JP2003345017A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in a film forming property and film strength and useful for a recording layer in a positive lithographic printing original plate. <P>SOLUTION: The resin composition contains a polymer compound containing a monomer unit expressed by general formula (1) and an IR absorber and changes its solubility with an alkali aqueous solution by irradiation of IR rays. In general formula (1), A represents a divalent organic group having polymerizable double bond, X<SP>1</SP>represents -O- or -NR<SP>2</SP>-, R<SP>1</SP>represents an alkyl group when X<SP>1</SP>is -O- and represents a hydrogen atom, an alkyl group or an aryl group when X<SP>1</SP>is -NR<SP>2</SP>-, and R<SP>2</SP>represents a hydrogen atom or an alkyl group. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a resin composition,
More specifically, it is directly from a digital signal such as a computer.
Infrared laser for so-called direct plate making that can make plate making
Resin that can be suitably used for the recording layer of positive lithographic printing plate precursors
Relates to the composition. [0002] 2. Description of the Related Art Recent development of laser
In particular, a solid-state laser with a light emitting region from near infrared to infrared
Semiconductor lasers are easily available in high output and small size
It is like. Is it digital data such as a computer?
These lasers are used as exposure light sources for direct plate-making.
Very useful. The positive lithographic printing plate material for infrared laser is
Binder resin that is soluble in alkaline aqueous solution and absorbs light
An IR dye that generates heat, an essential component, and an IR dye
However, in the unexposed area (image area),
The solubility of the binder resin is substantially reduced by the action.
It acts as a dissolution inhibitor, and in exposed areas (non-image areas)
Interaction between IR dyes and binder resin due to generated heat
Use is weakened and dissolved in an alkaline developer to form a lithographic printing plate
To do. Alkaline water in positive planographic printing plate materials
As a solution-soluble binder resin, novolak resin
A polymer compound having a phenolic hydroxyl group such as
Used. However, novolac resin was used
In the recording layer of positive planographic printing plate precursors, film-forming properties
In addition, there is a case where the film strength is insufficient and improvement is desired.
It was. For the purpose of improving film strength,
No. 10-282463 discloses a photothermal conversion substance and an al
In addition to a positive photosensitive composition containing potash-soluble resin,
An example using polyacrylic acid in combination is shown.
Considering further enhancement of sensitivity, further improvement of film strength
Is desired. Also, in JP 2001-324808 A
Is a positive type containing a photothermal conversion substance and a novolac resin
To the photosensitive composition, methyl methacrylate- (meth) acrylate is further added.
Although an example using a crylic acid copolymer is also shown, the sensitivity
Insufficient level in terms of improving film strength while maintaining
It is le. [0006] Accordingly, it is an object of the present invention.
Is useful for the recording layer in positive type lithographic printing plate precursors.
To provide a resin composition excellent in film formability and film strength.
It is in. [0007] [Means for Solving the Problems] The inventor has conducted intensive research.
As a result of stacking, polymer compounds containing specific monomer units
The above problem can be solved by the resin composition contained.
As a result, the present invention has been completed. That is, the present invention
The resin composition comprises a monomer unit represented by the following general formula (1).
Polymer compound containing a position (hereinafter referred to as “specific polymer compound”
It is called "thing". ) And an infrared absorber, and infrared
Solubility in alkaline aqueous solution changes by irradiation
It is characterized by doing. [0008] [Chemical 2] In the general formula (1), A has a polymerizable double bond.
Represents a divalent organic group. X¹Is —O— or —NR²−
Represent. R¹X¹Is —O—, it represents an alkyl group.
X¹-NR²In the case of-, a hydrogen atom, an alkyl group,
Or represents an aryl group. R²Is a hydrogen atom or alkyl
Represents a group. The working mechanism of the present invention is not clear, but
Is guessed. That is, it is included in the resin composition of the present invention.
The specific polymer compound is a flexible polymer compound.
Such polymer compound containing novolac resin, etc.
When used for the recording layer of a positive lithographic printing plate precursor
It is possible to form a recording layer with excellent composition and film strength.
This makes the recording layer resistant to alkaline developer.
Remarkably improved. Also, a positive having such a recording layer.
The type lithographic printing plate has development latitude, printing durability, and halftone dots.
The reproducibility is remarkably excellent. This is a novolak
Specially used for alkali dissolution channels (cracks, etc.) in resin
It is thought that this is caused by the sealing of certain polymer compounds
It is done. The specific polymer compound according to the present invention
Also has the feature of excellent manufacturing stability. That is,
Like certain polymer compounds according to the present invention, flexible hydrophobicity
High molecular compounds containing both functional groups and acidic groups
When obtained by copolymerization of each monomer,
From the point of compatibility etc., a monomer having a hydrophobic group and an acidic group
Control the proportion of monomers
It may be difficult to obtain a polymer. However,
The general formula contained in the specific polymer compound according to the present invention.
The monomer unit represented by (1) is a single monomer unit.
Because it has both a flexible hydrophobic group and an acidic group inside,
Without considering copolymerization, etc., flexible hydrophobic groups and acidic groups
It is possible to stably obtain high molecular compounds contained in
It has the feature of being able to. For this reason, the present invention
Specific polymer compounds such as positive planographic printing plate precursors
When used as a recording layer, it covers the entire formed film.
It becomes possible to achieve uniform image forming properties. [0012] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below. [Resin composition] The resin composition of the present invention comprises:
Polymerization containing a monomer unit represented by the general formula (1)
Compound (specific polymer compound) and an infrared absorber.
And dissolved in an alkaline aqueous solution by infrared irradiation.
It is characterized by the change in solution. The resin of the present invention
The composition is applied to the recording layer of a positive planographic printing plate precursor.
Are preferred. Hereinafter, the components constituting the resin composition of the present invention are described.
Minutes will be described sequentially. [Specific polymer compound]
Specific polymer compounds that are characteristic components have the following general formula:
A polymer compound containing the monomer unit represented by (I)
The [0015] [Chemical 3] In general formula (1), A has a polymerizable double bond.
Represents a divalent organic group. X¹Is —O— or —NR²−
Represent. R¹X¹Is —O—, it represents an alkyl group.
X¹-NR²In the case of-, a hydrogen atom, an alkyl group,
Or represents an aryl group. R²Is a hydrogen atom or alkyl
Represents a group. The general formula (1) will be described in detail below.
The In general formula (1), A is divalent having a polymerizable double bond.
Represents an organic group of
Any divalent organic group that can be formed is not limited.
Yes. However, from the viewpoint of polymerizability, availability, etc., there is little A
It is preferable that one of the ends is a polymerizable double bond.
Yes. Particularly preferred A has the following structure
Is mentioned. [0018] [Formula 4] X¹Each independently represents —O— or —NR—²−
From the viewpoint of availability and the like, it may be -O-.
More preferred. R²Represents a hydrogen atom or an alkyl group,
R²As an alkyl group represented by C1-C20,
Preferably 1-12, more preferably 1-12
2 to 8 is particularly preferable. R²In the table
The alkyl group to be substituted may have a substituent.
Suitable substituents include aryl groups, alkoxy groups,
Alkyloxy group, hydroxyl group, amino group, alkylamino group,
A dialkylamino group, a halogen atom, etc. are mentioned. R¹X¹When-is -O-, an alkyl group
X¹-NR²In the case of-, hydrogen atom, alkyl
Represents a group or an aryl group. R¹And R²And each other
To form a ring. R¹Archi represented by
Is a straight chain, branched chain or cyclic alkyl group.
Preferably having 1 to 20 carbon atoms,
From the viewpoint of hydrophobicity, solubility in a solvent, etc., the number of carbon atoms is 1-8.
It is more preferable that the number of carbon atoms is 2 to 6.
Particularly preferred. R¹The alkyl group represented by
A preferable substituent may be aryl.
Group, alkoxy group, aryloxy group, hydroxyl group, amino group
Group, alkylamino group, dialkylamino group, nitro
Group, cyano group, halogen atom and the like. R¹In the table
The aryl group to be substituted may have a substituent.
Examples of the substituent include the same substituents as in the case of the alkyl group.
I can get lost. Preferred monomer units represented by the general formula (1)
A good example is: [0022] [Chemical formula 5][0023] [Chemical 6] [0024] [Chemical 7] [0025] [Chemical 8] These monomer units may be used alone or
Multiple types may be used in combination to form a copolymer. further,
Copolymer other than the monomer unit represented by the general formula (1)
Improve other physical properties by copolymerizing components
Or it can be modified. As such physical properties
For example, alkali developability, chemical resistance, printing durability, sensitivity
Etc. are included. Monomer represented by the general formula (1)
Examples of the copolymer component other than the above are as follows:
Mention of the monomers listed in (m1) to (m12)
Can do. (M1) For example, 2-hydroxyethyla
Chlorate or 2-hydroxyethyl methacrylate, etc.
Acrylates having aliphatic hydroxyl groups and
Tacrylic acid esters. (M2) Methyl acrylate, ethyl acrylate, acrylic
Propyl lurate, butyl acrylate, amyl acrylate,
Hexyl acrylate, octyl acrylate, acrylic acid
Benzyl, 2-chloroethyl acrylate, glycidyl
Acrylate, N-dimethylaminoethyl acrylate
Alkyl acrylates such as (M3) methyl methacrylate, ethyl methacrylate, me
Propyl tacrylate, butyl methacrylate, methacryl
Amyl acid, hexyl methacrylate, cyclomethacrylate
Hexyl, benzyl methacrylate, methacrylic acid-2-
Chloroethyl, glycidyl methacrylate, N-dimethyl
Alkyl methacrylate such as ruaminoethyl methacrylate
To. (M4) Acrylamide, methacrylamide, N-methyl
Roll acrylamide, N-ethyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl aqua
Rilamide, N-hydroxyethylacrylamide, N
-Phenylacrylamide, N-nitrophenyl acrylic
Luamide, N-ethyl-N-phenylacrylamide, etc.
Acrylamide or methacrylamide. (M5) Ethyl vinyl ether, 2-chloroethyl vinyl
Ether, hydroxyethyl vinyl ether, propylene
Ru vinyl ether, butyl vinyl ether, octyl bi
Vinyl ethers such as nil ether and phenyl vinyl ether
Tells. (M6) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate
Kind. (M7) Styrene, α-methylstyrene,
Styrene such as methylstyrene and chloromethylstyrene
Kind. (M8) Methyl vinyl ketone, ethyl vinyl ketone, plastic
Vinyl such as propyl vinyl ketone and phenyl vinyl ketone
Ketones. (M9) Ethylene, propylene, isobutylene, butadi
Olefins such as ene and isoprene. (M10) N-vinylpyrrolidone, N-vinylcarbazo
, 4-vinylpyridine, acrylonitrile, methacrylate
Rilonitrile and the like. (M11) N-acryloylacrylamide, N-ace
Til methacrylamide, N-propionyl methacrylate
Mido, N- (p-chlorobenzoyl) methacrylamide
Unsaturated imides such as (M12) such as acrylic acid, methacrylic acid, itaconic acid
Unsaturated carboxylic acid and 2-hydroxyethyl acrylate
Or aliphatic such as 2-hydroxyethyl methacrylate
Acrylic acid ester having hydroxyl group and methacrylic acid
Carboxyl groups such as condensates of esters and cyclic acid anhydrides
Containing monomer. Among these copolymer components, the film property is improved.
For this purpose, alkyl acrylate (m2) and alkyl
It is preferable to use dimethacrylate (m3). The monomer unit represented by the general formula (1) is included.
When the high molecular compound is a copolymer, it is represented by the general formula (1).
The monomer unit contained in the copolymer is 5 mol% or more.
Preferably 10 mol% or more
Is more preferable. Monomer unit represented by general formula (1)
The weight average molecular weight of the polymer compound containing
00 to 200,000 is preferred, 10,000 to 10
More preferably, 20,000, 20,000-60,00
0 is particularly preferred. If the molecular weight is too low, a sufficient coating
If it is not obtained and is too large, the developability tends to be inferior. Also, the resin composition of the present invention can be used as a lithographic printing plate precursor.
When used for the photosensitive layer (recording layer) of a plate, the entire photosensitive layer
The solid content is preferably 1% by mass to 50% by mass.
More preferably, the content is 5% by mass to 20% by mass.
If the development latitude is narrower than 1% by mass,
If the amount exceeds 50% by mass,
This is not preferable because printing durability tends to be low. Including a monomer unit represented by the general formula (1)
The polymer compound uses a known radical polymerization initiator,
Conventionally known graft copolymerization and block copolymerization
Method, random copolymerization method, etc.
it can. The monomer unit represented by the general formula (1) is contained.
Among the polymer compounds that can be suitably used in the present invention
Examples of (AP-1 to AP-18) are shown below.
Is not limited to these. [0034] [Chemical 9][0035] Embedded image [0036] Embedded image[0037] Embedded image[0038] Embedded image[0039] Embedded image [Infrared absorber] Infrared absorber in the present invention
The collecting agent will be described. Infrared absorption used in the present invention
As an agent, it absorbs the irradiation energy of light energy used for recording.
However, if the substance generates heat, the limit of the absorption wavelength range is
High power laser that can be used without
Wavelength from 760 nm to 1200 nm
Infrared absorbing dyes or pigments that have an absorption maximum
Can be mentioned. Examples of the dye include commercially available dyes and, for example, “dye”.
"Handbook for Handbook"
The well-known thing described in literature can be utilized. concrete
Azo dyes, metal complex azo dyes, pyrazolone azo dyes
, Naphthoquinone dye, anthraquinone dye, phthalose
Anine dye, carbonium dye, quinone imine dye,
Chin dye, cyanine dye, squarylium dye, piliri
Um salt, metal thiolate complex, oxonol dye, dii
Such as monium dye, aminium dye, croconium dye, etc.
Dyes. Preferred dyes include, for example, JP-A-5.
No. 8-125246, JP 59-84356, JP
Sho 59-202829, JP-A 60-78787, etc.
Cyanine dyes described in JP-A-58-1736
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in each publication of No. 94595, etc.
JP-A-58-112793, JP-A-58-22479
3, JP-A-59-48187, JP-A-59-739
96, JP-A-60-52940, JP-A-60-63
Naphthoquinone dye described in each publication of No. 744
Described in Japanese Patent Application Laid-Open No. 58-112792, etc.
Squarylium dye, British Patent 434,875
And the cyanine dyes described in the book. US Pat. No. 5,156,938
The near-infrared absorption sensitizer described in the booklet is also preferably used.
The device described in US Pat. No. 3,881,924
Substituted arylbenzo (thio) pyrylium salts,
57-142645 (US Pat. No. 4,327,169)
No.), trimethine thiapyrylium salt, JP-A 58-
181051, 582-22014, 59-4
1363, 59-84248, 59-8424
No. 9, No. 59-146063, No. 59-146061
Pyryllium compounds described in each of the publications
Cyanine dyes described in JP-A-59-216146, rice
The pentame described in Japanese Patent No. 4,283,475
Chinthiopyrylium salt, etc.
Pyrylium disclosed in each publication of Japanese Patent No. 5-19702
Compounds are also preferably used. Another preferred example of the dye is rice.
In Japanese Patent No. 4,756,993, formula (I),
Name near-infrared absorbing dyes listed as (II)
You can. Of these dyes, particularly preferred
Cyanine dyes, phthalocyanine dyes, oxonol
Dyes, squarylium pigments, pyrylium salts, thiopyri
Examples thereof include a lithium dye and a nickel thiolate complex. The
In addition, dyes represented by the following general formulas (a) to (e)
Is preferable because of its excellent photothermal conversion efficiency.
The cyanine dye represented by (a) is the resin composition of the present invention.
High interaction with alkali-soluble resin when used in
Most preferred because of its stability and economy.
That's right. [0046] Embedded image In general formula (a), X¹Is a hydrogen atom, halo
Gen atom, -NPh₂, X²-L¹Or the following groups
The Where X²Represents an oxygen atom or a sulfur atom, and L¹
Has a hydrocarbon group having 1 to 12 carbon atoms and a hetero atom.
An aromatic ring having 1 to 12 carbon atoms including a hetero atom
A hydrocarbon group is shown. Here, the hetero atom is N,
S, O, a halogen atom, and Se are shown. [0048] Embedded image R¹And R²Are each independently a carbon atom
The hydrocarbon group of number 1-12 is shown. Safe storage of photosensitive layer coating solution
From qualitative, R¹And R²Is a hydrocarbon with 2 or more carbon atoms
It is preferably a basic group, and further R¹And R²And each other
In particular to form a 5- or 6-membered ring
preferable. Ar¹, Ar²Are the same or different
Aromatic hydrocarbons that may have a substituent
Indicates the basis. Preferred aromatic hydrocarbon groups include ben
Zen ring and naphthalene ring may be mentioned. Also preferred
As the substituent, a hydrocarbon group having 12 or less carbon atoms,
A halogen atom, an alkoxy group having 12 or less carbon atoms
Can be mentioned. Y¹, Y²Are the same but different
Or a sulfur atom or a dial with 12 or less carbon atoms
A kilmethylene group is shown. R^Three, R^FourAre the same
Carbon atoms which may be different and may have a substituent
A hydrocarbon group having 20 or fewer children is shown. With preferred substituents
An alkoxy group having 12 or less carbon atoms, a carbo
A xyl group and a sulfo group are mentioned. R^Five, R⁶, R⁷as well as
R⁸May be the same or different,
A child or a hydrocarbon group having 12 or less carbon atoms is shown. material
From the availability of the hydrogen atom, a hydrogen atom is preferable. Za^-
Represents a counter anion. However, R¹~ R⁸Either
When the sulfo group is substituted, Za^-Is not necessary. Good
Zai^-Because of the storage stability of the photosensitive layer coating solution,
Ion, perchlorate ion, tetrafluoroborate ion
ON, hexafluorophosphate ion, and sulfo
Acid ions, particularly preferably perchlorate ions,
Hexafluorophosphate ion and aryls
It is a sulfonic acid ion. In the present invention, it can be suitably used.
Specific examples of the cyanine dye represented by the general formula (a)
In addition to those exemplified below, JP-A-2001-1339
69, paragraph numbers [0017] to [0019], JP
Paragraph Nos. [0012] to 2002-40638
[0038], paragraph number of Japanese Patent Application No. 2002-23360
Nos. [0012] to [0023]
Can. [0052] Embedded image [0053] Embedded image[0054] Embedded image [0055] Embedded image [0056] Embedded imageIn the general formula (b), L is a conjugated carbon atom number of 7 or more.
Represents the upper methine chain, and the methine chain has a substituent.
The substituents are bonded to each other to form a ring structure.
Also good. Zb⁺Indicates a counter cation. Preferred counter cation
As ammonium, iodonium, sulfoniu
Phosphonium, pyridinium, alkali metal cation
(Ni⁺, K⁺, Li⁺). R⁹~ R¹⁴
And R¹⁵~ R²⁰Are independently of each other hydrogen atoms or halogen atoms.
Child, cyano group, alkyl group, aryl group, alkenyl
Group, alkynyl group, carbonyl group, thio group, sulfonyl
Group, sulfinyl group, oxy group, or amino group
Substituents, or combinations of two or three of these
Which are bonded to each other to form a ring structure.
May be. Here, in general formula (b), L is a conjugated carbon atom.
Those representing the methine chain of formula 7, and R ⁹~ R¹⁴And R¹⁵
~ R²⁰That all represent hydrogen atoms are readily available and effective
It is preferable from the viewpoint of fruit. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (b) include
Can be mentioned as examples. [0059] Embedded image [0060] Embedded image In general formula (c), Y^ThreeAnd Y^FourIs that
Oxygen, sulfur, selenium, or tellurium atoms
Represents. M represents a methine chain having 5 or more conjugated carbon atoms. R
^{twenty one}~ R ^{twenty four}And R^{twenty five}~ R²⁸Are the same, but different
May be hydrogen atom, halogen atom, cyano
Group, alkyl group, aryl group, alkenyl group, alkini
Group, carbonyl group, thio group, sulfonyl group, sulfi
Represents a nyl group, an oxy group, or an amino group. In the formula, Z
a^-Represents a counter anion, and Za in the general formula (a)^-
It is synonymous with. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (c) include the following:
Can be mentioned as examples. [0063] Embedded image[0064] Embedded image In the general formula (d), R²⁹Or R³¹Each is German
In addition, a hydrogen atom, an alkyl group, or an aryl group is shown.
R³³And R³⁴Each independently represents an alkyl group, a substituted oxy
A group or a halogen atom; n and m are each independently 0
Or an integer of 4. R²⁹And R³⁰Or R³¹And R³²Is
Each may be bonded to form a ring, and R²⁹as well as/
Or R³⁰Is R³³And also R³¹And / or R³²Is R³⁴And conclusion
May be combined to form a ring, and R³³Or R³⁴But
R when there are multiple³³Each other or R³⁴Each other
To form a ring. X²And X^ThreeAre independent of each other
And a hydrogen atom, an alkyl group, or an aryl group, and X
²And X^ThreeAt least one of a hydrogen atom or an alkyl group
Show. Q is a trimethine group which may have a substituent, or
It is a pentamethine group and has a ring structure together with a divalent organic group.
It may be formed. Zc^-Represents a counter anion, the general formula
Za in (a)^-It is synonymous with. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (d) are as follows:
Can be mentioned as examples. [0067] Embedded image [0068] Embedded image In the general formula (e), R³⁵~ R⁵⁰Each
In addition, a hydrogen atom which may have a substituent, a halogen atom,
A cyano group, an alkyl group, an aryl group, an alkenyl group, an
Lucinyl group, hydroxyl group, carbonyl group, thio group, sulfoni
Ru group, sulfinyl group, oxy group, amino group, onium
The salt structure is shown. M is two hydrogen atoms or metal atoms,
Shows halometal group and oxymetal group, but is included
As the metal atom, IA, IIA, IIIB, I in the periodic table
VB group atoms, 1st, 2nd and 3rd transition metals, lanta
Noid elements such as copper, magnesium,
Iron, zinc, cobalt, aluminum, titanium, vanadium
Are preferred. In the present invention, it can be suitably used.
Specific examples of the dye represented by the general formula (e) are as follows:
Can be mentioned as examples. [0071] Embedded image Used as an infrared absorber in the present invention
Commercially available pigments and color indexes
(CI) Handbook, “Latest Pigment Handbook” (Japan Pigment Technical Association)
Edition, 1977), "Latest Pigment Application Technology" (CMC
Published in 1986), "Printing ink technology" issued by CMC
Edition, published in 1984)
The 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. Specifically, insoluble
Zo pigment, azo lake pigment, condensed azo pigment, chelate azo
Pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, key
Nacridone pigments, dioxazine pigments, isoindole
Non-based pigments, quinophthalone pigments, dyed lake pigments,
Azine pigment, nitroso pigment, nitro pigment, natural pigment, firefly
Light pigments, inorganic pigments, carbon black, etc. can be used.
Of these pigments, carbon black is preferred.
is there. These pigments may be used without surface treatment.
Alternatively, a surface treatment may be applied. For surface treatment method
The method of surface coating with resin and wax, surfactant
Method of adhering, reactive substances (eg silane cups)
Ring agents, epoxy compounds, polyisocyanates, etc.)
A method of bonding to the pigment surface is conceivable. Above surface
The treatment method is "Characteristics and application of metal soap" (Shoshobo)
“Printing Ink Technology” (CMC Publishing, 1984) and
To "Latest Pigment Applied Technology" (CMC Publishing, 1986)
Has been described. The particle size of the pigment is in the range of 0.01 μm to 10 μm.
Preferably in the range of 0.05 μm to 1 μm
More preferably, it is particularly 0.1 μm to 1 μm.
It is preferable that it exists in the range. The particle size of the pigment is 0.01μ
If it is less than m, the stability of the dispersion in the image-sensitive layer coating solution
In view of the above, it is not preferable.
It is not preferable in terms of the uniformity of the optical layer. As a method for dispersing the pigment, ink production is possible.
And well-known dispersion techniques used for toner production, etc.
The Dispersers include ultrasonic dispersers, sand mills, and atomizers.
Lighter, Pearl mill, Super mill, Ball mill, Y
Impeller, despather, KD mill, colloid mill, da
Inatron, 3-roll mill, pressure kneader, etc.
It is. For details, see “Latest Pigment Application Technology” (CMC Publishing, 1
986). These pigments or dyes constitute the recording layer.
0.01 to 50% by weight, preferably based on the total solid content
Is 0.1 to 10% by weight, particularly preferably in the case of dyes.
5 to 10% by weight, particularly preferably 0.1 to 1 in the case of pigments
It can be added at a ratio of 0% by mass. Pigment or
When the added amount of the dye is less than 0.01% by mass, the sensitivity is low.
And when it exceeds 50% by mass,
As the blending amount increases, the uniformity of the photosensitive layer and the recording layer
There is a risk of adversely affecting durability. As described above, the resin composition of the present invention has a
It is preferable to apply to the recording layer of di-type planographic printing plate precursor
In this case, the resin composition of the present invention is listed below.
It is preferable that each component is further included. [Alkali-soluble resin] Can be used in the present invention.
Alkali-soluble resins include main chains and / or
Is a homopolymer containing an acidic group in the side chain, copolymer of these
Body or mixtures thereof. Above all, (1)
The acidic group listed in (6) is the main chain and / or side chain of the polymer
What is in it is soluble in alkaline developer
This is preferable in terms of expression of dissolution inhibiting ability. (1) Phenol group (-Ar-OH) (2) Sulfonamide group (—SO₂NH-R) (3) Substituted sulfonamide acid group (hereinafter referred to as “active imide”
It is called "base". ) [-SO₂ NHCOR, -SO₂NHS
O₂R, -CONHSO₂R] (4) Carboxylic acid group (—CO₂H) (5) Sulfonic acid group (-SO_ThreeH) (6) Phosphate group (-OPO_ThreeH₂) In the above (1) to (6), Ar has a substituent.
Represents a divalent aryl linking group which may be
The hydrocarbon group which may have a substituent is represented. An acidic group selected from the above (1) to (6)
Among the alkali-soluble resins we have, (1) phenol
Groups, (2) sulfonamide groups and (3) active imide groups
An alkali-soluble resin is preferable.
Alkaline having an enol group or (2) a sulfonamide group
The re-soluble resin is soluble in alkaline developer.
Image latitude, preferred from the viewpoint of ensuring sufficient film strength
(1) An alkali-soluble resin having a phenol group
Most preferred. An acidic group selected from the above (1) to (6)
Examples of the alkali-soluble resin having:
Can be mentioned. (1) As an alkali-soluble resin having a phenol group
For example, polycondensation of phenol and formaldehyde
Body, condensation polymer of m-cresol and formaldehyde,
a condensation polymer of p-cresol and formaldehyde, m-
Polymerization of p / p-mixed cresol and formaldehyde
Body, phenol and cresol (m-, p-, or m- /
p-mixed) and formaldehyde
Novolak resins such as polymers, and pyrogallol and aceto
And a polycondensation polymer. Furthermore, Feno
A copolymer obtained by copolymerizing a compound having a vinyl group in the side chain.
It can also be mentioned. Alternatively, it has a phenol group in the side chain.
It is also possible to use a copolymer obtained by copolymerizing the compound to be
The As the compound having a phenol group,
Acrylamide having enolic group, methacrylamido
, Acrylic acid ester, methacrylic acid ester, or
Hydroxystyrene etc. are mentioned. (2) Alkali having a sulfonamide group
Examples of the soluble resin include a sulfonamide group
The smallest structural unit derived from a compound
Mention may be made of constructed polymers. As above
As a compound, at least one hydrogen atom per nitrogen atom
And a polymerizable unsaturated group
And compounds having one or more in the molecule.
The Among them, acryloyl group, allyl group, or vinyloxy
A substituted or monosubstituted aminosulfonyl group or
Low molecular weight with substituted sulfonylimino group in the molecule
Compounds are preferred, for example, the following general formula (i) to general formula
The compound represented by (v) is mentioned. [0086] Embedded image Where X¹, X² Are each independently -O
-Or-NR⁷Represents. R¹, R^FourEach independently water
Elementary atom or -CH_ThreeRepresents. R², R^Five, R⁹, R¹², And
And R¹⁶Each independently may have a substituent.
An alkylene group having 1 to 12 carbon atoms, a cycloalkylene group,
Represents an arylene group or an aralkylene group; R^Three, R⁷, And
And R¹³Each independently has a hydrogen atom or a substituent.
An optionally substituted alkyl group having 1 to 12 carbon atoms, cycloalkyl
Represents an alkyl group, an aryl group or an aralkyl group. Also,
R⁶, R¹⁷Each independently may have a substituent.
An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an
Reel group, aralkyl group. R⁸, R^Ten, R^{1 Four}Is
Each independently a hydrogen atom or -CH_ThreeRepresents. R¹¹, R
¹⁵Each independently has a single bond or a substituent.
Good C1-C12 alkylene group, cycloalkylene
Represents a group, an arylene group or an aralkylene group. Y¹, Y²
Each independently represents a single bond or CO. Formulas represented by general formula (i) to general formula (v)
Among the compounds, the positive lithographic printing plate precursor of the present invention has a special
M-aminosulfonylphenyl methacrylate, N
-(P-aminosulfonylphenyl) methacrylami
N- (p-aminosulfonylphenyl) acrylic
A mid or the like can be suitably used. (3) Alkali-soluble with an active imide group
Examples of the functional resin include compounds having an active imide group
The smallest structural unit derived from
Can be mentioned. With compounds like the above
Can be polymerized with an active imide group represented by the following structural formula:
A compound having at least one functional unsaturated group in the molecule
You can list things. [0090] Embedded image Specifically, N- (p-toluenesulfoni
) Methacrylamide, N- (p-toluenesulfoni
E) Acrylamide and the like can be preferably used. (4) Alkali soluble having a carboxylic acid group
Examples of the polymerizable resin are polymerizable with a carboxylic acid group.
A compound having at least one unsaturated group in the molecule
Polymers whose main constituent is the smallest constituent unit
I can make it. (5) An alkali-soluble polymer having a sulfonic acid group
For example, a sulfonic acid group and a polymerizable unsaturated group
Derived from a compound having one or more in the molecule
List polymers with the smallest building block as the main building block
Can do. (6) As an alkali-soluble resin having a phosphate group,
For example, a phosphate group and a polymerizable unsaturated group
The minimum structural unit derived from a compound having 1 or more in each
Can be cited as a main component. Consists of the alkali-soluble resin as described above
And having an acidic group selected from the above (1) to (6)
There is no need to have only one kind of small structural unit.
2 or more or different minimum structural units having an acidic group of
Two or more kinds of minimum structural units having acidic groups are copolymerized
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 the present invention, a compound is copolymerized to form an alcohol.
When potash-soluble resin is used as a copolymer,
As a compound to contain, the acidic group of said (1)-(6) is included.
Other compounds that are not available can also be used. (1)-(6)
Examples of other compounds not containing the acidic group of
As a copolymerization component with the monomer unit represented by the formula (1)
The monomer of (m1)-(m12) illustrated similarly is mentioned similarly
However, the present invention is not limited to these. As the alkali-soluble resin, an infrared ray resin is used.
The pheno
Preferably have a hydroxyl group, such as phenol
Formaldehyde resin, m-cresol formal
Dehydric resin, p-cresol formaldehyde resin, m
-/ P-mixed cresol formaldehyde resin, pheno
Mole / cresol (m-, p-, or m- / p-mixed
Any)) Novola such as mixed formaldehyde resin
Preferable examples are lacquer resin and pyrogallol acetone resin.
It is. Further, an alkenyl having a phenolic hydroxyl group
As the resoluble resin, further, US Pat. No. 4,123,
As described in US Pat.
Enol formaldehyde resin, octyl phenol resin
Alkyl having 3 to 8 carbon atoms such as lumaldehyde resin
Phenol and formaldehyde as substituents
As described in JP-A-2000-241972.
A phenolic structure with an electron-withdrawing group on the aromatic ring
Examples thereof include alkali-soluble resins. In the present invention, these phenolic compounds
Among alkali-soluble resins having a hydroxyl group, the resin composition
From the viewpoint of film properties as a product, as phenols
Phenol, o-cresol, m-cresol, p-
Cresol, 2,5-xylenol, 3,5-xyleno
And resorcinol and aldehydes or ketones
Formaldehyde, acetaldehyde, propio
Polycondensates with aldehydes are preferred, especially m-clei.
Zole: p-cresol: 2,5-xylenol: 3,
5-xylenol: resorcinol mixing ratio is mole
40 to 100: 0 to 50: 0 to 20: 0 to 20: 0 in ratio
~ 20 mixed phenols or phenol: m-c
The mixing ratio of resol: p-cresol: 0 to 0 in molar ratio
100: 1 to 70: 1-60 mixed phenols,
A polycondensate with rumaldehyde 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. The alkali-soluble resin in the present invention is
The total content of is 30 to 99 mass in the total solid content of the recording layer.
% Is preferable, and 40 to 95% by mass is more preferable. Contains
When the amount is less than 30% by mass, the durability is deteriorated.
If the amount is over 99% by mass,
This is preferable because the image forming property tends to decrease.
Yes. [Other components] The resin compound of the present invention is used.
It is necessary to form a positive recording layer.
Depending on the situation, various additives can be added. example
Onium salt, o-quinonediazide compound, aromatic sulfur
Heat content of phono compounds, aromatic sulfonate compounds, etc.
It is degradable, and in the state where it does not decompose, the alkali soluble resin
Using substances that substantially reduce solubility
This is preferable in terms of improving the dissolution inhibition of the image area in the developer.
That's right. Examples of onium salts are diazonium salts and ammonium
Salt, phosphonium salt, iodonium salt, sulfonium
Salt, selenonium salt, arsonium salt, etc.
Yes. As the onium salt used in the present invention
For example, S. I. Schlesinger,
 Photogr. Sci. Eng., 18, 387 (1974), T. S. Bal et
al, Polymer, 21, 423 (1980), JP-A-5-158230
Diazonium salts described in US Pat.
9,055, 4,069,056, JP-A 3-1
Ammonium salt described in the specification of No. 40140, D.C.
Necker et al, Macromolecules, 17, 2468 (1984), C.
S. Wen et al, Teh, Proc. Conf. Rad. CuringASIA, p4
78 Tokyo, Oct (1988), US Pat. No. 4,069,055
No. 4,069,056
Ni salt, J. V. Crivello et al, Macromorecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31
(1988), European Patent No. 104,143, US Patent No. 5,
Each specification of 041,358 and 4,491,628
, JP-A-2-150848, JP-A-2-29651
Iodonium salt described in each publication of No. 4, J. V. Crivello
et al, Polymer J. 17, 73 (1985), J. V. Crivello et
 al. J. Org. Chem., 43, 3055 (1978), W. R. Watt et
al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), J. V. Crivello et al, Polymer Bull., 14, 27
9 (1985), J. V. Crivello et al, Macromorecules, 1
4 (5), 1141 (1981), J. V. Crivello et al, J. Polyme
r Sci., Polymer Chem. Ed., 17, 2877 (1979), Europe
Patent Nos. 370,693, 233,567, 29
7,443, 297,442, U.S. Pat. No. 4,9
33,377, 3,902,114, 5,04
1,358, 4,491,628, 4,76
0,013, 4,734,444, 2,83
3,827, German Patent 2,904,626, the same
Each light of 3,604,580 and 3,604,581
The sulfonium salt described in the booklet, J. V. Crivello et al,
Macromorecules, 10 (6), 1307 (1977), J. V. Crivello
 et al, J. Polymer Sci., Polymer Chem. Ed., 17, 104
7 (1979), selenonium salts, C. S. Wen etal, T
eh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct
(1988) and the like. Among onium salts, diazonium salts are
Particularly preferred. Also, as a particularly suitable diazonium salt
Are described in JP-A-5-158230.
It is. The counter ion of the onium salt is tetrafluoride.
Boric acid, hexafluorophosphoric acid, triisopropylnaphthalene
Sulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfo
Acid, 2,4,6-trimethylbenzenesulfonic acid, 2
-Nitrobenzenesulfonic acid, 3-chlorobenzenesulfuric acid
Phosphonic acid, 3-bromobenzenesulfonic acid, 2-fluoro
Capryl naphthalene sulfonic acid, dodecyl benzene sul
Phosphonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy
Ci-4-hydroxy-5-benzoyl-benzenesulfo
Acid, p-toluenesulfonic acid, etc.
Yes. Among these, especially hexafluorophosphoric acid, triisopropyl
Lopylnaphthalenesulfonic acid and 2,5-dimethylbenze
Alkyl aromatic sulfonic acids such as sulfonic acids are preferred
It is. Suitable quinonediazides include o-kis.
Non-diazide compounds can be mentioned. For the present invention
At least one o-quinonediazide compound can be used
The compound having o-quinonediazide group of
It increases the solubility in alkali and is a combination of various structures.
Can be used. That is, o-quinonediazide
Loses the ability to inhibit the dissolution of the binder by thermal decomposition, and o-
Quinonediazide itself turns into an alkali-soluble substance
Both effects help the solubility of the sensitive material system. Main departure
Examples of o-quinonediazide compounds used for light
For example, J.H. By Korser "Light-sensitive system"
Muse "(John Wiley & Sons. Inc.) pp. 339-352
Can be used, but various aromatic poly
Reacts with hydroxy compounds or aromatic amino compounds
O-quinonediazide sulfonate or sulfo
Phonamide is preferred. In addition, Japanese Patent Publication No.43-28403
Benzoquinone (1,2)-as described in the publication
Diazide sulfonic acid chloride or naphthoquinone
(1,2) -Diazide-5-sulfonic acid chloride and pic
Rogalol-ester with acetone resin, US Patent No.
No. 3,046,120 and No. 3,188,21
Benzoquinone- (1,2) described in No. 0 specification
-Diazide sulfonic acid chloride or naphthoquinone-
(1,2) -Diazide-5-sulfonic acid chloride and fluorine
Esters with enol-formaldehyde resin are also suitable
used. Further, naphthoquinone- (1,2) -dia
Zido-4-sulfonic acid chloride and phenol formua
Rudehydr resin or cresol-formaldehyde tree
Esters with fat, naphthoquinone- (1,2) -diazide
-4-sulfonic acid chloride and pyrogallol-acetone
Ester with resin is also preferably used. Other
Useful o-quinonediazide compounds include a number of special features.
Reported to Huh and known. For example, JP-A-47-53
03, JP-A-48-63802, JP-A-48-63
803, JP-A-48-96575, JP-A-49-3
8701, JP 48-13354, JP 41-
No. 11222, No. 45-9610, No. 49-
17481 and other publications, US Pat. No. 2,797,2
13, No. 3,454,400, No. 3,544
No. 323, No. 3,573,917, No. 3,67
No. 4,495, No. 3,785,825, British Patent No.
Nos. 1,227,602, Nos.1,251,345,
No. 1,267,005, No. 1,329,888,
No. 1,330,932, German Patent No. 854,89
List items described in each specification such as No. 0
You can. As addition amount of o-quinonediazide compound
Is preferably 0 to 10 mass based on the total solid content of the recording layer
%, More preferably 0 to 5% by mass, particularly preferably 0 to
The range is 2% by mass. These compounds can be used alone
However, it may be used as a mixture of several kinds. Additives other than o-quinonediazide compounds
The addition amount is preferably 0 to 5% by mass, more preferably 0.
~ 2% by weight, particularly preferably 0.1 to 1.5% by weight
The The additive and binder of the present invention may be contained in the same layer.
And are preferred. 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. Cyclic acid anhydrides include U.S. Pat. No. 4,115,
Phthalic anhydride, tetra, as described in No. 128
Hydrophthalic anhydride, hexahydrophthalic anhydride, 3,
6-endooxy-Δ4-tetrahydrophthalic anhydride,
Tetrachlorophthalic anhydride, maleic anhydride, no chloro
Maleic anhydride, α-phenylmaleic anhydride, succinic anhydride
Succinic acid, pyromellitic anhydride, etc. can be used. Fenault
Bisphenol A, p-nitrophenol
, P-ethoxyphenol, 2,4,4'-trihydride
Loxybenzophenone, 2,3,4-trihydroxybenzene
Nzophenone, 4-hydroxybenzophenone, 4,
4 ', 4 "-trihydroxytriphenylmethane, 4,
4 ', 3 ", 4" -tetrahydroxy-3,5,3',
And 5'-tetramethyltriphenylmethane.
The Further, as organic acids, JP-A-60-88942
No. 2, JP-A-2-96755, etc.
Sulfonic acids, sulfinic acids, alkyl sulfuric acid
, Phosphonic acids, phosphate esters and carboxylic acids
Specifically, p-toluenesulfonic acid,
Decylbenzenesulfonic acid, p-toluenesulfin
Acid, ethyl sulfate, phenylphosphonic acid, phenylphosphine
Phosphoric acid, phenyl phosphate, diphenyl phosphate, benzoic acid
Acid, isophthalic acid, adipic acid, p-toluic acid, 3,
4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4
-Cyclohexene-1,2-dicarboxylic acid, erucic acid,
Lauric acid, n-undecanoic acid, ascorbic acid, etc.
Can be mentioned. The above cyclic acid anhydrides, phenols and
The proportion of mechanical acids in the printing plate material is 0.05-20.
% By mass is preferred, more preferably 0.1 to 15 mass.
%, Particularly preferably 0.1 to 10% by mass. In addition, the recording layer is subjected to processing for development conditions.
In order to expand stability, Japanese Patent Application Laid-Open No. 62-251740
And as described in JP-A-3-208514
Nonionic Surfactant, JP 59-121044
As described in Japanese Patent Laid-Open No. 4-13149
Amphoteric surfactants, described in EP 950517
Such siloxane compounds, JP-A-11-288093
Monomer containing fluorine as described in
A polymer can be added. Nonionic surfactant
Specific examples include sorbitan tristearate, sorbi
Tan monopalmitate, sorbitan trioleate,
Arylic acid monoglyceride, polyoxyethylene nonylph
Examples include phenyl ether. Specific examples of double-sided activators and
Alkyl di (aminoethyl) glycine, alkyl
Rupolyaminoethylglycine hydrochloride, 2-alkyl-N
-Carboxyethyl-N-hydroxyethyl imidazoli
Nium betaine and N-tetradecyl-N, N-betaine
Type (for example, trade name “Amorgen K”: Daiichi Kogyo Co., Ltd.)
Manufactured) and the like. Examples of siloxane compounds include di
Block of methylsiloxane and polyalkylene oxide
A copolymer is preferred, and as a specific example, manufactured by Chisso Corporation,
DBE-224, DBE-621, DBE-712, D
BP-732, DBP-534, Tego, Germany, Te
polyalkylene oxide modification such as go Glide 100
Can be mentioned. Non-ionic interface above
Activators and amphoteric surfactants occupy the total solid content of the recording layer
The proportion is preferably 0.05 to 15% by mass, more preferably
It is 0.1-5 mass%. In the recording layer in which the resin composition of the present invention is used
In order to obtain a visible image immediately after heating by exposure,
Add dyes and pigments as a color remover and image colorant
Can do. The print-out agent can be heated by exposure.
Can form a salt with a compound that releases acid (photoacid releasing agent)
A combination of organic dyes can be mentioned as a representative. Ingredients
Specifically, JP-A-50-36209, 53-812.
O-Naphthoquinonediazi described in each publication of No. 8
Combination of do-4-sulfonic acid halide and salt-forming organic dye
And JP-A-53-36223, 54-7472.
No. 8, No. 60-3626, No. 61-143748,
Each of 61-151644 and 63-58440
Trihalomethyl compounds and salt-forming properties described in the publication
Mention may be made of combinations of organic dyes. Such a triha
Rhomethyl compounds include oxazole compounds and trimethyl
There are azine compounds, both of which have excellent temporal stability,
Gives clear printout images. As the colorant of the image, the above-mentioned salt forming property is present.
Other dyes can be used in addition to the machine dye. Salt formation
Oil-soluble dyes and bases as suitable dyes, including organic dyes
Sex dyes can be listed. Specifically, oil yellow
-# 101, Oil Yellow # 103, Oil Pink #
312, Oil Green BG, Oil Blue BOS, Oh
Ilblue # 603, Oil Black BY, Oil Bra
BS, Oil Black T-505 (orientated
Chemical Industry Co., Ltd.), Victoria Pure Blue, Chris
Tal violet (CI42555), methyl violet
(CI42535), ethyl violet, loader
Min B (CI145170B), Malachite Green
(CI42000), methylene blue (CI5201)
5). JP-A 62-2
The dyes described in Japanese Patent No. 93247 are particularly preferred
Yes. These dyes are 0.01% of the total solid content of the recording layer.
10 mass%, preferably 0.1 to 3 mass%
Can be added to the recording layer. Further, recording using the resin composition of the present invention.
In the layer, if necessary, to give the film flexibility etc.
A plasticizer is added. For example, butylphthalyl, poly
Ethylene glycol, tributyl citrate, diphthalate
Ethyl, dibutyl phthalate, dihexyl phthalate, lid
Dioctyl phosphate, tricresyl phosphate, tributy phosphate
, Trioctyl phosphate, tetrahydrofurate oleate
Oligomers of furyl, acrylic acid or methacrylic acid and
A polymer or the like is used. In addition to these, epoxy compounds,
Vinyl ethers, and further, JP-A-8-276558
Phenol having a hydroxymethyl group described in No. 1
Compound, phenol compound having alkoxymethyl group
And JP-A-11-16 previously proposed by the present inventors
Has an alkali dissolution inhibiting effect described in Japanese Patent No. 0860
It is possible to add a crosslinkable compound etc. according to the purpose.
Yes. [Lithographic printing plate precursor] Resin composition of the present invention
Should be used as a recording layer for lithographic printing plate precursors
Can do. Such a lithographic printing plate precursor is a resin composition of the present invention.
Recording layer coating liquid containing a product or coating liquid for a desired layer such as a protective layer
The ingredients are dissolved in a solvent and coated on a suitable support.
Thus, a lithographic printing plate precursor can be produced. here
Solvents used in ethylene dichloride, cyclohexane
Xanone, methyl ethyl ketone, methanol, ethanol
Propanol, ethylene glycol monomethyl ether
Ter, 1-methoxy-2-propanol, 2-methoxy
Ethyl acetate, 1-methoxy-2-propylacete
, Dimethoxyethane, methyl lactate, ethyl lactate,
N, N-dimethylacetamide, N, N-dimethylform
Muamide, tetramethylurea, N-methylpyrrolide
, Dimethyl sulfoxide, sulfolane, γ-butyro
Kuton, toluene, etc. can be raised but limited to this
Is not to be done. These solvents can be used alone or as a mixture
Used. The above components in the solvent (total solid including additives
The concentration of (form) is preferably 1 to 50% by weight. Ma
Coating amount (solid content) on the support obtained after coating and drying
Depends on the application, but for photosensitive printing plates
Generally 0.5 to 5.0 g / m²Is preferred. Application amount
As the value decreases, the apparent sensitivity increases.
The film properties of the photo film are degraded. As a method of applying, seed
Various methods can be used, for example, bar coater
-Coating, spin coating, spray coating, curtain coating,
Coating, air knife coating, blade coating, roll coating
Cloth etc. can be mentioned. In the photosensitive layer in the present invention
Include surfactants for improving coating properties, such as
As described in Japanese Patent Publication Sho 62-170950.
A nitrogen-based surfactant can be added. Preferred supplement
The added amount is 0.01 to 1% by mass in the total solid content of the recording layer, and
Preferably it is 0.05-0.5 mass%. [Resin intermediate layer] Necessary for lithographic printing plate precursors
Depending on the situation, a resin intermediate layer may be provided between the recording layer and the support.
You can. By providing this resin intermediate layer, exposure
Infrared sensitive layer with improved solubility in alkaline developer
A certain recording layer is provided on or near the exposed surface.
Good sensitivity and support for infrared lasers
Resin intermediate layer made of a polymer between the body and the infrared sensitive layer
Functions as a heat insulation layer, and for infrared laser exposure
The heat generated is not diffused to the support, allowing efficient image formation
The advantage of high sensitivity from being used in
Have. In unexposed areas, use alkaline developer.
The non-permeable recording layer itself is a protective layer of the resin intermediate layer
As well as improved development stability.
Produces an image with excellent discrimination, and
In addition, it is thought that stability over time is secured, and exposure
In the part, the components of the recording layer whose dissolution inhibiting ability is released
Dissolve and disperse quickly in the developer, and next to the support
This resin intermediate layer itself in contact with the
Because it consists of molecules, its solubility in the developer is
Good, for example, when using a developer with reduced activity
Even if it is, it dissolves quickly without residual film,
This resin intermediate layer is also useful because it contributes to improved developability.
it is conceivable that. [Support] Support used for planographic printing plate precursor
As a holder, it is a dimensionally stable plate-like material and has the necessary strength.
As long as it satisfies physical properties such as degree and flexibility
For example, paper, plastic (eg, polyethylene
(Polypropylene, polystyrene, etc.)
Paper, metal plate (eg, aluminum, zinc, copper)
Etc.), plastic film (eg, cellulose acetate)
, Cellulose triacetate, cellulose propionate, butyric acid
Cellulose, cellulose acetate butyrate, cellulose nitrate, polyethylene
Reethylene terephthalate, polyethylene, polystyrene
Polypropylene, polycarbonate, polyvinyl alcohol
Settal, etc.), and the above metal is laminated,
Is vapor-deposited paper or plastic film.
I can get lost. As the support, polyester film or
Is preferably an aluminum plate, among which dimensional stability
Aluminum plates that are good and relatively inexpensive are especially preferred
Yes. Suitable aluminum plates include pure aluminum plates and aluminum.
An alloy plate with ruminium as the main component and a trace amount of foreign elements.
In addition, aluminum is laminated or vapor-deposited
Plastic film may be used. Aluminum alloy
The different elements included include silicon, iron, manganese, copper, mug
Nesium, chromium, zinc, bismuth, nickel, titanium
and so on. The content of foreign elements in the alloy is at most 10% by mass
It is as follows. Aluminum particularly suitable in the present invention
Is pure aluminum but completely pure aluminum
Is difficult to manufacture due to refining technology.
It may be contained. Aluminum plate has the composition
It is not specified and is a publicly known material.
A suitable aluminum plate can be used. Main departure
The thickness of the aluminum plate used in the light is about 0.1m
m to about 0.6 mm, preferably 0.15 mm to 0.4
mm, particularly preferably 0.2 mm to 0.3 mm. Prior to roughening the aluminum plate,
If desired, for example, the surface activity to remove surface rolling oil
Degreasing treatment with an organic agent, organic solvent or alkaline aqueous solution
Is done. The roughening treatment of the surface of the aluminum plate
This can be done in various ways, for example mechanically roughening
A method for electrochemically dissolving and roughening a surface; and
It is carried out by a method of selectively dissolving the surface chemically. Machine
Mechanical methods include ball polishing, brush polishing, and bra
Use known methods such as strike polishing and buff polishing
Can do. As an electrochemical surface roughening method, hydrochloric acid or
There is a method of performing AC or DC in nitric acid electrolyte.
Moreover, it is disclosed by Unexamined-Japanese-Patent No. 54-63902.
You can also use a method that combines both
The The roughened aluminum plate can be used as needed.
After the alkaline etching treatment and neutralization treatment,
Anodic acid to increase surface water retention and wear resistance as desired
Processing is performed. For anodizing of aluminum plates
The electrolyte that can be used is a species that forms a porous oxide film.
Various electrolytes can be used, generally sulfuric acid, phosphoric acid,
Succinic acid, chromic acid or a mixed acid thereof is used. So
The concentration of these electrolytes is determined appropriately according to the type of electrolyte.
It is. The treatment conditions for anodization depend on the electrolyte used.
Since it varies, it cannot be specified unconditionally.
The solution has a concentration of 1 to 80% by mass, the liquid temperature is 5 to 70 ° C,
Flow density 5-60A / dm², Voltage 1-100V, during electrolysis
It is suitable if it is in the range of 10 seconds to 5 minutes. Anodized leather
The amount of membrane is 1.0 g / m²If it is less, the printing durability is insufficient.
Or scratches on non-image areas of planographic printing plates
The so-called `` scratch that ink adheres to the scratched part during printing
Dirt "tends to occur. After anodizing,
The ruminium surface is subjected to a hydrophilic treatment if necessary. Book
As the hydrophilization treatment used in the invention, US Pat.
No. 714,066, No. 3,181,461, No. 3,
Each specification of 280,734 and 3,902,734
Alkali metal silicates as disclosed in the documents (eg
For example, there is a sodium silicate aqueous solution method. In this way
In this case, the support is immersed in an aqueous sodium silicate solution.
Or electrolytically treated. In addition, Shoko 36-220
Potassium fluoride zirconate disclosed in Japanese Patent No. 63
And U.S. Pat. Nos. 3,276,868 and 4,15.
No. 3,461, No. 4,689,272
Treat with polyvinylphosphonic acid as disclosed
A method or the like is used. Lithographic printing to which the resin composition of the present invention is applied
A plate precursor is a substrate in which a positive recording layer is provided.
However, if necessary, an undercoat layer can be provided between them.
The Various organic compounds are used as the primer layer component,
For example, carboxymethylcellulose, dextrin,
Ami such as gum arabic and 2-aminoethylphosphonic acid
A phosphonic acid having an amino group,
Nylphosphonic acid, naphthylphosphonic acid, alkylphospho
Acid, glycerophosphonic acid, methylene diphosphonic acid and
Organic phosphonic acids such as ethylenediphosphonic acid, substituents
Phenyl phosphoric acid, naphthyl phosphoric acid, alkyl
Organic phosphoric acids such as luric acid and glycerophosphoric acid, substituents
Phenylphosphinic acid, naphthylphosphine
Phosphoric acid, alkylphosphinic acid and glycerophosphine
Organic phosphinic acids such as acids, glycine and β-alanine
Which amino acids and triethanolamine hydrochloride
Selected from the hydrochloride of amines with any hydroxy group
However, a mixture of two or more may be used. This organic undercoat layer is provided by the following method.
be able to. Water or methanol, ethanol,
Organic solvents such as methyl ethyl ketone or mixtures thereof
A solution in which the above organic compound is dissolved in a solvent mixture is mixed with aluminum.
A method of coating and drying on a metal plate and water or methanol
Organic solvents such as alcohol, ethanol, methyl ethyl ketone
Or the above organic compounds are dissolved in the mixed solvent.
An aluminum plate is immersed in the soaked solution to absorb the above compound.
And then wash and dry with water, etc. to dry the organic primer
This is a method of providing a layer. In the former method, the above organic
Various solutions with a concentration of 0.005 to 10% by mass of the compound
It can be applied by the method. In the latter method, the concentration of the solution is
0.01 to 20% by mass, preferably 0.05 to 5% by mass
The immersion temperature is 20 to 90 ° C., preferably 25 to 5
0 ° C., immersion time is 0.1 second to 20 minutes, preferably
2 seconds to 1 minute. The solution used for this is ammonia,
Basic substances such as triethylamine and potassium hydroxide
PH 1-12 due to acidic substances such as hydrochloric acid and phosphoric acid
The range can also be adjusted. In addition, adjustment of image recording materials
Yellow dye can be added to improve the reproducibility
The The coverage of the organic undercoat layer is 2 to 200 mg / m²Is suitable
Preferably 5 to 100 mg / m²It is. Up
The coating amount is 2 mg / m²Less than enough press life
No performance can be obtained. 200 mg / m²Bigger
Is the same. A positive type lithographic stamp produced as described above.
The plate precursor is usually subjected to image exposure and development. Statue
The light source used for light is from near infrared to infrared.
A light source with an emission wavelength in the range is preferred, solid-state laser, semiconductor
A body laser is particularly preferred. Lithographic printing to which the resin composition of the present invention is applied
Conventionally known as plate developer and replenisher
An alkaline aqueous solution can be used. For example, sodium silicate
, Potassium, tribasic sodium phosphate, potassium,
Same ammonium, dibasic sodium phosphate, same potassium,
Same ammonium, sodium carbonate, same potassium, same an
Monium, sodium bicarbonate, potassium, ammo
Ni, Sodium borate, Potassium, Ammonium
Sodium hydroxide, ammonium hydroxide, potassium
And inorganic alkali salts such as lithium. Ma
Monomethylamine, dimethylamine, trimethylamine
Min, monoethylamine, diethylamine, triethyl
Amine, monoisopropylamine, diisopropylamine
, Triisopropylamine, n-butylamine, mono
Ethanolamine, diethanolamine, triethanol
Luamine, monoisopropanolamine, diisopropa
Noramine, ethyleneimine, ethylenediamine,
Organic alkali agents such as lysine are also used. These a
Lucari is used alone or in combination of two or more.
It is. Among these alkali agents, particularly preferred developers
Silicate water such as sodium silicate and potassium silicate
It is a solution. The reason is silicon oxide, a component of silicate
SiO₂And alkali metal oxide M₂Depending on the ratio and concentration of O
This makes it possible to adjust the developability.
In Sho 54-62004 and Shokoku 57-7427
Effective use of alkali metal silicates as described
I can. Furthermore, when developing using an automatic processor.
Is an aqueous solution (replenisher) with higher alkali strength than the developer.
In the developer tank for a long time by adding
A large amount of PS plates can be processed without changing the developer.
Is known. This replenishment method is also preferred in the present invention.
Applied well. Developer and replenisher promote development
Suppression, dispersion of development residue and ink affinity of printing plate image area
Various surfactants and organic solvents are used as needed
An agent can be added. Preferred surfactants include anio
Ionic, cationic, nonionic and amphoteric surfactants
I can get lost. In addition, if necessary, the developer and replenisher
Idroquinone, resorcin, sulfurous acid, bisulfite, etc.
Reducing agents such as sodium salts and potassium salts of inorganic acids,
Add organic carboxylic acid, antifoaming agent, water softener
Yes. Marks developed using the developer and replenisher
The printing plate should be washed with water, rinse solution containing surfactant, etc.
Post-treated with a desensitizing solution containing beer gum or starch derivatives
The When the image recording material of the present invention is used as a printing plate
As a post-processing, various combinations of these processes are used.
Can be. In recent years, the plate making work has been rationalized in the plate making / printing industry.
Widely used for automatic processing machines for printing plates for standardization and standardization
It has been. This automatic processor is generally used for developing and post-processing.
Consists of an apparatus for conveying the printing plate
Consisting of a playing device, it conveys the exposed printing plate horizontally.
While spraying each processing liquid pumped up by the pump
And then developing. Also recently
In-liquid guide roll in a processing liquid tank filled with processing liquid
Also known is the method of immersing and transporting printing plates
ing. In such automatic processing, each processing solution is processed.
Process while replenishing the replenisher according to the amount of work or operating time.
Can. Also, treatment with virtually unused processing solution
A so-called disposable processing method can also be applied. In the lithographic printing plate precursor to which the present invention is applied
Image exposure, development, rinsing and / or rinsing and / or
Or unnecessary image area in planographic printing plate obtained by gumming
(For example, film edge traces of original film)
In that case, the unnecessary image portion is erased. This
Erasing such as is disclosed in, for example, Japanese Patent Publication No. 2-13293
Apply the erasing solution as described to the unnecessary image area,
By leaving it for a predetermined time and washing it with water
Although the method of carrying out is preferred, JP-A-59-174842
Optical fiber as described in the official gazette
Develop after irradiating unnecessary image area with guided actinic ray
You can also use this method. A lithographic printing plate obtained as described above is
Applying desensitized gum as desired, then use in printing process
It is possible to make a lithographic printing plate with even higher printing durability.
If desired, a burning process is performed as desired.
In particular, in a lithographic printing plate using the resin composition of the present invention
The printing durability is significantly improved by performing a general-purpose burning process.
Improve. When burning a planographic printing plate,
Before burning, Shoko 61-2518, 55-28
062, JP-A-62-31859, 61-159
Treated with surface conditioning liquid as described in each publication of No. 655
It is preferable to do. As a method for this, the surface conditioning liquid is immersed.
Apply on lithographic printing plate with sponge or absorbent cotton
Or immerse the printing plate in a bat filled with surface-adjusting liquid
Application methods and automatic coater application are applied.
It is. Also, after application, squeegee or ski
It is more preferable to use a di-roller to make the coating amount uniform.
Give good results. The coating amount of the surface conditioning liquid is generally 0.03 to 0.8.
g / m²(Dry mass) is appropriate. The surface-adjusting solution is applied
If necessary, the planographic printing plate is dried and then burned.
Processor (for example, Fuji Photo Film Co., Ltd.)
Burning processor on sale: “BP-130
0 ") or the like. In this case, the heating temperature and
Depending on the type of ingredients that form the image,
The range of 1 to 20 minutes is preferable in the range of 180 to 300 ° C.
Yes. A lithographic printing plate that has been burned is necessary.
Depending on the conventional method, washing with water, gumming, etc.
Water-soluble polymer compounds, etc.
Such as gumming, etc.
So-called desensitizing treatment can be omitted. Like this
Lithographic printing plate obtained by various processing is offset printing machine
And is used for printing a large number of sheets. [0131] The present invention will be described in detail with reference to the following examples.
However, the present invention is not limited to these. (Preparation of support) JIS with a thickness of 0.3 mm
-A-1050 Aluminum plate
The support A, B, C, and
And D were produced. (A) Mechanical roughening treatment Polishing suspension of abrasive (silica sand) with specific gravity of 1.12 and water
While supplying the slurry liquid to the surface of the aluminum plate
And a mechanical roller rough nylon brush
Surfaced. The average particle size of the abrasive is 8μm and the maximum particle size is
It was 50 μm. The material of nylon brush is 6 · 10
Iron, hair length 50mm, hair diameter is 0.3mm
It was. Nylon brush is a 300mm stainless steel tube
The hair was planted so as to be dense with a hole. 3 rotating brushes
Used this book. Two support rollers at the bottom of the brush (φ200
mm) was 300 mm. Brush roller
The load of the drive motor that rotates the brush
7 kW against the load before pressing against the aluminum plate
Pressed until it was positive. The direction of brush rotation is
The direction of movement of the ruminium plate was the same. Brush rotation
The number was 200 rpm. (B) Alkali etching treatment NaOH having a temperature of 70 ° C. was applied to the aluminum plate obtained above.
Aqueous solution (concentration 26 mass%, aluminum ion concentration 6.
5 mass%) is sprayed to perform the etching process.
Minium plate 6g / m²Dissolved. Then use well water
The water was washed by spraying. (C) Desmut treatment 1% by mass aqueous solution of nitric acid with a temperature of 30 ° C.
Contains 0.5% by mass of ON. )
And then washed with water by spraying. Said de
The aqueous nitric acid solution used for the smut is exchanged in the aqueous nitric acid solution.
The waste liquid from the process of electrochemical roughening was used. (D) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. The electrolyte at this time was 10.5 g of nitric acid.
/ Liter aqueous solution (5g / lit of aluminum ions
The temperature was 50 ° C. The AC power supply waveform has a current value of zero.
Time from peak to peak reaches TP 0.8mse
c, DUTY ratio 1: 1, trapezoidal rectangular wave AC
-Electrochemical roughening treatment with the Bon electrode as the counter electrode
It was. Ferrite was used for the auxiliary anode. Electrolyzer used
A radial cell type was used. Current density is electric
30 A / dm at the peak value of the flow²The quantity of electricity is aluminum
The total amount of electricity when the plate is an anode is 220 C / dm²So
It was. The auxiliary anode shunts 5% of the current flowing from the power source
It was. Then, wash with water using well water
It was. (E) Alkali etching treatment Aluminum plate with caustic soda concentration of 26% by mass, aluminum
Etching by spray at a concentration of 6.5% by mass
Processing at 32 ° C. and 0.20 g of aluminum plate
/ M²Dissolve and electrochemical roughening using the previous stage alternating current
Mainly made of aluminum hydroxide produced when
The smut component is removed and the generated pit edge is removed.
The edge portion was melted to smooth the edge portion. after that,
Water washing by spraying was performed using well water. (F) Desmut processing 15% by weight aqueous solution of sulfuric acid with a temperature of 30 ° C.
It contains 4.5% by mass of ions. ) And spray death
Perform mat treatment, then spray water with well water
Washed. The aqueous nitric acid solution used for the desmut is nitric acid water.
Process of electrochemical surface roughening using alternating current in solution
Waste liquid was used. (G) Electrochemical roughening treatment Continuous electrochemical rough surface using 60Hz AC voltage
The treatment was performed. The electrolyte at this time was 7.5 g of hydrochloric acid /
Liter aqueous solution (aluminum ion 5g / liter
Including. ), And the temperature was 35 ° C. AC power supply waveform is rectangular
Electrochemical roughening with carbon electrode as counter electrode
Processed. Ferrite was used for the auxiliary anode.
The electrolytic cell used was a radial cell type. Current density
Degree is 25A / dm at peak current²The amount of electricity is aluminum
50C / dm as the total amount of electricity when the nickel plate is the anode²In
It was. Then, wash with water using well water
It was. (H) Alkali etching treatment Aluminum plate with caustic soda concentration of 26% by mass, aluminum
Etching with spray at a concentration of 6.5% by mass
Processing at 32 ° C. and 0.10 g of aluminum plate
/ M²Dissolve and electrochemical roughening using the previous stage alternating current
Mainly aluminum hydroxide produced during processing
Remove the smut component and also generate pits
The edge portion was melted to smooth the edge portion. That
Thereafter, water was washed by spraying using well water. (I) Desmut processing Sulfuric acid concentration 25 mass% aqueous solution (aluminum at 60 ° C.
Contains 0.5% by mass of ions. ) And spray death
Perform mat treatment and then spray with well water.
The water was washed. (J) Anodizing treatment Sulfuric acid was used as the electrolytic solution. All electrolytes are sulfur
Acid concentration 170 g / liter (aluminum ions
Contains 5% by mass. ), The temperature was 43 ° C. Then well
Water was washed by spraying with water. Current density is
About 30A / dm²Met. The final oxide film amount is
2.7 g / m²Met. <Support A> Steps (a) to (j) above
The etching amount in step (e) is 3.5.
g / m²The support A was prepared as described above. <Support B> Of the above steps (g) and (h)
Except that the step (i) is omitted, the steps are performed in order and the support is performed.
B was produced. <Support C> Of the above steps, (a) and
(G) (h) Steps were repeated except that step (i) was omitted.
Then, a support C was prepared. <Support D> Of the above steps, (a) and
(D) (e) The steps were sequentially performed except that the step (f) was omitted.
The total amount of electricity in step (g) is 450 C /
dm²Thus, a support D was produced. Supports A, B, C obtained as described above
And D followed by the following hydrophilization treatment and undercoating treatment
It was. (K) Alkali metal silicate treatment The temperature of the aluminum support obtained by anodizing treatment
In the treatment layer of 1 mass% aqueous solution of No. 3 sodium silicate at 30 ° C
To alkali metal silicate by soaking for 10 seconds
Processing (silicate processing) was performed. Then use well water
Washed with water by spray. With silicate at that time
Wearing amount is 3.5mg / m²Met. (Undercoating treatment) Obtained as described above.
On each aluminum support after alkali metal silicate treatment
Apply an undercoat solution of the following composition and dry at 80 ° C. for 15 seconds.
Dried. The coating amount after drying is 15 mg / m²Met. [0150] <Undercoat liquid composition> ・ The following polymer compound 0.3g ・ Methanol 100g ・ Water 1.0g [0151] Embedded image (Examples 1 to 10, Comparative Examples 1 to 3)
The following photosensitive solution was applied to the supports A to D, and 150 ° C.
After drying for 1 minute in the oven, the dry film thickness is 1.8 g / m²Of the
Positive lithographic printing plate having a di-type infrared-sensitive composition layer
An original plate was prepared. [0153] [Photosensitive solution] M, p-cresol novolak (m / p ratio = 6/4, amount described in Table 1     Weight average molecular weight 7300,     Unreacted cresol containing 0.4% by mass) -Polymer compounds listed in Table 1 Quantity listed in Table 1 ・ The following infrared absorber (cyanine dye A) 0.016 g ・ The following infrared absorber (cyanine dye B) 0.024 g ・ 2,4,6-Tris (hexyloxy) benzeneazonium-2-humanoxy- 0.01g     4-Methoxybenzophenone-5-sulfonate ・ 0.002 g of p-toluenesulfonic acid ・ Cyclohexane-1,2-dicarboxylic anhydride 0.06g ・ 0.015g counter anion of Victoria Pure Blue BOH     1-Naphthalenesulfonate anion dye ・ Fluorosurfactant (Megafac F-176, 0.02g       Dainippon Ink & Chemicals, Inc.) ・ Methyl ethyl ketone 15g ・ 7g of 1-methoxy-2-propanol [0154] Embedded image [0155] Embedded image The polymer compound used in Comparative Example 2 (AP-
C) is shown below. [0157] Embedded image [Evaluation of planographic printing plate precursor] [Evaluation of development latitude] Photosensitive lithographic printing plate obtained
Beam strength with a Trend setter manufactured by Creo
Test pattern at 9W, drum rotation speed 150rpm
I drew the image. Then, the following A composition and B
By changing the amount of alkaline developer water in the composition,
Fuji equipped with different conductivity by changing dilution rate
Using PS processor 900H manufactured by Photo Film Co., Ltd.
The liquid temperature was kept at 30 ° C., and development was performed with a development time of 20 seconds.
At this time, the image area is not eluted and the photosensitive layer is poorly developed.
Current development has been achieved with no stains or coloring caused by residual film
The difference between the highest and lowest conductivity of the image liquid
Evaluated as image latitude. The results are shown in Table 1.
The [0159] <Alkali developer A composition> ・ SiO₂・ K₂O (K₂O / SiO₂= 1/1 (molar ratio)) 4.0% by mass ・ Citric acid 0.5% by mass ・ Polyethylene glycol lauryl ether 0.5% by mass     (Weight average molecular weight 1,000) ・ Water 95.0 mass% <Alkali developer B composition> ・ D sorbit 2.5% by mass -Sodium hydroxide 0.85 mass% ・ Polyethylene glycol lauryl ether 0.5% by mass     (Weight average molecular weight 1,000) ・ Water 96.15% by mass [Evaluation of printing durability] Evaluation of development latitude
The image area is not eluted and development is not
Good development without smudges or coloration caused by good photosensitive layer residual film
A lithographic printing plate obtained in the conductivity of the developer
With a Lithrone printing machine manufactured by Komori Corporation
DIC-GEOS (N) made by Nippon Ink Chemical Co., Ltd.
Printing with ink, the density of solid images begins to fade
The printing durability is determined by the number of printed sheets
evaluated. The results are shown in Table 1. [Evaluation of printing durability after burning]
The plate surface of a lithographic printing plate obtained by developing in the same way as the evaluation of printing durability
, Burning surface preparation BC manufactured by Fuji Photo Film Co., Ltd.
After wiping with -3, burning treatment at about 240 ° C for 7 minutes
Went. Then washed with water, manufactured by Fuji Photo Film Co., Ltd.
The plate surface is treated with a solution obtained by diluting the gum GU-7 with water.
I managed. After that, as with the printing durability evaluation, Komori Corporation
Dai Nippon Ink Chemical Co., Ltd.
Printing using DIC-GEOS (N) black ink
However, it is visually recognized that the density of the solid image has started to decrease.
Depending on the number of prints at the time, the printing durability after the burning process
evaluated. The results are shown in Table 1. [Evaluation of halftone dot reproducibility] The obtained lithographic printing plate
The original version, Trend setter 3244 made by Creo
At 9 W output and 150 rpm drum resolution
A halftone dot image was exposed under the condition of a degree of 175 lpi.
Next, Fuji Photo Fiber charged with the alkali developer A
Using Lum Co., Ltd. PS processor 900H
Development was carried out at a temperature of 30 ° C. and a development time of 22 seconds. Developed
The halftone dot area ratio of the lithographic printing plate was calculated using the X-Rite spectral densitometer 5
28 and measured according to the evaluation criteria shown below.
It was. The results are shown in Table 1. -Evaluation criteria- A Halftone dot area ratio 48-52% B halftone dot area ratio 45-47%, 53-55% C Halftone dot area ratio less than 45%, 56% or more [0163] [Table 1] As shown in Table 1, the resin composition of the present invention
A lithographic printing plate using a recording layer as a recording layer is a silicate, non-silica.
Regardless of which type of developer is used, the development latitude
It turns out that it is excellent in the speed. Also, printing durability, mesh
It was found that the point reproducibility was also excellent. on the other hand,
Comparative Examples 1 and 3 not using the specific polymer compound according to the present invention
3 and a module having an ester group as a linear polymer.
Copolymerized monomers and monomers having acidic groups
In Comparative Example 2 using the film, the development latitude is inferior.
won. Examples 11 and 12 Obtained support B
The undercoat liquid was applied in the same manner as in Examples 1 to 10.
Thereafter, a lower layer coating solution having the following composition was applied at a wet coating amount of 23.
ml / m²Apply with a wire bar of 1.2g
/ M²And then in a drying oven at 150 ° C for 60 seconds
Dried. An image of the following composition was applied to the obtained primer-coated support.
11 ml wet coating amount of recording layer (upper layer) coating solution
/ M²Apply with a wire bar of 1.5g and apply a total amount of 1.5g
/ M²It was. After application, in a drying oven at 140 ° C for 7
Drying for 0 second was performed to prepare a positive planographic printing plate precursor. [0166] [Lower layer coating solution] N- (p-aminosulfonylphenyl) methacrylamide and 2.133 g     Copolymer of methyl methacrylate and acrylonitrile   (Molar ratio 37:33:30, weight average molecular weight 650,000) ・ Cyanine dye A (the above structure) 0.098 g ・ 4,4'-bishydroxyphenylsulfone 0.126g ・ Cyclohexanedicarboxylic anhydride 0.100g ・ Bis (hydroxymethyl) -p-cresol 0.090 g ・ 0.008 g of p-toluenesulfonic acid ・ 0.100 g of counter anion of ethyl violet     Changed to 6-hydroxynaphthalenesulfonic acid ・ 3-Methoxy-4-diazodiphenylamine 0.03g       Hexafluorophosphate (thermally decomposable compound) ・ Fluorosurfactant 0.035g   (Megafuck F-176, manufactured by Dainippon Ink Industries, Ltd.) ・ Methyl ethyl ketone 26.6g 1-methoxy-2-propanol 13.6 g ・ N, N-dimethylacetamide 13.8 g [0167] [Coating liquid for image recording layer (upper layer)] -Polymer compounds listed in Table 2 Amounts listed in Table 2 ・ Cresol novolac resin Amounts listed in Table 2     (PR-54046, manufactured by Sumitomo Bakelite Co., Ltd.) ・ Cyanine dye C (the following structure) 0.008g ・ Tetrabutylammonium bromide 0.030g ・ Fluorosurfactant 0.035g     (Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.) 1-methoxy-2-propanol 40.2g [0168] Embedded image [Evaluation of development latitude] The obtained lithographic plate
For the printing plate precursor, the same method as in Examples 1 to 10
Exposure and development were performed, and development latitude was evaluated. Result
The results are shown in Table 2. [Evaluation of printing durability] The obtained lithographic printing plate precursor
In the same manner as in Examples 1 to 10, a lithographic printing plate was obtained.
That is, printing durability was evaluated. The results are shown in Table 2. [0171] [Table 2] As shown in Table 2, the resin composition of the present invention
A lithographic printing plate using an object as a recording layer has a multilayer structure.
Excellent development latitude and printing durability even when taking
The performance is further improved by providing a lower layer in this way.
I found out that [0173] According to the present invention, a positive lithographic printing plate precursor
Useful for the recording layer at
An improved resin composition can be provided. In addition, the present invention tree
Positive lithographic printing plates to which the oil composition is applied
Excellent in screen, printing durability, and halftone dot reproducibility.

[Procedure Amendment] [Submission Date] May 29, 2002 (2002.5.2
9) [Procedure Amendment 1] [Document Name to be Amended] Description [Name of Item to be Amended] 0051 [Correction Method] Change [Content of Amendment] [0051] Specific examples of the cyanine dye shown include those exemplified below and JP-A-2001-1339.
69, paragraph numbers [0017] to [0019], and Japanese Patent Application Laid-Open No. 2002-40638, paragraph numbers [0012] to
[0038], paragraph [0012] of JP-Open 2002-23360 JP-may be mentioned those described in [0023].

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ken Sasakawa             4,000 Kawajiri, Yoshida-cho, Kashihara-gun, Shizuoka Prefecture Fuji             Within Shin Film Co., Ltd. (72) Inventor Mitsumasa Tsuchiya             4,000 Kawajiri, Yoshida-cho, Kashihara-gun, Shizuoka Prefecture Fuji             Within Shin Film Co., Ltd. F-term (reference) 2H025 AA04 AA13 AB03 AC08 AD03                       BF08 CC11 FA17                 2H096 AA06 BA11 EA04 GA08                 4J002 AA03X AA05X AA06W AA06X                       AA07W AA07X BH02W EE026                       EL086 EN056 EU026 EU136                       EV306 EV326 EV346 EZ006                       FD096 GP03

Claims (1)

What is claimed is: 1. A polymer compound containing a monomer unit represented by the following general formula (1), and an infrared absorber,
A resin composition, wherein solubility in an alkaline aqueous solution is changed by irradiation with infrared rays. [Chemical 1] (In General Formula (1), A represents a divalent organic group having a polymerizable double bond. X ¹ represents —O— or —NR ² —. R ¹
Represents an alkyl group when X ¹ is —O—, and X ¹ is —
NR ² - For, represents a hydrogen atom, an alkyl group, or an aryl group. R ² represents a hydrogen atom or an alkyl group. )