JP2003307844A - Original plate of planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original plate of a planographic printing plate which can directly record digital data by using an infrared laser, which has a recording layer exhibiting excellent sensitivity and strength of an image area and which has such excellent printing durability as to give a large number of good prints. <P>SOLUTION: The original plate of the planographic printing plate adaptable to an infrared laser is obtained by disposing on a hydrophilic support an image recording layer containing at least one of the IR absorbents represented by formulae (I) and (II), wherein R<SP>1</SP>and R<SP>2</SP>are each independently an aliphatic group, aryl or a heterocyclic group; R<SP>3</SP>is H, halogen or a monovalent organic residue; B is an organic residue forming a 5- or 6-membered heterocycle or a condensed polycyclic ring including the heterocycle; L<SP>1</SP>, L<SP>2</SP>and L<SP>3</SP>are each independently methine; p is 1, 2 or 3; q is 0, 1, 2, 3 or 4; A<SP>-</SP>is a counter anion which is present when it is necessary to neutralize an electric charge; and m is 0 or 1. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a computer or the like.
Scanning an infrared laser based on digital signals
Flat plate capable of direct plate making, so-called direct plate making
It relates to a printing plate precursor. [0002] 2. Description of the Related Art Recent developments in lasers
In particular, an individual having a light emitting region from the near infrared to the infrared region.
For body lasers and semiconductor lasers, high output and downsizing
It is. Therefore, digital data such as computers
These records are used as exposure light sources when making plates directly from
The user is very useful. Such an infrared laser
The lithographic printing plate precursor that can be recorded by the method disclosed in JP-A-7
The thing of -285275 gazette is mentioned. this
The invention absorbs light and absorbs heat in an aqueous alkali-soluble resin.
Generated substances and quinonediazide compounds, etc.
An image recording material to which a di-type photosensitive compound is added.
The positive photosensitive compound is dissolved in an alkali-soluble resin.
Acts as a dissolution inhibitor that substantially lowers dissolution,
In the image area, it is decomposed by the generated heat and exhibits dissolution inhibiting ability
The image can now be removed from the developer
Form. International application WO 97/39894 includes water
A polymer that dissolves in a developer and a developer of the polymer
Red, which decreases the solubility of but improves the solubility by heat
Contains an external line absorber and is positively irradiated with infrared rays.
An image forming material for forming an image on a mold is disclosed. here
Infrared absorbers used in
It has a function to suppress solutionability. Image formation for forming such a positive image
In materials, it usually absorbs laser light and converts it into heat.
Cyanine infrared absorbing dyes are mainly used as
Although these are highly sensitive, they are sensitive to light and heat.
It was easy to deteriorate and there was a problem in storage stability. On the other hand, as a negative type lithographic printing plate precursor,
For example, JP-A-10-39509 and JP-A-2000-347.
393 and 2000-347393.
The acid generated by heat as an initiator
An image is generated by curing the recording layer in the exposed area by causing a crosslinking reaction.
Part forming method, or Japanese Patent Application Laid-Open No. 2001-12526
Radicals generated by heat, as disclosed in No. 0
Is used as an initiator to cause a polymerization reaction to form a recording layer in the exposed area.
A method for forming an image portion by curing has been proposed. Such a negative type image forming material is an infrared ray.
Of recording layer caused by energy of X-ray laser irradiation
Compared to the positive type, the image forming property is low, and crosslinking or
Accelerates curing reactions such as polymerization to form strong image areas
Therefore, after the development process, burning treatment or baking
In general, heat treatment called treatment is performed. Special
In addition, the lithographic printing plate precursor having the recording layer described above is coated with aluminum.
By using an infrared laser
The energy diffuses to a highly thermally conductive support and forms an image
It is not used efficiently for image formation and sufficient sensitivity and image area
There was a problem that strength could not be obtained. In the recording layer
In general, infrared light that converts infrared laser light into heat
Used as an infrared absorber, although it contains a line absorber
If the resulting dye has poor stability, the dye in the recording layer
Is decomposed, and its light-to-heat conversion ability decreases, and image formation
The reaction is not promoted, and the sensitivity and image area intensity are greatly affected.
There was a concern about the effect. On the other hand, in the recent plate making and printing industries, plate making work
Is being streamlined, and wet development processes such as those described above
Without processing and without developing after exposure
Development-free lithographic printing plate precursor that can be printed on a printing press
For example, image recording by supplying heat energy
Only the heated area of the recording layer changes polarity (hydrophobic becomes hydrophilic, or
Or the change of hydrophilicity to hydrophobicity)
Proposed method to form aqueous and hydrophilic on / off
Yes. Specifically, for example, JP-A-7-186562
Uses a polymer that generates carboxylic acid by heat and acid.
Japanese Patent Application Laid-Open No. 10-282672 discloses a method by which heat is applied.
Disclosed is a method using a polymer that generates sulfonic acid.
Yes. Other methods include, for example, Japanese Patent No. 293839.
7 or WO99 / 10186, etc.
Disperse hydrophobic thermoplastic polymer particles in aqueous binder
Hydrophobic by infrared laser exposure
Hydrophobic image area by heat fusion of water-soluble thermoplastic polymer particles
After forming the plate, attach the plate to the cylinder of the printing press.
Technology for on-press development with ink and / or fountain solution
No. 2001-293971, 2001-277
In the hydrophilic binder matrix described in No. 42
And a thermoplastic containing a compound having a thermally reactive functional group
Heat-sensitive resin fine particles or microcapsules dispersed
A planographic printing plate having a mold recording layer has been proposed. this
On-press development type or completely non-processing type lithographic printing plate
The photothermal conversion material is also important in the original thermal recording layer.
Excellent sensitivity to infrared laser light
It is desirable to have good stability that does not deteriorate over time.
ing. [0007] The present invention solves the above problems.
The object of the present invention is to provide infrared rays.
Recording using solid-state and semiconductor lasers
From digital data such as computers
It can be recorded directly and has excellent sensitivity and image strength.
Printing durability with a good recording layer and many good prints
It is to provide an excellent lithographic printing plate precursor. [0008] The inventor of the present invention has provided an infrared laser.
It is used to efficiently convert the light irradiated by the heat into heat.
As a result of intensive studies, the stability over time
A dye with an excellent specific structure is used as an infrared absorber
The above-mentioned object can be achieved by the present invention.
It came to complete. That is, the lithographic printing for infrared laser of the present invention
The plate precursor is formed on a hydrophilic support with the following general formula (I) and
At least one of the infrared absorbers represented by the general formula (II)
Compatible with infrared lasers with an image recording layer containing
A lithographic printing plate precursor. [0010] [Chemical 2] In the general formulas (I) and (II), R¹
And R²Each independently represents an aliphatic group, an aryl group, or
Represents a heterocyclic group. R^ThreeIs a hydrogen atom or halogen atom
It represents a child or a monovalent organic residue. B is nitrogen atom, oxygen
A small amount selected from atoms, sulfur atoms, Se atoms, Te atoms
5- or 6-membered containing at least one heteroatom
An organic residue forming a heterocyclic ring or a condensed polycyclic ring containing the heterocyclic ring
Represents a group. L¹, L²And L^ThreeEach independently represents a methine group
Represents. p represents 1, 2, or 3. q is 0, 1,
2, 3, or 4 is represented. A^-If there is a need for charge neutralization
Represents a counter anion present together. Where m is 0 or 1
Represent. In the compound represented by the general formula (I)
A^-If neutralization of the charge by A is not necessary, A^-The
The anion and cation present in the excluded molecule
It has a structure in which an inner salt is formed. A^-Excluding
As anions present in the most part of the molecule, SO
_ThreeH, COOH, PO_ThreeH₂, P (= O) (OR) OH,
SO₂At least one acidic group selected from H dissociates
It is preferable that it is an anion generated by this. Above
Among acid groups, -SO_ThreeH, -COOH, -PO
_ThreeH₂, -OPO_ThreeH₂It is more to have any one of
preferable. On the other hand, the compound represented by the general formula (I)
A^-If neutralization of the charge by
A^-And A^-An anion present in the portion of the molecule excluding
And has a structure in which an inner salt is formed. Although the operation of the present invention is not clear, the general formula
The infrared absorber represented by (I) and general formula (II) is
Good stability over time due to good stability over time
In addition, the irradiation light of the infrared laser is more efficiently converted into heat.
Since it is possible to convert, the sensitivity of the recording layer increases.
Recording layer containing negative or hydrophobic precursor
Promotes curing reaction or hydrophobized region formation reaction
It is speculated that it will be possible to form a strong image area.
It is. Moreover, it is represented by general formula (I) and general formula (II).
In the recording layer.
What is due to the structure of such compounds,
Some type of interaction is formed, negative or positive recording
The alkali developability in the layer is improved, which is
It is thought that it contributes to improvement. Therefore, like this
A lithographic plate obtained from a lithographic printing plate precursor provided with an image recording layer
According to the printing plate, many good prints can be obtained and the printing durability is improved.
Excellent. [0014] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
To do. [(A) Infrared absorber] The lithographic printing plate precursor according to the invention comprises
Can record images with a laser emitting infrared rays
It has a functional configuration. Such an image recording layer (hereinafter referred to as “image recording layer”).
Hereinafter referred to as a recording layer, a photosensitive layer, or a heat-sensitive recording layer, as appropriate.
The ) By using the infrared absorbent according to the present invention.
Thus, a highly sensitive image forming reaction can be performed. Main departure
The specific infrared absorber related to Ming converts the absorbed infrared rays into heat.
It has a function to change. The heat generated at this time
An image formation reaction occurs and proceeds. Used in the present invention
Infrared absorbers have specific wavelength ranges (red light to infrared
A dye having the following specific structure having absorption in the region)
Hereinafter, it is referred to as a specific dye as appropriate. In the present invention, (A) an infrared absorber and
The compounds represented by the above general formula (I) and general formula (II)
It is necessary to use at least one of the compounds.
In the above general formula (I) and general formula (II), each substitution
Preferred examples of the group include the following. In the above general formula (I),
Having a lysine ring structure, in which R¹And R²
Each independently represents an aliphatic group, an aryl group, or a heterocyclic group.
Represents. R^ThreeIs a hydrogen atom, a halogen atom, or
Represents a monovalent organic residue. R in the above general formula (I)¹And R²Represented by
Aliphatic groups include straight-chain or branched ones having 1 to 22 carbon atoms.
Branched alkyl groups (eg methyl, ethyl, pro
Pyr group, butyl group, pentyl group, hexyl group, heptyl
Group, octyl group, nonyl group, decyl group, undecyl group,
Dodecyl group, tridecyl group, tetradecyl group, pentadec
Sil group, hexadecyl group, heptadecyl group, octadecyl group
Group, nonadecyl group, eicosanyl group, heneicosanyl group
Group, docosanyl group, etc.), straight chain having 2 to 22 carbon atoms
Is a branched alkenyl group (eg, vinyl group, propenyl
, Butenyl, pentenyl, hexenyl, octyl
Tenenyl, decenyl, dodecenyl, tridecenyl
Group, tetradecenyl group, hexadecenyl group, octadecenyl group
Nyl group, eicosenyl group, dococenyl group, butadienyl
Group, pentadienyl group, hexadienyl group, octadienyl
Nyl group, etc.), linear or branched having 2 to 22 carbon atoms
Alkynyl groups (for example, ethynyl group, propynyl group,
Tinyl group, hexynyl group, octanyl group, decanyl group,
Dodecanyl group, etc.), C5-C22 alicyclic hydrocarbon group
(As the alicyclic hydrocarbon group, monocyclic, polycyclic, bridged ring
An aliphatic cyclic hydrocarbon group of the formula
Cyclopentane, cyclopentene, cyclopenta
Diene, cyclohexane, cyclohexene, cyclohex
Sadiene, cycloheptane, cycloheptene, cyclohe
Ptadiene, cyclooctane, cyclooctene, cyclo
Octadiene, cyclooctatriene, cyclosonane,
Cyclosonene, cyclodecane, cyclodecene, cyclode
Candiene, cyclodecatriene, cycloundecane,
Cyclododecane, bicycloheptane, bicyclohexa
, Bicyclohexene, tricyclohexane, norkara
, Norpinane, norbornane, norbornene, norvo
Lunadiene, tricycloheptane, tricyclohepte
Ring structure hydrocarbons such as N, decalin and adamantane
It is done. ) Among these, straight chain having 1 to 12 carbon atoms
, Branched with 3 to 12 carbon atoms, and 5 carbon atoms
10 to 10 cyclic aliphatic groups are more preferred. Such an aliphatic group may have a substituent,
The substituents that can be introduced are monovalent non-gold excluding hydrogen.
Genus groups are used. As a concrete example of a nonmetallic atomic group
Are halogen atoms (fluorine atoms, chlorine atoms, bromine atoms
Child, iodine atom), formyl group, cyano group, nitro group,
Hydroxy group, thiol group, carboxy group, sulfo group,
Phosphono group, phosphonooxy group (-OPO _ThreeH₂Group),-
OR^b1, -SR^b1, -COR^b1, -COOR^b1, -OC
OR^b1, -SO²R^b1, -NHCONHR^b2, -N (R
^b2) COR^b1, -N (R^b2) SO²R ^b1, -N (R^b3)
(R^b4), -CON (R^b3) (R^b4), -SO²N (R
^b3) (R^b4), -P (= O) (R^b5) (R^b6), -OP
(= O) (R^b5) (R^b6), Alkyl having 1 to 18 carbon atoms
Group, C 2-18 alkenyl group, C 2-18
Alkynyl group, C5-C10 alicyclic hydrocarbon group, charcoal
An aryl group having a prime number of 6 to 18 (the aryl ring includes
Zen, naphthalene, dihydronaphthalene, indene, a
Ndan, anthracene, phenanthrene, fluorene,
Acenaphthylene, acenaphthene, biphenylene, naphtha
Cene, benzoanthracene, pyrene, triphenylene,
Aceanthrene, etc.), oxygen atom, sulfur atom, nitrogen atom
Monocyclic or polycyclic containing at least one of
Heterocyclic groups having a cyclic ring structure (Examples of heterocyclic groups include
For example, furanyl group, tetrahydrofuranyl group, pyranyl
Group, pyroyl group, chromenyl group, phenoxathiinyl
Group, imidazolyl group, pyrazoyl group, pyridiyl group,
Razinyl group, pyrimidinyl group, indoyl group, iso
Undoyl, quinoniyl, pyrrolidinyl, pyrrolini
Group, imidazolinyl group, pyrazolidinyl group, piperidyl
Nyl group, piperazinyl group, morpholinyl group, thienyl
Group, benzothienyl group, etc.). Said al
Kenyl group, alkynyl group, alicyclic hydrocarbon group, aryl
Group, heterocyclic group may further have a substituent, the substitution
As the group, as a substituent that can be introduced into the aliphatic group.
The thing similar to what was illustrated is mentioned. Also, the above
Carboxy group, sulfo group, phosphono group and phosphonooxy
Each Si group has its conjugated base group (carboxyl
Group, sulfonate group, phosphonate group, phosphonate
An oxy group). R^b1Is an aliphatic group having 1 to 22 carbon atoms,
An aromatic group having 6 to 18 carbon atoms or a heterocyclic group is represented. R^b1
The aliphatic group in R is R¹And R²An aliphatic group represented by
It is synonymous with. R^b1As the aryl group in the above,
R¹And R²As a substituent that can be introduced into the aliphatic group represented by
And the same aryl groups as exemplified above. Heels
The aryl group may further have a substituent, and the substituent
As said R¹And R²Introduced into the aliphatic group represented by
Examples of the substituent to be obtained are the same as those exemplified.
The R^b2Is a hydrogen atom or R^b1Same table as
The R^b3And R^b4Each independently represents a hydrogen atom, or
R^b1Represents the same as R^b3And R^b4Combined with each other
Forming a 5- or 6-membered ring containing an N atom
Also good. R^b5And R^b6Are each independently -OH, charcoal
A primary aliphatic group having 1 to 22 carbon atoms and an aryl group having 6 to 14 carbon atoms
Group, or -OR^b1Represents a group. R^b5And R^b6Fat in
The group is R¹And R²It is synonymous with the aliphatic group represented by
The R^b5And R^b6As the aryl group in the above, R
¹And R²As a substituent that can be introduced into the aliphatic group represented by
The thing similar to the illustrated aryl group is mentioned. Take
The aryl group may further have a substituent, and the substituent and
The R¹And R²It can be introduced into an aliphatic group represented by
And the same as those exemplified as the substituent.
The R in the above general formula (I)¹And R²Represented by
Examples of the aryl group include aryl groups having 6 to 18 carbon atoms.
Specifically, the R¹And R²Aliphatic represented by
Same as the aryl group exemplified as the substituent that can be introduced into the group
Can be mentioned. Such aryl groups are further
It may have a substituent, and as the substituent, the R ¹
And R²As a substituent that can be introduced into the aliphatic group represented by
The thing similar to what was illustrated is mentioned. R in the above general formula (I)¹And R²Represented by
Heterocyclic groups include nitrogen, oxygen, and sulfur atoms
A monocycle containing at least one heteroatom selected from
Represents a formula or polycyclic heterocyclic group. Specifically, the above
R¹And R²As a substituent that can be introduced into the aliphatic group represented by
Examples thereof are the same as the heterocyclic groups exemplified above. Also,
Such a heterocyclic group may further have a substituent.
As the substituent, R ¹And R²Derived into an aliphatic group represented by
Examples of the substituents that can be entered are the same as those exemplified above.
It is done. R in the above general formula (I)^ThreeThe hydrogen field
Child, halogen atom (fluorine atom, chlorine atom, bromine atom,
Iodine atom), cyano group, nitro group, -OH, -COO
H, -SO_ThreeH, -PO_ThreeH₂, -OR^a1, -SR^a1,-
OCOR^a1, -COOR^a1, -SO₂R^a1, -CO
R^a1, -NHCONHR^a2, -N (R^a2) (R^a3),-
N (R^a2) SO₂R^a1, -N (R^a2) COR^a1, -CO
N (R^a2) (R^a3), -SO₂N (R^a2) (R^a3), Charcoal
Alkenyl group having 1 to 18 prime atoms and 2 to 18 carbon atoms
Group, alicyclic hydrocarbon group having 5 to 10 carbon atoms, 6 to 6 carbon atoms
14 aryl groups and heterocyclic groups. R^a1
R^b1Is synonymous with R^a2And R^a3R^b3
And R^b4It is synonymous with. Also, alkyl group, alkenyl
Group, alicyclic hydrocarbon group, aryl group, and heterocyclic group
Examples are R¹And R²It can be introduced into an aliphatic group represented by
And the same as those exemplified as the substituent.
The Such a heterocyclic group may further have a substituent.
As the substituent, R¹And R²Fat represented by
The same as those exemplified as the substituent which can be introduced into the aliphatic group
Things. In the above general formula (I), B is a nitrogen atom.
Selected from children, oxygen atoms, sulfur atoms, Se atoms, Te atoms
5-membered containing at least one heteroatom
Or a 6-membered heterocyclic ring or a condensed polycyclic ring containing the heterocyclic ring
Represents a divalent organic residue. Where B in general formula (I)
As the organic residue represented, the structure of the following general formula (B-1)
It is preferable to have a structure. [0024] [Chemical 3] In the general formula (B-1), Z¹The oxygen
Atom, sulfur atom, Se atom, Te atom, or> N—R
⁰Represents. However, R⁰Represents an aliphatic group. X¹Is Z¹Including
5-membered or 6-membered heterocyclic ring or a condensed ring containing the heterocyclic ring
It represents an atomic group necessary for forming a polycyclic ring. Y¹And Y²
Each independently represents a hydrogen atom, an aliphatic group, or an aryl group
Represents. However, Z¹Is oxygen atom, sulfur atom, S
Y represents Y atom or Te atom.¹And Y²Is more
Represents a cyano group, a nitro group, -OR, or -SR.
Here, R represents an aliphatic group or an aryl group. l is
0, 1, 2 or 3 is represented. Z in the above general formula (B-1)¹But nitrogen source
Of children, oxygen atoms, sulfur atoms, Se atoms, or Te atoms
If X¹Or a heterocyclic ring containing the heterocyclic ring
Specific examples of polycycles include pyran, benzopyran, and naphthopiyl.
Orchid, xanthene, thiopyran, benzothiopyran, na
Ftthiopyran, thioxanthene, serenapyran, ben
Zoselenapiran, Naftselenapyran, Ternapyran,
Benzoternapyran, naphthoternapyran
The Z in the above general formula (B-1)¹> N-R⁰
The X containing the structure¹Or a heterocyclic ring represented by
The condensed polycycle containing the heterocycle is specifically thiazole.
Ring, benzothiazole ring, naphthothiazole ring (eg
Naphtho [2,1-d] thiazole ring, naphtho [1,
2-d] thiazole ring, naphtho [2,3-d] thiazole
Ring), thionaphthene [7,6-d] ring, benzooxy
Sazole ring, naphthoxazole ring (for example, naphtho ring
[2,1-d] oxazole ring, naphtho [1,2-d]
Oxazole ring, naphtho [2,3-d] oxazole ring
Etc.), selenazole ring, benzoselenazole ring, naphtho
Selenazole ring (eg, naphtho [2,1-d] selena
Zole ring, naphtho [1,2-d] selenazole ring, naphth
[2,3-d] selenazole ring), oxazoline
Ring, selenazoline ring, thiazoline ring, pyridine ring, quino
Phosphorus rings (eg, 2-quinoline ring, 4-quinoline ring,
Nzo [t] quinoline ring, etc.), isoquinoline ring (for example,
1-isoquinoline ring, 3-isoquinoline ring, benzoiso
Quinoline ring, etc.), acridine ring, 3,3-dialkyli
Andrenen ring, 3,3-dialkylbenzoindolenine
Ring, 3,3-dialkyl [1,7] diazo-2-indene
Ring, imidazole ring, benzimidazole ring, naphtho
Imidazole ring (for example, 1H-naphtho [2,3-d]
Imidazole ring, etc.), imidazoquinoline ring (for example, 1
H-imidazo [4,5-b] quinoline ring, etc.), imidazo
[4,5-b] quinoxaline ring and the like. Z in the above general formula (B-1)¹> N in
-R⁰R⁰The group represents an aliphatic group which may be substituted. Or
Such aliphatic groups are linear or branched having 1 to 22 carbon atoms.
Branched alkyl group, C2-C22 alkenyl group, charcoal
Alkynyl group having 2 to 22 primes and alicyclic group having 5 to 22 carbons
A hydrocarbon group is preferred. These aliphatic groups are R¹
And R²It is synonymous with the aliphatic group represented by these. Such fat
The group may further have a substituent, and the R¹And R²so
Also exemplified as substituents that can be introduced into the aliphatic group represented
The same thing is mentioned. X in the above general formula (B-1)¹
Or a condensed polycyclic ring containing the heterocyclic ring represented by
It may have a substituent, and as the substituent, the R¹
And R²As a substituent that can be introduced into the aliphatic group represented by
The thing similar to what was illustrated is mentioned. Y in the general formula (B-1)¹And Y²
Each independently represents a hydrogen atom, an aliphatic group, or an aryl group
Represents. However, Z¹Is oxygen atom, sulfur atom, S
Y represents Y atom or Te atom.¹And Y²Is more
Represents a cyano group, a nitro group, -OR, or -SR.
Also good. Here, R represents an aliphatic group or an aryl group.
Among these, a hydrogen atom, an aliphatic group having 1 to 22 carbon atoms,
Is preferably an aryl group having 6 to 22 carbon atoms.
Yes. Y¹And Y²The aliphatic group represented by the general formula
R of (I)¹And R²It is synonymous with the aliphatic group represented by these.
Y¹And Y²An aryl group represented by the general formula
R of (I)¹And R²As an aryl group represented by
The same thing is mentioned. These are further substituents
As the substituent, the general formula may be
R of (I)¹And R²A position that can be introduced into the aliphatic group represented by
The thing similar to what was illustrated as a substituent is mentioned. Further, an organic residue represented by B in the general formula (I)
As the group, a divalent nitrogen atom-containing heterocyclic ring or the nitrogen atom
A condensed polycyclic ring containing a heterocyclic ring containing a nitrogen atom
It may be a ring that can form a structure. For example,
Naphlactam ring, pyrrolo [1,2-a] indoline
Ring, thiazolo [3,4-a] pyrimidine ring, cyclohept
[B] pyrrol-2 [1H] -one ring, the following general formula
The oxyindolizine ring structure represented by (B-2)
I can get lost. [0032] [Formula 4] R in the general formula (B-2)¹~ R^Threeof
Each substituent is represented by the above general formula (I) and general formula (II).
R¹~ R^ThreeIt is synonymous with each substituent. The general formula
The ring structure represented by (B-2) may further have a substituent.
Well, as the substituent, as the substituent,
R¹And R²As a substituent that can be introduced into the aliphatic group represented by
Examples similar to those exemplified above. In the above general formula (I) and general formula (II),
And L¹, L²And L^ThreeEach independently represents a methine group.
The In the general formula (I), p is 1, 2, or 3
Represents [-(L¹= L²) _p-L^Three=] Is the number of methine chains (total
(Carbon number) 3-7 polymethine group, that is, trimethine group,
Pentamethine group or heptamethine group, the leftmost oxy
An indolizine ring structure and a ring structure at the right end represented by B;
Join. In the general formula (II), q is 0,
Represents 1, 2, 3, or 4, and when q = 0,
Cyindolizine ring structure and rightmost ring structure represented by B
And will be directly combined, otherwise
[= (L¹-L²)_q=] Is the number of methine chains (total carbon number) 2
8 polymethine groups, preferably dimethine groups, tetramethine
Chin chain, hexamethine group, left end ring structure and right end ring structure
Combine structure. In this way, the general formulas (I) and (I
The leftmost oxyindolizine ring structure in I) and B
By combining the rightmost ring structure represented by
Wavelength suitability for external lines and compound stability are obtained. L¹, L²And L^ThreeIs substituted or unsubstituted
Alkyl group, substituted or unsubstituted alkoxy group,
Substituted or unsubstituted aryloxy group, substituted or unsubstituted
Substituted alkylthio group, substituted or unsubstituted aryl
Thio group, substituted or unsubstituted amino group, halogen atom
Child, substituted or unsubstituted aryl group, substituted or unsubstituted
Substituted iminium ion group, represented by the following general formula (1)
May be substituted with a group selected from
Substituents on these substituents include halogen atoms, hydroxy acids
Group, alkoxy group, alkoxycarbonyl group, alkoxy
Sisulfonyl group, carboxylic acid group, sulfonic acid group, etc. are preferred.
As a new substituent. Among these, L¹,
L²And L^ThreeAs the above substituent, methyl group, ethyl group, etc.
Alkyl groups, aryl groups such as phenyl groups, chlorine atoms, etc.
Diaryl groups such as halogen atoms and diphenylamino groups
And arylthio groups such as mino group and phenylthio group
Diaryl such as halogen atom and diphenylamino group
Amino group and arylthio group such as phenylthio group
Is preferred. [0036] [Chemical formula 5] Where R¹And R²Each independently
An elementary atom, an optionally substituted alkyl group having 1 to 8 carbon atoms,
Or an optionally substituted aryl group having 6 to 10 carbon atoms
The Y¹Represents an oxygen atom or a sulfur atom. These positions
As the substituent, R¹And R ²Derived into an aliphatic group represented by
Examples of the substituents that can be entered are the same as those exemplified above.
It is done. [-(L¹= L²)_p-L^Three=] Or [= (L
¹-L²)_qThe polymethine chain represented by
May form a cycloalkene ring containing two methine chains
Cyclohexene ring, cyclopentene ring or cyclo
It preferably has a ten ring from the viewpoint of stability.
Nthene ring or cyclohexene ring is particularly preferred. Cyclo
Has hexene, cyclopentene or cyclobutene ring
The propylene group necessary to form a ring,
It may have a substituent on the tylene group or methylene group.
Preferred substituents include alkyl groups, alkoxy groups, and ants.
Alkyloxy group, alkylthio group, arylthio group, dia
Alkylamino group, diarylamino group, halogen atom,
Aryl group, hydroxyl group, alkoxy group, alkoxycarbo
Nyl, alkoxysulfonyl, carboxylic acid, sulfo
Phonic acid group, phosphonic acid group, sulfinic acid group, etc.
A plurality of these substituents bonded to each other to form a bicyclo ring,
A tricyclo ring may be formed. Also these ring formation
An alkylene group (for example, a methylene group) necessary for
-O-, -S-, -Se-, -NR^{twenty one}-, -CO-,-
COO-, -SO-, -SO₂-, -SO_Three-, -CON
H-, -OCONH-, -NHCONH-, -NHCS
Substituted by a divalent atom or atomic group selected from NH-
May be. Where R^{twenty one}Is a substitution of 1 to 22 carbon atoms
Represents a hydrocarbon group which may be Specifically, the R^Three
Same as each hydrocarbon group exemplified as a substituent which can be introduced into
Can be mentioned. Also, in the following formula (2) or (3)
Substituting the squarylium or croconium ring represented
As a cyclobutene ring or cyclopentene ring having a group
It is also preferable to have it. [0039] [Chemical 6] [-(L¹= L²)_p-L^Three=] Or
[= (L¹-L²)_q=] In the polymethine chain
Two or more consecutive two methine chains (-CH =
CH- or = CH-CH =) is the following formula (4), (5) or
May be substituted by the structure represented by (6). [0041] [Chemical 7] In the formula (4), R^ThreeAnd R^FourAre each independently
Represents a hydrogen atom, an aliphatic group or an aryl group. Where fat
Specific examples of the aliphatic group and the aryl group include the R¹And R²
It is synonymous with the aliphatic group and aryl group which are represented by these. Y²
Represents an oxygen atom, a sulfur atom or a selenium atom. [0043] [Chemical 8] In the formula (5), R^FiveAnd R⁶Are each independently
Hydrogen atom, alkyl group, alkoxy group, hydroxy group,
A substituted or unsubstituted amino group or halogen atom is represented.
And R^FiveAnd R⁶Are bonded to each other to form a condensed 6-membered ring.
May be. Y^ThreeRepresents an oxygen atom or a sulfur atom. [0045] [Chemical 9]In the formula (6), R⁷, R⁸And R⁹Each
Vertically, hydrogen atom, halogen atom, alkyl group, alkoxy
Si group, hydroxy group, substituted or unsubstituted amino group,
Aryloxy group, alkylthio group, arylthio group, N
-Mono- or di-substituted carbamoyl group (N substituent)
As an alkyl group or an aryl group), an alkyl group
Phonyl, alkoxycarbonyl, aryloxy
Bonyl group, carboxy group, sulfo group, or phosphono group
R⁷And R⁸, R⁷And R⁹And R⁸And R⁹At least
One may form a condensed 6-membered ring. Y^ThreeThe acid
Represents an elementary atom or a sulfur atom. Preferred examples of the structure represented by the above formula (5)
Examples include (5-1) to (5-7) shown below.
It is done. [0048] Embedded image In the above general formula (I) and general formula (II),
A^-Is present when there is a need for charge neutralization.
Represents a nonion. However, m represents 1 or 2. Against
Nonions include inorganic or organic anions.
The Specific examples of the counter anion include the following:
However, it is not limited to these. For example, C
l^-, F^-, Br^-, I^-, ClO_Four ^-, BrO_Four ^-, Sb
F₆ ^-, PF₆ ^-, Borate anions (eg BF_Four ^-, Te
Traphenylborate anion, butyl-triphenyl
Borate anion, butyl-tris (2,4,6-tris
Methylphenyl) borate anion, butyl-methyl-
Diphenylborate anion, butyl-tris (fluoro
Rophenyl) borate anion, butyl-tris (meth)
Xylphenyl) borate anion, tetra (chlorophene)
Nyl) borate anion, etc.) sulfonate anion (eg
For example, alkanesulfonic acid anion (alkanesulfonic acid
As methane sulfonic acid, ethane sulfonic acid, pro
Pan sulfonic acid, butane sulfonic acid, allyl sulfone
Acid, phenylmethanesulfonic acid, hydroxypropane
Acid, 2-chloroethanesulfonic acid, 10-camphors
Sulfonic acid, trifluoromethanesulfonic acid, pentafur
Oroethanesulfonic acid, etc.) Aromatic sulfonic acid anion
(Aromatic sulfonic acids include benzene sulfonic acid,
Ruene sulfonic acid, methoxybenzene sulfonic acid, hydride
Loxybenzene sulfonic acid, chlorobenzene sulfone
Acid, nitrobenzenesulfonic acid, acetylbenzenesulfuric acid
Phosphonic acid, pentafluorobenzene sulfonic acid, o-sulfur
Phobenzenecarboxylic acid, mesitylenesulfonic acid, naphtha
Rensulfonic acid, naphthalene disulfonic acid, naphthol
Sulfonic acid, anthraquinone sulfonic acid, quinoline sulfate
Phosphonic acid anion (specifically,
Aliphatic compounds and aromatic compounds exemplified for the sulfonate anion
At least phosphonic acid groups instead of sulfonic acid groups
Is also exemplified by a single-substituted compound)
The In the compound represented by the above general formula (I)
A^-If neutralization of the charge by A is not necessary, A^-The
The anion and cation present in the molecule
It has a structure in which an inner salt is formed. A^-Excluding
As anions present in the most part of the molecule, SO
_ThreeH, COOH, PO_ThreeH₂, P (= O) (OR) OH,
SO₂At least one acidic group selected from H dissociates
It is preferable that it is an anion generated. Above
Among acid groups, -SO_ThreeH, -COOH, -PO
_ThreeH₂, -OPO_ThreeH₂It is more to have any one of
preferable. On the other hand, the compound represented by the general formula (I)
A^-If neutralization of the charge by
A above^-A counter anion represented by^-The part of the molecule except
An internal salt is formed with the cation present inside
It has a structure. The general formula (I) and the above used in the present invention
Exemplary compounds of the specific dye represented by the general formula (II) are as follows:
Although shown in Table 1 to Table 16, it is not limited to these.
Absent. [0052] [Table 1] [0053] [Table 2][0054] [Table 3] [0055] [Table 4][0056] [Table 5] [0057] [Table 6][0058] [Table 7] [0059] [Table 8] [0060] [Table 9][0061] [Table 10] [0062] [Table 11] [0063] [Table 12][0064] [Table 13] [0065] [Table 14][0066] [Table 15] [0067] [Table 16] In addition, the specific dye used in the present invention
US Pat. No. 4,577,024, or Wadwar
Su, Day, Tetrahedron Letters, No. 37, 356
9 (1981) (Wadsworth, D., et.
al, Tet. Letters, 37, 3569 (19
81) easily synthesized by the synthesis method described in 81)
be able to. Only one infrared absorber may be used.
In addition, two or more kinds may be used in combination. Previous in the recording layer
The specific infrared absorber content depends on the characteristics of the image recording layer.
More appropriately. Preferred in each image recording layer
The content will be described below together with other components of the image recording layer.
The In addition, within the range where the effects of the present invention are not impaired.
In addition to the specific infrared absorber,
Can be used in combination with known infrared absorbers for
In this case, the content of the general-purpose infrared absorber used in combination is red.
It is preferably 40% by mass or less in the total solid content of the external line absorbent.
Good. Infrared absorbers that can be used in combination are used for recording.
Absorbs light energy radiation used and generates heat
If there is no quality, there is no particular limitation on the absorption wavelength range.
From the viewpoint of compatibility with readily available high-power lasers
Has an absorption maximum from a wavelength of 800 nm to 1200 nm.
Infrared absorbing dyes or pigments are preferred. Examples of the dye include commercially available dyes such as “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
Names described in issue [0050] to [0051]
You can. Especially preferred among these dyes
Cyanine dye, squarylium dye, pyrylium
Salt, organometallic complex (eg dithiolate complex)
Is mentioned. 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 are carbon black, aniline black,
Nigrosine Black, Cyanine Black, Titanium Black
And the like. [Configuration of Image Recording Layer] Planographic printing plate of the present invention
The image recording layer applicable to the original is recorded by infrared exposure.
If possible, there is no particular limitation, and infrared laser exposure
Materials whose solubility in alkaline aqueous solution changes with light
Negative or positive type image recording layer, ink receiving
Contains a hydrophobizing precursor that can form
An image recording layer in which a hydrophobic region is formed in the exposed portion,
An ink receiving layer and a hydrophilic layer are sequentially laminated on the support, and red
In the external laser exposure area,
Sudden heat generation, expansion, or explosion in any layer
The hydrophilic layer is peeled off, the ink receiving layer is exposed, and the image area is formed.
Any known image recording method such as the image recording layer
Selected. First, a positive type or negative type image recording layer is formed.
Describe. Such an image recording layer is an infrared laser
After imagewise exposure by, developed with alkaline aqueous solution,
Alkaline developability is reduced by irradiation with actinic rays.
In contrast to the negative type in which the (exposure) part becomes the image part area, the developability is conversely
Improved, positive (exposed) area becomes a non-image area
Divided into two. As a negative recording layer, a known acid catalyst frame is used.
Bridge-based (including cationic polymerization) recording layer, polymerization-cured recording layer
Is mentioned. These are generated by light irradiation or heating.
Acid serves as a catalyst, and the compounds that make up the recording layer undergo a crosslinking reaction.
Raise and cure to form image area, or light irradiation
Or radicals generated by heating
The reaction proceeds and cures to form the image area.
The Further, as a positive recording layer, a known acid contact is used.
Decomposition system, o-quinonediazide compound-containing system, interaction
Release system (thermal positive) recording layer and the like. These are light
To acid and heat energy generated by irradiation and heating
As a result, the bonding of the polymer compound forming the layer is released.
It becomes soluble in water and alkaline water by the action of
To form a non-image portion. Less than
Hereinafter, each recording layer will be described in detail. 1. Negative type image recording layer 1-1. Polymerized hardened layer One of the negative recording layers is a polymerized and hardened layer.
This polymerized and hardened layer includes (A) an infrared absorber and (B) a radiator.
Cal generator (radical polymerization initiator) and generated radical
(C) radical polymerization that cures by causing a polymerization reaction
Preferably (D) binder poly
Contains mer. The infrared rays absorbed by the infrared absorber are used as heat.
The heat generated at this time is converted into a radiant such as an onium salt.
The cal polymerization initiator is decomposed to generate radicals. Radio
At least one ethylenically unsaturated compound
Has double bonds and at least terminal ethylenically unsaturated bonds
Are selected from compounds having 1, preferably 2 or more,
The generated radical causes a chain polymerization reaction and hard
Turn into. 1-2. Acid cross-linked layer Another aspect of the negative recording layer is an acid cross-linked layer.
I can get lost. The acid cross-linking layer (E) emits acid by light or heat.
The resulting compound (hereinafter referred to as an acid generator), (F)
A compound that crosslinks with the generated acid (hereinafter referred to as a crosslinking agent)
And a layer containing these is formed.
(G) Alkaline, which can react with a crosslinking agent in the presence of an acid
Contains water-soluble polymer compounds. In this acid cross-linked layer
Is generated by decomposition of the acid generator by light irradiation or heating.
Acid promotes the function of the cross-linking agent, and cross-linking agents or cross-linking
A strong cross-linking structure is formed between the agent and the binder polymer
As a result, the alkali solubility is reduced, and the developer
Becomes insoluble. At this time, the energy of the infrared laser
(A) Infrared absorption in the recording layer for efficient use
An agent is blended. For each compound used in the negative type image recording layer
This is described below. [(A) Infrared absorbing agent]
An image can be recorded with a laser that emits light. like this
To the image recording layer (hereinafter referred to as the recording layer as appropriate).
By using the infrared absorber according to Ming, high-sensitivity images
An image forming reaction can be performed. Total content of infrared absorber in the recording layer
The amount is from 0.01 to the total solid weight of the recording layer.
50% by mass is preferable, and 0.1-10% by mass is more preferable.
0.5 to 10% by mass is most preferable. In this range
High-sensitivity recording is possible in the non-image area.
High-quality image formation is possible without the occurrence of contamination. Na
Of these infrared absorbers, the characteristics of the present invention
The proportion of fixed infrared absorbers exceeds 60% by mass.
As mentioned above, it is preferable. [(B) Radical generator (radical polymerization initiation
Initiator)] Radical generators are light, heat, or both
Generate radicals by energy, polymerizable unsaturated groups
A compound that initiates and accelerates the polymerization of a compound having
The As a radical generator applicable to the present invention, publicly known
Have a bond with small bond dissociation energy.
Can be selected and used, for example,
For example, a diazonium salt (SI Schlesinge
r, Photogr. Sci. Eng. , 18, 387
(1974), T.W. S. Bal etal, Polym
er, 21, 423 (1980), etc.), ammoni
Um salt (US Pat. No. 4,069,055, JP
Described in Japanese Patent Laid-Open No. 4-365049), phosphonium salts
(U.S. Pat. Nos. 4,069,055 and 4,069,0)
56), iodonium salts (European special
Permit 104,143, U.S. Pat. No. 339,049,
Nos. 410 and 201, JP-A-2-1508
48, JP-A-2-296514, etc.
), Sulfonium salts (European Patent No. 370,693,
390, 214, 233, 567, 297,
No. 443, No. 297,442, US Pat. No. 4,93
3,377, 161,811, 410,201
No., No. 339,049, No. 4,760,013, No.
4,734,444, 2,833,827, Germany
Patent Nos. 2,904,626 and 3,604,580
, No. 3,604,581)
Rusonium salt (C. S. Wen et al, Teh, P
roc. Conf. Rad. Curing ASIA,
p478 In Tokyo, Oct (1988)
), Selenonium salt (JV Crivello e)
tal, Macromolecules, 10 (6),
1307 (1977), J. MoI. V. Crivello e
tal, J.M. Polymer Sci. , Polyme
r Chem. Ed. , 17, 1047 (1979) etc.
Onium salts such as Iminosulfonate (European Patent No. 19
9,672, 84,515, 44,115,
No. 101,122, US Pat. No. 4,618,564
No. 4,371,605, No. 4,431,774
, JP-A 64-18143, JP-A 2-2
No. 45756, JP-A-4-365048, etc.
Description), ester having o-nitrobenzyl type protecting group
Compound (European Patent Nos. 290,750 and 46,083)
No., No. 156, 535, No. 271, 851, No. 38
No. 8,343, US Pat. No. 3,901,701,
No. 4,181,531, JP-A-60-198
538, JP-A-53-133022, etc.
), Hexaarylbiimidazole (Japanese Patent Publication No. 47-2)
528, JP 54-155292 A, etc.
), Cyclic cis-α-dicarbonyl compounds (JP-A-48).
-84183, etc.), cyclic triazine
Described in Japanese Laid-Open Patent Publication No. 54-151024), Biimidazo
(Described in JP-A-59-140203), organic
Peroxides (Japanese Patent Laid-Open Nos. 59-1504 and 59-1402)
03, 59-189340, 62-17420
No. 3, Japanese Patent Publication No. 62-1641, US Patent No.
No. 4,766,055 etc.), organic halogen
Compound (Japanese Patent Laid-Open No. 63-258903, Japanese Patent Laid-Open No. 2-63)
054), organometallic / organic halogen
Compounds (described in JP-A-2-161445), Borate compounds (Japanese Patent Laid-Open No. 62-14304)
No. 4, No. 62-150242, No. 64-13140
No., No. 64-13141, No. 64-13142, No.
64-13143, 64-13144, 64-64
17048, JP-A-1-229003, 1-29
No. 8348, No. 1-138204, No. 11-8464
7), thiol compounds (Japanese Patent Laid-Open No. Sho 59)
Described in JP-A-140203), disulfone compounds
(Described in Japanese Patent Application Laid-Open No. 61-166544), titano
Sen compounds (Japanese Patent Laid-Open Nos. 59-152396 and 61-1)
51197, JP-A-4-219756, 4-22
1958, 6-295061, 8-33489
7, JP 2000-147663 A, 2000-4
2524), iron-arene cast (special feature)
Public officials of Kaihei 1-304453 and 1-152109
And organic boric acid compounds (Japanese Patent Laid-Open No. 62-143).
No. 044, No. 62-150242, No. 64-1314
No. 0, No. 64-13141, No. 64-13142,
64-13143, 64-13144, 64
-17048, JP-A-1-229003, and 1-29
No. 8348, No. 1-138204, No. 11-8464
7) Organic boron sulfonium complex or organic boron
Elementary oxosulfonium complex (JP-A-6-157623)
No., No. 6-175564, No. 6-175561
Described in Japanese Patent Laid-Open Publication No. 2005-111, etc.), organoboron iodonium complex
6-175554, 6-175553, etc.
), Organoboron phosphonium complexes (JP-A-9-1)
88710), organoboron transition metal coordination
Complexes (JP-A-6-348011, 7-128785)
No. 7-140589 No. 7-306527 No. 7
7-292014), and the like.
Functional groups or compounds that generate these radicals
Preferred examples include compounds introduced into the main chain or side chain of the mer.
For example, US Pat. No. 3,849,137
No. 3, German Patent No. 3,914,407, JP, JP,
Sho 63-26653, 55-164824, 6
2-69263, 63-146037, 63-
No. 163452, No. 62-153853, No. 63-1
Examples thereof include compounds described in each publication of No. 46029. In the present invention, a laser used particularly preferably.
Examples of the dical generator include onium salts.
Are represented by the following general formulas (i) to (iii)
Salt. [0087] Embedded image In the formula (i), Ar¹And Ar²Each
The number of carbon atoms which may have a substituent is 20 or less.
An aryl group of This aryl group has a substituent
Preferred substituents in this case include halogen atom, nitro
Group, alkyl group having 12 or less carbon atoms, 1 carbon atom
2 or less alkoxy groups or 12 or less carbon atoms
An aryloxy group is mentioned. Z^1-Is an inorganic anion
Or represents an organic anion. In formula (ii), Ar^ThreeHas a substituent
And an aryl group having 20 or less carbon atoms.
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group having 12 or less atoms and 12 or less carbon atoms
Lower alkoxy group, arylo having 12 or less carbon atoms
Xyl group, alkylamino group having 12 or less carbon atoms, charcoal
Dialkylamino group with up to 12 atoms and carbon atoms
12 or fewer arylamino groups or 12 carbon atoms
The following diarylamino groups are mentioned. Z^2-Is Z^1-When
Represents a synonymous counter ion. In the formula (iii), R¹, R²And R^ThreeThe
Each may be the same or different and has a substituent.
And a hydrocarbon 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
Or an aryl having 12 or less carbon atoms
An oxy group is mentioned. Z^3-Is Z^1-Counter ion synonymous with
Represent. Z in the general formulas (i) to (iii)^1-,
Z^2-, Z^3-Represents an inorganic or organic anion
However, as an inorganic anion, halogen ion F^-, C
l^-, Br^-, I^-), Perchlorate ion (ClO)_Four ^-)
Boronate ion (BrO_Four ^-), Tetrafluoroborate
Ion (BF_Four ^-), SbF₆ ^-, PF₆ ^-Etc.
Organic anions include organic borate anions and sulfones.
Acid ion, phosphonate ion, carboxylate ion, R^Four
-SO₂ ^-, R^Four-SO₂S^-, R^Four-SO₂N^--YR^FourB
On (where R^FourIs alkyl having 1 to 20 carbon atoms
Represents a group or an aryl group having 6 to 20 carbon atoms, Y
Is a single bond, -CO-, -SO₂-Represents. ),as well as,
The pentacoordinate silane compound Io represented by the following general formula (iv)
And the like. Where R^FourHas a ring structure
The alkyl group and aryl group may further have a substituent.
May be. Specific examples of the substituent that can be introduced here include
For example, alkyl group, alkoxy group, alkenyl
Group, alkynyl group, amino group, cyano group, hydroxyl group, halo
Gen atom, amide group, ester group, carbonyl group, cal
And the like, and these are further substituted as described above.
It may have a substituent. 2 or more substitutions
The groups may combine with each other to form a ring, and the ring structure is nitrogen.
It may be a heterocyclic structure containing atoms, sulfur atoms, etc.
Yes. Above all, from the viewpoint of synthesis suitability, R^FourIs an aryl group
It is preferable that As the organic borate anion, JP-A-9
General formula (I) and general formula described in JP-A-188685
And a compound represented by (I '). Sulfonic acid
As on, the paragraph of JP-A-11-143064
Compounds described in the numbers [0025] to [0027]
It is done. Examples of phosphonate ions include aliphatic phosphonic acids
Ions (for example, aliphatic, methane, ethane,
Lopan, butane, hexane, octane, decane, dodeca
, 2-ethoxyethane, cyclohexane, 2-pheny
Rumethane, etc.), aromatic phosphonate ion (aromatic and
Benzene, naphthalene, methylbenzene, metho
Compounds such as xylbenzene, fluorobenzene, etc.)
I can get lost. Carboxylate ions are aliphatic carboxylic acids or
Is an aromatic carboxylic acid, monocarboxylic acid or poly
Any of carboxylic acids may be used. Specifically, JP-A-200200
Nos. 1-334374, paragraph numbers [0048] to [00]
57] and the like. [0093] Embedded image In general formula (iv), A, B, C, D and E are
Represents monovalent nonmetallic atoms (groups) independent of each other. Where
A, B, C, D, and E are independent monovalent nonmetallic atoms.
(Group), preferably hydrogen atom and carbon, respectively
An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms
Group, alkenyl group, alkynyl group, alkoxy group,
Noxy group, amino group, vinyl group, allyl group, cyano group or
Represents a halogen atom. One more of these groups
Or may have two or more substituents.
Examples of the substituent include halogen atoms and those having 1 to 8 carbon atoms.
Linear or branched alkyl group, aryl group, alkeni
Group, carbonyl group, carboxyl group, amide group,
Til, ether, thioether, ester,
Mino groups, or combinations of two or more of these
It is done. Two or more non-adjacent ones of A, B, C, D and E
Metal atoms (groups) may be connected to each other to form a ring.
Of these five-coordinate silane compound ions, preferred
As for any of A, B, C, D, E is halogen
Atom, aryl group, or alkoxy group
And more preferably, A, B, C, D, E
Compound ion in which any one or more of them are fluorine atoms
Can be mentioned. In the present invention, it can be suitably used.
Specific examples of the onium salt include JP-A-2001-133.
No. 696, paragraph numbers [0030] to [0033]
What has been described can be mentioned. 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
Lithographic printing by setting the absorption wavelength to the ultraviolet region
The original plate can be handled under white light. Only one kind of these radical generators is used.
Or two or more of them may be used in combination. These la
The dical generator is 0.1% of the total solid content of the recording layer coating solution.
To 50% by weight, preferably 0.5 to 30% by weight, particularly preferred
Preferably it can be added at a rate of 1-20% by mass
The High-sensitivity recording is achieved within the above range.
In addition, the occurrence of smudges in the non-image area during printing is suppressed.
It is. Also, these radical generators are not necessarily image recording.
It does not have to be added to the recording layer, and it is installed adjacent to the image recording layer.
It may be added to another layer. [(C) Radical polymerizable compound] In this embodiment,
There are few radical polymerizable compounds used in the recording layer.
Radius with at least one ethylenically unsaturated double bond
It is a cal-polymerizable compound and has a terminal ethylenically unsaturated bond.
From compounds having at least one, preferably two or more
To be elected. Such compounds are widely used in the industry.
In the present invention, these are particularly known.
It can be used without limitation. These are, for example, mono
Polymers, prepolymers, ie dimers, trimers and oligos
Sesame, or a mixture thereof and a copolymer thereof.
Any chemical form. Examples of monomers and their copolymers
As unsaturated carboxylic acids (eg acrylic acid,
Tacrylic acid, itaconic acid, crotonic acid, isocroton
Acid, maleic acid, etc.), its esters and amides
Preferably, unsaturated carboxylic acid and aliphatic polyvalent
Esters with alcohol compounds, unsaturated carboxylic acids and fats
Amides with aliphatic polyvalent amine compounds are used. Further, hydroxyl group, amino group, mel
An unsaturated carboxylic acid having a nucleophilic substituent such as a capto group.
Steal, amides and monofunctional or polyfunctional isocyanates
Addition reaction with epoxy, epoxy, monofunctional or polyfunctional
Also suitable for use are dehydration condensation products with functional carboxylic acids.
It is. Electrophilic groups such as isocyanate groups and epoxy groups
Unsaturated carboxylic acid ester or amide having a functional substituent
Monofunctional or polyfunctional alcohols, amines
And addition reaction products with thiols, halogen groups and
Unsaturated carboxylic acid having a leaving substituent such as siloxy group
Acid esters or amides and monofunctional or polyfunctional amides
Substitution reaction products with alcohols, amines and thiols
Is preferred. Another example is the unsaturated carbo described above.
Instead of acid, place it in unsaturated phosphonic acid, styrene, etc.
It is also possible to use different compound groups. Forming unsaturated carboxylic acid and ester monomer
Specific examples of the aliphatic polyhydric alcohol compound to be formed include
Ethylene glycol, triethylene glycol, 1,3
-Propanediol, 1,3-butanediol, tetra
Methylene glycol, propylene glycol, neopen
Til glycol, trimethylolpropane, trimethylo
Ethane, hexanedio, 1,4-cyclohexanedi
All, pentaerythritol, dipentaerythritol
Sorbitol, tri (2-hydroxyethyl) iso
Cyanurate, bis [p- (3-hydroxypropoxy
B) phenyl] dimethylmethane, bis [p- (3-hydride)
Roxyethyloxy) phenyl] dimethylmethane, etc.
I can get lost. However, trihydric or higher alcohol compounds are molecules
Contains at least two polymerizable unsaturated groups
Any of them may be used. As a specific example, JP
Paragraph No. [0037] of Japanese Patent Laid-Open No. 2001-133696
~ [0042] etc. can be mentioned
The Forming amino monomers with unsaturated carboxylic acids
Specific examples of the aliphatic polyamine compound to be used include methyl
Diamine, ethanediamine, propanediamine, teto
Ramethylene diamine, hexamethylene diamine, diethyl
Rentriamine, xylylenediamine, cyclohexane
Examples thereof include dimethylamine. Examples of other esters include, for example, special
Kosho 46-27926, JP-B 51-47334, JP
Aliphatic alcohol-based esthetics described in Sho 57-196231
JP-A-59-5240, JP-A-59-524
1, having an aromatic skeleton described in JP-A-2-226149
Containing an amino group described in JP-A-1-165613
What is used is also suitably used. In addition, other preferred amide monomers
Examples of the cyclohexane described in JP-B-54-21726
The thing which has a xylene structure can be mention | raise | lifted. As another example, Japanese Patent Laid-Open No. 48-417.
In the molecule described in No. 08, two or more i.e.
To the polyisocyanate compound having a socyanate group,
A vinyl monomer having a hydroxy group is disabled 1
Vinylure having two or more polymerizable vinyl groups in the molecule
Tan compounds, JP 51-37193 A
Urethanes as described in Japanese Patent No. 2-332293
Acrylates, JP-B 58-49860, JP-B 5
6-17654, Shoko 62-39417, Shoko
Ethylene oxide described in each publication of No. 62-39418
Urethane compounds having a skeleton, JP-A-48-64
183, Shoko 49-43191, Shoko 52-3
Polyester as described in each publication of No. 0490
Acrylates, epoxy resins and (meth) acrylic acid
Multifunctional such as epoxy acrylates reacted with
Mention may be made of (meth) acrylates. Furthermore, the day
This Adhesion Association Vol. 20, no. 7, p. 300-3
08 (1984) with photocurable monomers and oligomers
You can also use what has been introduced. 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 is good, and different functional numbers and different polymerizable groups
(E.g., acrylic ester compounds)
, 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
Highly hydrophobic compounds are excellent in sensitivity and film strength,
Preferred in terms of development speed and precipitation in developer
There may be no. Also, other components in the recording layer (e.g.
Compatibility with inder polymers, initiators, colorants, etc.)
How to select and use radically polymerized compounds
Important factors such as the use of low purity compounds,
Compatibility with more than one species can improve compatibility
There is. Adhesiveness of support, overcoat layer, etc.
A specific structure may be selected for the purpose of improving
obtain. For the mixing ratio of radically polymerizable compounds in the image recording layer
In terms of sensitivity, the greater the number, the better the sensitivity.
In some cases, undesirable phase separation occurs or the image recording layer
Problems in the manufacturing process due to adhesiveness (for example, recording layer components
Manufacturing defects due to transfer and adhesion) and deposition from developer
This may cause problems such as From these viewpoints, radically polymerizable compounds
The preferred blending ratio is often based on the total composition
5 to 80% by mass, preferably 20 to 75% by mass
The These may be used alone or in combination of two or more.
Good. In addition, the usage of radical polymerizable compounds is
Of polymerization inhibition for silicon, resolution, fogging, refractive index
Appropriate structure, blending, addition from the viewpoint of change, surface tackiness, etc.
The amount can be selected arbitrarily, and depending on the case, it may be an undercoat or topcoat
A layer structure and a coating method such as can also be implemented. [(D) Binder polymer]
In the image recording layer, it is further updated from the viewpoint of improving the film properties of the recording layer.
It is preferable to use a binder polymer for
It is preferable to use a linear organic polymer as the binder.
Yes. Which of these “linear organic polymers” is
You can use it. Preferably water development or weak arc
To enable re-water development, water or weak alkaline water is acceptable.
A linear organic polymer that is soluble or swellable is selected.
Linear organic polymer forms a film to form a recording layer
Water, weak alkaline water or organic solvent
It is selected and used according to the application as a developer. For example,
When a water-soluble organic polymer is used, water development becomes possible.
Such linear organic polymers include carboxylic acids in the side chain.
Radical polymers having acid groups, for example, JP-A-59-44
No.615, No.54-34327, No.58-1
No. 2577, Japanese Examined Patent Publication No. 54-25957, Japanese Unexamined Patent Publication No. 54-
No. 92723, JP-A-59-53836, JP-A-59
-71048, that is, meta
Crylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer
Polymer, crotonic acid copolymer, maleic acid copolymer, part
For example, a partially esterified maleic acid copolymer. Similarly
Acidic cellulose derivatives with carboxylic acid groups in the side chain
The In addition, a cyclic acid anhydride is attached to a polymer having a hydroxyl group.
Those added are useful. Of these, in particular benzyl or allyl
And (meth) acrylic having a carboxyl group in the side chain
The resin has an excellent balance of film strength, sensitivity, and developability.
It is preferable. Also, Japanese Patent Publication No.7-12004 and Japanese Patent Publication No.7
-120041, JP 7-120042, JP
8-12424, JP 63-287944, JP
Sho 63-287947, JP-A 1-271744,
Contains acid groups as described in JP-A-11-352691
Urethane-based binder polymer is extremely strong
Since it is excellent, it is advantageous in terms of printing durability and suitability for low exposure. 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. The weight average content of the polymer used in the present invention
The amount of the child is preferably 5,000 or more, and
Preferably it is in the range of 10,000 to 300,000, and the number average molecular weight is
About 1,000 or more is preferable, and more preferable
The range is from 2,000 to 250,000. Polydispersity (weight
(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,
Either block polymer or graft polymer
Yes. The binder polymer used in the present invention is
They may be used alone or in combination. These polymers
Is 20 to 95% by mass with respect to the total solid content of the recording layer coating solution,
Preferably, it is added to the recording layer in a proportion of 30 to 90% by mass.
It is. When the added amount was less than 20% by mass, an image was formed.
At this time, the strength of the image portion is insufficient. The amount added is 95% by mass.
If it exceeds, no image is formed. Also radical polymerization
Linear with compounds with possible ethylenically unsaturated double bonds
The organic polymer is in the range of 1/9 to 7/3 by weight.
Is preferred. Next, the components of the acid cross-linked layer will be described.
The The infrared absorber used here is related to the present invention.
(A) The same infrared absorber can be used.
The The preferred content is based on the total solid weight of the recording layer.
0.01-50 mass% is preferable, 0.1-10 mass%
Is more preferable, and 0.5 to 10% by mass is most preferable.
Yes. In the range of the content, highly sensitive recording is achieved.
Furthermore, stains in the non-image area of the resulting lithographic printing plate
Is suppressed. [(E) Acid generator] In this embodiment
An acid generator that decomposes by heat to generate an acid is 200
Irradiate light in the wavelength region of ~ 500 nm or 100 ° C or higher
It refers to a compound that generates an acid when heated upward.
Examples of the acid generator include a photo-initiator for photo-cationic polymerization, light
Photoinitiator for radical polymerization, photodecolorant for dyes, photochromic
Known for use in chemicals or microresists
Known compounds that can generate acid by thermal decomposition
Products and mixtures thereof. For example, onium salts, hexaarylbiy
Midazole compounds, organohalogen compounds, organometallic / existing
Halogen compounds, organic boric acid compounds, o-nitroben
Jyl-type protecting group-containing ester compound, iminosulfonate
Compounds, disulfone compounds, organoboric acid / onium salts
Compounds such as complexes, or groups or compounds that generate these acids
Compound in which compound is introduced into main chain or side chain of polymer
Etc. Specifically, (B) radical generation
The same compounds as the publicly known materials described in the explanation of the agent are listed.
I can get lost. Of the above acid generators, the following general formula (1)
The compound represented by (5) is preferable. [0118] Embedded image In the general formulas (1) to (5), R¹, R²,
R^FourAnd R^FiveMay be the same or different and
It represents a hydrocarbon group having 20 or less carbon atoms which may have.
R^ThreeIs a halogen atom or an optionally substituted carbon
A hydrocarbon group having a carbon number of 10 or less or an alkoxy having a carbon number of 10 or less
Represents the Si group. Ar¹, Ar²Can be the same or different
Well, an ant having 20 or less carbon atoms which may have a substituent
Represents an alkyl group. R⁶Is an optionally substituted carbon
This represents a divalent hydrocarbon group having a number of 20 or less. n is 0-4
Represents an integer. In the above formula, R¹, R², R^FourAnd R^FiveThe carbon
A hydrocarbon group having 1 to 14 is preferable. Acid generation represented by the general formulas (1) to (5)
A preferred embodiment of the crude agent is disclosed in Japanese Patent Application Laid-Open No.
Paragraph No. [0197] of Japanese Patent Laid-Open No. 2001-142230
To [0222] as compounds of general formulas (I) to (V)
It is described in detail. Further, (E) an onium salt as an acid generator
Can also be preferably used. Among onium salts,
Preferably, iodonium salt, sulfonium salt, diazo
Examples thereof include nium salts. Such onium salts are disclosed in JP
No. 10-39509, paragraph number [0010] to
[0035] are compounds of general formulas (I) to (III).
It is described. The amount of the acid generator added is the total solid content of the recording layer.
0.01-50 mass% is preferable with respect to the part weight,
1 to 25% by mass is more preferable, and 0.5 to 20% by mass is more preferable.
Most preferred. The addition amount is less than 0.01% by mass
The image may not be obtained, exceeding 50% by mass.
Then, when printing a lithographic printing plate precursor,
Part may become dirty. The above acid generator is independent
May be used in combination with two or more
Good. [(F) Crosslinking agent] Next, the crosslinking agent will be explained.
Light up. The following are mentioned as a crosslinking agent. (I) Hydroxymethyl group or alkoxymethyl group
Aromatic compounds substituted with (Ii) N-hydroxymethyl group, N-alkoxymethyl
Compound having a ru group or N-acyloxymethyl group (Iii) Epoxy compound In the following, the compounds (i) to (iii) will be described.
The details will be described. Said (i) hydroxymethyl group
Is an aromatic compound substituted with an alkoxymethyl group
Is, for example, hydroxymethyl group, acetoxymethyl
Group or polysubstituted with alkoxymethyl groups
An aromatic compound or a heterocyclic compound is mentioned. However,
Phenols and aldehydes known as sol resins
Including resin-like compounds obtained by condensation polymerization under basic conditions
It is. The hydroxyl group or alkoxymethyl group
Among the substituted aromatic compounds or heterocyclic compounds,
Above all, hydroxymethyl at the position adjacent to the hydroxy group.
A compound having an alkyl group or an alkoxymethyl group is preferred.
Yes. Also aromatics polysubstituted with alkoxymethyl groups
Among the compounds or heterocyclic compounds, among others, alkoxymethyl
A compound having a ru group of 18 or less carbon atoms is preferred. Specifically
Is, for example, the paragraph of JP 2000-267265 A
Numbers described in the numbers [0077] to [0083]
Compounds of the general formulas (8) to (11) are mentioned. (Ii) N-hydroxymethyl group, N
-Alkoxymethyl group or N-acyloxymethyl
As a compound having a ruthenium group, European patent publication (hereinafter referred to as
Shown as “EP-A”. No. 0,133,216, West Germany
Patent Nos. 3,634,671 and 3,711,264
Monomers and oligomers described in each specification of No.
-Melamine-formaldehyde condensates and urea-forms
Mualdehyde condensate, EP-A 0,212,482
Examples include alkoxy-substituted compounds described in the specification
It is done. Among them, for example, at least two free N-hys
A droxymethyl group, an N-alkoxymethyl group, or
Melamine-former with N-acyloxymethyl group
Rudehydr derivatives are preferred, N-alkoxymethyl derivatives
The body is most preferred. As the (iii) epoxy compound,
Monomers, dimers, or monomers having one or more epoxy groups
Examples include ligomers and polymeric epoxy compounds.
For example, the reaction between bisphenol A and epichlorohydrin
Product, low molecular weight phenol-formaldehyde resin and
Examples include reaction products with epichlorohydrin. So
In addition, US Patent No. 4,026,705, British Patent No.
Epochs described in each specification of 1,539,192
Mention may be made of xyresins. As the crosslinking agent, the above (i) to (iii)
The amount added when using a compound is the total solids of the recording layer.
5-80 mass% is preferable with respect to the part weight, 10-75 quality
% By weight is more preferred, and 20 to 70% by weight is most preferred.
Yes. When the addition amount is less than 5% by mass, an image to be obtained is obtained.
The durability of the recording layer of the image recording material may be reduced.
If it exceeds 0% by mass, the stability during storage may decrease.
is there. In the present invention, as a crosslinking agent, JP-A-2
No. 000-267265, paragraph number [0088] to
[0097] represented by the general formula (12) described in [0097]
Phenol derivatives that can be used are also suitable. [(G) Alkali water soluble polymer compound]
Alkaline water soluble that can be used in the crosslinked layer applicable to the present invention
As a functional polymer compound, a novolac resin or a side chain has a hydride.
Examples thereof include a polymer having a roxyaryl group. Previous
As the novolak resin, phenols and aldehydes
And resins obtained by condensing the compounds under acidic conditions. Among them, for example, phenol and formal
Novolac resin obtained from Dehydr, m-cresol and
Novolac resin, formaldehyde obtained from formaldehyde
Novolac tree derived from resole and formaldehyde
From oil, o-cresol and formaldehyde
Borak resin, octylphenol and formaldehyde
Novolak resin obtained from m- / p-mixed creso
Novolac resin obtained from
Enol / cresol (m-, p-, o- or m- / p
-, M- / o-, o- / p-mixed)
Novolac resin obtained from mixture and formaldehyde
And using phenol and paraformaldehyde as raw materials,
Obtained by reaction under high pressure in a sealed state without using a catalyst
High molecular weight novolac resin with high ortho bond rate is preferred
Yes. The novolac resin has a weight average molecular weight of 800 to
300,000 and a number average molecular weight of 400-60,00
Select a suitable one according to the purpose from zero
Use it. Further, a hydroxyaryl group is added to the side chain.
Also preferred is a polymer having hydroxy in the polymer
As the aryl group, aryl having one or more OH groups bonded thereto
Groups. Examples of the aryl group include fluorine.
Enyl, naphthyl, anthracenyl, phenant
Renyl group etc. are mentioned, among others, availability and physical properties
From this viewpoint, a phenyl group or a naphthyl group is preferable. ~ side
Specific examples of polymers having a hydroxyaryl group in the chain
The paragraph number of JP 2000-142230 A
It is described in detail in [0130] to [0163]
Things. Alkaline water soluble polymer
A compound may be used in only one type, or two or more types
You may use it in combination. Addition amount of alkaline water-soluble polymer compound and
Therefore, 5 to 95% by mass is preferable with respect to the total solid content of the recording layer.
10 to 95% by mass is more preferable, and 20 to 90 quality.
The amount% is most preferred. Addition amount of alkaline water soluble resin
In this range, the durability of the recording layer and image formation
Good properties are maintained. In addition, a public application to which the method of the present invention can be applied.
As a known recording material, JP-A-8-276558 is disclosed.
Negative type image recording material containing the phenol derivative described in
And diazonium described in JP-A-7-306528
Negative-type recording material containing a sulfur compound, JP-A-10-20
There is an unsaturated bond in the ring described in Japanese Patent No. 3037
By using an acid-catalyzed polymer having a heterocyclic group
Examples include negative-type image-forming materials that use a crosslinking reaction.
The recording layer described in these is a negative recording in the present invention
It can be applied to an acid cross-linked layer as a layer. [Other components] Such a negative image
In addition to these, various other compounds may be added to the recording layer as required.
Things may be added. For example, a large absorption in the visible light range
The dye possessed can be used as an image colorant.
Also, phthalocyanine pigments, azo pigments, carbon
Pigments such as racks and titanium oxide can also be used suitably.
Yes. These colorants are used for image areas and non-images after image formation.
Since it is easy to distinguish the parts, it is preferable to add them. Na
The amount added is 0.01 with respect to the total solid content of the recording layer coating solution.
It is a ratio of -10 mass%. In the present invention, the recording layer is polymerized hard.
In the case of coating layer, during preparation or storage of coating solution
Has radically polymerizable ethylenically unsaturated double bonds
A small amount of thermal polymerization protection to prevent unwanted thermal polymerization of compounds
It is desirable to add a stopper. With a suitable thermal polymerization inhibitor
P-methoxyphenol, di-t-butyl-p
-Cresol, t-butylcatechol, benzoquinone,
4,4'-thiobis (3-methyl-6-t-butylphenol
Nol), 2,2'-methylenebis (4-methyl-6-
t-butylphenol), N-nitroso-N-phenyl
Examples include hydroxylamine aluminum salts. heat
The addition amount of the polymerization inhibitor is about 0. 0 with respect to the weight of the total composition.
01% by weight to about 5% by weight is preferred. Also if necessary
In order to prevent polymerization inhibition by oxygen, behenic acid and
Add higher fatty acid derivatives such as henoamide,
It may be unevenly distributed on the surface of the recording layer during the drying process after coating.
Yes. The amount of higher fatty acid derivative added is about 0.1% of the total composition.
From mass% to about 10 mass% is preferred. In the recording layer coating solution of the present invention,
In order to widen the stability of processing with respect to development conditions,
In Sho 62-251740 and JP-A-3-208514
Nonionic surfactants as described, JP 59
No.-121044 and JP-A-4-13149
Amphoteric surfactants can be added. As specific examples of the nonionic surfactant,
Rubitan tristearate, sorbitan monopalmitate
, Sorbitan triolate, monoglyceride stearate
Lido, polyoxyethylene nonylphenyl ether, etc.
Can be mentioned. As specific examples of the amphoteric surfactant,
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 Nonionic surfactant and amphoteric surfactant
The proportion of the agent in the recording layer coating solution is 0.05 to 15 quality.
% By weight is preferred, more preferably 0.1 to 5% by weight.
The Furthermore, in the recording layer coating solution of the present invention,
Is plasticized to give the film flexibility, etc.
The agent is added. For example, polyethylene glycol,
Tributyl enoate, diethyl phthalate, dibuty phthalate
, Dihexyl phthalate, dioctyl phthalate, phosphoric acid
Tricresyl, tributyl phosphate, trioctyl phosphate
, Tetrahydrofurfuryl oleate, etc.
The In order to produce the planographic printing plate precursor of the present invention,
Normally, the above components required for the recording layer coating solution are dissolved in a solvent.
Then, it may be coated on a suitable support. In the solvent
The concentration of the minute (total solid content including additives) is preferably 1 to
50% by mass. Further, the description on the support obtained after coating and drying.
The recording layer coating amount (solid content) varies depending on the application, but it is a lithographic plate.
Generally speaking, the printing plate precursor is 0.5 to 5.0 g /
m²Is preferred. As the amount applied decreases, it looks
However, the sensitivity of the recording layer that performs the image recording function
Film properties are reduced. 2. Positive image recording layer As a positive-type image recording layer, an interaction cancellation system (thermal
Di), o-quinonediazide compound-containing systems, etc.
The The order will be described below. 2-1. Interaction cancellation system (thermal positive) The interaction release system is described below as (H) water-insoluble and
Lucari water soluble polymer, and (B) radical generator
(B ')
And (A) infrared absorption according to the present invention
Contains the agent. In such a recording layer, (B ′) onium salt
Compound and (H) A in water-insoluble and alkali-soluble resin
Alkaline in the recording layer due to the interaction with
Resistant to aqueous solution, but exposed area (non-image
In the (image part) region, (A) by heat derived from the infrared absorber
(B ') The interaction of onium salt compounds by decomposition
Is released and the solubility in alkaline aqueous solution is improved.
An image is formed. [(H) Water-insoluble and alkali-soluble tree
Fat] (H) Water-insoluble and usable for positive recording layer
Lucari-soluble resin (hereinafter referred to as alkaline water-soluble resin as appropriate)
Called. ) As main chain and / or side chain in polymer
Homopolymers containing acidic groups, their copolymers or
These mixtures are included. Above all, the following (1) ~
(6) The acidic group listed in the main chain and / or side chain of the polymer
Has a solubility in an alkaline developer.
This is preferable in terms of expression of dissolution inhibiting ability. (1) Phenol group (2) Sulfonamide group (3) Substituted sulfonamide acid group (hereinafter referred to as “active imide”
It is called "base". ) [-SO₂NHCOR, -SO₂NHSO₂R, -CON
HSO₂R] (4) Carboxylic acid group (5) Sulfonic acid group (6) Phosphate group In the above (3), R may have a substituent.
An aliphatic group having 1 to 20 carbon atoms (for example, methyl
Group, ethyl group, propyl group, butyl group, hexyl group,
Cutyl group, decyl group, dodecyl group, linoleyl group, ben
Zyl group, phenethyl group, cyclohexyl group, cyclodeca
An aromatic group having 6 to 14 carbon atoms which may have a substituent.
Group (eg, phenyl, naphthyl, anthranyl)
Group, etc.), optionally having a substituent, oxygen atom, sulfur source
A single ring containing at least one of a child and a nitrogen atom
Heterocyclic groups having a cyclic structure or a polycyclic ring structure (for example,
Thienyl, pyranyl, pyridyl, pyrazyl,
Midazole group, carbazole group, thiazole group, benzo
Represents an oxazole group, an indoyl group, and the like. These are further
May have a substituent, and the substituent is particularly limited.
Although not specified, for example, a halogen atom, an alkyl group, an
Lucoxy group, alkenyl group, alkynyl group, amino group,
Cyano group, hydroxyl group, amide group, ester group, carboxy
Group, acyl group and the like. An acidic group selected from the above (1) to (6)
Among the alkaline water-soluble resins we have (1) Phenol
Group, (2) sulfonamide group and (3) active imide group
Alkaline water-soluble resin having a preferable and alkaline
Ensure sufficient solubility in developer, development latitude, and film strength.
It is most preferable from the viewpoint of securing minutes. An acidic group selected from the above (1) to (6)
Examples of the alkaline water-soluble resin having:
Things can be mentioned. (1) An alkaline water-soluble resin having a phenol group
For example, the degeneracy of phenol and formaldehyde
Polymerization, condensation polymerization of m-cresol and formaldehyde
Body, polycondensation product of p-cresol and formaldehyde,
Degeneracy of m- / p-mixed cresol and formaldehyde
Coalesce, phenol and cresol (m-, p-, or m-
/ P-mixed) and formaldehyde
Novolak resin such as condensation polymer, pyrogallol and aceto
A polycondensation polymer with Ton. Furthermore, Feno
A compound having an alcohol group in the side chain (for example, acrylic
, Methacrylamide, methacrylate, acrylic
Derivatives such as oxalic acid esters and crotonic acid esters)
Mention may also be made of combined copolymers. Or
Copolymer obtained by copolymerizing a compound having a nor group in the side chain
Can also be used. Weight average molecular weight of alkaline water soluble resin
Is 5.0 × 10²~ 2.0 × 10^FourAnd the number average molecular weight is
2.0 × 10²~ 1.0 × 10^FourThat is image-forming
This is preferable. Also, these resins are only used alone
Alternatively, two or more types may be used in combination. set
When combining, t-butylphenol and formaldehyde
Condensation polymer with aldehyde, alkyl group having 3 to 8 carbon atoms
Condensation of phenol and formaldehyde as a substituent
Polymer (described in US Pat. No. 4,123,279, etc.)
), Phenolic structure with electron-withdrawing group on aromatic ring
Alkali water-soluble polymer (Japanese Patent Laid-Open No. 2000-24)
1972) and the like may be used in combination. (2) Alkali having a sulfonamide group
Examples of water-soluble resins include sulfonamide groups.
The smallest structural unit derived from the compound
The polymer comprised by these can be mentioned. As above
Such compounds include at least one hydrogen atom on the nitrogen atom.
A sulfonamide group bonded with a dimer and a polymerizable unsaturated group
And compounds having one or more in the molecule.
The Among them, acryloyl group, allyl group, or vinyloxy
A substituted or monosubstituted aminosulfonyl group or a
Low molecular weight compound having a substituted sulfonylimino group in the molecule
Things are preferred. Such compounds include, for example, special
In General Publication No. 8-123029, general formula (I) to
The compound shown by (V) is mentioned. In the positive recording layer in the present invention, in particular,
m-aminosulfonylphenyl methacrylate, N-
(P-aminosulfonylphenyl) methacrylamide,
N- (p-aminosulfonylphenyl) acrylamide
Etc. can be used suitably. (3) Alkaline water having an active imide group
As the soluble resin, for example, JP-A-11-84657
Derived from compounds having an active imide group described in the publication
The weight composed of the smallest constituent unit as the main constituent
Coalescence can be mentioned. As a compound as above
Is polymerizable with an active imide group represented by the following structural formula
A compound having at least one unsaturated group in the molecule
Can be mentioned. [0153] Embedded image Specifically, N- (p-toluenesulfoni
) Methacrylamide, N- (p-toluenesulfoni
E) Acrylamide and the like can be preferably used. (4) Carboxylic acid group, (5) Sulfonic acid
Group or (6) an alkaline water-soluble resin having a phosphate group
For example, in one molecule, these acidic groups and heavy
A compound having at least one unsaturated group capable of being combined
Polymers whose main constituent is the smallest constituent unit
I can make it. Alkali water soluble tree used for positive recording layer
An acidic group selected from the above (1) to (6) that constitutes fat
The minimum structural unit with
2 or more minimum structural units having the same acidic group,
Or two or more minimum structural units with different acidic groups
Combined materials can also be used. The copolymer is copolymerized (1) to (1) to
The compound having an acidic group selected from (6) is in the copolymer
Are preferably contained in an amount of 10 mol% or more,
More preferably, it is contained in an amount of at least 1%. 10 mol%
If it is less than 1, development latitude can be improved sufficiently.
There is a tendency not to be able to. In addition, copolymerization of compounds
When using Lucari water soluble resin as a copolymer,
As the compound to be combined, the acidic groups of the above (1) to (6)
Other compounds not included can also be used. Alkaline water
Examples of soluble resins include exposure using infrared lasers.
U.S. Pat. No. 4,12 in that it has excellent image-forming properties with light.
Phenolic properties described in the specification of No. 3,279
Novolak resins having hydroxy groups, pyrogallol
Acetone resin is preferred. The alkali-soluble resin has a weight average molecule.
The amount is preferably 500 or more from the viewpoint of image formability.
More preferably 1,000 to 700,000
That's right. The number average molecular weight is 500 or more.
Is preferable, and is more preferably 750 to 650,000
preferable. Dispersity (weight average molecular weight / number average molecular weight) is
It is preferable that it is 1.1-10. Alkali solubility in a positive type image recording layer
Each of the resins may be contained alone or in combination of two or more.
The total content is 30 to 9 in the total solid content of the recording layer.
8% by mass is preferable, and 40 to 95% by mass is more preferable.
Yes. If the content is in the above range, durability, sensitivity, image shape
An image recording layer having excellent creativity can be obtained. [(A) Infrared Absorber] Such a positive type
Efficient interaction cancellation is achieved in the image recording layer
Therefore, it is important to use (A) an infrared absorber.
The Infrared absorption in positive image recording layer of interaction release system
The total amount of the collecting agent is 0. 0% in the total solid content of the recording layer.
01 to 50% by mass is preferable, and 0.1 to 10% by mass is preferable.
More preferable. If the content is in the above range, sensitivity, image shape
It becomes an image recording layer excellent in synthesizing properties. 2-2. o-quinonediazide compound-containing system As the o-quinonediazide compound-containing system,
No. 246171 and JP-A-6-230582
The o-quinonediazide compound described is made photosensitive.
And a positive recording layer containing as a component. [Other components] Such positive image recording
Other components in the recording layer are recorded with actinic radiation such as infrared rays.
The components of various known image recording materials that can be recorded are appropriately selected.
Can be used. Recording of planographic printing plate precursor of the present invention
Various additives can be added to the layer as needed.
it can. For example, other onium salts, aromatic sulfone compounds
, Aromatic sulfonate compounds, polyfunctional amination
When a compound is added, an alkaline water-soluble polymer developer
It is preferable because it can improve the dissolution inhibition function
Yes. Further, in order to further improve the sensitivity, an annular shape is used.
Use of acid anhydrides, phenols, and organic acids in combination
it can. Description of cyclic acid anhydrides, phenols and organic acids
The proportion in the recording layer is preferably 0.05 to 20% by mass.
More preferably 0.1 to 15% by weight, particularly preferably
Is 0.1 to 10% by mass. Besides these,
Epoxy compounds, vinyl ethers, and further, JP-A-8
It has a hydroxymethyl group described in JP-A-276558
Phenol compounds that have alkoxymethyl groups
Enol compounds, and JP-A previously proposed by the present inventors
Inhibition of alkali dissolution described in JP-A-11-160860
Add appropriate crosslinkable compounds depending on the purpose
can do. In the recording layer coating solution of the present invention, development is performed.
In order to broaden the stability of processing against conditions,
Various surfactants similar to those in the recording layer, siloxane
Add compounds, fluorine-containing monomer copolymers, etc.
be able to. In addition, a visible image is obtained immediately after heating by exposure.
Baking agents to obtain, dyes and face as image colorants
The same as the negative type recording layer can be added.
It is. The formation of the positive recording layer is the same as that of the negative recording layer.
Next, dissolve the recording layer coating solution in the desired solvent to obtain an appropriate support.
It can be manufactured by applying on the body. solvent
The concentration of the above components (total solids including additives) is preferred.
It is 1-50 mass%. Also obtained after coating and drying
The coating amount (solid content) on the support is generally 0.5.
~ 5.0 g / m²Is preferred. As application amount decreases
The apparent sensitivity increases, but the film characteristics of the recording layer
descend. [Platform having a negative or positive recording layer
Production of planographic printing plate precursor] The planographic printing plate precursor of the present invention is produced.
In general, each of the negative type and positive type recordings described above is used.
Dissolve each of the above components required for the layer coating solution in a solvent, and
What is necessary is just to apply | coat on a support body. The solvent used here is
Physically, for example, alcohols (methanol, ethanol
, Isopropanol, tetrahydrofurfuryl alcohol
Coal, diacetone alcohol, ethylene glycol,
Propylene glycol, ethylene glycol monomethyl
Ether, ethylene glycol monoethyl ether, 1
-Methoxy-2-propanol, etc.), hydrocarbons (torr
Ene, cyclohexane, etc.), halogenated hydrocarbons (d
Tylene chloride, etc.), ketones (acetone, acetyl)
Acetone, methyl ethyl ketone, methyl isobutyl keto
, Cyclohexanone, etc.), esters (ethyl acetate,
Methyl lactate, ethyl lactate, 2-methoxyethyl acetate
And 1-methoxy-2-propyl acetate), A
Tells (ethylene glycol dimethyl ether, diethyl)
Lenglycol dimethyl ether, propylene glycol
Rudiethyl ether), amides (dimethylacetoa)
Mido, dimethylformaldehyde, N-methylpyrrolide
), Γ-butyrolactone, dimethyl sulfoxide,
Appropriately selected from water and mixtures of these solutions
can do. In addition, the description on the support obtained after coating and drying.
Recording layer coating amount (solid content) varies depending on the application, but negative
Type or positive type lithographic printing plate precursor
As described above. As a method of applying, public
Various known coating methods can be applied.
Bar coater coating, spin coating, spray coating, car
Ten coating, dip coating, air knife coating, blade
Examples thereof include coating and roll coating. [Support] In the lithographic printing plate precursor according to the invention,
The negative or positive image recording layer can be applied.
Examples of the support include dimensionally stable plates, examples
For example, paper, plastic (eg, polyethylene, poly
Propylene, polystyrene, etc.) laminated paper,
Metal plate (eg, aluminum, zinc, copper, etc.), plus
Tick film (eg cellulose diacetate,
Roulose, cellulose propionate, cellulose butyrate,
Cellulose acetate butyrate, cellulose nitrate, polyethylene
Phthalate, polyethylene, polystyrene, polypro
Pyrene, polycarbonate, polyvinyl acetal
Etc.) The above metal was laminated or vapor-deposited
Examples include paper or plastic film. preferable
As the support, polyester film or aluminum
Plate. Support for use in the lithographic printing plate precursor according to the present invention
As a lightweight, excellent surface treatment, workability, and corrosion resistance
It is preferable to use an aluminum plate. For this purpose
The aluminum material provided is JIS 1050
Material, JIS 1100 material, JIS 1070 material, Al-M
g alloy, Al-Mn alloy, Al-Mn-Mg alloy
Gold, Al-Zr alloy. Al-Mg-Si alloy etc.
Can be mentioned. The surface of the aluminum plate is roughened.
Surface treatment is performed and a recording layer is applied to form a lithographic printing plate precursor
be able to. The roughening treatment includes mechanical roughening, chemical
Roughening and electrochemical roughening are performed alone or in combination.
It is. In addition, the anode to ensure the scratch resistance of the surface
Oxidation treatment or treatment to increase hydrophilicity
Both are 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 with organic solvent or alkaline aqueous solution
It may be broken. In the case of alkali, then with an acidic solution
Processing such as sum and smut removal may be performed. Next, the adhesion between the support and the recording layer is improved.
In order to provide water retention to the non-image area,
Roughening, so-called graining treatment has been made
The As a specific means of this graining method, sand
There are mechanical graining methods such as blasting, and alkaline
Or an etchant comprising an acid or a mixture thereof.
There is a chemical graining method that roughens the surface. Also,
Electrochemical graining method, bonding granular material to support material
The surface is roughened by bonding with an agent or a method that has its effect
Supports continuous belts and rolls with fine irregularities
Known methods such as roughening method for transferring unevenness by pressure bonding to body material
The method 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.
Are generally preferred. Of the aluminum support used in the present invention
In some cases, after the pretreatment as described above,
Anodizing to improve wear, chemical resistance and water retention
To form an oxide film on the support. Used for anodizing of aluminum plate
Any electrolyte that can form a porous oxide film
Anything can be used, generally sulfuric acid,
Phosphoric acid, succinic acid, chromic acid or a mixed acid of these is used
The The concentration of those electrolytes depends on the type of electrolyte.
It is decided. The anodizing treatment conditions depend on the electrolyte used.
Since it varies, it cannot be specified unconditionally.
Concentration of quality is 1-80% solution, liquid temperature is 5-70 ° C.
Degree 5-60A / dm², Voltage 1-100V, electrolysis time 1
It is appropriate if it is in the range of 0 seconds to 5 minutes. Of anodized film
The amount is 1.0g / m²The above is preferred, but more preferred
Is 2.0 to 6.0 g / m²Range. Anodized film
1.0g / m²If it is less than 1, the printing durability was insufficient.
As a result, the non-image part of the planographic printing plate is easily damaged and printed.
So-called “scratch stains” where ink sometimes adheres to the scratched area
It tends to occur. Such an aluminum support is an anodic acid.
Treatment with an organic acid or a salt thereof, or a recording layer
It can be used by applying an undercoat. Note that the adhesion between the support and the recording layer is improved.
An intermediate layer may be provided. For improved adhesion
In general, the intermediate layer is a diazo resin, such as aluminum.
It consists of phosphoric acid compounds adsorbed on the surface. Middle tier
Thickness is arbitrary and uniform with the upper recording layer when exposed
The thickness must be such that a proper bond formation reaction can be performed. Through
Usually about 1 to 100 mg / m dry solid²The application ratio of
5-40mg / m²Is particularly good. In the middle layer
The proportion of diazo resin used is preferably 30-100%
It is 60 to 100%. The surface of the support is treated as described above or
After coating, the back side of the support is
A back coat is provided. As such a backcoat
The organic polymer compound described in JP-A-5-45885
And organic or inorganic metals described in JP-A-6-35174
Metal oxides obtained by hydrolysis and polycondensation of compounds
A coating layer made of is preferably used. Preferred features as a support for a lithographic printing plate precursor
The centerline average roughness is 0.10 to 1.2 μm.
is there. In this range, adhesion to the recording layer and printing
This is because the soiling property of the film becomes good. Furthermore, the support table
Finely control the surface shape, for example,
It has a small triple uneven structure, and the wavelength of the large uneven structure is 3-10.
μm, medium uneven structure is the pit, and small uneven structure
It is preferable that the structure has the fine concavo-convex structure of the pit.
That's right. The support surface has an average opening diameter of 0.5 to 5 μm.
Medium wave structure and small wave structure with an average aperture of 0.01 to 0.2 μm
It is preferable to have a grain shape with a structure that overlaps with the structure.
Yes. By using these supports, the density of the recording layer is increased.
Improves adherence, maintains recording layer strength, and stain resistance during printing
Will be excellent. In addition, the color density of the support is
The degree value is preferably in the range of 0.15 to 0.65.
That's right. In this range, the halation during image exposure
Plate inspection after development without any obstacles to image formation.
This is because it can be performed without problems. As described above, the negative in the present invention.
A lithographic printing plate precursor having a positive or positive recording layer
Can be created. This lithographic printing plate precursor is infrared
Can be recorded with a laser. Also, UV lamps and thermal heads
Thermal recording by the head is also possible. In the present invention
Emits infrared light with a wavelength of 760 nm to 1200 nm
Image exposure by solid-state laser and semiconductor laser
And are preferred. The laser output is preferably over 100mW
In order to shorten the exposure time,
It is preferable to use a chair. Also, the dew per pixel
The light time is preferably within 20 μsec. Recording material
The energy irradiated to 10 to 300 mJ / cm²so
Preferably there is. 3. Non-processing type image recording layer The negative type or positive type image recording layer is used in the plate making process.
In general, development with an alkaline developer is required.
In short. On the other hand, as an image recording layer, image exposure was performed.
After that, install it in the printing machine without special wet development treatment,
Some can supply water and ink for printing,
This is referred to as an unprocessed image recording layer. Above all, image dew
After being exposed to light, it can be installed in a printing press without wet development and moistened.
Developing with water or ink is also called on-machine development.
The A lithographic printing plate having such an unprocessed image recording layer
The original plate (unprocessed planographic printing plate precursor) is transferred to a printing machine.
After applying, laser exposure on the printing press
It can also be printed. In either case, the ink
And start printing with dampening water, the initial stage of printing
In the surface hydrophilic region and surface hydrophobic region,
And ink are received or unnecessary thermal recording layer
And the exposed hydrophilic support surface is removed as soon as the photosensitive layer is removed.
Dampening water on the surface is the remaining recording layer area.
Ink fills the area and printing starts.
become. No treatment applicable to the lithographic printing plate precursor of the present invention
The physical image recording layer can be heated or irradiated with radiation.
(3-1) The hydrophobic / hydrophilic polarity of the image recording layer is changed.
For example, the irradiated part has a specific acidic group (phospho group,
(Ruho group, carboxy group) and become hydrophilic
Polarity conversion type image recording layer using-, (3-2) irradiated portion
Is a compound capable of forming a hydrophobic region (hereinafter, appropriately hydrophobized
Hydrophilic polymer matrix containing the precursor)
Or (3-3) ink reception
A layer and a hydrophilic layer are laminated in order, and the infrared laser exposure area
And the hydrophilic layer is peeled off and the ink receiving layer is exposed.
Image recording layer for image formation (interfacial peeling method recording described later)
Layer). 3-1. Polarity conversion type image recording layer In non-processing type image recording, is the polarity of the recording layer surface hydrophilic?
Hydrophobic, or image recording that converts from hydrophobic to hydrophilic
The recording layer can be illuminated, for example, by heating or irradiation with radiation.
The projectile moiety is a specific acidic group (phospho group, sulfo group, carboxyl group)
It has a polymer that generates hydrophilic groups or solubilizes
An image recording layer. Generate specific acidic groups to make them hydrophilic or soluble
As the polymer to be converted, a sulfonic acid generating type is preferable.
For example, it is described in JP-A-10-282672.
Listed sulfonic acid esters, disulfonic acid groups,
Is a side chain of sec- or tert-sulfonamide group
And the like. 3-2. Hydrophobized precursor-containing image recording layer As another non-process type image recording layer, the irradiated part is before hydrophobization.
Sense of hydrophilic polymer matrix containing precursor
A thermal recording layer is mentioned. The irradiated part is affected by thermal energy.
As a hydrophobizing precursor contained in a hydrosensitive recording layer
Is (a) a hydrophobic particulate polymer, or (b) a thermal reaction
A microcapsule enclosing a compound having a functional functional group
Can be mentioned. These were fused to each other by heating.
Or the inclusion may cause a chemical reaction by heat.
The image area, that is, the hydrophobic area (parent ink area)
Containing compounds that form, these are preferably hydrophilic
Image formation (dew
After light), install the lithographic printing plate precursor on the press cylinder
By supplying water, fountain solution and / or ink,
Capable of on-machine development without development processing
It becomes. (A) As the hydrophobic fine particle polymer,
Thermoplastic fine particle polymer, thermosetting fine particle polymer, heat
A reactive fine particle polymer is mentioned. (A) Hydrophobic fine
The particle polymer has an average particle size of 0.01 to 20 μm.
Preferably, it is 0.05 to 5.0 μm
Is more preferable. In this range, high-definition image formation
In addition, the stability of the particles over time is good. The thermoplastic fine particle polymer may be Res.
search Disclosure No. 33303 (1
January 1999), JP-A-9-123387, 9-13.
1850, 9-171249, 9-17125
No. 0 publication, European Patent Application Publication No. 931,647
The thermoplastic fine particle polymer described in the booklet is suitable.
It can be given as something. Thermosetting fine particle poly
As the polymer, a resin having a phenol skeleton, a urea-based tree
Fat (eg urea or urea such as methoxymethylated urea)
Derivatives with aldehydes such as formaldehyde
Oiled), alkyd resin, unsaturated polyester tree
Examples thereof include fats, polyurethane resins, and epoxy resins.
Among these, phenol is particularly preferable.
Resin having skeleton, melamine resin, urea resin and epoxy
SHI resin is mentioned. Of these fine particle polymers, particularly preferred.
The best one is heat-reactive fine particles with heat-reactive functional groups.
It is a polymer. Used for thermally reactive fine particle polymer
As the thermoreactive functional group, an ethylenic group that performs the polymerization reaction is used.
Saturated groups (e.g. acryloyl, methacryloyl,
Vinyl group, allyl group, vinyloxy group, etc.);
Isocyanate group to be performed or block body thereof, reaction phase thereof
A functional group having an active hydrogen atom in hand (eg amino
碁, hydroxy group, carboxy group, etc.); perform addition reaction
Epoxy group, amino group that is the reaction partner, carboxy
Group or hydroxy group;
Droxy group or amino group; acid anhydride for ring-opening addition reaction
And amino group or hydroxy group.
However, it has a function to form a chemical bond by heating.
Any functional group capable of performing any reaction may be used. Fine particles having such a heat-reactive functional group
Polymers include acryloyl groups and methacryloyl
Group, vinyl group, allyl group, vinyloxy group, epoxy
Group, amino group, hydroxy group, carboxy group, isocyanate
Have acid groups, acid anhydride groups, and groups protecting them
Can be mentioned. These base polymer grains
The introduction into the polymer may be performed at the time of polymerization, or may be performed after polymerization.
You may carry out using a child reaction. When introduced during polymerization
Emulsion polymerize monomers having these groups, or
It is preferable to perform turbid polymerization. In addition, introduction of heat-reactive functional groups
Examples of the polymer reaction used when
As described in the pamphlet of International Publication No. 96/34316
Can be mentioned. Specific examples of monomers having these groups
For example, paragraph number of JP 2001-293971 A
Nos. [0018] to [0035]
However, the present invention is not limited to these. These models
Monomers that do not have thermoreactive functional groups and can be copolymerized with monomers
Examples of mer include styrene and alkyl acrylate.
, Alkyl methacrylate, acrylonitrile, acetic acid
Vinyl etc. can be mentioned, but it has a heat-reactive functional group.
If it is a monomer which does not, it will not be limited to these. Heat
The solidification temperature of the fine particle polymer having a reactive functional group is 70.
It is preferable that the temperature is higher than or equal to ° C.
More preferably, the temperature is 00 ° C or higher. (A) Content of hydrophobic fine particle polymer
Is 50% by mass or more based on the total solid content of the heat-sensitive recording layer.
Preferably, there is more than 60% by mass
preferable. Ethylenically unsaturated group for polymerization reaction (polymerization)
Specific examples of compounds having an unsaturated group) are unsaturated
Carboxylic acids (eg acrylic acid, methacrylic acid, ita
Conic acid, crotonic acid, isocrotonic acid, maleic acid
Etc.), and its esters and amides are preferred,
Is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol.
Amines of tellurium and unsaturated carboxylic acids with aliphatic polyamines.
Do. Also, hydroxy group, amino group, mel
An unsaturated carboxylic acid having a nucleophilic substituent such as a capto group.
Steal or unsaturated rubonic acid amide and monofunctional or
Addition reaction product with polyfunctional isocyanate or epoxide,
And dehydration condensation reaction with monofunctional or polyfunctional carboxylic acid
A thing etc. are mentioned suitably. In addition, isocyanate groups,
Unsaturated carboxylic acid having electrophilic substituent such as poxy group
Esters or amides and monofunctional or polyfunctional alcohols
Addition reaction products with amines, amines and thiols, as well as halogens
Unsaturation with leaving substituents such as thione and tosyloxy groups
Carboxylic acid ester or amide and monofunctional or polyfunctional amide
Suitable for substitution reaction with alcohol, amine and thiol
Can be mentioned. As another preferred example, the above unsaturated
Carboxylic acid can be converted to unsaturated phosphone or chloromethyl
And compounds substituted with len. Unsaturated carboxylic acid and aliphatic polyhydric alcohol
Of a compound having a polymerizable unsaturated group, which is an ester with
Specific examples of monomers include photopolymer type descriptions.
As an ethylenically unsaturated bond-containing compound used for recording layers
Each acrylic ester, each methacrylic
Acid ester, each itaconic acid ester, each crotonic acid ester
Tellurite, each isocrotonic acid ester and each maleic acid ester
Tell. As specific examples of these compounds,
For example, paragraph number of JP 2001-293971 A
[0021] to those described in [0030]
The Examples of compounds having other polymerizable unsaturated groups
Is a polymerized hardened layer which is one of the negative recording layers described above.
(C) The same as exemplified in the radical polymerizable compound
Is mentioned. (A) The hydrophobic fine particle polymer
Self-water-dispersed fine particles whose surface is hydrophilic and disperse in water
Are particularly preferred. Because it maintains self-water dispersibility,
Easily and evenly dispersed in the recording layer coating solution
Even in the dry film layer after drying, it is made of hydrophilic polymer matrix.
The particles are uniformly dispersed in the recording layer without agglomeration.
Exist. From this, the effect of the present invention is further improved.
The As suitable self-water dispersible fine particles,
(1) Having a lipophilic resin structure and a hydrophilic group in the molecule
A resin having a structural part is disclosed in JP-A-3-221137.
And JP-A-5-66600
No phase emulsifier or protective colloid
Resin fine particles dispersed in water, (2) core / shell structure
The core part is a lipophilic resin and the shell part is a hydrophilic component
(3) hydrophobic substance inside
The microcapsule is wrapped and protected on its surface with a hydrophilic wall material.
Psel fine particles can be mentioned. A method for making the surface of fine particles hydrophilic is, for example,
For example, paragraph number [0 of Japanese Patent Laid-Open No. 2001-315452
[052] to [0056]
A good thing is mentioned. But that way to these
It is not limited. (B) A compound having a thermally reactive functional group is contained.
The encapsulating microcapsule has the thermal reaction biofunctional group described above.
The compound to be included is included. This heat-reactive functional group
Compounds include polymerizable unsaturated groups, hydroxy groups, carbohydrates.
Xy group, carboxy group, acid anhydride, amino group,
Poxy and isocyanate groups and their block bodies
A compound having at least one functional group selected from
Can be mentioned. As the compound having a polymerizable unsaturated group,
Ethylenically unsaturated bonds such as acryloyl groups, meta
At least one acryloyl group, vinyl group, allyl group, etc.
Compounds, preferably two or more, are preferred.
Such compounds are widely known in the industry.
In the present invention, these are not particularly limited.
Can be. These chemical forms include mono
Mer, prepolymer, ie dimer, trimer and oligo
Polymers or mixtures thereof or copolymers thereof.
I can get lost. As specific compounds, for example, JP-A-200200
Paragraph Nos. [0016] to [0] of JP-A-277742
032]. Coordination of compounds having an ethylenically unsaturated bond
As the polymer, an allyl methacrylate copolymer is preferred.
Named appropriately. Specifically, allyl methacrylate /
Methacrylic acid copolymer, allyl methacrylate / ethyl
Methacrylate copolymer, allyl methacrylate / buty
And dimethacrylate copolymer. (B) Including a compound having a heat-reactive functional group
As a manufacturing method of the microcapsule to be wrapped, the capsule
Heterogeneous polymerization method to make membrane, in-situ method, complex
Publicity such as score-cervate method, phase separation method from organic solvent system, etc.
Knowledge methods can be applied. Specifically, for example, JP-A-20
Recorded in paragraph No. [0036] of Japanese Patent No. 01-293971
The method described in this document can be used. (B) A compound having a thermally reactive functional group is contained.
Microcapsule used for wrapping microcapsule
The wall has a three-dimensional cross-link and swells with a solvent.
It is preferable to have it. From this point of view, the microphone
Locapsule wall materials are polyurea, polyurethane, poly
Ester, polycarbonate, polyamide, or these
A mixture of polyurea and / or polyurea is preferred.
Riurethane is more preferred. This micro capsule
Introducing the above-mentioned compounds with heat-reactive functional groups
May be. (B) Including a compound having a heat-reactive functional group
The microcapsules to be wrapped are heated with each other.
May or may not merge
It may be. In short, the microcapsule inclusions
In other words, it spreads on the capsule surface or outside the microcapsule during application
Extruded or infiltrated into the microcapsule wall
However, a chemical reaction may be caused by heat. Also added
Reacts with added hydrophilic resin or added low molecular weight compound
May be. In addition, two or more types of microcapsules
Functional groups that react with each other with different functional groups
Give the microcapsules a reaction.
It may be allowed. Therefore, the microcapsules are heated by heat
However, melting and coalescence with heat is preferable for image formation.
Yes, but not essential. (B) Thermally reactive functional group in the thermal recording layer
Content of microcapsules enclosing a compound having
Is 10 to 60% by mass relative to the total solid content of the recording layer
It is preferable that it is 15 to 40% by mass.
That's right. If it is within the above range, good on-press developability and
In addition, good sensitivity and printing durability can be obtained. (B) Including a compound having a heat-reactive functional group
Place the microcapsule to be included in the thermal recording layer
The inclusions can be dissolved and the wall material swells
In a microcapsule dispersion medium
Can be added. The inclusion by such a solvent
MICROCAPSE OF COMPOUND HAVING THERMAL REACTIVE FUNCTIONAL GROUP
Diffusion outside The choice of such solvents is
Microcapsule dispersion medium, microcapsule wall material,
Depending on wall thickness and inclusion, many commercially available solutions
It can be easily selected from agents. For example, cross-linked poly
Water-dispersible microcaps made of urea or polyurethane walls
In the case of cells, alcohols, ethers, acetals
, Esters, ketones, polyhydric alcohols, amides
, Amines, fatty acids and the like are preferred. Specifically, the negative type or the positive type described above.
Type and the same solvent as used for each recording layer coating solution.
However, the present invention is not limited to these. Also this
Two or more of these solvents may be used. Further, it dissolves in the microcapsule dispersion.
However, it is also possible to use a solvent that dissolves when the solvent is mixed.
You can. The amount added depends on the combination of materials.
If it is round but less than the suitability value, image formation
If the amount is too large, the stability of the dispersion will deteriorate.
The Usually, it is effective to be 5 to 95% by mass of the coating solution.
10 to 90% by mass is preferable.
More preferably, it is mass%. The hydrophobized precursor-containing image recording layer is thermally reactive.
Fine particle polymer having functional group and / or (b) thermal reaction
Microcapsules enclosing a compound having a functional functional group
If contained, start these reactions as needed
Alternatively, a promoting compound may be added. Start reaction or
As a compound to be promoted, a radical or cation by heat is used.
The compound which generate | occur | produces thione can be mentioned.
For example, lophine dimer, trihalomethyl compound,
Oxides, azo compounds, onium salts (diazonium salts, di
Phenyliodonium salt), acylphosphine, imi
Examples thereof include dosulfonate. Specifically, (B) La
Exemplified as a dical generator, or (E) acid generator
The same compounds as those exemplified as the herbicide can be mentioned. The amount of these compounds added is the total solid content of the recording layer.
The content is preferably 1 to 20% by mass with respect to the shape.
More preferably, it is 10 mass%. Within the above range
Then, on-machine developability is not impaired, good reaction initiation effect or
A reaction promoting effect is obtained. (Hydrophilic resin) Hydrophobic precursor in the present invention
A hydrophilic resin may be added to the body-containing image recording layer.
On-machine developability is improved by adding a hydrophilic resin.
In addition, the film strength of the recording layer itself is improved. Hydrophilic
Examples of the resin include hydroxyl, carboxyl,
Hydroxyethyl, hydroxypropyl, amino, amino
Parents such as noethyl, aminopropyl, carboxymethyl
Those having a water group are preferred. As a specific example of the hydrophilic resin, Arabico
, Casein, gelatin, starch derivatives, carboxymethyl
Cellulose and its sodium salt, cellulose acetate
, Sodium alginate, vinyl acetate-maleic acid
Copolymers, styrene-maleic acid copolymers,
Riacrylic acids and their salts, polymethacrylic acids and
And salts thereof, hydroxyethyl methacrylate homo
Polymers and copolymers, hydroxyethyl acrylate
Homopolymers and copolymers of hydroxypropyl
Methacrylate homopolymers and copolymers, hydro
Homopolymers and copolymers of xypropyl acrylate
-Hydroxyptyl methacrylate homopolymer and
And copolymers of hydroxybutyl acrylate
Limers and copolymers, polyethylene glycols,
Droxypropylene polymers, polyvinyl alcohol
As well as a hydrolysis degree of at least 60% by weight
Or at least 80% by weight of hydrolyzed polyvinyl acetate.
, Polyvinyl formal, polyvinyl butyral,
Homopolymer of polyvinylpyrrolidone and acrylamide
And copolymers, homopolymers of methacrylamide and
Homopolymer of polymer, N-methylolacrylamide
-And copolymers. [0211] The amount of hydrophilic resin added to the recording layer is as follows.
1-40 mass% of solid content is preferable, and 5-30 mass%
Further preferred. Within this range, good on-press developability and film
Strength is obtained. Furthermore, as another preferred embodiment of the recording layer,
Hydrophobic such as (a) hydrophobic fine particle polymer as described above
A water-insoluble high-order cross-linking structure
And contained in a hydrophilic polymer matrix.
After the irradiation area is hydrophobized by energy irradiation, it is developed.
Can be used as a printing plate immediately
Possible image recording layer containing cross-linked hydrophobizing precursor
The In this type of recording layer, the above parent
Combination of aqueous resin and compound that can be cross-linked and cured in the film
Are preferably used. Hydrophilic resin content is recorded
It is preferably 5 to 70% by mass based on the total solid content of the layer.
10 to 55% by mass is more preferable. the above
Within the range, good film strength and water retention can be obtained.
As a crosslinking agent, a compound usually used as a crosslinking agent is used.
Can be mentioned. Specifically, Shinzo Yamashita and Tosuke Kaneko
Edited by Taiseisha (1981)
Molecular Science Society "Polymer Data Handbook, Basics" Culture
Use compounds described in the museum (1986) etc.
You can. As more specific compound examples, for example,
Paragraph No. [005] of JP 2002-36745 A
3] and the like. In addition, chloride
Ammonium, silane coupling agent, titanate cup
A crosslinking catalyst such as a ring agent can also be used in combination. Such a crosslinked hydrophobizing precursor-containing image
In the recording layer, among the hydrophilic resins, sol-gel conversion system
It is preferable to use a binder resin. The details are described below.
The As a sol-gel conversion binder resin used suitably
The bonding group coming out of the polyvalent element is networked via oxygen atoms.
Hydroxyl that forms an eye-like structure and has an unbound polyvalent element.
Si and alkoxy groups are also present, and these are mixed
A polymer having a resinous structure,
At the stage where there are many groups, alkoxy groups, etc., it is in a sol state and
As the ether linkage progresses, the network resin structure
Examples thereof include a polymer that is strong. The sol-gel conversion binder resin is a parent of the resin structure.
In addition to the property of changing water content, some hydroxy groups etc.
The surface of the solid fine particles by binding to the solid fine particles
It also has the function of modifying the hydrophilicity.
The Hydroxyl group, alkoxy group, etc. for sol-gel conversion
The polyvalent elements having the following are aluminum, silicon, titanium,
Zirconium etc. are mentioned. Among them, silicon is used
A sol-gel conversion system using a siloxane bond is preferred. After
The following explains the sol-gel conversion system using siloxane bonds.
But use aluminum, titanium, zirconium, etc.
Each of the sol-gel conversion systems uses silicon described below for each.
It can replace with an element and can implement. Siloxane
The sol-gel conversion system by combination is capable of sol-gel conversion.
Contains silane compounds with at least one silanol group
System. Inorganic hydrophilic formed by sol-gel conversion
Preferably, the binder resin is a siloxane bond and a silanol
It is a resin having a ru group. Cross-linked hydrophobized precursor containing image
The recording layer is a sila having at least one silanol group.
Apply a coating solution, which is a sol system containing a copper compound, to a support.
After application, silanol group hydrolytic condensation proceeds and
That the structure of xane skeleton is formed and that gelation proceeds
Thus formed. In addition, this sol-gel conversion system
The formed recording layer has physical properties such as film strength and flexibility.
For the purpose of improving and improving coating properties,
An aqueous polymer, a crosslinking agent, etc. can also be contained. A siloxane resin forming a gel structure and a small amount
A silane compound having at least one silanol group
As a specific example, Japanese Patent Application Laid-Open No. 2002-6504
The numbers described in the drop numbers [0054] to [0057]
Compound may be mentioned. For the formation of the inorganic hydrophilic binder resin, the above-mentioned sila
Ti, Zn, Sn, Zr, Al, etc.
Metallization capable of bonding to resin during sol-gel conversion
A compound can be used in combination. Such metal compounds and
For example, Ti (OR ')_FourTiCl_Four, Zn
(OR ’)₂, Zn (CH_ThreeCOCHCOCH_Three)₂, Sn
(OR ’)_Four, Sn (CH_ThreeCOCHCOCH_Three)_Four, Sn
(OCOR ’)_Four, SnCl4, Zr (OR ') _Four, Zr
(CH_ThreeCOCHCOCH_Three)_Four, Al (OR ’)_Three, Al
(CH_ThreeCOCHCOCH_Three)_ThreeEtc. Further, the above silane compound and the silane compound are also used.
Hydrolysis reaction of the above metal compounds that can be used and
In order to accelerate the polycondensation reaction, conventionally known inorganic acids, charcoal
Acid catalyst such as carboxylic acid, ammonia, organic amino acid
It is preferable to use a basic catalyst such as thiones together. catalyst
Is an acid or basic compound as it is, or water,
Use as dissolved in solvents such as alcohol
(Hereinafter referred to as "acid catalyst", base using acid)
A compound using a basic compound is called a “basic catalyst”. ). Melting
The concentration in the case of dissolving in the medium is not particularly limited.
The higher the degree, the faster the hydrolysis and polycondensation reactions.
Tend to be. However, use a concentrated basic catalyst.
Then, a precipitate may be generated in the sol solution,
Basic catalyst concentration (concentration in aqueous solution) is less than 1N
Preferably there is. As described above, containing a crosslinked hydrophobizing precursor
The image recording layer is prepared by a sol-gel method
Recording layer (including sol-gel conversion binder resin as hydrophilic resin)
The recording layer provided) is preferable. Details of the sol-gel method
Sakuo Sakuo "Sol-gel Method Science"
(Published) (1988), Satoshi Hirashima “To the latest sol-gel method
Functional thin film fabrication technology ", General Technology Center (published) (1
992) and the like. In the image-recording layer containing a crosslinked hydrophobizing precursor,
In addition to the components described above, various compounds may be included as necessary.
Can have. For example, further improve printing durability
Polyfunctional monomer for recording layer polymer matrix
It can be contained. Such a multifunctional monomer
-As the monomer included in the microcapsule
What was illustrated as can be used. Especially preferred
As a monomer, trimethylolpropane triac
Relates can be mentioned. Furthermore, before cross-linking hydrophobization
The precursor-containing image-recording layer can be used as needed, such as the flexibility of the coating film.
A plasticizer can be included to impart the above-mentioned properties. Plasticity
As a plasticizer, a plasticizer added to the recording layer coating liquid
The same compounds are exemplified. Further, an image recording layer containing a crosslinked hydrophobizing precursor
Inorganic or organic fine particles (eg silica, aluminum
Na, magnesium oxide, magnesium carbonate, etc.)
Can. In particular, the average particle size is preferably 1 to 50
nm hydrophilic sol-like particles. Inclusion of these fine particles
The amount is 1.0 to 70% by mass based on the national shape of the recording layer.
It is preferable that it is 5.0 to 50% by mass.
More preferable. In this range, the film strength of the recording layer is sufficient.
Can also be held by exposure to laser light, etc.
When making a plate and printing it as a lithographic printing plate
Excellent hydrophilicity without ink smudge
The effect that it becomes that which was made is obtained. Examples of the hydrophilic sol-like particles include:
Silica sol, alumina sol, magnesium oxide sol, charcoal
Magnesium acid sol and calcium alginate sol are suitable
It is mentioned in. Among them, silica sol, alumina sol, aluminum
Preference is given to calcium oxalate sols or mixtures thereof.
Yes. These hydrophilic sol-like particles are all commercially available products.
And can be easily obtained. [(A) Infrared absorber] Such thermal response
The image recording layer by scanning exposure with infrared laser light, etc.
(A) Infrared absorption according to the present invention for image formation
An agent is contained in the image recording layer. The preferred addition amount is recorded
1-30 mass% is preferable in the total solid content of the layer coating solution,
25 mass% is more preferable. Content is in the above range
Thus, the image recording layer is excellent in both sensitivity and image formability.
Here, in the case of an image recording layer containing a crosslinked hydrophobizing precursor
(A) presence of the infrared absorbent and the hydrophilic sol-like particles
The present ratio is 100/0 to 30/70 by mass ratio.
And is preferably 100/0 to 40/60
More preferable. Further, (A) infrared absorber, hydrophobized precursor
Body, and the total content of the hydrophilic sol-like particles is recorded
It is preferable that it is 2-95 mass% with respect to the total solid of a layer.
Preferably, it is more preferably 5 to 85% by mass. The hydrophobic recording material containing an image recording layer is necessary
Each component is recorded in the above-described negative type or positive type recording layer.
Dissolve or disperse in the same solvent used for the coating solution
Prepare a coating solution and apply it on the hydrophilic surface of the support
Is done. The solid content concentration of the coating solution is preferably 1 to 50 quality
%. Also note on the support obtained after coating and drying.
Recording layer coating amount (solid content) varies depending on the application, but in general
0.5-5.0 g / m²Is preferred. From this range
As the amount applied decreases, the apparent sensitivity increases, but the image
The film properties of the thermal recording layer that performs the function of image recording are reduced.
The 3-3. An ink receiving layer and a hydrophilic layer are sequentially laminated.
The hydrophilic layer is peeled off in the infrared laser exposure area.
The image is formed when the ink receiving layer is exposed.
Recording layer (interfacial peeling method recording layer) Interfacial peeling type recording layer as one embodiment of non-process type image recording layer
Consists of at least two layers, an ink receiving layer and a hydrophilic layer.
Any layer contains the infrared absorber of the present invention.
Or a photosensitive layer containing an infrared absorber between the two layers.
The structure to provide can be taken. Such a layered image
In the image recording layer, the infrared of the layer containing the infrared absorber
Rapid heat generation, melting, expansion, or explosion in the line laser exposure area
Occurs and the hydrophilic layer on the ink receiving layer is peeled off.
This is called interfacial peeling in the present invention. This world
The hydrophilic layer is removed by surface peeling, and the ink receiving layer is exposed.
Forming the image area, and the remaining hydrophilic layer in the unexposed area
A non-image portion is formed, and image formation is performed. Such a world
In the image forming method using the surface peeling method,
Images can be formed without developing with a developer.
There are advantages. [Ink receiving layer] The ink receiving layer is oleophilic.
Containing a polymer having the ability to form a film. Ink acceptance
When coating the layer by dissolving it in a coating solvent on the substrate,
The polymer is soluble in the coating solvent for the ink receiving layer.
However, it is not suitable for the coating solvent for the upper hydrophilic layer described later.
The two layers prevent miscibility at the interface.
It is desirable from the viewpoint of maintaining the uniformity. Only
However, part of the lipophilic polymer swells in the coating solvent for the hydrophilic layer
In some cases, it is desirable to have excellent adhesion to the upper layer.
In such a configuration, the solvent of the ink receiving layer
Damage, non-uniform film thickness, reduced ink receptivity, etc.
In order to prevent this problem, devise measures such as adding a crosslinking agent in advance.
It is desirable to cure the oily polymer film. The oleophilic polymer constituting the ink receiving layer of the present invention.
Limer is compatible with the hydrophilic layer as described above, or
Both the ease of interfacial peeling described below and the stability of the coating film
Select two or more types with different weight average molecular weights.
They can also be used in combination. That is, interface peeling
Low molecular weight poly which is easy to occur and can express high sensitivity during recording
Resistant to plate cleaner and hydrophilic layer
Blended with high molecular weight polymer with excellent resistance to chemicals
By doing so, well-balanced interface peelability and sensitivity,
A polymer having solvent properties is obtained. Preferably, weight
Low molecular weight polymer with an average molecular weight of 500-3000 and weight
High molecular weight polymer having an average molecular weight of 3000 to 100,000
And the composition ratio is heavy.
Low molecular weight polymer / high molecular weight polymer 5/9 by weight
5-50 / 50, more preferably 10 / 90-40 /
The range is 60. In addition, the lipophilic oil constituting the ink receiving layer
100% of the above composition is preferred
However, as long as it does not interfere with the above characteristics,
High molecular weight polymers can be blended.
Of course. An oleophilic polymer useful for an ink receiving layer
Polyester, polyurethane, polyurea, poly
Imide, polysiloxane, polycarbonate, phenoxy
Resin, epoxy resin, phenol formaldehyde
Resin, alkylphenol / formaldehyde resin, plastic
Livinyl acetate, acrylic resin and its copolymer,
Polyvinylphenol, polyvinyl halide pheno
, Methacrylic resin and its copolymer, acrylamide
Copolymer, methacrylamide copolymer, polyvinyl
Lumar, polyamide, polyvinyl butyral, police
Tylene, cellulose ester resin, polyvinyl chloride and polyethylene
And vinylidene chloride. Among these
As a more preferred compound, a hydroxy group in the side chain,
Carboxy group, epoxy group, sulfonamide group and tria
A resin having a alkoxysilyl group is adjacent to the support substrate.
Excellent adhesion to the hydrophilic layer, and may be filled with a crosslinking agent in some cases.
Desirable because it hardens easily. Others, acrylonitrile
Polymer, polyurethane, side chain with sulfonamide group
Copolymers having a hydroxy group in the side chain
What was photocured with the azo resin is preferable. In addition, phenol, cresol (m-c
Resole, p-cresol, m / p mixed cresol),
Phenol / cresol (m-cresol, p-cresol
, M / p mixed cresol), phenol-modified xyle
, Tert-butylphenol, octylphenol
Le, resorcinol, pyrogallol, catechol, black
Rophenol (m-Cl, p-Cl), bromopheno
(M-Br, p-Br), salicylic acid, phlorogluci
Novolak tree of condensation with formaldehyde such as knoll
Fats and resole resins, and phenol compounds
A condensation resin with Seton is useful. As other suitable polymers, JP-A-20
No. 00-335131, paragraph number [0083] to
[0086] may be mentioned. These things
1 type or 2 types or more as a structural unit
In addition, other monomers may be used as constituent units.
It may have as a position, but its content is 40 mol%
The following is preferable. Infrared absorption according to the present invention to the ink receiving layer.
The added amount of the collecting agent is 1 to 40 of the total solid content of the ink receiving layer.
% By weight is preferred, particularly preferably 5 to 20% by weight.
The If the amount added is in the above range, highly sensitive recording and ink
Both the durability of the receiving layer can be achieved. The ink receiving layer contains a lipophilic polymer and red.
In addition to the external line absorber, the film quality of the ink receiving layer has been improved.
In order to improve the appearance, cross-linking agent, adhesion aid, coloring
Agent, inorganic or organic fine particles, coated surface condition improver or plastic
An agent can be added. In addition, after printing
A heating coloring or decoloring system to form a photo image
It may be added. As a crosslinking agent for crosslinking a polymer, for example
For example, Shinzo Yamashita
And the compounds described in Taiseisha (1981) and the like.
It is. Specifically, a diazo resin, an aromatic azide compound,
Epoxy resin, isocyanate compound, block isocyanate
Initial hydrolysis of anate compound, tetraalkoxy silicon
Condensate, metal chelate compound, glyoxal, alde
Examples thereof include hydride compounds and methylol compounds.
As the bonding aid, the diazo resin is a substrate and a hydrophilic layer.
In addition to this, silane coupling agent,
Isocyanate compounds and titanium coupling agents are also useful
It is. As the colorant, ordinary dyes and pigments are used.
As described above for the negative-type image recording layer.
These compounds can be used. The dye is ink
When added in the receiving layer, the total solid content of the receiving layer,
Usually about 0.02 to 10% by weight, more preferably about 0.
There is a ratio of 1 to 5% by mass. Inorganic or inorganic materials that can be used in the ink receiving layer.
Is from 10nm to 100nm as organic fine powder
Colloidal silica, colloidal aluminum,
Inert particles larger in size than these colloids, eg
Silica particles, surface-hydrophobized silica particles, alumina
Particles, titanium dioxide particles, other heavy metal particles, clay and
Examples include talc. These inorganic or organic
By adding a fine powder of
Improves the adhesion of the layer to the hydrophilic layer and improves the printing durability in printing
There is an effect to increase. These in the ink receiving layer
The proportion of fine powder added is preferably 80% by mass or less of the total amount.
Or 40% by mass or less. In addition, the ink receiving layer has an image when exposed.
Coloring or decoloring system to make the image area and non-image area clear
It is preferable that a compound is added. For example, diazo compound
And thermal acid generators such as diphenyliodonium salts
Leuco dye (leucomalachite green, leuco chestnut
Star violet, crystal violet lact
Etc.) and PH discoloration dyes (for example, ethyl violet dye)
And dyes such as Victoria Poor Blue BOH)
It is. Others are described in EP 897134 specification.
The combination of acid coloring dye and acid binder
It is valid. In this case, the dye is formed by heating.
The association state is broken and the lactone form is colored
Changes to colorless. The addition ratio of these coloring systems is the receiving layer
10% by mass or less, preferably 5% by mass or less, based on the total amount of
It is below. Also, in preparing the ink receiving layer coating solution,
Is a well-known compound as a coating surface condition improver.
Added fluorine-based surfactant and silicon-based surfactant
Add a plasticizer to give the film flexibility
These can be similar to the other image recording layers mentioned above
Can be used. A solvent used for coating the ink receiving layer and
The negative or positive recording layer coating described above.
The solvent similar to what was used for the liquid is mentioned. These melts
The medium is used alone or in a mixed state. Prepare coating solution
The ink receiving layer constituents (additives) in the solvent
The total solid content) is preferably 1 to 50% by mass.
is there. In addition, only application from organic solvents as described above
Not only to form a film from an aqueous emulsion
Can do. In this case, the concentration is preferably 5 to 50% by mass.
Yes. The quality of the ink-receiving layer in the present invention after coating and drying
The amount is not particularly limited, but 0.05 g / m²That's it
Preferably 0.1 g / m²That's it. upper limit
The value is not particularly limited, but generally from the viewpoint of film strength
30g / m²The following is preferable. Al
When using a metal plate such as minium for the support, a heat insulating layer
It is preferable from the viewpoint of improving sensitivity
Therefore, the coating amount is 0.4 g / m²Desirably
That's right. On the other hand, a lipophilic plastic film is used as a support base.
When using as a plate, the amount of coating is the same as when using a metal plate.
0.05g / m²That's all,
0.1-30 g / m²The range of is preferable. Each of the above categories
Within the range, the durability and sensitivity of the film are good. [Hydrophilic layer] In the other layer of the interface peeling type recording layer
Some hydrophilic layers are beryllium, magnesium, aluminum
Silicon, titanium, boron, germanium, tin, zirco
From nickel, iron, vanadium, antimony and transition metals
Oxides or hydroxides of at least one selected element
It is formed by applying a solution containing the colloid. here
Constitutes colloidal oxides or hydroxides used in
Among the elements, aluminum, silicon,
Mention may be made of titanium and zirconium, particularly preferred
Or silicon. Colloidal particles are typically 2 nm to 5
00 nm, and 5 to 100 nm for silica
A spherical shape is preferable in the present invention. 10 nm to 50
nm spherical particles with a length of 50 nm to 400 nm
A pearl neck colloid can also be used.
Furthermore, like aluminum colloid, 100 nm ×
A feather-shaped material such as 10 nm is also effective. these
Colloids are halides or alkoxy compounds of the above elements.
Various things such as hydrolysis of substances or condensation of hydroxides of the above elements
It can be made by a known method. Of these colloids
For the dispersion, purchase a commercial product such as Nissan Chemical Industries, Ltd.
You can also The hydrophilic layer coating solution further contains a hydrophilic resin.
Preferably, the hydrophilic resin includes the hydrophobic
Examples are the same as those used in the precursor-containing image recording layer
It is done. The ratio of addition of these hydrophilic resins is the total hydrophilic layer
1-30 mass% of solid content is preferable, and 5-20 mass% is
Particularly preferred. In this range, sufficient printing durability and dirt prevention
Stopper is demonstrated. If the amount added is too small, the film strength decreases.
Tend to have insufficient printing durability, too much
In this case, the removability of the hydrophilic layer is reduced and the hydrophilic layer remains.
Tends to cause printing stains. In the hydrophilic layer, the above colloid and hydrophilic resin are used.
In addition to promoting colloidal cross-linking to increase printing durability
Cross-linking agent and / or hydrophilic resin cross-linking agent
Also good. Specifically, the above-mentioned “hydrophobic precursor-containing image recording”
Examples similar to those exemplified in
The As other preferred hydrophilic resin of the hydrophilic layer,
The same thing as a Lugel conversion type | system | group binder resin is mentioned. In this embodiment, an infrared absorber is added to the hydrophilic layer.
Can be added. Red according to the present invention to the hydrophilic layer
The amount of external line absorbent added is 0.01% of the total solid content of the hydrophilic layer.
-50 mass% is preferred, particularly preferably 0.1-20.
% By mass. If the amount added is in the above range, highly sensitive
Both recording and layer durability can be achieved. In the hydrophilic layer coating solution, the surface shape of the coating is improved.
Therefore, well-known fluorine-based surfactants, silicon-based
Added surfactant, polyoxyethylene surfactant, etc.
You may add. The weight of the hydrophilic layer after coating and drying was 0.1 g /
m²To 3g / m²It is preferable that More preferable
Is 0.4 g / m²To 2g / m²It is. In this range
Good sensitivity and printing performance (ground stain resistance, high printing durability)
Is obtained. Drawing using general commercially available semiconductor lasers
About 0.5 g / m²300-400 in thickness
mJ / cm²Energy of about 1.5 g / m²In thickness
400-500mJ / cm²Of energy. When an interfacial peeling type photosensitive layer is used,
An infrared absorber-containing layer is provided between the hydrophilic layer and the ink receiving layer.
You can also When taking such a configuration, exposure
Therefore, abrupt emission occurs in the exposed area of the infrared absorber-containing layer.
Heat is generated, and the adhesion between the ink receiving layer and the hydrophilic layer decreases,
The upper hydrophilic layer can be easily peeled off and image formation
Done. The infrared absorber-containing layer is suitable for infrared absorbers.
Including an infrared binder
The content of the infrared absorber in the layer is 0. 0% in the total solid content of the layer.
It is preferable that it is about 05-30 mass%. Also red
The preferred coating amount of the external line absorber-containing layer is the coating amount after drying.
0.1 g / m²~ 5g / m²Preferred to be in the range
More preferably 0.2 g / m²~ 4g / m²In
The A lithographic stamp using these non-process type image recording layers
The negative or positive recording layer is also used for the printing plate precursor.
It is possible to use the same support as the lithographic printing plate precursor using
it can. <Overcoat layer> Recording in the present invention
An overcoat layer may be provided on the layer as necessary.
You can. Overcoat used in the present invention
The layer is a water-soluble layer and can be easily removed during development or printing.
It will be left. Overcoat layer is a lithographic printing plate
Prevents sticking when originals are stacked and stored
In order to stop, it is preferable to have releasability. The main component of the overcoat layer is water-soluble.
Machine or inorganic polymer compound and apply aqueous solution
And the film formed by drying
Have the formation of. Specifically, for example,
Paragraph No. [0011] of Japanese Patent Laid-Open No. 2001-162961
Water-soluble resin described in JP-A-2002-1931
Examples include celluloses described in No. 5 publication
The In addition, the overcoat layer has other additions.
You may contain the thing as needed. For example, releasability
Water-soluble or water-dispersible fluorine atoms to increase
And / or containing a compound containing a silicon atom
Is preferred. Furthermore, it is preferable to contain a photothermal conversion substance.
That's right. As the photothermal conversion substance, for example, JP-A-2001-2001
The compounds described in Japanese Patent No. 162961 are preferably listed.
I can get lost. The overcoat layer has a surface dynamic friction coefficient.
(Μk) is preferably 2.5 or less, 0.03
More preferably, it is -2.0. Dynamic friction coefficient of surface
Is within the above range, the transportability of the lithographic printing plate precursor is good.
Yes, alkali developability or on-press developability and printing durability
Becomes better. Here, the “dynamic friction coefficient” of the surface is standard A
Measured by the measurement method according to STMD1894
is there. That is, the bottom surface of the material is the top surface of the underlying material
A lithographic printing plate precursor is placed in contact with. "back
"Surface" means an image recording layer and an overcoat on a support.
It means the surface where no layer is provided.
An image recording layer and an overcoat layer are provided on the body.
It means the surface. The coefficient of dynamic friction is the same as that of the planographic printing plate precursor.
3,000 stacked, 3 days at 35 ° C and 75%
After standing for a while, measure the sample at the bottom
Can do. Such an overcoat of a preferred embodiment
The layer can be a type of water-soluble resin, etc.
Kinds of compounds containing elementary atoms and / or silicon atoms and
Can be obtained by appropriately combining the added amount
The For example, containing fluorine atom and / or silicon atom
Of the compound to the total solid content of the overcoat layer
Is preferably 0.05 to 5.0 mass%,
It is more preferable to set it as 0.1-3 mass%. <Backcoat layer> In this way, support is provided.
The lithographic plate of the present invention in which various image recording layers can be provided on the body
If necessary, the back side of the printing plate
In order to prevent damage to the image recording layer, organic polymers
Compound coating layer (hereinafter referred to as “backcoat layer”)
Can be provided. Main component of backcoat layer
As a saturated copolymer polyester having a glass transition point of 20 ° C. or higher.
Steal resin, phenoxy resin, polyvinyl acetal tree
Selected from the group consisting of fat and vinylidene chloride copolymer resin
At least one kind of resin is preferably used. Saturation
Polyester resin is composed of dicarboxylic acid units and
Unit. As dicarboxylic acid unit
Phthalic acid, terephthalic acid, isophthalic acid, tetrabutyl
Aromatic dicals such as lomphthalic acid and tetrachlorophthalic acid
Boronic acid; adipic acid, azelaic acid, succinic acid, shu
Acid, peric acid, sebacic acid, malonic acid, 1,4-cycl
Saturated aliphatic dicarboxylic acids such as rhohexanedicarboxylic acid
Is mentioned. The back coat layer is further dyed for coloring.
Materials, pigments, etc .; sila to improve adhesion to the support
Coupling agent, diazo tree consisting of diazonium salt
Fat, organic phosphonic acid, organic phosphoric acid, cationic polymer
Etc .; wax, high-grade fat usually used as a slipping agent
An acid, higher fatty acid amide, dimethylsiloxane
Ricone compound, modified dimethylsiloxane, polyethylene
A powder or the like can be appropriately contained. The thickness of the back coat layer is basically the same.
Even if there is no paper, it should be hard to damage the image recording layer
It is preferable that it is 0.01-8 micrometers. Thickness is
If the thickness is less than 0.01 μm, remove the planographic printing plate precursor
It is difficult to prevent scratches on the image recording layer when handling
It becomes. If the thickness exceeds 8 μm, the planographic printing plate is being printed.
Backcoat layer is swollen by chemicals used around
The thickness changes, and the printing pressure changes to deteriorate the printing characteristics.
Sometimes. [0259] A back coat layer is formed on the back surface of the planographic printing plate precursor.
Various methods can be applied for coating. Example
For example, each of the above components is made into an appropriate solvent solution or emulsified.
A method of coating and drying in a dispersion, pre-film
A method of bonding a molded product with adhesive or heat, melting
Forming a melt film with an extruder and bonding
Can be mentioned. Above all, ensure the above coating amount (thickness).
The method of applying the solution and drying is preferable.
It is. As the solvent, JP-A-62-251739
Organic solvents as described in the
Used. Application method and conditions include image recording
Many of the methods and conditions of applying layers can be utilized
The That is, a method using a coating rod, an ext
A method using a rouge type coater, slide beadco
A method using a filter can be used. The backcoat layer
It may be provided before or after the image recording layer is provided.
It may be provided simultaneously with the image recording layer. The lithographic printing plate precursor according to the present invention has such a structure.
Even if various image recording layers are used,
Excellent recording sensitivity and printing durability
Several sheets can be obtained. [0261] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. <Thermal negative planographic printing plate precursor> (Example N-1) [Preparation of Support A] 99.5% or more of aluminum;
Fe 0.30%, Si 0.10%, Ti 0.02%, C
u For molten metal of JIS A 1050 alloy containing 0.013%
A cleaning treatment was performed and the product was cast. In the molten metal for cleaning
Degassing treatment to remove unwanted gases such as hydrogen
Then, the ceramic tube filter treatment was performed. Casting
The manufacturing method was DC casting. With a solidified plate thickness of 500 mm
The ingot is chamfered 10mm from the surface, and the intermetallic compound becomes coarse.
Homogenization at 550 ° C for 10 hours
went. Then, hot-rolled at 400 ° C and in a continuous annealing furnace
After performing an intermediate annealing at 500 ° C. for 60 seconds, cold rolling is performed,
A rolled aluminum plate having a thickness of 0.30 mm was used. Rolling roll
The center line after cold rolling by controlling the roughness of the roll
The surface roughness (Ra) was controlled to 0.2 μm. Then flat
A tension leveler was applied to improve surface quality. Next, a support for a lithographic printing plate precursor is used.
Surface treatment was performed. First, the pressure on the aluminum plate surface
5% with 10% sodium aluminate aqueous solution to remove rolled oil
Degreased at 0 ° C for 30 seconds, 50% aqueous solution with 30% sulfuric acid
Neutralization and smut removal treatment were performed at 30 ° C. for 30 seconds. Then
Improves the adhesion between the support and the recording layer and keeps it in the non-image area.
In order to give water, the surface of the support is roughened.
The graining process was performed. 1% nitric acid and 0.5% glass
Keep the aqueous solution containing acid aluminum at 45 ° C
Current flow through an indirect power supply cell
20 A / dm², With an alternating waveform with a duty ratio of 1: 1
Anode-side electricity of 240 C / dm²Giving electrolysis
We performed graining. 10% sodium aluminate water solution
Etching with liquid at 50 ° C for 30 seconds, 30% sulfuric acid
Neutralization and smut removal treatment at 50 ° C for 30 seconds with aqueous solution
It was. Furthermore, wear resistance, chemical resistance and water retention are improved.
In order to form an oxide film on the support by anodic oxidation.
Made. Uses 20% sulfuric acid aqueous solution at 35 ° C as electrolyte
Indirect power feeding while carrying the aluminum web through the electrolyte
14 A / dm depending on the cell²Electrolytic treatment with direct current
2.5g / m²An anodic oxide film was prepared. After this,
In order to ensure hydrophilicity as the non-image part of the printing plate,
Treatment was performed. Treatment is No. 3 sodium silicate 1.5% water-soluble
Keeping the liquid at 70 ° C, the contact time of the aluminum web is 15 seconds
And then washed with water. The adhesion amount of Si is 10mg
/ M²Met. The center line of the support A created as described above
The surface roughness (Ra) was 0.25 μm. [Undercoating] Next, this aluminum support.
Apply the following undercoat liquid to A with a wire bar and dry with hot air
It dried for 30 seconds at 90 degreeC using the drying apparatus. Cover after drying
The dose is 10 mg / m²Met. <Undercoat liquid> ・ Ethyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfur Copolymer with molar ratio of sodium phonate 75:15 ... 0.1g ・ 2-Aminoethylphosphonic acid ... 0.1g ・ Methanol: 50g ・ Ion-exchanged water ... 50g [Formation of Recording Layer] Next, the following recording layer coating solution
Adjust [NL-1] and apply the above primed aluminum
Apply to the substrate support using a wire bar and dry with hot air
Dry at 115 ° C. for 45 seconds and set the negative planographic printing plate
Version [N-1] was obtained. The coating amount after drying is 1.2 to 1.3
g / m²It was in the range. [0266] <Recording layer coating solution [NL-1]> Infrared absorber [specific dye: exemplary compound (A-5)] 0.08 g ・ Polymerization initiator [O-1 (the following structure)] 0.30 g ・ Dipentaerythritol hexaacrylate ・ ・ ・ 1.00g ・ Copolymer of allyl methacrylate and methacrylic acid ・ ・ ・ 1.00g   (Molar ratio 80:20, weight average molecular weight 120,000) ・ Victoria pure blue naphthalene sulfonate 0.04g ・ Fluorosurfactant: 0.01g   (Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone ... 9.0g ・ Methanol: 10.0 g ・ 1-methoxy-2-propanol: 8.0g [0267] Embedded image [Exposure] The obtained negative type planographic printing plate precursor
[N-1] is a Trendsetter 3 manufactured by Creo
Infrared semiconductor laser at 244VFS has a wavelength of 980
A plate energy of 150 nm is used instead of the one of nm.
mJ / cm²It exposed so that it might become. [Development Processing] After exposure, Fuji Photo Film
Development processing using an automatic processor Stablon 900N manufactured by Co., Ltd.
did. The developer is Fuji Photo Fiber for both the feed and replenishers.
A 1: 1 water dilution of DN-3C manufactured by Rum Co., Ltd. was used. Present
The temperature of the image bath was 30 ° C. The finisher
A 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd.
Using. [Printing] Next, the planographic printing plate [N-1] is
Using a printing press Lithron made by Komori Corporation
Printed. [Evaluation] 1. Sensitivity evaluation In the above exposure process, the output is about 40% up to 2-20W.
The sensitivity was obtained by changing each time. Here, sensitivity is dew
Minimum energy at which the light part starts to decrease in density due to development
-Amount of energy, and the amount of energy (E) is expressed by the following formula.
Is done. E = W × 2350 / rpm (W: output, rpm: rotation
number) The results are shown in Table 14. [0272] 2. Evaluation of printing durability In the above printing process, how many inks are enough
It was visually evaluated whether printing was possible while maintaining the density. Result is
Table 14 shows. 3. Evaluation of stability over time Unexposed negative planographic printing plate precursor [N-1] at room temperature
Left under for 3 months. Negative-type planographic printing plate precursor after being left
In the same manner as above. Sensitivity evaluation, and 2. Printing durability
Evaluation was performed. The results are also shown in Table 14. [0274] [Table 17] (Comparative Example 1) In Example N-1, recording
The infrared absorbing agent in the layer coating solution [NL-1] is replaced with a specific dye:
Dye having structure shown below from exemplary compound (I-5)
The negative lithographic printing of Comparative Example 1 was performed in the same manner except that
A plate precursor [NR-1] was prepared. Then Example N-1
1. Perform exposure, development and printing in the same manner as described above. Sensitivity review
2. 2. Evaluation of printing durability, and Evaluation of stability evaluation over time
did. The results are also shown in Table 1. [0276] Embedded imageExample N-2 [Preparation of Support B] Aluminum plate with a thickness of 0.30 mm
(Material 1050) is trichlorethylene washed and degreased
Nylon brush and 400 mesh pumiston
Using a water suspension, the surface is grained and washed thoroughly with water.
did. This plate is a 25% aqueous sodium hydroxide solution at 45 ° C.
2 seconds after etching for 9 seconds.
It was immersed in nitric acid for 20 seconds and washed with water. Graining table at this time
The etching amount of the surface is about 3g / m²Met. Then this
Current density 15A / dm using 7% sulfuric acid as electrolyte²so
3g / m²After providing a direct current anodic oxide film, washing with water and drying
As a result, a support B was obtained. [Undercoat] Next, this aluminum support.
Apply the following undercoat liquid to B with a wire bar and dry with warm air
It dried for 30 seconds at 80 degreeC using the drying apparatus. Cover after drying
Coverage is 10mg / m²Met. <Undercoat liquid> ・ Β-Alanine ・ ・ ・ 0.1g ・ Phenylphosphonic acid ... 0.05g ・ Methanol ・ ・ ・ 40g ・ Pure water ... 60g [Formation of Recording Layer] Next, the following recording layer coating solution
Adjust [NL-2] and apply the above primed aluminum
Apply to the substrate support using a wire bar and dry with hot air
And then dry at 100 ° C. for 1 minute in a negative lithographic printing plate precursor
[N-2] was obtained. The coating amount after drying is 1.5 g / m²so
there were. [0280] <Recording layer coating solution [NL-2]> ・ Nonylphenol (isomer mixture, manufactured by Aldrich) ... 0.05g ・ Acid generator [SH-1 (following structure)] 0.3 g ・ Crosslinking agent [KZ-1 (following structure)] 0.5 g ・ Binder polymer: Poly (p-hydroxystyrene) ... 1.5g   (Marca Linker MS-4P, manufactured by Maruzen Petrochemical Co., Ltd.) Infrared absorber [specific dye: exemplary compound (A-1)] 0.07 g ・ AIZEN SPILON BLUE C-RH ... 0.035g   (Hodogaya Chemical Co., Ltd.) ・ Fluorosurfactant: 0.01g   (Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 12g ・ Methyl alcohol ・ ・ ・ 10g ・ 1-Methoxy-2-propanol 8g Acid generation used in recording layer coating solution [NL-2]
The structure of the agent [SH-1] is shown below. Embedded image Cross-linking agent used in recording layer coating solution [NL-2]
The synthesis method and structure of [KZ-1] are shown below. <Synthesis of Crosslinking Agent [KZ-1]> 1- [α-Methyl-α-
(4-Hydroxyphenyl) ethyl] -4- [α, α-
Bis (4-hydroxyphenyl) ethyl] benzene,
Reaction with formalin in aqueous potassium hydroxide solution.
The reaction solution is acidified with sulfuric acid and crystallized.
By recrystallization from a cross-linking agent [KZ-
1] was obtained. The purity was measured by reverse phase HPLC.
It was 92%. [0283] Embedded image[Exposure] The obtained negative planographic printing plate precursor
[N-2] was exposed under the same conditions as in Example N-1. [Development processing] After exposure, Fuji Photo Film
Development using an automatic processor Stablon 900NP manufactured by KK
I managed. The developer is Fuji Photo Film for both the feed and replenishers.
A 1: 8 water dilution of DP-4 manufactured by Irum Co., Ltd. was used. Present
The temperature of the image bath was 30 ° C. The finisher
A 1: 1 water dilution of FP-2W manufactured by Fuji Photo Film Co., Ltd.
Was used. [Printing] Next, obtained by exposure and development.
A lithographic printing plate [N-2] is marked in the same manner as in Example N-1.
Printed. [Evaluation] In the same manner as in Example N-1,
Sensitivity evaluation, 2. 2. Evaluation of printing durability, and Evaluation of stability over time
Went. The results are also shown in Table 1. (Comparative Example 2) Recording in Example N-2
The infrared absorbing agent in the layer coating solution [NL-2] is replaced with a specific dye:
A color having the structure shown below from the exemplified compound (I-12)
The negative type lithographic seal of Comparative Example 2 is the same except that it was changed to
A printing plate precursor [NR-2] was prepared. Then Example N-
1. Perform exposure, development and printing in the same manner as in 1. Sensitivity review
2. 2. Evaluation of printing durability, and Evaluation of stability evaluation over time
did. The results are also shown in Table 1. [0289] Embedded image As is apparent from Table 17, the lithographic mark of the present invention
Printing plate precursor (lithographic printing plate precursor N of Examples N-1 and N-2)
-1 and N-2) show good sensitivity in plate making,
Get more than 50,000 prints with clear print quality without background stains
It was. Furthermore, these lithographic printing plate precursors are used immediately after
There is no change in printing durability after time, and stability over time is high.
I understood it. On the other hand, the lithographic printing plate precursor NR- of the comparative example
1 and NR-2 have low sensitivity and printing durability in plate making
Furthermore, the printing durability is large immediately after plate making and after aging.
It was found that the performance decreased significantly. Special
In addition, the lithographic printing plate precursor NR-2 after aging has a sensitivity measurement.
It was impossible and printing was impossible. This is the time
The infrared absorber used in the comparative example was degraded and deteriorated over time.
As a result, the photothermal conversion function is not manifested, and the image formation reaction occurs.
This is because he was unable to start and proceed. Examples N-3 to N-10 Example N-1
Infrared absorber in recording layer coating solution [NL-1]
From the specific dye: Exemplified Compound (I-5) to Table 18 below
Example N-1 except that each of the exemplified compounds shown was replaced with
Similarly, negative lithographic printing of Examples N-3 to N-10
Plate original plates [N-3] to [N-10] were prepared. after that,
Exposing, developing and printing in the same manner as in Example N-1,
evaluated. [0292] [Table 18] Negative type lithographic printing of Examples N-3 to N-10
The plate original plates [N-3] to [N-10] are examples respectively.
Performance equivalent to N-1 negative planographic printing plate precursor [N-1]
The sensitivity, printing durability, and stability over time are all good.
It was. Examples N-11 to N-19 Example N-
1, infrared absorption in the recording layer coating solution [NL-1]
Agent and polymerization initiator are specific dyes: exemplary compound A-5;
0.08 g, polymerization initiator [O-1]; 0.30 g
The exemplified compounds shown in Table 19 below;
And polymerization initiator; implemented except that each was replaced with 0.30 g
In the same manner as in Example N-1, the samples of Examples N-17 to N-25
Ga type lithographic printing plate precursors [N-11] to [N-19] are produced.
did. Thereafter, in the same manner as in Example N-1, exposure, development and
Printed and evaluated. [0295] [Table 19]Negative lithographic stamps of Examples N-11 to N-19
The printing plate precursors [N-11] to [N-19]
Equivalent to negative lithographic printing plate precursor [N-1] in Example N-1
Shows performance, with good sensitivity, printing durability, and stability over time
Met. (Examples N-20 to N-25) [Formation of recording layer] The following recording layer coating solution [NL-3] was prepared.
And the same as that used in Example N-2 above.
Using a wire bar on a painted aluminum support
And dry for 1 minute at 100 ° C. with a warm air dryer
The negative lithographic printing plate precursor [N-20] to [N-25]
Obtained. The coating amount after drying is 1.6 g / m²Met. [0298] <Recording layer coating solution [NL-3]> Infrared absorber [specific dye: exemplary compounds described in Table 20 below] 0.10 g ・ Acid generator [SH-2 (the following structure)] ... 0.15 g ・ Crosslinking agent [KZ-2 (the following structure)] 0.50 g ・ Novolac resin obtained from cresol and formaldehyde     (Meta: para = 8: 2, weight average molecular weight 5800) ... 1.1 g ・ Resol resin obtained from bisphenol A and formaldehyde     (Weight average molecular weight 1600) ・ ・ ・ 1.0g ・ Fluorosurfactant: 0.06g     (Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 20g ・ 1-Methoxy-2-propanol 7g [0299] [Table 20] Acid generation used in recording layer coating solution [NL-3]
The structure of the agent [SH-2] is shown below. Embedded imageCross-linking agent used in recording layer coating solution [NL-3]
The structure of [KZ-2] is shown below. Embedded image [Exposure, development processing, and printing]
The lithographic printing plate precursor [N-20] to [N-25]
Exposure, development processing, and printing in the same manner as in Example N-1.
did. [Evaluation] In the same manner as in Example N-1,
Sensitivity evaluation, 2. 2. Evaluation of printing durability, and Evaluation of stability over time
Went. Examples N-20 to N-25 negative lithographic stamps
Each of the printing plate precursors [N-20] to [N-25]
Performance equivalent to the planographic printing plate precursor [N-2] of Example N-2
The sensitivity, printing durability, and stability over time were all good.
It was. <Thermal positive lithographic printing plate precursor> [Undercoating] Same aluminum support B as in Example N-1
Next, apply the following undercoat liquid with a wire bar and dry with warm air.
It dried for 1 minute at 90 degreeC using the drying apparatus. Coating after drying
The amount is 10mg / m²Met. <Composition of undercoat liquid> ・ Β-Alanine 0.5g ・ Methanol: 95g ・ Water 5g [Formation of photosensitive layer (image recording layer)]
Adjust the layer coating solution [PL-1],
The coating amount is 1.8 using a wire bar on the minium support.
g / m²And apply at 100 ° C for 1 minute.
In this way, a positive type lithographic printing plate precursor [P-1] was obtained. [0307] <Photosensitive layer coating solution [PL-1]> ・ M, p-cresol novolak ・ ・ ・ 1.0g   (M / p = 6/4, weight average molecular weight 3500, unreacted cresol 0.5% by weight Contains) Infrared absorber [specific dye: exemplary compound (A-18)] 0.3 g -Victoria Pure Blue BOH counter anion is 1-naphthalenesulfonic acid ani Dye turned on ... 0.02g ・ Fluorosurfactant ... 0.05g   (Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Γ-butyrolactone 3g ・ Methyl ethyl ketone 8g ・ 1-Methoxy-2-propanol 7g [Exposure] The obtained positive type lithographic printing plate precursor
[P-1] was exposed under the same conditions as in Example N-1. [Development processing] After exposure, non-reducing sugar and base are added.
Combined D-sorbite / potassium oxide K₂From O
And 5.0% by mass of potassium salt and Olfine AK-02
Aqueous solution 1 containing 0.015% by mass (manufactured by Nissin Chemical)
Using an alkaline developer obtained by adding a predetermined compound to L
Image processing was performed. Development processing is performed at a development humidity of 25 ° C. for a time of 1
The test was performed for 2 seconds. [Printing] Next, obtained by exposure and development.
A lithographic printing plate [P-1] is marked in the same manner as in Example N-1.
Printed. [Evaluation] As in Example N-1, 2.
2. Evaluation of printing durability, and Evaluation of stability over time (6 months)
went. The results are shown in Table 21. [0312] [Table 21](Comparative Example 3) In Example P-1, photosensitivity
The infrared absorbent in the layer coating solution [PL-1] is selected from the specific dye:
From Example Compound (A-18), the color used in Comparative Example 1
The positive lithographic seal of Comparative Example 3 is the same except that the raw material is changed.
A printing plate precursor [PR-1] was prepared. Thereafter, Example P-
1. Perform exposure, development and printing in the same manner as in 1. Printing durability
2. evaluation, and Evaluation of stability over time (6 months)
It was. The results are also shown in Table 21. As is apparent from Table 21, the lithographic mark of the present invention
The printing plate precursor [P-1] prints clear images without background stains.
More than 80,000 items were obtained. Also, after leaving it for 6 months
However, there is no decrease in printing durability, and stability over time is high.
I understood. On the other hand, the lithographic printing plate precursor PR-1 of Comparative Example 3
Has low printing durability in plate making, and moreover, scum
Or printing failure has occurred. (Examples P-2 to P-11) [Formation of photosensitive layer (image recording layer)] The following photosensitive layer coating solution [P
L-2] and the same as that used in Example N-1
The wire bar is attached to the pre-coated aluminum support.
Applied and dried at 100 ° C for 1 minute in a hot air dryer
Dried negative lithographic printing plate precursor [P-2] to [P-11]
Got. The coating amount after drying is 1.6 g / m²Met. [0316] <Photosensitive layer coating solution [PL-2]> Infrared absorber [specific dye: exemplary compounds described in Table 22 below] 0.12 g Naphthoquinone-1,2-diazide-sulfonyl chloride and pyrogallol-acetate (Embodiment 1 in US Pat. No. 3,635,709) Listed) ・ ・ ・ 1.00g ・ Novolac resin obtained from cresol and formaldehyde   (Meta: para = 6: 4, weight average molecular weight 1800) 2.00 g ・ P-octylphenol-formaldehyde novolak ・ ・ ・ 0.02g ・ Naphthoquinone-1,2-diazide-4-sulfonyl chloride ・ 0.01 g ・ Tetrahydrophthalic anhydride ・ ・ ・ 0.05g 4- (p-N, N-bis (ethoxycarbonylmethyl) aminophenyl) -2 , 6-Bis (trichloromethyl) -s-triazine 0.02 g 4- (p-N- (p-hydroxybenzoyl) aminophenyl) -2,6-bi Su (trichloromethyl) -s-triazine 0.02g 6-hydroxy-β-naphthalenesulfonic acid counterion of ether violet Dye made ... 0.02g ・ Megafuck F-177 0.06g   (Dainippon Ink & Chemicals, Fluorosurfactant) ・ Methyl ethyl ketone 20g ・ Methyl alcohol ・ ・ ・ 7g [0317] [Table 22] [Exposure, development processing, and printing]
Implementation of di-type planographic printing plate precursor [P-2] to [P-11]
In the same manner as in Example P-1, exposure, development, and printing
It was. [Evaluation] In the same manner as in Example P-2, 2.
2. Evaluation of printing durability, and The stability with time was evaluated. Positive type lithographic printing of Examples P-2 to P-11
The plate original plates [N-2] to [N-11] are examples respectively.
Performance equivalent to P-1 planographic printing plate precursor [P-1]
In addition, both printing durability and stability over time were good. <Unprocessed planographic printing original plate> (Example M-1) [Synthesis of heat-reactive microcapsules]
Silylene diisocyanate 40g, trimethylolpro
10 g pan diacrylate, allyl methacrylate and
Copolymer of til methacrylate (molar ratio 60/40) 1
0 g, Pionein A41C (Takemoto Yushi Co., Ltd.) 10 g
Was dissolved in 60 g of ethyl acetate. As an aqueous phase component, PV
Prepare 120g of 4% aqueous solution of A205 (Kuraray Co., Ltd.)
Made. Using a homogenizer for oil phase components and water phase components
And emulsified at 10,000 rpm. Then add 40g of water.
The mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. This
Solid content of the microcapsule dispersion obtained as described above
The concentration is 20% and the average particle size of the microcapsules is
It was 0.5 μm. [Preparation of support C having hydrophilic layer]
The composition 1A, paint shaker (Toyo Seiki Co., Ltd.)
After using glass beads and dispersing for 10 minutes at room temperature,
Furthermore, 33 g of the following composition 1B was added, and it was for 1 minute at room temperature.
After the dispersion, the crow beads are separated by filtration to disperse the hydrophilic layer composition.
Got. [0323] <Composition 1A> ・ Strontium titanate 35g   (Wako Pure Chemical Industries, Ltd., average particle size 2 μm) ・ Polyvinyl alcohol 5% aqueous solution ... 60g   (PVA117 manufactured by Kuraray Co., Ltd.) ・ Colloidal silica 20% aqueous solution 55g   (Snowtex C manufactured by Nissan Chemical Industries, Ltd.) [0324] <Composition 1B> ・ Tetraethoxysilane ... 92g ・ Ethanol 163g ・ Water 163g ・ Nitric acid ・ ・ ・ 0.1g Next, the dispersion composition for hydrophilic layer is treated with corona treatment.
Processed polyethylene terephthalate support (Toray
(Made by Co., Ltd., thickness 180μm) on the wire bar
The coating amount after drying is 5 g / m²Attach to be
Support with a hydrophilic layer dried at 100 ° C for 10 minutes
Body C was prepared. [Formation of image recording layer] The composition is shown below.
After preparing the image recording layer coating solution [ML-1], it has a hydrophilic layer
Bar is coated on the substrate C to be heated, and oven is 90 ° C. for 120 seconds.
Dry to produce an unprocessed planographic printing original plate [M-1].
It was. The dry coating amount of the image recording layer is 0.5 g / m.²So
It was. [0327] <Image recording layer coating solution [ML-1]> ・ Water 70g ・ The above heat-reactive microcapsule (in terms of solid content) 5 g ・ Polyhydroxyethyl acrylate 0.5g ・ P-diazodiphenylamine sulfate ... 0.3g Infrared absorber [specific dye: exemplary compound (A-32)] 0.3 g [Exposure and printing] Unprocessed planographic stamp obtained
The printing original plate [M-1] was used in Example N-1 (infrared ray
(The semiconductor laser was replaced with one with a wavelength of 980 nm)
Use o Trendsetter 3244VFS,
After exposure under the same conditions, without processing, high
Installed on the cylinder of the SOR-M printing machine manufactured by Delberg
After supplying dampening water, supply ink, and further paper
Supply and print. It can be developed on-machine without problems.
Printable. [Evaluation] The printed material on the 10th printed sheet was multiplied by 20 times.
When evaluated using a magnifying glass, there is no background stain and a solid image
The uniformity of the density of the image area was very good. Furthermore, printing
Continued, it was found that fine lines and characters were missing and solid images were dark.
There is no unevenness of the degree, and the non-image area is not smudged.
More than 20,000 prints were obtained. (Example M-2) Same support as Example N-1
Using the body A, the following coating for the image recording layer was prepared.
The coating weight after drying the liquid [ML-2] is 1.2 g / m²
After coating and drying, unprocessed planographic printing plate
[M-2] was produced. [0331] <Coating liquid for image recording layer [ML-2]> ・ Poly (P-vinylbenzenesulfonic acid cyclooxyl ester) ・ 1.00g   (Mw1.2 × 10^Four) Infrared absorber [specific dye: exemplary compound (A-29)] 0.15 g ・ Victoria Pure-BOH counter ion is changed to 1-naphthalene-sulfonic acid Dye ... 0.05g ・ Fluorosurfactant: 0.06g   (Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 20g ・ Methyl alcohol ・ ・ ・ 7g [Exposure, printing and evaluation] Non-processed type obtained
A lithographic printing plate precursor [M-2] is red with a wavelength of 1064 nm.
Exposure was with a YAG laser emitting an external line. After exposure, 11
After heat treatment at 0 ° C for 1 minute, with Heidel KOR-D machine
Printed. At this time, the non-image area of the printed matter is stained.
Observed whether or not. Good with no stains on non-image area
More than 10,000 prints were obtained. [0333] The lithographic printing plate precursor according to the present invention comprises an infrared laser.
By using the
It can be recorded directly from digital data, and sensitivity and
Has a recording layer with excellent image area strength, and many good printed materials
Sheets are obtained, and the effect is excellent in printing durability.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA11 AA12 AA13 AB03                       AC08 AD01 AD03 BC13 BC42                       BE01 BJ03 CA42 CB54 CC13                       FA10 FA17                 2H096 AA06 BA05 BA09 EA04 EA23                       GA08

Claims (1)

1. An image recording layer containing at least one of infrared absorbers represented by the following general formula (I) and general formula (II) is provided on a hydrophilic support. Infrared laser lithographic printing plate precursor. [Chemical 1] In general formula (I) and general formula (II), R ¹ and R ² each independently represents an aliphatic group, an aryl group, or a heterocyclic group. R ³ represents a hydrogen atom, a halogen atom, or a monovalent organic residue. B is an organic compound that forms a 5- or 6-membered heterocyclic ring containing at least one heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom, a Se atom, and a Te atom, or a condensed polycycle containing the heterocyclic ring. Represents a residue. L
¹ , L ² and L ³ each independently represent a methine group. p
Represents 1, 2 or 3. q represents 0, 1, 2, 3, or 4; A ⁻ represents a counter anion present when charge neutralization is required. However, m represents 0 or 1.