol / cresol (m-, p-, or m- /
Any of p-mixed) mixed formaldehyde resin
Such as novolac resin and pyrogallol acetone resin.
Can be mentioned. Copolymerization of alkaline water-soluble polymer compounds
As a combination method, conventionally known graft copolymerization
Method, block copolymerization method, random copolymerization method, etc.
You can. The alkali-soluble polymer is the phenol.
Polymerizable monomer having a functional hydroxyl group, sulfonamide group
Polymerizable monomer having an active imide group
In the case of homopolymers or copolymers of functional monomers,
Average molecular weight is 2,000 or more, number average molecular weight is 500 or more
Are preferred. More preferably, the weight average molecular weight is
5,000 to 300,000, number average molecular weight is 800
~ 250,000, dispersity (weight average molecular weight / number
Average molecular weight) is 1.1-10. In addition, this departure
In the light, the alkali-soluble polymer is phenolformer
Resin such as aldehyde resin and cresol aldehyde resin
When the weight average molecular weight is 500 to 20,000
Yes, those with a number average molecular weight of 200 to 10,000 are preferred
Good. These alkali-soluble polymer compounds are
You may use one type or a combination of two or more types
In the total solid content of the photosensitive layer, 30 to 99% by weight is preferable.
40 to 95% by weight, particularly preferably 50 to 90% by weight
% Added. Addition of alkali-soluble polymer
If the amount is less than 30% by weight, the durability of the photosensitive layer deteriorates,
Also, if it exceeds 99% by weight, it is preferred for both sensitivity and durability.
It ’s not good. As one of the substances for imparting photosensitivity
And o-quinonediazide compounds. Representative
Examples include o-naphthoquinonediazide compounds.
The As the o-naphthoquinonediazide compound,
1,2-dia described in Japanese Patent No. 43-28403
Zonaftquinone sulfonic acid chloride and pyrogallol
What is ester with a seton resin is preferable. Other
The preferred o-quinonediazide compounds of U.S. Pat.
3,046,120 and 3,188,210
1,2-diazonaphthoquinonesulfo described in
Of acid chloride and phenol formaldehyde resin
There is a stealth. Other useful o-naphthoquinone diadinations
As a compound, it is reported and known in many patents.
Things. For example, JP-A-47-5303,
48-63802, 48-63803, 48
-96575, 49-38701, 48-13
No. 354, Shoko 37-18015, 41-112
No. 22, No. 45-9610, No. 49-17478,
JP-A-5-11444, JP-A-5-19477, Special
Kaihei 5-19478, JP-A-5-107755, rice
National Patent No. 2,797,213, No. 3,454,400
No., No. 3,544,323, No. 3,573,917
No. 3,674,495 No. 3,785,825
No. 1, British Patent No. 1,227,602, No. 1,251,3
No. 45, No. 1,267,005, No. 1,329,88
No. 8, No. 1,330,932, German Patent No. 854,
Listed in each specification such as 890
be able to. In addition, other o-quinonediazide compounds
A polyhydroxy compound having a molecular weight of 1,000 or less and
Reaction with 1,2-diazonaphthoquinonesulfonic acid chloride
O-Naphthoquinonediazide compounds obtained by reaction are also used.
Can be used. For example, Japanese Patent Laid-Open No. 51-139402
No. 58-150948, 58-203434
No. 59-165503 No. 60-121445
No. 60-134235 No. 60-163043
No. 61-118744, 62-10645,
62-10646, 62-153950, 6
2-178562, 64-76047, US patent
No. 3,102,809, No. 3,126,281, No.
No. 3,130,047, No. 3,148,983, No.
No. 3,184,310, No. 3,188,210, No.
It is described in each public information or description such as 4,639,406
You can list what you have. These o-naphthoquinonediazide compounds
When synthesizing the polyhydroxy compound hydroxy
1,2-diazonaphthoquinonesulfonic acid group
It is preferable to react 0.2 to 1.2 equivalents of loride,
More preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent.
As 1,2-diazonaphthoquinonesulfonic acid chloride
1,2-diazonaphthoquinone-5-sulfonic acid chloride
Lido is preferred, but 1,2-diazonaphthoquinone-4-
Sulfonic acid chloride can also be used. Also obtained
The o-naphthoquinonediazide compound is 1,2-diazona
Location of phthaloquinone sulfonate group and species introduced
It is a mixture of different ones, but all hydroxyl groups are
To 1,2-diazonaphthoquinonesulfonic acid ester
Percentage of converted compound in this mixture (completely
The content of the stealted compound is 5 mol% or more
And more preferably 20 to 99 mol%.
is there. Included in the photosensitive layer of the lithographic printing plate precursor used in the present invention.
These photosensitive compounds acting on the positive type (see above)
1-50 mass% is appropriate for the amount of
More preferably, it is 10 to 40% by mass. One of the substances for imparting photosensitivity
As such, a photothermal conversion substance can be used. Photothermal conversion material and
Absorbs mainly light in the near infrared region of an image exposure light source.
It converts to heat. Where this photothermal conversion material and
As long as it is a compound that can convert absorbed light into heat,
Although not limited to, a part of wavelength range 650-1300nm
Or a light-absorbing dye having an absorption band all over is particularly effective.
The These light absorbing dyes include nitrogen atoms,
Heterocycles containing oxygen or sulfur atoms are polymethines.
The so-called cyanine color in a broad sense bound by (-CH =) n
Element is cited as a typical example.
For example, quinoline (so-called cyanine in the narrow sense), Indian
Lu (so-called indocyanine), benzothiazole
(So-called thiocyanine type), iminocyclohexadiene
Series (so-called polymethine series), pyrylium series, thiapyril
Um, squarylium, croconium, azuleni
And quinoline and indole.
, Benzothiazole, iminocyclohexadiene
A system, a pyrylium system, or a thiapyrylium system is preferred.
Also, phthalocyanine dyes are listed as typical examples.
It is. In addition, "special function pigment" (Ikemori, Pilaraya edition)
Shu, 1986, issued by CMC Corporation), "Functionality
Chemistry of dyes "(edited by Higaki, 1981, CM Co., Ltd.)
Issued by Sea), "Dye Handbook" (Taiga, Hirashima, Matsuoka
・ Edited by Kitao, published by Kodansha), 19
Catalog published in 1995, Exciton Inc.
Laser dye catalog published in 1989 by Epo
lin Inc. Catalog “E” published in 1996
color having absorption in the near-infrared region as described in "polite" etc.
Among these, among these,
"NK-123", "NK-124", "NK-220
4 "," NK-2268 "," NK-2545 "," N
K-2675 "," NK-3027 "," NK-350 "
8 "," NK-3555 "," NKX-113 "," N
Excit, such as “KX-114” and “NKX-1199”
on Inc. "IR-26", "IR-132",
"IR-140", "DNTPC-P", "DNDTP
CP ”,“ Q-Switch5 ”, etc., Epolin
Inc. "Epolite III-57", "Ep
"olite III-117", "Epolite II"
I-130 "," Epolite III-178 ",
"Epolite III-184", "Epolit
e III-189 "," Epolite III-19 "
2 "," Epolite IV-62A "," Epol
"ite V-63", "Epolite V-73",
“Epolite V-99”, “Epolite V-
149 "or the like is preferable. The photothermal conversion in the photosensitive layer
The content ratio of the substance is preferably 1 to 70% by mass.
2 to 60% by weight is particularly preferable, and 3 to 40%.
More preferably, it is mass%. The positive photosensitive layer has an exposed portion and a non-exposed portion.
The purpose of increasing the difference in solubility in alkaline developers
And forming a hydrogen bond with the alkali-soluble resin.
Dissolution inhibitor having a function of reducing the solubility of molecular substances
May be contained. Examples of dissolution inhibitors include
For example, polyethylene glycols, polyethylene glycol
Polypropylene glycol block copolymers,
Polyethylene glycol alkyl ethers, polyethylene
Ren glycol polypropylene glycol alkyl A
Tellurium, polyethylene glycol alkylphenyl ether
Tellurium, polyethylene glycol fatty acid esters, polyester
Liethylene glycol alkylamines, polyethylene
Glycol alkylamino ethers, glycerin fat
Acid esters and their polyethylene oxide adducts,
Sorbitan fatty acid ester and polyethylene oxalate thereof
Id adducts, sorbite fatty acid esters and poly
Ethylene oxide adducts, pentaerythritol fat
Acid esters and their polyethylene oxide adducts,
Nonionic surface activity such as polyglycerol fatty acid esters
Sex agents. Further, sulfonic acid esters, phosphoric acid ester
Tellurium, aromatic carboxylic acid esters, aromatic disulfo
, Carboxylic anhydrides, aromatic ketones, aromatic amines
Rudehydr, aromatic amines, aromatic ethers, etc.
Lactone skeleton, N, N-diarylamide skeleton, dia
A dye having a reel methylimino skeleton, thiolactone bone
Examples include dyes having a sulfolactone skeleton.
it can. Among the above, the dissolution inhibitor in the present invention
Have lactone skeletons and lactone skeletons
An acid coloring dye and an HLB of 10 or more,
Tylene glycols, polyethylene glycol polypro
Pyrene glycol block copolymers, polyethylene
Glycol alkyl ethers, polyethylene glycol
Rualkylphenyl ethers, polyethylene glycol
Fatty acid esters, glycerin fatty acid esters and
Polyethylene oxide adducts, sorbitan fatty acids
Esters and their polyethylene oxide adducts,
Rubit fatty acid ester and its polyethylene oxide
Adducts, pentaerythritol fatty acid esters,
Nonionic surface activity such as liglycerin fatty acid esters
Agents are preferred. The solution in the photosensitive layer composition of the present invention.
It is preferable that the content ratio of the anti-determination agent is 0 to 50% by mass.
It is particularly preferably 0 to 30% by mass, and 0 to 2%.
More preferably, it is 0 mass%. The photosensitive layer composition of the present invention includes
For the purpose of improving developability, such as providing
Preferably, an organic acid having a pKa of 2 or more and anhydrous organic acid
A thing may be contained. Its organic acid and its anhydride
For example, Japanese Patent Laid-Open No. 60-88942 and Japanese Patent Laid-Open No.
63-276048, JP-A-2-96754
In particular, glycerin is used.
Acid, methylmalonic acid, dimethylmalonic acid, propylmalonic acid
Ronic acid, succinic acid, malic acid, mesotartaric acid, glutar
Acid, β-methylglutaric acid, β, β-dimethylglutar
Acid, β-ethylglutaric acid, β, β-diethylglutar
Acid, β-propylglutaric acid, β, β-methylpropyl
Such as glutaric acid, pimelic acid, suberic acid, sebacic acid
Aliphatic saturated carboxylic acid, maleic acid, fumaric acid, gluta
Aliphatic unsaturated carboxylic acids such as conic acid, 1,1-cyclobut
Tandicarboxylic acid, 1,3-cyclobutanedicarboxylic
Acid, 1,1-cyclopentanedicarboxylic acid,
Clopentanedicarboxylic acid, 1,1-cyclohexanedi
Carboxylic acid, 1,2-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclo
Carbocyclic saturated carboxylic acids such as hexanedicarboxylic acid,
1,2-cyclohexene dicarboxylic acid, 2,3-dihydride
Loxybenzoic acid, 3,4-dimethylbenzoic acid, 3,4-
Dimethoxybenzoic acid, 3,5-dimethoxybenzoic acid, p
-Toluic acid, 2-hydroxy-p-toluic acid, 2-
Hydroxy-m-toluic acid, 2-hydroxy-o-to
Ruylic acid, mandelic acid, gallic acid, phthalic acid, isophthalic acid
Carbocyclic unsaturated carboxylic acids such as phosphoric acid and terephthalic acid, and
Meldrum acid, ascorbic acid, succinic anhydride, none
Water glutaric acid, maleic anhydride, cyclohexenedical
Bonic acid anhydride, cyclohexanedicarboxylic acid anhydride, none
There may be mentioned anhydrides such as hydrophthalic acid. The organic acid in the photosensitive layer composition and its
The content of organic acid anhydride is 0-30% by mass
Is preferred, with 0 to 20% by weight being particularly preferred,
More preferably, it is 0-10 mass%. In the photosensitive layer composition, in addition to the above components, for example
Dyes, pigments, coatability improvers, adhesion improvers, sensitivity modifiers
Various commonly used in photosensitive compositions such as benign and sensitizing agents
Is further 20 mass% or less, preferably 10 mass%
You may contain in the following ranges. The photosensitive layer composition usually contains the above components.
The solution was applied to the support surface as a solution dissolved in an appropriate solvent.
After that, the photosensitive assembly is applied to the support surface by heating and drying.
It is formed as a composition layer. Here, the solvent is different from the component used.
With sufficient solubility and good coating properties
If there is no particular limitation, for example, methyl cellosolve,
Ethyl cellosolve, methyl cellosolve acetate, ethyl
Cellosolve solvents such as lucerosolve acetate, propylene
Lenglycol monomethyl ether, propylene glycol
Monoethyl ether, propylene glycol monob
Till ether, propylene glycol monomethyl ether
Ruacetate, propylene glycol monoethyl ether
Ruacetate, propylene glycol monobutyl ether
Ruacetate, dipropylene glycol dimethyl ether
Propylene glycol solvent such as butyl acetate, acetic acid
Amyl, ethyl butyrate, butyl butyrate, diethyl oxale
, Ethyl pyruvate, ethyl-2-hydroxybutyrate
, Ethyl acetoacetate, methyl lactate, ethyl lactate
And ester solvents such as methyl 3-methoxypropionate
Medium, heptanol, hexanol, diacetone alcohol
Alcohol, furfuryl alcohol, etc.
Ketone solvents such as rhohexanone and methyl amyl ketone;
Dimethylformamide, dimethylacetamide, N-me
High polar solvents such as til pyrrolidone, or a mixed solution thereof
Medium, and those added with aromatic hydrocarbons.
Can be mentioned. The proportion of solvent used is the total amount of the photosensitive layer composition.
On the other hand, it is usually in the range of about 1 to 20 times by weight. As the coating method, a conventionally known method is used.
Methods such as spin coating, wire bar coating, dip coating
Cloth, air knife application, roll application, blade application,
And curtain coating can be used. Application amount is application
Depends on the dry film thickness, usually 0.3-7μ
m, preferably 0.5-5 μm, particularly preferably 1-3
The range is μm. In addition, as a drying temperature in that case, as an example
For example, about 60 to 170 ° C., preferably 70 to 150 ° C.
For example, the drying time is about 5 seconds to 10 minutes.
Degree, preferably about 10 seconds to 5 minutes. Note that the improvement in contrast during image formation, and
And for the purpose of improving the stability of image formation over time, etc.
For example, about 40 to 120 ° C., preferably about 40 to 70 ° C.
At a temperature of about 5 minutes to 100 hours, preferably 30 minutes
You may perform a post-heating process for about -75 hours. As the support, an aluminum plate is used.
Electrolytic etching or blocking in hydrochloric acid or nitric acid solution
Graining by lapping, anodizing in sulfuric acid solution
Treatment and surface treatment such as sealing treatment are performed if necessary.
An aluminum plate is more preferable. Also, rough surface of the support
The average roughness specified in JIS B0601
Ra is usually 0.3 to 1.0 μm, preferably 0.4.
˜0.8 μm. In the present invention, the lithographic printing plate precursor is subjected to image exposure.
Examples of light sources that can be used include carbon arc lamps, mercury lamps,
Luhalide lamp, xenon lamp, tungsten run
And chemical lamps. As radiation, electron
There are X-rays, X-rays, ion beams, far-infrared rays, and the like. Also,
g-line, i-line, Deep-UV light, high-density energy beam
(Laser beam) is also used. With laser beam
Helium neon laser, argon laser,
Krypton laser, helium, cadmium laser,
KrF excimer laser, semiconductor laser, YAG laser
And so on. In particular, heat generated by absorbing light
650-1300 nm for image formation
A light source that emits near-infrared laser light is preferred, for example
Ruby laser, YAG laser, semiconductor laser
-Solid state lasers such as LEDs can be mentioned.
In addition, small and long-life semiconductor lasers and YAG lasers
preferable. The laser light source is usually a lens.
For lithographic printing plates as a concentrated high intensity beam
The present invention is sensitive to scanning the surface of the photosensitive layer of the original.
Sensitivity characteristics of photosensitive layer of lithographic printing plate precursor in mJ / cm
²) Is the light intensity (mJ / s · c) of the received laser beam.
m²). Where the laser beam
The light intensity of the laser was measured with an optical power meter.
The amount of energy per unit time (mJ / s) of the beam
Laser beam irradiation area on the surface of the photosensitive layer (c
m²) Can be obtained by dividing by. laser
-The irradiation area of the beam is usually 1 of the laser peak intensity.
/ E²It is defined by the area of the part exceeding the strength, but simple
Is measured by exposing a photosensitive composition exhibiting a reciprocity law.
You can also. In the present invention, as the light intensity of the light source,
2.0 × 10⁶mJ / s · cm²It is preferable that
1.0 × 10⁷mJ / s · cm²It is special
Is preferred. If the light intensity is within the above range, the feeling of the present invention
Shortens the scanning exposure time, which can improve the sensitivity characteristics of the optical layer
This is a great advantage in practice. After the exposure, development processing is performed using the developer described above.
The treated lithographic printing plate contains washing water, surfactant, etc.
Desensitizing oil containing rinsing liquid, gum arabic and starch derivatives
After-treatment with liquid. Printing made by the method of the present invention
As post-processing of the plate, various combinations of these processes
Can be used. In recent years, the plate making work has been rationalized in the plate making / printing industry.
Automatic processing machines for lithographic printing plates have become widespread
It is often used. This automatic processor generally has a developing unit and
A device that consists of a post-processing unit and transports a lithographic printing plate and each process
An exposed lithographic seal consisting of a liquid tank and a spray device
Each treatment pumped up by the pump while transporting the printing plate horizontally
The liquid is sprayed from the spray nozzle and developed.
is there. In addition, recently, the liquid in the processing liquid tank filled with the processing liquid
The lithographic printing plate is immersed and transported by a middle guide roll.
A method of processing is also known. For such automatic processing
In this case, replenish each processing solution according to the processing amount, operating time, etc.
Processing can be performed while replenishing the liquid. Also substantial
So-called disposable treatment method that uses unused treatment liquid
Is also applicable. Image exposure, development, rinsing and / or phosphorus
Unnecessary for lithographic printing plates obtained by scrubbing and / or gumming
Image area (for example, film edge traces of original film)
)), The unnecessary image part is deleted.
It is. Such erasure is, for example, Japanese Patent Publication No. 2-13293.
For the unnecessary image area.
Apply and leave it for a specified time before washing with water.
The method performed by is preferable. The lithographic printing plate obtained as described above is
Applying desensitized gum as desired, then use in printing process
Lithographic printing plates with even higher printing durability
If so, a burning process is performed. Lithographic printing plate
Before burning process.
In Japanese Patent Publication Nos. 61-2518 and 55-28062,
JP-A-62-31859 and JP-A-61-159655
It can be treated with a surface conditioning liquid as described in each publication.
preferable. As the method, the surface conditioning liquid was immersed.
Apply on a lithographic printing plate with sponge or absorbent cotton, or adjust
A method in which a printing plate is dipped in a vat filled with surface liquid.
Or coating by an automatic coater. Ma
After application, squeegee or squeegee roller
It is more preferable to make the coating amount uniform.
Give fruit. The coating amount of the surface conditioning liquid is generally 0.03 to 0.8.
g / m²(Dry weight) 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. Burning processed lithographic printing plate is required
Depending on the situation, water washing, gumming, etc. have been performed
Water-soluble polymer compound
If a surface-conditioning solution containing
Any so-called desensitizing treatment can be omitted. This
The lithographic printing plate obtained by processing such as
It is applied to a printing machine and used for printing a large number of sheets. Incidentally, a lithographic printing plate to which the developer of the present invention is applied.
As a master plate for the thermal positive type as described above
As described above in detail, the application of the developer of the present invention is as described above.
It is not limited to a lithographic printing plate precursor of a thermal positive type,
Conventional positive type and negative type, and thermal negative
It can be applied to all lithographic printing plate precursors such as
In addition, the above-described various types of developing machines loaded with the developer of the present invention.
The lithographic printing plate precursor can be mixed. [0061] The present invention will be described in more detail with reference to the following examples.
As will be described, the present invention is as follows unless the gist of the present invention is exceeded.
The present invention is not limited to the examples. (Examples 1 to 25 and Comparative Examples 1 to 4) (Preparation of photosensitive lithographic printing plate A) (a) JIS A1050 aluminum plate with a thickness of 0.24 mm
Surface of nylon brush and 400 mesh pumiston
After being grained using an aqueous suspension of, it was thoroughly washed with water. (b) Concentrate 2.6 wt% of caustic soda with aluminum plate
Spray at a minium ion concentration of 6.5 wt% and a temperature of 70 ° C.
Etching process with-7g aluminum plate
/ M²Dissolved. Thereafter, washing with water was performed by spraying. (c) Nitric acid concentration 1wt% aqueous solution at 30 ° C (aluminum
(Including 0.5 wt% ion)
The treatment was performed and then washed with water by spraying. The death mask
The nitric acid aqueous solution used for the
The waste liquid from the process of electrochemical surface roughening was used. (D) Continuously using 60 Hz AC voltage
Aerochemical roughening treatment was performed. The electrolyte at this time is glass
1 wt% acid aqueous solution (0.5 wt% aluminum ion, aluminum
(Containing 0.007 wt% of ammonium ions) at a temperature of 50 ° C.
there were. The AC power supply waveform reaches its peak from zero
Time TP is 2 msec, duty ratio is 1: 1, unit
Using a rectangular wave AC shape, the carbon electrode is the counter electrode
Aerochemical roughening treatment was performed. The auxiliary anode has a
A light was used. The current density is 30A / at the peak current value.
dm²The amount of electricity is the total amount of electricity when the aluminum plate is anode.
230C / dm in sum²Met. From the power supply to the auxiliary anode
5% of the flowing current was shunted. Then spray
The water was washed. (E) An aluminum plate is made of caustic soda concentration 26
Spray at wt%, aluminum ion concentration 6.5wt%
Etching with-is performed at 70 ° C, aluminum
0.2 g / m of plate²Dissolve and electrochemistry using the previous stage alternating current
Hydroxide produced by roughening the surface
Removal of smut components mainly composed of
The edge portion was melted to smooth the edge portion. That
After washing with water by spraying. (f) Sulfuric acid 25wt% aqueous solution with a concentration of 60 ° C (Aluminium
(Including muon 0.5wt%)
The treatment was performed, followed by washing with water by spraying. (g) A sulfuric acid concentration of 170 g / l (aluminum) using an anodizing device
Including 0.5% by weight of nitrogen ions), temperature 30 ° C., 20 A /
dm²The amount of anodized film is 2.4 g / m²To be substantial
After anodic oxidation, rinse with water.
A substrate [A] was prepared. When measuring its surface roughness
The roller was 0.55 μm (Ra indication). (h) Next, the substrate [A] is made into a No. 3 sodium silicate 0.1% aqueous solution.
Treat at 20 ° C for 10 seconds, then wash with spray water
A substrate [B] was prepared. Apply the following undercoat liquid [A] to the substrate [B].
And dry at 90 ° C. for 10 seconds.
[A] was applied to prepare a photosensitive lithographic printing plate A1. Dry
The coating amount after drying was 10 mg / m for the undercoat liquid [A].²so,
The photosensitive solution [A] is 1.3 g / m.²Met. In addition, the group
Undercoat liquid [B] is applied to plate [A], and then at 90 ° C. for 10 seconds.
After drying, the following photosensitive solution [A] is applied to the photosensitive layer.
A printing plate A2 was prepared. The coating amount after drying is the undercoat liquid
[B] is 10 mg / m²The photosensitive solution [A] was 1.3 g /
m ²Met. [0066] Undercoat liquid [A] 0.1 g of a polymer compound described in JP-A-10-301262 (The structural formula is shown below) Methanol 100 g [0067] Undercoat liquid [B] β-Alanine 0.2g Methanol 100 g 1 g of water [0068] [Chemical 2] [0069] [Photosensitive solution A] 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetate Esterified product with Ton resin (in Example 1 of US Pat. No. 3,635,709) What is described) 0.7 g ·binder   Cresol novolac (Meta, para ratio 6: 4, weight average molecular weight 4000) 1.60 g   Phenol novolac (Weight average molecular weight 12000) 0.3 g ・ P-octylphenol-formaldehyde resin (Described in US Pat. No. 4,123,279) 0.01 g ・ Naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.02 g ・ Tetrahydrophthalic anhydride 0.02g ・ Pyrogallol 0.02g ・ Benzoic acid 0.02g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl] -2, 0.05 g of 6-bis (trichloromethyl) -S-triazine ・ Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) Dye changed to phthalene sulfonic acid) 0.10g ・ F176PF (Fluorosurfactant, manufactured by Dainippon Ink & Chemicals, Inc.)                                                               0.06g Methyl ethyl ketone 30.0 g 1-methoxy-2-propanol 10.0 g (Preparation of photosensitive lithographic printing plate B) Aluminum
A 3% by weight sodium hydroxide plate (thickness 0.24mm)
After degreasing at 60 ° C. for 1 minute in a bath, 12 g /
25 ° C, 80 A / dm in a hydrochloric acid bath with a concentration of 1 liter²Current density
At 10 degrees for 10 seconds, and after water washing, 10
3 seconds at 50 ° C. in a sodium hydroxide bath with a concentration of g / liter
After desmutting, washing with water and 3% in 30% sulfuric acid bath
0 ° C, 10A / dm²Anodizing for 15 seconds at a current density of
Went. Furthermore, hot water sealing treatment is performed at 90 ° C. and pH 9.
Wash and dry the aluminum plate for lithographic printing plate support
Produced. On the surface of the obtained aluminum plate support,
Photosensitive solution B is applied using a wire bar and 3 minutes at 85 ° C.
By drying for a while, the dry film thickness is 2.5 g / m²Of the
A positive photosensitive lithographic printing plate B having a di-type photosensitive layer was prepared.
It was. [0071]   (Photosensitive solution B)   Photothermal conversion substance: 4 parts by weight of the following indole dye A   Alkali-soluble organic polymer: phenol / m-cresol 100 parts by weight     / P-cresol = 50/30/20 (molar ratio) mixed phenol     Novolac resin polycondensed with formaldehyde (Mw9400,     (Manufactured by Sumitomo Durez)   Dissolution inhibitor: Crystal violet lactone 10 parts by weight   Additive 1: Cymel 300 (Mitsui Cytec Co., Ltd.) 10 parts by weight   Additive 2: 5 parts by weight of cyclohexane-1,2-dicarboxylic acid   Additive 3: Tetraoleic acid polyoxyethylene sorbit 4 parts by weight   Solvent 1: 720 parts by weight of methyl cellosolve   Solvent 2: 180 parts by weight of ethyl cellosolve [0072] [Chemical 3] (Preparation of photosensitive lithographic printing plates C1 and C2)
On the substrate [A] prepared in the same manner as the photolithographic printing plate A,
The following undercoat liquid was applied, and the coating film was dried at 90 ° C. for 1 minute.
Then, apply Photosensitizer C and dry at 100 ° C. for 2 minutes.
Thus, a photosensitive lithographic printing plate C1 was formed. Of the coating after drying
The coating amount is 10 mg / m for the following undercoat liquid², 1.9g of photosensitive solution
/ M²Met. Also, the substrate [A] is attached to C1.
Photosensitive lithographic printing is the same except that the substrate [B] is changed.
Version C2 was created. The coating amount after drying is the following undercoat
10 mg / m of liquid², 1.9g / m of photosensitive solution²Met. [0074]   [Undercoat liquid]   ・ The following compound 0.3g   ・ Methanol 100 g   ・ Water 1 g [0075] [Formula 4] [0076]   [Photosensitive solution C]   m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 7500     , Containing 0.5% by weight of unreacted cresol) 0.75 g   Acrylic polymer of methacrylic acid / n-butyl methacrylate = 75/25 0.05 g   Photothermal conversion substance (cyanine dye A) having the following structure 0.04 g   4,4-bis (hydroxyphenyl) sulfone 0.02 g   Tetrahydrophthalic anhydride 0.05 g   Ethyl violet 0.015g   2,4,6-tris (hexyloxy) benzenediazonium-2-     Hydroxy-4-methoxybenzophenone-5-sulfonate 0.01 g   Fluorosurfactant (Megafac F-176,     Dainippon Ink & Chemicals, Inc.) 0.02 g   Methyl ethyl ketone 15 g   1-methoxy-2-propanol 7 g [0077] [Chemical formula 5] (Preparation of photosensitive lithographic printing plate D) Photosensitive lithographic plate
The following lower recording layer coating solution D1 on the same substrate as the printing plate C1
The coating amount is 0.85 g / m²After applying to become 1
Dry at 40 ° C. for 50 seconds, and then coating solution for upper recording layer
D2 applied at 0.15 g / m²I applied so that
After drying at 120 ° C. for 1 minute, a photosensitive lithographic printing plate D is obtained.
It was. [0079] [Lower recording layer coating solution D1]   N- (4-aminosulfonylphenyl) 1.896 g     Methacrylamide / Acrylonitrile /     Methyl methacrylate (36/34/30:     Weight average molecular weight 50000)   Cresol novolak (m / p = 6/4, 0.237g     Weight average molecular weight 4500, residual monomer 0.8% by mass)   Photothermal conversion substance (cyanine dye A) 0.109 g   4,4'-bishydroxyphenylsulfone 0.063 g   Tetrahydrophthalic anhydride 0.190g   p-Toluenesulfonic acid 0.008g   0.05 g of 6-hydroxy counter ion of ethyl violet     What changed to naphthalenesulfonic acid   Fluorosurfactant (Megafac F176, 0.035g     Dainippon Ink Industries, Ltd.)   Methyl ethyl ketone 26.6 g   1-methoxy-2-propanol 13.6 g   γ-butyrolactone 13.8 g [0080] [Upper recording layer coating solution D2]   m, p-cresol novolak (m / p ratio = 6/4, 0.237 g   (Weight average molecular weight 4500, 0.8% by mass of unreacted cresol)   Photothermal conversion substance (Cyanine dye A) 0.047g   0.060 g dodecyl stearate   3-methoxy-4-diazodiphenylamine 0.030 g     Hexafluorophosphate   Fluorosurfactant (Megafac F176, 0.110g     Dainippon Ink Industries, Ltd.)   Fluorosurfactant (Defenser MCF312 (30%), 0.120 g     Dainippon Ink Industries, Ltd.)   Methyl ethyl ketone 15.1 g   1-methoxy-2-propanol 7.7 g (Preparation of photosensitive lithographic printing plate E) Photosensitive lithographic plate
The following photosensitive solution E is applied on the same substrate as the printing plates C and D:
0g / m²And then apply at 140 ° C for 50 seconds
It dried and the photosensitive lithographic printing plate E was obtained. [0082] [Photosensitive solution E]   N- (4-aminosulfonylphenyl) 1.896 g     Methacrylamide / Acrylonitrile     / Methyl methacrylate (35/35/30:     Weight average molecular weight 50000)   Cresol novolak (m / p = 6/4, 0.332 g     Weight average molecular weight 4500, residual monomer 0.8% by mass)   Photothermal conversion substance (cyanine dye A) 0.155g   4,4'-bishydroxyphenylsulfone 0.063 g   Tetrahydrophthalic anhydride 0.190g   p-Toluenesulfonic acid 0.008g   0.05 g of ethyl violet counter ion     Changed to 6-hydroxynaphthalenesulfonic acid   Fluorosurfactant (Megafac F176, 0.145g   Dainippon Ink Industries, Ltd.)   Fluorosurfactant (Defenser MCF312 (30%), 0.120 g     Dainippon Ink Industries, Ltd.)   Methyl ethyl ketone 26.6 g   1-methoxy-2-propanol 13.6 g   γ-butyrolactone 13.8 g (Development of developer) Mixing with the following formulation
A developer was prepared. As a comparative example, glycosides were added.
Those not added were also made in the same way. [0084]     Glycosides (types listed in Table 1) Amounts listed in Table 1 below     [SiO₂] / [K₂O] = 1/1 potassium silicate              Amounts listed in Table 1 below     D-sorbitol Amount shown in Table 1 below     Potassium hydroxide listed in Table 1 below     DEQUEST 2066 0.25 wt%       (Chelant made by Monsanto, USA)     Development inhibitor (listed substances) 0.25% by weight     Water listed in Table 1 below Glycosides listed in Table 1 used in the developer of the present invention.
Is shown below. [0086] [Chemical 6]Development inhibitor (1): “Pluronic” manufactured by Asahi Denka Co., Ltd.
Ku-P-85 "(polyethylene oxide derivative) Development inhibitor (2); “Nissan PEG100” manufactured by NOF Corporation
0 "(polyethylene oxide) Development inhibitor (3); “Pionin D-110” manufactured by Takemoto Yushi Co., Ltd.
7 "(polyethylene oxide derivative) Development inhibitor (4); Polyethylene oxide sorbitol (polyethylene oxide)
Ethylene oxide derivatives) Development inhibitor (5): Polyethylene oxide / Polypropylene oxide
Ethylenediamine (polyethylene oxide derivative) (Exposure method) Photosensitive planographic printing plates A1 and A2 Plate making film (silver salt mass)
3kW from a distance of 1m through
The image was exposed for 1 minute with a ride lamp. Photosensitive planographic printing plates B, C1, C2, D, E Creo Trendsetter beam intensity 9w, drum rotation speed
Draw a test pattern as an image at 150 rpm
It was. [Evaluation of lithographic printing plate precursor] (Evaluation of residue in developing bath, washing bath and finisher bath
Method) Exposed photosensitive lithographic printing plate, Fuji Photo Film
First bath using PS processor 900H manufactured by Mu Co., Ltd.
(Development bath) is charged with the developer shown in Table 1 below, and the second bath (water
Tap water into the wash bath) and into the third bath (finisher bath)
Filled with doubling dilution of Fuji Photo Film gum solution FP-2W
Thus, development was performed while maintaining the temperature of the developing bath at 30 ° C. Changes in developability
Develop 20 plates a day while adding developer so as not to disturb
And observe the residue accumulated in the developing bath after 1 month
The sensory evaluation was performed with x as the sum and ◯ when there was none. Also washed with water
Similarly for scum accumulated in the bath and finisher bath
Observed. (Method for evaluating printing durability)
Komori, a lithographic printing plate obtained in the same way as the development process
Incorporated with Lilithon printing machine manufactured by Corporation.
DIC-GEOS (N) Black (Dainippon Ink & Chemicals, Inc.
Printed), the density of solid images began to fade
The printing durability is determined by the number of printed sheets
evaluated. (Evaluation Method of Stain) Planographic Printing Plate Obtained
Mitsubishi diamond type F2 printing machine (Mitsubishi Heavy Industries, Ltd.)
DIC-GEOS (s) Beni (Dai Nippon
Nki Chemical Industry Co., Ltd.)
After that, the dirt on the blanket was visually evaluated. Dirty
O, Δx, and x were assigned in order from the least. [0091] [Table 1] [0092] [Table 2]As apparent from Table 1 above, the present invention is
By using the image liquid, it is caused by silicate in the developing bath.
Dissolved aluminum in dregs, washing bath and finisher bath
Lithographic plate with reduced printing residue and dirt, and excellent printing durability
It was confirmed that a printing plate could be obtained. [0094] The developer of the present invention is a silicate in a developing bath.
Dissolved aluminum, leaching aluminum in washing bath and finisher bath
It is hard to produce scum caused by nium, and aluminum elution prevention treatment
To obtain a lithographic printing plate with excellent printing durability.
It can be done.

Claims (1)

1. A lithographic printing plate developer comprising a glycoside and a base.