JPS6061752A - Photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To enhance reproducibility of image lines and printing resistance by giving a photosensitive layer a spectral sensitivity distribution having the max. spectral sensitivity in a specified region and a small spectral sensitivity up to 1/10 of said max sensitivity in a specified wavelength region. CONSTITUTION:A photosensitive layer formed on a flexible support has a spectral sensitivity distribution having the max. sensitivity in the wavelength region longer than 700mum, and a spectral sensitivity up to 1/10 of said max. sensitivity in the wavelength region of 450-480mum. The flexible support is, preferably, selected from a sheet material having especially superior dimensional stability and a hydrophilic surface. The compsn. of the photosensitive layer having such a spectral sensitivity distribution is exemplified by a photosensitive resin compsn. composed of, e.g., a compd, having groups represented by the formula on the main chain or side chains of a polymer, and a sensitizer capable of initiating cross-linking and hardening of this compd. on absorbing the light of wavelengths longer then 700mum. A photosensitive lithographic plate having such a structure exhibits excellent reproducibility of an image when it is imagewise exposed to semiconductor laser beams.

Description

[Detailed description of the invention]

The present invention can be used mainly in a plate-making system that includes an exposure process using semiconductor laser light, and can provide a lithographic printing plate with excellent image reproducibility and high printing durability. The present invention relates to a photosensitive lithographic printing plate that can be handled under a bright safelight. Conventionally, a plate-making system including a process of engraving using a laser beam is known. The laser beams used in this plate making system include Ar and Ne. Gas lasers such as He, and dye lasers that use specific organic dyes, both of which are 300rrLμ to 7oo
It is a laser beam of mμ. However, this type of laser light generating device generally has a low power consumption efficiency and has serious drawbacks in that the device is large. On the other hand, if a semiconductor laser is used, for example,
As described in /j/ri No. 33, it is expected that the exposure apparatus can be made smaller, the consumption power can be reduced, and the running cost of plate making can be reduced. For semiconductor lasers, for example, H. Kressel et al.
8emiconductor L, xser and
Ga / kl / A 8 ;Ga/
Semiconductors of systems such as As/P; Ga/As; In/P and In/A8 are used, and the wavelength of this laser light is generally 7.
There are many wavelengths longer than oo71μ, especially longer wavelengths than 7tomμ. A photosensitive lithographic printing plate suitable for using semiconductor laser light, which is light with such a long wavelength, as a light source for image exposure is
had not been developed until now. Accordingly, a seventh object of the present invention is to provide a photosensitive lithographic printing plate suitable for imagewise exposure with semiconductor laser light. The first object of the present invention is to provide a photosensitive lithographic printing plate that has excellent image reproducibility and high printing durability. Thirdly, the purpose is to provide a photosensitive lithographic printing plate that has high sensitivity and can be handled under relatively bright safelight light while being able to use low-output semiconductor laser light.Other purposes are as follows. This will become clear from the description. As a result of various research methods, the present inventors have discovered that a photosensitive lithographic printing plate using a photosensitive layer having a specific spectral sensitivity distribution can achieve the above-mentioned purpose, and have accomplished the present invention. That is, the present invention provides a photosensitive lithographic printing plate comprising at least one photosensitive layer on a flexible support, wherein the photosensitive layer has a maximum spectral sensitivity in a wavelength region longer than 7oo and 11μ,
The photosensitive lithographic printing plate is characterized in that it has a spectral sensitivity distribution such that the minimum spectral sensitivity is at most 7 IO times or less of the maximum spectral sensitivity in the wavelength range from ≠60 mμ to tzaomμ. Various types of flexible support can be used in the present invention, but it is particularly preferably selected from sheet-like materials that have excellent dimensional stability and a hydrophilic surface. Such supports include U.S. Patent No. μ, 21. t, 40
It is explained in detail in row 6 of column 3 to column j 6 of column 3, and the surface is grained, sodium silicate,
It is preferable that the surface be subjected to a surface treatment such as immersion treatment in an aqueous solution of potassium fluorozirconate or phosphate, or anodization treatment. Also, U.S. Patent No. 2゜71≠,
Aluminum plate grained and then immersed in an aqueous sodium silicate solution as described in U.S. Patent No. 066; A plate obtained by anodizing the plate and then immersing it in an aqueous solution of an alkali metal silicate is also suitably used. The above-mentioned anodizing treatment is carried out using, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or oxalic acid,
Applying an electric current to the aluminum plate in an aqueous solution or a non-aqueous solution of an organic acid such as sulfamic acid or a salt thereof or a combination of two or more thereof, particularly preferably an aqueous solution of phosphoric acid, sulfuric acid, or a mixture thereof. Implemented by Also effective is silicate electrodeposition as described in US Pat. No. J.A.TF.J7-. Further preferred are aluminum plates which are electrolyzed with alternating current in a hydrochloric acid electrolyte and then anodized in a sulfuric acid electrolyte as described in British Patent No. Further, it is preferable to provide an undercoat layer of a cellulose resin containing a water-soluble salt of a metal such as zinc on the aluminum plate anodized in the above process in order to prevent scum during printing. At least one photosensitive layer is provided on such a flexible support, and at least one of the photosensitive layers has a spectral sensitivity distribution as described above, that is, a maximum spectral sensitivity in a long wavelength region of 700 mμ. and ≠jO7rLμ or t to
It has a spectral sensitivity distribution such that the minimum spectral sensitivity is at most lθ/less than the maximum spectral sensitivity in the wavelength region of @μ, preferably 7! OWLμ inishirioooy
1μ, most preferably maximum spectral sensitivity according to the wavelength of the laser light used during image exposure, and '130
It has a band-like minimum spectral sensitivity in the wavelength range from μ to tiromμ, which is at most j0/less than the maximum spectral sensitivity, and most preferably less than 1/ioo. By the way, having a mountain-shaped low spectral sensitivity range of about jOrrLμ width to about 230 mμ width is called "arrow height". This arrow height measurement method uses a band filter that transmits only light in a wavelength range that has minimal spectral sensitivity and a band pass filter that transmits only light in a specific wavelength range that corresponds to the arrow height. This can be determined by calculating the ratio with the spectral sensitivity, and a specific measuring method for determining whether or not the spectral sensitivity distribution has a specific spectral sensitivity distribution as in the present invention is exemplified in Examples. In the present invention, the composition of the photosensitive layer having the above-mentioned specific spectral sensitivity distribution includes, for example, a compound having a polymer main chain or side chain 1(1-(: H=CH-C-) (e.g. polyester, polyamide, polycarbonate, etc.) and 7
A photosensitive resin composition comprising a sensitizer that initiates a crosslinking/curing reaction of the compound when it absorbs light with a longer wavelength than 0rrLμ; a) an addition polymerizable unsaturated compound, more preferably at least Consisting of a monomer-stripped oligomer having two terminal ethylenically unsaturated groups, and b) a photopolymerization initiator, which generates radicals when the photopolymerization initiator is irradiated with light with a wavelength longer than 700 μ There are photopolymerizable compositions that are spectrally sensitized in a wavelength region longer than 700 mμ, but in the present invention, photopolymerizable compositions that are relatively easy to adjust to a desired spectral sensitivity distribution are used. Particularly preferred are silver halide emulsions, which will be described in detail below. Preferred silver halide emulsions for the present invention include gelatin, US Pat. J Rihiro, λri No. 3, Same No. 2. &/4'
, No. 2.2r, No. 2,763,637, No. 2,1
3/, No. 7A7, No. 3. //f, No. 7AA, No. 3.
/za &, fvt issue, special public show 3 taichi 11/hiro issue, same≠2-
Seratin derivatives, casein, etc. described in 2tl Hiroj issue etc.
Silver bromide, silver chloride, iodide in hydrophilic storage colloids such as sodium alginate, cellulose derivatives, polyvinyl alcohol partial acetals, polyvinyl pyrrolidone, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole and other homo- or copolymers. Silver or its mixed silver halide is dispersed therein. Preferably, mixed silver halide grains having an average grain size of 0.01μ to λμ are dispersed in a protective colloid containing at least gelatin paste or a seratin derivative. The silver halide grains may be of either surface latent image type or internal latent image type. These are P. I"Chimie Photographique" by Grafikidea
Methods such as ammonia bed, neutral method, acid method, or single or double jet controller are used as described in the bottom test published by Paul Montel Co., Ltd.

[Created by using the gold double jet method etc. The protective colloid is used in an amount of about 10 g to uog per gram of emulsion. Silver halide emulsions contain active vinyl compounds such as divinyl sulfone and methylene bismaleimide, and λ
A small amount of a highly active hardening agent such as an active halogen compound such as , Hiro-dichloro-6-hydroxy-S-)riazine may also be added. Other commonly used additives may be added, such as coating aids such as stabilizers, antifoggants, surfactants, and dyes or pigments. If necessary, for example, hydroquinone, a hydroquinone derivative, catechol, catechol 84, pyrogallol or a derivative thereof can be dispersed and incorporated into the silver halide emulsion J@. Furthermore, a resin such as a phenol resin can be dispersed and incorporated into the silver halide emulsion layer. The silver halide grains may be prepared, for example, by sulfur sensitization, reduction sensitization, Ir%R,h, Pt,
It is chemically sensitized, such as sensitization with a noble metal salt such as Au, and then spectrally sensitized so that it has maximum spectral sensitivity in a wavelength region longer than 700 mμ. Such spectral sensitization can generally be achieved by adding a sensitizing dye. Suitable sensitizing dyes are:
cyanine pigment, merocyanine pigment, rhodacyanine pigment,
You can choose from the group of hemicyanine pigments. i.e. 70
It has a high molecular extinction coefficient at a specific wavelength in the wavelength range longer than 0ytμ, and has sensitization, and is ≠5oylμ or t 1
A sensitizing dye that has an arrow height of 0 y /A and is stable over time and does not cause fogging is selected. Preferred examples of such sensitizing dyes include the following general formulas (I) to (IV
) can be selected from among the pigment groups represented by In the above formula, zl and Z2 may be the same or different, and each! Represents a group of nonmetallic atoms necessary to complete a nitrogen-containing or 6-membered nitrogen-containing heterocycle. R1 and l(, 2 may be the same or different, and each represents an alkyl group or a substituted alkyl group. R3 represents an alkyl group, a substituted alkyl group, or an aryl group. " 4 + " 5 + " 6 and R7 may be the same or different, and each represents a hydrogen atom, a halogen atom, a lower alkyl group, a phenyl group, or a habenzyl group.However, R6 and R7 are connected to each other to form a j-membered or 1lt
A six-membered ring can also be formed. R, 8 and R, 9 may be the same or different, and each is T Lukil! N1 represents a substituted argyl group, aryl group, or substituted aryl group, and R8 and R9 can also be linked to each other to form a j-membered or t-membered ring. However, R represents an alkyl group or a substituted alkyl group. X represents an acid anion. A, nSm, p and q each represent l or λ. In the compounds of the above general formulas (I) to (IV), Zl and Z2 may each be the same or different, and each represents a group of nonmetallic atoms necessary to complete a J-membered or t-membered nitrogen-containing heterocycle. The expression, for example, a thiazole nucleus [e.g. benzothiazole, ≠-chlorobenzothiazole, ! -Chlorbenzothiazole, t-chlorobenzothiazole, 7-chlorobenzothiazole, goomethylbenzothiazole, j
-Methylbenzothiazole, t-methylbenzothiazole, j-bromobenzothiazole, t-7'' lomobenzothiazole, !-iodobenzothiazole, j-phenylbenzothiazole, j-methoxybenzothiazole,
t-Methoxybenzothiazole! -Ethoxybenzothiazole, j-carboxybenzothiazole, j-ethoxycarbonylbenzothiazole, j-phenethylbenzothiazole,! -fluorobenzothiazole, J-trifluoromethylbenzothiazole, 'l'l dithylbenzothiazole, j-hydroxy-t-methylbenzothiazole, tetrahydrobenzothiazole, ≠-phenylbenzothiazole, naphtho [co, l-d] Thiazole, naphtho (/,, 2-d) Thiazole, naphtho [co,
J-d) Thiazole, j-methoxynaphtho ('+'
a ] Thiazole, 7-ethoxynaphtho [λ+' a
) Thiazole, a-methoxynaphtho (' + 'a
] Thiazole! -methoxynaphtho [λ, J-d] thiazole, etc.], zelenazole core [e.g., penzozelenasole, j-chlorobenzozelate A[, z-methylbenzothiazole, ! -methylbenzozelenazole,
! -Hydroxybenzozelenazole, naphtho [λ, l-
d] zelenazole, naphtho(/,, 2-d) zelenazole, etc.], oxazole nucleus [benzoxazole, j-
Chlorobenzoxazole, j-methylbenzoxazole, j-bromobenzoxazole, j-fluorobenzoxazole, j-phenylbenzoxazole,
j-methoxybenzoxazole, j-)lifluorobenzooxazole, j-hydroxybenzoxazole, j-carboxybenzoxazole, t-methylbenzoxazole, 6-chlorobenzoxazole, 6
-methoxybenzoxazole, t-hydroxybenzoxazole,! , 6-dimethylbenzoxazole,
≠. 6-dimethylbenzoxazole, j-ethoxybenzoxazole, naphtho(L2./-d)oxazole,
naphtho(/,,2-d)oxazole, naphtho[,2,
J-d]oxazole, etc.], quinoline nucleus [e.g. λ-
Quinoline, 3-methyl-coquinoline! -Ethyl 2
-quinoline, t-methyl-,2-ki/! J-n, t-fluoro-1-quinoline, t-methoxycoquinoline,
t-hydroxy-λ-quinoline, Z-chlorochoquinoline, Hiro-quinoline, t-fluoro-≠-quinoline, etc.], 3,3-dialkylindolenine nucleus (for example, 3゜3-dimethylindolenine, 3 .3-diethylindolenine, 3,3-dimethyl-y-cyanoindolenine, 3
．． 3-dimethyl-yo-methoxyindolenine, 3,3-
dimethyl-j-methylindolenine, 3,3-dimethyl-y-chloroindolenine, etc.), imidazole nuclei (e.g., l-methylbenzimidazole, l-ethylbenzimidazole, l-methyl-yo-chlorobenzimidazole, l -ethyl-j-chlorobenzimidazole,
l-methyl-! , 6-dichlorobenzimidazole, l
-Ethyl-! , A-dichlorobenzimidazole, /-
Alkyl-yo-methoxybenzimidazole, /-methyl-j-cyanobenzimidazole, /-methyl-yo-
Fluorobenzimidazole, l-ethyl-! -fluorobenzimitazole, /-phenyl-j, A-dichlorobenzimidazole, l-'aryl, 6-dichlorobenzimidazole, l-allyl-! -Chlorbenzoimidazole, /-phenylbenzothiazole, l-phenyl-! -Chlorbenzoimidazole, l-methyl-
! -trifluoromethylbenzimidazole, l-ethyl-3-trifluoromethylbenzimidazole, l-
Ethylnaphtho [/, 2-d) imidazole, etc.), pyridine nucleus (eg, pyridine, j-methyl-2-pyridine, 3-methyl-≠-pyridine, etc.), and the like. Among these, thiazole nuclei, oxazole nuclei, and quinoline nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, a benzoxazole nucleus or a quinoline nucleus is advantageously used. R1 and R2 may be the same or different, and each represents an alkyl group (preferably number of carbon atoms/~g, for example, methyl group, ethyl group, propyl group, butyl group, methyl group, heptyl group, etc.), substituted Alkyl group (substituents such as carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.),
Hydroxy group, alkoxycarbonyl group (number of carbon atoms, g
Hereinafter, for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkoxy group (7 or less carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.)
, aryloxy group (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group (3 or less carbon atoms,
For example, acetyloxy group, propionyloxy group, etc.)
, acyl group (up to j carbon atoms, e.g. acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group (e.g. evacarbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group) groups), sulfamoyl groups (e.g. ebasulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl groups (e.g. phenyl group, p-hydroxyphenyl group, p-carboxyphenyl & , !'-sulfophenyl group, α-naphthyl group, hinyl group, etc. (preferably the number of carbon atoms is below). However, these substituents may be substituted with an alkyl group in combination of more than one. ). R3 is an alkyl group or a substituted alkyl group as defined in R.1, 11.2, or an aryl group (e.g., phenyl group, p-hydroxyphenyl group, p-carboxyphenyl L p-
sulfophenyl group, λ-pyridyl group, t-pyridyl group, etc.). "4 + "5 r "6 and R7 may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom), a lower alkyl group (for example, a methyl group, an ethyl group) group, propyl group, etc.), phenyl group, or benzyl group.However, R6
and R7 can be linked to each other to form a j- or t-membered ring (for example, an isophorone ring). R8 and R9 may be the same or different, and each represents an alkyl group (preferably carbon atom number/~'s, e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.), substituted alkyl group (e.g. benzyl group, 7enethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), substituted aryl group (e.g. tolyl group, p-
chlorophenyl group, etc.). Also, R8 and R9 are connected to each other! It is also possible to form a membered or t-membered ring. vinegar. However, R, [alkyl group (e.g. methyl group, ethyl group, propyl group, methyl group, pentyl group, allyl group, etc.)
, substituted alkyl groups (e.g. hydroxy group, alkoxy group (methoxy group, etquine group, propoxy group, butquine group, etc.), aryloxy group (e.g. phenoxy group, p-
) lyloxy group, etc.), acyloxy group (e.g., acetyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), carbamoyl group (e.g., carbamoyl group, N, N-cy)tylcarbamoyl group, morpholinocarbamoyl group, etc. ), sulfamoyl group (e.g. sulfamoyl group, N,N-,9methylsulfamoyl group, morpholinosulfate, aryl group (e.g. phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group) , p-sulfophenyl group), carboxy group, sulfo group, cyan group, halogen atom (e.g. chlorine atom, bromine atom, fluorine atom, etc.), etc. However, this substituent is λ
(which may be substituted with an alkyl group in combination of two or more). X represents an acid anion (eg chloride, bromide, iodide, p-toluenesulfone-1., methanesulfonate, methylsulfate, ethylsulfate, verchlorate, etc.). l + n Hm + p and q each represent/or λ. Such sensitizing dyes are added with a sickle that imparts the desired maximum spectral sensitivity in the wavelength region longer than 7θ0.7μ, but as a general guideline, the amount of sensitizing dyes is 10
-10 mol, more preferably 70-6 to io-' mol. Among the sensitizing dyes represented by the above general formulas (1) to (IV),
Particularly preferable results are given by the following general formula (Ia)
and a sensitizing dye represented by (Tb). General formula (Ia) (X)n. In the formula, R1, 11, and z are each an alkyl group or a substituted alkyl group, R is a 111 lower alkyl group, a phenyl group, or a benzyl group; is an atomic group necessary to form a conjugated nitrogen heterocycle, X is an acid anion, and m, n, and p each represent an integer of 1 or co. General formula (Ib) In the formula, D represents an atomic group necessary to form a t-membered ring containing a methylene chain, and "% R1, n, 2, and X represent the general formula (Ia
), and Z and zl may be the same or different from each other, and each has the same meaning as Z in general formula (Ia). When using a sensitizing dye selected from the group represented by the above general formulas (Ia) and (Ib), the following general formula (Va
) and/or (Vb) are preferably used in combination. As a result, it has a high spectral sensitivity that meets the purpose of the present invention to an unforeseeable extent, no arrow height or fog, and excellent stability over time, and surprisingly, because of the effect it has on the developing process. The reproducibility of lines is improved. General formula (Va) In the formula, R73, R4, R5, R6 are each H, OH, alkyl group, alkoxy group, arylamine group, halogen, heterocycle, heterocyclylthio group, arylthio group, amino group, alkylamino group, arylamine group, aralkylamino group, aryl group, and mercapto group. General formula (Vb) 6 In the formula, Z2 is j, the atomic group necessary to complete the bounty nitrogen heterocycle R6 is a H1 alkyl group or alkenyl group, R7 is a H1 lower alkyl group, and Xl is an acid anion. . The compound represented by the general formula (Va) and/or (Vb) has a supersensitizing effect when used in combination with a sensitizing dye selected from the group represented by the general formula (Ia) and (Ib). can get. Therefore, it should be added in an amount within the range that produces a supersensitizing effect, and the general guideline is silver halide 1
The range is 0, oo5 to v, 1 mole, more preferably 1 to ρ, 1 mole. By spectrally sensitizing as described above, 70077
It has maximum spectral sensitivity in the wavelength region longer than 1μ, and
Although it is possible to obtain a silver halide emulsion having a minimum spectral sensitivity in the wavelength range of 1μ to tromμ, which is at most 1/IO of the maximum spectral sensitivity, 4'romμ to 60.0. μ
About 4AzoIBμ or about t to improve the feel of the
A non-sensitizing compound having an absorption maximum at iro@μ is added to the silver halide emulsion or added to a layer close to the exposure light source provided adjacent to the silver halide emulsion layer provided on the support. It is advantageous to add A silver halide emulsion having a specific spectral sensitivity distribution as described above is provided on a flexible support as described above. In one embodiment of the present invention, the above silver halide emulsion is provided directly on an aluminum plate having an anodized film. In this embodiment, U.S. Patent No. μ, 22/,
As described in U.S. Pat. It is preferable to provide a protective layer containing a lipophilic resin on the \halogen-1arsenic emulsion layer as shown in FIG. In another embodiment of the present invention, there is provided a photosensitive lithographic printing plate in which a subbing layer containing a hydrophilic binder, a physical development nucleus layer and a photosensitive silver halide emulsion layer are sequentially superposed on a support, the photosensitive A silver halide emulsion having a specific spectral sensitivity distribution as described above is used as the silver halide emulsion layer. This photosensitive lithographic printing plate undergoes silver salt diffusion transfer development after image exposure with semiconductor laser light, the silver halide emulsion layer is removed, and the silver image formed on the physical development nucleus layer is transferred to the lipophilic ink receiving area. It is said to be a lithographic printing plate used as a lithographic printing plate. Photosensitive lithographic printing plates according to particularly preferred embodiments of the invention are disclosed, for example, in US Pat. A photosensitive lithographic printing plate having a layer structure as described in No. A light-sensitive lithographic plate having a silver emulsion layer, etc.) and a photosensitive halogen [arsenic emulsion layer, which has a specific spectral sensitivity distribution as described above, It uses a silver halogenide emulsion. After image exposure using the photosensitive lithographic printing plate and semiconductor laser light, the Rodin silver emulsion emulsion 11 is developed, and if necessary, further fixing treatment is performed to form a silver image. A lithographic printing plate is obtained by exposing the non-silver photosensitive layer as a mask, then removing the emulsion layer having a silver image, and finally developing the non-silver photosensitive layer to remove the non-silver photosensitive MA in the non-image area. Details of such plate-making processing process - 1 U.S. Patent No.
．． It is described in detail in 2 Tade, Ri No. 72. In the photosensitive lithographic printing plate of the present invention, a compound having a maximum spectral absorption in a wavelength range longer than 1.700 TrLμ is contained in the silver halide emulsion having a specific spectral sensitivity distribution and/or in the lower layer thereof. This is preferable because it improves the solidity of the image. Preferred examples of such compounds include the following general formula % formula % general formula (Vl) R. ), Zl and Z
Each l may be the same or different, and n is a nonmetallic atom necessary to complete a j-membered or m-membered nitrogen-containing heterocycle.
), represents. Specific examples of such a heterocycle include the same examples of Zl and Zl in the above general formulas (I) to (IV). Q and Ql may each be the same or different;
isoxacilone, 3-oxythionaphthene, or/or
Represents the atomic group necessary to complete the 3-indation. Q2 is pyrazolone, barbylic acid, thiobarbylic acid, isoxacilone, 3-oxynaphthene, l,3-
Represents the atomic group necessary to complete interdione, -monothiooxazolidinedione, rhodanine, and thiohydantoin. (1), (2) and (3) may be the same or different, and each represents an alkyl group or a substituted alkyl group. W~w, w2. w3. W4 each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a nitro group, a cyano group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, or a hydroxyl group. Furthermore, Wl and W2 or W3 and W4 may be linked to each other to form a ring. A represents a sulfo group or a carboxyne group. m, n and p each represent/or 2. 1, (l and r each represent /, , 2.3 or Hiroshi. The compounds represented by the above general formulas <vi> to (X) particularly preferably have the above-mentioned specific spectral sensitivity distribution A lower layer of halogen-specific emulsion J-, for example, a non-silver photosensitive layer on which a lipophilic image is entirely formed and a halogen-specific silver emulsion layer having the above-mentioned specific spectral sensitivity distribution are provided in order on a support having a hydrophilic ridge surface. In the case of a photosensitive lithographic printing plate, the above-mentioned compound is contained in the non-silver photosensitive layer.For example, the above-mentioned compound is contained in an organic solvent such as methanol, methyl ethyl ketone, ethyl acetate, methyl cellosolve or cellosolve acetate, or water. As a liquid, the spectral reflectance is good for the wavelength of 700＠μ longer semiconductor laser) Y;23
It is added so that the temperature is 91+F or higher. The photosensitive layer of the photosensitive 1" printing plate of the present invention is 700 mμ
It has maximum spectral sensitivity in the longer wavelength region and
The maximum spectral sensitivity is at most in the wavelength range μ~l, 10@μ/
Because it has a minimum spectral sensitivity of θ minutes/less than 700
Image exposure can be performed with semiconductor laser light having a wavelength of @μ or more. Moreover, since it has a long wavelength in the wavelength range of p, S'o, . Human visibility! Oθ~t
, 0 omμ range, plate making work including the exposure process can be performed under a visually bright safelight, which has the advantage of improving work efficiency. In a particularly preferred embodiment of the photosensitive lithographic printing plate of the present invention, a compound having a maximum spectral absorption in a wavelength range longer than 700 mμ is added to the lower layer of the photosensitive layer having a specific spectral sensitivity distribution and optionally further to the photosensitive layer. , it is possible to obtain a lithographic printing plate with excellent image reproducibility even when imagewise exposed with semiconductor laser light containing wavelengths longer than 700 mμ. In general, with long wavelength light, for example, light with a wavelength longer than 700 mμ, it is known that the resedimentability of images tends to deteriorate due to light scattering in the photosensitive layer due to the ration effect, but in the present invention, semiconductor laser light (coherent By using monochromatic light (monochromatic light) and by using a compound having a high absorber a in the sensitive wavelength range, a remarkable effect that image reproducibility does not deteriorate is achieved. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that "chi" indicates weight unless otherwise specified. Example 1 A grained JIS A /ioo aluminum plate was placed in a 2 part sodium hydroxide aqueous solution kept in HiroOOC.
The surface was partially corroded by soaking for a minute. After washing with water, it was immersed in a sulfuric acid solution for about 1 minute and exposed to a pure aluminum surface. Immersed in 20% sulfuric acid maintained at 300C, DC voltage /,jV. After performing anodic oxidation treatment for 2 minutes under the condition of current sensitivity JA/dm2, it was washed with water and dried. Next, a photosensitive solution having the following composition was continuously coated using a roll coater so that the dry weight was approximately 129/m<2 >to form a non-silver photosensitive layer. Acetone-Pyrogallol Wi'I N'fr No. 7 Tokinon-/, Nidiazide T2)-j-sulfonic acid ester (Synthesis method is described in U.S. Pat.
4-Fish example/by method) Ko,! β Novolak molded resol-formaldehyde resin j, Oji Methyl ethyl ketone 719 Cyclohexanone tog On the other hand, dye (XI) −/ described later is added at 0.0 to the non-silver photosensitive layer.
A sample was obtained in which the amount was added to 21 g/m2. Next, the dry weight of a photosensitive solution having the following composition was 3. sg/rrL
Samples A, B, C, I), and E=i were obtained by continuous coating in the second place and drying with hot air at a final temperature of 710°C. The silver halide gelatin emulsion used was α-70 mol%.
, the halogen composition of Br30molti, its average particle size is O
, core μ contains /, /4 moles of silver halide per emulsion/yield. The resin dispersion used was dissolved in a mixture of ethyl acetate 3309 and methyl ethyl ketone/209 of phenol formaldehyde resin MP/Co0HH (manufactured by Gunei Chemical Industry ■), gelatin IO%, and aqueous solution 6
In o oy, IO% sodium nonylbenzenesulfonate solution was dispersed in 750ml of a mixed solution of AOml and 10% methanol solution of funnel oil. The compounds used in this example are as follows. Compound abbreviation (1a) -/ < , 03 molar methanol solution) < io a molar methanol solution) (Va ) -/ ≠, ≠l-bis[≠, 6-di(su'7thyl-2-oxy)pyrimidine- λ-ylamino]stilbene-2,2'
-Disodium disulfonate (0,5% methanol solution) (j% aqueous solution) M3 Lε (Vb) - / (0,3% methanol solution) Each sample is an image using halftone dots of /30 lines/inch. ,
From the pattern pasted with Japanese characters, JP-A-17-7
Scanning image exposure was carried out using the apparatus described in No. 233. This writing device was manufactured by Mitsubishi Electric and K. Manufactured semiconductor laser element ML-μ10 Hiro (output 3 doors W13
01rLA) using a semiconductor laser (wavelength 7t0mμ
), the spot diameter is 12μ, the output on the plate is 2jμW, and the scanning speed is λ.
j, kume/second. Add this to the developer (T) at 32°C.
for 20 seconds, and fixed with fixer (I) for io seconds. Next, the ultraviolet ray exposure unit consisting of three reflector-type mercury lamps was passed through for 73 seconds, and the μ of Hiro O or ≠ s 'C was
Thiprotease (Chasolon AF manufactured by Teikoku Kozo)
The silver halide photosensitive layer was de-smoothed through an aqueous solution, and then passed through a developer (n)t3'''C for 30 seconds, and GP-1 was coated on Fuji film using a gum coater tooG made by Manufacturer, to obtain a printing plate. Liquid CI) Water...7oo'me Metol...3.og Sodium sulfite...≠s, op Hydroquinone.../2.0g Sodium carbonate (l
water salt)...♂0. Og Potassium Bromide 2g Add water to make up to /l This stock solution is used by diluting it with water (1:2). Developer (II) JISI No. Sodium silicate... 1009 Putrium metasilicate sog Pure water... / 100 Fixer (1) Water...700ml Ammonium thiosulfate...22 ≠y Sodium sulfite ・・・・・・ Add 20g water 101
Samples A, B, C, D, and E' (i: each of them are filters made by Fuji Film 8C- that transmit approximately 70011Hμ long wavelength light through a light wedge to white light (color temperature λg!Hiroshi'K)). 70(
The spectral transmittance curve is shown in FIG. Sensitometry was carried out using red light transmitted through a 5C-43 lens manufactured by Fuji Film Co., Ltd. (the spectral transmittance curve is shown in FIG. 7). Sensitivity was defined as the ratio of the sensitivity obtained with green light using a 5C-13 filter to the sensitivity obtained with red light using an 8C-70 filter. Use this printing plate to print and print using a printing press! I got 191. The reproducibility of the image was visually evaluated from this printed proboscis. The results are shown in Table 1. These results show that the photosensitive lithographic printing plate of the present invention exhibits excellent image reproducibility when exposed to image by semiconductor laser light. Especially in the non-silver sensitive layer -5,700 mμ
It can be seen that the image reproducibility is particularly excellent when all the compounds exhibiting extremely thick spectral absorption in the longer wavelength region are added.

[Brief explanation of drawings]

FIG. 1 is a spectral transmittance curve diagram of an 8C-j3 filter and a 5C-70 filter manufactured by Fuji Photo Film Co., Ltd., where the vertical axis shows the transmittance and the horizontal axis shows the wavelength. Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendments Showa J < 1 month t7 day 1, case indication Showa TR year patent application no. 170777 2,
Title of the invention Photosensitive lithographic printing plate 3, Relationship with the case of the person making the amendment Patent 11 Notification u'1 person 4, Subject of amendment The column of "Detailed description of the invention" and "Brief description of the drawings" in the specification ” Column 5, contents of correction (1) JP, Grafkides J 'k on page 7, line l1, amend to "P, Glafkides J." (2) General formula f1) and general formula on page 1 and page 31 (■
) in the structural formula, [Rs [R5] is corrected. (3) In the general formula 1lal on page 23, amend it as follows. (4) Insert all ", n" next to "X" in the λth line from the bottom of the second page. (5) Insert the entire text "W indicates -N- or -CH=" between line j and line 6 of page 26. (6) Correct "Xl" on page 26, line 16 to XJ. (7) Correct “oleophilic surface” in line 2 of page 27 to “hydrophilic surface”. (8) On page 32, line 3, rRo in front of "Zl" represents a hydrogen atom or a lower alkyl group having t-hi carbon atoms. M is a hydrogen atom, an alkali metal atom (for example, N
a, ni, etc.). ” is inserted. (9) ≠ Correct to page 3, line 1 and Hiroyuki's "5C-43j gold rBPI3-jos". (Corrected to [5C-J meeting rBPI3-J in 1 [≠ page ♂ line ♂].

Claims (2)

[Claims] (1) In a photosensitive lithographic printing plate having at least one photosensitive layer provided on a flexible support, the photosensitive layer has minimum spectral sensitivity II in a wavelength region longer than 700@μ, and ≠so
A photosensitive lithographic printing plate characterized by having a spectral sensitivity distribution having a minimum spectral sensitivity at most 1/10 of the maximum spectral sensitivity in the wavelength range of 7nμ to tgOrILμ. (2) A non-silver photosensitive layer and a silver halide photosensitive layer on which a lipophilic image is formed on a support having a hydrophilic surface; has a maximum spectral sensitivity in a wavelength region longer than 700 mμ, excluding intrinsic sensitivity, and has a minimum spectral sensitivity of at most 1/70 of the maximum spectral sensitivity in a wavelength range of 700 mμ to 200 mμ. a photosensitive lithographic printing plate,