JP2002090989A - Photopolymerizable composition and photopolymerizable planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable composition having high sensitivity to light in the visible region and further in a longer wavelength region such as the near IR region, having low sensitivity to light in the UV region and excellent in handleability under a white fluorescent lamp and to provide a photopolymerizable planographic printing plate. SOLUTION: The photopolymerizable composition contains (A) an ethylenically unsaturated compound, (B) a dye having a structure in which heteroatoms bond to each other through a polymethine chain as the basic structure and having (B-1) a substituent having an ether bond which generates an oxonium cation or a thio-ether bond which generates a sulfonium cation by resonance in the dye molecule on the polymethine chain or (B-2) substituents forming a cyclic structure by bonding to each other through an ether bond which generates an oxonium cation or a thio-ether bond which generates a sulfonium cation by resonance in the dye molecule on the polymethine chain and (C) a photopolymerization initiator. The photopolymerizable planographic printing plate is obtained by forming a layer of the photopolymerizable composition on the surface of a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition and a photopolymerizable lithographic printing plate, and more particularly to a photopolymerizable composition and a photopolymerizable lithographic printing plate exhibiting high sensitivity to light in a long wavelength region. About the edition.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an image by exposing a photopolymerizable composition, for example, a photopolymerizable composition comprising an ethylenically unsaturated compound and a photopolymerization initiator, or further comprising an organic polymer binder is used. A method of forming a layer on the surface of a support, exposing an image, polymerizing and curing an ethylenically unsaturated compound in an exposed portion, and then dissolving and removing an unexposed portion to form a cured relief image, and photopolymerization by exposure. Utilizing the method of forming an image by causing the adhesive strength of the photosensitive composition layer to the support to be changed and then peeling the support, and the change in toner adhesion of the photopolymerizable composition layer due to light Various methods such as the following image forming methods are known, and all of the photopolymerization initiators include benzoin, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, and benzene. Ketone, or the like Michler's ketone, which can be sensitive has been used for the following ultraviolet region of the short wavelength center of the light 400 nm.

On the other hand, in recent years, with the development of image forming technology,
There is a strong demand for a photosensitive material exhibiting high sensitivity to light in the visible region, for example, 488 nm of an argon ion laser.
50 corresponding to the laser plate making method using the oscillation beam of
A number of photopolymerizable compositions having a sensitivity range extended to about 0 nm have been proposed, and further, a long wavelength region exceeding 600 nm corresponding to a laser plate making method using a He-Ne laser or a semiconductor laser or a full-color image duplication technique. Research on a photopolymerizable composition for light of the same has been active.

For example, JP-A-62-143044 discloses a photocurable composition containing a cationic dye-borate anion complex as a radical generator. λmax is 740n
Examples of an indole cyanine dye and a borate anion complex at m. However, usually, the active radical generating ability of the photopolymerization initiator is 500 nm or more, and particularly, for light having a wavelength exceeding 600 nm,
It is known that the sensitivity rapidly decreases with a decrease in photoexcitation energy, and any of the photopolymerizable compositions conventionally proposed for such light in a long wavelength region has a high sensitivity. In addition, it was not satisfactory, and in addition, there was a problem that a photopolymerization reaction proceeded during handling under a white fluorescent lamp, and it was difficult to obtain a product of stable quality.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and therefore, the present invention is directed to light in a long wavelength region such as a visible region and a near infrared region. An object of the present invention is to provide a photopolymerizable composition and a photopolymerizable lithographic printing plate which exhibit high sensitivity, are insensitive to light in the ultraviolet region, and have excellent handleability under a white fluorescent lamp.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, the present invention relates to a dye having a basic structure in which a heteroatom is bonded via a polymethine chain. It has been found that a photopolymerizable composition containing a dye having a specific substituent on the chain can achieve the above object, and the present invention has been completed. That is, the present invention provides the following component (A): A photopolymerizable composition comprising the component (B) and the component (C), and a photopolymerizable lithographic printing plate having a layer of the photopolymerizable composition formed on a support surface;
Is the gist. (A) an ethylenically unsaturated compound; (B) a dye having a structure in which a hetero atom is bonded via a polymethine chain as a basic structure. A dye having a substituent having an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation, or (B-2) having at least two substituents on a polymethine chain, wherein the two substituents are Dye which resonates in the dye molecule to form a cyclic structure linked by an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation (C) Photopolymerization initiator

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylenically unsaturated compound (A) constituting the photopolymerizable composition of the present invention will be described later (C) when the photopolymerizable composition is irradiated with actinic rays. )
A monomer having an ethylenically unsaturated double bond such that it undergoes addition polymerization by the action of the photopolymerization initiator of the component and is optionally crosslinked and cured, and has such a double bond in the main chain or side chain Refers to polymer. The meaning of the monomer here is a concept corresponding to a so-called polymer,
In addition to monomers in a narrow sense, it includes dimers, trimers, and other oligomers.

Specific examples of such monomers include (1) acrylic acid and methacrylic acid (both of which may be collectively referred to as “(meth) acrylic acid”). Unsaturated carboxylic acids, (2) these alkyl esters, (3) ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and Esters of the same aliphatic polyhydroxy compounds as itaconate, crotonate, maleate and the like with unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds such as quinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and unsaturated carboxylic acids, (5) ethylene glycol, (meth) acrylic acid and phthalic acid Of diethylene glycol, (meth) acrylic acid and maleic acid, condensate of pentaerythritol, (meth) acrylic acid and terephthalic acid, and of butanediol, glycerin, (meth) acrylic acid and adipic acid Condensates of polyhydroxy compounds such as condensates with unsaturated carboxylic acids and polycarboxylic acids, (6) polyisocyanate compounds such as tolylene diisocyanate and hydroxyethyl (meth)
Urethane (meth) acrylates such as addition products with hydroxyl group-containing (meth) acrylates such as acrylates, (7)
(8) Epoxy such as an addition reaction product of a polyisocyanate compound and a hydroxyl group-containing vinyl compound, such as a vinyl urethane; (8) an addition reaction product of a polyvalent epoxy compound with a hydroxyl group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate; (Meth) acrylates, (9) acrylamides such as ethylenebis (meth) acrylamide, (10) allyl esters such as diallyl phthalate, (11) vinyl group-containing compounds such as divinyl phthalate, (12) (meth) acryloyl And (meth) acryloyl group-containing phosphates such as oxyethyl phosphate and bis ((meth) acryloyloxyethyl) phosphate.

As the polymer, specifically, for example, as those having a double bond in the main chain, (1) polyesters obtained by a polycondensation reaction of an unsaturated dicarboxylic acid and a dihydroxy compound, 2) Polyamides obtained by a polycondensation reaction between an unsaturated dicarboxylic acid and a diamine compound, such as polyamides having a double bond in a side chain, (3) itaconic acid, ethylidene malonic acid, propylidene succinic acid, etc. and a dihydroxy compound (4) Polyamides obtained by polycondensation reaction of itaconic acid, ethylidene malonic acid, propylidene succinic acid, etc. with diamine compound, (5) polyvinyl alcohol, poly (2- Hydroxyethyl methacrylate), polyepichlorohydrin and other side chains with hydroxyl groups and methyl halide groups A polymer obtained by a reaction between the polymer and the unsaturated carboxylic acids having active functional groups,
And the like.

(B) Constituting the Photopolymerizable Composition of the Invention
The component dye is a dye having a structure in which a hetero atom is bonded via a polymethine chain as a basic structure. (B-1) On the polymethine chain, resonance occurs in the dye structure to generate an oxonium cation. A dye having a substituent having an ether bond or a thioether bond generating a sulfonium cation, or (B-2) having at least two substituents on a polymethine chain, wherein the two substituents are contained in the dye molecule. Are dyes that form a cyclic structure by resonance with an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation.
In addition, “resonating in a dye molecule” means in other words “resonating with a chromophore of a dye”. Since the dye of the present invention has the substituent or the cyclic structure, the π-electron system of the chromophore in the dye molecule expands, and the absorption peak is usually 20 n.
m to the longer wavelength side, especially in the wavelength range of 700 to 13
It can improve the absorption efficiency in the near infrared region of 00 nm. These near-infrared absorbing dyes efficiently absorb light in the above-mentioned wavelength range, transmit the photoexcitation energy to the photopolymerization initiator of the component (C) described below, decompose the photopolymerization initiator, and form the component (A) While having a sensitizing function of generating an active radical that induces the polymerization of the ethylenically unsaturated compound, it hardly absorbs light in the ultraviolet region or does not substantially respond to absorption, and is included in white fluorescent lamps. It is a compound that has no action of denaturing the composition depending on such weak ultraviolet rays.

In the present invention, these dyes include:
The basic structure is a structure in which a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom is linked by a polymethine (-CH =) _n chain. Typically, the hetero atom forms a heterocyclic ring. A broadly-defined so-called cyanine dye having a structure in which a heterocyclic ring is bonded via a polymethine chain, specifically, for example, quinoline-based (so-called cyanine-based), indole-based (so-called indocyanine-based) Benzothiazoles (so-called thiocyanines), pyryliums, thiapyryliums, squaryliums, croconiums, azureniums, and so-called polymethine dyes having a structure in which an acyclic heteroatom is bonded through a polymethine chain. Among them, quinoline, indole, benzothiazole, pyrylium, thiapyrylium and other cyanine dyes, and polymers Emissions-based dye is preferable.

In the present invention, among the cyanine-based dyes, quinoline-based dyes include those represented by the following general formula (I)
Those represented by a), (Ib) or (Ic) are preferred.

[0013]

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[In the formulas (Ia), (Ib) and (Ic), R ¹ and R
² each independently has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a group which has a substituent. L ¹ represents (1) a tri-substituted group having at least a substituent having an ether bond which generates an oxonium cation or a thioether bond which generates a sulfonium cation by resonance in a dye molecule; Exhibiting a penta, hepta, nona, or undecamethine group, or (2) having at least two substituents on the penta, hepta, nona, or undecamethine group, wherein the two substituents Then, they are linked by an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation to form a cyclic structure. Two substituents on the penta, hepta, nona, or undecamethine group are linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, a cycloalkeneone ring, a cycloalkenedione ring, or a cycloalkenethione ring; The quinoline ring may have a substituent, and in this case, two adjacent substituents may be connected to each other to form a fused benzene ring. X _a ^- represents a counter anion. ]

Here, R in formulas (Ia), (Ib) and (Ic)¹
And R^TwoIs an alkyl group, the number of carbon atoms is usually 1 to
15, preferably 1 to 10, alkenyl group, alkynyl
When it is a group, it usually has 2 to 15, preferably 2 carbon atoms.
-10, and those substituents including a phenyl group
In general, the number of carbon atoms is usually 1 to 15, preferably 1 to 10.
Lucoxy, phenoxy, hydroxy, or phenyl
And a group such as L ¹The ether bond in or
As a substituent other than a substituent having a thioether bond
Is an alkyl group having the same number of carbon atoms, an amino group, or a halogen
Atoms and the like, and as a substituent on the quinoline ring
Is an alkyl group having the same number of carbon atoms as defined above,
Group, a nitro group, or a halogen atom.

The indole and benzothiazole dyes are particularly preferably those represented by the following formula (II).

[0017]

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[In the formula (II), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ³ and R ⁴ each independently may have a substituent. L ² represents an alkyl group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent; Represents a tri-, penta-, hepta-, nona- or undecamethine group having at least a substituent having an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation in resonance in a dye molecule, or (2 ) Having at least two substituents on the penta, hepta, nona, or undecamethine group;
The two substituents resonate in the dye molecule and are joined by an ether bond to produce an oxonium cation or a thioether bond to produce a sulfonium cation to form a cyclic structure. Two substituents on the penta, hepta, nona, or undecamethine group are linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, a cycloalkeneone ring, a cycloalkenedione ring, or a cycloalkenethione ring; The condensed benzene ring may have a substituent,
In that case, two adjacent substituents may be connected to each other to form a fused benzene ring. X _a ^- represents a counter anion. ]

Here, when R ³ and R ⁴ in the formula (II) are an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 10, and the number of carbon atoms when it is an alkenyl group or an alkynyl group. Is usually 2 to 15, preferably 2 to 10, and as a substituent thereof including a phenyl group, an alkoxy group having a carbon number of usually 1 to 15, preferably 1 to 10, a phenoxy group, a hydroxy group, or a phenyl group and the like, and the substituent other than a substituent substituted by the ether bond or a thioether bond in L ^2, supra alkyl group carbon atoms, an amino group, or a halogen atom and the like, fused benzene Examples of the substituent in the ring include an alkyl group having the same carbon number as described above, an alkoxy group having the same number of carbon atoms, a nitro group, and a halogen atom.

Further, as the pyrylium-based and thiapyrylium-based dyes, the following general formulas (IIIa), (IIIb), or
Those represented by (IIIc) are preferred.

[0021]

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[In the formulas (IIIa), (IIIb) and (IIIc), Z ¹
And Z ² each independently represent an oxygen atom or a sulfur atom; R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom or an alkyl group, or R ⁵ and R ⁷ , and R ⁶ and R
⁸ may be linked to each other to form a cycloalkene ring having 5 or 6 carbon atoms, and L ³ is (1) as a substituent, an ether bond which resonates in the dye molecule to generate an oxonium cation, or A mono-, tri-, penta-, or heptamethine group having at least a substituent having a thioether bond generating a sulfonium cation, or (2)
The penta, hepta, nona, or undecamethine group having at least two substituents, wherein the two substituents resonate in the dye molecule to form an oxonium cation or an thioether to form a sulfonium cation. Joined by bonds to form a ring structure. Two substituents on the tri, penta, or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, a cycloalkenenone ring, a cycloalkenedione ring, or a cycloalkenethione ring. , A pyrylium ring and a thiapyrylium ring may have a substituent, in which case,
Two adjacent substituents may be linked to each other to form a fused benzene ring. X _a ^- represents a counter anion. ]

Here, in the formulas (IIIa), (IIIb) and (IIIc)
R^Five, R⁶, R⁷, And R⁸Is an alkyl group
Has usually 1 to 15, preferably 1 to 10
L ^ThreeSaid ether bond or thioether bond in
Substituents other than the substituents substituted by
Number of alkyl groups, amino groups, or halogen atoms, etc.
In the pyrylium and thiapyrylium rings
Examples of the group include an aryl group such as a phenyl group.
You.

Further, as the polymethine dye, those represented by the following general formula (IV) are particularly preferable.

[0025]

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[In the formula (IV), R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
Each independently represents an alkyl group; R ¹³ and R ¹⁴ each independently represent an aryl group, furyl group or thienyl group which may have a substituent, and L ⁴ represents (1) substituted As a group, a mono-, tri-, penta- or heptamethine group having at least a substituent substituted with an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation in resonance in a dye molecule, or 2) having at least two substituents on the penta, hepta, nona, or undecamethine group, wherein the two substituents resonate in the dye molecule to form an oxonium cation, or an ether bond, or a sulfonium cation. They are linked by the resulting thioether bond to form a cyclic structure. Two substituents on the tri, penta, or heptamethine group may be linked to each other to form a cycloalkene ring having 5 to 7 carbon atoms, a cycloalkenenone ring, a cycloalkenedione ring, or a cycloalkenethione ring. , A quinone ring and a benzene ring may have a substituent. X _a
^- represents a counter anion. ]

Here, the carbon number of the alkyl group of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² in the formula (IV) is usually 1 to 15, preferably 1 to 10, and R ¹³ and R ¹⁴ are aryl. When it is a group, the number of carbon atoms is usually 6 to 20, preferably 6 to 15,
Specific examples of R ¹³ and R ¹⁴ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, a 3-furyl group, a 2-thienyl group, and a 3-thienyl group. Examples of the substituent, ibid alkyl carbon atoms, ibid alkoxy group carbon atoms, a dialkylamino group, hydroxy group, or a halogen atom and the like, other than a substituent substituted with an ether bond or a thioether bond in L ⁴ Examples of the substituent include an alkyl group having the same number of carbon atoms, an amino group, and a halogen atom.Examples of the substituent on the quinone ring and the benzene ring include an alkyl group having the same number of carbon atoms, an alkoxy group having the same number of carbon atoms, and a nitro group. And a halogen atom and the like.

The above-mentioned general formulas (Ia to c), (II) and (IIIa to
c) and the counter anion X in (IV) _a ^-As a concrete
Specifically, for example, Cl^-, Br^-, I^-, ClO_Four ^-,
PF ₆ ^-, SbF₆ ^-, AsF₆ ^-, And BF_Four ^-,
BCl_Four ^-Inorganic acid anions such as inorganic boric acid
Benzenesulfonic acid, toluenesulfonic acid, naphtha
Lensulfonic acid, acetic acid and methyl, ethyl, propyl
Butyl, phenyl, methoxyphenyl, naphthyl,
Fluorophenyl, difluorophenyl, pentafluor
With organic groups such as rophenyl, thienyl, pyrrolyl, etc.
Organic acid anions such as organic boronic acid can be exemplified.

The quinoline compounds represented by the above formulas (Ia to c), the indole compounds or the benzothiazole compounds represented by the above formula (II), and the pyrylium compounds represented by the above formulas (IIIa to c) Or cyanine dyes such as thiapyrylium,
Among the polymethine dyes represented by the general formula (IV), the indole or benzothiazole dyes represented by the general formula (II) are particularly preferable in the present invention.

Also, L ¹ , L ² , L ³ ,
And a polymethine chain, including L ^4, the wavelength range 700 to
The heptamethine chain for 850 nm, the nonamethine chain for the wavelength range of 850 to 950 nm, and the undecamethine chain for the wavelength range of 950 to 1300 nm are preferable.

In the present invention, the dye of the component (B) is formed by forming, on the polymethine chain (B-1), an ether bond which generates an oxonium cation or a thioether bond which generates a sulfonium cation by resonance in the dye molecule. Or (B-2) having at least two substituents on the polymethine chain, and the two substituents resonate in the dye molecule to form an oxonium cation. And a thioether bond which generates a sulfonium cation to form a cyclic structure. (B
In the case of -1), the resonance mechanism is as follows, for example, in the case of a dye having a structure in which a nitrogen atom is bonded via a nonametin chain.

[0032]

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In the case of (B-2), the resonance mechanism is as follows, for example, in the case of a dye having a structure in which a nitrogen atom is bonded via a nonamethane chain.

[0034]

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In the present invention, specific examples of the substituent having an ether bond or a thioether bond on the polymethine chain in the case of the above (B-1) include those represented by the following general formula (Va). Can be

[0036]

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[In the formula (Va), W ¹ represents an oxygen atom or a sulfur atom, and R ^a represents an alkyl group which may have a substituent, an aryl group which may have a substituent, Or a heterocyclic group which may have a substituent. ]

Here, when ^Ra in the formula (Va) is an alkyl group, the number of carbon atoms is usually 1 to 15, preferably 1 to 1
0, the number of carbon atoms when the aryl group is usually 6 to 20,
The number of carbon atoms when the heterocyclic ring is preferably 6 to 15, usually 2 to 15, preferably 2 to 10, and the substituents thereof include an alkyl group having 1 to 5 carbon atoms and 1 carbon atom.
An alkoxy group or a thioalkoxy group having 5 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms,
An alkoxycarbonyl group having 2 to 5 carbon atoms, a phenyl group, a naphthyl group, an isocyanate group or an isothiocyanate group, an oxo group or a thioxo group;
A heterocyclic group, a hydroxyl group, or a halogen atom. The group represented by the general formula (Va) may be linked to the polymethine chain of the dye via a polymethine chain.

In the compound represented by the general formula (Va), R
Those in which ^a is a phenyl group and those in which R ^a is a heterocyclic group represented by the following general formula (Vb) are preferred.

[0040]

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[In the formula (Vb), W ¹ represents an oxygen atom or a sulfur atom, W ² represents an oxygen atom, a sulfur atom, a nitrogen atom or a dialkylmethylene group, and W ¹ and W ² are the same. And the heterocyclic ring is a 4- to 6-membered ring, and may have a substituent.
Two substituents may be linked to each other to form a condensed ring. ]

Further, among the compounds represented by the general formula (Vb), those represented by the following general formulas (Vc), (Vd) and (Ve) are preferable, and the compounds represented by the following general formula (Vc) are preferable. Are particularly preferred.

[0043]

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[In the formula (Vc), W ¹ represents an oxygen atom or a sulfur atom, two W ^1s may be the same or different, and R ^b may have a substituent. Good alkyl group,
It represents an alkoxy group or thioalkoxy group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. ]

[0045]

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[In the formula (Vd), W ¹ represents an oxygen atom or a sulfur atom, and two W ^1s may be the same or different, and R ^c may have a substituent. Good alkyl group,
It represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. ]

[0047]

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[In the formula (Ve), W ¹ represents an oxygen atom or a sulfur atom, W ² represents an oxygen atom, a sulfur atom, a nitrogen atom, or a dialkylmethylene group, and W ¹ and W ² are the same. And the condensed ring represents an aromatic hydrocarbon ring. ]

Here, when R ^b and R ^c in the formulas (Vc), (Vd) and (Ve) are alkyl groups, the number of carbon atoms is 1 to 5.
5, the number of carbon atoms when it is an alkoxy group or a thioalkoxy group is 1 to 5, and the number of carbon atoms when it is an aryl group is 6 to 5.
10, when the heterocyclic group has 2 to 5 carbon atoms,
When W ^{2 in} (Ve) is a dialkylmethylene group, it has 3 to 15 carbon atoms.

In the present invention, the dye may be such that a substituent substituted by an ether bond or a thioether bond on the polymethine chain is directly or further a divalent bonding group via another ether bond or a thioether bond. For example, a cross-linked structure bonded to the polymethine chain of the same or different dyes via a dye may be employed. In the present invention, the specific ether cyclic structure or thioether cyclic structure on the polymethine chain in the case of the above (B-2) includes the following general formula (VIa).

[0051]

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[In the formula (VIa), W ³ represents an oxygen atom or a sulfur atom, the heterocyclic ring containing W ³ represents a 5- or 6-membered ring which may have a substituent, and R ^d is A hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an amino group or a halogen atom which may have a substituent are shown. As the substituent which the heterocyclic ring containing W ³ may have,
An alkyl group having 1 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, a phenyl group, a naphthyl group, an amino group, a heterocyclic group having 2 to 5 carbon atoms, a hydroxyl group, or And a halogen atom. Among the compounds represented by the above general formula, the following general formula (VIb) or (VI
Those represented by c) are preferred.

[0053]

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[0054] wherein (VIb) and (VIc), R ^e is a hydrogen atom,
Represents an alkyl group or an aryl group, and R ^e may be the same or different. ] Wherein in Formula (VIa), (VIb), the number of carbon atoms when R ^d and R ^e in (VIc) is an alkyl group 1-5 carbon atoms when it is an aryl group with 6 to 10 is there.

Further, the dye of the component (B) in the present invention is described, for example, in N. Narayanan et al., "Near-Infrared Dyes".
for High Technology Applications "S. Daehne, URGe
nger, OSWolfbeis (Kluwer Academic Publishers), specifically, for example, a dye having a structure in which a heterocycle is bonded via a polymethine chain having a chlorine atom as a substituent, and a corresponding alcohol Or a corresponding sodium salt compound of a thioalcohol, or the like.

Among the above, cyanine-based dyes having a structure having at least a substituent on the polymethine chain which is resonated in a dye molecule with an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation, And specific examples of polymethine dyes are shown below. In the following specific examples, A represents a substituent substituted by an ether bond or a thioether bond, and X _a ^- represents a counter anion.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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In the above specific examples, the substituents substituted by an ether bond or a thioether bond of A are specifically shown below. .

[0066]

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In the above specific examples, the counter anion X _a
^{-, specifically,} Cl ^-, Br ^-, I -, Cl
O ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , p-toluenesulfonic acid, or 1-naphthalenesulfonic acid. Further, specific examples of cyanine dyes and polymethine dyes in which a substituent on a polymethine chain is resonated to form an oxonium cation, or a thioether bond which generates a sulfonium cation, and is bonded to form a cyclic structure, Formulas (I-1) to (I-3), (II-1) to (II-3),
(II-10), (III-2), (III-11), (III-
13) to (III-14), (III-20), (IV-1) to
In (IV-6)

[0068]

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The dye of the component (B) is preferably (B-1) because it has high sensitivity to light in the long wavelength region and low sensitivity to light in the ultraviolet region. The photopolymerization initiator of the component (C) constituting the photopolymerizable composition of the present invention includes:
(B) a radical generator that generates an active radical when irradiated with light in the presence of the dye of the component,
For example, halogenated hydrocarbon derivatives, JP-A-62-14
No. 3044, JP-A-62-150242, JP-A-9-
188865, JP-A-9-188686, JP-A-9-18886
Publication Nos. 188710 and 276,769, and Kunz, Martin "Rad Tech'98. Proceeding Apri.
l 19-22,1998, Chicago "and the like.
JP-A-59-152396, JP-A-61-15119
No. 7 titanocene compounds, Japanese Patent Publication No. 6
Hexaarylbiimidazole compounds described in -29285 and the like, and diaryliodonium salts,
Organic peroxides and the like are mentioned, and in the present invention, halogenated hydrocarbon derivatives and organic borates are preferred.

Here, the halogenated hydrocarbon derivative is preferably an s-triazine ring having at least one mono-, di- or trihalogen-substituted methyl group bonded to an s-triazine ring.
Triazine derivatives, specifically, for example, 2,4,6-
Tris (monochloromethyl) -s-triazine, 2,
4,6-tris (dichloromethyl) -s-triazine,
2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)
-S-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α,
α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-
Bis (trichloromethyl) -s-triazine, 2- (p
-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl ) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-
Methoxyphenyl) -2,4-butadienyl] -4,6
-Bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (pi
-Propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-
4,6-bis (trichloromethyl) -s-triazine,
2-benzylthio-4,6-bis (trichloromethyl)
-S-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromo Methyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like, among which 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) ) -4,6-bis (trichloromethyl)
-S-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl)-
A bis (trihalomethyl) -s-triazine compound such as 4,6-bis (trichloromethyl) -s-triazine is preferable because of excellent stability over time.

Other halogenated hydrocarbon derivatives include, for example, JP-A-53-133428, JP-A-62-58241, and German Patent No. 333702.
No. 4, MPHutt, EFFlslager, LMWerbel "Jurn
al of Heterocyclic Chemistry "Vol. 7, No. 3 (1970) and the like.

As the organic borate, those represented by the following general formula (VI) are particularly preferred.

[0073]

Embedded image

[In the formula (VI), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸
Are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, A good aryl group or a heterocyclic group is shown, which may be linked to each other to form a cyclic structure, and at least one of them is an alkyl group which may have a substituent. X _b ⁺ is a counter cation. ]

Here, when R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in the formula (VI) are alkyl groups, the number of carbon atoms is usually from 1 to 1.
5, preferably 1 to 5, the number of carbon atoms when it is an alkenyl group or an alkynyl group is usually 2 to 15, preferably 2 to 5,
When it is an aryl group, it usually has 6 to 20, preferably 6 to 15, and when it is a heterocyclic group, it usually has 4 to 4 carbon atoms.
20, preferably 4 to 15, and examples of the substituent therefor include a halogen atom, an alkyl group, an alkoxy group, a trifluoromethyl group, and a trimethylsilyl group.

Specific examples of the organoboron anion of the organoboron salt represented by the formula (VI) include, for example, n-butyl-methyl-diphenylboron and n-butyl-anion.
Triphenyl boron anion, n-butyl-tris (2,
4,6-trimethylphenyl) boron anion, n-butyl-tris (p-methoxyphenyl) boron anion, n
-Butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n-butyl-tris (2 , 4,
6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (Trifluorophenyl) boron anion, n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) -boron anion, n-butyl-tris (3-fluoro-4-methylphenyl) -boron anion, etc. No.

Further, as the counter cation X _b ⁺ , for example,
Onium compounds such as alkali metal cations, ammonium cations, phosphonium cations, sulfonium cations, iodonium cations, and pyriumium cations, thiapyrylium cations, indolium cations, and the like, and organic ammonium cations such as tetraalkylammonium Is preferred.

Among the above components (C), the use of a bis (trihalomethyl) -s-triazine compound or an organic borate is particularly preferred because of its high sensitivity. In the present invention, in order for the dye of the component (B) and the organic borate as the photopolymerization initiator of the component (C) to be present in the photopolymerizable composition, the dye cation of the dye is appropriately selected. In addition to the usual method of compounding a salt with a counter anion and an organic boron anion of the organic borate and a salt of an appropriately selected counter cation, a dye cation of the dye and an organic boron anion of the organic borate A method of blending the salt formed by the above method can also be adopted. In the present invention, the latter method is preferable.

The photopolymerizable composition according to the present invention comprises: an ethylenically unsaturated compound as the component (A), a dye as the component (B),
And the photopolymerization initiator of the component (C). The proportion of the component (A) in the entire photopolymerizable composition is from 20 to 80% by weight due to the inclusion of other components described below. Preferably, it is 30 to 70% by weight. The total amount of the components (B) and (C) is preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the component (A). It is particularly preferred.

The ratio of the component (B) to the component (C) is such that (B) :( C) is 1:20 to 1 by weight.
It is preferably in the range of 0: 1, particularly preferably in the range of 1: 8 to 4: 1. As mentioned above,
When a salt formed of the dye cation in the component (B) and the organic boron anion in the component (C) is used, the component (B) and the component (C) are added to 100 parts by weight of the component (A). The total amount is preferably from 0.1 to 30 parts by weight, particularly preferably from 0.5 to 20 parts by weight.

The photopolymerizable composition of the present invention may contain, in addition to the above components, for example, (meth) acrylic acid, (meth) acrylate, (meth) acrylonitrile, (meth) acrylonitrile,
Acrylamide, maleic acid, styrene, vinyl acetate,
The above-mentioned component (A), wherein a homopolymer or a copolymer such as vinylidene chloride or maleimide, or an organic polymer such as polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinylpyrrolidone, polyethylene oxide or acetylcellulose is used as a binder. Is preferably in the range of 10 to 500 parts by weight, particularly preferably 20 to 200 parts by weight, based on 100 parts by weight of the ethylenically unsaturated compound.

In addition, if necessary, various additives such as hydroquinone, p-methoxyphenol, 2,6-
Thermal polymerization inhibitor such as di-t-butyl-p-cresol
5 parts by weight or less of a coloring agent comprising an organic or inorganic dye or pigment
0 parts by weight or less, plasticizers such as dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, dioctyl adipate, and triethylene glycol dicaprylate are 40 parts by weight or less, and sensitizing agents such as tertiary amines and thiols are 5 parts by weight. Hereinafter, dye precursors such as triarylmethane, bisarylmethane, xanthene compounds, fluorane compounds, thiazine compounds, and dye leuco bodies such as compounds having a lactone, lactam, sultone, or spiropyran structure as a partial skeleton thereof are 10 It may be added in each range of not more than parts by weight.

The use form of the photopolymerizable composition of the present invention as a light-sensitive material may be determined, for example, by coating it on the surface of a support without a solvent or by diluting it with a suitable solvent, and then drying. A form, or a form in which an overcoat layer for blocking oxygen is further provided thereon, a form in which droplets are dispersed in a heterogeneous medium and applied in multiple layers as a plurality of types of photosensitive materials, and a support in which microcapsules are included Although the form and the like coated on the photopolymerizable composition of the present invention can be adopted, the composition is coated on a support surface as a solution in which the composition is dissolved in an appropriate solvent,
The use form as a photopolymerizable lithographic printing plate in which a layer of the photopolymerizable composition of the present invention is formed on the surface of a support by heating and drying is suitable.

Here, the solvent is not particularly limited as long as it has a sufficient solubility for the components used and gives good coating properties. Examples of the solvent include methyl cellosolve,
Cellosolve solvents such as ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate , Propylene glycol solvents such as dipropylene glycol dimethyl ether, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, Ester solvents such as methyl 3-methoxypropionate, heptanol Hexanol, diacetone alcohol, alcohol solvents such as furfuryl alcohol, cyclohexanone, ketone solvents such as methyl amyl ketone,
Highly polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, or a mixed solvent thereof, and further a mixture thereof with an aromatic hydrocarbon may be used. The usage ratio of the solvent is usually in the range of about 1 to 20 times by weight based on the total amount of the photopolymerizable composition.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating and the like can be used. The coating amount varies depending on the application, but is usually 0.3 to 7 μm
m, preferably 0.5-5 μm, particularly preferably 1-3
μm range. The drying temperature at that time is, for example, about 60 to 170 ° C, preferably 70 to 150 ° C.
The drying time is about 5 seconds to 10 minutes, preferably about 10 seconds to 5 minutes.

Incidentally, an oxygen barrier layer of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, cellulose or the like is usually provided on the photopolymerizable composition layer in order to prevent a polymerization inhibition effect by oxygen.

The support is made of aluminum,
Metal plate such as zinc, copper, steel, aluminum, zinc, copper,
Metal plates plated or evaporated with iron, chromium, nickel, etc.
Examples include paper, paper coated with resin, paper to which metal foil such as aluminum is adhered, plastic film, plastic film subjected to hydrophilic treatment, and glass plate. Inside,
Preferable is an aluminum plate, which has been subjected to surface treatment such as graining by electrolytic etching or brush polishing in a hydrochloric acid or nitric acid solution, anodizing treatment in a sulfuric acid solution, and, if necessary, sealing. Aluminum plates are more preferred. The surface roughness of the support is JIS B0
Average roughness R _a as defined in 601, typically 0.3
The thickness is 1.0 μm, preferably about 0.4 to 0.8 μm.

Light sources for imagewise exposing the photopolymerizable composition layer of the lithographic printing plate of the present invention include a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a HeNe laser, and an argon ion. Laser, YAG laser, H
Laser light sources such as eCd lasers, semiconductor lasers, and ruby lasers are mentioned. In particular, a light source that generates near-infrared laser light from visible light of 600 nm or more is preferable, for example, a solid-state laser such as a ruby laser, a YAG laser, or a semiconductor laser. In particular, a small-sized and long-life semiconductor laser or a YAG laser is preferable. Usually, after scanning and exposure with these light sources, an image is formed by developing with a developer.

The photopolymerizable composition of the present invention has a composition of 700 to 13
In the near-infrared region of 00 nm, for example, when exposed with a semiconductor laser using a high-density light intensity of 10 ⁸ W / m ² or more, when exposed with a low-density light intensity of 10 ² W / m ² or less The sensitivity is 5 times or more, preferably 10 times or more as compared with the above, and the difference in the sensitivity makes it possible to develop the safelight property (workability) under a normal white fluorescent lamp.

The developer used for developing the photoreceptor obtained by imagewise exposing the photopolymerizable lithographic printing plate of the present invention includes, for example,
Sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate, potassium metasilicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Inorganic alkali salts such as sodium carbonate, sodium bicarbonate, potassium carbonate, dibasic sodium phosphate, tertiary sodium phosphate, dibasic ammonium phosphate, tertiary ammonium phosphate, sodium borate, potassium borate and ammonium borate, monomethylamine, dimethylamine, Trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Use is made of an alkali developer consisting of an aqueous solution of an organic amine compound such as monobutylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and the like in a concentration of about 0.1 to 5% by weight. Among them, alkali metal silicates such as sodium silicate and potassium silicate which are inorganic alkali salts are preferable.

[0091]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Example 1 An aluminum plate (0.24 mm thick) subjected to graining treatment and anodizing treatment was used as a support, and trimethylolpropane triacrylate 100 was used as a component (A) on the aluminum plate support surface. 5 parts by weight of an indole cyanine dye represented by the following formula as a component (B):
2- (p-methoxyphenyl) -4,
5 parts by weight of 6-di (trichloromethyl) -s-triazine and, as a polymer binder, methyl methacrylate / methyl acrylate / methacrylic acid copolymer (molar ratio 70 /
20/10, 100 parts by weight of weight average molecular weight 50000) and 1400 parts by weight of methyl cellosolve were stirred at room temperature for 10 minutes, and the prepared coating solution was applied using a wire bar, and dried at 80 ° C. for 2 minutes. A 2 μm-thick photopolymerizable composition layer is formed, and an aqueous polyvinyl alcohol solution is further applied thereon, and dried at 80 ° C. for 2 minutes to form a 3 μm-thick film.
To form a photopolymerizable lithographic printing plate.

[0093]

Embedded image

The resulting photopolymerizable lithographic printing plate was coated with a diameter of 7c.
m on a rotating drum made of aluminum so that the photopolymerizable composition layer is on the outside, and a beam of a semiconductor laser (manufactured by Applied Techno Co.) of 830 nm and 30 mW was applied.
Using a beam spot focused at 0 μm, 500 to 1
Scanning exposure was performed at various rotation speeds of 000 rpm, and then an alkali developing solution (a negative developing solution “SDN-21” manufactured by Konica Corporation) was used.
(8-fold diluted solution of the above) to form a scanning line image. The higher the maximum number of rotations of the exposure drum on which a line image is formed, the higher the sensitivity is. However, in this embodiment, the maximum number of rotations was 700 rpm.

On the other hand, a lithographic printing plate left for 10 minutes under a white fluorescent lamp having a light intensity of 400 lux (36 W white fluorescent lamp manufactured by Mitsubishi Electric Corporation, "Neorumi Super FLR40S-W / M / 36") was used. The same lithographic printing plate as above was subjected to the same development treatment as described above, and then ink was applied using a developing ink ("PI-2" manufactured by Fuji Photo Film Industry Co., Ltd.). No adhesion of ink was observed, and it was confirmed that there was no difference in the decrease in solubility of the photopolymerizable composition layer by the white fluorescent lamp.

Example 2 The procedure of Example 1 was repeated except that 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine was used as the component (C). When a photopolymerizable lithographic printing plate was prepared and developed, the maximum rotation number of the exposure drum was 700 rpm.

Example 3 The same procedure as in Example 1 was carried out except that an organic borate salt of a salt of n-butyl-triphenylboron anion and tetra-n-butylammonium cation was used as the component (C). When a polymerizable lithographic printing plate was prepared and developed, the maximum rotation number of the exposure drum was 800 rpm.

Example 4 A photopolymerizable lithographic printing plate was prepared and developed in the same manner as in Example 3 except that an indole cyanine dye represented by the following formula was used as the component (B). Had a maximum rotation speed of 600 rpm.

[0099]

Embedded image

Comparative Example 1 Example 1 was repeated except that only the cyanine dye having no substituent substituted by a thioether bond in the indole cyanine dye used in Example 1 was used as the component (B). When a photopolymerizable lithographic printing plate was prepared and developed in the same manner as described above, the maximum rotation number of the exposure drum was 400 rpm or less. In the photopolymerizable composition layer, coating defects due to crystal particles of the cyanine dye were observed.

Comparative Example 2 The procedure of Example 1 was repeated, except that only the cyanine dye having no substituent substituted by a thioether bond in the cyanine dye used in Example 4 was used as the component (B). When a photopolymerizable lithographic printing plate was prepared and developed, the maximum rotation number of the exposure drum was 400 rpm or less. still,
Coating defects due to crystal particles of the cyanine dye were observed in the photopolymerizable composition layer.

Example 5 An aluminum plate (0.24 mm thick) subjected to graining treatment and anodizing treatment was used as a support, and trimethylolpropane triacrylate 100 as a component (A) was placed on the surface of the aluminum plate support. 5 parts by weight of a cyanine dye represented by the following formula as the component (B), 5 parts by weight of 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as the component (C), and Methyl methacrylate / methacrylic acid copolymer (molar ratio 90/10, weight average molecular weight 50,000) as a polymer binder
100 parts by weight of methylcellosolve 700 parts by weight and cyclohexanone 700 parts by weight were stirred to prepare a coating solution, which was applied using a wire bar, and dried at 80 ° C. for 2 minutes to form a 2 μm-thick photopolymerizable composition. Layer, and an aqueous solution containing polyvinyl alcohol and polyvinylpyrrolidone at a polymerization ratio of 90:10 is applied thereon, and dried at 80 ° C. for 2 minutes to form an overcoat layer having a thickness of 3 μm and photopolymerization. A lithographic printing plate was prepared.

[0103]

Embedded image After fixing the obtained photopolymerizable lithographic printing plate on an aluminum rotating drum having a diameter of 7 cm so that the photopolymerizable composition layer is on the outside, a beam of a semiconductor laser (manufactured by Applied Techno) of 830 nm and 30 mW is used. Using a beam spot focused at 20 μm,
, And then developed using an alkali developing solution (8-fold dilution of negative developing solution “SDN-21” manufactured by Konica Corporation) to form a scanning line image. The higher the maximum number of revolutions of the exposure drum on which a line image is formed, the higher the sensitivity is. However, in this embodiment, the maximum number of revolutions was 650 rpm.

On the other hand, a lithographic printing plate left for 10 minutes under a white fluorescent lamp having a light intensity of 200 lux (36 W white fluorescent lamp manufactured by Mitsubishi Electric Corporation, "Neorumi Super FLR40S-W / M / 36") The same lithographic printing plate as above was subjected to the same development treatment as described above, and then ink was applied using a developing ink ("PI-2" manufactured by Fuji Photo Film Industry Co., Ltd.). No adhesion of ink was observed, and it was confirmed that there was no difference in the decrease in solubility of the photopolymerizable composition layer by the white fluorescent lamp.

Example 6 As the component (C), 2- (p-iso-propyloxystyryl) -4,6-bis (trichloromethyl) -s-
Except for using triazine, a photopolymerizable lithographic printing plate was prepared and developed in the same manner as in Example 5, and the maximum rotation number of the exposure drum was 650 rpm.

Example 7 Example 5 was repeated except that an organic borate salt of a salt of n-butyl-tris (m-fluorophenyl) boron anion and tetra-n-butylammonium cation was used as the component (C). Similarly, when a photopolymerizable lithographic printing plate was prepared and developed, the maximum rotation number of the exposure drum was 500 rpm.

Example 8 A photopolymerizable lithographic printing plate was prepared and developed in the same manner as in Example 7 except that a cyanine dye represented by the following formula was used as the component (B). The number is 600r
pm.

[0108]

Embedded image

Comparative Example 3 The procedure of Example 5 was repeated, except that only the cyanine dye having no substituent on the polymethine chain in the cyanine dye used in Example 5 was used as the component (B). When a photopolymerizable lithographic printing plate was prepared and developed, the maximum rotation number of the exposure drum was 200 rpm or less. In the photopolymerizable composition layer, coating defects due to crystal particles of the cyanine dye were observed.

[0110]

According to the present invention, the white fluorescent lamp has high sensitivity to light in the long wavelength region such as the visible region and, consequently, the near infrared region, and has low sensitivity to light in the ultraviolet region. It is possible to provide a photopolymerizable composition and a photopolymerizable lithographic printing plate having excellent handleability underneath. Furthermore, since the photopolymerizable composition of the present invention has excellent solubility in a solvent, the photopolymerizable composition layer can be efficiently formed by coating the support surface as a solution, and productivity can be improved. An excellent lithographic printing plate can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/00 105 C09K 3/00 105 G03F 7/00 503 G03F 7/00 503 7/027 502 7/027 502 F-term (reference) 2H025 AA01 AB03 AC08 AD01 BC13 BC31 CA00 CA14 CA28 CA39 CA42 2H096 AA06 BA05 EA04 4H056 CA02 CB01 CB06 CC02 CC08 CE03 DD03 DD19 FA05 FA06 4J011 QA02 QA13 QA21 QA22 QA23 QA78 QA23 QA78 VA01 WA01

Claims (12)

[Claims] 1. A photopolymerizable composition comprising the following components (A), (B) and (C). (A) an ethylenically unsaturated compound; (B) a dye having a structure in which a hetero atom is bonded via a polymethine chain as a basic structure. A dye having a substituent having an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation, or (B-2) having at least two substituents on a polymethine chain, wherein the two substituents are Dye which resonates in the dye molecule to form a cyclic structure linked by an ether bond generating an oxonium cation or a thioether bond generating a sulfonium cation (C) Photopolymerization initiator 2. The photopolymerizable composition according to claim 1, wherein the dye as the component (B) is a cyanine dye having a basic structure in which a heterocyclic ring is bonded via a polymethine chain. 3. The photopolymerizable composition according to claim 2, wherein the cyanine dye as the component (B) is a near-infrared absorbing dye represented by the following general formula (II). Embedded image [In the formula (II), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ³ and R ⁴ each independently represent an alkyl group which may have a substituent, An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent; L ² represents a substituent in the dye molecule; An ether bond that resonates to produce an oxonium cation,
Or a tri, penta, hepta, nona, or undecamethine group having a substituent having a thioether bond that generates a sulfonium cation, and the penta, hepta, nona,
Alternatively, two substituents on the undecamethine group may be connected to each other to form a cycloalkene ring having 5 to 7 carbon atoms, a cycloalkeneone ring, a cycloalkenedione ring, or a cycloalkenethione ring, and the fused benzene ring It may have a substituent, and in that case, two adjacent substituents may be connected to each other to form a fused benzene ring.
X _a ^- represents a counter anion. ] 4. The dye according to claim 1, wherein the substituent having an ether bond or a thioether bond on the polymethine chain is represented by the following formula (Va). The photopolymerizable composition as described in the above. Embedded image [In the formula (Va), W ¹ represents an oxygen atom or a sulfur atom;
^a represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ] 5. The dye according to claim 1, wherein the substituent having an ether bond or a thioether bond on the polymethine chain in the component (B) is represented by the following general formula (Vb). A photopolymerizable composition. Embedded image [In the formula (Vb), W ¹ represents an oxygen atom or a sulfur atom;
² represents an oxygen atom, a sulfur atom, a nitrogen atom, or a dialkylmethylene group; W ¹ and W ² may be the same or different; the heterocyclic ring is a 4- to 6-membered ring; And in this case, two adjacent substituents may be connected to each other to form a fused benzene ring. ] 6. The method according to claim 1, wherein the substituent having an ether bond or a thioether bond on the polymethine chain in the dye of the component (B) is represented by the following general formula (Vc). A photopolymerizable composition. Embedded image [In the formula (Vc), W ¹ represents an oxygen atom or a sulfur atom, and two W ^1s may be the same or different;
^b is an alkyl group which may have a substituent, an alkoxy group or a thioalkoxy group which may have a substituent, an aryl group which may have a substituent, A heterocyclic group or a hydrogen atom. ] 7. The cyanine dye as the component (B) is a near-infrared absorbing dye represented by the following general formula (II-2).
3. The photopolymerizable composition according to item 1. Embedded image [In the formula (II), Y ¹ and Y ² each independently represent a dialkylmethylene group or a sulfur atom, and R ³ and R ⁴ each independently represent an alkyl group which may have a substituent, L ² represents an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a phenyl group which may have a substituent, and L ² represents a tri having at least two substituents; Penta, hepta, nona, or undecamethine group, wherein two substituents on the penta, hepta, nona, or undecamethine group resonate in the dye molecule to form an oxonium cation, an ether bond, or a sulfonium cation. The two substituents on the penta, hepta, nona, or undecamethine group are linked to each other by a thioether bond to form a cyclic structure. May form a ring, a cycloalkeneone ring, a cycloalkenedione ring or a cycloalkenethione ring, and the fused benzene ring may have a substituent, in which case two adjacent substituents are connected to each other To form a fused benzene ring. X _a ^- represents a counter anion. ] 8. The cyclic structure of the component (B), which is formed by an ether bond or a thioether bond, is represented by the following general formula (VI).
The photopolymerizable composition according to any one of the above. Embedded image [In the formula (VIa), W ³ represents an oxygen atom or a sulfur atom;
^The heterocyclic ring containing ³ represents a 5- or 6-membered ring which may have a substituent, and R ^d represents a hydrogen atom, an alkyl group which may have a substituent, or a substituent which may have a substituent. It represents a good aryl group, an amino group or a halogen atom which may have a substituent. ] 9. W ³ in the formula (VIa) is an oxygen atom,
Heterocycle photopolymerizable composition according to claim 8, characterized in that represent may 6-membered ring optionally having a substituent containing a W ^3. 10. The photopolymerizable composition according to claim 1, wherein the photopolymerization initiator of the component (C) is a bis (trihalomethyl) -s-triazine compound or an organic borate. . 11. The dye of component (B) and the photopolymerization initiator of component (C) are each composed of a dye cation of component (B) and (C)
The photopolymerizable composition according to any one of claims 1 to 10, which is a salt formed with an organic boron anion of an organic borate as a component. 12. A photopolymerizable lithographic printing plate comprising a support and a layer of the photopolymerizable composition according to claim 1 formed thereon.