JP2003255561A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method which forms an image excellent in printing resistance and excellent also in resolving power even when post- exposure heating is not carried out, significantly diminishes waste liquor due to replenishment with a developing solution, can significantly diminish development scum accumulating in a developing bath and enables long-term stable processing. <P>SOLUTION: In the image forming method, a negative image forming material obtained by disposing on a support an image recording layer comprising (A) a radical generator, (B) a radical-polymerizable compound, (C) an IR absorbent and (D) a binder polymer is imagewise exposed with infrared laser light and developed with an alkali developing solution containing an alkali silicate and a nonionic surfactant having an aromatic ring. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a computer or the like.
Direct scanning by scanning infrared laser from digital signal
So-called negative engraving that allows direct engraving
The present invention relates to an image forming method applicable to an image forming material. [0002] 2. Description of the Related Art In recent years, laser development has been remarkable.
High output and small size, especially with light emitting region from near infrared to infrared
Molds are now readily available. These reports
The user can sign directly with digital data such as a computer.
Making a printing plate (Computer to Plate)
e: hereinafter abbreviated as CTP as appropriate)
And very useful. For example, a wavelength from 760 nm to 120
Solid-state laser and semiconductor laser emitting 0 nm infrared light
Is useful because of its high output compared to other wavelength regions.
The Therefore, it is very sensitive to such lasers.
Image-forming materials, i.e.
In recent years, there has been an increasing demand for image forming materials whose solubility changes greatly.
ing. As such an image forming material, radicals are used.
Image forming materials using addition polymerization reactions have been proposed.
Usually, an alkaline aqueous solution after imagewise laser exposure
To develop an image. In that case, post-exposure heat treatment
And then developing without exposure and exposure without heat treatment
There has been proposed a method in which development is performed immediately thereafter. The former is automatic
Since it is necessary to attach a heating oven to the processor,
There is a drawback that the equipment is enlarged and the cost is increased. While the latter
Is not enough to promote radical polymerization by heating.
Hardening of light part is difficult to proceed, and as a result, printing durability is heating type
There are low disadvantages. But need heating oven
The non-heating method is a great advantage for users
Long-awaited. Gives sufficient printing durability by non-heating method
As a means, you can damage the image area in the development process
It is desirable to reduce this. For example, JP-A-8-108
No. 621 discloses a negative image using a photopolymerizable composition.
An imaging material is disclosed and has a strong pH above 12.5
A caustic aqueous solution is used. Such a high pH
The developer has a large damage to the image area and insufficient printing durability.
There was a problem to become. Therefore, p as low as possible
H value reduces damage to the image area and at the same time non-image area
By using a developer that can be sufficiently developed,
It becomes possible to raise the highest. From the viewpoint of developer,
It is requested to reduce developing waste liquid as much as possible.
It is. Therefore, increase the alkali concentration of the developer replenisher.
By widening the pH difference from the developing solution,
The amount can be reduced, but the replenishment amount is small.
The pH of the developing solution is greatly affected.
Therefore, it becomes difficult to keep the pH constant. Present
Factors that consume alkali in the image solution are mixed into the developer.
In addition to the components in the photosensitive composition, carbon dioxide, other plates
When an aluminum substrate is used as the material,
Can be considered. Therefore, the contribution of either of these
If it is possible to increase the pH of the developer replenisher,
Can also reduce waste liquid. Conventionally used as a buffer
By adding the silicate to be added to the developer,
Since the compound adsorbs to the aluminum surface, alkali
Suppressing aluminum dissolution, one of the causes of consumption
As a result, the amount of developing waste liquid is reduced. Only
When the pH of the developer is low, the silicate compound gels.
There has been a problem of causing development debris.
Therefore, in developing a negative type image forming material,
Reduce the pH value of the developer to reduce damage to the image area.
While reducing the resolution and ensuring sufficient resolution,
It is required to suppress the amount of discharge and development waste.
The [0005] The object of the present invention is to achieve infrared
From negative-working imaging materials recorded with a line laser
In the image forming method, sufficient image can be obtained without the need for heat treatment.
To provide an image forming method that achieves image intensity and resolution.
It is in. More specifically, without post-exposure heat treatment
However, it produces images with excellent printing durability and has excellent resolving power.
Reducing waste liquid due to replenishment and accumulating in the developing bath
Development waste can be significantly reduced, and processing can be performed stably over a long period of time.
Another object of the present invention is to provide an image forming method that can be used. [0006] SUMMARY OF THE INVENTION The inventor has disclosed a negative image.
Focusing on the physical properties of the forming material and developer,
The developer contains alkali silicate and a specific nonionic field
By adding a surfactant to the developer, the pH value is
The non-image area can be sufficiently developed even under relatively low conditions.
Found that silicate-induced gelation does not occur,
The invention has been completed. Accordingly, the present invention provides (A) a radio decal on a support.
(B) Radical polymerizable compound, (C) Infrared ray
An image containing an absorbent and (D) a binder polymer
A negative type image forming material provided with a recording layer is made of an infrared ray
After image exposure with ZA, it has alkali silicate and aromatic ring
Using alkaline developer containing nonionic surfactant
An image forming method characterized by developing. The present invention
According to the image forming method, it is difficult to be influenced by carbon dioxide gas.
Excellent developability even at relatively low pH conditions, image area
Improving printing durability by reducing damage to
It was found that it can be significantly reduced. Also has an aromatic ring
Nonionic surfactant disperses insoluble components in the image recording layer
Since it also acts as an improver,
It can be seen that the development waste accumulated in the image tank can be significantly reduced.
won. [0008] The image forming method of the present invention will be described in detail below.
Explain in detail. First, an application used in the image forming method of the present invention.
The Lucari developer will be described. [Developer] The developer used in the image forming method of the present invention is small.
Nonion having at least alkali silicate and aromatic ring
This is an alkaline aqueous solution containing a surfactant. Its pH
The value is suitably pH 10.0-12.0, preferably
It is 10.0-11.0. With the alkali silicate used
It shows alkalinity when dissolved in water.
For example, sodium silicate, potassium silicate, silicate lithium
Um and ammonium silicate. These alkalis
Silicates can be used alone or in combination of two or more.
Also good. The alkaline aqueous solution is a component of silicate.
Silicon oxide SiO₂And alkali oxide M₂O (M is al
Represents a potassium metal or ammonium group. Mixing ratio with)
And developability can be adjusted easily by adjusting the density.
it can. In the developer of the present invention, SiO₂/ M₂O molar ratio
It is appropriate and preferred to be in the range of 0.75 to 6.0.
It is 1.0 to 5.0. SiO₂/ M₂O molar ratio is
If it is less than 0.75, the alkali strength increases.
Therefore, general-purpose aluminum as a support for lithographic printing plate precursors
This will cause a negative effect such as etching
And if it exceeds 6.0, developability may decrease.
is there. As the concentration of alkali silicate in the developer
Is silicon dioxide (SiO₂) 0.1-3 mass% in terms of conversion
Is suitable, and it is preferably 0.5 to 2% by mass. This
If the density of the toner is less than 0.1% by mass, developability and processing ability
On the other hand, if the content exceeds 3% by mass, precipitation or condensation may occur.
It is easy to produce crystals, and further gels during neutralization during waste liquid.
This may cause trouble in waste liquid treatment. Base used in combination with alkali silicate
Conventionally used as an alkaline agent in developers
It can select suitably from a well-known thing. The alkali
Examples of the agent include sodium hydroxide and potassium hydroxide.
Lithium hydroxide, trisodium phosphate, triphosphate
Lithium, triammonium phosphate, disodium phosphate,
Dipotassium phosphate, diammonium phosphate, sodium carbonate
Um, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate
Lithium, potassium bicarbonate, ammonium bicarbonate,
Sodium oxalate, potassium borate, ammonium borate
Inorganic alkaline agents such as potassium citrate and tricitrate
Examples include potassium and sodium citrate. Further, monomethylamine, dimethylamino
, Trimethylamine, monoethylamine, diethylamine
Min, triethylamine, monoisopropylamine, di
Isopropylamine, triisopropylamine, n-butyl
Tylamine, monoethanolamine, diethanolamine
, Triethanolamine, monoisopropanolamine
, Diisopropanolamine, ethyleneimine, ethyl
Range amine, pyridine, tetramethylammonium
Organic alkali agents such as droxide are also preferred.
it can. These alkaline agents can be used alone or in combination of two or more.
A combination of the above may be used. Above all, sodium hydroxide
And potassium hydroxide are preferred. In addition, trisodium phosphate
, Tripotassium phosphate, sodium carbonate, potassium carbonate
It is also preferable because it has a buffering effect on itself. Al
As a combination of potash, sodium hydroxide and hydroxy acid
Alkali metal hydroxides such as potassium hydroxide and sodium carbonate
Combination with carbonates such as um and potassium carbonate
It is used well. (Nonionic surfactant having an aromatic ring)
Nodes having an aromatic ring to be included in the developer used in the present invention
Nonionic surfactants include those represented by the following formula:
The Formula: X-Y-O- (A) n- (B) m-H (In the formula, X represents an aromatic ring, and Y represents a single bond or a carbon atom.
Represents an alkylene group of 1 to 10, and A and B are different from each other.
A group of₂CH₂O- or -CH₂CH
(CH_Three) Represents any one of O-, and n and m are 0 or 1 to 1.
Represents an integer of 100, where n and m are not 0 at the same time
Yes. ) In the above formula, as the aromatic group of X, phenyl group, naphthyl
Group, anthranyl group and the like. These aromatics
The group may have a substituent. Where A and B are both
When present in a random or block copolymer
Good. More specifically, these compounds include:
There are those represented by the general formulas (IA) and (IB).
The(In the above formula, R₁, R₂Each is a hydrogen atom
Or an organic group having 1 to 100 carbon atoms;
Each represents 1 or 2; Y₁, Y₂Are each a single bond or
Represents an alkylene group having 1 to 10 carbon atoms;
Each represents 0 or an integer from 1 to 100, where r and s are the same.
Sometimes not 0, r 'and s' are 0 or 1 to 10 respectively
Represents an integer of 0, provided that r 'and s' are not 0 at the same time.
Yes. ) p represents 2 and R₁Is an organic group having 1 to 100 carbon atoms
R₁May be the same or different R₁Together
And may form a ring, and q represents 2 and R
₂Is an organic group having 1 to 100 carbon atoms, R₂Is the same
Can be one or different R₂Together to form a ring
You may do it. Specific examples of the organic group having 1 to 100 carbon atoms
Examples may be saturated or unsaturated, linear or branched
Aliphatic hydrocarbon group, aromatic hydrocarbon group such as alkyl
Group, alkenyl group, alkynyl group, aryl group, arral
Other than kill groups, alkoxy groups, aryloxy
Group, N-alkylamino group, N, N-dialkylamino
Group, N-arylamino group, N, N-diarylamino
Group, N-alkyl-N-arylamino group, acyloxy group
Si group, carbamoyloxy group, N-alkylcarbamoy
Ruoxy group, N-arylcarbamoyloxy group, N,
N-dialkylcarbamoyloxy group, N, N-diary
Carbamoyloxy group, N-alkyl-N-ary
Rucarbamoyloxy group, acylamino group, N-alkyl
Ruacylamino group, N-arylacylamino group, acyl
Group, alkoxycarbonylamino group, alkoxycal
Bonyl group, aryloxycarbonyl group, carbamoyl
Group, N-alkylcarbamoyl group, N, N-dialkyl
Carbamoyl group, N-arylcarbamoyl group, N, N
-Diarylcarbamoyl group, N-alkyl-N-ali
Carbamoyl group, polyoxyalkylene chain, polio
The above organic groups, etc., to which the xyalkylene chain is bonded
The The alkyl group may be linear or branched. Preferred R₁, R₂As a hydrogen atom or
C1-C10 linear or branched alkyl group, charcoal
Alkoxy group having 1 to 10 atoms, alkoxycarbon
Group, N-alkylamino group, N, N-dialkylamino group
Group, N-alkylcarbamoyl group, acyloxy group or
Is an acylamino group, poly having about 5 to 20 repeating units
Oxyalkylene chain, aryl having 6 to 20 carbon atoms
Group, polyoxyalkylene having 5 to 20 repeating units
An aryl group to which a chain is bonded. Compounds of general formula (IA) and (IB)
The number of repeating units of the polyoxyethylene chain is favorable.
Preferably it is 3-50, More preferably, it is 5-30. Po
The number of repeating units of the reoxypropylene chain is preferably 0
-10, more preferably 0-5. Polyoxyethylene
The len and polyoxypropylene parts are random or blocked.
Copolymers of mulberry may be used. As a compound represented by the general formula (IA)
Polyoxyethylene phenyl ether, polyoxy
Ethylene methyl phenyl ether, polyoxyethylene
Octylphenyl ether, polyoxyethylene nonyl
And phenyl ether. In general formula (IB)
As the compound represented, polyoxyethylene naphthyl
Ether, polyoxyethylene methyl naphthylate
Polyoxyethylene octyl naphthyl ether,
And reoxyethylene nonyl naphthyl ether.
The Nonionic surfactants with aromatic rings are in the developer
Can be used alone or in combination of two or more
May be used. Nonionic interface in developer
The content of the activator is suitably 1 to 20% by mass in the developer.
More preferably, it is 2-10 mass%. Add here
If the amount is too small, the developability deteriorates and the photosensitive layer components dissolve.
If the amount is too large, the printing durability of the printing plate is reduced.
Let Shown below in general formula (IA) or (IB)
Examples of nonionic surfactants are shown. [0020] [Chemical 1][0021] [Chemical 2] [0022] [Chemical Formula 3]The developer may contain a chelating agent.
Yes. Examples of chelating agents include Na.₂P₂O₇, Na_FiveP
_ThreeO_Three, Na_ThreeP_ThreeO₉, Na₂O_FourP (NaO_ThreeP) PO_ThreeNa₂,
Polyphosphones such as calgon (sodium polymetaphosphate)
Acid salts such as ethylenediaminetetraacetic acid, its potash
Salt, sodium salt thereof; diethylenetriaminepenta
Acetic acid, its potassium salt, sodium salt;
Tolamine hexaacetic acid, its potassium salt, its sodium
Salt; hydroxyethylethylenediaminetriacetic acid, its
Potassium salt, sodium salt thereof; nitrilotriacetic acid, salt
Potassium salt thereof, its sodium salt; 1,2-diaminosilane
Chlohexanetetraacetic acid, its potassium salt, its sodium
Um salt; 1,3-diamino-2-propanol tetraacetate
Acids such as acids, potassium salts, sodium salts, etc.
2-phosphonobutanetrical in addition to minopolycarboxylic acids
Bonic acid-1,2,4, its potassium salt, its sodium
Salt; 2 monophosphonobutanone tricarboxylic acid-2,3
4, its potassium salt, its sodium salt; 1-phosphono
Ethanetricarboxylic acid-1,2,2, its potassium salt,
Its sodium salt; 1-hydroxyethane-1,1-di
Phosphonic acid, its potassium salt, its sodium salt;
Notori (methylenephosphonic acid), its potassium salt, its
List organic phosphonic acids such as sodium salts
You can. The optimal amount of such chelating agent is used
It varies depending on the hardness of hard water and the amount used.
Generally, 0.01 to 5% by mass in the developer at the time of use.
More preferably, it is contained in the range of 0.01 to 0.5% by mass.
The Also used in the image forming method of the present invention.
The developer is represented by the above general formulas (IA) and (IB).
In addition to the nonionic surfactant used,
Other surfactants may be added. Other surfactants
For example, polyoxyethylene lauryl ether
, Polyoxyethylene cetyl ether, polyoxye
Polyoxyethylene alcohols such as ethylene stearyl ether
Kill ethers, polyoxyethylene stearate, etc.
Polyoxyethylene alkyl esters, sorbitan
Nolaurate, sorbitan monostearate, sorbita
Distearate, sorbitan monooleate, sorbi
Such as tansesquioleate, sorbitan trioleate, etc.
Sorbitan alkyl esters, glycerol monostea
Monoglycerides such as allate and glycerol monooleate
Nonionic surfactants such as doalkylesters: Dodeci
Alkylbenzene such as sodium rubenzenesulfonate
Sulfonates, sodium butylnaphthalenesulfonate
, Sodium pentylnaphthalene sulfonate, hex
Lunaphthalene sodium sulfonate, octyl naphthalate
Alkylnaphthalene sulfones such as sodium sulfonate
And alkyl sulfates such as sodium lauryl sulfate
, Alkyl sulfonic acids such as sodium dodecyl sulfonate
Salts, sulfos such as sodium dilauryl sulfosuccinate
Anionic surfactants such as succinic acid ester salts: Lauri
Alkyl betaines such as lubetaine and stearyl betaine
Amphoteric surfactants such as amino acids and amino acids can be used
However, alkyl naphthalene sulfonate is particularly preferable.
Anionic surfactants. These surfactants are
It can be used alone or in combination. Ma
The content of these surfactants in the developer is effective.
0.1 to 20% by mass in terms of components is preferable. Developer used in the image forming method of the present invention
In addition to the above ingredients, the following ingredients
Can be used in combination. For example, benzoic acid, phthalic acid,
p-ethylbenzoic acid, pn-propylbenzoic acid, p-
Isopropylbenzoic acid, pn-butylbenzoic acid, p-
t-butylbenzoic acid, pt-butylbenzoic acid, p-2
-Hydroxyethylbenzoic acid, decanoic acid, salicylic acid,
Organic carboxylic acids such as 3-hydroxy-2-naphthoic acid;
Isopropyl alcohol, benzyl alcohol, ethyl
Cellosolve, butyl cellosolve, phenyl cellosolve,
Organic such as propylene glycol and diacetone alcohol
Solvent; other chelating agents, reducing agents, dyes, pigments, hard water
Examples include softeners and preservatives. The above developer is an exposed negative type image.
Can be used as developer and developer replenisher
It is preferably applied to an automatic processor. Automatic processor
When developing with, the developer becomes fatigued according to the processing amount.
Processing capacity with replenisher or fresh developer
You may restore power. The image forming method of the present invention is provided on a support.
(A) radical generator, (B) radical polymerizable compound,
(C) Infrared absorber and (D) binder polymer
A negative type image forming material provided with an image recording layer containing
Applicable. This image forming material has an image recording layer
(A) radical generator, (B) radical polymerization
Compound, (C) infrared absorber, and (D) binder poly
A layer containing a mer. Such an image forming material
The material is imagewise exposed by an infrared laser,
(C) Infrared absorber is photothermally converted and generated heat
(A) The radical generator decomposes to generate radicals.
(B) a radical polymerizable compound by the radical of
(D) The image recording layer containing the binder polymer is cured.
To form an image portion. After that, the alkali development mentioned above
By developing with liquid, uncured unexposed recording layer
It is removed to form a non-image part. Each component of the image recording layer will be explained in turn.
Light up. [(A) Radical generator] The polymer used in the present invention
Zical generator is used in combination with (C) infrared absorber.
Generate radicals when irradiated with an infrared laser
Point out the compound. Radical generators include onium salts and
S-triazine having a rear halomethyl group, a peroxide,
Examples include azo polymerization initiators, azide compounds and borate salts
It is done. Onium salts are preferred because of their high sensitivity. Oniu
Salts include iodonium salts, diazonium salts,
Examples include onium salts. In the present invention, these options are
The nium salt is not an acid generator, but an initiator for radical polymerization.
And function. Oni-o suitable for use in the present invention
The salt is an onium represented by the following general formulas (1) to (3)
Salt. [0029] In the formula (1), Ar¹¹And Ar¹²Respectively
Independently, the number of carbon atoms which may have a substituent is 20 or less.
The lower aryl group is shown. This aryl group has a substituent
Preferred substituents in the case of halogen atom, nitro
B group, alkyl group having 12 or less carbon atoms, carbon atom number
12 or less alkoxy groups or 12 or less carbon atoms
The following aryloxy groups are mentioned. Z^11-Is halogen
Ion, perchlorate ion, tetrafluoroborate ion
, Carboxylate ion, hexafluorophosphate
Represents a counter ion such as an ion and a sulfonate ion,
Preferably, perchlorate ion, carboxylate ion, and
And aryl sulfonate ions. In the formula (2), Ar^{twenty one}Has a substituent
And an aryl group having 20 or less carbon atoms. Good
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group having 12 or less atoms, 12 or less carbon atoms
An alkoxy group having 12 or less carbon atoms
Si group, alkylamino group having 12 or less carbon atoms, carbon
Dialkylamino group having 12 or less atoms, 1 carbon atom
2 or less arylamino groups or 12 carbon atoms
The following diarylamino groups are mentioned. Z^{twenty one -}Is Z^11-
Represents a counter ion having the same meaning as. In the formula (3), R³¹, R³²And R³³It
Each may be the same or different and have a substituent.
And a good hydrocarbon group having 20 or less carbon atoms. Like
New substituents include halogen atoms, nitro groups, and carbon atoms.
Alkyl group with 12 or fewer children, 12 or fewer carbon atoms
An alkoxy group or an aryl having 12 or less carbon atoms
An oxy group is mentioned. Z^31-Is Z^11-Counter ion synonymous with
Represents. An onium salt ingredient which can be suitably used.
Examples are shown below, but the present invention is not limited to these.
Is not to be done. [0034] [Formula 4][0035] [Chemical formula 5][0036] [Chemical 6][0037] [Chemical 7][0038] [Chemical 8]Radical generator used in the present invention
Preferably has a maximum absorption wavelength of 400 nm or less.
Furthermore, it is preferable that it is 360 nm or less. this
By making the absorption wavelength in the ultraviolet region,
The material can be handled under white light. These radical generators are used for coating the image recording layer.
0.1 to 50% by mass, preferably based on the total solid content of the cloth liquid
0.5-30% by weight, particularly preferably 1-20% by weight
It can be added to the image recording layer coating solution in a proportion. Attendant
When the added amount is less than 0.1% by mass, the sensitivity is lowered, and
If it exceeds 50% by mass, the non-image area will become dirty during printing.
The These radical generators may be used alone.
Or two or more of them may be used in combination. Also these radio
The calorifier may be added to the same layer as other components,
Another layer may be provided and added thereto. [(B) Radical polymerizable compound] In the present invention,
The radically polymerizable compound used is at least one
Radical polymerizable compounds with ethylenically unsaturated double bonds
At least 1 terminal ethylenically unsaturated bond
It is selected from compounds having, preferably two or more. This
Are widely known in the industry.
In the present invention, these are used without any particular limitation.
Can be. These include, for example, monomers,
Limers, ie dimers, trimers and oligomers,
Or their mixtures and their copolymers
It has a morphological form. Examples of monomers and their copolymers
Unsaturated carboxylic acids (e.g. acrylic acid,
Rilic acid, itaconic acid, crotonic acid, isocrotonic acid,
Rainic acid, etc.) and their esters and amides
Preferably, unsaturated carboxylic acid and aliphatic polyvalent alcohol
Esters with alcohol compounds, unsaturated carboxylic acids and aliphatic poly
Amides with divalent amine compounds are used. Also Hide
Nucleophilic substitution such as roxyl, amino and mercapto groups
Unsaturated carboxylic acid ester having a group, amides and simpler
With functional or polyfunctional isocyanates and epoxies
Removal from reaction product, monofunctional or polyfunctional carboxylic acid
A water condensation reaction product or the like is also preferably used. Isocyana
Unsaturation with electrophilic substituents such as carbonate groups and epoxy groups
Carboxylic esters or amides and monofunctional or
With multifunctional alcohols, amines and thiols
Addition reaction products, halogen groups, tosyloxy groups, etc.
An unsaturated carboxylic acid ester having a leaving substituent or
Amides, monofunctional or polyfunctional alcohols, alcohols
Also suitable are substitution reaction products with amines and thiols.
As another example, instead of the above unsaturated carboxylic acid
And compounds substituted with unsaturated phosphonic acid, styrene, etc.
It is also possible to use groups. Aliphatic polyhydric alcohol compound and unsaturated cal
Specific examples of radically polymerizable compounds that are esters with boronic acid
Examples include acrylic acid esters, ethylene glycol
Coal diacrylate, triethylene glycol diac
Relate, 1,3-butanediol diacrylate, te
Tramethylene glycol diacrylate, propylene glycol
Recall diacrylate, neopentyl glycol dia
Chlorate, trimethylolpropane triacrease
Trimethylolpropane tri (acryloyloxy)
Propyl) ether, trimethylol ethane triacryl
Rate, hexanediol diacrylate, 1,4-silane
Chlohexanediol diacrylate, tetraethylene
Glycol diacrylate, pentaerythritol dia
Acrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, dipentae
Lithritol diacrylate, dipentaerythritol
Hexaacrylate, sorbitol triacrylate,
Sorbitol tetraacrylate, sorbitol penta
Acrylate, sorbitol hexaacrylate, tri
(Acryloyloxyethyl) isocyanurate, poly
There are ester acrylate oligomers and the like. Methacrylic acid esters include tetrameth
Tylene glycol dimethacrylate, triethylene glycol
Cold dimethacrylate, neopentyl glycol dimethyl
Tacrylate, trimethylolpropane trimethacrylate
, Trimethylolethane trimethacrylate, ethyl
Lenglycol dimethacrylate, 1,3-butanedio
Dimethacrylate, hexanediol dimethacrylate
, Pentaerythritol dimethacrylate, penta
Erythritol trimethacrylate, pentaerythrito
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, sorbitol trimethacrylate, sorbite
Tetramethyl methacrylate, bis [p- (3-methacrylic
(Luoxy-2-hydroxypropoxy) phenyl] dimethyl
Tylmethane, bis- [p- (methacryloxyethoxy
B) Phenyl] dimethylmethane. 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
Steal includes ethylene glycol dimaleate, tri
Ethylene glycol dimaleate, pentaerythritol
Examples include dimalate and sorbitol tetramaleate. Examples of other esters include, for example, special
Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-47334
And fat described in JP-A-57-196231
Aromatic alcohol esters, JP-A-59-5240,
Japanese Patent Laid-Open Nos. 59-5241 and 2-226149
Having an aromatic skeleton described in Japanese Patent Publication No. 1-16
Those containing amino groups described in Japanese Patent No. 5613 are also preferable.
Appropriately used. Also, an aliphatic polyvalent amine compound and an unsaturated catalyst.
Specific examples of amide monomers with rubonic acid include
Renbis-acrylamide, methylenebis-methacrylic
Amide, 1,6-hexamethylenebis-acrylamid
1,6-hexamethylenebis-methacrylamide,
Diethylenetriaminetrisacrylamide, Xylile
Bisacrylamide, Xylylenebismethacrylami
There are Examples of other preferred amide monomers
The cyclohexylene described in JP-B-54-21726
Can be mentioned. Also, addition reaction of isocyanate and hydroxyl group
Also suitable for urethane-based addition-polymerizable compounds produced using
As a specific example, for example, Japanese Patent Publication No. 4
2 per molecule described in Japanese Patent No. 8-41708
Polyisocyanate having isocyanate groups above
The compound contains a hydroxyl group represented by the following general formula (4)
Polymerization of 2 or more in one molecule with vinyl monomer added
Vinyl urethane compounds containing a functional vinyl group
It is. General formula (4) CH₂= C (R⁴¹) COOCH₂CH (R⁴²) OH (However, R⁴¹And R⁴²Is H or CH_ThreeShow
The ) Japanese Patent Publication No. 51-37193, Japanese Patent
Described in No. 2-332293 and Japanese Patent Publication No. 2-16765
Urethane acrylates such as
No. 49860, Shoko Sho 56-17654, Shoko Sho 62
-Equipment described in Japanese Patent Publication No. 62-39418
Urethane compounds having an oxide skeleton are also suitable.
is there. Further, JP-A 63-277653, JP-A 63-277653
Sho 63-260909, JP-A-1-105238
It has an amino or sulfide structure in the molecule.
Radical polymerizable compounds may be used. Other examples include JP-A-48-641.
83, JP-B 49-43191, JP-B 52-30
490, polyester as described in each publication
Acrylate, epoxy resin and (meth) acrylic acid
Multifunctional acrylics such as reacted epoxy acrylates
Rate and methacrylate can be raised. Also,
No.46-43946, No.1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinylphosphonic acid compounds described in JP-A-2-25493
You can also list things. In some cases, JP
A perfluoroalkyl group described in Sho 61-222048
The containing structure is preferably used. Furthermore, Japan Adhesion Association
Magazine vol.20, No.7, 300-308 pages (1984)
Introduced as a photo-curable monomer and oligomer
What is being used can also be used. Regarding these radically polymerizable compounds,
What kind of structure is used, used alone or in combination
The details of how to use, such as how much is added,
Can be set arbitrarily according to the performance design of typical recording materials.
The For example, it is selected from the following viewpoints. Sensitivity point
In this case, a structure with a high content of unsaturated groups per molecule is preferred.
In many cases, 2 or more functionalities are preferable. Also images
In order to increase the strength of the part, that is, the cured film, trifunctional or higher
The above ones are good, and different functionalities and different polymerizability
A compound having a group (for example, an acrylic ester compound)
, Methacrylate compounds, styrene compounds
Etc.) are used in combination to achieve both photosensitivity and strength
It is also effective to adjust this. Large molecular weight compounds
In addition, a highly hydrophobic compound is excellent in sensitivity and film strength,
Preferred in terms of development speed and precipitation in developer
There may be no. In addition, other components in the image recording layer (for example,
Compatible with binder polymers, initiators, colorants, etc.)
Select and use radically polymerized compounds for their properties and dispersibility
Usage is an important factor, for example the use of low purity compounds
Or by using two or more compounds in combination to improve compatibility
There is a possibility. In addition, support, overcoat layer, etc.
Selecting a specific structure for the purpose of improving adhesion
There is also a possibility. Arrangement of radical polymerizable compounds in the image recording layer
As for the ratio, a larger number is more advantageous in terms of sensitivity.
If this is the case, undesirable phase separation may occur or image recording may occur.
Problems in the manufacturing process due to adhesiveness of the recording layer (for example, recording layer
Inferior manufacturing due to component transfer and adhesion) and from developer
This may cause problems such as precipitation. From these perspectives
Therefore, the preferable blending ratio of the radical polymerizable compound is many
The case, preferably 5 to 80% by weight, preferably
Is 20-75 mass%. These are used alone
Or you may use together 2 or more types. In addition, radical polymerization
The use of a reactive compound is based on the magnitude of inhibition of polymerization by oxygen.
From the viewpoints of image quality, fog, refractive index change, surface tackiness, etc.
Appropriate structure, blending and addition amount can be selected arbitrarily.
Depending on the case, the layer composition and application method such as undercoating and overcoating
Can also be implemented. [(C) Infrared Absorber] Image Formation of the Present Invention
In this method, the image is recorded with an infrared laser.
It is essential to include an infrared absorber in the recording layer. Infrared
The absorber has a function to convert the absorbed infrared rays into heat.
Yes. The radical generator is decomposed by the heat generated at this time.
And generate radicals. Red used in the present invention
External absorber absorbs from 760nm to 1200nm wavelength
A dye or pigment having a maximum. Examples of the dye include commercially available dyes and “dye”.
"Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1968)
Known materials described in the literature can be used. concrete
For example, paragraph number of JP-A-10-39509
Mention those listed in [0050] to [0051]
Azo dyes, metal complex azo dyes, pyrazolone azo
Dye, naphthoquinone dye, anthraquinone dye, phthalo
Cyanine dye, carbonium dye, quinone imine dye,
Methine dye, cyanine dye, squarylium dye, pyri
Examples thereof include dyes such as a lithium salt and a metal thiolate complex. As a preferred dye, for example, JP-A-5
No. 8-125246, JP 59-84356, JP
Sho 59-202829, JP-A 60-78787, etc.
Cyanine dyes described in JP-A-58-1736
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in Japanese Patent No. 94595, JP-A-5
8-112793, JP-A-58-224793, Special
No. 59-48187, JP-A-59-73996,
JP-A-60-52940, JP-A-60-63744
Naphthoquinone dyes described in JP-A-58-1
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent 434,875
Can. Also, US Pat. No. 5,156,938
The near-infrared absorption sensitizer described above is also preferably used.
Substituted aryl radicals as described in U.S. Pat. No. 3,881,924
Nzo (thio) pyrylium salt, JP-A 57-142645
No. (US Pat. No. 4,327,169)
Nthiapyrylium salt, JP 58-181051 A
58-220143, 59-41363, 59
-84248, 59-84249, 59-14
6063 and 59-146061
Pyrylium compounds, described in JP-A-59-216146
Cyanine dyes described in US Pat. No. 4,283,475
Pentamethine thiopyrylium salt, etc.
No. 514, No. 5-19702
Umum compounds are also preferably used. Another preferred example of the dye is rice.
In Japanese Patent No. 4,756,993, formula (I),
Name near-infrared absorbing dyes listed as (II)
You can. Of these dyes, particularly preferred
Cyanine dye, squarylium dye, pyrylium
Examples thereof include salts and nickel thiolate complexes. In addition,
Anine dyes are preferred, and are particularly represented by the following general formula (5)
Most preferred are cyanine dyes. [0059] [Chemical 9]In general formula (5), X¹Is a halogen atom,
X²-L¹Or NL²L^ThreeIndicates. Where X²Is oxygen field
Child or sulfur atom, L¹Has 1 to 1 carbon atoms
2 represents a hydrocarbon group, L²And L^ThreeAre charcoal independently
A hydrocarbon group having 1 to 12 atoms is shown. R¹And R
²Are each independently a hydrocarbon having 1 to 12 carbon atoms
Indicates a group. From the storage stability of the recording layer coating solution, R¹and
R²Is a hydrocarbon group having 2 or more carbon atoms
Preferably, furthermore, R¹And R²Are bonded to each other and are 5-membered rings
It is particularly preferable that a 6-membered ring is formed. Ar
¹, Ar²May be the same or different,
An aromatic hydrocarbon group which may have a substituent is shown.
Y¹, Y²May be the same or different,
Dialkyl methylene having 12 or less carbon atoms or yellow atoms
Indicate group. R ^Three, R^FourAre the same but different
20 carbon atoms which may have a substituent
The following hydrocarbon groups are shown. Preferred substituents include charcoal
An alkoxy group having 12 or less atoms, a carboxyl group,
A sulfo group is mentioned. R^Five, R⁶, R⁷And R⁸The
Each may be the same or different, hydrogen atoms or charcoal
A hydrocarbon group having 12 or less elemental atoms is shown. Raw material availability
Therefore, a hydrogen atom is preferable. Z^1-Is
Indicates a nonion. However, R¹~ R⁸A sulfo group
Z is replaced by Z^1-Is not necessary. Preferred Z
^1-From the storage stability of the recording layer coating solution.
, Perchlorate ion, tetrafluoroborate ion,
Hexafluorophosphate ion and sulfone
Acid ions, particularly preferably perchlorate ions,
Lifluoromethylsulfonate ion and aryls
It is a sulfonic acid ion. In general formula (5) which can be preferably used
Specific examples of the cyanine dyes shown are listed below.
Ming is not limited to these. [0062] Embedded image[0063] Embedded image[0064] Embedded image[0065] Embedded image As the pigment used in the present invention,
Commercial pigment and color index (CI) handbook,
"Latest pigment handbook" (edited by the Japan Pigment Technology Association, 1977)
Published), "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Published), "Printing Ink Technology" CMC Publishing, published in 1984)
Can be used. The types of pigment include black pigment, yellow face
, Orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Examples include polymer-bound dyes. Details of these pigments
Is the paragraph number [005] of JP-A-10-39509.
2] to [0054], which are described in detail.
The present invention can also be applied. Of these pigments
Preferred is carbon black. Dye or face as described above in the image recording layer
The content of the material is relative to the total solid mass of the image recording layer.
0.01-50 mass% is preferable, 0.1-10 quality
% Is more preferred, and in the case of dyes, 0.5 to
10% by mass is most preferable, and in the case of a pigment, 1.0 to
10% by mass is most preferred. The content is 0.01 quality
If the amount is less than%, the sensitivity may be low, and the quality is 50
If it exceeds the amount%, it will be a non-image when used as a lithographic printing plate precursor
Part may become dirty. [(D) Binder polymer] Image recording layer
Adding a binder polymer to the film improves film properties
From the viewpoint of As the binder, linear organic poly
It is preferable to use a mer. Such “linear organic
Any “remmer” may be used. Like
Or water development or weak alkaline water development
It is soluble or swellable with water or weak alkaline water
A linear organic polymer is selected. Linear organic polymers
Not only as a film-forming agent for forming image recording layers
As water, weak alkaline water or organic solvent developer
It is selected and used according to the application. For example, water-soluble organic polymer
Using a remmer enables water development. Like this linear
Organic polymers include carboxylic acid groups in the side chain.
Dical polymers such as JP-A-59-44615, JP
Sho 54-34327, JP-B 58-12777, JP
No. 54-25957, JP 54-92723,
JP 59-53836, JP 59-71048
That is, methacrylic acid copolymerization
, Acrylic acid copolymer, itaconic acid copolymer, kuroto
Acid copolymer, maleic acid copolymer, partially esterified polymer
For example, there may be a lane acid copolymer. Similarly, the side chain
There are acidic cellulose derivatives having acid groups. Besides this, water
A cyclic acid anhydride is added to a polymer having an acid group.
Is useful. Among these, in particular benzyl or ant
(Meth) acrylic having a carboxyl group and a carboxyl group in the side chain
Resin has an excellent balance of film strength, sensitivity, and developability.
It is preferable. In addition, Japanese Patent Publication No. 7-120040, Japanese Patent Publication
No. 7-120041, No. 7-120042, No.
Hei 8-12424, JP-A 63-287944, Special
Japanese Utility Model Laid-Open No. 63-287947, Japanese Patent Application Laid-Open No. 1-271741
Urethane binder binders containing acid groups described in
Rimmer is very strong, so printing durability and low exposure
It is advantageous in terms of aptitude. In addition to these, a water-soluble linear organic polymer and
Polyvinyl pyrrolidone or polyethylene oxide
Etc. are useful. In order to increase the strength of the cured film,
Lucol soluble nylon and 2,2-bis- (4-hydro
Xylphenyl) -propane and epichlorohydrin poly
Ethers and the like are also useful. Weight average content of the polymer used in the present invention
The amount of the child is preferably 5000 or more, and
Preferably it is in the range of 10,000 to 300,000, and the number average molecular weight is
About 1000 or more is preferable, and more preferable
Or in the range of 2000-250,000. Polydispersity (weight level
(Average molecular weight / number average molecular weight) is preferably 1 or more, and
Preferably it is the range of 1.1-10. These polymers are random polymers,
Any of block polymer, graft polymer, etc.
Is preferably a random polymer. The binder polymer used in the present invention is
They may be used alone or in combination. These polymers
Is 20 to 95 mass based on the total solid content of the image recording layer coating solution.
%, Preferably 30 to 90% by mass in the image recording layer
To be added. If the amount added is less than 20% by weight, the image
When formed, the strength of the image area is insufficient. The addition amount is 9
When it exceeds 5% by mass, no image is formed. Also Raji
Compounds with cal-polymerizable ethylenically unsaturated double bonds
Product and linear organic polymer have a mass ratio of 1/9 to 7/3.
It is preferable to use a range. [Other components] The image recording layer further comprises
Various compounds other than these may be added as necessary.
Yes. For example, dyes that have a large absorption in the visible light range
Can be used as a colorant. Specifically, oy
Le Yellow # 101, Oil Yellow # 103, Oil
Pink # 312, Oil Green BG, Oil Blue B
OS, Oil Blue # 603, Oil Black BY, Oh
Il Black BS, Oil Black T-505
Reent Chemical Co., Ltd.), Victoria Pure Bull
-Crystal violet (CI42555), Mechi
Le violet (CI42535), ethyl violet
, Rhodamine B (CI145170B), Malachite
Green (CI42000), methylene blue (CI5
2015) and the like, and described in JP-A-62-293247
Can be mentioned. Also, phthalos
Pigments such as anine pigments, azo pigments, and titanium oxide are also preferred.
It can be used appropriately. These colorants are used for image formation.
Later, it is easy to distinguish between the image area and the non-image area.
Is preferred. The amount added is the total amount of the image recording layer coating solution.
The ratio is 0.01 to 10% by mass with respect to the solid content. Further, during the preparation or storage of the coating solution
Have radically polymerizable ethylenically unsaturated double bonds
A small amount of heat to prevent unwanted thermal polymerization of the compound
It is desirable to add a combination inhibitor. Appropriate thermal polymerization prevention
As the agent, hydroquinone, p-methoxyphenol,
Di-t-butyl-p-cresol, pyrogallol, t-
Butylcatechol, benzoquinone, 4,4'-thiobis
(3-methyl-6-tert-butylphenol), 2,2 '
-Methylenebis (4-methyl-6-tert-butylphenol)
), N-nitroso-N-phenylhydroxylamine
An aluminum salt etc. are mentioned. Addition amount of thermal polymerization inhibitor
Is about 0.01% by weight to about 5% by weight of the total composition
% By weight is preferred. If necessary, friction of the image recording layer
Behenic acid or behenic acid to lower the coefficient and prevent scratches
Higher fatty acid derivatives such as amides and 1-docosanol
In the process of drying after application
It may be unevenly distributed on the surface of the image recording layer. Higher fatty acid induction
The amount of body added is about 0.1% to about 10% by weight of the total composition
% Is preferred. In the image recording layer coating solution, the development conditions
In order to broaden the stability of the treatment against
1740 and JP-A-3-208514
Nonionic surfactants, such as those disclosed in JP-A-59-12104
4, as described in JP-A-4-13149
Amphoteric surfactants can be added. Specific examples of nonionic surfactants include so
Rubitan tristearate, sorbitan monopalmitate
, Sorbitan trioleate, monoglyceride stearate
Lido, polyoxyethylene nonylphenyl ether, etc.
Can be mentioned. Specific examples of amphoteric surfactants include
Rudi (aminoethyl) glycine, alkylpolyamino ester
Tilglycine hydrochloride, 2-alkyl-N-carboxyl
Chill-N-hydroxyethylimidazolinium betai
N-tetradecyl-N, N-betaine type (for example,
Product name Amorgen K, manufactured by Daiichi Kogyo Co., Ltd.)
The Images of the above nonionic surfactants and amphoteric surfactants
The proportion of the recording layer coating solution is 0.05 to 15% by mass.
Is more preferable, and 0.1 to 5% by mass is more preferable. Further, in the image recording layer coating solution, it is necessary.
If necessary, add a plasticizer to give the coating film flexibility.
It is. For example, polyethylene glycol, tricitrate
Butyl, diethyl phthalate, dibutyl phthalate, phthalate
Dihexyl acid, dioctyl phthalate, tricresic acid phosphate
, Tributyl phosphate, trioctyl phosphate, olein
Acid tetrahydrofurfuryl and the like are used. For producing the image forming material used in the present invention.
Usually, the above-mentioned components necessary for the image recording layer coating solution are used as a solvent.
What is necessary is just to melt | dissolve in and apply | coat on a suitable support body. here
Solvents used include ethylene dichloride, cyclohexane
Hexanone, methyl ethyl ketone, methyl isobutyl ketone
T, methanol, ethanol, propanol, ethyl
Glycol monomethyl ether, 1-methoxy-2-
Propanol, 1-methoxy-3-propanol, 2-
Methoxyethyl acetate, 1-methoxy-2-propi
Acetate, dimethoxyethane, methyl lactate, lactate ester
Til, N, N-dimethylacetamide, N, N-dimethyl
Ruformamide, tetramethylurea, N-methylpyro
Lidon, dimethyl sulfoxide, sulfolane, γ-buty
Examples include lolactone, toluene, water, etc.
However, it is not limited to this. These solvents can be used alone or
Used as a mixture. Ingredients (including additives) in solvent
The concentration of the total solids) is preferably 1 to 50% by mass
The Also, the image on the support obtained after coating and drying.
The image recording layer coating amount (solid content) varies depending on the application,
Generally speaking, the lithographic printing plate precursor is 0.5 to 5.0.
g / m²Is preferred. There are various ways to apply
For example, bar coater coating
Cloth, spin coating, spray coating, curtain coating, dip
Application, air knife application, blade application, roll application, etc.
Can be mentioned. As the coating amount decreases,
Although the apparent sensitivity is increased, the image recording function can be achieved.
The film properties of the image recording layer are degraded. (Oxygen barrier protective layer) Negative image forming material
On the image recording layer, a water-soluble vinyl polymer is the main component.
An oxygen barrier protective layer may be provided. Oxygen barrier protective layer
Water-soluble vinyl polymers contained in
Lucol, and its partial esters, ethers, and
Make acetals or the water solubility they need
Containing substantial amounts of unsubstituted vinyl alcohol units such as
And its copolymers. With polyvinyl alcohol
Is 71 to 100% hydrolyzed and the degree of polymerization is 300.
The thing of the range of -2400 is mentioned. Specifically, stock
PVA-105, PVA-110, PV manufactured by Kuraray
A-117, PVA-117H, PVA-120, PV
A-124, PVA-124H, PVA-CS, PVA
-CST, PVA-HC, PVA-203, PVA-2
04, PVA-205, PVA-210, PVA-21
7, PVA-220, PVA-224, PVA-217
EE, PVA-220, PVA-224, PVA-21
7EE, PVA-217E, PVA-220E, PVA
-224E, PVA-405, PVA-420, PVA
-613, L-8, and the like. As the above copolymer
88-100% hydrolyzed polyvinyl acetate
Toto chloroacetate or propionate, polyvinyl chloride
Luformal and polyvinyl acetal and their
The copolymer of these is mentioned. Other useful polymers
Polyvinylpyrrolidone, gelatin and arabic
These can be used alone or in combination.
Also good. Used when applying this oxygen barrier protective layer.
The solvent is preferably pure water, but methanol, ethanol
Alcohol, acetone, methyl ethyl keto
Ketones such as water may be mixed with pure water. And application
The concentration of the solid content in the solution is suitably 1 to 20% by weight.
This oxygen barrier protective layer further improves the coatability.
Surfactant, water-soluble to improve film properties
You may add well-known additives, such as a plasticizer. Water-soluble plasticity
Examples of the agent include propionamide, cyclohexa
Diol, glycerin, sorbitol and the like. Ma
Add water-soluble (meth) acrylic polymer, etc.
May be. The coating amount is about 0.1 g / weight in dry weight.
m²~ About 15g / m²The range of is appropriate. More preferable
Is 1.0 g / m²~ About 5.0g / m²It is. [Support] As an image forming material used in the present invention,
As the support on which the image recording layer can be applied,
Is a stable plate-like material, for example, paper, plastic
(For example, polyethylene, polypropylene, polystyrene
Paper, metal plates (for example, aluminum)
Nickel, zinc, copper, etc.), plastic film (for example,
For example, cellulose diacetate, cellulose triacetate, propion
Acid cellulose, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyester
Tylene, polystyrene, polypropylene, polycarbonate
Metal, polyvinyl acetal, etc.)
Minated or evaporated paper or plastic fill
Or the like. Preferred supports are polyesters.
A tellurium film or an aluminum plate is mentioned. The support used for the image forming material used in the present invention.
The holder is lightweight and has excellent surface treatment, workability, and corrosion resistance.
It is preferable to use a prepared aluminum plate. This eye
As an aluminum material to be provided, JIS 10
50 materials, JIS 1100 materials, JIS 1070 materials, A
l-Mg alloy, Al-Mn alloy, Al-Mn-Mg
Alloy, Al-Zr alloy. Al-Mg-Si alloy
And so on. The surface of the aluminum plate is roughened.
Surface treatment, apply image recording layer, and lithographic printing plate precursor
can do. For roughening treatment, mechanical roughening
Surface roughening and electrochemical surface roughening alone or in combination
Done. Also, to ensure the surface is difficult to scratch
Anodizing treatment or treatment to increase hydrophilicity
It is also preferable. The surface treatment of the support will be described below.
The Before roughening the aluminum plate, if necessary
For example, a surfactant for removing rolling oil on the surface,
Degreasing treatment with organic solvent or alkaline aqueous solution
It may be done. In the case of alkali, then with an acidic solution
Processing such as sum and smut removal may be performed. Next, good adhesion between the support and the image recording layer
In order to provide water retention to the non-image area.
So-called graining treatment is applied to roughen the surface.
The As a specific means of this graining method, sand
There are mechanical graining methods such as blasting, and alkaline
Or an etching agent comprising an acid or a mixture thereof
There is a chemical graining method that roughens the surface. Ma
Electrochemical graining method, support material, granular material
Glue the surface with adhesive or a method that has its effect
Roughening method, continuous band or roll with fine irregularities
Surface roughening method, etc.
Known methods can be applied. A plurality of roughening methods such as these are combined.
The order and the number of repetitions are arbitrary.
Can be selected. Do not roughen the surface as described above.
On the surface of the support obtained by the graining process,
In order to remove this smut.
If necessary, perform water washing or alkali etching treatment.
It is generally preferred. In the case of an aluminum support,
After such a pre-treatment, it is usually the case that wear resistance, chemical resistance,
In order to improve aqueous properties, the substrate is acidified by anodic oxidation.
A chemical film is formed. For anodizing of aluminum plates
As the electrolyte used, a porous oxide film is formed.
Anything can be used, generally
Is sulfuric acid, phosphoric acid, oxalic acid, hydrochloric acid, nitric acid or a mixture of these
An acid is used. The concentration of those electrolytes is the type of electrolyte
As appropriate. Anodizing treatment conditions are used
Since it varies depending on the electrolyte, it cannot be specified in general.
Generally, the electrolyte concentration is 1-80% solution, and the liquid temperature is 5-7.
0 ° C, current density 5-60A / dm², Voltage 1-100
V and electrolysis time of 10 seconds to 5 minutes are suitable.
The amount of anodized film is 1.0 g / m²The above is suitable
Is more preferably 2.0 to 6.0 g / m.²In the range
The Anodized film 1.0g / m²Less than the printing durability
Is insufficient or the non-image part of the planographic printing plate is scratched
It becomes easier and ink is attached to the scratched part during printing.
Loose “scratch stains” are likely to occur. After the anodizing treatment, the above al
If necessary, the surface of the minium is a parent such as silicate treatment.
Water treatment is performed. Such an aluminum support is
After anodizing treatment or treatment with organic acid or its salt
Apply an undercoat layer applied to the image recording layer.
it can. Note that the adhesion between the support and the image recording layer is increased.
An intermediate layer may be provided. For improved adhesion
The intermediate layer is diazo resin, phosphonic acid or phosphorylated
Compound or aluminum alkoxide
A minium compound or the like may be used. The thickness of the intermediate layer is arbitrary
Even when exposed, uniform bonding with the upper image recording layer
It must be thick enough to allow the formation reaction. Usually dry
About 1 to 100 mg / m dry solid²The application ratio of 5 is good
~ 40mg / m²Is particularly good. Over the support surface
After being treated or undercoating, the support
A back coat is provided on the back surface of the as required.
As such a back coat, JP-A-5-45885
Organic polymer compounds described in Japanese Patent Application Laid-Open No. 6-35174
Hydrolysis and heavy
A coating layer made of a metal oxide obtained by condensation is preferred.
Used frequently. As described above, the negative type used in the present invention.
An imaging material can be created. This image forming material
The material can be recorded with an infrared laser. Also UV lamp
Thermal recording with a thermal head is also possible. Main departure
In the bright, the infrared wavelength of 760nm to 1200nm
Image exposure by solid-state and semiconductor lasers emitting radiation
Preferably it is illuminated. Laser output is 100mW or more
Multi-beam is preferred to reduce exposure time
It is preferable to use a laser device. One pixel
Per exposure time is preferably within 20μs
Yes. The energy applied to the image forming material is 10-30.
0 mJ / cm²It is preferable that After the image forming material is exposed by a laser,
Development is performed with the developer described in detail above. Developed
The image forming material may be washed with water, surfactant, etc. if desired.
Contains no rinsing liquid, gum arabic or starch derivatives
Used as a lithographic printing plate after post-treatment with a sensitizing solution
It is. In recent years, the plate making work has been rationalized in the plate making and printing industries.
Automatic processing machines for printing plate materials are widely used
It is used. This automatic processor generally has a developing section and a rear
An apparatus that consists of a processing unit and conveys a printing plate and each processing liquid
It consists of a tank and a spray device.
Each processing solution pumped up by the pump
-It develops by spraying from the nozzle. Ma
Recently, a submerged guide in a processing liquid tank filled with the processing liquid.
Process printing plate by dipping and transporting it with rolls
Methods are also known. In such automatic processing,
Replenish each treatment solution with a replenisher according to the processing amount, operating time, etc.
Can be processed. Also, electrical conductivity and pH
Can be detected automatically by the sensor and replenished automatically.
The Also, a so-called treatment with a substantially unused treatment solution
A disposable processing method is also applicable. 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 desired, post-exposure or burning is performed.
If you plan to burn a lithographic printing plate,
Japanese Patent Publication Nos. 61-2518 and 55-28062, JP
Each official of Sho 62-31859 and 61-159655
It is preferable to treat with surface-conditioning liquid as described in the report.
That's right. As a method for this, a spot in which the surface conditioning liquid is immersed is used.
Apply it on the lithographic printing plate using a cotton pad or absorbent cotton,
Method of dipping and applying the printing plate in a bat filled with
Or application by an automatic coater is applied. Also paint
After applying, apply with squeegee or squeegee roller.
A uniform amount gives more favorable results. Adjustment
The amount of surface liquid applied is generally 0.03 to 0.8 g / m.²(Dry
Weight) is appropriate. A lithographic printing plate coated with surface-adjusting liquid is necessary
After drying, a burning processor (for example,
Burning sold by Fuji Photo Film Co., Ltd.
Processor: BP-1300) etc.
The The heating temperature and time in this case are not forming an image.
1 in the range of 100 to 300 ° C.
A range of ˜20 minutes is preferred. A lithographic printing plate that has been burned is necessary.
Depending on the situation, water washing, gumming, etc. have been performed as appropriate.
Can be treated with water-soluble polymer compounds, etc.
If the surface preparation liquid contained is used, do not gum it.
So-called desensitizing treatment can be omitted. The flat image obtained by the image forming method of the present invention is used.
Plate printing plates are applied to offset printing machines, etc.
Used for printing. [0101] 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 to be done. [Example 1] [Production of support] Aluminum wafer having a thickness of 0.30 mm
The tube (material 1050) is washed with trichlorethylene.
After degreasing, nylon brush and 400 mesh pumice
Ton-water suspension, use a grained surface,
Washed with. 25% hydroxylation of this aluminum web
Immerse in an aqueous sodium solution (45 ° C) for 9 seconds and etch
2% HNO after washing with water_ThreeIn aqueous solution
It was immersed for 20 seconds and washed with water. The surface of the grained surface at this time
The etching amount is about 3 g / m.²Met. Then the electrolyte
7% sulfuric acid was used for the solution, and the current density was 15 A / dm.²According
3 g / m on the aluminum web²DC positive
A polar oxide film was provided. [Formation of image recording layer] Application of the following image recording layer
A liquid bar is placed on the support on which the undercoat layer is formed.
And dried at 120 ° C for 45 seconds with a warm air dryer
To form an image recording layer, and the lithographic printing plate precursor of Example 1
[P-1] was obtained. The coating amount after drying is 2.0 g / m ²so
there were. The following polymer (PB-1) is methacrylic
Acid, acrylamide and benzyl methacrylate
After synthesizing the polymer, 3-chloro-2-hydroxypro
Pyrmethacrylate with base and potassium iodide present
Synthesized by reacting under: The composition molar ratio is 1
5: 30: 15: 40 and the weight average molecular weight is 100,000.
Met. [0103] <Coating liquid for image recording layer [P-1]> ・ Onium salt [OS-7] 0.25g ・ Polymerizable compound [RM-1] 0.60 g ・ Infrared absorber [IR-13] 0.06 g ・ Polymer [PB-1] 1.40 g ・ Victoria Pure Blue Naphthalenesulfonate 0.04g ・ 1-Docosanol 0.01g ・ Polymerization inhibitor 0.005g   (Irganox 1010, manufactured by Ciba Specialty Chemicals) ・ Fluorine surfactant 0.03g   (Megafuck KF309, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 10g ・ Γ-Butyrolactone 5g ・ Methanol 7g 1-methoxy-3-propanol 5g Note that each chemical used in the coating solution for image recording was used.
The structural formula of the compound is shown below. [0105] Embedded image [Evaluation of Developer] Plate Material Supply Device (SA-L
8000), exposure apparatus (Luxel T-9000CT)
P), conveyor (T-9000 Conveyor),
Automatic processor (LP-1310H), stocker (ST-
1160) Fuji Photo Film Co., Ltd. CTP output
The system was used. In the development tank of the automatic processor,
Each developing solution was charged and kept at 30 ° C. Automatic processor
In the second bath, tap water is charged, and in the third bath, FN
-6 (Fuji Photo Film Co., Ltd.): Water = 1: 1 dilution
The finishing gum solution was charged. Products used in the following developers and developer replenishers
Name: 2K potassium silicate and A potassium silicate are Nippon Chemical Industry Co., Ltd.
It is a trade name of manufactured potassium silicate. Preparation of developer The following compounds were dissolved in water to prepare each developer. [Developer 1] (pH = 10.0, SiO₂/ M₂O molar ratio = approx. 3.6) 5% by weight of surfactant of formula Y-1, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
Add 1% by mass of Lithium (JIS 2K potassium silicate) to pH 1
Developer set to 0.0. [Developer 2] (pH = 11.0, SiO₂/ M₂O molar ratio = about 3.0) 5% by weight of surfactant of formula Y-1, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
Add 1% by mass of Lithium (JIS A Potassium Silicate) to pH 1
1.0 developer. [Developer 3] (pH = 12.0, SiO₂/ M₂O molar ratio = about 2.0) 5% by weight of surfactant of formula Y-1, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
1% by mass of potassium (JIS A potassium silicate), potassium hydroxide
Developer with pH added to 12.0. [Developer 4] (pH = 10.0, SiO₂/ M₂O
Ratio = approx. 3.6) 5% by weight of surfactant of formula Y-1, ethylenediamine tet
La acetic acid, 4Na salt (chelating agent) 0.2% by mass, silicic acid
1% by mass of potassium (JIS 2K potassium silicate), potassium carbonate
0.2% by mass of potassium and 0.5% by mass of potassium bicarbonate added
To a pH of 10.0. [Developer 5] (pH = 10.0, SiO₂/ M₂O molar ratio = approx. 3.6) 5% by weight of surfactant of formula Y-2, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
Add 1% by mass of Lithium (JIS 2K potassium silicate) to pH 1
Developer set to 0.0. [Developer 6] (pH = 10.0, SiO₂/ M₂O molar ratio = approx. 3.6) 5% by weight of surfactant of formula Y-3, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
Add 1% by mass of Lithium (JIS 2K potassium silicate) to pH 1
Developer set to 0.0. Next, the lithographic printing plate precursor [P-1]
It is loaded into the material supply device, fully automatic and continuous exposure,
Development was carried out with image liquids 1 to 6 and discharged to a stocker. exposure
The resolution at that time is 175 lines at 2400 dpi, and the halftone dot is 0.
The change was made in the range of 5 to 99.5%. The resulting lithographic stamp
Visual observation of halftone dot formation on printing plate [P-1] using loupe
Observed. As a result, all of 0.5% to 99.5%
All the dots were formed. Also obtained lithographic printing plate
About [P-1] R201 model made by Man Roland
Uses GEOS G black (N) manufactured by Dainippon Ink Co., Ltd.
And printed with developer 1, 2, 4, 5, 6
The number of prints was 100,000 and printing defects occurred.
What was processed with image liquid 3 had 90,000 prints and print defects.
Occurred. [Example 2] [Evaluation of replenishment amount of developer and aging] Development replenisher preparation Development replenishment corresponding to each of the developers 1, 4 and 5
The liquid was prepared. [Development replenisher 1] (pH = 11.0, SiO₂/ M₂O molar ratio = approx.
3.0) 5% by weight of surfactant of formula Y-1, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
Add 1% by mass of Lithium (JIS A Potassium Silicate) to pH 1
Development replenisher of 1.0. [Development replenisher 4] (pH = 10.0, SiO₂/ M₂O molar ratio = approx.
3.6) 5% by weight of surfactant of formula Y-1, ethylenediamine tet
La acetic acid, 4Na salt (chelating agent) 0.2% by mass, silicic acid
1% by mass of potassium (JIS 2K potassium silicate), potassium carbonate
0.5% by mass and 0.2% by mass potassium bicarbonate
Development replenisher with a pH of 10.5. [Development replenisher 5] (pH = 11.0, SiO₂/ M₂O molar ratio = approx.
3.0) 5% by weight of surfactant of formula Y-2, ethylenediamine tet
La acetic acid and 4Na salt (chelating agent) 0.2% by mass
Add 1% by mass of Lithium (JIS A Potassium Silicate) to pH 1
Development replenisher of 1.0. In the same manner as in Example 1, Developers 1, 4, 5
Are loaded into the development tank of the automatic processor,
1000m for original plate [P-1] for printing plate²Over 3 weeks
Image processing is performed and changes in image formation are confirmed in the same manner as in Example 1.
I confirmed. Formation of halftone dots of the obtained lithographic printing plate [P-1]
The situation was visually observed using a loupe. As a result, development
Treatment 10m in any of liquids 1, 4 and 5²50
0m²1000m²0.5% -99.
All 5% halftone dots were formed. Keep pH stable
Therefore, replenishment was performed with development replenishers 1, 4, and 5, respectively. That
The replenishment amount required was 60cc / m for development replenisher 1.²Development replenishment
Liquid 4 is 40cc / m²Development replenisher 5 is 60cc / m²Met. The
Also leave it for a week, then remove the developer and tank
The accumulation of scum was observed. Developer 1, 4, 5
There was no development residue accumulation even in the deviation. [Comparative Example 1] The following formulation was used instead of the developer.
In the same manner as in Example 1 except that Comparative Developer 1 was used.
A negative planographic printing plate [P-1] was obtained and used as Comparative Example 1. [Comparative developer 1] (pH = 10.0) Sodium dibutylnaphthalenesulfonate (anion field)
Surfactant) 5% by mass, ethylenediaminetetraacetic acid
4Na salt (chelating agent) 0.2% by mass potassium hydroxide
A developer with a pH of 10.0. [Comparison developer replenisher 1] (pH = 11.0) Sodium dibutylnaphthalenesulfonate (anion field)
Surfactant) 5% by mass, ethylenediaminetetraacetic acid
4Na salt (chelating agent) 0.2% by mass potassium hydroxide
A developer with a pH of 11.0. An original plate for lithographic printing plate [P-1] was prepared as Example 1.
Images were formed in the same manner as described above. The lithographic printing plate obtained at this time
The formation of halftone dots of [P-1] is visually confirmed using a loupe.
Observed. As a result, halftone dots are formed only from 2% to 90%.
Was not. In addition, a partial film was generated in the non-image area. Fruit
When printed in the same manner as in Example 1, the number of printed sheets was 70,000.
In this case, printing failure occurred and some stains occurred. As with Example 2, the time course of Comparative Developer 1
Sex was evaluated. 100m of lithographic printing plate precursor [P-1]
²Example 3: Development with Comparative Developer 1 over 3 weeks
In the same manner as in Example 1, changes in image formation were confirmed. Obtained
Use a loupe to check the halftone dot formation on the planographic printing plate [P-1].
It was observed visually. As a result, processing 10m²Time is 2%
~ 99.5% halftone dot is formed, 500m²Hour, 100
0m²Sometimes 2% to 98.5% halftone dots are formed
It was. Therefore, as the development process proceeds,
It was found that the reproducibility of the dough portion deteriorated. Stable pH
In order to keep, replenishment was performed with the comparative development replenisher 1. In that case
Replenishment amount was 120cc / m²Met. 1 week
After standing for a while, the developer is removed and the accumulation of debris in the tank
The situation was observed. In comparison developer 1, significant development residue
Deposition was observed. [Comparative Example 2] The following formulation was used instead of the developer.
In the same manner as in Example 1 except that Comparative Developer 2 was used.
A negative planographic printing plate [P-1] was obtained and used as Comparative Example 2. [Comparison developer 2] (pH = 12.5) Sodium dibutylnaphthalenesulfonate (anion field)
Surfactant) 5% by mass, ethylenediaminetetraacetic acid, 4
Potassium hydroxide to 0.2% by mass of Na salt (chelating agent)
Developer added to pH 12.5. [Comparison developer replenisher 2] (pH = 13.3) Sodium dibutylnaphthalenesulfonate (anion field)
Surfactant) 5% by mass, ethylenediaminetetraacetic acid, 4
Potassium hydroxide to 0.2% by mass of Na salt (chelating agent)
Developer added to pH 13.3. The original lithographic printing plate precursor [P-1] was prepared as Example 1.
Images were formed in the same manner as described above. The lithographic printing plate obtained at this time
The formation of halftone dots of [P-1] is visually confirmed using a loupe.
Observed. As a result, halftone dots of 5% to 99.5% are formed.
Small dots of 0.5%, 1%, 2%, 3%, 4%
Not formed. Also, printing was performed in the same manner as in Example 1.
As a result, defective printing occurred when the number of printed sheets was 40,000. Fruit
In the same manner as in Example 2, the aging of Comparative Developer 2 was evaluated.
100m of lithographic printing plate precursor [P-1]²3 weeks
And developing with comparative developer 2, as in Example 1.
The change in image formation was confirmed. The resulting lithographic printing plate
The formation of halftone dots of [P-1] is visually confirmed using a loupe.
Observed. As a result, processing 10m²Time is 5% to 99.5
% Dots were formed. Comparative development to keep pH stable
Replenishment was performed with replenisher 2. The replenishment amount required at that time was 210cc /
m²Met. Furthermore, after developing for 1 week, develop
The liquid was drained and the accumulation of scum in the tank was observed. Comparison
With regard to the developer 2, significant development residue accumulation was observed. [0117] According to the present invention, an infrared laser beam is used.
Digital data on a computer, etc.
It can be applied to negative image forming materials that can be recorded directly from
An excellent image forming method can be provided. Details
Alternatively, after exposure, image forming properties can be achieved without applying heat treatment to the plate.
That can produce lithographic printing plates with excellent printing durability and high printing durability
Can provide a method of formation. Further, according to the present invention, the developing waste liquid
It has been found that the amount can be significantly reduced. In addition, image recording
It also acts as a dispersion improver for insoluble components in the recording layer.
The development residue accumulated in the developing tank is marked
Image forming method that can be reduced and can be stably processed for a long time
Can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA02 AA12 AA13 AB03 AC08                       AD01 BC32 BC42 BC51 CA23                       CA26 CA28 CA39 CA48 CB10                       CB13 CB14 CB43 CC20 FA03                       FA17                 2H096 AA07 AA08 BA05 BA16 BA20                       EA04 GA08 GA09 GA11

Claims (1)

1. A radical generator (A) on a support,
A negative-type image-forming material provided with an image recording layer containing (B) a radical polymerizable compound, (C) an infrared absorber, and (D) a binder polymer is exposed to an alkali silicate and aroma after image exposure with an infrared laser. An image forming method comprising developing with an alkaline developer containing a nonionic surfactant having an aromatic ring.