JP2001133968A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition excellent in work efficiency, profitableness and preservation stability, usable as a material of an original plate for a planographic printing plate for scanning exposure adaptable to a CTP system or a planographic printing plate having high sensitivity to the oscillation wavelength of a low-cost short-wavelength semiconductor laser and using a new photopolymerization initiating system having high sensitivity in the wide wavelength range of 350-450 nm. SOLUTION: The photosensitive composition contains (i) a triplet sensitizing dye having its maximum absorption at 350-450 nm wavelength, (ii) an acylphosphine compound and (iii) a compound which reacts under at least one of a radical and an acid, varies at least one of its physical and chemical characteristics and retains the varies characteristic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel photoinitiating system, and more particularly to a photosensitive composition containing a photoinitiating system having high sensitivity and excellent stability. In addition, the present invention particularly relates to a photosensitive composition excellent as a material for a lithographic printing plate precursor that can be made by scanning exposure based on digital signals. Further, the present invention relates to a sensitive composition used for image formation such as stereolithography, holography, and color hard copy, in the field of manufacturing electronic materials such as photoresists, and in photocurable resin materials such as inks, paints, and adhesives.

[0002]

2. Description of the Related Art Hitherto, as a lithographic printing plate, a PS plate having a structure in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used. After the mask exposure (surface exposure), the non-image portion is dissolved and removed to obtain a desired printing plate.

In recent years, digitalization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and various new image output methods corresponding to the technology have come into practical use. As a result, computer-to-plate (CTP) technology for scanning a highly directional light such as a laser beam in accordance with digitized image information and directly manufacturing a printing plate without passing through a lithographic film is desired. It is an important technical issue to obtain an adapted printing plate precursor.

One of the methods for obtaining such a lithographic printing plate capable of being scanned and exposed has been a conventional method in which an ink-receiving photosensitive resin layer (hereinafter referred to as a photosensitive layer) formed on a hydrophilic support has a photosensitive speed. A composition using a photopolymerizable composition having excellent properties has been proposed and is already on the market.

[0005] The photopolymerizable composition basically comprises an ethylenically unsaturated compound, a photopolymerization initiation system, and a binder resin. For image formation, the photoinitiation system absorbs light to generate active radicals and the ethylenically unsaturated compound. It causes addition polymerization of a saturated compound and insolubilizes the photosensitive layer. Most of the conventional proposals for photopolymerizable compositions capable of scanning exposure expose the use of photoinitiating systems with good photosensitivity.

A photopolymerizable composition comprising these photoinitiating systems and an Ar laser (488 nm) or FD-YA
With respect to a conventional CTP system using a visible light source having a long wavelength such as a G laser (532 nm), it is desired to perform writing at a higher speed in order to increase the productivity of the plate making process.

On the other hand, in recent years, for example, a semiconductor laser using an InGaN-based material and capable of continuously oscillating in a range of 350 nm to 450 nm has been put into practical use. A scanning exposure system using these short-wave light sources has a sufficient output because a semiconductor laser can be manufactured at a low cost due to its structure.
It has the advantage that an economical system can be constructed.
Further, compared with a system using a conventional FD-YAG or Ar laser, a light-sensitive material having a shorter photosensitive area capable of working under a brighter safelight can be used.

Further, to obtain a photoinitiating system with high sensitivity,
This technology is widely desired in the field of imaging. The photoinitiating system composed of a dye and an activator can generate an acid or a base in addition to the above-mentioned active radical by selecting the activator. However, a photoinitiating system having sufficient sensitivity for scanning exposure in a short wavelength range of 350 nm to 450 nm has not been known so far.

Photopolymerizable compositions using an acylphosphine compound as a photoinitiator are well known and are used for inks, coating materials, printing plates and the like. U.S. Pat. No. 4,292,152 describes the use of an acylphosphine oxide initiator to improve the photosensitivity of a polymerizable composition. The acylphosphine photoinitiator can be used alone, but it is also known that a sensitizing effect can be obtained by adding an appropriate compound. JP-A-4-
No. 220404 has a combination with benzophenone,
No. 305018 has a combination with coumarin and thiophene, WO
No. 97/31051 discloses a combination with fluoranthene. JP-A-3-296759 discloses a method using a benzdithiol-type compound as a photopolymerization initiator. These are certainly high sensitivities, but are not sufficient, and practically sufficient sensitivities cannot be obtained when a laser light source having a wavelength of 450 nm or less is used. JP10
-101719 discloses a combination of a dye having a five-membered heterocyclic acidic nucleus and titanocene, which has high sensitivity, but is unfavorable in terms of yellow light safety because titanocene itself has light absorption up to around 550 nm. Is the current situation.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lithographic printing plate for scanning exposure or an inexpensive short-wave semiconductor laser which is excellent in workability, economy and storage stability and is suitable for a CTP system. To provide a photosensitive composition used as a material for a lithographic printing plate precursor having high sensitivity. Another object of the present invention is to provide a photosensitive composition using a novel photopolymerization initiation system which is highly sensitive to wavelengths from 350 nm to 450 nm.

[0011]

Means for Solving the Problems In order to achieve the above object, the present inventors have intensively studied a photopolymerization initiation system which can cope with short wavelength light and has no problem of fog (yellow light safety). As a result, using an acylphosphine compound as a photoinitiator,
When a photopolymerizable composition combining a triplet sensitizing dye having a maximum absorption wavelength in the range of 350 nm to 450 nm is used as the photosensitive layer, it has sufficient sensitivity to the oscillation wavelength of the short-wavelength semiconductor laser, and The present inventors have found that a photopolymerizable composition having excellent storage stability can be obtained, and have reached the present invention.

That is, the present invention is as follows. (1) (i) a triplet sensitizing dye having a maximum absorption wavelength at 350 to 450 nm, (ii) an acylphosphine compound, and
(Iii) A photosensitive composition containing a compound that reacts with at least one of a radical and an acid and changes and retains at least one of its physical and chemical properties. (2) The sensitizing dye (i) is at least one of a sensitizing dye represented by the following general formula (1) and a sensitizing dye represented by the following general formula (2). 3. The photosensitive composition according to item 1.

[0013]

Embedded image

(Wherein, A represents an S atom or NR ₁ , R ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Y represents adjacent A and adjacent carbon atoms It represents a non-metallic atomic group forming a basic nucleus of jointly dye, respectively X _1, X ₂ are independently a hydrogen atom or a monovalent non, X _1,
X ₂ may combine with each other to form an acidic nucleus of the dye. W represents an O atom or a sulfur atom. )

[0015]

Embedded image

(Wherein, Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted aryl group, which are linked via a bond by -Z-, wherein Z is -O- or -S And W has the same meaning as that shown in the general formula 1.) (3) Reacts with at least one of the radical and the acid of the above (iii), and at least one of its physical and chemical properties. The photosensitive composition according to the above (1), wherein the compound which is changed and held is an addition polymerizable compound having an ethylenically unsaturated double bond. (4) 450 nm of the photopolymerizable composition according to (1).
A photopolymerization method comprising exposing with a laser beam having the following wavelength.

The photosensitive composition of the present invention, when used in the photosensitive layer of a lithographic printing plate precursor, has a sufficient sensitivity suitable for scanning exposure with a short-wavelength semiconductor laser such as InGaN and has a long printing life. It can be excellent in properties and dirt. The lithographic printing plate for scanning exposure using the photosensitive composition of the present invention for the photosensitive layer has remarkably improved fog under a yellow light, and can greatly improve the workability of handling the plate. The photosensitive composition of the present invention has excellent sensitivity to wavelengths of 350 to 450 nm, and at the same time has an effect of exhibiting extremely excellent storage stability.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail. The photosensitive composition of the present invention reacts with (A) a photopolymerization initiation system and (B) at least one of a radical and an acid to change at least one of its physical and chemical properties. The retained compound is an essential component, and if necessary, further comprises (C) a binder polymer. Hereinafter, these components will be specifically described.

The photopolymerization initiation system which is an essential component of the photopolymerization layer of the present invention contains (I) a sensitizing dye having a specific structure and (II) an acylphosphine compound. Initiating system in the present invention,
It is considered that the sensitizing dye mainly absorbs light and promotes the initiation of radical generation from the coexisting acylphosphine compound (this process is hereinafter referred to as dye sensitization).
The present inventors have found that by using a triplet sensitizing dye as the sensitizing dye, the acylphosphine compound is dye-sensitized. As an example of such a sensitizing dye, it has been found that, when it has a structure represented by (general formula 1), it is particularly strong and the above-mentioned characteristics can be obtained, and has led to the present invention. The reason why the sensitizing dye having a specific structure in the present invention is particularly excellent in dye sensitizing ability cannot be described in detail because the mechanism of dye sensitization is unknown, but can be considered as follows. That is, the sensitizing dye of the present invention shows a high-intensity phosphorescence spectrum. This indicates that these dyes are triplet sensitizing dyes, meaning that photoinitiators can be triplet sensitized. Here, it is known that the acylphosphine compound generates a radical via a triplet state in a photopolymerization reaction. Considering these facts, the sensitizing dye of the present invention having the above partial structure forms a triplet excited state having a relatively long lifetime, and acts to increase the efficiency of radical generation of the photoinitiator. It is possible.

(A1) Sensitizing dye The sensitizing dye used in the present invention has a maximum absorption wavelength of 350 nm.
~ 450 nm, any dye capable of triplet sensitization may be used, specifically, thioxanthone, naphthalene,
And cyanine dyes and merocyanine dyes. Preferred examples of the sensitizing dye used in the present invention are those represented by any of the following general formulas (1) and (2).

[0021]

[Formula 5]

(Wherein, A represents an S atom or NR ₁ , R ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Y represents adjacent A and adjacent carbon atoms It represents a non-metallic atomic group forming a basic nucleus of jointly dye, respectively X _1, X ₂ are independently a hydrogen atom or a monovalent non, X _1,
X ₂ may combine with each other to form an acidic nucleus of the dye. W represents an O atom or a sulfur atom. )

[0023]

Embedded image

(Wherein, Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted aryl group, which are connected via a bond by -Z-, wherein Z is -O- or-
Represents S-. W has the same meaning as that shown in the general formula (1). )

The general formula (1) will be described in detail. A
Represents an S atom or NR ₁ , R ₁ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, Y represents a basic nucleus of a dye in cooperation with adjacent A and an adjacent carbon atom. Represents a non-metallic atomic group.

Preferred examples of R ₁ will be specifically described. Examples of preferred alkyl groups include those having 1 carbon atom.
To 20 linear, branched, and cyclic alkyl groups. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1- Methyl butyl group,
Isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-
Norbornyl groups can be mentioned. Among them, a straight chain having 1 to 12 carbon atoms, 3 carbon atoms.
From 12 to 12 and from 5 to 10 carbon atoms
More preferred are cyclic alkyl groups up to.

As a substituent of the substituted alkyl group, hydrogen is
A monovalent non-metallic atomic group excluding is used, and as a preferable example,
Represents a halogen atom (-F, -Br, -Cl, -I),
Droxyl group, alkoxy group, aryloxy group, merka
Group, alkylthio group, arylthio group, alkyldi
Thio group, aryldithio group, amino group, N-alkyl
Mino group, N, N-dialkylamino group, N-aryla
Mino group, N, N-diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyl
Oxy group, N-alkylcarbamoyloxy group, N-A
Reel carbamoyloxy group, N, N-dialkyl carb
Bamoyloxy group, N, N-diarylcarbamoylo
Xy group, N-alkyl-N-arylcarbamoyloxy
Si group, alkylsulfoxy group, arylsulfoxy group,
Acylthio group, acylamino group, N-alkylacyla
A mino group, an N-arylacylamino group, a ureido group,
N'-alkylureido group, N ', N'-dialkyl
Raid group, N'-arylureido group, N ', N'-di
Arylureido group, N'-alkyl-N'-aryl
Ureido group, N-alkyl ureido group, N-aryl
A raid group, an N'-alkyl-N-alkylureido group,
N'-alkyl-N-arylureido group, N ', N'
-Dialkyl-N-alkylureido group, N ', N'-
Dialkyl-N-arylureido group, N'-aryl
-N-alkylureido group, N'-aryl-N-ali
Ureureid group, N ', N'-diaryl-N-alkyl
Luureido group, N ', N'-diaryl-N-aryl
Ureido group, N'-alkyl-N'-aryl-NA
Alkylureido group, N'-alkyl-N'-aryl-
N-arylureido group, alkoxycarbonylamino
Group, aryloxycarbonylamino group, N-alkyl-
N-alkoxycarbonylamino group, N-alkyl-N
-Aryloxycarbonylamino group, N-aryl-N
-Alkoxycarbonylamino group, N-aryl-N-
Aryloxycarbonylamino group, formyl group, acyl
Group, carboxyl group, alkoxycarbonyl group, aryl
Roxycarbonyl group, carbamoyl group, N-alkyl
Rubamoyl group, N, N-dialkylcarbamoyl group, N
-Arylcarbamoyl group, N, N-diarylcarba
Moyl group, N-alkyl-N-arylcarbamoyl
Group, alkylsulfinyl group, arylsulfinyl group
Group, alkylsulfonyl group, arylsulfonyl group,
Ruho group (-SO_ThreeH) and its conjugated base group (hereinafter referred to as sulf
Honato group), alkoxysulfonyl group, arylo
Xisulfonyl group, sulfinamoyl group, N-alkyl
Sulfinamoyl group, N, N-dialkylsulfinamo
Yl group, N-arylsulfinamoyl group, N, N-di
Arylsulfinamoyl group, N-alkyl-N-ali
Sulfinamoyl group, sulfamoyl group, N-al
Killsulfamoyl group, N, N-dialkylsulfamo
Yl group, N-arylsulfamoyl group, N, N-dia
Reel sulfamoyl group, N-alkyl-N-aryl
Sulfamoyl group, phosphono group (-PO_ThreeH_Two) And that
Conjugate base group (hereinafter, referred to as phosphonate group), dial
A killed phosphono group (-PO_Three(alkyl)_Two), Diarylho
Suphono group (-PO_Three(aryl)_Two), Alkyl aryl phos
Phono group (-PO_Three(alkyl) (aryl)), monoalkyl phos
Phono group (-PO_ThreeH (alkyl)) and its conjugated base group (hereinafter
Later referred to as an alkylphosphonato group),
Suphono group (-PO _ThreeH (aryl)) and its conjugate base group
(Hereinafter referred to as arylphosphonate group), phosphono
Oxy group (-OPO_ThreeH_Two) And its conjugated base group (hereinafter, referred to as
A phosphonatooxy group), a dialkylphosphono
Oxy group (-OPO_Three(alkyl)_Two), Diarylphospho
Nooxy group (-OPO_Three(aryl)_Two), Alkylarylho
Suphonoxy group (-OPO3 (alkyl) (aryl)), monoa
Alkylphosphonooxy group (-OPO_ThreeH (alkyl)) and
The conjugate base group (hereinafter referred to as alkylphosphonatooxy group
), A monoarylphosphonooxy group (-OPO
_ThreeH (aryl)) and its conjugated base group (hereinafter referred to as aryl
Sulfonatooxy group), cyano group, nitro group, ant
, Heteroaryl, alkenyl, alkynyl
Groups.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl and the like. , Cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, acetoxyphenyl, benzoyloxyphenyl, methylthiophenyl, phenylthiophenyl A methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group,
Examples thereof include a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group, a phosphonophenyl group, and a phosphonatophenyl group.

Examples of the heteroaryl group include nitrogen, oxygen,
A monocyclic or polycyclic aromatic ring containing at least one sulfur atom is used, and preferably a 5- or 6-membered aromatic substituent such as furan, pyrrole, pyridine and the like can be used.

Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 1-butenyl group, a cinnamyl group and a 2-chloro-1-ethenyl group. Examples of the alkynyl group include an ethynyl group. Group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ₁ in the acyl group (G ₁ CO ⁻ ) include hydrogen and the above-described alkyl and aryl groups. Of these substituents, still more preferred are halogen atoms (-F, -Br, -Cl,
-I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N
-Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-
Alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphono Examples include an oxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a straight-chain alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms.

Of the substituted alkyl groups preferred as R ₁ obtained by combining the above substituents with an alkylene group,
Specific examples include a chloromethyl group, a bromomethyl group,
-Chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyl Oxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-
Methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group,
N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N
-(Sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group , Tolylphosphonohexyl group, tolylphosphonatohexyl group,
Phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl Group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, and the like.

Specific examples of preferred aryl groups as R ₁ include those in which one to three benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Yes, specific examples include a phenyl group,
Examples include a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

Specific examples of preferred substituted aryl groups as R ₁ include those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of such substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, and trifluoromethylphenyl. , Hydroxyphenyl group,
Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, A carbamoylphenyl group, an N-methylcarbamoylphenyl group,
N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N -Ethylsulfamoylphenyl group,
N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphono Phenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methyl Allylphenyl group, 2
-Methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

Next, X ₁ and X ₂ in the general formula (1)
Will be specifically described. X ₁ and X ₂ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, for example,
Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-
Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-ary Rucarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N ′
An alkylureido group, an N ′, N′-dialkylureido group, an N′-arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group; N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N '
-Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N
-Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N '-Aryl-N-alkylureido groups, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl-N-
Alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group,
Carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-ary Rucarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, Sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group , Rufamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group , a phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphono group (-PO ₃ (alkyl) _2), diaryl phosphono group (-PO ₃ (aryl) ₂ ), alkyl aryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO3H (alkyl)) and its conjugated base group (hereinafter,
Alkyl phosphonium referred to as diisocyanato group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎ and The conjugate base group (hereinafter referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group Group (-OPO3 (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO3H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (- OPO ₃ H
(aryl)) and its conjugated base group (hereinafter, referred to as arylphosphonatooxy group), cyano group, nitro group, substituted or unsubstituted aryl group, heteroaryl group, alkenyl group, and alkynyl group. A more specific example is that described for R ₁ above.

X ₁ and X ₂ are bonded to each other to form
LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5358 (19
51). And the acid nuclei in the merocyanine dyes described in the references.

Specific examples of the acidic nucleus include 1,3-dicarbonyl nuclei (for example, 1,3-indandione, 1,3-
Cyclohexanedione, 5,5-dimethylcyclohexanedione, 1,3-dioxane-4,6-dione, etc.),
Pyrazolinone nucleus (for example, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3-
Methyl-2-pyrazolin-5-one, etc.), isoxazolinone nucleus (for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5)
-One or the like), an oxindole nucleus (for example, 1-alkyl-2,3-dihydro-2-oxindole or the like),
2,4,6-trioxohexahydropyrimidine nucleus (for example, barbituric acid or 2-thiobarbituric acid and its N-substituted derivative, for example, 1,3-diethylbarbituric acid, 1,3-diethyl-2-thiobarbituric acid, 1,
3-dibutyl barbituric acid, 1,3-dibutyl-2-thiobarbituric acid, 1,3-diphenyl barbituric acid,
1,3-diphenyl-2-thiobarbituric acid, 1,3-
Dimethoxycarbonylmethylbarbituric acid, 1,3-dimethoxycarbonylmethyl-2-thiobarbituric acid, etc., 2-thio-2,4-thiazolidinedione nucleus (for example, rhodanine and its N-substituted derivative, for example, 3-
Methyl rhodanine, 3-ethyl rhodanine, 3-phenyl rhodanine, 3-allyl rhodanine, 3-benzyl rhodanine, 3-carboxymethyl rhodanine, 3-carboxyethyl rhodanine, 3-methoxycarbonyl methyl rhodanine, 3-hydroxyethylrhodanine, 3-
Morpholinoethylrhodanine, etc.), 2-thio-2,
4-oxazolidinedione nucleus (ie, 2-thio-
2,4- (3H, 4H) -oxazoledione nucleus, for example, 2-ethyl-2-thio-2,4-oxazolidinedione, etc., and thianaphthenone nucleus (for example, 3 (2H) -thianaphthenone, 3 (2H)- Tianaphthenone-1,1-
Dioxide, etc.), 2-thio-2,5-thiazolidinedione nucleus (for example, 3-ethyl-2-thio2,5-thiazolidinedione), 2,4-thiazolidinedione nucleus (for example, 2,4-thiazolidine) Dione, 3-ethyl-2,
4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.), thiazolidinone nucleus (for example,
Thiazolidinone, 3-ethyl-4-thiazolidinone, 2
-Ethylmercapto-4-thizolidinone, 2-methylphenylamino-4-thizolidinone, etc.), 2-imino-2
An oxazoline-4-one nucleus (i.e., a pseudohydantoin nucleus), a 2,4-imidazolidinedion nucleus (i.e., a hydantoin nucleus such as 2,4-imidazolidinedione, 3
-Ethyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, etc.), 2-thio-2,4-imidazolidinedione nucleus (that is, thiohydantoin nucleus, for example, 2- Thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, 1,3-diethyl-2-thio-2,4-imidazolidinedione, etc.), imidazoline-5- On nucleus (eg, 2-propylmercapto-2-imidazoline-5)
-One), furan-5-one nucleus, 4-hydroxy-2
(1H) -pyridinone nucleus (for example, N-methyl-4-hydroxy-2 (1H) -pyridinone, N-methyl-4-
Hydroxy-2 (1H) -quinolinone, N-butyl-4
-Hydroxy-2 (1H) -quinolinone, etc.), 4-hydroxy-2H-pyran-2-one nucleus (for example, 4-hydroxycoumarin and the like), thioindoxyl nucleus (for example, 5
-Methylthioindoxyl, etc.), and these acidic nuclei may further have a substituent.

Next, Y in the general formula (1) will be described. Y represents the above-mentioned A and a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with an adjacent carbon atom.
Examples of such a heterocyclic ring include a 5-, 6- or 7-membered nitrogen-containing or sulfur-containing heterocyclic ring, and a 5- or 6-membered heterocyclic ring is preferable.

Examples of the nitrogen-containing heterocycle include LGBrooker
et al., J. Am. Chem. Soc., 73, 5326-5358 (1951); and any of those known as constituting basic nuclei in merocyanine dyes described in References are preferably used. be able to. Specific examples include thiazoles (eg, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole,
Benzothiazoles (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6- Methylbenzothiazole,
5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6
-Methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole , 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.),
Naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,
1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole,
Etc.), thianaphtheno-7 ', 6', 4,5-thiazoles (e.g., 4'-methoxythianaphtheno-7 ',
6 ′, 4,5-thiazole, etc.), oxazoles (eg, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole) , 5-phenyloxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-
Phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6
-Dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), Naphthooxazoles (e.g., naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (e.g., 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzo selenazole, 5-chlorobenzo selenazole, 5-methoxy benzo selenazole, 5-hydroxy benzo selenazole, tetrahydro benzo selenazole, etc., naphtho selenazoles (for example, naphtho [1,2 Selenazole, naphtho [2,
1] selenazole, etc.), thiazolines (eg, thiazoline, 4-methylthiazoline, etc.), 2-quinolines (eg, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline) ,
6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc., 4-quinolines (for example, quinoline, 6-methoxyquinoline, 7-methyl) Quinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3
-Diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (eg, 3,3-dimethylindolenin, 3,3,5, -trimethylindolenin, 3, 3,
7, -trimethylindolenine, etc.), 2-pyridines (eg, pyridine, 5-methylpyridine, etc.), 4-
Pyridine (for example, pyridine and the like) can be mentioned.

Examples of the sulfur-containing heterocyclic ring include, for example, a dithiol partial structure in dyes described in JP-A-3-296759. Specific examples of dithiols include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.) and naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2 , 1] dithiols, etc.), dithiols (eg, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonylbenzodithiols, 4,5-ditrifluoro Methyldithiol, 4,5-dicyanodithiol, 4-
Methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

In the general formula (1) described above, Y is
Among the examples of the nitrogen-containing or sulfur heterocyclic ring formed in combination with the above-mentioned A and the adjacent carbon atom, a dye having a structure represented by the following general formula (3) or (4) is high. It is particularly preferable because it provides a photopolymerizable composition having not only sensitizing ability but also extremely excellent storage stability.

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In the general formulas (3) and (4),
R ₁ , X ₁ , X ₂ , W and Z have the same meanings as in the general formulas (1) and (2), and R 2 and R 3 are each independently
It represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heteroaryl group, and R2 and R3 may combine with each other to form a 5-, 6-, or 7-membered ring. R ₂ ,
Specific examples of R ₃ include the examples of the substituted or unsubstituted alkyl group and aryl group described above as examples of R ₁ . Next, the general formula (2) will be described in detail.

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(Wherein, Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted aryl group, which are connected via a bond by -Z-, wherein Z is -O- or -S And W has the same meaning as shown in the general formula 1.) The substituted or unsubstituted aryl groups in Ar ₁ and Ar ₂ are the same as those described in detail in the general formula 1. Is raised. In the structure represented by the general formula (2),
Dyes having a structure represented by the following general formula (5) are particularly preferable because they provide a photopolymerizable composition having high sensitizing ability and very excellent storage stability.

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(In the formula, R _{4 to} R ₁₁ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and may be bonded to each other.)

Preferred specific examples of the compound represented by formula (1) are (D-1) to (D27), (E-1) to (E-28), and compounds represented by formula (2). Preferred specific examples of the compounds represented by (F-1) to (F-17) are shown below, but the present invention is not limited thereto. Further, isomers due to a double bond connecting the acidic nucleus and the basic nucleus are not clear, and the present invention is not limited to either isomer.

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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(A2) Acylphosphine Compound The acylphosphine compound used as the photopolymerizable initiation system in the present invention is an acylphosphine compound capable of generating an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye. Any may be used as long as it is, for example, JP-A-5-345790, JP-B-9-2604172, JP-A-7-278215, JP-A-10-29997, JP-T10-505352, JP-A-10-95788, U.S. Patent Known compounds described in US Pat. No. 5,407,969 can be appropriately selected and used.

More specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucillin ^R TPO from BASF) (hereinafter referred to as "AP-3"), bis (2,
6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (CGI ^R 40 available from Ciba)
3)) (hereinafter referred to as “AP-4”), screws (2, 4, 6)
-Trimethylbenzoyl) isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide,
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (hereinafter referred to as “AP-1”), bis (2,4,6-trimethylbenzoyl) -2,4-dibutoxyphenylphosphine oxide (hereinafter “AP-1”) -2 "), 1,10-bis [bis (2,4,6-trimethylbenzoyl) phosphine oxide] decane, tris (2
-Methylbenzoyl) phosphine oxide and the like.

As with the sensitizing dyes described above, the acylphosphine compound of the present invention can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, binding with sensitizing dyes, addition-polymerizable unsaturated compounds and other radical-generating parts, introduction of hydrophilic sites, improvement of compatibility, introduction of substituents for suppressing crystal precipitation, introduction of substituents for improving adhesion And methods such as polymerization.

The use of these acylphosphine compounds is the same as in the above-mentioned addition-polymerizable compound and sensitizing dye.
It can be set arbitrarily and arbitrarily according to the performance design of the photosensitive material. For example, by using two or more kinds, the compatibility with the photosensitive layer can be enhanced. It is advantageous that the amount of the acylphosphine compound used is usually large in terms of photosensitivity.
Sufficient photosensitivity can be obtained by using parts by weight and ranges.
In addition, sufficient photosensitivity can be obtained even when the amount of acylphosphine used is reduced to 6 parts by weight or less, further 1.9 parts by weight or less, and further down to 1.4 parts by weight in combination with the sensitizing dye of the present invention. be able to.

(B) A compound which reacts with at least one of at least one of a radical and an acid and which is retained by changing at least one of its physical and chemical properties. Third essential component in the present invention (Iii) is a compound generated by the photoreaction of the above-mentioned photoinitiating system and whose physical or chemical properties are changed and retained by the action of the active species, and the component (iii) has such properties. Any compound can be used without particular limitation as long as it has the following formula. For example, in many cases, the compounds mentioned in the above-mentioned initiating system themselves have such properties. Radicals generated from the photoinitiating system,
A component (ii) changed by an acid and / or a base;
The characteristics of i) include, for example, an absorption spectrum (color),
Chemical properties, molecular properties such as polarizability, solubility, strength,
Includes changes in physical properties such as refractive index, fluidity, adhesiveness, etc.

For example, if a compound whose absorption spectrum changes with pH, such as a pH indicator, is used as the component (iii) and an acid or base is generated from the starting system,
Although the color of only the exposed portion can be changed, such a composition is useful as an image forming material. Similarly, (ii
When a compound whose absorption spectrum is changed by oxidation / reduction or nucleophilic addition reaction is used as i), oxidation, reduction or the like is caused by radicals generated from the initiation system, and image formation is possible. Such examples are, for example, J. Am. Chem. So
c., 108 , 128 (1986)., J. Imaging.Sci., 30 , 215 (198
6)., Israel. J. Chem., 25 , 264 (1986).

Further, addition polymerization as (iii) or
By using a compound capable of polycondensation and combining it with an initiation system, a photocurable resin or a negative photopolymer can be formed. As (iii), a radical polymerizable compound (eg, a compound having an ethylenically unsaturated bond), a cationic polymerizable compound (eg, an epoxy compound, a vinyl ether compound, a methylol compound), or an anion polymerizable compound (eg, an epoxy compound) is used. Such examples are described in, for example, Photopolymer Society, edited by Photopolymer Handbook, Industrial Research Council (1989), Polymer, 45,786 (19)
96). Further, a composition in which a thiol compound is used as (iii) and combined with a photoradical generation system is also well known.

It is also useful to use an acid-decomposable compound as (iii) and combine it with a photoacid generator. For example, a material that uses a polymer whose side chain or main chain is decomposed by an acid and changes solubility or hydrophilicity / hydrophobicity by light is widely used as a photodecomposable photosensitive resin or a positive photopolymer. Such an embodiment, for example, ACS.Symp.Ser. 242, 11
(1984), JP-A-60-3625, USP-51027.
71, 5206317, 5212047, JP-A-4-24-2
6850, JP-A-3-1921731, JP-A-60-1
0247, JP-A-62-40450 and the like.

The compound capable of addition polymerization, which is one of the objects of the present invention, which is a particularly excellent component (iii) for obtaining a highly sensitive lithographic printing plate precursor, will be described in more detail. (B-1) Addition-Polymerizable Compound The addition-polymerizable compound having at least one ethylenically unsaturated double bond, which is a preferred component (iii) used in the present invention, has at least one terminal ethylenically unsaturated bond. , Preferably two or more compounds. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These include, for example, monomers, prepolymers, ie, dimers, trimers and oligomers,
Or a chemical form such as a mixture thereof and a copolymer thereof. Examples of monomers and their copolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid,
Maleic acid), its esters and amides, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds. Used. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of an amide with a monofunctional or polyfunctional isocyanate, an epoxy, a monofunctional or A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used.

Further, unsaturated carboxylic esters, amides and monofunctional or polyfunctional alcohols having an electrophilic substituent such as an isocyanate group or an epoxy group,
Amines, addition products with thiols, halogen groups,
Substitution products of unsaturated carboxylic esters and amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are also suitable. As another example, it is also possible to use a group of compounds in which unsaturated phosphonic acid, styrene, vinyl ether or the like is substituted for the above unsaturated carboxylic acid.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231, and JP-A-59-5240 and JP-A-59-5240. 59-524
1, those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Further, the above-mentioned ester monomers can be used as a mixture.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Examples of other preferred amide-based monomers include those having a cyclohexylene structure described in JP-B-54-21726.

Further, urethane-based addition-polymerizable compounds produced by an addition reaction between an isocyanate and a hydroxyl group are also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups in one molecule and a hydroxyl-containing vinyl monomer represented by the following general formula (6) added to one molecule. Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups.

CH ₂ CC (R) COOCH ₂ CH (R ′) OH (6) (where R and R ′ represent H or CH ₃ )

Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and
No. 49860, No. 56-17654, No. 62
Urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable.

Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909 and JP-A-1-105238. Can obtain a photosensitive composition having an extremely high photosensitive speed.

Another example is disclosed in JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

Regarding these addition polymerizable compounds, what kind of structure is used, whether they are used alone or in combination,
Details of the method of use, such as the amount of addition, can be arbitrarily set in accordance with the final performance design of the light-sensitive material. For example, it is selected from the following viewpoints. From the viewpoint of the photosensitive speed, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or more functional structure is preferable. In order to increase the strength of the image area, that is, the cured film, those having three or more functional groups are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylates, methacrylates, styrene compounds, vinyl ethers) It is also effective to adjust both the photosensitivity and the intensity by using the compound (1) in combination. A compound having a large molecular weight or a compound having a high hydrophobicity is excellent in photosensitive speed and film strength, but may not be preferable in terms of developing speed and precipitation in a developing solution.

Further, compatibility with other components (eg, binder polymer, initiator, colorant, etc.) in the photosensitive composition,
The selection and use of the addition polymerization compound is also an important factor for the dispersibility. For example, the use of a low-purity compound or the combination of two or more compounds may improve the compatibility. In the case of a lithographic printing plate precursor, a specific structure may be selected for the purpose of improving the adhesion of a support, an overcoat layer, and the like described below. Regarding the compounding ratio of the addition polymerizable compound in the photosensitive composition, the larger the proportion, the more advantageous in sensitivity. Process problems (for example, improper production due to transfer of photosensitive material components or adhesion)
In the case of a lithographic printing plate precursor, problems such as precipitation from a developing solution may occur. From these viewpoints, the preferred compounding ratio is often 5 to 8 based on all components of the composition.
0% by weight, preferably 25 to 75% by weight. Also,
These may be used alone or in combination of two or more. In addition, the method of using the addition polymerizable compound can be arbitrarily selected from the viewpoints of the degree of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, etc. Depending on the case, a layer structure and a coating method such as undercoating and overcoating may be performed.

(C) Binder Polymer When applied to a lithographic printing plate precursor, which is a preferred embodiment of the present invention, it is preferable to further use a binder polymer in the photosensitive layer. It is preferable to contain a linear organic high molecular polymer as the binder. Any of such “linear organic high molecular polymers” may be used. Preferably, a water- or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is selected and used not only as a film forming agent of the composition but also as a water, weakly alkaline water or organic solvent developing agent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, JP-A-59-44615.
No., JP-B-54-34327, JP-B-58-1257
7, JP-B-54-25957, JP-A-54-927
No. 23, JP-A-59-53836, JP-A-59-71
048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. There is. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain.
In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers as needed) copolymer,
It is suitable because it has an excellent balance of film strength, sensitivity and developability.

In addition, Japanese Patent Publication No. 7-12004,
JP-A-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271174,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 is very excellent in strength, and therefore is advantageous in terms of printing durability and low exposure suitability.

Further, the binder having an amide group described in JP-A-11-171907 has excellent developability and film strength and is suitable.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be incorporated in any amount in the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 30 to 85
% By weight. The weight ratio of the photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3.

In a preferred embodiment, a binder polymer which is substantially water-free and soluble in alkali is used. By doing so, it is possible to use no organic solvent which is environmentally unfavorable or to use a very small amount as the developer. In such a usage, the acid value (acid content per gram of polymer represented by chemical equivalent number) and molecular weight of the binder polymer are appropriately selected from the viewpoint of image strength and developability. Preferred acid value is 0.4 to 3.0 m
eq / g, and the preferred molecular weight is in the range of 3,000 to 500,000, and more preferably the acid value is in the range of 0.6 to 2.0, and the molecular weight is in the range of 10,000 to 300,000.

(D) Other Components The photosensitive composition of the present invention may further contain other components suitable for its use and production method.
Hereinafter, preferred additives will be exemplified. (D1) Co-sensitizer The sensitivity can be further improved by using a certain additive (hereinafter referred to as a co-sensitizer). Although their mechanism of action is not clear, most are thought to be based on the following chemical processes. That is, various intermediate active species (radicals, radicals, etc.) generated in the course of the photoreaction initiated by the above-described photoabsorption of the initiation system and the subsequent addition polymerization reaction.
Peroxides, oxidizing agents, reducing agents, etc.) and co-sensitizers,
It is presumed to generate new active radicals. These are largely (a) those that can be reduced to form active radicals, (b) those that can be oxidized to form active radicals, and (c) those that react with less active radicals and are more active radicals. Or acting as a chain transfer agent, but there is often no myth as to which of these compounds each belongs to.

(A) Compound which generates an active radical by being reduced Compound having a carbon-halogen bond: It is considered that the carbon-halogen bond is reductively cleaved to generate an active radical. Specifically, for example, trihalomethyl-s-
Triazines, trihalomethyloxadiazoles and the like can be suitably used. Compound having a nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is cleaved reductively to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used. Compound having an oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is cleaved reductively to generate an active radical. Specifically, for example, organic peroxides and the like are preferably used.

As the “organic peroxide”, oxygen-
Almost all organic compounds having one or more oxygen bonds are included, and examples thereof include, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide,
3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t
-Butyl hydrooxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, g-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3-acetyl peroxide, isobutyryl peroxide, octanoyl peroxide , Decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide,

2,4-dichlorobenzoyl peroxide, metal oil peroxide, diisopropyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di 2-ethoxyethyl peroxy dicarbonate, dimethoxy diisopropyl peroxy carbonate, (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxyvivalate, t-
Butyl peroxy neodecanoate, t-butyl peroxyoctanoate, t-butyl peroxy-3,5
5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-tert-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t
-Butyl maleic acid, t-butyl peroxyisopropyl carbonate, 3,3'4,4'-tetra-
(T-butylperoxycarbonyl) benzophenone,
3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4 ' -Tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-
Tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butyldiperoxydihydrogen diphthalate),
Carbonyl di (t-hexylperoxy dihydrogen diphthalate) and the like.

Of these, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4
Peroxide esters such as 4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone and di (t-butyldiperoxyisophthalate) Systems are preferred.

Onium compound: It is considered that a carbon-hetero bond or an oxygen-nitrogen bond is cleaved reductively to generate an active radical. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used. Ferrocene, iron arene complexes: Active radicals can be generated reductively.

(B) Compound which is oxidized to form an active radical Alkyl ate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to form an active radical. Specifically, for example, triarylalkyl borates are preferably used. Alkylamine compound: It is considered that the CX bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group, or the like.
Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines and the like. Sulfur-containing and tin-containing compounds: The above-mentioned amines in which the nitrogen atom is replaced with a sulfur atom or a tin atom can generate an active radical by the same action. Compounds having an SS bond are also known to be sensitized by SS cleavage.

Α-Substituted methylcarbonyl compound: An active radical can be generated by the cleavage of the carbonyl-α carbon bond by oxidation. In addition, those obtained by converting carbonyl to oxime ether also show the same action. In particular,
2-alkyl-1- [4- (alkylthio) phenyl]
-2-Morpholinopronones-1 and oxime ethers obtained by reacting these with hydroxyamines and then etherifying N-OH. Sulfinates: Active radicals can be generated reductively. Specific examples include sodium arylsulfinate and the like.

(C) Compounds that react with radicals to convert them into highly active radicals or act as chain transfer agents: For example, compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate a radical by donating hydrogen to a low-activity radical species, or can generate a radical by being oxidized and then deprotonated. Specific examples include 2-mercaptobenzimidazoles.

More specific examples of these co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity. Hereinafter, some of the examples will be exemplified, but the present invention is not limited thereto.

[0097]

Embedded image

These co-sensitizers can also be subjected to various chemical modifications to improve the characteristics of the photosensitive layer, as in the case of the above-mentioned sensitizing dyes. For example, bonding with sensitizing dyes, activators, addition polymerizable unsaturated compounds and other parts, introduction of hydrophilic sites, improvement of compatibility, introduction of substituents for suppressing crystal precipitation, introduction of substituents for improving adhesion And methods such as polymerization.

These co-sensitizers can be used alone or in combination of two or more. The amount used is 0.0 to 100 parts by weight of the compound having an ethylenically unsaturated double bond.
A suitable range is 5 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 3 to 50 parts by weight.

(D2) Polymerization Inhibitor In the present invention, in addition to the above basic components, unnecessary heat of a compound having an ethylenically unsaturated double bond, which can be polymerized during the production or storage of the photosensitive composition, It is desirable to add a small amount of thermal polymerization inhibitor to prevent polymerization. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% By weight to about 5% by weight is preferred. In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition by oxygen, and when used as a lithographic printing plate precursor, after application to a support or the like, During the drying process, it may be unevenly distributed on the surface of the photosensitive layer. The amount of the higher fatty acid derivative to be added ranges from about 0.5% by weight to about 10% by weight of the total composition.
% By weight is preferred.

(D3) Colorant, etc. When the photosensitive composition of the present invention is used for a lithographic printing plate precursor, a dye or pigment may be added for the purpose of coloring the photosensitive layer. As a result, as a printing plate,
It is possible to improve so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring device. As a coloring agent, since many dyes cause a decrease in the sensitivity of the photopolymerizable photosensitive layer,
As the colorant, use of a pigment is particularly preferable. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. Dyes and pigments may be added in an amount of about 0.5% to about 5% by weight of the total composition.
% By weight is preferred.

(D4) Other Additives When the photosensitive composition of the present invention is used for a lithographic printing plate precursor, an inorganic filler, other plasticizers, a surface of the photosensitive layer, and the like are used to improve the physical properties of the cured film. A known additive such as a sensitizer that can improve the ink adhesion of the ink may be added.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. A binder was used. In this case, it can be added in an amount of 10% by weight or less based on the total weight of the compound having an ethylenically unsaturated double bond and the binder.

Further, a UV initiator, a thermal crosslinking agent and the like can be added to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) described later.

In addition, additives for improving the adhesion between the photosensitive layer and the support and for improving the development removal property of the unexposed photosensitive layer;
It is possible to provide an intermediate layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, the adhesion is improved, and the printing durability can be increased.
On the other hand, by adding or undercoating a hydrophilic polymer such as polyacrylic acid or polysulfonic acid, the developability of the non-image area is improved, and the stain resistance is improved.

When the photosensitive composition of the present invention is coated on a support to provide a lithographic printing plate, it is used after being dissolved in various organic solvents. As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate,

3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N -Dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50% by weight.

The amount of the photosensitive layer to be coated on the support mainly affects the sensitivity, developability of the photosensitive layer, and the strength and printing durability of the exposed film, and is desirably appropriately selected according to the application. If the coating amount is too small, the printing durability will be insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, and it takes a long time for exposure, and a longer time is required for the developing process, which is not preferable. The lithographic printing plate for scanning exposure, which is the main object of the present invention, has a coating amount of about 0.1 g / m 2 after drying.
The range of ² to about 10 g / m ² are suitable. More preferably, it is 0.5 to 5 g / m ² .

[Support] In order to obtain a lithographic printing plate, which is one of the main objects of the present invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used for a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate-like material, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc) , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.),
Paper or plastic film on which the metal is laminated or vapor-deposited as described above is included, and if necessary, a known physical or chemical property suitable for the purpose of imparting hydrophilicity or improving the strength to these surfaces, if necessary. May be applied.

Particularly preferred examples of the support include paper, polyester film and aluminum plate. Among them, the dimensional stability is good, the cost is relatively low, and the hydrophilicity and strength are excellent by the surface treatment as required. Aluminum plates that can provide a surface are particularly preferred. In addition, Shoko 4
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-8-18327 is also preferable. A preferred aluminum plate is a pure aluminum plate and aluminum as a main component,
It is an alloy plate containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or deposited. The foreign elements contained in the aluminum alloy include silicon,
There are iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and a conventionally known and used raw material of A-luminium plate can be appropriately used. The thickness of the aluminum plate used in the present invention is approximately 0.1 mm to 0.1 mm.
It is about 6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.3 mm.

In the case of a support having a metal surface, particularly an aluminum surface, a roughening (graining) treatment, an immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodic oxidation Preferably, a surface treatment such as a treatment is performed.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, a buffing method and a polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used. Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface.

Further, an aluminum plate which has been roughened and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is performed, for example, in an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. This is performed by flowing a current using an aluminum plate as an anode.

Electrodeposition of silicate as described in US Pat. No. 3,658,662 is also effective. Furthermore, JP-B-46-27481 and JP-A-52-5860.
No. 2, JP-A-52-30503, and a surface treatment obtained by combining the anodizing treatment and the sodium silicate treatment with a support provided with electrolytic grains are also useful.

[0115] Further, it is preferable to sequentially perform mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893. Furthermore, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable.

Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-7-159983 is preferably used.

As another preferred example, there can be mentioned a support in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. As such a surface layer, for example, US30
55295, a layer composed of an inorganic pigment and a binder described in JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, a titanium oxide, a polyvinyl alcohol, and a silicate described in JP-A-8-507727. Sol-gel films and the like can be raised.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon, and to adhere to the photosensitive layer. This is performed for the purpose of improving the performance.

[Protective Layer] A preferred embodiment of the present invention is:
In a lithographic printing plate for scanning exposure, usually, since the exposure is performed in the air, it is preferable to further provide a protective layer on the layer of the photopolymerizable composition. The protective layer prevents low-molecular compounds such as oxygen and basic substances present in the atmosphere that inhibit the image formation reaction caused by exposure in the photosensitive layer from entering the photosensitive layer, and enables exposure in the atmosphere. And Therefore, a desired property of such a protective layer is that the permeability of low molecular compounds such as oxygen is low, and further, the transmission of light used for exposure is not substantially inhibited, and the adhesion to the photosensitive layer is excellent. In addition, it is desirable that it can be easily removed in a developing step after exposure.

Such a device for the protective layer has been conventionally devised, and is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, it is preferable to use a water-soluble polymer compound having relatively excellent crystallinity. Although water-soluble polymers such as acrylic acid are known, use of polyvinyl alcohol as a main component gives the best results in terms of basic characteristics such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component.

As a specific example of polyvinyl alcohol, 7
1-100% hydrolyzed, molecular weight 300-240
A range of 0 can be given. Specifically, Kuraray's PVA-105, PVA-110, PVA
A-117, PVA-117H, PVA-120, PV
A-124, PVA-124H, PVA-CS, PVA
-CST, PVA-HC, PVA-203, PVA-2
04, PVA-205, PVA-210, PVA-21
7, PVA-220, PVA-224, PVA-217
EE, PVA-217E, PVA-220E, PVA-
224E, PVA-405, PVA-420, PVA-
613 and L-8.

The components of the protective layer (selection of PVA, use of additives), amount of coating, etc. are selected in consideration of fogging properties, adhesion and scratch resistance in addition to oxygen blocking properties and development removability. Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the oxygen barrier properties, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that an unnecessary polymerization reaction occurs at the time of production or raw storage, and that unnecessary fogging and thickening of an image occur at the time of image exposure. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling due to insufficient adhesive force is apt to occur, and the peeled portion causes defects such as poor film curing due to inhibition of oxygen polymerization.

On the other hand, various proposals have been made to improve the adhesiveness between these two layers. For example, US Patent No. 2
No. 92,501 and U.S. Pat. No. 44,563, an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer is mixed in a hydrophilic polymer mainly composed of polyvinyl alcohol in an amount of 20 to 60% by weight. It is described that sufficient adhesiveness can be obtained by laminating on a polymer layer. Any of these known techniques can be applied to the protective layer in the present invention. Regarding the method of applying such a protective layer,
For example, U.S. Pat. No. 3,458,311;
No. 9729.

Further, other functions can be imparted to the protective layer. For example, 350nm to 450n used for exposure
Addition of a coloring agent (such as a water-soluble dye) having excellent light transmittance of m and capable of efficiently absorbing light having a wavelength of 500 nm or more can further enhance the safelight suitability without lowering the sensitivity.

When a photosensitive material using the photosensitive composition of the present invention is used as an image forming material, usually, after image exposure, an unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developers for using these photopolymerizable compositions for preparing a lithographic printing plate include JP-B-57-742.
No. 7, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate, and the like.
An aqueous solution of an inorganic alkali agent such as dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia or an organic alkali agent such as monoethanolamine or diethanolamine. Is appropriate. The alkaline solution is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Further, such alkaline aqueous solutions include:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
Nos. 0-26601, 58-54341, Tokubo Sho56
The developers described in JP-A-39464 and JP-A-56-42860 are also excellent.

In addition, as a plate making process of a lithographic printing plate precursor using the photosensitive composition of the present invention, if necessary,
The entire surface may be heated before, during, or between exposure and development. By such heating, an image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity can be brought about. Further, for the purpose of improving image strength and printing durability, it is also effective to post-heat or expose the entire surface of the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, there arises a problem that the non-image portion is covered. Very strong conditions are used for heating after development. Usually, it is in the range of 200 to 500 ° C. If the temperature is too low, a sufficient image strengthening effect cannot be obtained.

As the method of exposing a lithographic printing plate for scanning exposure using the photosensitive composition of the present invention, known methods can be used without any limitation. Desirable light source wavelength is from 350 nm to 45
The thickness is 0 nm, and specifically, an InGaN-based semiconductor laser is preferable. The exposure mechanism may be any of an internal drum type, an external drum type, a flat bed type, and the like. Further, the photosensitive composition of the present invention can be made soluble in neutral water or weakly alkaline water by using a highly water-soluble one, but a lithographic printing plate precursor having such a configuration can be used. After loading on a printing machine, a method such as exposure-development can be performed on the machine.

As the available laser light source of 350 nm to 450 nm, the following can be used.
Ar ion laser (364n) as a gas laser
m, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He
-Cd laser (441 nm, 325 nm, 1 mW to 1
00mW), and Nd: YAG (YV
O ₄ ) and SHG crystal × 2 times (355 nm,
5 mW to 1 W), a combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW),

As a semiconductor laser system, a KNbO ₃ ring resonator (430 nm, 30 mW), a combination of a waveguide type wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a waveguide type wavelength conversion element and an AlGaInP , AlGaAs semiconductor combination (300 nm to 350 nm, 5 mW to 1
00mW), AlGaInN (350 nm to 450 n
m, 5 mW to 30 mW), and N ₂ laser (337 nm, pulse 0.1 to 10 m) as a pulse laser
J), XeF (351 nm, pulse 10-250 mJ)
Etc. are used.

Particularly, an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 n)
m, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

As the lithographic printing plate exposure apparatus of the scanning exposure type, there are an inner drum type, an outer drum type and a flat bed type as an exposure mechanism, and a light source capable of continuous oscillation among the above light sources is preferably used. be able to. Actually, the following exposure apparatus is particularly preferable in relation to the sensitivity of the photosensitive material and the plate making time.

Single-to-triple-beam exposure apparatus using one or more gas lasers or solid-state laser light sources so that a semiconductor laser having a total output of 20 mW or more can be obtained by the internal drum method. Multi-beam (1 to 10) exposure equipment using one or more semiconductor lasers, gas lasers or solid-state lasers ・ Semiconductor lasers, gas lasers or solid-states so that the total output is 20 mW or more by the external drum method Laser 1
Multi-beam (1 to 9) exposure equipment using more than one ・ Multi-beam (10 or more) exposure equipment using one or more semiconductor lasers or solid-state lasers so that the total output is 20 mW or more by the external drum method.

In the lithographic printing plate of the laser direct drawing type described above, the sensitivity of the photosensitive material X (J / cm ² ), the exposure area S (cm ² ) of the photosensitive material, the power q
Equation (eq 1) holds between (W), the number of lasers n, and the total exposure time t (s).

X · S = n · q · t − (eq 1)

I) In the case of the internal drum (single beam) system: Laser rotation speed f (radian / s), sub-scanning length L of the photosensitive material
x (cm), resolution Z (dot / cm), total exposure time t
Equation (eq 2) generally holds during (s).

F · Z · t = Lx − (eq 2)

Ii) In the case of an external drum (multi-beam) system, the drum rotation speed F (radian / s), the sub-scanning length Lx of the photosensitive material
(Cm), resolution Z (dot / cm), total exposure time t
(S) and the number of beams (n) generally have the formula (eq 3)
Holds.

F · Z · nt · L = Lx (eq 3)

Iii) In the case of the flat head (multi-beam) system The rotation number H (radian / s) of the polygon mirror, the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dot / cm), and the total exposure time t ( s) and the number of beams (n), the equation (eq 4) generally holds.

F · Z · nt · L = L −− (eq 4)

The resolution required for the actual printing plate (256
0 dpi), plate size (A1 / B1, sub-scan length 42 in)
ch), exposure conditions of about 20 sheets / hour and the photosensitive characteristics of the photosensitive composition of the present invention (photosensitive wavelength, sensitivity: about 0.1 mJ /
By substituting (cm ² ) into the above formula, it can be understood that a combination with a multi-beam exposure method using a laser having a total output of 20 mW or more is particularly preferable in a photosensitive material using the photosensitive composition of the present invention. Furthermore, by multiplying the operability, cost, and the like, the combination with an external drum type semiconductor laser multi-beam (10 or more) exposure apparatus is most preferable.

Other exposure light rays for the photosensitive composition of the present invention include ultrahigh-pressure, high-pressure, medium-pressure and low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet lamps. Various laser lamps, fluorescent lamps, tungsten lamps, sunlight and the like can also be used. In addition, the photosensitive composition of the present invention can be applied without limitation to lithographic printing plates for scanning exposure and those widely known as uses of photocurable resins. For example, when applied to a liquid photosensitive composition used in combination with a cationically polymerizable compound as required, a material for stereolithography with high sensitivity can be obtained. In addition, a hologram material can be formed by utilizing a change in refractive index due to photopolymerization. It can be applied to various transfer materials (peeling-sensitive material, toner-developing material, etc.) by utilizing the change in surface tackiness accompanying photopolymerization. It can also be applied to light curing of microcapsules. It can also be applied to the manufacture of electronic materials such as photoresists, and photocurable resin materials such as inks, paints, and adhesives.

[0144]

[Examples 1 to 7, Comparative Examples 1 to 6]

(Preparation of support) An aluminum plate having a thickness of 0.3 mm
After etching by immersion in 0% by weight sodium hydroxide at 60 ° C. for 25 seconds, the film was washed with running water, neutralized and washed with 20% by weight nitric acid, and then washed with water. This was converted to 300 coulomb / dm in a 1% by weight nitric acid aqueous solution using a sinusoidal alternating current.
Electrolytic surface-roughening treatment was performed with the quantity of electricity at the time of anode No. ² . Subsequently, it was immersed in a 1% by weight aqueous solution of sodium hydroxide at 40 ° C. for 5 seconds, and then immersed in a 30% by weight aqueous solution of sulfuric acid.
After desmutting for 0 second, anodizing was performed for 2 minutes in a 20% by weight sulfuric acid aqueous solution at a current density of 2 A / dm ^{2 so} that the thickness of the anodized film became 2.7 g / m ² . The surface roughness was measured to be 0.3 μm (J
Ra display according to IS B0601).

The following sol-gel reaction solution was applied to the back surface of the substrate thus treated with a bar coater,
The support was provided with a back coat layer having an applied amount of 70 mg / m ² after drying.

Sol-gel reaction liquid Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

When the above components were mixed and stirred, exotherm started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a backcoat coating solution.

Pyrogallol formaldehyde condensation resin (molecular weight: 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant 0.7 parts by weight (N-butyl perfluorooctanesulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 2) 10,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., methanol 30% by weight) 50 parts by weight Methanol 800 parts by weight

[0149] (Preparation of photosensitive layer) to the thus treated aluminum plate, a photopolymerizable composition having the following composition dry coating amount was coated to a ^{1.0g / m 2, 80 ℃,} 2
After drying for a minute, a photosensitive layer was formed.

• Pentaerythritol tetraacrylate 15 g • Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17) 2.0 g • Photopolymerization initiation system (described in Table 1) Sensitizing dye Acylphosphine compound Co-sensitization Sensitizer-Fluorinated nonionic surfactant (F-177P) 0.02 g-Thermal polymerization inhibitor N-nitrosophenylhydroxyl 0.01 g-Colored pigment dispersion 2.0 g (Composition of pigment dispersion) Composition: Pigment Blue 15: 615 Parts by weight allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 83/17) 10 parts by weight cyclohexanone 5 parts by weight methoxypropyl acetate 20 parts by weight propylene glycol monomethyl ether 40 parts by weight ・ methyl ethyl ketone 20.0 g ・ propylene glycol monomethyl ether 20.0 g

(Preparation of Protective Layer) On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (98 mol% of saponification degree, polymerization degree of 550) was applied so as to have a dry coating weight of 2 g / m ² . Dry at 100 ° C. for 2 minutes.

(Evaluation of photosensitivity and suitability for safelight) On the thus obtained light-sensitive material, a Fuji step guide manufactured by Fuji Photo Film Co., Ltd. (A gray scale in which the value changes), and exposure was performed using a xenon lamp passed through an optical filter (Kenko BP-40) so as to have a known exposure energy. As an optical filter, Kenko BP-40 capable of exposing with monochromatic light of 400 nm was used for the purpose of estimating the suitability for exposure to a short-wavelength semiconductor laser. Thereafter, the film was immersed in a developer having the following composition at 25 ° C. for 10 seconds, developed, and the sensitivity (clear sensitivity) was calculated from the maximum number of steps at which the image was completely removed (Table 1). Here, the clear sensitivity represents the minimum energy required for image formation,
The lower the value, the higher the sensitivity.

[0153]

[Table 1]

As shown in Table 1, the planographic printing plate of the present invention has a very high sensitivity, and shows a sufficient sensitivity for the scanning exposure method. Further, the starting system of the present invention has higher sensitivity as compared with the case where no sensitizing dye is used, and shows a sufficient sensitivity even when the amount of added acylphosphine is small. The developers used in Examples 1 to 7 and Comparative Examples 1 to 6 are aqueous solutions having the following composition and having a pH of 13.

1 K potassium silicate 3.0 parts by weight Potassium hydroxide 1.5 parts by weight Compound of the following formula (Perex NBL; (manufactured by Kao Atlas Co., Ltd.)) 0.2 parts by weight Water 95.3 parts by weight

[0156]

Embedded image

In the formula, R represents H or C ₄ H ₉ .

Examples 8 to 15 and Comparative Example 7 A lithographic printing plate was prepared according to the following procedure, and the printing performance was evaluated. Table 2 shows the results. "Pretreatment of the support" An aluminum plate of material 1S having a thickness of 0.3 mm was grained using a No. 8 nylon brush and an aqueous suspension of 800 mesh pamistone, and then its surface was sanded.
Washed well with water. 70% in 10% by weight sodium hydroxide
After immersion at 60 ° C. for 60 seconds for etching, the substrate was washed with running water, neutralized and washed with 20% by weight of nitric acid, and then washed with water. This was converted to 300 coulomb / dm in a 1% by weight nitric acid aqueous solution using a sine wave alternating waveform current under the condition of _VA = 12.7V.
Electrolytic surface-roughening treatment was performed with the quantity of electricity at the time of anode No. ² . The surface roughness was measured to be 0.45 μm (JIS B06
Ra display of 01).

[0159] The above support "hydrophilizing treatment of the surface of support", sodium silicate No. 3 _{(SiO 2 = 28~30%, Na} 2
O = 9-10%, Fe = 0.02% or less) 2.5% by weight, pH = 11.2, immersed in 70 ° C. aqueous solution for 13 seconds,
Subsequently, it was washed with water. S determined by X-ray fluorescence analysis of the surface
The amount of the surface silicate was determined to be 10 mg / m ² from the amount of the i element.

"Coating of Intermediate Layer" A coating liquid having the composition shown in the following (A) was prepared so that the amount of phenylphosphonic acid applied was 20 mg / m ² on the surface of the above-mentioned hydrophilized support. Then, after coating with a wheeler under the condition of 180 rpm, 80
Dry at 30 ° C. for 30 seconds.

(Intermediate layer coating liquid A) Phenylphosphonic acid 0.07 g to 1.4 g Methanol 200 g

"Coating of photosensitive layer" A photosensitive solution having the following composition was prepared on a support provided with the above-mentioned intermediate layer, and the coating amount was 1.0 to 1.0.
Apply with a wheeler to 2.0 g / m ² ,
Dry at 0 ° C. for 1 minute.

(Photosensitive solution) Addition polymerizable compound (compound described in Table 2) 1.5 g Binder polymer (compound described in Table 2) 2.0 g Sensitizing dye (compound described in Table 2) 0 0.1 g Activator (compound described in Table 2) 0.1 g Co-sensitizer (compound described in Table 2) 0.3 g Colored pigment dispersion 2.0 g (Composition of pigment dispersion) Pigment Blue 15: 6 15 parts by weight Allyl methacrylate / methacrylic acid copolymer 10 parts by weight (copolymerization molar ratio 83/17) thermal polymerization cyclohexanone 15 parts by weight methoxypropyl acetate 20 parts by weight propylene glycol monomethyl ether 40 parts by weight Thermal polymerization inhibitor (N- Nitrosophenylhydroxylamine aluminum salt) 0.01 g Surfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0 .02 g Methyl ethyl ketone 20.0 g Propylene glycol monomethyl ether 20.0 g

"Coating of Protective Layer" A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 550) was coated on the photosensitive layer so that the dry coating weight was 2 g / m ^2. And dried at 100 ° C. for 2 minutes.

"Exposure of lithographic printing plate precursor" Using the lithographic printing plate precursor obtained as described above as a light source, a plate surface exposure energy density of 200 µJ / c using monochromatic light of 400 nm.
The exposure power was adjusted to m ^2, and solid image exposure and halftone image exposure at 175 lines / inch in 1% increments from 1 to 99% were performed.

[Development / plate making] A predetermined developing solution (described in Table 2) and a finisher FP-manufactured by Fuji Photo Film Co., Ltd. were loaded into an automatic developing machine LP-850 manufactured by Fuji Photo Film Co., Ltd.
2 W each was charged and the developer temperature was 30 ° C. and the development time was 18
The plate that had been exposed under the conditions of seconds was developed / plate-making to obtain a lithographic printing plate.

"Printing durability test" R201 manufactured by Roland was used as a printing machine, and G was manufactured by Dainippon Ink.
EOS-G (N) was used. The printed matter in the solid image area was observed, and the printing durability was examined based on the number of sheets at which the image began to fade. The greater the number, the better the printing durability.

"Dot dot printing durability test" R201 manufactured by Roland was used as a printing machine, and GEOS-G (N) manufactured by Dainippon Ink was used as an ink. 5 from the start of printing
On the 000 th sheet, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked into a printing sponge, halftone dots were wiped off, and the ink on the plate surface was washed. Then, 10,0
The printing of 00 sheets was performed, and the presence or absence of halftone dot skipping in the printed matter was visually observed.

"Stain test" R201 manufactured by Roland was used as a printing machine, and G was manufactured by Dainippon Ink Co., Ltd. as an ink.
EOS-G (S) was used. The printed matter in the non-image area (unexposed area) was observed, and the stain property was evaluated.

[0170]

[Table 2]

(Addition polymerizable compound in Table 2) (M-1) pentaerthritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester A-TMM)
T) (M-2) Glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .; UA101H)

(Binder polymer in Table 1) (B-1) Allyl methacrylate / methacrylic acid / N-isopropylacrylamide (copolymer molar ratio: 67/13/20) Actual acid value determined by NaOH titration: 1.15 meq / g Weight average molecular weight determined by GPC measurement: 130,000 (B-2) Allyl methacrylate / methacrylic acid copolymer (copolymer molar ratio: 83/17) Actual acid value determined by NaOH titration: 1.55 meq / g GPC measurement Weight-average molecular weight: 125,000 (B-3) Polyurethane resin 4,4'-diphenylmethane diisoisocyanate (MD) which is a condensation polymer of the following diisocyanate and diol
I) Hexamethylene diisocyanate (HMDI) polypropylene glycol, weight average molecular weight 1000
(PPG1000) 2,2-bis (hydroxymethyl) propionic acid (DMPA) copolymer molar ratio (MDI / HMDI / PPG1000 / D
MPA) 40/10/15/35 Acid value measured by NaOH titration: 1.05 meq / g Weight average molecular weight obtained by GPC measurement: 45,000

(Developer in Table 2) (DV-1) Aqueous solution of pH 10 having the following composition: monoethanolamine 0.1 parts by weight triethanolamine 1.5 parts by weight Compound of the following formula 1 (１Rex NBL; Kao) 4.0 parts by weight Compound of the following formula 2 (Newcol B4SN; manufactured by Nippon Emulsifier Co., Ltd.) 2.5 parts by weight Compound of the following formula 3 0.2 parts by weight Water 91.7 parts by weight

[0174]

Embedded image

(Wherein, R represents H or C ₄ H ₉ and n is about 4 (average value))

(DV-2) Aqueous solution of pH 10 having the following composition 1.2 parts by weight of sodium hydrogen carbonate 0.8 parts by weight of sodium carbonate Compound of the above formula 1 (Perex NBL; manufactured by Kao Atlas Co., Ltd.) 3.0 Parts by weight Compound of the above formula 2 (Newcol B4SN; manufactured by Nippon Emulsifier Co., Ltd.) 2.0 parts by weight Compound of the above formula 3 0.2 parts by weight Water 92.8 parts by weight

(DV-3) Aqueous solution having the following composition and having a pH of 13: 1K potassium silicate 3.0 parts by weight Potassium hydroxide 1.5 parts by weight Compound of formula 3 0.2 parts by weight Water 95.3 parts by weight

As is evident from Table 2, the lithographic printing plate according to the present invention provides an excellent lithographic printing plate even under conditions that allow plate making with high productivity by scanning exposure, that is, under very low energy exposure conditions. . On the other hand, in Comparative Example 7 in which the starting system of the present invention was not used, a practical planographic printing plate was not obtained.

Example 16 A lithographic printing plate was prepared in the same manner as in Examples 1 to 6, except that the photoinitiating system was changed to the following composition and the thickness of the photopolymerized layer was changed to 1.5 g / m ^2. A master was prepared.

Photoinitiating system Content in total solid content of photopolymerization layer Sensitizing dye D20 1.2 wt% Titanocene T-2 1.5 wt% Co-sensitizer H-1 7.0 wt%

The obtained lithographic printing plate precursor was subjected to oscillation wavelength
Using a 400 nm InGaN-based semiconductor laser,
Beam system 25 μm, exposure energy density 0.2 mJ /
cm ^TwoScanning exposure was performed under the following conditions. Next, change the version
After heating at 00 ° C. for 10 seconds, the development processing described above was performed.
Was. A lithographic printing plate with a blue image with excellent visibility
Obtained. Using the obtained plate, Heidelberg KOR
-When offset printing was performed using a D machine,
It is possible to obtain more than 50,000 prints with excellent density and stain resistance.
Came.

[Embodiment 17] The plate of Embodiment 16 was used at a humidity of 6
After storage for 3 days under the condition of forced storage at 5% and 45 ° C., plate making and printing were performed in the same manner as in Example 16. The same good results as in Example 16 were obtained.

Example 18 The emission intensity distribution of a generally used safelight was measured, and the position where the emission intensity distribution rises on the short wave side (short wave end) was measured. The workability under each safelight was evaluated. Table 3 shows the results.

[0184]

[Table 3]

As described above, a yellow lamp is desirable in consideration of workability, and a photosensitive material that can be handled under the yellow lamp needs to have a low photosensitivity at least at 520 nm, preferably at a wavelength longer than 490 nm. The dye group of the present invention has an advantage also in this point since it has an absorption maximum near 400 nm.

Example 19 A lithographic printing plate precursor was prepared in the same manner as in Example 16 except that the photoinitiating system was changed to the following composition and the thickness of the photopolymerized layer was changed to 2.0 g / m ^2. Prepared.

Photoinitiating system Content in total solid content of photopolymerization layer Sensitizing dye D20 1.5 wt% Titanocene T-2 1.5 wt% Co-sensitizer H-1 5.0 wt%

The obtained lithographic printing plate precursor was irradiated with a beam system of 25 μm and an exposure energy density of 0.15 mJ using an InGaN-based semiconductor laser having an oscillation wavelength of 400 nm.
Scanning exposure was performed under the conditions of / cm ² . Next, the plate was heated at 100 ° C. for 10 seconds, and then the above-described developing treatment was performed. A planographic printing plate having a blue image with excellent visibility was obtained. The obtained plate was further heated at 300 ° C. for 5 minutes, and then subjected to offset printing using a Heidelberg KOR-D machine. As a result, it was possible to obtain 200,000 or more printed matter having excellent image density and stain resistance. Was.

Example 20 The plate of Example 19 was exposed to a yellow light for 30 minutes before exposure, and then plate making and printing were performed in exactly the same manner. The same excellent results as in Example 19 were obtained.

Comparative Example 8 A lithographic printing plate precursor was prepared in the same manner as in Example 16 except that the sensitizing dye was changed from D1 (maximum absorption wavelength: 409 nm) to DR-4 (maximum absorption wavelength: 500 nm). Was prepared. When the obtained lithographic printing plate precursor was subjected to plate making using an InGaN-based semiconductor laser having an oscillation wavelength of 400 nm in the same manner as in Example 16, no sensitizing action by the dye was observed. Further, after the obtained lithographic printing plate precursor was exposed to a yellow light for 30 minutes before exposure in the same manner as in Example 20, plate-making and printing were carried out in exactly the same manner. .

Comparative Example 9 A lithographic printing plate precursor was prepared in the same manner as in Example 16, except that acylphosphine (AP-1) was replaced with titanocene (H-5). When the obtained lithographic printing plate precursor was subjected to plate making using an InGaN-based semiconductor laser having an oscillation wavelength of 400 nm as in Example 16, a high-sensitivity printing plate (clear sensitivity: 0.1 mJ / cm ² ) was obtained. The obtained lithographic printing plate precursor was exposed to a yellow light for 30 minutes before exposure in the same manner as in Example 20, and the plate-making and printing were performed in exactly the same manner. There has occurred.

Comparative Example 10 A lithographic printing plate precursor was prepared in the same manner as in Example 16. The obtained lithographic printing plate precursor is
When plate making was performed in the same manner as in Example 16 except that an FD-YAG laser having an oscillation wavelength of 530 nm was used instead of the InGaN-based semiconductor laser having an oscillation wavelength of 400 nm, there was no absorption at 530 nm for both the acylphosphine and the sensitizing dye. , Image flow. The sensitizing dyes in the examples are those exemplified in the present specification, and the structures of other compounds are as follows.

[0193]

Embedded image

[0194]

Embedded image

[0195]

The photosensitive composition of the present invention, when used in the photosensitive layer of a lithographic printing plate precursor, has a sufficient sensitivity suitable for scanning exposure with a short-wavelength semiconductor laser such as InGaN and has an anti-resistance property. A lithographic printing plate excellent in printability and stain resistance can be obtained. The lithographic printing plate for scanning exposure using the photosensitive composition of the present invention for the photosensitive layer has remarkably improved fog under a yellow light, and can greatly improve the workability of handling the plate. The photosensitive composition of the present invention has excellent sensitivity to wavelengths of 350 to 450 nm, and at the same time, has excellent storage stability, which greatly contributes to the industry.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AB03 AB17 AC01 AC08 BC14 BC15 BE07 BE10 BG00 CA09 CA35 CA41 CA42 CB41 2H096 AA07 AA27 BA05 BA06 BA11 EA02 EA04 EA23 4J011 QA02 QA03 QA06 QA12 QA13 QA13 QA13 QA13 QA13 QA13 QA13 QA13 QA12 SA64 SA78 SA84 SA88 TA01 TA03 TA05 UA01 VA01 WA01 WA02 WA05 WA06

Claims (4)

[Claims] (1) reacting with (i) a triplet sensitizing dye having a maximum absorption wavelength of 350 to 450 nm, (ii) an acylphosphine compound, and (iii) at least one of a radical and an acid to obtain a physical and A photosensitive composition containing a compound that is retained by changing at least one of its chemical properties. (I) at least one of a sensitizing dye represented by the following general formula (1) and a sensitizing dye represented by the following general formula (2), (ii) an acylphosphine compound, and (iii) A) a photosensitive composition containing a compound which reacts with at least one of a radical and an acid and which is retained while changing at least one of its physical and chemical properties. Embedded image (Wherein, A represents an S atom or NR ₁ , R ₁ represents an alkyl group or an aryl group, and Y represents a non-metal which forms a basic nucleus of a dye in cooperation with an adjacent A and an adjacent carbon atom. X ₁ and X ₂ each independently represent an atomic group,
It is a hydrogen atom or a monovalent nonmetal atomic group, and X ₁ and X ₂ may combine with each other to form an acidic nucleus of the dye. W represents an O atom or a sulfur atom. ) (Wherein, Ar ₁ and Ar ₂ each independently represent an aryl group and are linked via a bond by —Z—. Here, Z represents —O— or —S—. In addition, W represents It is synonymous with that shown in general formula (1).) 3. An addition polymerizable compound having an ethylenically unsaturated double bond, wherein the compound which reacts with at least one of the radical and the acid and which is retained by changing at least one of its physical and chemical properties is retained. The photosensitive composition according to claim 1, which is: 4. The photopolymerizable composition according to claim 1, which has a wavelength of 450 nm.
A photopolymerization method comprising exposing with a laser beam having the following wavelength.