JP2003098653A - Photopolymerizable photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable photosensitive planographic printing plate keeping a paper surface corresponding to its edge portions from staining, free of a problem even on conveyability in a laser exposure setter and having improved aging stability and sensitivity. SOLUTION: In the photopolymerizable photosensitive planographic printing plate obtained by disposing a photopolymerizable photosensitive layer on an aluminum support with an anodic oxide coating, edge portions of opposite two sides or four sides are curved from the photosensitive layer side toward the bottom side and a photopolymerization initiator contained in the photosensitive layer generates a radical by energy transfer.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable photosensitive lithographic plate.
It relates to the printing plate. More specifically, dirt on the edge
For photopolymerizable photosensitive lithographic printing plates that do not generate
Is. [0002] A photosensitive flat plate having an aluminum plate as a support.
As a method for producing a plate printing plate, there is generally a sheet form.
Or coiled aluminum plate, grained and anodized
Apply various surface treatments alone or in combination,
Applying and drying the photosensitive solution, then cutting to the desired size
The law is adopted. Such a photosensitive lithographic printing plate image
Mark using a printing plate obtained by processing such as exposure and development.
When printing, the size of the printing plate as in a normal sheet-fed press
Corresponds to the edge of the printing plate when printing on smaller paper.
There is no problem with the edges because the printed part does not become the printing surface, but the new
Continuously on a roll of paper using a rotary press
When printing, roll paper is also used as the edge of the printing plate.
Will be on the printing surface and contact with the
The prints are also printed on paper and become dirty, creating a value for the printed product
I was damaging. Prevent contamination of the edges of such printing plates
As a method, for example, in Japanese Examined Patent Publication No. 57-46754
The end of the aluminum support is placed against the aluminum surface.
And a method of cutting to 10 degrees to 45 degrees is disclosed.
However, when 10,000 sheets or more are printed, ink accumulates at the edges.
Dirt is generated. Also, Japanese Patent Publication No. 62-6194
No. 6 discloses a desensitizing treatment for the end face of an aluminum support.
The method to keep it in Japanese Unexamined Patent Publication No. Sho 63-256495
The hydrophilic end of the printing plate on the aluminum support is previously treated.
The method to manage, Japanese Patent Application Laid-Open No. 11-52558,
Printing plate of aluminum support having a diazo photosensitive layer
Although a method of cutting the end face convexly is disclosed,
It is still not enough for a photosensitive photosensitive lithographic printing plate
A further improvement was desired. [0003] The present invention addresses the end.
Laser exposure set without causing stains on the paper
Improved stability over time and sensitivity.
To provide an improved photopolymerizable photosensitive lithographic printing plate
And The above object of the present invention is as follows.
This was achieved by adopting the following configuration. That is, the present invention
Photopolymerization on an aluminum support with an anodized film
A photopolymerizable photosensitive lithographic printing plate provided with a photosensitive layer
The opposite two or four sides are on the photosensitive layer side.
And is contained in the photosensitive layer.
Photoinitiator generates radicals by energy transfer
Photopolymerizable photosensitive lithographic printing, characterized by
It is a version. DETAILED DESCRIPTION OF THE INVENTION The photopolymerizable photosensitive lithographic printing of the present invention.
The version is described in detail below. [Photopolymerizable photosensitive layer] First, the photopolymerizable photosensitive lithographic plate of the present invention.
The photopolymerizable photosensitive layer of the printing plate will be described. Light of the present invention
The photopolymerizable photosensitive layer (hereinafter simply referred to as “polymerizable photosensitive lithographic printing plate”).
The photopolymerizable photosensitive composition constituting the photosensitive layer) is
Addition-polymerizable ethylenically unsaturated compound, photopolymerization started
Agent and polymer binder as essential components, colored as required
Various compounds such as plasticizers, plasticizers, thermal polymerization inhibitors, etc.
be able to. Among these, photopolymerization is a particularly important component.
The initiator will be described. Photopolymerizable photosensitive lithographic plate of the present invention
Examples of the photopolymerization initiator contained in the photosensitive layer of the printing plate include:
If radicals are generated by energy transfer,
Known in patents, literature, etc., depending on the wavelength of the light source used
Various photoinitiators or a combination system of two or more photoinitiators
(Photoinitiation system) can be appropriately selected and used. Less than
Specific examples are listed below, but are not limited to these.
Yes. Visible light of 400 nm or more, Ar laser
-Second harmonic of semiconductor laser, SHG-YAG
Various light initiation systems have also been proposed when using a laser as the light source.
For example, as described in US Pat. No. 2,850,445
Certain photoreductive dyes listed, such as rose bengal,
Osin, erythrosine, etc. or dye and initiator
A system based on the combination of titanocene and 3-ketocoumarin
Dye system (Japanese Patent Laid-Open No. 63-221110), titanocene
Xanthene dye and amino group or urethane group
Contains addition polymerizable ethylenically unsaturated compounds containing
System (JP-A-4-221958, JP-A-4-219)
756), a system of titanocene and specific merocyanine dyes
(JP-A-6-295061), titanocene and benzopi
A dye system having a orchid ring (Japanese Patent Laid-Open No. 8-3344897)
Etc. Recently, a wavelength of 400 to 410 nm has been recorded.
The laser (violet laser) was developed and felt
A photoinitiating system that exhibits high sensitivity at wavelengths below 450 nm
These photoinitiating systems are also used. example
For example, a merocyanine dye / titanocene system
14763), carbazole type dye / titanocene system
(Japanese Patent Laid-Open No. 2001-42524)
The There are various titanocene compounds.
For example, Japanese Patent Laid-Open No. 59-1523 can be used.
96, and JP-A 61-151197.
Select from various titanocene compounds
Can do. More specifically, di-cyclopentadieni
Ru-Ti-di-chloride, di-cyclopentadienyl
-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorofe
Ni-1-yl, di-cyclopentadienyl-Ti-bis
-2,3,5,6-tetrafluorophen-1-yl,
Di-cyclopentadienyl-Ti-bis-2,4,6-
Trifluorophen-1-yl, di-cyclopentadie
Nyl-Ti-bis-2,6-di-fluorophen-1-
Yl, di-cyclopentadienyl-Ti-bis-2,4
-Di-fluorophen-1-yl, di-methylcyclope
Tantadienyl-Ti-bis-2,3,4,5,6-teto
Rafluorophen-1-yl, di-methylcyclopenta
Dienyl-Ti-bis-2,6-difluorophen-1
-Yl, di-cyclopentadienyl-Ti-bis-2,
6-Difluoro-3- (pyr-1-yl) -pheni-1
-Yl etc. can be mentioned. Further, 2-mer may be added to the photoinitiator as required.
Captobenzthiazole, 2-mercaptobenzimid
Thio such as sol, 2-mercaptobenzoxazole
Compounds, N-phenylglycine, N, N-dialkyl
Water such as amine compounds such as amino aromatic alkyl esters
Higher photoinitiating ability by adding elemental donor compound
It is known that These photoinitiators
The amount of (system) used is 100 parts by weight of ethylenically unsaturated compound
0.05 to 100 parts by weight, preferably 0.1 to
70 parts by weight, more preferably in the range of 0.2 to 50 parts by weight
Used in The photopolymerizable photosensitive lithographic printing plate of the present invention
The ethylenically unsaturated compound contained in the photosensitive layer of
When the polymerizable photosensitive composition is irradiated with actinic rays,
Addition polymerization, crosslinking and curing by the action of the initiator
It is a compound having an ethylenically unsaturated bond. Additional weight
A compound containing an ethylenic double bond capable of
At least one, preferably two or more lentic unsaturated bonds
Any of the above compounds can be selected.
For example, monomer, prepolymer, ie dimer, 3 quantity
Bodies and oligomers, or mixtures thereof and
These copolymers have a chemical form. Examples of monomers and copolymers thereof
Unsaturated carboxylic acids (e.g. acrylic acid, methacrylate)
Formic acid, itaconic acid, crotonic acid, isocrotonic acid, male
Esthetic acid etc. and aliphatic polyhydric alcohol compounds
Of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound
And the like. Aliphatic polyhydric alcohol compound and unsaturated cal
Specific examples of monomers of esters with boric acid include
Ethyl glycol diacrylate
, Triethylene glycol diacrylate, 1,3
-Butanediol diacrylate, tetramethylene glycol
Cold diacrylate, propylene glycol diacryl
Rate, neopentyl glycol diacrylate, tri
Methylolpropane triacrylate, trimethylol
Propanetri (acryloyloxypropyl) ate
, Trimethylolethane triacrylate, hexane
Diol diacrylate, 1,4-cyclohexanedio
Diacrylate, tetraethylene glycol diac
Relate, pentaerythritol diacrylate, pen
Taerythritol triacrylate, pentaerythritol
Tetraacrylate, dipentaerythritol dia
Chryrate, dipentaerythritol pentaacrean
Dipentaerythritol hexaacrylate, sol
Bitol triacrylate, sorbitol tetraacrylate
Rate, sorbitol pentaacrylate, sorbitol
Lehexaacrylate, tri (acryloyloxyethyl)
L) Isocyanurate, polyester acrylate
There are gomers. Methacrylic acid esters include tetrameth
Tylene glycol dimethacrylate, triethylene glycol
Cold dimethacrylate, neopentyl glycol dimethyl
Tacrylate, trimethylolpropane trimethacrylate
, Trimethylolethane trimethacrylate, ethyl
Lenglycol dimethacrylate, 1,3-butanedio
Dimethacrylate, hexanediol dimethacrylate
, Pentaerythritol dimethacrylate, penta
Erythritol trimethacrylate, pentaerythritol
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, dipentaerythritol pentamethacrylate
Sorbitol trimethacrylate, sorbitol
Tetramethacrylate, bis [p- (3-methacrylo
Xyl-2-hydroxypropoxy) phenyl] dimethyl
Methane, bis- [p- (methacryloxyethoxy) phenyl
Nenyl] dimethylmethane and the like. Itaconic acid esters include ethylene glycol
Recall Diitaconate, Propylene Glycol Diita
Conate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethyle
Glycol diitaconate, pentaerythritol di
Itaconate, sorbitol tetritaconate, etc.
The As crotonic acid ester, ethylene glycol
Dicrotonate, tetramethylene glycol dicrotone
, Pentaerythritol dicrotonate, sorbite
And tetratetracrotonate. Isocrotonic acid
As stealth, ethylene glycol diisocrotonate
, Pentaerythritol diisocrotonate, sorbi
Examples include tall tetraisocrotonate. Maleic acid esters include ethylene glycol
Recall dimaleate, triethylene glycol dimale
, Pentaerythritol dimaleate, sorbitol te
There are trauma rates. In addition, the ester monomers described above
-Can also be mentioned. In addition, aliphatic polyvalent polymers
Of amide monomer of amine compound and unsaturated carboxylic acid
Specific examples include methylene bis-acrylamide, methyl.
Renbis-methacrylamide, 1,6-hexamethylene
Bis-acrylamide, 1,6-hexamethylene bis-
Methacrylamide, diethylenetriamine trisacryl
Luamide, xylylene bisacrylamide, xylylene
Examples include bismethacrylamide. Other examples include Japanese Patent Publication No. 48-417.
Two or more a) molecules per molecule described in No. 08
To the polyisocyanate compound having a socyanate group,
Vinyl containing a hydroxyl group represented by the following general formula (A)
Two or more polymerizable polymers in one molecule with added monomers
And vinyl urethane compounds containing nyl groups.
The CH ₂ = C (R ^Five ) COOCH ₂ CH (R ⁶ ) OH (A) (where R is ^Five And R ⁶ Is H or CH
_Three Indicates. In addition, JP-A-51-37193 and JP-B-2-229
Urethane acrylates as described in No. 3,
JP-A-48-64183, JP-B-49-43191
And Japanese Patent Publication No. 52-30490
Such as polyester acrylate, epoxy resin
Epoxy acrylate reacted with (meth) acrylic acid
List of polyfunctional acrylates and methacrylates
be able to. Furthermore, Vol. 20, no.
7, pages 300-308 (1984)
Also used as monomers and oligomers
Can be used. These ethylenically unsaturated
The amount of the compound used is preferably 5 to 80% by weight of the total components of the photosensitive layer.
Alternatively, it is used in the range of 30 to 70% by weight. Photosensitization of the photopolymerizable photosensitive lithographic printing plate of the present invention
As a polymer binder used for the layer, a film of the composition
Not only as a forming agent, it must be dissolved in an alkaline developer.
It is soluble or swellable in alkaline water
An organic polymer is used. The organic polymer
For example, when a water-soluble organic polymer is used,
An image becomes possible. As such an organic polymer,
Addition polymers having carboxylic acid groups in the side chain, such as
59-44615, Shoko 54-34327, Shoko
Sho 58-12577, Shoko 54-25957, Sho
No. 54-92723, Japanese Patent Laid-Open No. 59-53836,
Those described in JP-A-59-71048;
That is, methacrylic acid copolymer, acrylic acid copolymer,
Taconic acid copolymer, crotonic acid copolymer, maleic acid copolymer
Examples include polymers and partially esterified maleic acid copolymers. Similarly, an acid having a carboxylic acid group in the side chain
There are functional cellulose derivatives. In addition to this
A product obtained by adding a cyclic acid anhydride to a polymer is useful.
is there. Especially among these [benzyl (meth) acrylate
G / (meth) acrylic acid / other additional weight as required
Compatible vinyl monomer] copolymer and [allyl (meth) a]
Acrylate (meth) acrylic acid / other as required
Addition-polymerizable vinyl monomer] is preferable. This
In addition to water-soluble organic polymers, polyvinylpyrrolidone
And polyethylene oxide are useful. Also hardened skin
To increase the strength of the membrane, alcohol-soluble polyamides and
2,2-bis- (4-hydroxyphenyl) -propane
And a polyether of epichlorohydrin are also useful.
Also, Japanese Patent Publication No. 7-120040 and Japanese Patent Publication No. 7-12004
No. 1, No. 7-120042, No. 8-1224
No. 4, JP-A 63-287944, JP-A 63-28
7947, JP-A-1-271741, JP-A-11-
The polyurethane resin described in 352691 is also used in the present invention.
Is useful. These high molecular polymers have a radical reaction in the side chain.
Improves the strength of the cured film by introducing a functional group
be able to. Ethylene as a functional group capable of addition polymerization reaction
Unsaturated unsaturated groups, amino groups, epoxy groups, etc.
Mercapto is a functional group that can be converted to radicals by irradiation.
Group, thiol group, halogen atom, triazine structure, oni
Um salt structure, etc.
And the like. A functional group capable of undergoing an addition polymerization reaction;
For example, acrylic group, methacryl group, allyl group,
Particularly preferred is an ethylenically unsaturated bond group such as
Amino group, hydroxy group, phosphonic acid group, phosphoric acid group, cal
Vamoyl group, isocyanate group, ureido group, ureire
Functional group selected from an amine group, a sulfonic acid group, and an ammonio group
Groups are also useful. In order to maintain the developability of the composition,
The bright polymer binder should have an appropriate molecular weight and acid value.
Preferably, the weight average molecular weight is 5,000 to 300,000, and the acid value is 2
0 to 200 high molecular weight polymers are effectively used. these
The organic polymer of this is mixed in any amount in the whole composition
be able to. However, if it exceeds 90% by weight, it is formed
Does not give a favorable result in terms of image strength and the like. Like
10 to 90%, more preferably 30 to 80%
The Also, photopolymerizable ethylenically unsaturated compounds and organic
The molecular polymer should be in the range of 1/9 to 9/1 by weight.
Is preferred. A more preferable range is 2/8 to 8/2
More preferably, it is 3/7 to 7/3. In the present invention, the above basic components
Other polymerization during production or storage of the photosensitive composition
Prevent unnecessary thermal polymerization of possible ethylenically unsaturated compounds
To add a small amount of thermal polymerization inhibitor
Yes. Suitable thermal polymerization inhibitors include haloid quinone, p-
Methoxyphenol, di-t-butyl-p-creso
, Pyrogallol, t-butylcatechol, benzoquino
4,4'-thiobis (3-methyl-6-t-butyl
Phenol), 2,2'-methylenebis (4-methyl-
6-t-butylphenol), N-nitrosophenyl
Droxylamine primary cerium salt, N-nitrosofeni
And the like.
The addition amount of the thermal polymerization inhibitor is approximately about the total composition weight.
0.01% to about 5% is preferred. If necessary, acid
Behenic acid and behenic acid to prevent polymerization inhibition by silicon
After coating with higher fatty acid derivatives such as amide
In the course of drying, it may be unevenly distributed on the surface of the photosensitive layer. Luxury
The amount of fatty acid derivative added is about 0.5% to about 1% of the total composition.
0% is preferable. Further, for the purpose of coloring the photosensitive layer, a colorant is added.
It may be added. As a colorant, for example, phthalocyan
Nin-based pigment (CI Pigment Blue 1
5: 3, 15: 4, 15: 6, etc.), azo pigments, car
Bon black, pigments such as titanium oxide, ethyl violet
, Crystal violet, azo dye, anthraki
Non dyes and cyanine dyes are available. Of dyes and pigments
The amount added is preferably from about 0.5% to about 20% of the total composition.
In addition, in order to improve the physical properties of the cured film, inorganic fillers
And dioctyl phthalate, dimethyl phthalate, tric
Additives such as plasticizers such as resin phosphate may be added
Yes. These additions are preferably 10% or less of the total composition.
Yes. Photosensitization of the photopolymerizable photosensitive lithographic printing plate of the present invention
When coating the layer composition on the support described later, various organic
Dissolved in a solvent for use. The solvent used here and
Acetone, methyl ethyl ketone, cyclohexa
, Ethyl acetate, ethylene dichloride, tetrahydro
Furan, toluene, ethylene glycol monomethyl ether
Tellurium, ethylene glycol monoethyl ether, ethyl
Glycol dimethyl ether, propylene glycol
Monomethyl ether, propylene glycol monoethyl
Ether, acetylacetone, cyclohexanone, dia
Seton alcohol, ethylene glycol monomethyl A
Teracetate, ethylene glycol ethyl ether
Cetate, ethylene glycol monoisopropyl ether
, Ethylene glycol monobutyl ether acetate
G, 3-methoxypropanol, methoxymethoxyethane
Nord, diethylene glycol monomethyl ether, di
Ethylene glycol monoethyl ether, diethylene glycol
Recall dimethyl ether, diethylene glycol die
Till ether, propylene glycol monomethyl ether
Ruacetate, propylene glycol monoethyl ether
Ruacetate-3-methoxypropyl acetate, N,
N-dimethylformamide, dimethyl sulfoxide, γ
-Butyrolactone, methyl lactate, ethyl lactate, etc.
The These solvents can be used alone or in combination.
You can. And the concentration of the solid content in the coating solution is 1 to
50% by weight is suitable. Photosensitization of the photopolymerizable photosensitive lithographic printing plate of the present invention
The photopolymerizable composition in the layer improves the coating surface quality
For this purpose, a surfactant can be added. The coverage is
0.3 g / m by weight after drying ² ~ 5.0 g / m ² Range is
Is appropriate. Preferably 0.5 g / m ² ~ 3g / m ² In
The Further, the polymerization of oxygen is prohibited on the photosensitive layer.
An oxygen barrier protective layer is necessary to prevent the stopping effect
The A water-soluble vinyl polymer contained in the oxygen barrier protective layer;
The polyvinyl alcohol and its partial esthetics
, Ether, and acetal, or required for them
A substantial amount of unsubstituted vinyl alcohol that is highly water soluble.
Mention may be made of copolymers thereof containing alcohol units. Po
71 to 100% hydrolysis as rivinyl alcohol
And those having a degree of polymerization in the range of 300-2400.
It is. Specifically, Kuraray Co., Ltd. PVA-105, P
VA-110, PVA-117, PVA-117H, P
VA-120, PVA-124, PVA-124H, P
VA-CS, PVA-CST, PVA-HC, PVA-
203, PVA-204, PVA-205, PVA-2
10, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, PVA
-220E, PVA-224E, PVA-405, PV
A-420, PVA-613, L-8, etc. are mentioned.
As said copolymer, it is hydrolyzed 88-100%
Polyvinyl acetate chloroacetate or propylene
Honate, polyvinyl formal and polyvinyl acetate
Tar and their copolymers. Other existence
Useful polymers include polyvinylpyrrolidone, gelatin and
And gum arabic, which can be used alone or in combination.
May be used. In the photopolymerizable photosensitive lithographic printing plate of the present invention,
As a solvent used when applying an oxygen barrier protective layer
Is preferably pure water, but methanol, ethanol, etc.
Alcohols, acetone, methyl ethyl ketone, etc.
Tons may be mixed with pure water. Then, in the coating solution
The concentration of the form is suitably 1 to 20% by weight. On the present invention
In order to further improve the coatability of the oxygen barrier protective layer
Surfactant, water-soluble to improve film properties
You may add well-known additives, such as a plasticizer. Water-soluble plasticizer
For example, propionamide, cyclohexane
There are diol, glycerin, sorbitol and the like. Also,
Even if water-soluble (meth) acrylic polymer is added
good. The coating amount is 0.5 g / m in weight after drying. ² ~ 1
0g / m ² The range of is appropriate. More preferably 1.0
g / m ² ~ 5.0 g / m ² It is. [Aluminum Support] Next, the light of the present invention is used.
The support for the polymerizable photosensitive lithographic printing plate will be described. Book
In order to obtain the photopolymerizable photosensitive lithographic printing plate of the invention, the above photosensitive layer is used.
Is provided on a support having a hydrophilic surface. Hydrophilic support
The aluminum support is a dimensionally stable plate.
A holding body is used. Against the surface of the aluminum support
Appropriate for the purpose of imparting hydrophilicity or improving strength as necessary
Such known physical and chemical treatments may be applied. The preferred aluminum plate is pure aluminum
Mainly composed of plate and aluminum, and contains trace amounts of foreign elements.
Alloy plate, and also aluminum laminated or
May be a deposited plastic film. Armini
The different elements contained in the aluminum alloy include silicon, iron, and manga.
Copper, magnesium, chromium, zinc, bismuth, nickel
There are Kell and Titanium. The content of foreign elements in the alloy is at most
10% by weight or less. Particularly suitable for the present invention
Minium is pure aluminum, but it is completely pure aluminum.
Since ruminium is difficult to manufacture due to refining technology,
It may contain foreign elements. Thus, it is suitable for the present invention.
The aluminum plate used has a specific composition
Rather than using a publicly known aluminum plate
It can be used as appropriate. Al used in the present invention
The thickness of the minium plate is preferably 0.15mm to 0.4mm
Or 0.2 mm to 0.3 mm. The aluminum support is a non-image area after development.
It is essential to anodize to prevent scratches on the
Surface roughening (graining), sodium silicate, zirconium fluoride
Such as immersion treatment in aqueous solution of potassium umerate, phosphate, etc.
It is preferable that surface treatment is performed. Anodized film
The film thickness of 0.5 to 5.0 g / m ² And prefer
1.0 to 4 g / m ² More preferably. The roughening treatment of the surface of the aluminum plate
For example, the surface is mechanically roughened.
A method for electrochemically dissolving and roughening the 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, buffing, and polishing.
it can. Electrochemical roughening methods include hydrochloric acid and glass.
There are methods that use alternating current or direct current in electrolytes such as acids.
The Moreover, it is disclosed by Unexamined-Japanese-Patent No. 54-63902.
You can also use a method that combines both
The Also, prior to roughening the aluminum plate, desired
For example, to remove rolling oil on the surface, the interface
Degreasing with activator, organic solvent or alkaline aqueous solution
Processing is performed. Further, after roughening, sodium silicate
Aluminum plate immersed in aqueous solution is preferably used
it can. As described in Japanese Patent Publication No. 47-5125
After anodizing the aluminum plate,
What is immersed in an aqueous solution of metal silicate is preferably used.
It is. Anodizing treatment is, for example, phosphoric acid, chromium
Inorganic acids such as acid, sulfuric acid, boric acid, or oxalic acid, sulfami
Aqueous or non-aqueous solutions of organic acids such as acids or their salts
Alcohol is used alone or in combination of two or more.
It is implemented by passing a current with the minium plate as the anode.
The Also described in US Pat. No. 3,658,662.
Silicate electrodeposition is also effective. More
JP-B-46-27481, JP-A-52-5860
2 and as disclosed in JP-A 52-30503
And a support with an appropriate electrolytic grain and the above-mentioned anodizing treatment
A surface treatment in combination with sodium silicate treatment is also useful.
Further, as disclosed in JP-A-56-28893
Mechanical roughening, chemical etching, electrolytic grain, positive
Preference is also given to polar oxidation treatment and sodium silicate treatment in order.
Is suitable. Furthermore, after these treatments,
Resin such as polyvinylphosphonic acid, sulfonic acid group
Polymers and copolymers having a pendant in the side chain, polyacryl
Acid, water-soluble metal salt (for example, zinc borate) or yellow dyeing
Also preferred is a primer or amine salt. further
Radiation as disclosed in JP-A-7-159983
A functional group capable of undergoing an addition reaction by cal is covalently bonded.
A sol-gel treated substrate is also preferably used. As another preferred example, on an arbitrary support.
In addition, the surface layer may be provided with a water-resistant hydrophilic layer.
be able to. As such a surface layer, for example, US3
No. 055295 or JP-A-56-13168
Layer comprising machine pigment and binder, JP-A-9-80744
The hydrophilic swelling layer described in JP-A-8-507727
Zo consisting of titanium oxide, polyvinyl alcohol and silicic acids
A Lugel membrane can be used. These hydrophilic treatments
Is applied to make the surface of the support hydrophilic.
In addition, the harmful reaction of the photopolymerizable composition provided thereon
To prevent and improve the adhesion of the photosensitive layer
Is. On the above support, the photopolymerizable composition
By forming a photosensitive layer made of a product, the photopolymerizability of the present invention
Make a photosensitive lithographic printing plate, but before applying the photosensitive layer
Even if an organic or inorganic subbing layer is provided as required
I do not care. [Cutting] Next, the photopolymerization feeling in the present invention.
The cutting of the photolithographic printing plate will be described in detail. Sheet
Photopolymerizable photosensitive lithographic stamp made in the shape of a coil or coil
The printing plate is cut into a predetermined size. At this time, FIG.
As shown in FIG. 5, the edge of the photopolymerizable photosensitive lithographic printing plate 30
Bent along the part and away from the surface.
Cut to have a curved surface. FIG. 2 is a sectional view showing a cutting portion of the slitter device.
FIG. The slitter device includes a pair of upper and lower cutting blades 10,
20 is arranged on the left and right. These cutting blades 10, 2
0 consists of a round blade on a disk, and the upper cutting blades 10a and 1
0b is on the rotating shaft 11, and the lower cutting blades 20a and 20b are
The rotary shaft 21 is supported on the same axis. And
The upper cutting blades 10a and 10b and the lower cutting blade 20a
And 20b are rotated in opposite directions. Photopolymerization
Photosensitive photosensitive lithographic printing plate 30 includes upper cutting blades 10a and 10b.
And a predetermined width passed between the lower cutting blades 20a and 20b
It is cut by. More specifically, the slitter device shown in FIG.
Between the upper cutting blade 10a and the lower cutting blade 20a of the cutting section
Clearance and gap between the upper cutting blade 10b and the lower cutting blade 20b
The interval is preferably set to 30 to 200 μm and FIG.
An end portion having a shape as shown in FIG. 5 is formed. Figure 3 shows the book
The shape of the upper cutting blade 10a and the lower cutting blade 20a of the invention is shown.
It is. FIG. 4 is an enlarged view of part A in FIG.
The tip shape of the upper cutting blade 10a and the lower cutting blade 20a
Tip shape and the gap between the upper and lower cutting blades
The 1 and 5 show the slitter apparatus of FIG. 2 and the cutting of FIG.
Photopolymerizable photosensitive lithographic printing plate 30 cut with a blade
The shape of the edge part of is shown. The shape of the notch in FIG. 5 is curved in a convex shape.
Preferably, more preferably a convex type having no bent portion
It is curved. If it has a bent part, ink will be applied to the bent part.
It may adhere and cause dirt. Sagging height in Figure 5
The preferred range of (X) is 30-200 μm, more preferred
The range is 40 to 180 μm. Area of the notch in FIG.
A preferable range of (Y) is 200 to 100,000 μm. ² , Yo
A more preferable range is 500 to 70000 μm. ² It is. FIG.
If the sag height (X) is less than 30 μm, it will become dirty on the edges.
Will occur. Also, the sagging height (X) is greater than 200 μm
In the case of a threshold, the burr height (Z, protrusion to the lower surface) in FIG.
Increased, automatic conveyance failure with laser exposure setter
The problem of life arises. The area of the notch (Y) in FIG.
00μm ² If it is smaller, the edge will become dirty.
Further, the area (Y) of the notch in FIG. 5 is 100,000 μm. ² Yo
Is larger, the burr height in FIG.
It is easy for automatic conveyance failure to occur in the exposure setter.
Sagging height (X), notch area (Y), burr height (Z)
Is an ultra-deep profile measuring microscope VK-8500 (Keyence
Can be measured. The diazo photosensitive lithographic printing plate has an edge after development.
When the part (non-image part) is observed with the SEM photograph, aluminum
Occurs during cutting of the anodized film 32 of the film support 31
Only the crack 34 that seems to be observed is observed.
A residual film of 3 is never observed. However, photopolymerization
Of the photopolymerizable photosensitive layer 33 in the photosensitive photosensitive lithographic printing plate
Electron transfer like triazine compound as the initiator
When using a photopolymerization initiator that generates radicals
The residual film of the photosensitive layer 33 that causes printing stains is observed.
The part is removed with oxygen plasma in vacuum
Underneath, a crack 34 of the anodic oxide film 32 is observed.
It was done. In the present invention, triazine compounds are used.
Photopolymerization initiator that generates radicals by electron transfer
Rather than generating radicals by energy transfer
By using a photopolymerization initiator,
To prevent the remaining film of the photosensitive layer 33 from being generated.
it can. The cause is not clear, but the anodic oxide film 32
This is thought to be caused by metal fogging due to this. That is, the bird
When an azine compound is used, the anodic oxide film 32
The metal aluminum or impurities of the support 31 through the crack 34
Electrons from metal (Fe, Cu, etc.) in the photosensitive layer 33
The triazine compound decomposes and
Cals are generated, and the ethylenically unsaturated compound in the photosensitive layer 33
Is polymerized to form the remaining film of the photosensitive layer 33.
-Use of photoinitiator that generates radicals by migration
In this case, generation of radicals due to electron transfer occurs.
Therefore, it is considered that the remaining film of the photosensitive layer 33 is not formed.
The [Exposure / Development] The photopolymerizable photosensitive film of the present invention
The photosensitive layer in a plate printing plate is, for example, helium cadmium
Minium laser, argon ion laser, FD / Y
AG laser, helium neon laser, semiconductor laser
-Conventionally known actinic rays such as (350 nm to 600 nm)
After image exposure with
An image can be formed on the surface. After laser exposure
For the purpose of increasing the degree of polymerization of the photopolymerizable photosensitive layer and increasing the printing durability
The plate may be heated. Further, the photopolymerizable photosensitive flat plate of the present invention.
On the photosensitive layer of the plate printing plate, as described above, oxygen blocking
The protective layer is provided, and the protective layer is first applied with water or warm water.
Then remove the unexposed photosensitive layer with a developer.
It is. Development of the photopolymerizable photosensitive lithographic printing plate of the present invention
As a developer for use in, it is not particularly limited,
Preferably, it is described in JP-B-57-7427
Developer such as sodium silicate, potassium silicate
Lithium, sodium hydroxide, potassium hydroxide, lithium hydroxide
Thium, tribasic sodium phosphate, dibasic sodium phosphate
, Ammonium triphosphate, ammonium phosphate
, Sodium metasilicate, sodium bicarbonate, ammonia
Inorganic alkaline agents such as near water and monoethanol alcohol
Organic alkenyl such as min or diethanolamine
An aqueous solution of the agent is suitable. Of such alkaline solutions
Concentration is 0.1-10% by weight, preferably 0.5-5%
% To be added. In addition, in such an alkaline aqueous solution,
Surfactant, benzyl alcohol, 2-ph as necessary
Like enoxyethanol, 2-butoxyethanol
A small amount of organic solvent can be included. For example, US Patent No.
Described in US Pat. Nos. 3,375,171 and 3,615,480.
Can be mentioned. Furthermore, JP-A-5
0-26601, 58-54341, Shoko 56
-39464, 56-42860 described in each publication
The developer that is used is also excellent. Photopolymerizable photosensitive lithographic printing plate in the present invention
The development with the developer is 0-60 in accordance with a conventional method.
At a temperature of about 15-40 ° C., for example, dew
Immerse the photopolymerized photopolymerizable photosensitive lithographic printing plate in a developer.
For example, rubbing with a brush. Furthermore, using an automatic processor
When developing, the developer becomes fatigued according to the processing amount.
Processing capacity with replenisher or fresh developer
You may restore power. It was developed in this way
A photopolymerizable photosensitive lithographic printing plate is disclosed in JP-A No. 54-8002,
51-115045, 59-58431, etc.
As described in the gazette, wash water, surfactant, etc.
Contains rinse solution, gum arabic, starch derivatives, etc.
It is post-treated with a desensitizing solution. Also, after development processing, printing durability
In order to improve the above, the entire surface may be exposed to UV light.
These are used in the post-treatment of the photopolymerizable photosensitive lithographic printing plate of the present invention.
These processes can be used in various combinations. The present invention will be described more specifically with reference to the following examples.
Of course, the scope of the present invention is of course limited by these.
Is not something [Preparation of photopolymerizable photosensitive lithographic printing plate] Thickness
A 0.30mm material 1S aluminum plate No. 8 Nairro
Use a water suspension of brush and 800 mesh pumiston
The surface was grained and washed thoroughly with water. 1
Immerse in 0% sodium hydroxide at 70 ° C for 60 seconds.
20% HNO after washing with running water _Three Neutralized washing with
Purified and washed with water. This is V _A = 12.7V sine
300 waves in 1% nitric acid aqueous solution using alternating wave current
-Ron / dm ² Electrolytic surface roughening with the amount of electricity at the anode
It was. The surface roughness measured was 0.45 μm (Ra
Display). Continuously 30% H ₂ SO _Four Aqueous solution
After dipping in and desmutting at 55 ° C. for 2 minutes, 33
℃, 20% H ₂ SO _Four Cathode on grained surface in aqueous solution
Current density 5A / dm ² Positive for 50 seconds
When oxidized, the thickness is 2.7 g / m ² Met. On the aluminum plate treated in this way
The undercoat layer was provided by the following procedure. The following undercoat liquid
The composition was mixed and stirred at 30 ° C. I saw a fever after about 5 minutes
After reacting for 60 minutes, transfer the contents to another container.
And liquid application by adding 30,000 parts by mass of methanol.
A liquid was prepared. (Liquid composition for undercoating) The following compound [Chemical Formula 1] 50 parts by mass Methanol 130 parts by mass Water 20 parts by mass Paratoluenesulfonic acid 5 parts by mass Tetraethoxysilane 50 parts by mass 3-Methacryloxypropyltrimethoxysilane 50 parts by mass Part [0052] [Chemical Formula 1] This liquid coating solution is treated with the above-mentioned treated alkane.
0.1 g / m on the minium plate ² Apply so that
Dry at 100 ° C. for 1 minute. On the undercoat layer thus obtained,
The photopolymerizable composition 1 having the composition described above had a dry coating weight of 1.5 g /
m ² And then dried at 100 ° C. for 1 minute,
A photosensitive layer was formed. (Photopolymerizable composition 1) Ethylenically unsaturated compound (A1) 2.0 parts by weight Linear organic polymer (B1) 2.0 parts by weight Sensitizer (C1) 0.15 parts by weight Photopolymerization initiators shown in Table 1 0.2 parts by weight Sensitization aid (E1) 0.2 parts by weight ε-phthalocyanine (F1) dispersion 0.02 parts by weight Fluorinated nonionic surfactant Megafac F176 0.03 Part by weight (Dainippon Ink Chemical Co., Ltd.) Methyl ethyl ketone 15.0 parts by weight Propylene glycol monomethyl ether acetate 15.0 parts by weight Embedded image 6 weights of the following materials are formed on this photosensitive layer.
% Aqueous solution as an oxygen barrier layer, dry coating weight 2.5g
/ M ² And then dried at 120 ° C. for 3 minutes,
A photopolymerizable photosensitive lithographic printing plate was obtained. Polyvinyl alcohol (PVA-105, manufactured by Kuraray Co., Ltd., saponification degree 98 mol%, polymerization degree 500) 2.2 parts by weight polyvinyl pyrrolidone (K30 manufactured by Wako Pure Chemical Industries, Ltd.) 0.12 parts by weight pionine D625 (manufactured by Takemoto Yushi Co., Ltd.) 0.073 parts by weight EMALEX 710 (manufactured by Nippon Emulsion Co., Ltd., surfactant) 0.043 parts by weight The thus obtained 0.3 mm, width 90
A coiled photopolymerizable photosensitive lithographic printing plate with a width of 80 cm
Using the slitter device of FIG. 1 and the cutting blade of FIG.
The clearance (D) between the cutting blade and the lower cutting blade is 100 μm, the upper side
The amount of biting (S) between the cutting blade and the lower cutting blade is 300 μm.
Set and slit continuously at both ends. Then 11
Cut into 0cm and 110x80cm (newspaper 4 page version)
A photosensitive photosensitive lithographic printing plate was obtained. Sagging height of this plate
(X) is 100 μm, notch area (Y) is 10000 μm
m ² The burr height (Z) on the back surface was 10 μm. This photopolymerizable photosensitive lithographic printing plate (110 ×
80cm) equipped with FD-YAG laser (532nm)
Luxel Plate Setter P-9 manufactured by Fuji Photo Film Co., Ltd.
0.1, 0.2, 0.5, 600 CTP NEWS
1, 2, 5 mJ / cm ² , 909dpi, 100lpi
The image was exposed. Immediately after that, Fuji Photo Film Co., Ltd.
Using an automatic processor FLP125NFS, the plate surface temperature is
Post-heated to 120 ° C at the center of the back surface,
The oxygen barrier layer was washed away with water. Thereafter, developer D manufactured by Fuji Photo Film Co., Ltd.
Development was performed at 25 ° C. for 22 seconds using V-2: water = 1: 4.
After that, it was washed with water and finished by Fuji Photo Film Co., Ltd.
Standard treatment with Gum gum FP-3W: water = 1: 1, 50
Dry with warm air at ℃. At that time, the amount of gum applied is dry weight
150mg / m ² Met. The smudges at the edges of the print are printed on the Tokyo machine.
4-color tower type rotary press CT7000 (170,000)
Machine), ink is Dainippon Ink Co., Ltd. newspaper ink, dampening
Water is News King Alky for newspaper made by Toyo Ink Co., Ltd.
pH = 10.2, paper is Oji Paper 44g / m ² Tomakomai
The banquet uses Kinyo MP-75R 2.07mm
Evaluation was performed after 100,000 copies were printed. Setter transportability is P-9600CTP N
Process 150 sheets continuously with an EWS setter and carry even one
If it could not be sent × (NG), all 150 issues
The case where it was able to carry without being evaluated as O (OK). Sensitivity is the highest for plates made at each exposure.
The image has no scratches and the 2% highlight is reproduced.
The minimum amount of light was used. Stability over time is photopolymerizable photosensitive lithographic plate
After forcibly storing the printing plate at 60 ° C for one week, the same
Evaluate the sensitivity and compare with the one that was not forced to age.
It was. ○ that the sensitivity did not change, the sensitivity decreased and the highest 5
mJ / cm ² However, the case where no image was formed was marked as x.
The evaluation results are shown in Table 1. [Table 1] From Table 1, the photopolymerizable photosensitivity according to the present invention is shown.
A lithographic printing plate has a print edge stain, setter transportability,
It is clear that the stability over time is excellent. As described above, according to the present invention, the print end stain resistance, setter
-Photopolymerizable photosensitivity with excellent transportability, sensitivity and stability over time
Plate printing plates can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partially broken perspective view of an end portion of a photopolymerizable photosensitive lithographic printing plate according to the present invention. FIG. 2 is a diagram showing a slitter device. FIG. 3 is a cross-sectional view of a cutting portion of the slitter device. 4 is an enlarged view of a part A in FIG. 3; FIG. 5 is a drawing showing the shape of the edge of the photopolymerizable photosensitive lithographic printing plate according to the present invention. [Description of Symbols] 10 (10a, 10b) Upper cutting blade 11 Rotating shaft 20 (20a, 20b) Lower cutting blade 21 Rotating shaft 30 Photopolymerizable photosensitive lithographic printing plate 31 Aluminum support 32 Anodized film 33 Photopolymerization Photosensitive layer 34 crack

Claims (1)

What is claimed is: 1. A photopolymerizable photosensitive lithographic printing plate comprising a photopolymerizable photosensitive layer provided on an aluminum support having an anodized film. A photopolymerizable photosensitive lithographic plate characterized in that the end is curved from the photosensitive layer side to the lower surface side, and the photopolymerization initiator contained in the photosensitive layer generates radicals by energy transfer Printed version.