JP3449818B2 - Image recording material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material which can be used as an offset printing master, and more particularly to a lithographic printing plate for so-called direct plate making which can be made directly from digital signals of a computer or the like.

[0002]

2. Description of the Related Art The development of lasers in recent years has been remarkable, and particularly solid-state lasers having an emission region from near infrared to infrared.
High-power and small-sized semiconductor lasers are easily available. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like.

Conventionally, as a lithographic printing plate which can be directly drawn from digital data of a computer, a printing plate used in an electrophotographic system, a photopolymerization type printing plate in which exposure by an argon laser or a YAG laser and, if necessary, post-heating are combined,
It is known that a silver salt sensitive material is laminated on a photosensitive resin, a silver salt diffusion transfer type, a printing plate of a type in which a silicone rubber layer is destroyed by discharge or laser light.

In the case of using the electrophotographic method, charging, exposure and development processing are complicated, and the apparatus is complicated and large.
The photopolymerizable printing plate originally has a limited sensitivity, and it is difficult to use a small laser and it is difficult to handle in a bright room. The one in which the silver salt sensitive material is laminated and the one in which the silver salt diffusion transfer type is used have the drawbacks that the processing is complicated and the cost is high. Also,
The type in which the silicone rubber layer is destroyed by a laser has a problem in removing the silicone residue remaining on the plate surface.

As a technique capable of forming an image using these light sources, Japanese Patent Application Laid-Open No. 52-113219 discloses a compound (for example, a diazonium compound) which decomposes with light and heat and absorbs light to convert it into heat. A positive type recording material composed of substance particles capable of forming and a binder is disclosed. Further, JP-A-58-148792 discloses a positive type photosensitive and heat-sensitive recording material containing thermoplastic resin particles, a light-heat converting substance and a photo-crosslinking substance (for example, a diazonium compound) as main components. There is.

However, the recording material which can use the above laser as a light source has low sensitivity, and in the case of direct plate making,
Since the digital data of a computer or the like is directly written on the plate material by scanning the laser beam, the positive type material requires a considerable writing time. Therefore, there has been a demand for the development of a highly sensitive material (preferably a negative type) capable of shortening the writing time and capable of solid-state laser / semiconductor laser (thermal mode) having an emission region from near infrared to infrared.

As described above, the lithographic printing plate capable of directly drawing from the digital data of the conventional computer is not sufficiently satisfactory. On the other hand, vinyl ether group-containing compounds are generally known as one type of polymerizable compounds. This vinyl ether group-containing compound is being developed mainly as a cationically polymerizable compound. Cationic polymerization is characterized in that it has no effect of inhibiting the polymerization of oxygen during polymerization and has a small volume contraction, as compared with radical polymerization. Therefore, the vinyl ether group-containing compound can be used as a UV curable resin in combination with a photo acid generator to form an ink, a paint,
Recently, it has been used to create 3D stereoscopic images.

Known examples of the photo-acid generator (photo-cationic polymerization initiator) include diazonium salts, sulfonium salts, iodonium salts, pyrilinium salts and thiopyrrinium salts. None of these combinations of cationic polymerization monomer and photoacid initiator have sufficient sensitivity. See Stephe
n C. Lapin, Polymers Paint Color Journal, 179 (423
7), 321 (1989) describes a highly sensitive photo-cationic polymerizable monomer, but most of the practically effective photo-acid generators used in this technology absorb at 450 nm or less, and As the light source, only a light source that emits light having a wavelength of 450 nm or less can be used.

[0009]

An object of the present invention is to provide an image recording material capable of recording without depending on the emission wavelength of the exposure light source, and particularly recording from near infrared to infrared (heat rays). It is to provide a possible image recording material. Further, an object of the present invention is to use a solid-state laser / semiconductor laser (thermal mode) having a light emitting region from near infrared to infrared to directly record digital data of a computer and the like, and a conventional processing device. Another object of the present invention is to provide a lithographic printing plate for heat mode writing type direct plate making that can be used as it is or a printing device.

[0010]

In order to achieve the above-mentioned object, as a result of studying the thermal change of various image recording materials (hereinafter sometimes referred to as photosensitive materials and photosensitive compositions), acid precursors ( Photoacid generator) and a compound having two or more enol ether groups (photovinyl ether groups) in the molecule and a cationically polymerizable composition solution containing a specific alkali-soluble resin, which absorbs radiation. The inventors have found that a film obtained by mixing (for example, a carbon black dispersion solvent) and coating and drying it on a support at a relatively low temperature becomes insoluble in an alkaline aqueous solution by irradiation with YAG laser light, and arrived at the present invention.

The present invention includes (1) a substance that absorbs radiation, an acid precursor, a compound having at least two enol ether groups represented by the following general formula (I) in the molecule,
And methacrylic acid copolymer, acrylic acid copolymer,
Taconic acid copolymer, crotonic acid copolymer, maleic acid copolymer
Polymers and partially esterified maleic acid copolymers
A negative-type image recording material containing at least one selected from the group consisting of:

[0012]

[Chemical 2]

In the formula, R ₁ , R ₂ and R ₃ represent hydrogen, an alkyl group or an aryl group, and may be the same or different. Also, two of them may combine to form a saturated or olefinically unsaturated ring. Preferred embodiments of the present invention include the following (2) to (10).

(2) A compound having at least two enol ether groups represented by the following general formula (I) in the molecule, a substance that absorbs infrared light or near infrared light, an acid precursor, and a support. And a negative-type image recording material which is a lithographic printing plate for direct plate-making for heat mode writing, containing an alkali-soluble resin. (3) On a support, a substance absorbing infrared light or near infrared light, an acid precursor, a compound having at least two enol ether groups of general formula (I) in the molecule, and an alkali-soluble resin Ne characterized by comprising providing a layer containing
Moth-type image recording material.

(4) The negative image recording material according to (3) above, which uses a dye as a substance that absorbs infrared light or near infrared light. (5) The negative image recording material according to the above (3), which uses a pigment as a substance that absorbs infrared light or near infrared light. (6) The negative image recording material according to the above (3), wherein carbon black is used as a substance that absorbs infrared light or near infrared light.

(7) The negative image recording material according to the above (3), which uses a polyester film as a support. (8) The negative of (3) above, which uses an aluminum plate as a support.
Type image recording material. (9) On the support, a substance that absorbs radiation , an acid precursor,
Compounds having at least two enol ether groups of the general formula (I) in the molecule, and as the alkali-soluble resin
Methacrylic acid copolymer, acrylic acid copolymer, itacone
Acid copolymer, crotonic acid copolymer, maleic acid copolymer
And a group consisting of partially esterified maleic acid copolymers
Negative image recording material containing at least one selected from
The lithographic printing plate with a photosensitive layer
Or a laser emitting infrared or near infrared light
An image recording method characterized by performing image exposure .

(10) The negative image recording material as described in (3) above, which is a heat-sensitive lithographic printing plate. The present invention, the thermal energy obtained by the absorption of the radiation of the substance that absorbs the radiation, the acid precursor is decomposed, generating an acid, as a result, the cationic polymerization of the enol ether group-containing compound proceeds, It creates a negative image.

Therefore, it is preferable that the radiation is infrared light or near-infrared light because good recording in the thermal mode can be achieved. In the present invention, the substance that absorbs infrared light or near infrared light is preferably a dye from the viewpoint of developability after exposure, and is preferably a pigment because sensitivity is good. Carbon black is preferable because it has a wide absorption wavelength range and high sensitivity.

In the present invention, the use of polyester as the support is preferable in that it is light in weight and a light-transmitting image can be obtained, and if an aluminum plate is used, it is excellent in dimensional stability and durability. The image recording material of the present invention is preferably subjected to a recording method in which the image recording material is exposed using a laser emitting infrared light or near infrared light and then developed with alkaline water.

When the image recording material of the present invention is a lithographic printing plate, it is preferably a heat mode writing type lithographic printing plate for direct plate making. The heat mode writing is to record on the image recording material by using an appropriate heat ray source, controlling the heat ray source based on digital data. The heat ray source at this time is a thermal head used in a facsimile machine or a thermal copying machine, or a laser emitting infrared light or near infrared light. For direct plate making, infrared light or near infrared light is used. Lasers that emit light are preferred.

The preferred light used in the present invention is near-infrared rays and infrared rays, of which infrared rays are generally called heat rays, and the present invention can be said to be heat-sensitive when the recording of the present invention is carried out by infrared rays.

The present invention will be described in detail below. In the present invention, a substance that absorbs radiation is a substance that absorbs light (radiation) and generates heat. Various pigments or dyes are used as such substances. As the pigment, commercially available pigments and color index (CI) handbooks,
Pigments recorded in "Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" (CMC Publishing, 1984) are used. it can.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Examples include blue pigments, green pigments, fluorescent pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacrid pigments, dioxazine pigments, isoindolinone pigments. ,
Quinophthalone pigment, dyed lake pigment, azine pigment,
Nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black and the like can be used.

These pigments may be used without surface treatment or may be subjected to surface treatment before use. Surface treatment methods include resin or wack surface coating, surfactant attachment, reactive substances (eg, silane coupling agents, epoxy compounds, polyisocyanates, etc.)
It is possible to consider a method of binding the pigment to the surface of the pigment. The above surface treatment method is "property and application of metal soap" (Koushobo),
"Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, and more preferably in the range of 0.05 μm to 1 μm. As a method of dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. As the disperser, ultrasonic disperser, sand mill, attritor, pearl mill, super mill, ball mill, impeller, disperser, 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 dyes, commercially available dyes and literatures (for example, "Dye Handbook" edited by the Society of Organic Synthetic Chemistry, Showa 4)
The publicly known thing described in the 5-year publication can be used. Specific examples thereof include dyes such as azo dyes, metal chain salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes.

Among these pigments or dyes, those absorbing infrared light or near infrared light are particularly preferable.
Carbon black is preferably used as a pigment that absorbs infrared light or near infrared light. Examples of the dye that absorbs infrared light or near infrared light include, for example, JP-A-58-12.
No. 5246, No. 59-84356, No. 59-2028.
29, 60-78787 and the like, cyanine dyes described in JP-A Nos. 58-173696 and 58-18.
1690, 58-194595 and the like, methine dyes described in JP-A-58-112793 and 58-
224793, 59-48187, 59-73
No. 996, No. 60-52940, No. 60-63744.
Naphthoquinone dyes described in JP-A-58-
Examples thereof include squarylium dyes described in 112792, cyanine dyes described in British Patent 434,875, and the like.

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

Another particularly preferable example is the near-infrared absorbing dyes 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 image recording material.
It can be added to the image recording material in an amount of 0% by weight, more preferably 0.5 to 15% by weight. Addition amount is 0.
If the amount is less than 01% by weight, an image cannot be obtained, and if the amount is more than 50% by weight, stains occur on the non-image portion during printing.

Next, the compound having two or more enol ether groups represented by the general formula (I) used in the present invention will be explained. Here, if the number of enol ether groups is one, it cannot be crosslinked and the effect of the present invention cannot be effectively obtained. In the enol ether group of the general formula (I), when R ₁ , R ₂ and R ₃ are aryl groups, they generally have 4 to 20 carbon atoms and are alkyl groups,
It may be substituted with an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylmercapto group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom.

When R ₁ , R ₂ and R ₃ represent an aryl group, it represents a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, a halogen atom, a cyano group,
It may be substituted with an ester group, an oxy group, an alkoxy group, an aryloxy group or an aryl group. Also,
When any _{two of} R ₁ , R ₂ and R ₃ are combined to form a cycloalkyl group or a cycloalkenyl group, it usually represents 3 to 8, preferably 5 or 6 ring members.

In the present invention, among the enol ether groups represented by the general formula (I), it is preferable that _one of R ₁ , R ₂ and R ₃ is a methyl group or an ethyl group,
The remainder is an enol ether group having hydrogen atoms, and more preferred is a vinyl ether group in which R ₁ , R ₂ and R ₃ are all hydrogen. Although various compounds containing two or more enol ether groups can be used in the present invention,
These are compounds having a boiling point of 60 ° C. or higher under atmospheric pressure, and preferable compounds having a vinyl ether group include vinyl ether compounds represented by the following general formula (II) or (III).

[0033] A - _{[- O- (R 4 -O) n} -CH = CH 2 ] _m (II) A - _{[- B-R 4 -O-CH} = CH 2 ] _m (III) wherein, A Is an m-valent alkyl group, an aryl group or a heterocyclic group, B is -CO-O-, -NHCOO- or -NHCONH-, and R ₄ is a linear or branched alkylene group having 1 to 10 carbon atoms. , N is an integer of 0 or 1 to 10, and m is an integer of 2 to 6.

The compound represented by the general formula (II) is, for example,
Stephen. C. Lapin, Polymers Paint Color Journal,
179 (4237), 321 (1988), i.e., a reaction between a polyhydric alcohol or a polyhydric phenol and acetylene, or a reaction between a polyhydric alcohol or a polyhydric phenol and a halogenated alkyl vinyl ether. You can

Specific examples include ethylene glycol divinyl ether, triethylene glycol divinyl ether,
1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol Divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene Recall diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether,
Pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether,
1,2-di (vinyl ether methoxy) benzene, 1,
Examples thereof include 2-di (vinyl ether ethoxy) benzene and compounds represented by the following general formulas (II-1) to (II-41), but the compounds are not limited thereto.

[0036]

[Chemical 3]

[0037]

[Chemical 4]

[0038]

[Chemical 5]

[0039]

[Chemical 6]

[0040]

[Chemical 7]

[0041]

[Chemical 8]

[0042]

[Chemical 9]

[0043]

[Chemical 10]

[0044]

[Chemical 11]

On the other hand, general formula (III) (B = CO-O-
In the case of) can be produced by reacting a polycarboxylic acid with a halogenated alkyl vinyl ether. Specifically, terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, terephthalic acid dipropylene vinyl ether, isophthalic acid dipropylene vinyl ether, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, itaconic acid diethylene. Examples thereof include vinyl ether, but are not limited thereto.

Further, as the enol ether group-containing compound preferably used in the present invention, the following general formula (I
Examples thereof include enol ether group-containing compounds synthesized by reacting an enol ether compound having active hydrogen represented by V), (V) or (VI) with a compound having an isocyanate group. _{CH 2 = CH-X-R} 5 -OH (IV) CH 2 = CH-X-R 5 -COOH (V) CH 2 = CH-X-R 5 -NH 2 (VI) wherein R ₅ is the number of carbon atoms 1-10 linear or branched alkylene groups are shown. X represents an oxygen atom or a sulfur atom. As the compound having an isocyanate group, for example, the compounds described in Crosslinking Agent Handbook (Taisei-sha, 1981) can be used.

Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, O- Polyisocyanate type such as tolylene diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylol propane, adduct of hexamethylene diisocyanate and water, xylene di Examples thereof include polyisocyanate adduct types such as adducts of isocyanate and trimethylolpropane.

By reacting the above isocyanate group-containing compound with the active hydrogen-containing enol ether group-containing compound, various compounds having an enol ether group at the terminal can be prepared. Examples of compounds having an enol ether group used in the present invention are listed below, but the scope of the present invention is not limited thereto.

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

The compounds containing at least two enol ether groups in the molecule described above can be used alone, but may be used as a mixture of several kinds. The addition amount of the compound containing an enol ether group in the photosensitive composition is
Generally, it is in the range of 1 to 80% by weight, preferably 5 to 50% by weight, based on the total solid content of the photosensitive composition.

Within this range, cationic polymerization is efficiently promoted and an image film having high film strength can be obtained.

Next, the acid precursor used in the present invention will be described. Examples of the acid precursor that can be used in the present invention include known photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decoloring agents for dyes, photo-discoloring agents, or known micro resists. Known compounds such as acid generators that thermally decompose to generate acids, and mixtures thereof can be appropriately selected and used.

For example, S. I. Schlesinge
r, Photogr. Sci. Eng. , 18,387
(1974), T.S. S. Bal et al, Poly
mer, 21, 423 (1980), diazonium salts, U.S. Pat. Nos. 4,069,055 and 4,06.
9,056, Re27,992, and JP-A-4-36.
Ammonium salts described in the specification of No. 5049, D.I. C.
Necker et al, Macromolecule
es, 17, 2468 (1984), C.I. S. Wen
et al, Teh, Proc. Conf. Rad, C
uring ASIA, p478 Tokyo, Oct
(1988), U.S. Pat. Nos. 4,069,055 and 4,069,056;
V. Crivello et al, Macromor
ecules, 10 (6), 1307 (1977), C
hem. & Eng. News, Nov. 28, p31
(1988), European Patent No. 104,143, US Patent Nos. 339,049, 410,201, and Japanese Patent Laid-Open No. Hei 2
-150848, the iodonium salts described in JP-A-2-296514, J. V. Crivello et a
1, Polymer J .; 17, 73 (1985),
J. V. Crivello et al. J. Org.
Chem. , 43, 3055 (1978), W.W. R. W
att et al. Polymer Sci. ，
Polymer Chem. Ed. , 22, 1789
(1984), J. V. Crivello et a
1, Polymer Bull. , 14, 279 (198
5), J. V. Crivello et al, Macr
Omorecules, 14 (5), 1141 (198)
1), J. V. Crivel. lo et al, J .;
Polymer Sci. , Polymer Che
m. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 3,902,114, and 23.
No. 3,567, No. 297,443, No. 297,442
U.S. Pat. Nos. 4,933,377 and 161,81.
1, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626.
Nos. 3,604,580 and 3,604,581,

J. V. Crivello et al,
Macromorecules, 10 (6), 1307
(1977), J. V. Clivel lo et a
l, J. Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979), selenonium salts, C.I. S. Wen et al, Te
h, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), US Pat. No. 3,9.
05,815, JP-B-46-4605, JP-A-48.
-36281, JP-A-55-32070, JP-A-6-
0-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241.
No. 62-212401, 63-702.
43, organic halogen compounds described in JP-A-63-298339, K.K. Meier et al. Ra
d. Curing, 13 (4), 26 (1986),
T. P. Gill et al, Inorg. Che
m. 19, 3007 (1980), D.I. Asru
c, Acc. Chem. Res. , 19 (12), 37
7 (1896), organic metal / organic halides described in JP-A-2-161445, S.I. Hayase eta
l, J. Polymer Sci. , 25,753 (1
987), E. Reichmanis et al,
J. Polymer Sci. , Polymer Ch
em. Ed. 23, 1 (1985), Q.I. Q. Zhu
et al, J .; Photochem. , 36, 8
5, 39, 317 (1987), B.I. Amit et
al, Tetrahedron Lett. , (24)
2205 (1973),

D. H. R. Barton et al,
J. Chem. Soc. 3571 (1965), P.
M. Collins et al. Chem. So
c. , Perkin I, 1695 (1975), M .;
Rudinstein et al, Tetrahedr
on Lett. , (17), 1445 (1975),
J. W. Walker et al. Am. Che
m. Soc. , 110, 7170 (1988), S.I.
C. Busman et al. Imaging
Technol. , 11 (4), 191 (1985),
H. M. Houlihan et al, Macrom
olecules, 21, 2001 (1988), p.
M. Collins et al. Chem. So
c. Chem. Commun. , 532 (197)
2), S. Hayase et al, Macromo
leules, 18, 1799 (1985), E.L. R
eichmanis et al. Electro
chem. Soc. , SolidState Sci.
Technol. 130 (6), F.I. M. Houli
han et al, Macromolecules,
21, 2001 (1988), European Patent No. 0290,7.
50, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat. Nos. 3,901,710, 4,181,531, JP 60-198538, JP-A-53-133022.
A photoacid generator having an o-nitrobenzyl type protecting group described in No. TUNOOKA et al, Polymer
r Preprints Japan, 38 (8),
G. Berner et al. Rad. Curi
ng, 13 (4), W.N. J. Mijs et al, C
oating Technology. , 55 (697), 4
5 (1983), Akzo, H .; Adachi eta
1, Polymer Preprints, Japan
n, 37 (3), European Patent Nos. 0199,672 and 8
4515, 199,672, 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 and Japanese Patent Application No. 3-140109, compounds represented by imino sulfonate and the like, which photolyze to generate sulfonic acid, and disulfone compounds described in JP-A No. 61-166544. it can.

Further, a group in which these acid-generating groups or compounds are introduced into the main chain or side chain of the polymer, such as M.I. E. Woodhouse et al. A
m. Chem. Soc. , 104, 5586 (198
2), S. P. Pappase et al. Image
ing Sci. , 30 (5), 218 (1986),
S. Kondo et al. Makromol. C
hem. , Rapid Commun. , 9,625 (1
988), Y. Yamada et al, Makro
mol. Chem. , 152, 153, 163 (197)
2), J. V. Crivello et al. J. P
oylmer Sci. , Polymer Chem.
Ed. 17,3845 (1979), U.S. Pat.
849,137, German Patent 3,914,407, JP-A-63-26653, JP-A-55-164824.
No. 62-69263, 63-1460.
387, JP-A-63-163452, JP-A-62-1.
The compounds described in JP-A No. 53853 and JP-A No. 63-146029 can be used.

Furthermore, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedr on Lett., (47) 4
555 (1971), DHR Barton et al, J. Chem, Soc.,
(C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used. Among the above acid precursors, those that are particularly effectively used will be described below.

(1) An oxazole derivative represented by the following general formula (VIII) substituted with a trihalomethyl group or an S-triazine derivative represented by the following general formula (IX).

[0061]

[Chemical 15]

[0062]

[Chemical 16]

In the formula, R ¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ² is 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 8 and compound IX-1.
However, the present invention is not limited to this.

[0064]

[Chemical 17]

[0065]

[Chemical 18]

[0066]

[Chemical 19]

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

[0068]

[Chemical 20]

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
Each ⁵ independently represents a substituted or unsubstituted alkyl group or aryl group. Preferred 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 of the numbers 1 to 8.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF
_{^{6 -, PF 6 -, SbF}} 6 -, SiF 6 -, ClO 4 -, CF 3 SO 3 -, BPh 4 - (pH
= Phenyl), condensed polynuclear aromatic sulfonate anions such as naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, sulfonate group-containing dyes, and the like, but are not limited thereto.

Two of R ³ , R ⁴ and R ⁵ , and Ar ¹ and Ar ² may be bonded via a single bond or a substituent. Onium salts represented by the general formulas (X) and (XI) are known, and for example, JW Knapczyk et al,
J. Am. Chem. Soc., 91, 145 (1969), AL Maycok et
al, J. Org. Chem., 35, 2532 (1970), E. Goethas et a
l, Bull. Soc. Chem. Belg., 73, 546 (1964), HM Le
icester, J. Am. Chem. Soc., 51, 3587 (1929), JB
Crivello et al, J. Polym. Chem. Ed., 18, 2677 (198
0), U.S. Pat. Nos. 2,807,648 and 4,24.
It can be synthesized by the method described in the specification or the gazette of JP-A-53-101331.

Specific examples of the onium compounds represented by the general formulas (X) and (XI) include compounds X-1 to 22 and
XI-1 to 34, but not limited thereto.

[0073]

[Chemical 21]

[0074]

[Chemical formula 22]

[0075]

[Chemical formula 23]

[0076]

[Chemical formula 24]

[0077]

[Chemical 25]

[0078]

[Chemical formula 26]

[0079]

[Chemical 27]

[0080]

[Chemical 28]

[0081]

[Chemical 29]

[0082]

[Chemical 30]

(3) A disulfone derivative represented by the following general formula (XII) or an iminosulfonate derivative represented by the following general formula (XIII).

[0084]

[Chemical 31]

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 the general formulas (XII) and (XIII) include the compounds XII-1 to
12 and XIII-1 to 12 but are not limited thereto.

[0086]

[Chemical 32]

[0087]

[Chemical 33]

[0088]

[Chemical 34]

[0089]

[Chemical 35]

The amount of the compound that decomposes upon irradiation with radiation to generate an acid is usually 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 alkali-soluble resin used in the present invention is a linear organic high molecular polymer, and can be arbitrarily selected and used from those having compatibility with the photopolymerizable vinyl ether compound. . When making a negative image recording material, as an alkali-soluble resin,
Addition polymers having a carboxylic acid in the side chain, such as JP-A-5-
9-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048. There are those described, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid in the side chain. In addition to these, a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / another addition-polymerizable vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. To increase the strength of the cured film, alcohol soluble nylon or 2,2
Polyethers of -bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. The linear organic high molecular polymer used for preparing these negative type image recording materials can be mixed in an arbitrary amount in the photosensitive composition. However, when it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the formed image. It is preferably 30 to 85% by weight. The weight ratio of the photopolymerizable vinyl ether compound to the linear organic polymer is preferably in the range of 1/9 to 7/3. A more preferable range is 3/7 to 5/5.

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

The image recording material of the present invention is coated on a support using a solvent which dissolves or disperses the above-mentioned components. As the solvent used here, methanol, ethanol, 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- There are methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc. , These solvents are used alone or as a mixture.

A mixed solvent obtained by adding a small amount of water, a solvent such as toluene, which does not dissolve the diazo resin or the polymer compound, to these solvents or the mixed solvent is also suitable. The concentration (solid content) of the above components in the solvent is 1 to 50% by weight.
A liquid dissolved or dispersed in these solvents is applied and dried to form a film, but it is preferable to dry at 50 ° C to 100 ° C.

Alkyl ethers (eg ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg fluorine-containing surfactants), plasticizers for imparting film flexibility and abrasion resistance. (For example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added.
The amount of these additives added varies depending on the purpose for which they are used, but is generally 0.5 to 0.5 based on the total solid content of the image recording material.
It is 30% by weight.

As a printout agent for obtaining a visible image immediately after absorption of radiation, a combination of a compound which releases an acid by heat from exposure and an organic dye which can form a salt can be mentioned as a representative. Specifically, JP-A-50-362
No. 09, JP-A-53-8128 and combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-362.
The combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A No. 23, JP-A-54-74728 can be mentioned. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used.
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 printout agents and dyes are used in an amount of 0 to 30% by weight in the image recording material. When a visible image having a sufficient density can be obtained by the substance that absorbs radiation according to the present invention, it is not necessary to add such a dye.
Although the coating amount varies depending on the use, for example, in the case of a photosensitive lithographic printing plate (heat-sensitive lithographic printing plate), the solid content is generally preferably 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate. Further, if necessary, a mat or a mat layer may be provided on the photosensitive film.

The support to which the image recording material of the present invention is applied is, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), such as aluminum (including aluminum alloy), zinc, Plates of metal such as copper, for example, plastics such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Film of
It includes paper or plastic film on which the above metal is laminated or vapor deposited. Of these supports, a polyester film or an aluminum plate is preferably used, and an aluminum plate is particularly preferable because it is remarkably dimensionally stable. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Further, in the case of a support having a surface of metal, especially aluminum, it is desirable to carry out a suitable hydrophilic treatment. Examples of such a hydrophilic treatment include a mechanical method such as wire brush graining, brush graining in which a surface of an aluminum surface is roughened with a nylon brush while pouring a slurry of abrasive particles, ball graining, HF or AlCl ₃ , Graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or complex graining performed by combining these surface roughening methods, and then acidifying as necessary. It is possible to form a strong passivation film on the aluminum surface by etching treatment with alkali, and subsequently by anodizing with sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulphamic acid or mixed acid of these with direct current or alternating current power supply. preferable. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, US Patent 2,714,
Silicate treatment (sodium silicate, potassium silicate) described in US Pat. No. 066 and US Pat. No. 3,181,461, potassium zirconium fluoride treatment described in US Pat. No. 2,946,638, US patent 3,201,24
Phosphomolybdate treatment described in No. 7,
Alkyl titanate treatment described in British Patent No. 1,108,559, polyacrylic acid treatment described in German Patent No. 1,091,433, described in German Patent Nos. 1,134,093 and British Patent No. 1,230,447 Polyvinylphosphonic acid treatment described in JP-B-44-6409, U.S. Patent No. 3,307,
Phytic acid treatment described in Japanese Patent No. 951 and a composite of a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18291. Those treated with a hydrophilizing treatment by undercoating a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651 are particularly preferable.
Other hydrophilic treatment methods include U.S. Pat. No. 3,658,662.
The silicate electrodeposition described in the specification can be mentioned.

Examples of the light source of actinic rays used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
Radiation includes electron beams, X-rays, ion beams, far infrared rays, and the like. Also, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are particularly preferable.

As the developing solution and the replenishing solution for the image recording material of the present invention, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, third
Sodium phosphate, potassium, ammonium, second
Sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Inorganic alkali salts such as In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Organic alkaline agents such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more.

If necessary, various surfactants and organic solvents may be added to the developing solution and the replenishing solution for the purpose of accelerating or suppressing the developing property, dispersing the development residue and enhancing the ink affinity of the image portion of the printing plate. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. If necessary, the developer and replenisher
It is also possible to add a reducing agent such as sodium salt or potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid or bisulfite, and further an organic carboxylic acid, an antifoaming agent or a water softener.

Among these developers, particularly preferable ones are, for example, JP-A-54-62004 and JP-B-57-.
Those described in Japanese Patent No. 7427 and Japanese Patent Laid-Open No.
No. 1-77401, a developer composition comprising benzyl alcohol, an anionic surfactant, an alkaline agent and water, and benzyl alcohol, an anionic surfactant described in JP-A-53-44202. Developer, a developer composition comprising an aqueous solution containing a water-soluble sulfite, an organic solvent having a solubility in water of 10% by weight or less at room temperature, an alkaline agent, and water, as described in JP-A-55-155355. And a developer composition containing the same.

When the image recording material of the present invention is used as a printing plate, it is washed with the above-mentioned developing solution and replenishing solution and then rinsed with water, a rinse solution containing a surfactant, gum arabic and a starch derivative. It is preferably post-treated with a desensitizing solution. Various combinations of these treatments can be used for the post-treatment.

In recent years, automatic developing machines for printing plates have been widely used in the plate making / printing industry in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like.

Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

The photosensitive lithographic printing plate using the image recording material of the present invention is subjected to imagewise exposure, development, washing with water and / or rinsing and / or gumming. For example, if there is a film edge mark of the original image film), the unnecessary image portion is erased. Such erasing can be carried out, for example, by applying an erasing liquid to an unnecessary image portion as described in Japanese Patent Publication No. 2-13293, leaving it as it is for a predetermined time, and then rinsing with water.

The lithographic printing plate thus obtained can be subjected to a printing step after applying a desensitizing gum if desired.

[0118]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 [Production of Substrate] A substrate was produced by the method disclosed in JP-A-56-28893. That is, the thickness is 0.24 m
The aluminum plate of m was washed with water after the surface of the aluminum plate was grained using a nylon brush and an aqueous suspension of 400 mesh pumice. Then, it is immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, and then neutralized and washed with 20% HNO 3.
Washed with water. Next, this plate was subjected to 16% in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the conditions that the voltage at the anode was 12.7 V and the ratio of the electricity at the cathode to the electricity at the anode was 0.8.
The electrolytic surface-roughening treatment was performed with an electric quantity at the anode of 0 coulomb / dm @ 2. The surface roughness at this time was measured to be 0.6μ.
(Ra indication). Subsequently, it was immersed in 30% sulfuric acid and desmutted at 55 ° C. for 2 minutes, and then, in 20% sulfuric acid, at a current density of 2 A / dm 2, the thickness was 2.7 g / m 2.
Anodizing treatment was performed for 2 minutes so as to be 2. Then 70 ° C
Was immersed in a 2.5% aqueous solution of sodium silicate for 1 minute, washed with water and dried.

[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 aluminum plate obtained above was coated with the following photosensitive solution, and 8
It was dried at 0 ° C for 2 minutes to obtain a negative photosensitive lithographic printing plate. The weight after drying was 2.0 g / m 2. Photosensitive liquid Carbon black dispersion 10 g Compound II-11 in the text 3 g Compound IX-2 in the text 0.3 g Methyl methacrylate / methacrylic acid 70/30 10 g Molar ratio copolymer, weight average molecular weight 30,000 FC-430 (US 3M Fluorine-based surfactant) 0.1 g Methyl ethyl ketone 50 g The negative photosensitive lithographic printing plate thus obtained 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 on a Heidel SOR-KZ machine, good printed matter was about 3
I got 10,000 copies. Comparative Example 1 In the photosensitive liquid composition of Example 1, 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 1 except that 0.3 g was used. When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 1, all the photosensitive film was dissolved in the developing solution, and no image was obtained. Examples 2 to 4 Samples were prepared in the same manner as in Example 1 except that the compound of Table 1 was used in place of 3 g of the compound (II-11) in the composition of the photosensitive solution of Example 1, and the same was performed using a YAG laser. writing,
After development, a negative image was obtained. When this printing plate was used and printed under the same conditions as in Example 1, the number of sheets shown in Table 1 and good printed matter were obtained.

[0122]

[Table 1]

Examples 5 to 7 In the photosensitive liquid composition of Example 1, compound (IX-2), 0.3 g
A negative image was obtained when a sample was prepared in the same manner as in Example 1 except that the compounds shown in Table 2 were used, writing was similarly performed with a YAG laser, and development processing was performed. When this printing plate was used and printed under the same conditions as in Example 1, the number of sheets shown in Table 2 and good printed matter were obtained.

[0124]

[Table 2]

Example 8 A negative photosensitive lithographic printing plate was obtained in exactly the same manner as in the photosensitive liquid composition of Example 1, except that the linear polymer was changed to the following resin.

[0126]

[Chemical 36]

The negative photosensitive lithographic printing plate thus obtained 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 with a Heidel SOR-KZ machine, about 50,000 good prints were obtained. Example 9 A negative photosensitive lithographic printing plate was obtained in the same manner as in Example 1, except that the following dye was used instead of the carbon black dispersion used in Example 1.

Dye 2,6-di-t-butyl-4- {5- (2,6-di-t-0.02g butyl-4H-thiopyran-4-ylidene) -penta-1,3-dienyl} Thiopyrylium tetrafluoroborate (compound described in U.S. Pat. No. 4,283,475) The obtained negative-type photosensitive lithographic printing plate was subjected to a semiconductor laser (wavelength 825 nm, spot diameter: 1 / e ² = 11.9 μ). ) Was used to adjust the plate surface output to 110 mW at a linear velocity of 8 m / sec, and exposure was performed. Next, when the same developing treatment as in Example 1 was performed, a fine line having a line width of 10 μ could be formed.

Next, the beam diameter is adjusted to 6 μ (1 / e ² ) and similarly, the writing resolution of 4000 dpi is set to 20 μm.
After the exposure of the dot image of 0 lpi, the same process was performed to form a dot image. When the obtained lithographic printing plate was used to print on high-quality paper with a commercially available ink using a SOR-KZ type printer manufactured by Heidelberg, excellent printability was obtained as in Example 1. Comparative Example 2 A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 6 except that 0.2 g of an oil-soluble dye (Victoria Pure Blue BOH) was used in place of the dye in the photosensitive liquid composition of Example 9. did. When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 6, all the photosensitive film was dissolved in the developing solution, and no image was obtained. Example 10 [Preparation of negative photosensitive lithographic printing plate] The aluminum plate prepared in Example 1 was coated with the photosensitive solution of Example 1 and dried at 120 ° C for 10 minutes to obtain a negative photosensitive lithographic printing plate. Obtained. The weight after drying was 2.0 g / m ² .

The negative photosensitive lithographic printing plate thus obtained 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 with a Heidel SOR-KZ machine, about 50,000 good prints were obtained.

[0131]

INDUSTRIAL APPLICABILITY The present invention can provide an image recording material capable of recording without depending on the emission wavelength of an exposure light source, and particularly an image recording material capable of recording from near infrared to infrared (heat rays). be able to. Further, according to the present invention, by recording using a solid-state laser / semiconductor laser (thermal mode) having an emission region from near infrared to infrared, it is possible to make a plate directly from digital data of a computer or the like, and further, a conventional processing device. It is possible to obtain a heat mode writing type lithographic printing plate for direct plate making which can be used as it is or as a printing device.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03F 7/033 G03F 7/033 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (2)

(57) [Claims] 1. A substance that absorbs radiation, an acid precursor, a compound having at least two enol ether groups represented by the following general formula (I) in the molecule, and methacrylic acid copolymerization.
Copolymer, acrylic acid copolymer, itaconic acid copolymer, black
Tonic acid copolymer, maleic acid copolymer, and partial ester
A small number selected from the group consisting of poly (maleic acid) copolymers
A negative image recording material comprising at least one kind . [Chemical 1] 2. A lithographic printing plate having a photosensitive layer made of the negative image recording material according to claim 1 on a support, and imagewise exposed by using a thermal head or a laser emitting infrared or near infrared light. An image recording method comprising: