JP2000267266A - Method for manufacturing lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for manufacturing the lithographic printing plate prevented from occurrence of flares and the like in the direct manufacture of the printing plate by using laser beams and capable of forming a sharp image and having high printing resistance. SOLUTION: The photopolymerizable material for the lithographic printing plate having a photosensitive layer containing a composition to be induced to start photopolymerization by absorbing a visible light and a compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet rays is characterized by being imagewise exposed to visible laser beams and developed and then overall exposed to ultraviolet rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for making a lithographic printing plate. In particular, the present invention relates to a lithographic printing plate making method in which image exposure is performed using a laser beam such as Ar ⁺ , YAG-SHG, or the like.

[0002]

2. Description of the Related Art Negative type lithographic printing plates have been widely known, and various types of photosensitive layers such as a diazo resin-containing type, a photopolymerization type, and a photocrosslinking type are used for such a negative type lithographic printing plate. ing. To create such a lithographic printing plate, it is common to place a transparent negative film original (lith film) on these lithographic printing plates and expose the image using ultraviolet light. It took time and effort. In recent years, with the development of image forming technology, a photopolymer having high photosensitivity to light in the visible region has been demanded. It is a photosensitive material suitable for, for example, non-contact type projection exposure plate making or visible light laser plate making, and a photopolymerization system has the highest sensitivity. As the visible light laser, 48 of Ar laser is used.
8, 514.5 nm light, second harmonic light of semiconductor laser (SHG-LD, 350 to 600 nm), SHG-YAG
Laser light of 532 nm or the like is used.

[0003] Therefore, by using a kind of high-sensitivity photopolymerizable photosensitive layer as the photosensitive layer, a laser beam with a narrow beam is scanned over the plate to form a character document, an image document, etc. directly on the plate. As a result, plate making can be directly performed without using a film original. However, the lithographic printing plate obtained by exposure and development under normal laser scanning conditions has an insufficient degree of curing of the image area, and when used for high-volume printing at high speed, solid images may be missing, thin lines or highlights may not be obtained. There is a problem that the portion becomes thin or the surface flies, and if the intensity of the laser beam is increased in order to obtain a sufficient degree of curing, a phenomenon called flare occurs and the surface image becomes unclear. This is presumably because the increase in the intensity of the laser light causes scattering of the laser light due to dust or the like in the air. For this reason, Japanese Patent Application Laid-Open No. 7-5699 discloses that a lithographic printing plate precursor was image-exposed and developed, and then, an attempt was made to completely cure it by exposing the entire surface. However, sufficient curing of the image area has not yet been achieved.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method of making a lithographic printing plate which can obtain a clear image without causing flare or the like and has high printing durability in laser direct plate making. It is to provide.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventor has conducted intensive studies and as a result, has been able to obtain a clear image by producing a lithographic printing plate using the following photosensitive material and plate making method. It has been found that a lithographic printing plate that can be made and has high printing durability can be obtained. That is, the above-mentioned object is to provide a photosensitive layer of a photopolymerizable lithographic printing plate with a composition that initiates photopolymerization by absorbing visible light, and a compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light. After performing visible light laser exposure and further development, and then performing overall exposure with ultraviolet light.

According to the method of the present invention, when a photopolymerizable lithographic printing plate is image-exposed by a laser exposure apparatus, the exposure can be performed with a low exposure amount, and a clear image can be obtained by preventing a decrease in resolution due to scattering of flare and the like. be able to. Then, after developing the photopolymerizable lithographic printing plate subjected to image exposure in this manner and removing the non-image portion, by performing the entire surface exposure with ultraviolet light, the image portion of the image portion was insufficient with the image exposure amount The degree of curing can be increased. By such a plate making method, a clear image can be obtained and a lithographic printing plate having high printing durability can be obtained. The reason for obtaining such a result is presumed as follows. That is, the image area exposed to the laser image is not necessarily completely cured, and a part of the components such as the initiator is eluted by the penetration of the developer. For this reason, the effect at the time of overall exposure after development is reduced. In contrast, compounds having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light are eluted into the developing solution during development because the polymerizable unsaturated group and the polymerization initiating group are in the same molecule. In addition, such compounds are highly efficient, so that the overall exposure to light after development has a great effect of improving image strength. Further, by further heating at the time of overall exposure after the development, preferably at a plate surface temperature of 30 to 150 ° C., a lithographic printing plate having higher printing durability can be obtained.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described below in detail. On the surface of the support, a composition that initiates photopolymerization by absorbing visible light, and a compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light, provided with a photosensitive layer containing a, After image exposure with a constant exposure amount by a laser exposure device and development, post-processing such as desensitization treatment is optionally performed. By performing overall exposure with ultraviolet light after or before the post-treatment, a lithographic printing plate having a surprisingly clear image and high printing durability was obtained.

[Compound Having a Polymerizable Unsaturated Group and a Polymerization Initiating Group Sensitive to Ultraviolet Radiation] First, the polymerizable unsaturated group contained in the photosensitive layer of the photopolymerizable lithographic printing plate, which is a feature of the method of the present invention. The compound having a group and a polymerization initiating group sensitive to ultraviolet light will be described. The polymerization initiation group of this compound which is sensitive to ultraviolet light is preferably a photopolymerization initiation group having sensitivity to light in the ultraviolet region. Specifically, 46
Those having no sensitivity at 0 nm or more and having sensitivity at 430 nm or less are preferable. Examples include benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, halomethyltriazine compounds, titanocene compounds,
Ferrocene compounds, hexaarylbiimidazole, organic peroxides, and the like can be given.

[0009] The introduction of a polymerizable unsaturated group into these compounds can be performed by known methods, for example, in Japanese Patent No. 2,736,678.
JP-A No. 7-509500, JP-A No. 1-3
19504, JP-A-5-239117, U.S. Pat. No. 5,248,805, JP-A-6-2117
No. 58, and the like.

Examples of such compounds include the following general formulas (1) to (4). However, none of the general formulas (1) to (4) limit the content of the present invention. First, a compound having a structure represented by the general formula (1) [compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light] is shown below.

[0011]

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Here, A is a group selected from the group consisting of mono-, di- and trihalomethyl groups, and Y is-
_{A, -L -, - NH 2} , -NHR, -NR 2, -OR , and -R '(wherein, R represents each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group , R ′ is a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted alkenyl group or substituted polyalkenyl group, substituted alkynyl group or substituted polyalkynyl group, and substituted or unsubstituted heteroaromatic group). A group selected from the group. L is a group or a covalent bond for linking the triazine nucleus to the compound having a polymerizable unsaturated group, and M is a site having a polymerizable unsaturated group. In many cases, L is useful for a bonding reaction or a polymerization reaction with a compound having a polymerizable unsaturated group in order to prepare a compound having a polymerizable unsaturated group containing a halomethyl-1,3,5-triazine moiety. Is selected to contain a reactive group or a polymerizable group. Contained in L
Typical reactive groups useful for coupling or polymerization reactions include hydroxyl; isocyanates; amines; carboxylic acids; acrylates, methacrylates, vinyl esters,
Vinyl monomers such as acrylamide, methacrylamide, and styrene; vinyl esters; and cyclic ethers. In other cases, L is selected to include a reactive group capable of binding a functional group that is bound to a compound having a preformed polymerizable unsaturated group. Examples of such reactive groups include, but are not limited to, isocyanate; hydroxyl; amine; carboxyl; acid anhydride; Hereinafter, specific examples of the compound having the structure represented by the general formula (1) will be shown. However, these do not limit the content of the present invention.

[0013]

[Table 1]

[0014]

[Table 2]

However, according to the above table, the compounds of the present invention
Halomethyl group suitable for the product is -CCl _ThreeConsidered to be limited to
Should not be.

Next, compounds having a structure represented by the general formula (2) [compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light] are shown below.

[0017]

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[Wherein, R^aIs H, Cl, CN, C_1-4−
X is CO-, COO
-, O-CO-, (CH_Two)_nY, COO (CH_Two)_nY,
CO (OCH_TwoCH_Two)_nY (where n = 1 to 10
And Y is a single bond, -O-, -S-, -CO-,-
COO-, -OCO-, -NH- or -N (C _1-4−
Alkyl)-), m is 0 or 1,
IN is the basic structure of the photoinitiator,

[0019]

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(Wherein R is -CR ³ R ⁴ R ⁵ or -P
(＝ O) (R ⁶ ) ₂ , wherein R ¹ and R ² are H, halogen, C _1-12 -alkyl or C _1-12 -alkoxy, and R ³ and R ⁴ are independently of each other , Respectively, H,
C _1-12 -alkyl, C _1-12 -alkenyl, C _1-12 -alkoxy or together is C _2-6 -alkylene, and R ⁵ is —OH, C _1-6 -alkoxy , C _1-6 −
Alkanoyloxy, -N (C _{1 -6} - alkyl) _2,

[0021]

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--SO ₂ R ⁷ or --OSO ₂ R ⁷ ,
⁶ is C _1-6 -alkyl, C _1-6 -alkanoyl, phenyl or benzoyl, any of which is optionally substituted by halogen, C _1-6 -alkyl or C _1-6 -alkoxy R ⁷ may be C _1-4
-Alkyl or phenyl).

Hereinafter, specific examples of the compound having the structure represented by the general formula (2) will be shown. However, these do not limit the content of the present invention. 4-vinylphenyl-2-hydroxy-2-propyl ketone (2a) 4-allyloxyphenyl 2-hydroxy-2-propyl ketone (2b) 4-2-allyloxyethoxyphenyl 2-hydroxy-2-propyl ketone (2c ) Vinyl 4- (2-hydroxy-2-methylpropionyl) phenoxy acetate (2d) 4-acryloyloxyphenyl 2-hydroxy-2-propyl ketone (2e) 4-methacryloyloxyphenyl 2-hydroxy-2-propyl ketone (2f ) 4-2-Acryloyloxyethoxyphenyl 2-hydroxy-2-propyl ketone (2 g) 4-2-methacryloyloxyethoxyphenyl 2-hydroxy-2-propyl ketone (2h) 4-2-acryloyloxydiethoxyphenyl 2- Hydroxy-2-propyl ketone (2i) 4-2 Acryloyloxyethylthiophenyll 2-hydroxy-2-propylketone (2j) 4-2-acryloyloxyethylthiophenyl 2-N-morpholino-2-propylketone (2k) 2- [2- (acryloyloxy) ethylthio Thioxanthone (2l) 2- [2- (acryloylamino) ethylthio] thioxanthone (2m) 2- [2- (allyloxy) ethylthio] thioxanthone (2n) 2- [2- (allylamino) ethylthio] thioxanthone (2o) 4- [2- (methacryloyloxy) ethoxycarbonyl] thioxanthone (2p)

Next, a compound having a structure represented by the benzophenone derivative represented by the general formula (3) [compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light] is shown below.

[0025]

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In the formula, R ¹ , R ² and R ³ may be the same or different and each represents an alkyl group or a cycloalkyl group; R ⁴ represents a hydrogen atom or a methyl group;
To 20. R ¹ and R ² may combine with each other to form a ring, or may form a ring condensed with a benzene ring.

In the general formula (3), R ¹ , R ² and R
Among the groups represented by ³ , an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms are preferable. Among them, an alkyl group having 2 to 8 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group are preferable. When R ¹ and R ² form a ring, a 5- to 7-membered ring containing a nitrogen atom is preferred. When R ¹ and R ² form a ring condensed with a benzene ring, those represented by the following formula are preferred.

[0028]

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In the general formula (3), among the integers represented by n, 3 is particularly preferable, and in this case, the carbon chain represents (CH ₂ ) ₃ .

Specific examples of the compound having the structure represented by the general formula (3) are shown below, but the present invention is not limited thereto.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The following are compounds having a structure represented by the general formula (4) [compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light].

[0037]

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Wherein X ^- represents one equivalent of an anion;
R ⁵ represents a hydrogen atom or a methyl group; each R ⁴ independently represents a methyl or ethyl group and R ¹ , R ² and R
³ is each independently a hydrogen or halogen atom, 1
An alkyl, alkoxy or alkylthio group having 4 to 4 carbon atoms, an arylthio group or a formula:

[0039]

Embedded image (Wherein R ⁴ , R ⁵ and X ⁻ have the meanings given above)]. The arylthio group can be, for example, a p-toluylthio group. Preferably R
¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms or a formula;

[0040]

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Represents the group of More preferably, R ² and R ³
Both represent a hydrogen atom and R ¹ is a hydrogen atom, a halogen atom, an alkyl or alkoxy group having 1 to 4 carbon atoms or a formula:

[0042]

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Represents a group represented by Particularly preferably, R ² and R ³
Represents a hydrogen atom and R ¹ represents a hydrogen atom, a chlorine atom, a methoxy group or a tert-butyl group. Preferably each R ⁴ is a methyl group. Preferably, R ⁵ represents a hydrogen atom. Preferably X ^- represents a halogen ion, such as a chloride ion or more preferably a bromide ion.

The group in the compound of the general formula (4):

[0045]

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Can be in the ortho, meta or para position to the benzoyl group. Preferably, this group is in the para position. Preferably, the group R ¹ is located para to the benzoylcarbonyl group.

Specific compounds include 4-benzoyl-N, N-dimethyl-N- (2- (1-oxo-2-propenyloxy) ethyl) benzenemethanaminium bromide and 4-benzoyl-N, N -Dimethyl-N-
(2- (2-methyl-1-oxo-2-propenyloxy) ethyl) benzenemethaneaminium chloride, 3
-Benzoyl-N, N-dimethyl-N- (2- (1-oxo-2-propenyloxy) ethyl) benzenemethanaminium bromide, 4- (4-chlorobenzoyl)
-N, N-dimethyl-N- (2- (1-oxo-2-propenyloxy) ethyl) benzenemethanaminium bromide, 4- (4-methoxybenzoyl) -N, N-
Dimethyl-N- (2- (1-oxo-2-propenyloxy) ethyl) benzenemethanaminium bromide;
4- (4-tert-butylbenzoyl) -N, N-dimethyl-N- (2- (1-oxo-2-propenyloxy) ethyl) benzenemethanaminium bromide, etc., but the present invention It is not limited by these.

[Composition Initiating Photopolymerization by Absorbing Visible Light] Next, by absorbing visible light contained in the photosensitive layer of the photopolymerizable lithographic printing plate used in the method of the present invention, light is absorbed. The composition that initiates polymerization will be described. The composition that initiates photopolymerization by absorbing visible light includes “(a) a compound having an ethylenically unsaturated bond capable of addition polymerization” and “(b) a polymerization initiator that absorbs visible light and And a photopolymerization initiator system comprising a sensitizer that activates the polymerization initiator. Among the components of the composition that initiates photopolymerization by absorbing visible light, the monomer component “(a) a compound having an addition-polymerizable ethylenically unsaturated bond” includes a terminal ethylenically unsaturated bond. At least one,
Preferably, it can be arbitrarily selected from compounds having two or more. For example, those having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds.

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 pentaacrylate, dipentaerythritol hexaacrylate, sorbitol Triacry Over DOO, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate 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, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetritaconate.

As the crotonic acid ester, 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. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Further, a mixture of the above-mentioned ester monomers can also be used.

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. Another example is JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound having two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula (aa) is added is exemplified. CH ₂ = C (Q ¹ ) COOCH ₃ CH (Q ² ) OH (aa) (However, Q ¹ and Q ² are independently H or CH ₃
Is shown. )

Further, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. In addition, Journal of the Adhesion Society of Japan Vol. 20, No. 7, 300-30
8 (1984) as photocurable monomers and oligomers can also be used. In addition, the amount of these used is 5-70 with respect to all components.
% By weight (hereinafter abbreviated as%), preferably 10 to 50%
%.

Photopolymerization comprising the component "(b) a polymerization initiator and a sensitizer which absorbs visible light and activates the polymerization initiator" contained in the composition which initiates photopolymerization by absorbing visible light. As the "initiator system", various photoinitiators known in patents and literature, or a combination system of two or more photoinitiators (photoinitiation system) are appropriately selected depending on the wavelength of the light source used. Although it can be used, those having sensitivity in the visible light region are preferred in the present invention. For example, when light near 400 nm is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used. In addition, visible light of 400 nm or more, Ar
Laser, second harmonic of semiconductor laser, SHG-YA
In the case of using a G laser as a light source, various photo initiation systems have been proposed, for example, US Pat. No. 2,850,445.
Certain photoreducing dyes such as rose bengal, eosin, erythrosine, and the like, or a system using a combination of a dye and an initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189). No.), a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-37377), and a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528; 54-1552
No. 92), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024),
3-Ketocoumarin and activator system (JP-A-52-1126)
No. 81, JP-A-58-15503), a system of biimidazole, styrene derivative and thiol (JP-A-59-14)
No. 0203), a system of an organic peroxide and a dye (Japanese Unexamined Patent Publication No.
No. 1504, JP-A-59-140203, JP-A-59-140203
No. 189340, JP-A-62-174203, JP-B-62-1041, U.S. Pat. No. 4,766,055.
No.), a system of a dye and an active halogen compound (JP-A-63-1)
78105, JP-A-63-258903, JP-A-2
63054), a system of a dye and a borate compound (JP-A-62-143044, JP-A-62-150242).
JP-A-64-13140, JP-A-64-1314
No. 1, JP-A-64-13142, JP-A-64-131
No. 43, JP-A-64-13144, JP-A-64-17
No. 048, JP-A-1-229003, JP-A-1-29
No. 8348, JP-A-1-138204 and the like, a system of a dye having a rhodanine ring and a radical generator (JP-A-2-138).
No. 179643, JP-A-2-244050), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-221).
No. 110), a system in which a titanocene is combined with a xanthene dye and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-4-22195).
8, JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061)
No.) and a dye system having titanocene and a benzopyran ring (Japanese Patent Application No. 7-164585).

Preferred photopolymerization initiator systems include a photopolymerization initiator system containing at least one compound selected from the group consisting of a trihalomethyltriazine compound and a titanocene compound, and the following general formulas (I) and (II). Examples include photopolymerization initiator systems containing at least one compound selected from the group consisting of the compounds shown. More preferred photopolymerization initiator systems include those containing a combination of the dyes represented by formulas (I) and (II) with a trihalomethyltriazine compound and / or a titanocene compound. Further, compounds of formulas (A), (B) and (C) may be included as sensitizers. Examples of the trihalomethyltriazine compound include a compound represented by the following general formula (III).

[0056]

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Wherein Hal represents a halogen atom.
^TwoIs -C (Hal)_Three, -NH_Two, −NHR^{twenty one}, -NR ^{twenty one} _Two, -OR^{twenty one}The table
I forgot. Where R^{twenty one}Is an alkyl group, a substituted alkyl group,
And a substituted aryl group. Also R²⁰Is -C (Hal)
_Three, An alkyl group, a substituted alkyl group, an aryl group,
Represents a reel group or a substituted alkenyl group. )
Compound. Specifically, Wakabayashi et al., Bull. Chem. Soc. Jap
compounds described in An, 42, 2924 (1969)
For example, 2-phenyl 4,6-bis (trichloromethyl)-
S-triazine, 2- (p-chlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2-
(P-tolyl) -4,6-bis (trichloromethyl)-
S-triazine, 2- (p-methoxyphenyl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
(2 ', 4'-dichlorophenyl) -4,6-bis (g
(Lichloromethyl) -S-triazine, 2,4,6-tri
(Trichloromethyl) -S-triazine, 2-methyl
-4,6-bis (trichloromethyl) -S-triazi
, 2-n-nonyl-4,6-bis (trichloromethy
) -S-triazine, 2- (α, α, β-trichloro)
Ethyl) -4,6-bis (trichloromethyl) -S-to
Riadin and the like. In addition, British Patent No. 1388
No. 492, for example, 2-styryl
-4,6-bis (trichloromethyl) -S-triazi
, 2- (p-methylstyryl) -4,6-bis (tri
Chloromethyl) -S-triazine, 2- (p-methoxy)
(Styryl) -4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methoxystyryl) -4-amido
No. 6-trichloromethyl-S-triazine and the like
Compounds described in 53-133428, for example, 2-
(4-methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (4-ethoxy
(Sinaphth-1-yl) -4,6-bis-trichlorme
Tyl-S-triazine, 2- [4- (2-ethoxyethyl
Ru) -Naphth-1-yl] -4,6-bis-trichloro
Methyl-S-triazine, 2- (4,7-dimethoxy-
Naphth-1-yl] -4,6-bis-trichloromethyl
-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
Compounds described in DE 3337024, for example
For example, the following compounds can be mentioned.

[0058]

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[0059]

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Also, J. Org. Ch. By FC Schaefer et al.
em .; 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl)-
S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,8-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-
6-Tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned. Further, JP-A-65-2824
The compounds described in No. 1 include, for example, the following compounds.

[0061]

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[0062]

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Further, compounds described in JP-A-5-281728, for example,

[0064]

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And the like. As the titanocene compound, for example, known compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl,
Di-cyclopentadienyl-Ti-bis-2,4,6-
Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-
Difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2 , 3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-T
Examples thereof include i-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium and the like.

Formula (I) or (II) used in “(b) a photopolymerization initiator system comprising a polymerization initiator and a sensitizer that absorbs visible light to activate the polymerization initiator”. The compounds represented are the following compounds.

[0068]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group Or A represents an aralkyl group, wherein A is an oxygen atom, a sulfur atom,
Represents a selenium atom, tellurium atom, alkyl or aryl substituted nitrogen atom, or dialkyl substituted carbon atom. X represents a nonmetallic atom group necessary to form a nitrogen-containing hetero five-membered ring. Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group; To form a ring. )

[0070]

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[0071] (wherein, R ³ to R ⁵ are independently of each other, represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. Further, R ³ ~
R ⁵ may form a ring consisting of a non-metallic atom together with the carbon atoms to which they can each be attached. R ⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁵ is a radical or -Z-R ⁷ is represented by R ^7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group or arylene dicarbonyl group. R ⁷ and R ⁸ may together form a ring composed of a nonmetallic atom.
A represents O, S, NH or a nitrogen atom having a substituent. B is a group

[0072]

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And G ₁ and G ₂ may be the same or different and each represents a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group. Group, arylsulfonyl group or fluorosulfonyl group. However, G ₁ and G ₂ are not simultaneously hydrogen atoms. G ₁ and G ₂ may form a ring composed of a non-metal atom together with a carbon atom. Examples of the compound represented by formula (I) or (II) include JP-A-8-129257 and JP-A-8-33.
And the compounds described in JP-A-4897. Examples of the compound represented by the general formula (I) include a compound represented by the following chemical formula.

[0074]

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Preferred specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s -Butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, allyl group, 1-
Propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenyl group, 2-propynyl group, 2
-Butynyl group, 3-butynyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-feethyl group, p-methylbenzyl group, cinnamyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group , Allyloxyethyl group, methoxyethoxyethyl group,
Ethoxyethoxyethyl, morpholinoethyl, morpholinopropyl, sulfopropyl, sulfonatopropyl, sulfobutyl, sulfonatobutyl, carboxymethyl, carboxyethyl, carboxypropyl, methoxycarbonylethyl, 2-ethylhexyl Oxycarbonylethyl group, phenoxycarbonylmethyl group, methoxycarbonylpropyl group, N-methylcarbamoylethyl group, N, N-ethylaminocarbamoylmethyl group, N-phenylcarbamoylpropyl group, N-tolylsulfamoylbutyl group, p- Toluenesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group, phosphonoethyl group, phosphonopropyl group, p-phosphonobenzylaminocarbonylethyl group, phosphana Methyl group, phosphonium Juana preparative propyl, phosphate Juana preparative butyl group, and a p- phosphate Juana preparative -benzylaminocarbonyl ethyl group.

Next, examples of the above R ² are shown below. R ² is -R
²³ -C (R ²⁴ ) = C (R ²⁵ ) (R ²⁶ ), and -R ²⁷
Represented by -C≡C-R ^28, a substituted or unsubstituted alkenyl group, alkynyl group, an alkenyl group,
Alternatively, it is an alkynyl group. Where R ²³ and R ²⁷
Represents a covalent bond or a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, more preferably a covalent bond or a linear chain having 1 to 6 carbon atoms, 2 carbon atoms. Represents a branched alkylene group of up to 8 and a cyclic alkylene group having 5 to 10 carbon atoms. R ²⁴ ,
R ²⁵ , R ²⁶ and R ²⁸ represent a hydrogen atom, a halogen atom,
Represents an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. More preferred substituents for R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁸ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. Preferred specific examples of R ² include an allyl group, a 2-butenyl group, a 3-butenyl group,
2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 5-hexenyl group, 2-octenyl group, 7-octenyl group, 1-methylpropenyl group, 1,1-dimethylpropenyl group, 2-methylpropenyl group, 2-ethylpropenyl group, 3,3-dimethylpropenyl group, 2-cyclohexenyl group, geranyl group (7,7,3,3-tetramethyl-2,6-heptadienyl group), citronenyl group (7,7,3 -Trimethyl-5-heptenyl group), 2-
Chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-pentynyl group, 1,1-dimethylpropynyl group, 1,1-diethylpropynyl Group, 4,4-dimethyl-2-butynyl group, vinyl group, chloroethynyl group, 1-
Examples include a propenyl group, a 1-butenyl group, a styryl group, an ethynyl group, and a 2-phenylethynyl group. R
The most preferred examples of ^2, can be exemplified allyl group, 2-propynyl group, a vinyl group, an ethynyl group. Next, preferred specific examples of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are shown below.

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

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Next, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R
Preferred examples of ¹⁸ are shown below.

[0081]

[Table 5]

[0082]

[Table 6]

[0083]

[Table 7]

The partial skeletons (a) represented by the above (a-1) to (а-65) and the partial skeletons (b) represented by the above (b-1) to (b-72) are sequentially combined to form a general Formula (I)
(R ¹ and R ²⁾
Can be arbitrarily selected from the groups described above. ). Preferred specific examples of the compound represented by formula (I) are shown below.

[0085]

[Table 8]

[0086]

[Table 9]

[0087]

[Table 10]

[0088]

[Table 11]

[0089]

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The compounds represented by the general formula (II) include the following compounds. The concentration of these photopolymerization initiator systems in the composition of the present invention is usually low. In addition, when the number is inappropriately large, undesired results such as blocking of the effective light beam occur. The amount of the photopolymerization initiator system in the present invention is 0.01 to the total of the compound having a photopolymerizable ethylenically unsaturated double bond and the linear organic high molecular weight polymer added as necessary. Preferably, it is used in the range of from 70% by weight to 70% by weight. More preferably, 1% to 50% by weight gives good results.

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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Specific examples of the compounds of the formulas (A) to (C) which are sensitizers of the photopolymerization initiator system used in the present invention include:
The following can be mentioned.

[0101]

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Here, Ar represents an aromatic group selected from one of the following general formulas, R ³ and R ⁴ represent a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other. It may represent an alkylene group.

[0103]

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In the formula, R ^{5 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, a carbon atom. An alkoxy group of 1 to 12 groups, a hydroxyl group,-
Represents a SR ¹¹ group, a -SO-R ¹¹ group, a -SO ₂ -R ¹¹ group, wherein R ¹¹ is an alkyl group or an alkenyl group, R ¹⁰ is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, or It represents an acyl group having 2 to 13 carbon atoms. These alkyl group, aryl group, alkenyl group, and acyl group may be further substituted with a substituent having 1 to 6 carbon atoms.

[0105]

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Here, R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³ and R ⁴ may combine to represent an alkylene group. Specific examples include U.S. Pat. No. 4,318,791 and EP 0284.
The following compounds described in No. 561A can be exemplified.

[0107]

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[0108]

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Next, the following general formula (B) used in the present invention:
The ketoxime compound represented by is described.

[0110]

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In the formula, R ¹² and R ¹³ are the same or different and represent a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group. R ¹⁴ and R ¹⁵ are the same or different and each represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, Represents a thio group. R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, and —O—, —NR ¹⁶ —, —O—CO—, and —N
H-CO -, - S-, and / or, -SO ₂ - represents an alkylene group having from 2 carbon atoms which may contain a linking backbone of the ring 8. R ¹⁶ and R ^{17 each} represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. Specific compounds include the following, but are not limited thereto.

[0112]

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[0113]

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[0114]

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[0115]

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Next, the following general formula (C) used in the present invention:
The oxime ether compound represented by is described.

[0117]

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In the formula, R ^{1 to} R ⁴ represent an alkyl group or an aryl group, and Ar represents an aryl group. R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form a ring. Z
Represents a hydrocarbon-containing linking group which may have a divalent substituent.

[0119]

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2 containing at least one group represented by
Represents a valent linking group or a single bond. Here, R ⁵ represents a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a carbonyl group or a sulfonyl group. R ^{5 to} R ⁸ are the same or different from each other, and represent a hydrocarbon group which may have a substituent or may contain an unsaturated bond. T ⁻ represents a monovalent anion composed of a halogen atom or a monovalent sulfonate anion. X is a group having an addition-polymerizable group represented by the following formula (Ca).

[0121]

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And r¹~ R^ThreeAre the same or different from each other
Hydrogen, methyl, ethyl, phenyl, halo
Gen atom, cyano group or -C (= O) -OR⁹Represents
n represents 0 or 1. However, when n is 0, r¹~ R^ThreeEverything
It does not become a hydrogen atom. r ^Four, R^FiveAre identical to each other
Is different from hydrogen atom, methyl group, ethyl group or phenyl
Represents a group. R⁹Represents an alkyl group or an aryl group.

The oxime ether compound represented by formula (C) used in the present invention will be described in detail. Examples of the alkyl group or aryl group for R ^{1 to} R ⁴ in the general formula (C) include the following groups. Examples of the alkyl group include straight-chain, branched and straight-chain alkyl groups having 1 to 20 carbon atoms.
Or a cyclic alkyl group, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl group,
Tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group,
Examples thereof include a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

These alkyl groups can form a substituted alkyl group by a bond between a substituent and an alkylene group. As the substituent, a monovalent nonmetallic atomic group other than hydrogen is used,
Preferred examples include a 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,
An N-dialkylcarbamoyloxy group, an N, N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group,

Alkylsulfoxy, arylsulfoxy, acylthio, acylamino, N-alkylacylamino, N-arylacylamino, ureido, N'-alkylureido, N ', N'-dialkyl Ureido group, N'-arylureido group, N ', N'
-A diaryl ureide group, an N'-alkyl-N'-aryl ureide group, an N-alkyl ureide group, an N-aryl ureide group, an N'-alkyl-N-alkyl ureide group, an N'-alkyl-N-aryl ureide group , N ',
An 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-
An N-alkylureido group, an N′-alkyl-N′-aryl-N-arylureido group,

An alkoxycarbonylamino group, an aryloxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, Aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and its conjugate base group (hereinafter, referred to as carboxylate), alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, An N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, an N, N-diarylcarbamoyl group,
N-alkyl-N-arylcarbamoyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO
₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxy sulfonyl group, ant - Rokishisuruhoniru group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfinamoyl group, N-
Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N −
Arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and its conjugate base group, N-alkylsulfonylsulfamoyl group ( -SO
₂ NHSO ₂ (alkyl)) and its conjugate base group, N-
Arylsulfonylsulfamoyl group (—SO ₂ NHS
O ₂ (aryl)) and its conjugate base group, N-alkylsulfonylcarbamoyl group (—CONHSO ₂ (alk
yl)) and its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group,

An alkoxysilyl group (—Si (Oalky)
l) ₃ ), an aryloxysilyl group (—Si (Oary
l) ₃ ), a hydroxysilyl group (—Si (OH) ₃ ) and its conjugate base group, a phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, referred to as a phosphonate group), a dialkylphosphono group ( —PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ), alkylarylphosphono group (—PO ₃ (alkyl) (aryl)), monoalkylphosphono group (—PO ₃ H) (Alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (ary
l)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), phosphonooxy group (-OPO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonatooxy group), dialkylphosphono group (-OPO ₃ (alky
l) ₂ ), a diarylphosphonooxy group (—OPO ₃ (a
ryl) ₂ ), an alkylarylphosphonooxy group (-
OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonatooxy group), monoarylphosphonooxy group (− OPO ₃ H
(Aryl)) and its conjugate base group (hereinafter, referred to as arylphosphonatooxy group), cyano group, nitro group, aryl group, alkenyl group, and alkynyl group.

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, and mesityl groups. , Cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylca Ba carbamoylphenyl group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group,
And a phosphonatophenyl group. Examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-
Examples thereof include a 1-ethenyl group and the like, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and a phenylethynyl group. Examples of the acyl group (R ¹⁰ CO—) include a hydrogen atom for R ¹⁰ and the above-described alkyl, aryl, alkenyl, and alkynyl groups.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the above hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a linear 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. Specific examples of preferred substituted alkyl groups 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, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, allyloxycarbonylmethyl Group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group,
N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N
-(Sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N
-Tolylsulfamoylpropyl group, N-methyl-N-
(Phosphonophenyl) sulfamoyloctyl group,

[0130]

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A phosphonobutyl group, a phosphonatohexyl group, a diethylphosphonobutyl group, a diphenylphosphonopropyl group, a methylphosphonobutyl group, a methylphosphonatobutyl group, a tolylphosphonohexyl group, a tolylphosphonatohexyl group, a phosphonooxy group Propyl 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, etc. Can be given.

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. And 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.

These aryl groups can form a substituted aryl group in which a substituent is bonded to an aryl group. As the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. 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 these substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, Hydroxyphenyl group,
Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methylbenzoylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chloro Phenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, -(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, diethylphosphonophenyl group, Diphenylphosphonophenyl, methylphosphonophenyl, methylphosphonatophenyl, tolylphosphonophenyl, tolylphosphonatophenyl, allylphenyl, 1-propenylmethylphenyl, 2-butenylphenyl, 2
-Methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

Next, the case where R ¹ and R ² are bonded to each other to form a ring will be described. Rings in which R ¹ and R ² are bonded to each other include —O—, —OC (＝ O) —, —S—,
Examples thereof include an alkylene group having 2 to 8 carbon atoms which may contain -NH-C (= O)-in the connecting main chain. Next, R ³ and R ⁴
Are bonded to each other to form a ring. The ring in which R ³ and R ⁴ are bonded to each other is —O—,
Examples thereof include an alkylene group having 2 to 8 carbon atoms which may contain -OC (= O)-, -S-, and -NH-C (= O)-in the connecting main chain. Next, Ar in the general formula [C] will be described. Aryl groups represented by Ar have the same meanings as those described in R ¹ to R ^4, may constitute the same substituted aryl group as R ¹ to R ^4.

Next, Z in the general formula (C) will be described in detail. Examples of the hydrocarbon-containing linking group which may have a divalent substituent in Z in the general formula (C) include a divalent hydrocarbon obtained by removing one hydrogen from carbon on either an alkyl group or an aryl group. And a linking group. These alkyl groups or aryl groups have the same meanings as those described above for R ^{1 to} R ⁴ and can form a substituted alkyl group or a substituted aryl group. Next, Y will be described in detail. Examples of the divalent linking group for Y include a divalent linking group obtained by removing one hydrogen from carbon on either an alkyl group or an aryl group. Here, the alkyl group and the aryl group have the same meanings as those described above for R ^{1 to} R ⁴ . Next, R ^{5 to} R ^{8 in} Y will be described in detail. Examples of the hydrocarbon group which may have a substituent of R ^{5 to} R ⁸ and may contain an unsaturated bond include an alkyl group, an aryl group, an alkenyl group and an alkynyl group.
Here, the alkyl group, aryl group, alkenyl group, and alkynyl group have the same meanings as those described above for R ^{1 to} R ⁴ . Further, in a substituted alkenyl group in which a substituent replaces and is bonded to a hydrogen atom of an alkenyl group, as the substituent, the substituent in the above-mentioned substituted alkyl group is used,
On the other hand, the above-mentioned alkenyl group can be used as the alkenyl group. Examples of preferred substituted alkenyl groups include

[0136]

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And the like. In the substituted alkynyl group in which the substituent is replaced by a hydrogen atom of the alkynyl group and bonded, as the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkynyl group can be the above-mentioned alkynyl group.

Next, the carbonyl group and the sulfonyl group of R ⁵ will be described. As the carbonyl group (R ¹¹ —CO—), those in which R ¹¹ is a monovalent nonmetallic atomic group can be used. Preferred examples of the carbonyl group include 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 and N-alkyl-N-arylcarbamoyl group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group and the aryl group. Of these, more preferred substituents include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, and N-arylcarbamoyl. And even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituents include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, allyloxycarbonyl, N-methylcarbamoyl, N-phenylcarbamoyl, N, N-diethylcarbamoyl, And a morpholinocarbonyl group.

As the sulfonyl group (R ¹² —SO ₂ —), those in which R ¹² is a monovalent nonmetallic atomic group can be used. More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group and the aryl group. Specific examples of such a sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

Next, T ^- will be described in detail. Examples of the halogen atom of T ⁻ include F, Cl, Br, and I, and examples of the sulfonate anion include any of the alkyl groups and aryl groups represented by R ^{1 to} R ⁷ above, and a sulfonato group (—S
O ₃ ⁻ ) is linked. Preferably,
Examples thereof include a methylsulfonic acid anion, a trifluoromethylsulfonic acid anion, a benzenesulfonic acid anion, and a toluenesulfonic acid anion.

Next, X will be described in detail. The alkyl group or aryl group for R ⁹ in X has the same meaning as that described above for R ^{1 to} R ⁵ , and may form a substituted alkyl group or a substituted aryl group. Examples of the compounds are shown below, but the compounds are not limited thereto.

[0142]

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[0143]

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[0144]

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[0145]

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[0147]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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And the like.

[Binder] Next, the binder contained in the photosensitive layer of the photopolymerizable lithographic printing plate used in the method of the present invention as a component other than the above-mentioned composition and compound will be described. As the binder, an organic high molecular polymer may be mentioned, but as such an organic high molecular polymer, as long as it is an organic high molecular polymer having compatibility with a photopolymerizable ethylenically unsaturated compound. , Any of which may be used.
Preferably, an organic high molecular polymer which is soluble or swellable in water or weakly alkaline water which enables water development or weakly alkaline water development is selected. The organic high molecular polymer is selected and used not only as a film-forming agent of the composition but also as a developer for water, weakly alkaline water or an organic solvent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Such organic high molecular polymers include:
Addition polymers having a carboxylic acid group in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25959, and JP-A-54-92723. JP-A-59-53836,
JP-A-59-71048, namely, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Acid copolymers and the like.

Similarly, there are acidic cellulose derivatives 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 / optionally And other addition-polymerizable vinyl monomers] copolymers.
In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, an alcohol-soluble polyamide, a polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These organic high-molecular polymers can be mixed in an arbitrary amount in the entire composition. However, when the content exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 10-90%, more preferably 30%
~ 80%. The weight ratio of the ethylenically unsaturated compound capable of addition polymerization and the organic high molecular weight polymer is 1/9 to 9/1.
It is preferable to set it in the range. A more preferred range is 2/8.
To 8/2, and more preferably 3/7 to 7/3.

[Other Components Included in Photosensitive Layer of Photopolymerizable Lithographic Printing Plate] In the photosensitive layer of the photopolymerizable lithographic printing plate used in the method of the present invention, in addition to the above basic components, a photosensitive layer is used. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during production or storage of the hydrophilic composition.
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-nitrosophenylhydroxylamine, aluminum aluminum N-nitrosophenylhydroxylamine and the like. The addition amount of the thermal polymerization inhibitor is about 0.0
1% to about 5% is preferred. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

A coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the colorant include phthalocyanine pigments (CIPigment Blue 5: 3, 15: 4, 1).
5: 6, etc.), azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, cyanine dyes. 0.5% to about 5% is preferred. In addition, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The amount of these additives is preferably 10% or less of the total composition. A surfactant can be added to the photosensitive (photopolymerizable) composition of the present invention in order to improve the coated surface quality.

The photopolymerizable lithographic printing plate used in the method of the present invention is prepared by coating the above photopolymerizable composition on a suitable support described later. When the composition is coated on a support, it is used after being dissolved in various tree-containing 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, Ethylene 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,
Examples include dimethyl sulfoxide, γ-butyrolactone, methyl lactate, and ethyl lactate. These solvents can be used alone or as a mixture. The concentration of the solid content in the coating solution is suitably from 1 to 50% by weight. In the present invention, the coating amount of the photopolymerizable composition is about 0.1% by weight after drying.
range of g / m ² ~ about 10 g / m ² are suitable. It is more preferably 0.3 to 5 g / m ² , and still more preferably 0.5 to 3 g / m ^2.
It is.

As the support of the photopolymerizable lithographic printing plate used in the method of the present invention, a dimensionally stable plate is used. Examples of the dimensionally stable plate include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), zinc, copper, etc. Metal plates, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, plastic films such as polyvinyl acetal, Paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited may be used. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Furthermore, Japanese Patent Publication No. 48-1
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in No. 8327 is also preferable.

In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing. Is preferably performed. Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. After anodizing the aluminum plate as described in JP-B-47-5125,
Those immersed in an aqueous solution of an alkali metal silicate are preferably used. The anodizing treatment may be, for example, an aqueous solution or a non-aqueous 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 a salt thereof, or an electrolytic solution in which two or more kinds are combined. It is carried out by passing a current through an aluminum plate as an anode. Also, silicate electrodeposition as described in U.S. Pat. No. 3,658,662 is effective. Furthermore, the above-mentioned anodizing treatment and sodium silicate treatment are combined with a support having been subjected to electrolytic graining as disclosed in JP-B-46-27481, JP-A-52-58602 and JP-A-52-30503. Surface-treated ones are also useful. Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable. Furthermore,
A sol-gel treated substrate to which a functional group capable of causing an addition reaction by a radical as described in JP-A-7-159983 is covalently bonded is also preferably used. 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 improve the adhesion of the photosensitive layer. Etc.

The photopolymerizable lithographic printing plate obtained by applying the above-mentioned photosensitive layer on the support is exposed to an image. The light source at the time of the image exposure is an electromagnetic wave active to the photopolymerization initiation system, specifically, a light source having a wavelength in the visible region, that is, a wavelength of 400 to 700 nm, more preferably 450 to 550 nm. A light source that emits visible light in a range is used. For example, argon laser light, FD-YA
G laser light and helium-neon laser light are exemplified. The exposure amount at the time of image exposure can be appropriately changed depending on the components of the photopolymerizable composition to be used, other conditions, and the like, in a range that gives high resolution without causing flare. A suitable image exposure amount is 0.01 mJ / cm ²
１1 mJ / cm ² . The imagewise exposed photopolymerizable lithographic printing plate is subjected to a development treatment to remove unexposed portions. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tertiary sodium phosphate, potassium,
Same ammonium, dibasic sodium, same potassium,
Inorganic alkali agents such as ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium Can be Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are used alone or in combination of two or more.

Among the above-mentioned alkaline aqueous solutions, the developing solution in which the effect of the present invention is further exhibited is an aqueous solution containing an alkali metal silicate and having a pH of 12 or more. The aqueous solution of the alkali metal silicate is composed of silicon oxide S which is a component of the silicate.
The ratio of iO ₂ and alkali metal oxide M ₂ O (generally [Si
O ₂ ] / [M ₂ O] (molar ratio) and the concentration can be adjusted. For example, JP-A-54-6200
No. 4, the molar ratio of SiO ₂ / Na ₂ O is 1.0 to 1.5 (that is, [SiO ₂ ] / [Na
₂ O] is 1.0 to 1.5 and the content of SiO ₂ is 1
Aqueous solution of sodium silicate of about 4% by weight;
[Si 7427]
O ₂ ] / [M] is 0.5 to 0.75 (that is, [SiO ₂ ] /
[M ₂ O] is 1.0 to 1.5), the concentration of SiO ₂ is 1 to 4% by weight, and the developer is based on gram atoms of all alkali metals present therein. An aqueous solution of an alkali metal silicate containing at least 20% potassium by weight is preferably used.

Further, the photosensitive material was prepared using an automatic developing machine.
(For example, a photosensitive lithographic printing plate)
Use an aqueous solution (replenisher) with a higher alkali strength than the developer
The developer in the developing tank for a long time.
A large amount of photosensitive material can be processed without replacement
It is known that This replenishment method is also used in the present invention.
Is preferably applied. For example, JP-A-54-6200
No. 4 JP_Two/ N
a_TwoO molar ratio is 1.0-1.5 (ie [SiO_Two] / [N
a_TwoO] is 1.0 to 1.5), and SiO_TwoContent of
Using an aqueous solution of 1 to 4% by weight of sodium silicate,
Moreover, it is continuous according to the throughput of the positive-type photosensitive lithographic printing plate.
Or intermittently SiO_Two/ Na_TwoThe molar ratio of O is 0.5 to
1.5 (ie [[SiO_Two] / [Na_TwoO] is 0.5-1.
5) Add the sodium silicate aqueous solution (replenisher) to the developer.
And further disclosed in Japanese Patent Publication No. 57-7427.
[SiO_Two] / [M] is 0.5 to 0.75
(That is, [SiO_Two] / [M_TwoO] is 1.0 to 1.5)
Oh, SiO_TwoHaving a concentration of 1 to 4% by weight
An aqueous solution of metal silicate is used as a developer and used as a replenisher.
Of alkali metal silicate used for_Two] / [M]
Is 0.25 to 0.75 (ie, [SiO_Two] / [M _TwoO]
Is 0.5 to 1.5), and the developer and the replenisher are
Each of the liquids contains a graph of the total alkali metal present in it.
Contains at least 20% potassium based on system atoms
Development method characterized in that
You.

The lithographic printing plate thus developed is described in JP-A-54-8002 and JP-A-55-115045.
As described in JP-A Nos. 59-58431 and the like, treatment is carried out with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and starch derivatives.
For the post-processing of the photosensitive lithographic printing plate of the present invention, these processings can be used in various combinations.

After development or, optionally, post-treatments such as the above desensitizing treatment, the entire surface is exposed to ultraviolet light, and the polymerizable unsaturated groups contained in the image area of the photosensitive layer are exposed to ultraviolet light. Is reacted with a compound having a polymerization initiating group which is photosensitive to the surface to completely cure the image area. As the light source at the time of the entire surface exposure, for example, a carbon arc lamp, a mercury lamp, a gallium lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, various laser beams, and the like can be mentioned. Further, in order to obtain sufficient printing durability, the overall exposure amount is preferably at least 10 mJ / cm ² or more, more preferably 1 mJ / cm ² or more.
It is not less than 00 mJ / cm ² .

Heating may be performed at the same time as the entire surface exposure. By performing the heating, the printing durability is further improved. Examples of the heating device include a conventional convection oven, IR irradiation device, IR laser, microwave device, Wisconsin oven and the like. At this time, the plate surface temperature is preferably from 30 ° C to 150 ° C, more preferably from 35 to 130 ° C, even more preferably from 40 to 130 ° C.
120 ° C. The lithographic printing plate thus obtained is set on an offset printing machine and used for printing a large number of sheets. As a plate cleaner used for removing stains on the plate at the time of printing, a conventionally known plate cleaner for PS plate is used. For example, CL-1 and CL-
2, CP, CN-4, CN, CG-1, PC-1, S
R, IC (manufactured by Fuji Photo Film Co., Ltd.) and the like. Preferably, CP and CN-4 are mentioned.

[0169]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Preparation of Sensitive Material 1) An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then washed thoroughly with water. After being immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, neutralized and washed with a 20% aqueous nitric acid solution, and then washed with water. This is V _A = 1
1% using a sinusoidal alternating current under the condition of 2.7V
The electrolytic surface roughening treatment was performed with a nitric acid aqueous solution at an anode electricity quantity of 160 coulomb / dm ² . When the surface roughness was measured, it was 0.6 μ (Ra display). Followed by 30%
Immersed in a 2% aqueous sulfuric acid solution and desmutted at 55 ° C. for 2 minutes, and then anodiced in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ² for 2 minutes so that the thickness of the anodic oxide film becomes 2.7 g / m ^2. It was oxidized. Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure.

[Sol Solution] Unichemical Co., Ltd .: Phosmer PE 24 parts by weight Methanol 130 parts by weight Water 20 parts by weight 85% phosphoric acid 16 parts by weight Tetraethoxysilane 50 parts by weight 3-methacryloxypropyltrimethoxysilane 48 parts by weight Were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the content was transferred to another container and 3,000 parts by weight of methanol was added to obtain a sol solution. This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio), applied with a wheeler so that the amount of Si on the substrate was 3 mg / m ^2, and dried at 100 ° C. for 1 minute. On the substrate thus treated, a photopolymerizable composition having the following composition was applied so as to have a dry coating weight of 1.4 g / m ^2.
It dried at 2 degreeC for 2 minutes, and formed the photopolymerizable photosensitive layer.

Photosensitive Liquid (Preparation of Sensitive Material 1) Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid 2.0 g (80/20 weight ratio) copolymer, molecular weight 30,000 Compound 1 (see the following formula) 0 .15 g Compound 2 (see the following formula) 0.20 g Compound 3 (see the following formula) 0.50 g Compound I-1 (see Table 12 and the following formula) X g Copper phthalocyanine Pigment Blue 15.6 / (A) = 3/2 dispersion Product 0.5 g Megafax F-177 (Dainippon Ink & Chemicals, Inc. 0.02 g Fluorosurfactant manufactured by Nippon Kagaku Co., Ltd.) N-nitrosophenylhydroxylamine 0.015 g Aluminum salt (manufactured by Wako Pure Chemical Industries) Propylene glycol monomethyl ether 27. 5 g methyl ethyl ketone 19.0 g On this photopolymerizable photosensitive layer, a water-soluble protective layer having the following composition was dried. Fabric weight. The coating is 2.5g / m ^2, 1
Dried at 00 ° C. for 3 minutes. Polyvinyl alcohol (degree of saponification 99.5 mol%, degree of polymerization 550) 22 g Nonionic surfactant (BMALBX NP-10 0.5 g, manufactured by Nippon Emulsion Co., Ltd.) Distilled water 450 g

(Preparation of Photosensitive Material 2) Photosensitive material 2 was prepared in the same manner as in Photosensitive Material 1 except that the photosensitive solution was changed to the following composition. Pentaerythritol tetraacrylate 1.7 g Allyl methacrylate / methacrylic acid 1.8 g (80/20 weight ratio) copolymer, molecular weight 30,000 Compound 4 (see the following formula) 0.15 g Compound 5 (see the following formula) 0.20 g Compound 3 (see the following formula) 0.50 g Compound I-1 or I-2 (see Table 12 and the following formula) X g Copper phthalocyanine Pigment Blue 15: 3 / (A) = 3/2 dispersion 0.5 g Megafax F-177 (manufactured by Dainippon Ink and Chemicals, Inc., 0.02 g fluorine surfactant) N-nitrosophenylhydroxylamine 0.015 g aluminum salt (manufactured by Wako Pure Chemical Industries) propylene glycol monomethyl ether 27.5 g methyl ethyl ketone 19.0 g

[0173]

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(Examples 1 to 5) In Example 1, an image exposure amount was 0.15 mJ / c using an XLP4000 platesetter (air-cooled Ar ⁺ laser, 488 nm) manufactured by Optronics.
and m ^2, 175 lpi number of lines, the resolution is 4000dpi
And image exposure was performed. In order to further increase the degree of film curing, a post-heating treatment was performed at 110 ° C. for 12 seconds. In Examples 2 to 5, a Rhinotype Hell Co. Gutenberg plate setter (SHG-YAG, 532 nm) was used.
The image exposure amount is 0.15 mJ / cm ² and the number of lines is 175 lP
i, image resolution was performed at a resolution of 2540 dpi. The temperature was then raised to 110 ° C to increase the degree of film curing.
A post-heating treatment was applied for seconds.

The development was carried out by Fuji Photo Film Co., Ltd. DP-4.
Using a solution obtained by diluting a developer 18-fold with water, 85
The immersion was carried out at 30 ° C. for 15 seconds using a 0NX automatic developing machine. FUJIFILM Corporation FP-2W gum solution with water 1:
After gumming with the solution diluted to 1, the whole surface was exposed and heated. Table 12 shows the conditions of the overall exposure and heating. The printing plate thus obtained was evaluated as follows. For the printing durability evaluation, SOR-KZ manufactured by Heidelberg Co. was used as a printing machine, emulald premium MXE 2% diluted solution of Anchor Co., Ltd. was used as a dampening solution, and GEOS-G (N) manufactured by Dainippon Ink Co., Ltd. was used as an ink. It was used. The solid printing durability refers to the number of sheets that can be printed normally without any solid omission in the solid printing portion. Highlight printing durability indicates the number of prints at which 3% of 175 lpi halftone dots are reproduced on a printed material. The results are shown in Table 12.

(Comparative Examples 1 to 8) In the same manner as in Examples 1 to 5, the photosensitive materials 1 and 2 were subjected to image exposure and development. Printing was performed on the obtained lithographic printing plate under the same conditions as in Examples 1 to 5, and the printing durability was evaluated. The results are shown in Table 12.

[0179]

[Table 12]

From the above results, it can be seen that the printing durability of the photographic material is greatly improved by performing the entire exposure after development, but the addition of a compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light. It is clear that the effect is further improved.

[0181]

As described above, according to the plate making method of the present invention, the photosensitive layer of the photopolymerizable lithographic printing plate contains a compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet rays. By performing image exposure of the photopolymerizable lithographic printing plate with a visible light laser and developing, and then performing full surface exposure with ultraviolet light, a clear image can be obtained without causing flare and the like, and A lithographic printing plate having greatly improved properties can be obtained. A compound having a polymerizable unsaturated group and a polymerization initiating group sensitive to ultraviolet light is difficult to be removed by development, so the effect of overall exposure is greater than in the case where it is not added, and a very practical lithographic printing plate making. Is the way.

Claims (1)

[Claims] 1. A photopolymerizable composition having a photosensitive layer containing a composition that initiates photopolymerization by absorbing visible light, and a compound having a polymerizable unsaturated group and a polymerization initiation group that is sensitive to ultraviolet light. A plate making method for a lithographic printing plate, comprising exposing the lithographic printing plate to an image with a visible light laser, developing the lithographic printing plate, and then exposing the entire surface to ultraviolet light.