JP2003307841A - 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 of a computer or the like by using IR emitting solid and semiconductor lasers and which exhibits high recording sensitivity and excellent printing durability. <P>SOLUTION: The original plate of the planographic printing plate is capable of recording digital data with an infrared laser and is obtained by disposing on a hydrophilic support an image recording layer containing an IR absorbent represented by formula (I) or (II), wherein X<SP>0</SP>and X<SP>1</SP>are each O, S, Se, Te or >N-R<SP>5</SP>; Z<SP>0</SP>is a group of atoms required to form a 5- or 6-membered heterocycle or a condensed ring including a 5- or 6-membered heterocycle; Z<SP>1</SP>is a group of atoms required to form a pyrylium ion structure; and W is O or S. <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 JP-A-2001-1252
Radika generated by heat as disclosed in No. 60
The recording layer of the exposed part is caused by polymerization reaction with the initiator as an initiator.
A method of forming an image portion by curing is 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 infrared laser irradiation
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.
It has excellent sensitivity to infrared laser light and is in the recording layer.
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 infrared laser of the present invention
A lithographic printing plate precursor has the following general formula on a hydrophilic support:
Including an infrared absorber represented by (I) or general formula (II)
An image recording layer is provided and an infrared laser is used.
And can be recorded. [0009] [Formula 4]In general formula (I), X⁰And X¹Is the same
May be different oxygen atom, sulfur atom, selenium source
Represents a child, a tellurium atom or a group shown below, where R^Five
Represents an aliphatic group which may be substituted. [0011] [Chemical formula 5] Z⁰And Z¹Is pyran, benzopyran, naphth
Topiran, thiopyran, benzothiopyran, naphthothio
Piran, Serenapyran, Benzoselenapyran, Naftose
Lenapyran, ternapyran, benzoternapyran, naphth
Toternapyran or 5-membered or 6-containing nitrogen atom
This represents a group of atoms necessary to form a member heterocycle. W is acid
Represents an elementary atom or a sulfur atom. Y¹, Y², Y^ThreeAnd Y^FourIs water
Elementary atom, aliphatic group, aromatic group, cyano group, nitro group,-
It represents OR or -SR. Where R is an aliphatic group or aromatic
Represents a group. R¹Represents a hydrogen atom or an alkyl group.
R², R^ThreeAnd R^FourEach may be the same or different,
Each hydrogen atom or monovalent nonmetallic atomic group excluding hydrogen
R², R^ThreeAnd R^FourAny two adjacent
They may combine to form a fused 6-membered ring. Q¹And Q²Each
4-thiazolidinone, 4-oxazolidinone, 4-imi
Dazolidinone, 5-thiazolidinone, 5-oxazolidin
Required to form a non- or 5-imidazolidinone ring
Represents an atomic group. L¹, L²Each independently represents a methine group.
The m and n each represents 0 or 1, and p represents 0, 1, 2 or
3 is represented. A^-Is present when charge neutralization is required
Represents a counter anion. However, q is an integer of 1-5. [0013] [Chemical 6] In the above general formula (II), X⁰, X¹, Z⁰,
Z¹, Y¹, Y², Y^Three, Y^Four, R^Five, R¹, R², R^Three, R^Four,
Q¹, Q², L¹, L², M, n, and p are the above general formulas
Same as in (I). B⁺The charge neutralization
Represents an onium cation present when necessary. However,
r is an integer of 1 to 3. In the compound represented by the general formula (I)
A^-If neutralization of the charge by A is not necessary, A^-The
Anions and benzopyrilyu present in the excluded molecule
It has a structure in which an inner salt is formed with muon.
A^-An anion present in the molecule other than
-SO_ThreeH, -OPO_ThreeH₂, -P (= O) (O
R) OH, -OP (= O) (OR) OH, -SO₂H or
Generated by dissociation of at least one acidic group selected from
It is preferable that the anion is formed. R is charcoal
Represents an optionally substituted aliphatic group having a prime number of 1 to 12; one
On the other hand, in the compound represented by the general formula (I), A^-
If charge neutralization by means of^-And benzo
A structure in which an inner salt is formed with pyrylium ions
Have. In the compound represented by the general formula (II)
And B⁺If neutralization of the charge due to is not necessary, B⁺
Anion and benzopyryl present in the molecule except for
An inner salt is formed with the um ion, and B⁺except for
Intramolecular with anions and cations present in the partial molecule
It has a structure in which a salt is formed. Meanwhile, the general formula
In the compound represented by (II), B⁺Due to the charge
If neutralization is required, B⁺In the part of the molecule except
Intramolecular with existing anions and benzopyrylium ions
A salt is formed and B⁺Exists in the part of the molecule except
Anion and B⁺And the structure in which the inner salt is formed
Have. B⁺Anis present in the molecule other than
On as -SO_ThreeH, -COOH, -PO_ThreeH₂,
-OPO_ThreeH₂, -P (= O) (OR) OH, -OP (=
O) (OR) OH, -SO₂At least selected from H
It is an anion generated by the dissociation of a kind of acidic group
It is preferable. R is a substituted group having 1 to 12 carbon atoms.
Represents an aliphatic group which may be Where B⁺Represented by
Examples of nium cations include iodonium ions, sulfo
Nium ion, phosphonium ion, diazonium ion
, Carbonium ion, trihalogen methyl group substitution
Oxazolium ion or S-triazinium ion
preferable. Although the operation of the present invention is not clear, the general formula
The infrared absorber represented by (I) or 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.
The In addition, records containing negative or hydrophobic precursors
Acceleration of curing reaction or hydrophobized region formation reaction in the layer
Guess that it will be possible to form a strong image area
Is done. Moreover, it represents with general formula (I) or general formula (II).
In the recording layer by adding the compound to be recorded in the recording layer.
Due to the structure of such compounds with coexisting components
Some kind of interaction is formed, and negative or positive
Alkali development resistance in the recording layer is improved, which is printing durability
It is thought that it contributes to improvement. So like this
A flat plate obtained by a lithographic printing plate precursor having a simple image recording layer
According to the plate printing plate, many good prints can be obtained and printing durability
Excellent. Further, as described above, in the general formula (II)
In the compounds represented, B⁺Onium katsushi represented by
On and B⁺Anions present in the molecule other than
When an inner salt is formed in⁺Represented by
The onium cation is converted into an acid or radical by heat or light.
A polymerization curing system or a later-described
Is applied to an acid-crosslinking negative image recording layer, or
When applied to positive-type image recording layer of interaction cancellation system
In particular, it seems that a particularly excellent sensitivity improvement effect can be obtained.
It is. More specifically, B⁺Onium cation represented by
The radical generation function of
More heat generated by the photothermal conversion agent is in the molecule, that is, very close
Acts on the functional group present in the cross-linking reaction or acid decomposition reaction
Efficient generation of acids and radicals necessary for the generation of
Negative type containing such compounds or
Is expected to improve sensitivity in the positive recording layer.
It is measured. [0018] 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 or a photosensitive layer).
High-sensitivity image formation by using an infrared absorber
The reaction can be performed. Specific infrared absorption according to the present invention
The collector has a function to convert the absorbed infrared rays into heat.
The The heat generated at this time causes the image formation reaction to occur and progress.
To do. The infrared absorbent used in the present invention is a special
Absorbs in a certain wavelength region (red light or infrared region)
It is a dye having the following specific structure.
To do. In the present invention, (A) as an infrared absorber
The compound represented by the general formula (I) or general formula (II)
It needs to be used. [0019] [Chemical 7] In the general formula (I) or the general formula (II),
The following are preferred as each substituent.
You can. In general formula (I), X⁰And X¹Is the same
May be different, oxygen atom, sulfur atom, selenium source
A child, a tellurium atom or a group shown below is represented. [0021] [Chemical 8] X⁰And X¹> N-R^FiveR^FiveIs
Represents an aliphatic group which may be substituted, and
Is substituted with a linear or branched chain having 1 to 22 carbon atoms.
May be substituted with 2 to 22 carbon atoms
Alkenyl group, optionally substituted alicyclic ring having 5 to 22 carbon atoms
A hydrocarbon group of formula is preferred. These aliphatic groups, and this
Specific examples of the substituent introduced in the above are Z described later.⁰
It is synonymous with the aliphatic group mentioned as the substituent which can be introduced in
The In the general formula (I), Z⁰And Z
¹Are pyran, benzopyran, naphthopyran, thiopyra
, Benzothiopyran, naphthothiopyran, serenapyra
, Benzoselenapyran, naphthoselenapyran, terna
Piran, benzoternapyran, naphthoternapyran,
Forms a 5- or 6-membered heterocycle containing a nitrogen atom
Represents a group of atoms necessary for the
It may have a group. Z⁰And Z¹Formed in
Examples of the heterocyclic ring include thiazole ring, benzothia
Sol ring, naphthothiazole ring (for example, naphtho [2,
1-d] thiazole ring, naphtho [1,2-d] thiazole
Ring), thionaphthene [7,6-d] ring, benzooxy
Sazole ring, naphthoxazole ring (for example, naphtho ring
[2,1-d] oxazole ring, etc.), selenazole ring,
Benzoselenazole ring, naphthoselenazole ring (for example,
Naphtho [2,1-d] selenazole ring, naphtho
[1,2-d] selenazole ring, etc.), oxazoline ring,
Serenazoline ring, thiazoline ring, pyridine ring, quinoline
Ring (eg, 2-quinoline ring, 4-quinoline ring, benzo
[T] quinoline ring, etc.), isoquinoline ring (for example, 1-
Isoquinoline ring, 3-isoquinoline ring, benzoisoquino ring
Phosphorus ring, acridine ring, 3,3-dialkylindole
Nin ring, 3,3-dialkylbenzoindolenin ring,
3,3-dialkyl [1,7] diazo-2-indene
Ring, benzimidazole ring, naphtholactam ring, etc.
It is done. Z⁰And Z¹Examples of substituents in
For example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom,
Iodine atom), cyano group, hydroxy group, nitro group,
Carboxy group, sulfo group, phospho group, oxyphosphono
Group, -OR⁰¹Group, -SR⁰¹Group, -COR⁰¹Group, -COO
R⁰¹Group, -OCOR⁰¹Group, -SO₂R⁰¹Group, -CON
(R⁰²) (R⁰³) Group, -SO₂N (R⁰¹) (R⁰²) Group,
-N (R⁰¹CO-R⁰¹Group, -N (R⁰²) SO₂-R⁰¹
Group, -NHCONH-R⁰¹Group, -NHCOOR⁰¹Group,-
Si (R⁰⁴)_ThreeGroup, -P (= O) (R⁰¹)₂Group, -OP
(= O) (R⁰¹)₂Group, substituted with 1 to 22 carbon atoms
A good alkyl group, a C2-C22 optionally substituted a
Lucenyl group, an alkyl having 2 to 22 carbon atoms which may be substituted
Nyl group, C5-C22 optionally substituted alicyclic carbonization
Hydrogen group, optionally substituted aryl having 6 to 18 carbon atoms
Selected from groups, oxygen atoms, nitrogen atoms, and sulfur atoms
Optionally substituted with at least one heteroatom
A heterocyclic group is mentioned. Where Z⁰And Z¹Place in
(R in the substituent⁰¹) Is an aliphatic group, an aryl group or a complex
Represents a cyclic group. These monovalent organic residues contain substituents.
May be. (R⁰¹As an aliphatic group represented by
Is a branched or straight chain alkyl group having 1 to 22 carbon atoms
(For example, methyl group, ethyl group, propyl group, butyl
Group, heptyl group, hexyl group, pentyl group, octyl
Group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl, tetradecyl, hexadecyl, oct
Tadecyl group), straight or branched chain having 2 to 18 carbon atoms
Alkenyl groups (e.g. vinyl, propenyl,
Tenenyl, pentenyl, hexenyl, octenyl
Group, decenyl group, dodecenyl group, tetradecenyl group,
Oxadecenyl group, octadecenyl group, etc.), C2-C1
8 linear or branched alkynyl groups (eg
Cetylenyl group, propynyl group, butyyl group, pentale
Group, hexyl group, octyl group, decyl group, dodece
Yl group, octadecyl group, etc.), C5-C10 alicyclic ring
Hydrocarbon group (eg, cyclopentyl group, cyclohexyl group)
Sil group, cyclooctyl group, cyclodecyl group, cyclohexane
Xenyl group, cyclooctenyl group, tricyclodecyl group
Group, tricyclodecenyl group, isobornyl group, adamanty
Group, etc.). Among these, carbon atoms
Straight chain up to number 1-12, minutes up to 3-12 carbon atoms
Branched and cyclic aliphatics with 5 to 10 carbon atoms
Groups are more preferred. (R⁰¹As an aryl group represented by
Is preferably an aryl group having 6 to 14 carbon atoms.
Enyl, naphthyl, dihydronaphthyl, tetrani
Group, indenyl group, indanyl group, benzocyclobute
Nyl group, benzocycloheptenyl group, anthral group, etc.
Is mentioned. (R⁰¹As a heterocyclic group represented by
Is a small number selected from oxygen atom, sulfur atom and nitrogen atom
5- or 6-membered compounds with at least one heteroatom
Consists of a polycyclic structure containing a prime ring or a heterocyclic ring thereof
A monovalent substituent of a heterocyclic ring can be mentioned. The above heterocyclic group
Examples of the body include, for example, tetrahydrofuran, dihydro
Furan, pyrrole, pyrroline, pyrrolidine, pyrazo
, Pyrazoline, pyrazolidine, imidazole, imida
Zolin, imidazolidine, triazole, triazoli
, Triazolidine, tetrazole, tetrazoline, te
Trazolidine, thiophene, dihydrothiophene, teto
Lahydrothiophene, isoxazole, isoxazo
Phosphorus, isoxazolidine, oxazole, oxazoly
Oxazolidine, isothiazole, isothiazolyl
, Isothiazolidine, thiazole, thiazoline, thia
Zolidine, pyridine, hydropyridine, piperidine,
Dropyridacin, pyrimidine, pyrazine, piperazine,
Pyran, hydropyran, thiopyran, hydrothiopyra
, Oxazine, morpholine, azepine, hydroazepi
, Oxepin, Thiepin, Isoindole, Indri
, Indole, isoindoline, carbazole, in
Dazole, benzimidazole, hydrobenzimidazo
, Benzotriazole, inbenzofuran, diben
Zofuran, hydrobenzofuran, benzoxazole,
Benzothiophene, benzodithiol, benzoxazo
, Hydrobenzoxazole, benzoisoxazol
, Benzothiazole, benzoisothiazole, ben
Zoxathiol, quinoline, isoquinoline, acrid
Phenanthridine, quinazoline, phenazine, ben
Zopyran, xanthene, benzothiopyran, hydroben
Zopyran, benzoxazine, benzothiazine, thiox
Santen, phenoxazine, phenothiazine, benzoa
Zepin, benzodiazepine, pyrrolidine, pyrrolizidi
Quinolidine, quinolizidine, isodonodine, pylori
Zidine, purine, isochroman, chroman, bipyridi
, Viteofene, quinuclidine, piperazine, etc.
It is done. These (R⁰¹) An aliphatic group represented by
The aryl group and the heterocyclic group may be substituted or substituted.
As the group, the above-mentioned “Z¹And Z²Same as `` Substituent in
Of the contents of. Z⁰And Z¹(R in the substituents in⁰²And
(R⁰³) Is a hydrogen atom, an aliphatic group, an aryl group, or
Represents a heterocyclic group, (R⁰²) And (R⁰³) Is a nitrogen atom
A ring structure may be formed. Where (R⁰²)as well as
(R⁰³) Is a monovalent organic residue excluding a hydrogen atom
(R⁰¹) Represents the same content. Z⁰And Z¹-Si which is a substituent in
(R⁰⁴)_Three-R in the group⁰⁴The group is a hydrocarbon having 1 to 22 carbon atoms
Prime group or -OR⁰¹Represents a group. Here, carbon with 1 to 22 carbon atoms
As the hydride group, (R⁰¹) Each replaced
Selected from aliphatic groups, aryl groups and heterocyclic groups
Represents a group. -OR⁰¹R in the group⁰¹R⁰¹Same as
is there. -Si (R⁰⁴)_ThreeThe group is -OR⁰¹When representing a group
(R⁰¹At least one of the hydrocarbon groups
Preferably two or more contain hydrocarbon groups
More preferred. Z⁰And Z¹Listed as substituents in
Alkyl group, alkenyl group, alkynyl group, alicyclic
Specific examples of the hydrocarbon group, aryl group, and heterocyclic group include
Each of the above (R⁰¹) Similar to those listed above
Can be mentioned. In the general formula (I), R¹Is hydrogen
Represents an atom or an alkyl group. R¹When is an alkyl group,
Charcoal like methyl group, ethyl group, propyl group, butyl group
The prime number is preferably 1 to 4. In the general formula (I), Y¹, Y², Y
^ThreeAnd Y^FourEach may be the same or different and hydrogen
Atom, aliphatic group, aromatic group, cyano group, nitro group, -O
R or -SR is represented. Where R is an aliphatic group or aromatic
Represents a group. Among these, a hydrogen atom, a C1-C22 arrangement
Aliphatic group which may be substituted, or substitution of 6 to 22 carbon atoms
An aryl group that may be used is preferred. these
Specific examples of the aliphatic group and substituents introduced therein
Z in the general formula (I)⁰Can be installed in
It is synonymous with the aliphatic group mentioned as a substituent. Also Ally
As specific examples of the ru group, Z in the general formula (I)⁰
An aryl group further introduced into an aliphatic group that can be substituted with
It is synonymous with those mentioned above. Q¹And Q²Are 4-thiazolidinone and 4 respectively.
-Oxazolidinone, 4-imidazolidinone, 5-thia
Zolidinone, 5-oxazolidinone or 5-imidazoli
This represents a group of atoms necessary to form a dinone ring. Chia
Zolizinone ring, oxazolidinone ring or imidazolidino
Examples of substituents that can be introduced into the ring include Z⁰Aliphatic in
Examples of substituents that can be introduced into the group are the same.
It is. L¹, L²Each independently represents a methine group.
These methine groups may have a substituent. This
Non-substituted groups that can be introduced into these methine groups include halogens.
Atom, carboxy group, substituted or unsubstituted alkyl
Group, substituted or unsubstituted aryl group, -OR^TenGroup,-
SR^TenGroup, -N (R¹¹) (R¹²) Groups, substituted or unsubstituted
Examples include a substituted iminium ion group. Z mentioned above⁰
The same substituents that can be introduced in
I can get lost. Among these, as substituents on L,
Aliases such as alkyl groups such as til groups and ethyl groups, and phenyl groups
Group, halogen atom such as chlorine atom, carboxy group, di
Diarylamino groups such as phenylamino group, phenylthio
An arylthio group such as o group is preferred. [0036] [Chemical 9]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. As a substituent
The R^oWith the same content. Ma
The methine groups are cross-linked with dimethylene groups and trimethylene groups.
And a carbon 5-membered or 6-membered ring is formed on the methine chain.
Also preferred are: In the present invention, = (L¹-L²)
As the chain length of the polymethine group containing =, the carbon chain length is 3 to 1
1 polymethine group is preferred, pentamethine group, hepta
A methine group or a nonamethine group is more preferable,
The heptamethine group is particularly suitable from the viewpoint of wavelength suitability and stability.
preferable. In the general formula (I), R², R^ThreeAnd R^Four
Each independently represents a hydrogen atom or a monovalent non-gold other than hydrogen
Represents a genus group. These may have further substituents
Well, the substituents that can be introduced include Z⁰In
And the same substituents as those described above. R², R^ThreeAnd R^Four
Any two adjacent to form a fused 6-membered ring
May be. In the general formula (I), A^-Is of charge
Represents a counter anion present when neutralization is required. Take
Counter anions are inorganic or organic anions.
The Here, n is an integer of 1 to 5, and is 1 or 2.
It is preferable. Specific examples of counter anions include
Are not limited to these.
Yes. For example, Cl^-, F^-, Br^-, I^-, ClO_Four ^-, Br
O_Four ^-, SbF₆ ^-, PF₆ ^-, Borate anions (eg,
BF_Four ^-, Tetraphenylborate anion, butyl-to
Riphenylborate anion, butyl-tris (2,
4,6-trimethylphenyl) borate anion, buty
Ru-methyl-diphenylborate anion, butyl-to
Lith (fluorophenyl) borate anion, butyl-
Tris (methoxyphenyl) borate anion, tetra
(Chlorophenyl) borate anion, etc.) sulfonic acid
Nion (eg, alkane sulfonate anion (alkaline
Examples of sulfonic acid include methanesulfonic acid and ethanesulfuric acid.
Phosphonic acid, propane sulfonic acid, butane sulfonic acid, ant
Sulfonic acid, phenylmethanesulfonic acid, hydroxy
Propanoic acid, 2-chloroethanesulfonic acid, 10-can
Fursulfonic acid, trifluoromethanesulfonic acid,
Ntafluoroethanesulfonic acid) aromatic sulfonic acid
Nion (As aromatic sulfonic acid, benzenesulfone
Acid, toluenesulfonic acid, methoxybenzenesulfone
Acid, hydroxybenzenesulfonic acid, chlorobenzenes
Luphonic acid, nitrobenzene sulfonic acid, acetyl benzene
Sulfonic acid, pentafluorobenzene sulfonic acid,
-Sulfobenzene carboxylic acid, mesitylene sulfonic acid,
Naphthalene sulfonic acid, naphthalene disulfonic acid, naphth
Tall sulfonic acid, anthraquinone sulfonic acid, monolith
Sulfonic acid, etc.), phosphonate anion (specifically,
Aliphatic compounds and aromatics exemplified for the sulfonate anion
Group of phosphonic acid groups instead of sulfonic acid groups
Examples include at least one kind of substituted compound)
It is done. In the compound represented by the general formula (I)
A^-If neutralization of the charge by A is not necessary, A^-The
Anions and benzopyrilyu present in the excluded molecule
It has a structure in which an inner salt is formed with muon.
A^-An anion present in the molecule other than
-SO_ThreeH, -COOH, -PO_ThreeH₂, -OPO_Three
H₂, -P (= O) (OR) OH, -OP (= O) (O
R) OH, -SO₂At least one acid selected from H
Preferably an anion generated by the dissociation of the functional group.
Good. Among the acidic groups, -SO_ThreeH, -COO
H, -PO_ThreeH₂, -OPO_ThreeH₂Having any one of
It is more preferable. Note that R is a C1-C12
Represents an aliphatic group which may be substituted; These aliphatic groups, and
Specific examples of the substituent introduced into these are as described above.
Q in general formula (I)¹Listed as possible substituents
Synonymous with aliphatic groups. On the other hand, represented by the general formula (I)
In the compound^-It is necessary to neutralize the charge by
In some cases, A^-Counter anion and benzo
A structure in which an inner salt is formed with pyrylium ions
Have. Next, the general formula (II) will be described.
In the general formula (II), X⁰, X¹, Z⁰, Z¹, Y
¹, Y², Y^Three, Y^Four, R^Five, R¹, R², R^Three, R^Four, Q¹, Q
², L¹, L², M, n, and p are defined in the general formula (I).
It is synonymous with In the general formula (II), B⁺Is in the charge
Represents an onium cation present when sum is required. However
M is an integer of 1 to 3. B⁺Charge neutralization by
B if not needed⁺Exists in the part of the molecule except
An anion and benzopyrylium ion form an inner salt
And B⁺Anis present in the molecule other than
It has a structure in which an internal salt is formed between on and cation.
To do. On the other hand, the compound represented by the general formula (II)
And B⁺If neutralization of the charge by means of⁺
Anion and benzopyryl present in the molecule except for
An inner salt is formed with the um ion, and B⁺except for
Anions and B present in the molecule⁺And the inner salt is
It has a formed structure. B⁺Except for
As an anion present in the molecule, -SO_ThreeH, -C
OOH, -PO_ThreeH₂, -OPO_ThreeH₂, -P (= O) (O
R) OH, -OP (= O) (OR) OH, -SO₂H or
Generated by dissociation of at least one acidic group selected from
It is preferable that the anion is formed. In the acidic group
-SO_ThreeH, -COOH, -PO_ThreeH₂, -OPO_Three
H₂It is more preferable to have any one of these. Na
R is an optionally substituted aliphatic group having 1 to 12 carbon atoms.
Represents. These aliphatic groups and the positions introduced into them
Specific examples of the substituent include Q in the general formula (I).¹
It is synonymous with the aliphatic group mentioned as the substituent which can be introduced in
The Where B⁺As an onium cation represented by
Are iodonium ion, sulfonium ion, phospho
Nium ion, Diazonium ion, Carbonium ion
Oxazolium ion substituted with trihalogenmethyl group
Or S-triazinium ion is preferable. Specifically
Is mentioned as “(B) radical generator” described later.
The cation moiety in the onium salt is preferred. The general formula (I) or the above used in the present invention
Specific examples of the compound represented by (II) are shown below.
It is not limited to these. [0044] [Table 1] [0045] [Table 2] [0046] [Table 3][0047] [Table 4] [0048] [Table 5][0049] [Table 6] [0050] [Table 7][0051] [Table 8] [0052] [Table 9]Further, the specific dye used in the present invention.
Can be synthesized using a conventionally known method. Together
Details regarding the formation method are described, for example, in JP-A-1-1244861.
Can be mentioned. 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 not impairing the effects of the present invention.
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 of materials" (edited by the Society of Synthetic Organic Chemistry, published in 1970)
The well-known thing described in literature can be utilized. 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.
Follow me. 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 area, the developability is
Improved, positive (exposed) area becomes a non-image area
Divided into two. As the 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 As one of the negative recording layers, a polymerization hardened layer can be mentioned.
This polymerization hardened layer includes (A) an infrared absorber and (B) a radio.
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 recording layer is an acid cross-linked layer.
The (E) Acid is generated in the acid cross-linking layer by light or heat.
Compound (hereinafter referred to as acid generator) and (F) generated
A compound that crosslinks with an acid (hereinafter referred to as a crosslinking agent)
To contain and further form a layer containing these
(G) Alkaline capable of reacting with a crosslinking agent in the presence of an acid
Contains soluble polymers. In this acid cross-linked layer, light irradiation
Or the acid generated by the decomposition of the acid generator by heating
Promotes the function of the cross-linking agent,
A strong cross-linked structure is formed with the base polymer.
As a result, alkali solubility is lowered and insoluble in the developer.
Become. At this time, the energy of the infrared laser is efficiently used.
In order to use, (A) Infrared absorber is blended in the recording layer
Is done. 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 specific red of the present invention
It is preferable that the ratio of the external line absorbent exceeds 60% by mass.
The best thing is as mentioned above. [(B) Compound generating radical] Radi
Cal generators produce energy from light, heat, or both.
Compounds that generate more radicals and have polymerizable unsaturated groups
It refers to a compound that initiates and accelerates the polymerization of a product. Suitable for the present invention
Usable radical generators include known thermal polymerization initiators
And compounds with bonds with small bond dissociation energy
Can be selected and used, for example, diazonium
Salt (SI Schlesinger, Photog
r. Sci. Eng. , 18, 387 (1974),
T.A. S. Bal etal, Polymer, 21, 4
23 (1980) etc.), ammonium salts (US special
No. 4,069,055, JP-A-4-3650
49), phosphonium salts (US Patent No.
Each light of 4,069,055 and 4,069,056
), Iodonium salts (European Patent No. 104,
143, U.S. Pat. Nos. 339,049 and 410,
No. 201 specification, JP-A-2-150848, JP-A-2-150848
Described in Japanese Patent Laid-Open No. 2-296514), sulfoniu
Salt (European Patent Nos. 370,693 and 390,214)
No., No. 233,567, No. 297,443, No. 29
No. 7,442, US Pat. No. 4,933,377, No. 1
61,811, 410,201, 339,04
9, No. 4,760,013, No. 4,734,444
No. 2,833,827, German Patent No. 2,904
626, 3,604,580, 3,604,5
81), an arsonium salt (C.I.
S. Wen et al, Teh, Proc. Conf.
Rad. Curing ASIA, p478 Tokyo
o, Oct (1988), etc.), selenonium salts
(JV Crivello et al, Macrom
orecules, 10 (6), 1307 (197
7), J.H. V. Crivello et al. Po
lymer Sci. , Polymer Chem. E
d. , 17, 1047 (1979) etc.)
Um salt, 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 Patent Laid-Open 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. H.
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, the laser is particularly preferably used.
Examples of the dical generator include onium salts.
Onium salts represented by the general formulas (B-1) to (B-3) are listed.
I can get lost. [0072] Embedded image In the formula (B-1), Ar¹¹And Ar¹²It
Each independently 20 carbon atoms which may have a substituent
Or less aryl groups. This aryl group is substituted
Preferred substituents when having a halogen atom,
Nitro group, alkyl group with 12 or less carbon atoms, carbon source
Alkoxy group having 12 or less children, or 12 carbon atoms
Or less aryloxy groups. Z^11-Is nothing
It represents a mechanical anion or an organic anion. In the formula (B-2), Ar^{twenty one}Has a substituent
An aryl group having 20 or less carbon atoms
The Preferred substituents include halogen atoms and nitro
Group, alkyl group having 12 or less carbon atoms, 1 carbon atom
2 or less alkoxy groups, 12 or less ants
Alkyloxy group having 12 or less carbon atoms
Groups, dialkylamino groups having up to 12 carbon atoms, carbon
Arylamino group or carbon atom having 12 or less atoms
A diarylamino group of several 12 or less is mentioned. Z
^{twenty one-}Is Z^11-Represents a counter ion having the same meaning as. In the formula (B-3), R³¹, R³²And R³³Is
Each may be the same or different and have a substituent
An optionally substituted hydrocarbon group having 20 or less carbon atoms is shown.
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group having 12 or less elementary atoms, 12 or less carbon atoms
Lower alkoxy group or ant having 12 or less carbon atoms
And an oxy group. Z^31-Is Z^11-Is synonymous with
Represents on. Z in the general formulas (B-1) to (B-3)
^11-, Z^{twenty one-}, Z^31-Is an inorganic anion or organic anion
Represents on, but as an inorganic anion, halogen ion
F^-, Cl^-, Br^-, I^-), Perchlorate ion (Cl
O_Four ^-), Perborate ion (BrO)_Four ^-), Tetrafluo
Roborate ion (BF_Four ^-), SbF₆ ^-, PF₆ ^-Etc.
As an organic anion, organic borate anio
, Sulfonate ion, phosphonate ion, carboxylic acid
Ion, R⁴⁰-SO_ThreeH^-, R⁴⁰-SO₂ ^-, R⁴⁰-SO₂
S^-, R⁴⁰-SO₂N^--YR⁴⁰Ion (where R⁴⁰
Is an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms
6 to 20 aryl groups, Y is a single bond, -CO-,
-SO₂-Represents. ) And the following general formula (B-4)
And a 5-coordinate silane compound ion.
Where R⁴⁰May have a ring structure and alkyl
The group and the aryl group may further have a substituent. This
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, halogen atom, amino group
Group, ester group, carbonyl group, carboxy group, etc.
These have further substituents as described above
It may be a thing. In addition, two or more substituents can be
They may combine to form a ring, and the ring structure is a nitrogen atom or sulfur
It may be a heterocyclic structure containing atoms and the like. in
From the viewpoint of synthesis suitability, R⁴⁰Is an aryl group
And are preferred. The organic borate anion is disclosed in 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
Examples of the 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. The carboxylate ion is an aliphatic carboxylic acid
Or aromatic carboxylic acid, monocarboxylic acid or
Any of polycarboxylic acids may be used. Specifically, JP-A-2
Paragraph Nos. [0048] to 001-34374
[0057], Japanese Patent Application No. 2000-266797
The compounds described in Nos. [0063] to [0068] are listed below.
I can get lost. R⁴⁰-SO₂ ^-A preferred embodiment of the ion is a patent application.
No. 2001-147429, paragraph number [0015]
To [0016], R⁴⁰-SO₂S^-Ionic
A preferred embodiment is Japanese Patent Application No. 2001-329129.
Those listed in paragraphs [0022] to [0032] are listed.
I can get lost. [0077] Embedded image In the general formula (B-4), A, B, C, D, E
Represents a monovalent nonmetallic atom (group) independent of each other. formula
A, B, C, D, E are monovalent nonmetals independent of each other
Represents an atom (group), preferably each a hydrogen atom,
C1-C10 alkyl group or C6-C10 ant
Group, alkenyl group, alkynyl group, alkoxy group,
Phenoxy group, amino group, vinyl group, allyl group, cyano
Represents a group or a halogen atom. In addition, these groups are further
May have one or more substituents,
Examples of preferred substituents are halogen atoms, carbon atoms
1-8 linear or branched alkyl groups, aryl groups,
Alkenyl group, carbonyl group, carboxyl group, amide
Group, acetyl group, ether group, thioether group, esthetic
Group, amino group, or a combination of two or more of these
Things. Adjacent among A, B, C, D, E
Two or more non-metallic atoms (groups) are linked together to form a ring.
May be. Of these five-coordinate silane compound ions,
Preferable one of A, B, C, D, E
Is a halogen atom, an aryl group or an alkoxy group
And more preferred are A, B,
A compound in which at least one of C, D, and E is a fluorine atom
Compound ions may be mentioned. A pentacoordinate silane represented by the general formula (B-4)
Specific examples of compound ions include Japanese Patent Application No. 2000-353.
151, paragraph numbers [0019] to [0021]
Anionic moieties in the exemplified compounds described are mentioned. Ma
Examples of the divalent or higher anion include Japanese Patent Application No. 200.
No. 1-69168, paragraph numbers [0018] to [00]
19]. 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. The onium salt used in the present invention is:
The maximum absorption wavelength is preferably 400 nm or less,
Furthermore, it is preferable that it is 360 nm or less. like this
By making the absorption wavelength in the ultraviolet region, lithographic printing plate
The original can be handled under white light. Only one 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.
Can be used without limitation. These are, for example, monomers
-Prepolymers, ie dimers, trimers and oligos
Gomer, or a mixture of them and their copolymerization
It has a chemical form such as the body. Monomers and their copolymerization
Examples of bodies include unsaturated carboxylic acids (e.g. acrylic
Acid, methacrylic acid, itaconic acid, crotonic acid, isochrome
Tonic acid, maleic acid, etc.) and their esters and amides
Preferably, unsaturated carboxylic acid and aliphatic
Esters with polyhydric alcohol compounds, unsaturated carboxylic acids
An amide of an aliphatic polyvalent amine compound is used.
In addition, hydroxyl group, amino group, mercapto group, etc.
Unsaturated carboxylic acid ester having a nucleophilic substituent, amino
And monofunctional or polyfunctional isocyanates, epoxy
Addition reaction product with moss, monofunctional or polyfunctional carbo
A dehydration condensation reaction product with an acid is also preferably used. Also,
Has an electrophilic substituent such as an isocyanate group or an epoxy group
Unsaturated carboxylic esters or amides
Functional or polyfunctional alcohols, amines and thios
Addition reaction products, and halogen groups and tosyl alcohol
Unsaturated carboxylic acid ester having a leaving substituent such as a xy group
Tellurium or amides and mono- or polyfunctional alcohols
Also preferred are substitution products with alcohols, amines and thiols.
Is suitable. Another example is the unsaturated carboxylic acid described above.
Replace with unsaturated phosphonic acid, styrene, etc. instead of acid.
It is also possible to use the obtained compound group. Form 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
Those that are used are also preferably used. In addition, other preferred amide monomers
Examples of the cyclohexane described in JP-B No. 54-21726
The thing which has a xylene structure can be mention | raise | lifted. Other examples include JP-A-48-417.
Two or more ions per molecule described in the 08 publication
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, Japanese Patent Laid-Open No. 51-37193 and Japanese Patent
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 ones are good, and different functionalities and different polymerizability
A compound having a group (for example, an acrylic ester compound)
, Methacrylate compounds, styrene compounds
Etc.) are used in combination to achieve both photosensitivity and strength
It is also effective to adjust this. Large molecular weight compounds
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 points of view,
In many cases, the preferred blending ratio of the cal-polymerizable compound is a combination.
5-80% by weight, preferably 20-
75% by mass. Moreover, even if these are used independently, they are 2 types.
You may use together. In addition, radically polymerizable compounds
Is used for the degree of polymerization inhibition to oxygen, resolution,
Appropriate structure from the standpoints of breathability, refractive index change, and surface adhesion
Structure, blending and addition amount can be selected arbitrarily.
The layer composition and coating method such as undercoating and overcoating are also implemented.
sell. [(D) Binder polymer]
In the image recording layer, from the viewpoint of improving the film properties of the recording layer.
In addition, it is preferable to use a binder polymer.
It is preferable to use a linear organic polymer as the inner.
That's right. Which of these “linear organic polymers” is
May be used. Preferably water development or weak
In order to enable the development of Lucari water,
Select a linear organic polymer that is soluble or swellable in water
Is done. A linear organic polymer is used to form a recording layer.
Not only as a film-forming agent, but also water or weak alkaline water
Is selected and used depending on the application as an organic solvent developer.
The For example, when a water-soluble organic polymer is used, water development is possible.
It becomes possible. Such linear organic polymers include the side
Radical polymers having carboxylic acid groups in the chain, for example
Sho 59-44615, Shoko 54-34327, Sho
No. 58-12777, JP-B 54-25957,
JP-A-54-92723, JP-A-59-53836
No., JP-A-59-71048,
That is, methacrylic acid copolymer, acrylic acid copolymer
, Itaconic acid copolymer, crotonic acid copolymer, male
Acid copolymer, partially esterified maleic acid copolymer, etc.
is there. Similarly, an acidic cell having a carboxylic acid group in the side chain
There is a loin derivative. In addition to the polymer having a hydroxyl group
What added the cyclic acid anhydride is useful. Of these, in particular, benzyl or ant
(Meth) acrylic having a carboxyl group and a carboxyl group in the side chain
Resin has an excellent balance of film strength, sensitivity, and developability.
It is preferable. 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 this, a water-soluble linear organic polymer and
Polyvinyl pyrrolidone or polyethylene oxide
Etc. are useful. In order to increase the strength of the cured film,
Lucol soluble nylon and 2,2-bis- (4-hydro
Xylphenyl) -propane and epichlorohydrin poly
Ethers and the like are also useful. Weight average content of the polymer used in the present invention
The amount of the child is preferably 5000 or more, and
Preferably it is in the range of 10,000 to 300,000, and the number average molecular weight is
About 1000 or more is preferable, and more preferable
Or in the range of 2000-250,000. Polydispersity (weight level
(Average molecular weight / number average molecular weight) is preferably 1 or more, and
Preferably it is the range of 1.1-10. These polymers are random polymers,
Any of block polymer, graft polymer, etc.
Is preferably a random polymer. The polymers used in the present invention are conventionally known.
It can be synthesized by the method. The solvent used in the synthesis and
For example, tetrahydrofuran, ethylene dichloro
Lido, cyclohexanone, methyl ethyl ketone, aceto
, Methanol, ethanol, ethylene glycol mono
Methyl ether, ethylene glycol monoethyl ether
, 2-methoxyethyl acetate, diethyleneglycol
Dimethyl ether, 1-methoxy-2-propano
1-methoxy-2-propyl acetate, N, N-
Dimethylformamide, N, N-dimethylacetami
, Toluene, ethyl acetate, methyl lactate, ethyl lactate,
Examples thereof include dimethyl sulfoxide and water. These melts
A medium is used individually or in mixture of 2 or more types. When synthesizing the polymer used in the present invention
As the radical polymerization initiator used in
Known compounds such as agents and peroxide initiators can be used. 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 constituent components of the acid crosslinking 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.
That's right. High-sensitivity recording achieved in the above content range
In the non-image part for lithographic printing obtained
The occurrence of dirt 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 salt, hexaarylbi
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 (E-
Compounds represented by 1) to (E-5) are preferred. [0103] Embedded image In the general formulas (E-1) to (E-5), R
¹, R², R^FourAnd R^FiveCan be the same or different,
Optionally substituted hydrocarbon group having 20 or less carbon atoms
Represents. R^ThreeMay have a halogen atom or a substituent
Good C10 or less hydrocarbon group or C10 or less
Represents an alkoxy group. Ar¹, Ar²Are the same or different
And may have a substituent and may have 20 or more carbon atoms
Represents the lower aryl group. R⁶Has a substituent
It represents a good divalent hydrocarbon group having 20 or less carbon atoms. n is
Represents an integer of 0 to 4; In the above formula, R¹, R², R^FourAnd R^Five
Is preferably a hydrocarbon group having 1 to 14 carbon atoms. Represented by the general formulas (E-1) to (E-5).
The preferred embodiments of the acid generator to be prepared are proposed previously by the present inventors.
Paragraph No. [0 of Japanese Patent Laid-Open No. 2001-142230
197] to [0222] are compounds of the general formulas (I) to (V)
It is described in detail as a product. These compounds are examples
For example, JP-A-2-100054, JP-A-2-1000
It can be synthesized by the method described in No.55. In addition, (E) onium salts as acid generators
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 numbers [0010] to [0
035] as compounds of general formulas (I) to (III)
Has been. The amount of acid generator added is the total solids of the recording layer.
0.01-50 mass% is preferable with respect to the shape 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, non-images at the time of printing when using the original for lithographic printing
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, a hydroxymethyl group, an acetoxymethyl group
Or fragrance poly-substituted with alkoxymethyl groups
Group compounds or heterocyclic compounds. However,
Phenols and aldehydes
Also includes resinous compounds that have been polycondensed under basic conditions
The Polyhydroxy group or alkoxymethyl group
Among the substituted aromatic compounds or heterocyclic compounds,
In the position adjacent to the hydroxy group
Or the compound which has an alkoxymethyl group is preferable. Ingredients
Specifically, for example, JP 2000-267265 A
Paragraph numbers [0077] to [0083]
And compounds of the general formulas (8) to (11). (Ii) N-hydroxymethyl group, N
-Alkoxymethyl group or N-acyloxymethyl
As the compound having a group, European Patent Publication (hereinafter referred to as “E
P-A ". No. 0,133,216, West German patent
Nos. 3,634,671 and 3,711,264
Monomers and oligomers-melamine-formal as described
Dehydride condensates and urea-formaldehyde condensates, E
Alkoxy described in PA-A 0,212,482
And bis-substituted compounds. Among them, for example, few
At least two free N-hydroxymethyl groups, N-arco
Has a xymethyl group or N-acyloxymethyl group
Melamine-formaldehyde derivatives are preferred, N-
Alkoxymethyl derivatives are most preferred. (Iii) As the epoxy compound, 1
Monomers, dimers and oligomers having the above epoxy groups
Examples include sesame and polymeric epoxy compounds.
For example, the reaction between bisphenol A and epichlorohydrin
Products, low molecular weight phenol-formaldehyde resins and resins
Examples include reaction products with picrolhydrin. That
US Patent No. 4,026,705, British Patent No. 1,
It is described and used in each specification of 539,192.
Can be mentioned. 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. These alkaline water soluble polymers
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 quality is maintained. In addition, known descriptions to which the method of the present invention can be applied.
The recording material is described in JP-A-8-276558.
Negative type image recording material containing a phenol derivative of
Diazonium compound described in Kaihei 7-306528
Negative recording material containing a product, JP-A-10-20303
A compound having an unsaturated bond in the ring described in No. 7 publication.
Acid-catalyzed cross-linking reaction using a polymer having a cyclic group
Negative type image forming material using
As a negative recording layer in the present invention.
It can be applied to the acid crosslinking layer. [Other components] Such a negative image
In addition to these, the recording layer can be variously modified as necessary.
A compound may be added. For example, large absorption in the visible light region
Dye with can be used as image colorant
The Also, phthalocyanine pigments, azo pigments, carbon
Also suitable for use are pigments such as carbon black and titanium oxide
Can do. These colorants are non-imaged after image formation.
Since it is easy to distinguish the image part, it is preferable to add it.
Yes. The amount added is based on the total solid content of the recording layer coating solution.
The ratio is 0.01 to 10% by mass. In the present invention, the recording layer is polymerized hard.
In the case of coating layer, during preparation or storage of coating solution
With an ethylenically unsaturated double bond capable of radical polymerization
A small amount of thermal polymerization to prevent unwanted thermal polymerization of compounds
It is desirable to add an inhibitor. Suitable thermal polymerization inhibitor
As hydroquinone, p-methoxyphenol, di
-T-butyl-p-cresol, pyrogallol, t-butyl
Tilcatechol, benzoquinone, 4,4'-thiobis
(3-methyl-6-tert-butylphenol), 2,2 '
-Methylenebis (4-methyl-6-tert-butylphenol)
), N-nitroso-N-phenylhydroxylamine
An aluminum salt etc. are mentioned. Addition amount of thermal polymerization inhibitor
Is about 0.01% to about 5% by weight of the total composition
% By weight is preferred. In addition, if necessary, polymerization inhibition by oxygen
Like behenic acid or behenic acid amide to prevent harm
In the process of drying after application by adding higher fatty acid derivatives, etc.
It may be unevenly distributed on the surface of the recording layer. Of higher fatty acid derivatives
The amount added is about 0.1% to about 10% by weight of the total composition.
preferable. Further, 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 trioleate, monoglyceride stearate
Lido, polyoxyethylene nonylphenyl ether, etc.
Can be mentioned. Specific examples of amphoteric surfactants include alkyl
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. In addition, 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 generated
Detailed as preferred compounds
(B ′) Onium salt compound and the present invention
(A) Infrared absorber is included. In such a recording layer,
(B ') onium salt compound and (H) water-insoluble and
By interaction with alkali-soluble groups in re-soluble resins
In addition, the recording layer is resistant to aqueous alkali solutions.
However, in the exposed area (non-image area), (A) infrared absorption
For decomposition of (B ') onium salt compounds by heat from the collector
The interaction is released, and
The solubility is improved and an image is formed. [(H) Water-insoluble and alkali-soluble tree
Fat] (H) a polymer compound that can be used in a positive recording layer
Therefore, an acidic group is added to the main chain and / or side chain in the polymer.
Containing homopolymers, these copolymers or these
Includes mixtures. Among them, listed below (1) to (6)
Have acidic groups in the main chain and / or side chain of the polymer
Is soluble in alkaline developer,
It is preferable in terms of the expression of efficacy. (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
An oxazole group, an indoyl group, etc.). 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 polymers that have (1) pheno
Group, (2) sulfonamide group and (3) active imi
Alkali water-soluble polymers having a group are preferred,
(1) a phenol group or (2) a sulfonamide group
Alkaline water-soluble polymer having an alkaline developer
Sufficient solubility, development latitude and film strength
It is most preferable from the point of keeping. An acidic group selected from the above (1) to (6)
Examples of the alkaline water-soluble polymer having:
Can be mentioned. (1) an alkaline water-soluble polymer having a phenol group;
For example, the condensation of phenol and formaldehyde
Polymer, polycondensation 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
A novolak resin such as a polycondensation polymer, and pyrogallol
Mention may be made of condensation polymers with acetone. further,
A compound having a phenol group in the side chain (for example, acrylic
Amides, methacrylamides, methacrylates,
Derivatives such as crylic acid esters and crotonic acid esters)
Mention may also be made of copolymerized copolymers. Or
Copolymerization of a compound having a phenol group in the side chain
A coalescence can also be used. Weight average molecular weight of alkaline water soluble polymer
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 polymers are used alone
Of course, two or more types may be used in combination.
When combined, t-butylphenol and form
Condensation polymer with aldehyde, C3-C8 alkyl group
Of phenol and formaldehyde as substituents
Condensation 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 polymers include sulfonamide groups.
The smallest structural unit derived from the compound having
The polymer comprised as mentioned above can be mentioned. Above
Such compounds include at least one hydrogen atom on the nitrogen atom.
Atom-bonded sulfonamide groups and polymerizable unsaturation
And compounds having at least one group in the molecule.
It is. Among them, acryloyl group, allyl group, or vinyl
Roxy group and substituted or mono-substituted aminosulfonyl group
Or a substituted sulfonylimino group and a low
Molecular compounds are preferred. Examples of such compounds are:
For example, in Japanese Patent Laid-Open No. 8-123029, a general formula
Examples include compounds represented by (I) to (V). In the present invention, the positive planographic printing material
In particular, m-aminosulfonylphenyl methacrylate
G, N- (p-aminosulfonylphenyl) methacryl
Amide, N- (p-aminosulfonylphenyl) acryl
Luamide and the like can be preferably used. (3) Alkaline water having an active imide group
Examples of the soluble polymer include, for example, JP-A-11-84657.
In the compound having an active imide group described in the publication No.
Consists of the smallest constituent unit derived as the main constituent
A polymer can be mentioned. As a compound as above
Is polymerizable with an active imide group represented by the following structural formula
Compounds having one or more of each unsaturated group in the molecule
Can be mentioned. [0138] 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. [0141] Alkali water soluble high used for positive recording layer
Acids selected from the above (1) to (6) constituting the molecule
The minimum constitutional unit having a group needs to be only one kind.
There are two or more minimum structural units having the same acidic group.
2 or more minimum structural units having upper or different acidic groups
What was copolymerized above 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 soluble resin as a copolymer, copolymerization
As the compound to be reacted, the acidic groups (1) to (6) are contained.
Other compounds can also be used. Alkaline water is acceptable
As soluble resin, exposure by infrared laser etc.
US Patent No. 4,123,
Phenolic hydride described in 279 specification etc.
Novolac resins having a roxy group, pyrogallol acetate
Ton 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 positive 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
If necessary, various additives may be added to the layer.
You can. For example, other onium salts, aromatic sulfones
Compound, aromatic sulfonate compound, polyfunctional amino
When an alkaline compound or the like is added,
It is preferable because it can improve the function of preventing dissolution in image liquid.
Good. 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,
The hydroxymethyl group described in 8-276558
Having phenolic compounds, having alkoxymethyl groups
Phenol compounds and special features previously proposed by the inventors
Alkaline dissolution suppression described in Kaihei 11-160860
Add crosslinkable compounds etc. for production according to purpose.
Can be added. 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. Also, immediately after heating by exposure, a visible image
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 to
5.0 g / m²Is preferred. As application amount decreases
The apparent sensitivity increases, but the film characteristics of the recording layer are low.
I will give you. [Platinum 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. Further, 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 thereof 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-
Mg 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. Hereinafter, the surface treatment of the support will be described.
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. Ma
Electrochemical graining method, support material, granular material
The surface is roughened by bonding with an adhesive or a method having its effect.
A method of surfaceizing, continuous belts and rolls with fine irregularities
Roughening method such as pressing the support material to transfer irregularities
Knowledge methods can be applied. A plurality of roughening methods such as these are combined.
The order and the number of repetitions are arbitrary.
Can be selected. Do not roughen the surface as described above.
On the surface of the support obtained by the graining process,
In order to remove this smut.
If necessary, perform water washing or alkali etching treatment.
It is generally preferred. 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 thereof is used.
It is. The concentration of these electrolytes depends on the type of electrolyte.
It is decided. The anodizing treatment conditions depend on the electrolyte used.
However, in general, it cannot be specified.
Solution concentration is 1-80% solution, liquid temperature is 5-70 ° C, current
Density 5-60A / dm², Voltage 1-100V, Electrolysis time
A range of 10 seconds to 5 minutes is appropriate. Anodized film
Is 1.0 g / m²The above is preferred, but more preferred
Or 2.0-6.0 g / m²Range. Anodized leather
The membrane is 1.0 g / m²If it is less than 1, the printing durability is insufficient.
Or the non-image area of the lithographic printing plate is easily scratched,
So-called “scratch stain” in which ink adheres to the scratched part during printing
Is likely to occur. Such an aluminum support has 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%. [0163] 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. Special features preferred 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 controlling the surface shape, for example, Japanese Patent Application No. 2000-39
It is preferable to have the characteristics described in No. 5007. Details
Has a large, medium and small triple uneven structure on the surface of the support,
The wavelength of the concavo-convex structure is 3 to 10 μm, and the middle concavo-convex structure is the front
Pits, and the small concavo-convex structure is the fine pits of the pits.
What has a convex structure is preferable. Also, Japanese Patent Application 2001-
As described in 309304, the surface of the support
Medium wave structure with an aperture of 0.5 to 5 μm and an average aperture of 0.01 to
Has a grained shape with a superposition of a 0.2 μm wave structure
Those that do are preferred. By using these supports
Improved adhesion to the recording layer, maintaining the strength of the recording layer,
The stain resistance during printing is excellent. Also, the support
Color density ranges from 0.15 to 0.65 as reflection density value
It is preferable that In this range, during image exposure
There is no obstacle to image formation due to halation, and
This is because the plate inspection after development can be performed without any problems.
The 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, both on-machine development
Called. A lithographic stamp having such an unprocessed image recording layer
The plate precursor is installed on the press and then on the press.
Can be exposed to laser and printed as it is. No
Even in the case of misalignment, print with ink and dampening water.
Once started, the surface hydrophilic areas, surface,
Dampening water and ink were received in the hydrophobic area.
Or unnecessary thermal recording layer and photosensitive layer are removed quickly.
And dampening water remained on the exposed hydrophilic support surface.
Ink fills the ink receiving area, which is the recording layer,
Printing will be started for each. No treatment applicable to the planographic 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-process 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 preferably has an average particle size of 0.01 to 20 μm.
It is more preferable that the thickness is 0.05 to 5.0 μm.
Yes. Within this range, high-definition image formation becomes possible.
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. Among 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
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 carried out 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.
It is preferable that it is 60% by mass or more.
That's right. 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
Examples include 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 Other compounds having a polymerizable unsaturated group
As an example, a polymerized hard which is one of the negative recording layers described above is used.
As exemplified in (C) radical polymerizable compound
Can be mentioned. (A) 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]. Copolymerization 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) A compound having a thermally reactive functional group is contained.
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) A compound having a thermally reactive functional group is contained.
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 outside the capsule surface or microcapsule
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 thermosensitive 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. When it is within the above range, good on-press developability and simultaneously
In addition, good sensitivity and printing durability can be obtained. (B) A compound having a thermally reactive functional group is contained.
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 positive type described above.
Examples include the same solvents as those used for each recording layer coating solution.
However, the present invention is not limited to these. Also these
Two or more of these solvents may be used. Further, it is dissolved 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 composed of (a) heat
Fine particle polymer having a reactive functional group and / or (b)
A microcap containing a compound having a heat-reactive functional group
If containing cells, these reactions are
A compound that initiates or promotes may be added. Reaction
Compounds that initiate or promote include radicals by heat
Or mention compounds that generate cations.
Yes. For example, lophine dimer, trihalomethyl compound
, Peroxides, azo compounds, onium salts (diazonium
Salt, diphenyliodonium salt, etc.), acylphosphite
And imide sulfonate. In particular,
(B) those exemplified as radical generators, or
(E) Compounds similar to those exemplified as the acid generator are listed.
I can get lost. 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. [0196] 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 non-processing type recording layers are mentioned. 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
Numonium, silane coupling agent, titanate cup
A crosslinking catalyst such as a ring agent can also be used in combination. In this type of unprocessed recording layer,
Sol-gel conversion binder resin among hydrophilic resins
It is preferable to use it. Details will be described below. Suitable for use
The sol-gel conversion binder resin that can be used is a polyvalent element.
Bonding groups coming out form a network structure through oxygen atoms
In addition, the polyvalent element is an unbonded hydroxy group, alkoxy
It also has a resin group, etc.
A hydroxy group, alkoxy
At the stage where there are many groups, it is in a sol state, and ether bond formation
As the process progresses, the net-like resin structure will become stronger
And high molecular weight materials. 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. Less than
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. The non-process type recording layer is small
Including a silane compound having at least one silanol group
After applying the coating liquid, which is
As the hydrolytic condensation of the alkyl group proceeds, the structure of the siloxane skeleton
Formed and gelation proceeds.
In addition, a recording layer formed by this sol-gel conversion system
Improves physical properties such as film strength and flexibility,
For the purpose of improvement, etc.
A bridging agent and the like 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,
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, this type of unprocessed
As a recording layer, a recording layer created by a sol-gel method
(Including sol-gel conversion binder resin as hydrophilic resin
Recording layer). Details of the above sol-gel method
Hanaeo "Sol-Gel Science" Agne Jofusha Co., Ltd.
(Published) (1988), Satoshi Hirashima “By the latest sol-gel method
Functional Thin Film Manufacturing Technology ”, General Technology Center (published) (19
1992) and the like. In the non-process type recording layer, if necessary,
In addition to the components described above, it can contain various compounds.
Yes. For example, in order to further improve printing durability,
Nomers are included in the polymer matrix of the recording layer
be able to. Such polyfunctional monomers include
Illustrated as a monomer encapsulated in a microcapsule
Things can be used. Especially preferred monomer
For example, trimethylolpropane triacrylate
Can. Further, the non-process type recording layer is provided as necessary.
It contains a plasticizer to give the film flexibility and the like.
Can be. As the plasticizer, the above recording layer coating solution
The same compound as the plasticizer added in the inside is illustrated. Also, this type of recording layer can be inorganic or organic.
Fine particles (eg, silica, alumina, magnesium oxide)
, Magnesium carbonate, etc.). Special
Preferably, a hydrophilic sol with an average particle size of 1 to 50 nm
Particles. The content of these fine particles is
It is preferable that it is 1.0-70 mass% with respect to the shape.
More preferably, it is 5.0-50 mass%. this
In the range, the film strength of the recording layer can be sufficiently maintained.
Can be made by exposing with laser light etc.
When printing as a printing plate, apply ink to non-image areas.
When it becomes extremely superior in hydrophilicity without causing soiling
This effect is obtained. As the hydrophilic sol-like particles, for example,
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 a hydrophobic precursor-containing image recording layer,
(A) Presence of the infrared absorbent and the hydrophilic sol-like particles
The mass ratio is 100/0 to 30/70
100/0 to 40/60 is more preferable.
Good. Further, (A) an infrared absorber, a hydrophobized precursor, and
And the total content of the hydrophilic sol-like particles is the total content of the recording layer.
It is preferable that it is 2-95 mass% with respect to solid content.
More preferably 5 to 85% by mass. The image recording layer containing a hydrophobizing precursor 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
And 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. As a lipophilic 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 the above phenolic compounds
A condensation resin with acetone 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
In addition to the infrared absorber, the film quality of the ink receiving layer was improved.
In order to improve the appearance, cross-linking agent, adhesion aid, coloring
Agent, inorganic or organic fine particles, coated surface conditioner or acceptable
A plasticizer can be added. In addition, pudding after exposure
Heating coloring system or eraser for forming toe-out images
Color systems 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. An inorganic or inorganic material 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. Further, 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 ratio of addition 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. In addition, in preparing the ink receiving layer coating solution,
Is a well-known compound as a coated 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;
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 other layers 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.
Species such as hydrolysis of products or condensation of hydroxides of the above elements
It can be made by various known methods. 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 for the precursor image recording layer.
The The addition ratio 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 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.
And 0.1 g / m²~ 5g / m²Preferred to be in the range
More preferably 0.2 g / m²~ 4g / m²In
The Lithographic printing 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.
it can. Overcoat layer used in the present invention
Is a water-soluble layer that is easily removed during development or printing
It is what is done. The overcoat layer is a planographic printing plate
Prevents sticking when plates are stacked and stored
Therefore, 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 additives.
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
3,000 stacked, 3 days at 35 ° C and 75%
After standing for a while, measure the sample at the bottom
Can do. An overcoat of such 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
Boric 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. A back coat layer is formed on the back side 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 planographic printing plate precursor of 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. [0246] 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 JIS A 1050 alloy melt containing 0.013%
The product was cleaned and cast. For cleaning process, molten metal
Degassing treatment to remove unnecessary 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
At 500 ° C. for 60 seconds and then cold rolling,
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 oil
Degreased at 0 ° C for 30 seconds, 50% with 30% sulfuric acid aqueous solution
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. [Undercoat] 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 [N-1] and apply the above primed aluminum
Apply to the support using a wire bar, hot air dryer
And dry at 115 ° C for 45 seconds at negative lithographic printing plate precursor
[N-1] was obtained. The coating amount after drying is 1.2 to 1.3 g
/ M²It was in the range. [0251] <Recording layer coating solution [N-1]> Infrared absorber [specific dye: exemplary compound (I-1)] 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, mass 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 [0252] Embedded image [Exposure] The obtained negative type planographic printing plate precursor
[N-1] equipped with water-cooled 40W infrared semiconductor laser
Creed Trendsetter 3244VF
13.5W output at S, outer drum rotation speed 210rp
m, plate surface energy 150 mJ / cm², Resolution 240
The exposure was performed at 0 dpi. [Development processing] After exposure, Fuji Photo Film
Development processing using an automatic processor Stablon 900N manufactured by KK
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 lithographic printing plate [N-1]
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 10. 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 10 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 10. [0259] [Table 10] In Example N-1, the recording layer coating solution [N
-1] is a specific dye: exemplified compound (I
-1) was changed to a pigment having the structure shown below,
Similarly, the negative planographic printing plate precursor [NR- of Comparative Example 1]
1] was produced. Then, in the same manner as in Example N-1,
Perform light, development and printing. Sensitivity evaluation, 2. Printing durability evaluation
2. and 3. The stability evaluation over time was evaluated. The results are in Table 1.
Write 0. [0261] Embedded image Example 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. [Undercoating] 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 [N-2] and apply the above primed aluminum
Apply to the support using a wire bar, hot air dryer
And dry at 100 ° C for 1 minute to obtain a negative planographic printing plate precursor
[N-2] was obtained. The coating amount after drying is 1.5 g / m²so
there were. [0265] <Recording layer coating solution [N-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 absorbent [specific dye: exemplary compound (I-9)] 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 generator used in recording layer coating solution [N-2]
The structure of [SH-1] is shown below. Embedded image Cross-linking agent used in recording layer coating solution [N-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%. [0268] 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 10. (Comparative Example 2) In Example N-2, recording
Infrared absorber in the layer coating solution [N-2], specific dye: example
A compound having the structure shown below from the compound (I-9))
The negative lithographic printing of Comparative Example 2 was performed in the same manner except that
An original plate [NR-2] was prepared. Then Example N-2
1. Perform exposure, development and printing in the same manner as described above. Sensitivity rating
2. 2. Evaluation of printing durability, and Evaluation of stability evaluation over time
did. The results are also shown in Table 10. [0274] Embedded image As is apparent from Table 10, 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. (Examples N-3 to N-8) In Example N-1,
Infrared absorbent in the recording layer coating solution [N-1]
Specific dye: From the exemplified compound (I-1), it is shown in Table 11 below
Same as Example N-1, except that each of the exemplified compounds was replaced
The negative lithographic printing plate precursors of Examples N-3 to N-8
[N-3] to [N-8] were produced. Then Example N
Perform exposure, development and printing in the same way as -1, and evaluate.
It was. [0277] [Table 11] Examples N-3 to N-8 negative lithographic printing plates
The original plates [N-3] to [N-8] are examples N-
Performance equivalent to 1 negative planographic printing plate precursor [N-1]
The sensitivity, printing durability, and stability over time were all good.
It was. Examples N-9 to N-17 Example N-1
In the recording layer coating solution [N-1], an infrared absorber and
And the polymerization initiator is a specific dye: Exemplified Compound I-1; 0.0
8 g, polymerization initiator [O-1]; 0.30 g
, Exemplified compounds shown in Table 12 below; 0.09 g and polymerization
Initiator; Example N- except that each was replaced with 0.30 g
1 negative lithographic plates of Examples N-9 to N-17
Printing plate precursors [N-9] to [N-17] were prepared. That
After that, exposure, development and printing were performed in the same manner as in Example N-1.
I evaluated. [0280] [Table 12]Negative type lithographic printing of Examples N-9 to N-17
The plate original plates [N-9] to [N-17] 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. Example N-18 [Formation of recording layer] Prepare the following recording layer coating solution [N-3].
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-18 was obtained. Cover after drying
Coverage is 1.6 g / m²Met. [0283] <Recording layer coating solution [N-3]> Infrared absorber [specific dye: exemplary compound (I-22)] 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, mass average molecular weight 5800)... 1.1 g ・ Resol resin obtained from bisphenol A and formaldehyde     (Mass average molecular weight 1600) ... 1.0 g ・ Fluorosurfactant: 0.06g     (Megafuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 20g ・ 1-Methoxy-2-propanol 7g Acid generator used in recording layer coating solution [N-3]
The structure of [SH-2] is shown below. Embedded image Cross-linking agent used in recording layer coating solution [N-3]
The structure of [KZ-2] is shown below. Embedded image [Exposure, development processing and printing]
Ga type lithographic printing plate precursor [N-18] is the same as in Example N-1.
In the same manner, exposure, development processing, and printing were performed. [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. Negative type lithographic printing plate precursor of Example N-18
[N-18] is a planographic printing plate precursor of Example N-2 [N-
2] with the same performance, sensitivity, printing durability and stability over time
Both were good. (Example N-19) In Example N-1
Infrared absorbent (I-
1) 0.08 g and polymerization initiator [O-1] 0.30 g
Instead, exemplary compound (D-1) 0.4 of an infrared absorber
Except that 5g was used, the negative type was carried out in the same manner as in Example N-1.
An original plate [N-19] for lithographic printing was obtained. The obtained original plate
In the same manner as in Example [N-1], plate making, development and printing were performed.
The same as the original plate for lithographic printing [N-1] of Example N-1
The above good results were obtained. (Example N-20) In Example N-19
Instead of 0.45 g of infrared absorber (D-1)
0.48 g of the exemplary compound (D-3) of the external line absorbent was used.
Otherwise, the image recording layer was applied in the same manner as in Example (N-1).
Set up. Then, on this, overcoat with the following contents
The coating solution for the layer is applied using bar coat to the coating weight after drying.
Amount 0.70 g / m²Apply and dry so that
A negative lithographic printing original plate [N-20] was produced. [0291]   <Coating liquid for overcoat layer (OC-1)> ・ PVA205 (Kuraray Co., Ltd.) 5.0g ・ MegaFuck F171 (Dainippon Ink Chemical Co., Ltd.) 1.0g ・ Water 95g The obtained original plate was treated in the same manner as in Example N-1.
The plate of Example (N-1) was printed after plate making and development.
Good results equivalent to or better than the original plate [N-1]
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 [P-1] and add the above primed aluminum
The coating amount is 1.8g using a wire bar on the nium support.
/ M²And then dry at 100 ° C for 1 minute
A positive type lithographic printing plate precursor [P-1] was obtained. [0295] <Photosensitive layer coating solution [P-1]> ・ M, p-cresol novolak ・ ・ ・ 1.0g   (M / p = 6/4, mass average molecular weight 3500, unreacted cresol 0.5% by mass Contains) Infrared absorber [specific dye: exemplary compound (I-14)] 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] Positive type lithographic printing plate precursor obtained
[P-1] was exposed under the same conditions as in Example N-1. [Development treatment] After exposure, non-reducing sugar and base
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. The development process is performed at a development humidity of 25 ° C. for 1 hour
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] In the same manner as in Example N-1.
2. Evaluation of printing durability, and Evaluation of stability over time (6 months)
went. The results are shown in Table 13. [0300] [Table 13] (Comparative Example 3) In Example P-1, photosensitivity
Infrared absorber in the layer coating solution [P-1], specific dye: example
Dye used in Comparative Example 1 from the compound (I-14)
The positive lithographic printing of Comparative Example 3 was performed in the same manner except that
An original plate [PR-1] was prepared. Thereafter, Example P-1
1. Perform exposure, development and printing in the same manner as in 1. Printing durability evaluation
2. and 3. Evaluation of stability over time (6 months)
It was. The results are also shown in Table 13. As is apparent from Table 13, 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 planographic printing plate precursor of Comparative Example 3 [PR-
1] has low printing durability in plate making, and after a long time,
Dirt has occurred. (Examples P-2 to P-7) [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
The negative lithographic printing plate precursors [P-2] to [P-7] are dried.
Obtained. The coating amount after drying is 1.6 g / m²Met. [0304] <Photosensitive layer coating solution [P-2]> Infrared absorber [specific dye: exemplary compounds described in Table 14 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, mass average molecular weight 1800) 2.00 g ・ P-octylphenol-formaldehyde novolak ・ ・ 0.02 g ・ 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 [0305] [Table 14][Exposure, development processing, and printing]
Di-type planographic printing plate precursors [P-2] to [P-7]
Using the same method as P-1, exposure, development processing, 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 plates of Examples P-2 to P-7
The original plates [P-2] to [P-7] are examples P-
1 performance equivalent to that of the planographic printing plate precursor [P-1]
Both printability 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. [0311] <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.) [0312] <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. [0315] <Image recording layer coating solution [ML-1]> ・ Water 70g ・ The above heat-reactive microcapsules (in terms of solid content) 5 g ・ Polyhydroxyethyl acrylate 0.5g ・ P-diazodiphenylamine sulfate ... 0.3g Infrared absorber [specific dye: exemplary compound (I-8)] 0.3 g [Exposure and printing] Unprocessed planographic stamp obtained
Printing master [M-1] is water-cooled 40W infrared semiconductor array
The Trend setter 32 made by Creo with the
44VFS, output 9W, outer drum rotation speed 210r
pm, plate surface energy 100 mJ / cm², Resolution 24
Do not process after exposure at 00 dpi.
Cylinder of SOR-M printing machine made by Heidelberg
After supplying dampening water and supplying ink,
In addition, paper was supplied for printing. Develop on-machine without problems
Could be printed. [Evaluation] The printed material on the 10th print was printed 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 mass after drying the liquid [M-2] is 1.2 g / m²When
It was applied and dried as shown. Next, over the following contents
The coating layer coating solution [OC-2] has a mass after drying,
0.75 g / m²Apply and dry so that
A printing plate precursor [M-2] was prepared. <Preparation of hydrophobized fine particles> As oil phase component
Epicoat 1004 (manufactured by Yuka Shell Epoxy Co., Ltd.)
Epoxy resin) 6.0 g, infrared absorber of the present invention (D-
5) 2.0 g and anionic surfactant bionin A-4
1 g of 1C (manufactured by Takemoto Yushi Co., Ltd.)
After dissolving in 0 g, water phase component polyvinyl alcohol
(Kuraray Co., Ltd. PVA205) 4% aqueous solution 36.0 g
And mix with a homogenizer at 10,000 rpm for 10 minutes
The mixture was emulsified and dispersed. Then add 24g of water, 60 ℃
The ethyl acetate was evaporated with stirring for 90 min. Gain
The resulting fine particle dispersion has a solid content concentration of 12.5% by weight.
It was. The average particle size was 0.22 μm. [0320] <Coating liquid for image recording layer [M-2]> ・ Hydrophobized fine particle layer (as solid content) ・ ・ ・ 5g ・ Polyacrylic acid (mass average molecular weight 2.5 × 10^Four) 0.5g ・ Water ・ ・ ・ 60g [0321] <Overcoat layer coating solution [OC-2]> ・ Gum Arabic ・ ・ ・ 2.2g ・ The infrared absorber (I-1) 0.4 g ・ Fluorosurfactant Surflon S-141 (Asahi Glass Co., Ltd.) ... 0.04g ・ Polyoxyethylene nonylphenyl ether: 0.04g ・ Water: 42g The obtained unprocessed planographic printing original plate [M-
2] was evaluated in the same manner as in Example M-1,
Equivalent or better than the lithographic printing original plate [M-1] in Example M-1
Good results were obtained. (Example M-3) Same support as Example N-1
The following image recording layer coating solution prepared on the body A and adjusted thereon
The coating weight after drying [M-3] is 1.2 g / m.²Become
Like, it was applied and dried. Next, overco
Coating layer coating solution [OC-3] having a weight after drying of 0.7
5g / m²Apply and dry so that
[M-3] was created. <Preparation of hydrophobized fine particles> As oil phase component
40 g of xylene diisocyanate, trimethylolpro
10 g pan diacrylate, allyl methacrylate and butyl methacrylate
Copolymer of til methacrylate (molar ratio 7/3) 10
g, Infrared absorber (D-6) 5.5 g, Pionine A4
Dissolve 0.1 g of 1C (made by Takemoto Yushi) in 60 g of ethyl acetate
did. As an aqueous phase component, 4 of PVA205 (made by Kuraray)
120 g of a% aqueous solution was prepared. Oil phase component and water phase component
Is emulsified at 10,000 rpm using a homogenizer.
It was. Then 40g of water was added and at room temperature for 30 minutes,
Stir at 40 ° C. for 3 hours. My obtained in this way
The solid concentration of black capsule liquid is 20% and the average particle size
Was 0.5 μm. [0325] <Image recording layer coating solution [M-3]> ・ Hydrophobized fine particles (as solid content) ・ ・ ・ 40g -Colloidal silica 20% by weight aqueous dispersion ... 200g ・ Sol-gel conversion adhesive resin adjustment solution with the following contents: 33 g ・ Water: 320g <Sol-gel conversion adhesive resin adjustment liquid> ・ A solution of the following composition is aged at room temperature for 2 hours to prepare a sol-gel preparation solution
Was prepared. Tetramethoxysilane (LS540 manufactured by Shin-Etsu Silicone Co., Ltd. 8.47 g ・ Methanol ・ ・ ・ 1.82g ・ Water: 14.5g ・ 0.1 mol / liter phosphoric acid ... 0.28g [0327] <Coating liquid OC-3 for overcoat layer> ・ Serogen 5A (Daiichi Kogyo Co., Ltd.) ・ ・ ・ 5.0g ・ Megafax F171 (Dainippon Ink Chemical Co., Ltd.) ・ ・ ・ 1.0g ・ The infrared absorbing agent (I-20): 0.3 g ・ Water: 95g The obtained lithographic printing original plate [M-3] was
Example where performance was evaluated in the same manner as Example [M-1]
Good quality equal to or better than M-1 lithographic printing original plate [M-1]
Results were obtained. [0329] 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 AA12 AA13 AB04 AC08                       AD01 AD03 BH03 BJ03 CC11                       DA36 FA17                 2H096 AA06 BA01 BA09 CA03 EA04                       GA08

Claims (1)

[Claims] [Claims] [Claims] [Claims] [Claim 1] Infrared laser, comprising an image recording layer containing an infrared absorber represented by the following general formula (I) or (II) on a hydrophilic support A lithographic printing plate precursor. [Chemical 1] In general formula (I), X ⁰ and X ¹ may be the same or different and each represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or a group shown below, wherein R ⁵ may be substituted. Represents a good aliphatic group. [Chemical 2] Z ⁰ and Z ¹ are pyran, benzopyran, naphthopyran, thiopyran, benzothiopyran, naphthothiopyran, serenapyran, benzoselenapyran, naphthoselenapyran,
Ternapyran, benzoternapyran, naphthoternapyran, or a group of atoms necessary to form a 5- or 6-membered heterocyclic ring containing a nitrogen atom. W represents an oxygen atom or a sulfur atom. Y ¹ , Y ² , Y ³ and Y ⁴ are a hydrogen atom, an aliphatic group, an aromatic group, a cyano group, a nitro group, —OR, or —
SR is represented. However, R represents an aliphatic group or an aromatic group.
R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴
Each may be the same or different and each represents a hydrogen atom or a monovalent non-metallic atomic group excluding hydrogen, and any two adjacent R ² , R ³ and R ⁴ are combined to form a condensed 6 A member ring may be formed. Q ¹ and Q ² are 4-thiazolidinone, 4-oxazolidinone, 4-imidazolidinone, 5
-Represents a group of atoms necessary to form a thiazolidinone, 5-oxazolidinone or 5-imidazolidinone ring. L
¹ and L ² each independently represent a methine group. m and n each represents 0 or 1, and p represents 0, 1, 2, or 3. A
^- represents a counter anion present when charge neutralization is required. However, q is an integer of 1-5. [Chemical 3] In the general formula (II), X ⁰ , X ¹ , Z ⁰ , Z ¹ , Y ¹ ,
Y ² , Y ³ , Y ⁴ , R ⁵ , R ¹ , R ² , R ³ , R ⁴ , Q ¹ , Q ² ,
L ¹ , L ² , m, n, and p have the same meanings as in the general formula (I). B ⁺ represents an onium cation present when charge neutralization is required. However, r is an integer of 1-3.