JPH10312056A - Photosensitive and thermosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel photosensitive and thermosensitive composition capable of forming a sharp negative image by cross-linking a polymer specified in structure with a specified imide or hydroxyimide in the presence of an acid. SOLUTION: This composition is exposed, and, when needed, heat-treated and developed, and the polymer having structural units represented by formula III is heat-crosslinked with the compound represented by formula I or II in the presence of an acid produced by a compound to be allowed to produce an acid by light or heat. In the formulae I-III, A is a divalent aliphatic optionally substituted straight or branched or cyclic group, preferably having 2-20 C or a divalent aromatic or heterocyclic aromatic optionally substituted, preferably, mono- or di-cyclic group; and R1 is an H atom or a methyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive and heat-sensitive composition which can be used as an offset printing plate master and can obtain a clear negative image, and a method for producing an image recording material. Proof printing for multicolor printing,
The present invention relates to a drawing for an overhead projector, and further relates to a photosensitive and heat-sensitive composition capable of forming an excellent resist pattern when an integrated circuit of a semiconductor element is manufactured, and a method for manufacturing an image recording material.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using various photocurable materials have been known, and printing plates, printed circuits,
It is used in a wide range of fields such as paint, ink, hologram recording, and three-dimensional modeling. For example, a method of forming a cured relief image by providing a photocurable material as a film layer on a support, exposing a desired image by image exposure to cure an exposed portion, and dissolving and removing an unexposed portion, at least one of which is transparent A method of forming an image by providing the above-mentioned photopolymerizable layer between two supports, exposing the image from the transparent support side to induce a change in adhesive strength by light, and then peeling off the support. ,
Create a photosensitive material provided with a microcapsule layer having a color material such as a photocurable composition and a leuco dye in the content,
The photosensitive material is image-exposed to light cure the exposed portion capsules, and the unexposed portion capsules are destroyed by pressure treatment or heat treatment, and color is formed by contact with a color material developer to form a colored image. In addition, there are known an image forming method using a change in toner adhesion of the curable composition due to light, an image forming method using a change in refractive index of the curable composition due to light, and the like.

[0003] A number of techniques have been disclosed as photocurable materials used for such image formation. Typical examples thereof include cross-linked materials using dichromate and vinyl cinnamate. Light dimerization type cross-linking material, azide group pendant type cross-linking material, cross-linking material with bis azide, photo-dimerization type cross-linking material of dimethylmaleimide, radical polymerizable monomer, photo-radical polymerization material mainly containing photo-radical initiator, cationic polymerization There are photo-cationic polymerizable materials composed mainly of a reactive monomer, a photo-acid generator, a photo-crosslinkable material composed of a resin containing an epoxy group and a photo-acid generator, diazo resin, a diazo-curable material composed of a binder, and the like. Depending on the purpose, it may be used alone or in combination. In any case,
A material having a large change in physical properties before and after exposure has a large latitude in processing during use and a latitude in use environment, and is more easily put to practical use. For example, if the exposed portion and the unexposed portion have significantly different solubilities in a developing solution (such as an aqueous alkaline solution), the image obtained by the development is less affected by changes in the concentration of the developing solution and the temperature of the developing solution and is sharp. It is easy to obtain a constant image quality. Conventional photo-curable materials that have been put to practical use have a significant change in the physical properties of the photo-curable material by applying light and other treatments such as heating as necessary. Further development of new materials having the same has been desired.

In recent years, the development of lasers has been remarkable. In particular, solid-state lasers and semiconductor lasers having a light-emitting region from near infrared to infrared have become easily available with high output and small size. These lasers are very useful as exposure light sources when making plates directly from digital data from a computer or the like. Conventionally, as a lithographic printing plate that can directly draw from digital data of a computer, a printing plate using electrophotography, a photopolymerization printing plate combining exposure with argon laser or YAG laser, and post-heating as needed, on photosensitive resin Laminated silver salt sensitive material on
A silver salt diffusion transfer type, a printing plate of a type in which a silicone rubber layer is destroyed by electric discharge or laser light, and the like are known.

In the case of using an electrophotographic system, charging, exposure and development processes are complicated, and the apparatus is complicated and large.
Photopolymerized printing plates inherently have limited sensitivity, making it difficult to use a small laser and difficult to handle in a bright room. Laminated silver salt photographic materials and silver salt diffusion transfer type have disadvantages in that processing is complicated and cost is increased. Also,
The type in which the silicone rubber layer is destroyed by laser has a problem in removing the silicone residue remaining on the plate surface. As a technology capable of forming an image using these light sources, Japanese Patent Application Laid-Open No. 52-113219 discloses a compound capable of decomposing by light and heat (for example, a diazonium compound) and a substance capable of absorbing light and converting it into heat. A positive-type recording material comprising particles and a binder is disclosed. JP-A-58-148792 discloses a positive photosensitive and heat-sensitive recording material containing thermoplastic resin particles, a light-to-heat conversion material and a photocrosslinkable material (for example, a diazonium compound) as main components. I have.

However, a recording material that can use the above laser as a light source has low sensitivity, and further, in the case of direct plate making,
Since the digital data from the computer or the like is directly written on the plate material by scanning the laser beam, the above positive type material requires a considerable writing time. Therefore, the development of a highly sensitive material (preferably a negative type) capable of shortening the writing time and capable of emitting a solid-state laser or a semiconductor laser (thermal mode) having a light emitting region from near infrared to infrared has been desired. A lithographic printing plate that can be directly drawn from digital data of a conventional computer as described above is not sufficiently satisfactory. On the other hand, there are various methods for producing image recording materials using the above novel materials. In these production methods, there is a demand for a method in which the excellent properties of the new materials are sufficiently exhibited to obtain excellent images.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel light- and heat-sensitive composition capable of forming a sharp negative image. A further object of the present invention is to provide a photosensitive and heat-sensitive composition that can be recorded without depending on the emission wavelength of an exposure light source, and in particular, a photosensitive and heat-sensitive composition that can be recorded from near infrared to infrared (heat ray). It is to provide a composition. Another object of the present invention is to provide a method for producing a novel image recording material capable of forming a clear negative image. Further, an object of the present invention is to provide a solid-state laser having an emission region from near infrared to infrared.
To provide a heat mode writing type lithographic printing plate capable of directly recording digital data of a computer or the like using a semiconductor laser (thermal mode) and capable of directly using a conventional processing device or printing device. It is.

[0008]

In order to achieve the above object, various negative photosensitive materials have been searched for. However, a polymer having a structure represented by the general formula (III) as a constituent unit has been developed in the presence of an acid. In the following, it was found that crosslinking was efficiently performed by the imide compound represented by the general formula (I) or the hydroxyimide compound represented by the general formula (II). Furthermore, a radiation-absorbing substance (for example, a carbon black dispersion solution) is mixed with the photosensitive heat-sensitive composition solution comprising the polymer, the compound generating an acid by light or heat, and the imide compound and / or the hydroxyimide compound. Then, it was found that the film coated and dried on the support was thermally crosslinked by irradiation with a YAG laser beam and became insoluble in a solvent or an aqueous alkaline solution. In addition, as a method of reducing damage of a portion crosslinked by heat in an exposed portion with a solvent or an aqueous alkali solution and having a film strength necessary for printing or the like, p.
The inventors have found that it is effective to use a binder having -hydroxystyrene or p-hydroxymethylstyrene as a structural unit, and have reached the present invention. The present invention provides: (1) a compound that generates an acid by light or heat, a compound represented by the following general formula (I), and / or a compound represented by the following general formula:
A photosensitive and heat-sensitive composition comprising a compound represented by the formula (II) and a polymer having a structure represented by the general formula (III) as a constitutional unit. The present invention can achieve the above object.

[0009]

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In the formula, A represents a divalent aliphatic residue or a divalent aromatic residue.

[0011]

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In the formula, R ₁ represents hydrogen or a methyl group.
As preferred embodiments of the present invention, the following (2) to (1)
1). (2) The photosensitive and heat-sensitive composition as described in (1) above, wherein the polymer further has a structure having a hydroxyl group as a constitutional unit. (3) The photosensitive and heat-sensitive composition according to the above (1), further comprising a substance that absorbs radiation. (4) A method for producing an image recording material, comprising subjecting the photosensitive and heat-sensitive composition according to (1) to a heat treatment after image exposure and a development treatment. (5) A substance that absorbs infrared light or near infrared light and generates heat, a compound that generates an acid by light or heat, and a structure represented by general formula (III) as a structural unit on a support. A photosensitive and heat-sensitive composition which is a lithographic printing plate for heat mode writing type direct plate making, comprising a layer containing a polymer compound and a compound represented by formula (I) or (II).

(6) The photosensitive and heat-sensitive composition according to (5), wherein a dye is used as a substance that absorbs infrared light or near infrared light and generates heat. (7) The photosensitive and heat-sensitive composition according to the above (5), wherein a pigment is used as a substance that absorbs infrared light or near infrared light and generates heat. (8) The photosensitive and heat-sensitive composition of (5) above, wherein carbon black is used as a substance that absorbs infrared light or near infrared light and generates heat. (9) The photosensitive and heat-sensitive composition according to the above (5), wherein a polyester film is used as a support. (10) The photosensitive and heat-sensitive composition according to the above (5), wherein an aluminum plate is used as a support. (11) On a support, a substance that absorbs infrared light or near-infrared light and generates heat, a compound that generates an acid by light or heat, and that has a structure represented by the general formula (III) as a structural unit A photosensitive and heat-sensitive composition comprising a polymer compound and a layer containing a compound represented by formula (I) or (II),
Exposure using a laser that emits near-infrared or infrared light,
Thereafter, development is performed with alkaline water.

The present invention provides a polymer compound having a structure represented by the general formula (III) as a constitutional unit and a polymer compound represented by the general formula (I) or (II) by performing exposure, and if necessary, heat treatment and development treatment. The compound represented is thermally crosslinked in the presence of an acid generated from a compound that generates an acid by light or heat to form an excellent negative image. The present invention also provides
A polymer compound having a structure represented by the general formula (III) as a structural unit and a compound represented by the general formula (I) or (II) by converting light energy by exposure to heat energy and generating the heat energy. Are thermally crosslinked in the presence of an acid generated from a compound which generates an acid by light or heat, thereby producing an excellent negative image. Where the radiation is
Infrared light or near-infrared light is preferable because recording in the thermal mode can be improved. In the present invention, a substance that absorbs infrared light or near-infrared light is preferably a dye from the viewpoint of developability after exposure, and a pigment is preferable because the sensitivity is good. Carbon black is preferred because it has a wide absorption wavelength range and high sensitivity.

In the present invention, it is preferable to use polyester as the support in terms of lightness and transparency, and to use an aluminum plate in terms of dimensional stability and durability. The photosensitive heat-sensitive composition of the present invention is preferably subjected to a recording method in which exposure is performed using a laser that emits infrared light or near-infrared light, followed by development with alkaline water. Also,
When the photosensitive heat-sensitive composition of the present invention is a planographic printing plate,
A lithographic printing plate for heat mode writing type direct plate making is preferable. Heat mode writing refers to controlling the heat radiation source based on digital data using an appropriate heat radiation source and recording on the photosensitive heat-sensitive composition. As a heat ray source at this time, a facsimile, a thermal head used in a thermal copying machine, or a laser emitting infrared light or near infrared light, but for direct plate making,
A laser emitting infrared light or near infrared light is preferred. The preferred light used in the present invention is near-infrared rays and infrared rays, of which infrared rays are generally also called heat rays, and when recording of the present invention is carried out with infrared rays, the present invention can be said to be heat-sensitive.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Next, the imide compound represented by the general formula (I) and the hydroxyimide compound represented by the general formula (II) used in the present invention will be described. In the general formulas (I) and (II), A can be a divalent aliphatic residue or a divalent aromatic residue. The divalent aliphatic residue of A in the general formulas (I) and (II) is a substituted or unsubstituted, linear, branched and / or cyclic one, and has a saturated bond and / or an unsaturated bond. And preferably has 2 to 20 carbon atoms. For example, ethylene group, triethylene group, propylene group, ethylethylene group, 1,
1-dimethylethylene group, 1-ethyl-1-methylethylene group, 1,2-dimethylethylene group, tetramethylethylene group, dodecylethylene group, octadecylethylene group, 2-methyltrimethylene group, 2-ethyltrimethylene group A 1,1-dimethyltrimethylene group, a 2,2-dimethyltrimethylene group, a 2-ethyl-2-methyltrimethylene group, a 1-ethyl-3-methyltrimethylene group,
2-cyclobutylene group, 1,2-cyclohexylene group,
1,2,2-trimethyl-1,3-cyclopentylene group, 2,3-norbornylene group, vinylene group, methylvinylene group, 1,1-dimethylvinylene group, methyleneethylene group, nonenylethylene group, dodecynylethylene Group,
Octadodecenylethylene group, 1-cyclohexene-
1,2-ylene group, 4-cyclohexene-1,2-ylene group, 5-methyl-4-cyclohexene-1,2-ylene group, 4,5,6-trimethyl-4-cyclohexene-
1,2-ylene group, 5-norbornene-2,3-ylene group, bicyclo [2,2,2] oct-5-ene-2,3
-Ylene group and the like.

Examples of the divalent substituted aliphatic residue of A include a divalent aliphatic residue as described above, which is substituted with an aryl group such as a phenyl group, and an ether having an oxygen atom in the structure. Examples include those in which a bond is formed and those in which a halogen group such as a chloro group is substituted. For example, 1-methyl-1-phenylethylene group, 1-benzyl-1-methylethylene group, 1-phenylethylene group, 1,1-diphenylethylene group, 1-phenyltrimethylene group, 2-phenyltrimethylene group, 1-ethyl-1-phenyltrimethylene group, phenylvinylene group,
Examples thereof include a 3,6-oxo-1,2,3,6-tetrahydrophthalyl group and a 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-ylene group. The divalent aromatic residue of A includes a substituted or unsubstituted arylene group and a heteroaromatic residue, and is preferably a monocyclic or bicyclic ring, for example, an O-phenylene group, 2-naphthylene group, 1,8-naphthylene group,
2,3-pyridylyl group, 2,3-pyrazindiyl group,
Includes a 2,3-benzo [b] thiophenediyl group and the like.

The divalent substituted aromatic residue of A may be a divalent aromatic residue as described above substituted with a lower alkyl group such as a methyl group, a chloro group or a bromo group. And those substituted with a nitro group, an acetamino group and the like, such as 3-methyl-1,2-phenylene group and 4-methyl-
1,2-phenylene group, 3-chloro-1,2-phenylene group, 4-chloro-1,2-phenylene group, 3-bromo-1,2-phenylene group, 3,6-dichloro-1,2-
Phenylene group, 3,6-dibromo-1,2-phenylene group, 3,4,5,6-tetrachloro-1,2-phenylene group, 3,4,5,6-tetrabromo-1,2-phenylene group , 3-nitro-1,2-phenylene group, 3-acetoamino-1,2-phenylene group, 4-chloro-1,8
-Naphthylene group, 4-bromo-1,8-naphthylene group,
4,5-dibromo-1,8-naphthylene group, 4-bromo-5-chloro-1,8-naphthylene group, 4-nitro-
1,8-naphthylene group, 5-methyl-2,3-benzo [b] thiophendiyl group, 5-chloro-2,3-benzo [b] thiophendiyl group, 1-ethyl-2,3-indolediyl And the like. Next, the imide compound and the hydroxyimide compound used in the present invention are exemplified, but not limited thereto.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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These compounds represented by the general formula (I) or (II) can be used alone or in combination, and the amount of the compound is usually 0.1 to 10% based on the total solid content of the photosensitive composition. 1 to 50% by weight, preferably 1 to 50% by weight.
-40% by weight, more preferably 5-30% by weight.

Next, the "compound capable of generating an acid by light or heat" used in the present invention will be described. "Compounds that generate acid by light or heat" that can be used in the present invention
As, a photo-initiator of photo-cationic polymerization, a photo-initiator of photo-radical polymerization, a photo-decolorizing agent of dyes, a photo-discoloring agent, or a known acid generator used in a micro resist or the like,
Known compounds that generate an acid upon thermal decomposition and mixtures thereof can be appropriately selected and used.

For example, S.I. I. Schlesinge
r, Photogr. Sci. Eng. , 18,387
(1974); S. Bal et al, Poly
mer, 21,423 (1980), U.S. Pat. Nos. 4,069,055 and 4,062.
No. 9,056, Re 27,992, JP-A-4-36
Ammonium salt described in the specification of JP-A No. 5049; C.
Necker et al, Macromolecul
es, 17, 2468 (1984); S. Wen
et al, Tech, Proc. Conf. Rad,
Curing ASIA, p478 Tokyo, Oc
t (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056;
V. Crivello et al, Macromol
ecules, 10 (6), 1307 (1977), C
hem. & Eng. News, Nov .; 28, p31
(1988), EP 104,143, U.S. Pat. No. 4,837,124, JP-A-2-150848,
An iodonium salt described in JP-A-2-296514,
J. V. Crivello et al, Polyme
rJ. 17, 73 (1985); V. Clive
Ilo et al. J. Org. Chem. , 43,
3055 (1978); R. Watt et a
1, J .; PolymerSci. , Polymer C
hem. Ed. , 22, 1789 (1984);
V. Crivello et al, Polymer
Bull. , 14, 279 (1985); V. Cr
ivelo et al, Macromolecul
es, 14 (5), 1141 (1981); V. C
riverello et al, J. Mol. Polymer S
ci. , Polymer Chem. Ed. , 17,2
877 (1979), European Patent Nos. 370,693, 390,214, 233,567, and 297,4.
No. 43, No. 297,442, No. 422,570, No. 279,210, U.S. Pat. No. 4,933,377,
No. 161, 811; No. 4, 760, 013; No. 4,
Nos. 7,34,444 and 2,833,827, German Patent Nos. 2,904,626, 3,604,580, and 3,604,581.

J. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977); V. Crivello et a
1, J .; Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979); S. Wen et al, Te
ch, Proc. Conf. Rad. Curing A
Onium salts such as arsonium salts described in SIA, p478 Tokyo, Oct (1988);
905,815, JP-B-46-4605, JP-A-Showa 4
8-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835,
JP-A-61-169837, JP-A-62-58241
JP-A-62-212401, JP-A-63-702
No. 43, the organic halogen compounds described in JP-A-63-298339, K.K. Meier et al, J. Mol. Ra
d. Curing, 13 (4), 26 (1986),
T. P. Gill et al, Inorg. Che
m. , 19, 3007 (1980); Astru
c, Acc. Chem. Res. , 19 (12), 37
7 (1896), and organometallic / organic halides described in JP-A-2-161445; Hayase eta
1, J .; Polymer Sci. , 25, 753 (1
987); Reichmanis et al,
J. Polymer Sci. , PolymerChe
m. Ed. , 23, 1 (1985); Q. Zhu
et al, J.A. Photochem. , 36,85,
39, 317 (1987); Amit et a
1, Tetrahedron Lett. , (24) 2
205 (1973),

D. H. R. Barton et al,
J. Chem. Soc. 3571 (1965);
M. Collins et al, J. Mol. Chem. So
c. , Perkin I, 1695 (1975);
Rudinstein et al, Tetrahedr
on Lett. , (17), 1445 (1975),
J. W. Walker et al, J.A. Am. Che
m. Soc. , 110, 7170 (1988);
C. Busman et al, J. M .; Imaging
Technol. , 11 (4), 191 (1985),
H. M. Houlihan et al, Macrom
olecules, 21, 2001 (1988);
M. Collins et al, J. Mol. Chem. So
c. Chem. Commun. , 532 (197
2), S.M. Hayase et al, Macromo
recules, 18, 1799 (1985); R
Eichmanis et al, J. Mol. Electro
chem. Soc. , SolidState Sci.
Technol. , 130 (6); M. Houli
han et al, Macromolecules,
21, 2001 (1988), EP 0290,7.
Nos. 50, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat. Nos. 3,901,710, 4,181,531, 60-198538, JP-A-53-133022
A photo-acid generator having an o-nitrobenzyl-type protecting group described in M. TUNOOKA et al, Polyme
r Preprints Japan, 38 (8),
G. FIG. Berner et al, J. Mol. Rad. Curi
ng, 13 (4); J. Mijs et al, C
coating Technology. , 55 (697), 4
5 (1983); Akzo, H .; Adachi eta
1, Polymer Preprints, Japan
n, 37 (3), EP 0199,672, 8
No. 4515, No. 199,672, No. 044, 115
No. 0101,122, U.S. Pat. No. 4,618,5.
No. 64, No. 4,371,605, No. 4,431,77
4, JP-A-64-18143, JP-A-2-2457
No. 56, compounds which generate sulfonic acid upon photolysis, such as iminosulfonates described in Japanese Patent Application No. 3-140109, and disulfone compounds described in JP-A-61-166544. it can.

Compounds in which these acid-generating groups or compounds are introduced into the main chain or side chain of the polymer, for example, M.P. E. FIG. Woodhouse et al, J. Mol. A
m. Chem. Soc. , 104, 5586 (198
2), S.M. P. Pappaset al, J .; Imag
ing Sci. , 30 (5), 218 (1986),
S. Kondo et al. Makromol. C
hem. , RapidCommun. , 9, 625 (1
988); Yamada et al, Makro
mol. Chem. , 152, 153, 163 (197
2). V. Crivello et al. J. P
oilmer Sci. , Polymer Chem.
Ed. , 17, 3845 (1979); U.S. Pat.
849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824.
JP-A-62-69263, JP-A-63-1460
37, JP-A-63-163452, JP-A-62-15
No. 3853 and JP-A-63-146029 can be used. In addition, VNR Pillai, Syn
thesis, (1), 1 (1980), A. Abad et al, Tetrahedron L
ett., (47) 4555 (1971), DHR Barton et al, J. Ch.
em, Soc., (C), 329 (1970); U.S. Pat. No. 3,779,7.
No. 78, EP 126,712 and the like, compounds which generate an acid by light can also be used.

Among the above compounds which generate an acid by light or heat, those which are particularly effectively used are described below. (1) The following general formula (VIII) substituted by a trihalomethyl group
Or an S-triazine derivative represented by the following general formula (IX).

[0034]

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[0035]

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In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —CY ₃ . Y represents a chlorine atom or a bromine atom. Specific examples of the oxazole derivative (VIII) and the S-triazine derivative (IX) include the following VIII-1 to VIII and compound IX-1
To 10, but is not limited thereto.

[0037]

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[0038]

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[0039]

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(2) An iodonium salt represented by the following general formula (X) or a sulfonium salt represented by the following general formula (XI).

[0041]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom. R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group or a halogen atom for the aryl group, and a carbon atom for the alkyl group. They are an alkoxy group, a carboxyl group, and an alkoxycarbonyl group represented by Formulas 1 to 8.

[0043] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 -, ClO 4 -, CF 3 S
Condensed polynuclear aromatic sulfonic acid anions such as O ₃ ⁻ , BPh ₄ ⁻ (Ph = phenyl), naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, and a sulfonic acid group-containing dye can be mentioned. It is not limited. Also, two of R ³ , R ⁴ and R ⁵
And Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

The onium salts of the general formulas (X) and (XI) are known and are described, for example, in JW Knapczyk et al, J. A.
m. Chem. Soc., 91, 145 (1969), AL Maycok et a
l, J. Org. Chem., 35, 2532 (1970), E. Goethas et al,
Bull. Soc. Chem. Belg., 73, 546 (1964), HM Lei
cester, J. Am. Chem. Soc., 51, 3587 (1929), JBCr
ivello et al, J. Polym. Chem. Ed., 18, 2677 (1980)
U.S. Pat. Nos. 2,807,648 and 4,24.
7,473, JP-A-53-101331, and the like. Specific examples of the onium compounds of the general formulas (X) and (XI) include, but are not limited to, compounds X-1 to 22 and XI-1 to 34 shown below.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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(3) Disulfone derivatives represented by the following general formula (XII) or iminosulfonate derivatives represented by the following general formula (XIII).

[0056]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenyl group or arylene group. Specific examples of the compounds represented by formulas (XII) and (XIII) include compounds XII-1 to XII-1 shown below.
12 and XIII-1 to XIII-12, but are not limited thereto.

[0058]

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[0059]

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[0060]

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[0061]

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The amount of the compound capable of decomposing upon irradiation with radiation to generate an acid is generally used in the range of 0.001 to 40% by weight, based on the total solid content of the photosensitive composition, and is preferably used. It is used in the range of 0.1 to 20% by weight.

The polymer compound used in the present invention thermally reacts with an imide compound or a hydroxyimide compound in the presence of an acid to form a cured film, and becomes insoluble in a solvent or an alkali developing solution. The film properties of the cured film and the resistance to solvents and alkali developing solutions are important factors in designing photosensitive materials in applications such as printing plates and resists. The polymer compound used in the present invention is a binder having a structure represented by the general formula (III) as a constituent unit, and has characteristics of high film properties after curing, and high resistance to solvents and alkali developing solutions. The polymer compound having a structure represented by the general formula (III) as a constituent unit preferably has a monomer structural unit containing a hydroxyl group, and further has another monomer structural unit copolymerizable with the monomer. Is also good.

The binder used in the present invention includes:
Specific examples include p-hydroxystyrene or a copolymer of p-hydroxymethylstyrene and another vinyl monomer copolymerizable therewith. The above p-
As the other vinyl monomer copolymerizable with hydroxystyrene or p-hydroxymethylstyrene, a vinyl monomer having a hydroxyl group is preferable. Specifically, butanediol monoacrylate, EHC-modified butyl acrylate, 3-chloro-2-hydroxy Propyl methacrylate, glycerol methacrylate, glycerol acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, phenoxypropyl hydroxyacrylate, E
O-modified phthalic acrylate, EO, PO-modified phthalic methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, p-2
-Hydroxyethylstyrene, m-hydroxystyrene, and the like, but are not limited thereto.

P-Hydroxystyrene or p-hydroxymethylstyrene and a hydroxyl-containing vinyl monomer can be copolymerized in any combination and in any ratio. For example, the ratio may be (p-hydroxystyrene) Or p-hydroxymethylstyrene) /
(Vinyl monomer containing hydroxyl group) = (10-70)
The range of / (0 to 90) is appropriate, and the preferable range is (30 to 60) / (0 to 70).

The molecular weight of these polymers is 1,000 to
1,000,000, preferably 1,500-200,
000, more preferably 2,000 to 100,000. Although the polymer of the present invention can be used alone, it may be used as a mixture of several kinds. The amount of the polymer added in the photosensitive composition is generally from 1 to the total solid content of the photosensitive composition.
It is in the range of 95% by weight, preferably 20-90% by weight, more preferably 30-80% by weight.

The radiation-absorbing substance which can be preferably used in the photosensitive and heat-sensitive composition of the present invention is light (radiation).
A substance that absorbs heat and generates heat. Various pigments or dyes are used as such substances. Examples of the pigment include commercially available pigments and Color Index (C.I.).
Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 197
7th year), “Latest Pigment Application Technology” (CMC Publishing, 198
6th year), "Printing ink technology" (CMC Publishing, 1984)
The pigments described in the annual publication can be used.

The pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigments, green pigments, fluorescent pigments, and other polymer-bound dyes are included. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments,
Inorganic pigments, carbon black and the like can be used.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Conceivable. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 198).
6th edition).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Dispersers include ultrasonic disperser, sand mill, attritor, pearl mill, super mill, ball mill, impeller, desparser, KD
Mill, colloid mill, dynatron, three roll mill,
A pressure kneader and the like can be mentioned. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

As the dyes, commercially available dyes and literatures (for example, “Handbook of Dyes” edited by the Society of Synthetic Organic Chemistry, Showa 4
A publicly known one described in the fifth edition can be used. Specific examples include dyes such as azo dyes, metal chain salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes.

Among these pigments or dyes, those that absorb infrared light or near infrared light are particularly preferred.
Carbon black is suitably used as a pigment that absorbs infrared light or near infrared light. Examples of dyes that absorb infrared light or near infrared light include, for example, JP-A-58-12.
No. 5246, No. 59-84356, No. 59-2028
Cyanine dyes described in JP-A-58-173696 and JP-A-58-18.
Methine dyes described in JP-A-58-112793 and JP-A-58-194595;
No.224793, No.59-48187, No.59-73
No. 996, No. 60-52490, No. 60-63744
Naphthoquinone dyes described in JP-A-58-
And squarylium dyes described in 112792 and the like and cyanine dyes described in British Patent No. 434,875.

Further, a near-infrared absorbing agent described in US Pat. No. 5,156,938 is also preferably used. Further, substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924, trimethinethiapyrylium salts described in JP-A-57-142645 (U.S. Pat. No. 4,327,169), JP-A-58-181051, 5
Nos. 8-220143, 59-41363 and 59-
No. 84248, No. 59-84249, No. 59-146
Nos. 063 and 59-146061; cyanine dyes described in JP-A-59-216146; pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475; Fairness 5-135
The pyrylium compounds disclosed in JP-A Nos. 14 and 5-19702 are particularly preferably used.

Another particularly preferred example is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 2% by weight, based on the total solid content of the photosensitive composition.
0% by weight, more preferably 0.5 to 15% by weight, can be added to the photosensitive composition. The amount added is 0.
If it is less than 01% by weight, no image can be obtained, and if it is more than 50% by weight, non-image portions are stained during printing.

The photosensitive and heat-sensitive composition of the present invention can be coated on a support using a solvent in which the above components are dissolved or dispersed. Further, for a resist material such as a semiconductor, it can be used as dissolved in a solvent. Examples of the solvent used here include methanol, ethanol, propanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-
Dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate,
Ethyl lactate, γ-butyrolactone, dimethoxyethane,
Tetramethylurea, N, N-dimethylacetamide,
There are N-methylpyrrolidone, sulfolane, toluene and the like, and these solvents are used alone or as a mixture.
Further, a mixed solvent obtained by adding a small amount of water or a solvent that does not dissolve a diazo resin such as toluene or a polymer compound to these solvents or a mixed solvent is also suitable.

The concentration of the above components (total solids including additives) in the solvent is preferably 2 to 50% by weight, preferably 3 to 30% by weight, more preferably 5 to 20% by weight. When used in the form of a coating, the amount of coating varies depending on the application. For example, a photosensitive lithographic printing plate generally has a solid content of 0.5 to 3.0 g / m ² , preferably 0.8 to ² as solid content. 0.5 g / m ² , more preferably 1.0 to ² .
0 g / m ² , and generally 0.1 to 3.0 g / m ² , more preferably 0.2 to 2.0 g / m ² , still more preferably 0 to 3.0 g / m ² as a solid content of the photoresist. 0.3 to 1.5 g / m ² . As the coating amount decreases, the photosensitivity increases, but the film characteristics of the photosensitive film deteriorate.

A solution dissolved or dispersed in these solvents is applied and dried to form a film, but when a negative photosensitive composition is prepared, it is desirable to dry at 50 ° C. to 100 ° C. Also, alkyl ethers (eg, ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg, fluorine-based surfactants), plasticizers for imparting film flexibility and abrasion resistance (eg, Cresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added.
The amount of these additives varies depending on the purpose of use, but generally ranges from 0.5 to 0.5% based on the total solid content of the photosensitive composition.
30% by weight.

As a printing-out agent for obtaining a visible image immediately after absorption of radiation, a combination of a compound capable of forming a salt with a compound capable of releasing an acid by heat upon exposure can be exemplified. Specifically, JP-A-50-362
No. 09, JP-A-53-8128, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes, and JP-A-53-362.
No. 23, JP-A-54-74728, and combinations of trihalomethyl compounds and salt-forming organic dyes. Dyes other than the salt-forming organic dyes described above can also be used as colorants for images.
Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue B
OS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above,
Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like. These dyes are used in an amount of 0.01 to 10% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the photosensitive composition.
It can be added to the photosensitive composition at a ratio of up to 3% by weight.

The compounds for adjusting the solubility of the photosensitive and heat-sensitive composition in the aqueous alkali solution in the present invention include:
Cyclic anhydrides, other fillers and the like can be added. US Pat. No. 4,115,1 discloses cyclic acid anhydrides.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride as described in US Pat.
3,6-Endoxy-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid and the like. These cyclic anhydrides are preferably used in an amount of 1 to 15% by weight, preferably 2 to 15% by weight, more preferably 3 to 1% by weight, based on the total solid content of the photosensitive composition.
By containing 0% by weight, the sensitivity can be increased up to about three times.

In the present invention, when a substance that absorbs radiation is used and a visible image having a sufficient density can be obtained, it is not necessary to add such a dye. The amount of coating varies depending on the application. For example, a photosensitive lithographic printing plate (heat-sensitive lithographic printing plate) generally has a solid content of preferably 0.5 to 3.0 g / m ² as the coating amount decreases. Although the photosensitivity increases, the physical properties of the photosensitive film decrease. If necessary, a mat or a mat layer may be provided on the photosensitive film.

Examples of the support on which the photosensitive heat-sensitive composition of the present invention is applied include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), such as aluminum (including aluminum alloy), Metal plates such as zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Plastic films, paper or plastic films on which the above-mentioned metal is laminated or vapor-deposited, and the like. Among these supports, it is preferable to use a polyester film or an aluminum plate, and an aluminum plate is particularly preferable because it is extremely stable in dimension. Furthermore, Japanese Patent Publication No. 48-1832
No. 7, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-A-7 is also preferable.

In the case of a support having a metal surface, particularly an aluminum surface, it is desirable to perform an appropriate hydrophilic treatment. Examples of such hydrophilization treatment include mechanical methods such as wire brush graining, brush graining in which a slurry of abrasive particles is poured to roughen the surface with a nylon brush, and ball graining, and HF and AlCl _3. After graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining performed by combining these roughening methods, acid or Etching with alkali, followed by anodic oxidation with a DC or AC power supply in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof to provide a strong passivation film on the aluminum surface preferable. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, U.S. Pat.
No. 066 and U.S. Pat. No. 3,181,461, silicate treatment (sodium silicate, potassium silicate), U.S. Pat. No. 2,946,638, potassium zirconate fluoride treatment, U.S. Pat. 3,201,24
Phosphomolybdate treatment described in the specification of No. 7,
Alkyl titanate treatment described in British Patent 1,108,559, polyacrylic acid treatment described in German Patent 1,091,433, described in German Patent 1,134,093 and British Patent 1,230,447 Polyvinylphosphonic acid treatment, the phosphonic acid treatment described in JP-B-44-6409, U.S. Pat.
No. 951, a composite comprising a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18291. It is particularly preferable to carry out the treatment, which has been subjected to a hydrophilization treatment with an undercoat of a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651.
U.S. Pat.No. 3,658,662 for other hydrophilic treatment methods
Silicate electrodeposition described in the above specification.

The photosensitive heat-sensitive composition of the present invention is coated on the above-mentioned support by a known coating technique. Examples of the above coating technique include spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, and spray coating. The layer of the photosensitive composition applied as described above is formed at 40 to 150 ° C. for 30 seconds to 10 seconds.
It is dried using a hot air drier, an infrared drier or the like for minutes. When the photosensitive heat-sensitive composition of the present invention is used as a photoresist, substrates of various materials such as a copper plate or a copper plated plate, a silicon plate, a stainless steel plate, and a glass plate can be used as a support. The photosensitive lithographic printing plate or photoresist containing the photosensitive heat-sensitive composition in the present invention,
Image exposure and, if necessary, heat treatment and development steps are performed.

Examples of the light source of the actinic ray used for the image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like.
Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Examples of the laser beam include a helium / neon laser, an argon laser, a krypton laser, a helium / cadmium laser, a KrF excimer laser, and the like. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable. The heat treatment after exposure performed in the method for producing an image recording material of the present invention can be performed at 50 ° C. to 250 ° C. for 1 second to 30 minutes, preferably at 70 ° C.
The processing time is from 5 seconds to 5 minutes at ~ 200 ° C.

As a developer and a replenisher for the photosensitive and heat-sensitive composition of the present invention, conventionally known aqueous alkali solutions can be used. For example, sodium silicate, potassium silicate,
Tribasic sodium, potassium, ammonium,
Dibasic sodium, potassium, ammonium,
Inorganic alkali salts such as sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. 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. Their concentration is added to be 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as required for the purpose of accelerating or suppressing the developing property, dispersing the developing residue, and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. In addition, if necessary for the developer and replenisher,
A reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid, and bisulfite, and an organic carboxylic acid, an antifoaming agent, and a water softener can also be added.

Among these developing solutions, particularly preferred are, for example, JP-A-54-62004 and JP-B-57-2004.
No. 7427, Japanese Patent Application Laid-Open No.
1-77401, a developer composition comprising benzyl alcohol, an anionic surfactant, an alkali agent and water; benzyl alcohol, anionic surfactant described in JP-A-53-44202. , A developer composition comprising an aqueous solution containing a water-soluble sulfite, an organic solvent described in JP-A-55-155355, having an solubility in water of not more than 10% by weight at room temperature, an alkali agent and water. And the like.

When the photosensitive and heat-sensitive composition of the present invention is used as a printing plate, it is subjected to a development treatment using the above-mentioned developer and replenisher, followed by washing water, a rinsing solution containing a surfactant and the like, gum arabic and starch derivatives. It is preferable to carry out post-treatment with a desensitizing solution containing These processes can be used in various combinations for post-processing. In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate, each processing solution tank and a spray device, and while pumping the exposed printing plate horizontally, each pumped by a pump. The developing process is performed by spraying a processing liquid from a spray nozzle. Recently, a method has been known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

An image unnecessary for a lithographic printing plate obtained by imagewise exposing, developing, washing and / or rinsing and / or gumming a photosensitive lithographic printing plate using the photosensitive heat-sensitive composition of the present invention. If there is a part (for example, a film edge mark of the original film), the unnecessary image part is erased. Such erasing can be performed by, for example, applying an erasing liquid described in Japanese Patent Publication No. 2-13293 to an unnecessary image portion, leaving the image to stand for a predetermined time, and then washing with water. The lithographic printing plate obtained as described above is coated with a desensitized gum if desired,
It can be subjected to a printing process.

[0090]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Examples 1 to 10 and Comparative Examples 1 to 3 A 1S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium tertiary phosphate maintained at 80 ° C. for 3 minutes, degreased, and sanded with a nylon brush. After dressing, the resultant was etched with sodium aluminate for about 10 minutes, and desmutted with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in a 20% sulfuric acid at a current density of 2 A / dm ² for 2 minutes. Using various compounds shown in Table 1 below, 13 types of photosensitive solutions [A] -1 to [A] -10, [A ']-1 to 13 in the following formulation.
[A ']-3 was prepared. This photosensitive solution was applied onto the anodized aluminum plate and dried at 100 ° C. for 10 minutes to prepare each photosensitive lithographic printing plate. The coating amount at this time was all adjusted to be 1.7 g / m ² in dry weight.

Photosensitive solution formulation [A] Polymer compound of Table-1 2.0 g Imide compound of Table-1, hydroxyimide compound 0.5 g Acid generating compound of Table-1 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Dye-making) 0.1 g 1-methoxy-2-propyl acetate 20.0 g Methyl ethyl ketone 40.0 g

Next, a gray scale having a density difference of 0.15 was brought into close contact with the photosensitive layer of the resulting photosensitive lithographic printing plate,
Exposure was performed for 20 seconds from a distance of 50 cm with a high-pressure mercury lamp of w. After heating the exposed photosensitive lithographic printing plate at 120 ° C. for 5 minutes, the plate is diluted with a two-fold diluted aqueous solution of the following developer stock solution (Y).
It was immersed at 60 ° C for 60 seconds and developed. Stock solution of developing solution (Y) Water 80 g Triethanolamine 3 g Sodium t-butylnaphthalenesulfonate 8 g Benzyl alcohol 9 g The sharpness of the obtained image was visually evaluated. Further, in order to show the sensitivity, up to which density of the gray scale a clear image was obtained is indicated by the number of gray scale steps. The higher the number of gray scale stages, the higher the sensitivity. The results are shown in Table 1 below.

[0094]

[Table 1] 高分子 Polymer Imit ゛ Compound or acid generating photosensitive compound Human peroxyimid compound Compound Image (G / S stage) Example 1 [A] -1 III-1 I-18 X-22 Sharp Neka image (7) Example 2 [A] -2 III-1 I-14 X -22 Clear Neural Image (8) Example 3 [A] -3 III-1 II-18 X-22 Clear Nematic Image (7) Example 4 [A] -4 III-1 II-14 X-22 Clear Neural Image (8) Example 5 [A] -5 III-1 II-18 XII-11 Clear Nematic Image (5) Example 6 [A] -6 III-1 II-18 IX-2 Clear Clear image (6) Example 7 [A] -7 III-1 II-18 XIII-12 Clear image (5) Example 8 [A] -8 III-2 I-14 X-22 Clear image (8) Example 9 [A] -9 III-3 II-14 X-22 Clear Nematic Image (8) Actual Example 10 [A] -10 III-4 II-14 X-22 Clear Nematic Image (7) Comparative Example 1 [A ']-1 III-5 None X-22 No image Comparative Example 2 [A']- 2 III-5 I-18 None Comparative example 3 with no image [A ']-3 III'-1 I-18 X-22 No image

The high molecular compounds III-1 to III'-1 are represented by the following structural formulas.

[0096]

Embedded image

From the results shown in Table 1, it can be seen that Examples 1 to 10, which are the photosensitive compositions of the present invention, all provided clear negative images. On the other hand, those containing no imide compound or hydroxyimide compound (Comparative Example 1),
When a compound that does not contain a compound that generates an acid by light or heat is used (Comparative Example 2), and a polymer compound that does not have a structural unit represented by the general formula (III) is used (Comparative Example 3).
No images were formed.

Example 11 [Production of Substrate] Japanese Patent Application Laid-Open No. 56-28893 discloses
The substrate was manufactured by the method described above. That is, a thickness of 0.24 m
m aluminum plate, nylon brush and 400 mesh
Using a water suspension of pumice stone
After that, it was washed well with water. Then 10% sodium hydroxide
Etching at 70 ° C for 60 seconds
After washing with running water, further 20% HNO_ThreeNeutralized and washed with
Washed with water. Next, this plate was used as an anode when the anode voltage was 12.7V.
Under the condition that the ratio of the amount of electricity at the cathode to the amount of electricity at the time is 0.8
In a 1% nitric acid aqueous solution, a 16
0 coulomb / dm ^TwoElectrolytic surface roughening treatment with the amount of electricity during anode
went. When the surface roughness at this time was measured, it was 0.6 μm.
(Ra display). Then immerse in 30% sulfuric acid
After soaking and desmutting at 55 ° C for 2 minutes, 20% sulfuric acid
Medium, current density 2 A / dm^Two2.7 g / m in thickness
^TwoFor 2 minutes. Then 70 ° C
Immersed in 2.5% aqueous sodium silicate solution for 1 minute, washed with water and dried
Was.

[Preparation of Carbon Black Dispersion] A composition having the following weight ratio was dispersed with glass beads for 10 minutes to obtain a carbon black dispersion. Carbon black 1 part by weight Copolymer of benzyl methacrylate and methacrylic acid 1.6 parts by weight (molar ratio 72:28, weight average molecular weight 70,000) Cyclohexanone 1.6 parts by weight Methoxypropyl acetate 3.8 parts by weight

[Preparation of negative photosensitive lithographic printing plate] The following photosensitive solution was applied to the aluminum plate obtained above,
After drying at 0 ° C for 2 minutes, a negative photosensitive lithographic printing plate was obtained. The weight after drying was 2.0 g / m ² . Photosensitive solution 10 g of the carbon black dispersion liquid Compound I-18 2 g Compound X-22 0.3 g Compound III-6 10 g FC-430 (fluorinated surfactant manufactured by 3M USA) 0.1 g methyl ethyl ketone 50 g

[0101]

Embedded image

The obtained negative photosensitive lithographic printing plate was exposed with a YAG laser adjusted to a plate surface output of 2 W, and then developed by Fuji Photo Film Co., Ltd., DN-3C (1: 1), gum solution FN- When processed through an automatic processor equipped with 2 (1: 1), a negative image was obtained. When this lithographic printing plate was printed by a Heidel SOR-KZ machine, about 30,000 good printed matters were obtained.

Comparative Example 4 In the photosensitive solution composition of Example 11, an oil-soluble dye (Victoria Pure Blue BOH) was used instead of the carbon black dispersion.
A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 11 except that 0.3 g was used. When the photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 11, the photosensitive film was completely dissolved in the developing solution and no image was obtained.

Examples 12 to 14 Samples were prepared in the same manner as in Example 11 except that the compounds shown in Table 2 were used in place of 2 g of Compound I-182 in the composition of the photosensitive solution of Example 11, and YAG When writing and development were performed with a laser, a negative image was obtained. When this printing plate was used for printing under the same conditions as in Example 11, the number of sheets shown in Table 2 and good printed matter were obtained.

[0105]

[Table 2] Imide compounds or Examples Hydroxyimide compounds Number of printed sheets 12 II-5 Approx. 30,000 13 I-5 Approx. 35,014 II-19 Approx. 30,000

Examples 15 to 17 In the photosensitive solution composition of Example 11, 0.3 g of compound X-22
Example 11 except that the compound of Table 3 was used instead of
A sample was prepared in the same manner as described above, and the sample was similarly written with a YAG laser and developed, whereby a negative image was obtained. When this printing plate was used for printing under the same conditions as in Example 11, the number of sheets shown in Table 3 and good printed matter were obtained.

[0107]

Example 3 Acid-generating compound Number of printed sheets 15 IX-5 0.5 g Approx. 30,16 XII-7 0.3 g Approx. 40,16 XIII-2 0.3 g Approx. 35,000

Example 18 A negative photosensitive lithographic printing plate was obtained in the same manner as in Example 11, except that the following dye was used in place of the carbon black dispersion used in Example 11. Dye 2,6-di-t-butyl-4- {5- (2,6-di-t-0.02 g) butyl-4H-thiopyran-4-ylidene) -penta-1,3-dienyl} thiopyrylium Tetrafluoroborate (compound described in U.S. Pat. No. 4,283,475) Using a semiconductor laser (wavelength 825 nm, spot diameter: 1 / e ² = 11.9 μm), the obtained negative photosensitive lithographic printing plate is used. The plate surface output was adjusted to 110 mW at a linear velocity of 8 m / sec, and exposure was performed. Next, when the same developing treatment as in Example 11 was performed, a thin line having a line width of 10 μm was formed.

Next, the beam diameter was adjusted to 6 μ (1 / e ² ), and the beam diameter was adjusted to 20 at a writing resolution of 4000 dpi.
After exposing the dot image of 0 lpi, the same processing was performed to form a dot image. Using the obtained lithographic printing plate and printing on high quality paper using a commercially available ink with a SOR-KZ type printing machine manufactured by Heidelberg Co., Ltd., excellent printability was obtained as in Example 11.

[0110]

According to the present invention, a novel photosensitive and heat-sensitive composition capable of forming a clear negative image can be provided.
Further, it is possible to provide a photosensitive and heat-sensitive composition that can be recorded without depending on the emission wavelength of an exposure light source, particularly a photosensitive and heat-sensitive composition that can be recorded from near infrared to infrared (heat ray). Further, it is possible to provide a novel method for producing an image recording material capable of forming a clear negative image. Furthermore, it is possible to directly record digital data from a computer or the like using a solid-state laser or semiconductor laser (heat mode) having an emission region from near infrared to infrared, and to use a conventional processing device or printing device as it is. A lithographic printing plate for heat mode writing type direct plate making that can be used can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 7/038 7/038

Claims (1)

[Claims] 1. A compound that generates an acid by light or heat, a compound represented by the following general formula (I) or a compound represented by the following general formula (II), and a structure represented by the following general formula (III): A photosensitive heat-sensitive composition comprising a polymer having a component. Embedded image In the formula, A represents a divalent aliphatic residue or a divalent aromatic residue. Embedded image In the formula, R ₁ represents hydrogen or a methyl group.