JPH11327140A - Negative image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative image recording material for a direct printing plate capable of stably performing development without causing image dropouts even when there is a scratch such as a fingerprint thereon. SOLUTION: The material comprises a compound which decomposes by light or heat to generate an acid; a cross-linking agent which forms cross-links by the acid; at least one type of an alkaline soluble resin; an infrared absorbent, and a compound represented by the formula (R<1> -X)n -Ar-(OH)m where R<1> is a C6 -C32 alkyl or alkenyl group; X is a single bond, O, S, COO, or COONH; Ar is an aromatic hydrocarbon, alicyclic hydrocarbon, or heterocyclic group; n is 1 to 3; and m is 1 to 3.

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 a lithographic printing plate material, and more particularly to a so-called direct lithographic printing plate capable of direct plate making using an infrared laser from a digital signal of a computer or the like. The present invention relates to a negative image recording material for printing plates.

[0002]

2. Description of the Related Art In recent years, a system for directly making a plate from digital data of a computer or the like has attracted attention. In addition, the development of laser is remarkable, especially the wavelength of 760 to 1200n.
m solid-state lasers and semiconductor lasers that emit infrared rays are
High power and small size are easily available, and these lasers are very useful as a recording light source for the above system. However, many photosensitive recording materials that are practically useful cannot be image-recorded with these infrared lasers because the photosensitive wavelength is in the visible light region of 760 nm or less.
Therefore, a material that can be recorded by an infrared laser is desired.

As an image recording material which can be recorded by such an infrared laser, there is a recording material composed of an onium salt, a resole resin, a novolac resin, and an infrared absorbent, which is described in JP-A-7-20629. Also,
Japanese Patent Application Laid-Open No. 7-271029 describes a recording material comprising a haloalkyl-substituted s-triazine, a resole resin, a novolac resin, and an infrared absorber. However, in the plate material using these image recording materials,
If the surface is scratched, such as when you touch it with your bare hands when handling it and the surface is scratched, laser exposure,
When each of the heating and developing processes is performed, there is a problem that an image is lost only in a scratched portion. Such a problem is that moisture contained in the outside air or the like enters from a portion in contact with the plate material, and as a result, the compound (A) (for example, diazonium salt) that decomposes by light or heat to generate an acid is decomposed. It is presumed that this is because curing does not occur and the portion that has come into contact with the plate material during development is dissolved.

[0004]

Therefore, an object of the present invention is to enable plate making directly from digital data of a computer or the like by recording with a solid-state laser or a semiconductor laser that emits infrared rays, and further to obtain fingerprints or the like. It is an object of the present invention to provide a negative image recording material which can be stably developed without causing image loss even when scratched, i.e., which is excellent in scratch resistance.

[0005]

[In the formula, X represents a single bond, O, S, COO or CONH, R ¹ is an alkyl group or an alkenyl group having 6 to 32 carbon atoms, Ar is an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group. Represents a ring group. In addition, n and m each independently represent an integer of 1 to 3. ]

In the negative type image recording material of the present invention,
Energy given by a solid-state laser and a semiconductor laser that emits infrared rays is converted into heat energy by the infrared absorbent (D), and the heat decomposes the compound (A) that decomposes by light or heat to generate an acid. Then, an acid is generated, and the acid accelerates the crosslinking reaction between the crosslinking agent (B) that crosslinks with the acid and the alkali-soluble resin (C), whereby image recording, that is, plate making of the recording material is performed. However, when the compound (E) represented by the general formula (a) is present in this system, even if the negative type planographic printing plate material before laser exposure is touched with bare hands, Laser exposure,
It is possible to prevent the image from coming off at the touched portion when a series of processing including heating and development is performed. Although the mechanism is unknown, the above general formula (a)
The compound (E) represented by is unevenly distributed on the surface of the image recording layer to form a barrier-like structure similar to the case where a protective coating is formed on the surface, and even if the surface is slightly scratched, moisture It is considered that this is because the invasion is suppressed and the curing action is not hindered.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Each constituent component and the like of the negative type recording material of the present invention will be sequentially described in detail below. First, the general formula (E) (which is a characteristic component of the present invention) The compound represented by a) will be described.

[(E) General formula (a) (R ¹ -X) _n -A
Compound Represented by r-(OH) _m ] The compound represented by the general formula (a) of the present invention has a substituent having a large number of carbon atoms that is unevenly distributed on the surface of the image recording layer and molecularly aligns in a barrier state. A monohydric or polyhydric phenol compound or a cyclic alcohol compound.

In the formula, R ¹ represents an alkyl group or an alkenyl group having 6 to 32 carbon atoms. The alkyl group or alkenyl group may have a branch, and as the alkyl group,
For example, linear alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, and n-undecyl group, 14-methylpentadecyl group, 1
Examples thereof include branched alkyl groups such as 6-methylheptadecyl group, and examples of the alkenyl group include 1-hexenyl group, 1-heptenyl group, 1-octenyl group, 2-methyl-1-heptenyl group and the like. When R ¹ has a carbon number of less than 6, the fingerprint resistance is inferior, which is not preferable. On the other hand, when the carbon number exceeds 32, the developability of the image recording material is deteriorated and the non-image area is developed. It is not preferable because it may be defective. From the viewpoint of solubility in the coating solvent, R ¹ is preferably an alkyl group or an alkenyl group having 25 or less carbon atoms.

In the formula, Ar represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group. The cyclic group represented by Ar may be a saturated ring or an unsaturated ring, specifically, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a cyclohexyl group, a cyclohexenyl group, a cyclopentyl group, a norbornyl group, a furyl group, A thienyl group,
Examples thereof include a pyridyl group, an indolyl group, a pyrrolidyl group and a pyranyl group.

In the general formula (a), X is a single bond,
It represents an O, S, COO or CONH group, and if it is not a single bond, it has either an ether bond, a thioether bond, an ester bond or an amide bond in the molecule.

Further, n and m in the formula are independently 1
Represents an integer of 3; Therefore, the compound (E) represented by the general formula (a) is a single group or a plurality of groups each having a substituent having a large carbon number within a range of integers n and m and a hydroxyl group at any position of the cyclic group, Alternatively, it is a monovalent or polyvalent phenol compound or cyclic alcohol compound having an arbitrary combination of a single group and a plurality of groups.

Specific examples of the compound (E) represented by the general formula (a) are shown below, but the invention is not limited thereto. In the general formula (a), first, A
Specific examples of the compound (E) in which r is an aromatic hydrocarbon group are given below. X represents a single bond, for example,
Monohydric phenol hexyl group as R ^1, octyl group,
Nonyl group, dodecyl group, 1-hexenyl group, or 2-
R is a divalent phenol such as hexylphenol, octylphenol, nonylphenol, dodecylphenol, 1-hexenylphenol, (2-methyl-1-heptenyl)phenol having a methyl-1-heptenyl group.
4-hexyl resorcinol or the like having a hexyl group as ¹ , or a hydroxyl group and R ¹ or the like at any position of the cyclic group within a range of integers n and m, respectively, a single group or a plurality of groups,
Alternatively, polyhydric phenol compounds having an arbitrary combination of a single group and a plurality of groups may be mentioned.

Further, when X represents O (ether bond), for example, monohydric phenol has (2-ethylhexyl)oxy group as R ¹ -O group or (2-ethylhexyl)oxy group having dodecyloxy group. R for trivalent phenol such as phenol and dodecyloxyphenol
^A disubstituted product of pyrogallol having a hexyloxy group as a ^1- O group or the like, or a R ¹ -O group or the like and a hydroxyl group at any position of the cyclic group within a range of integers n and m, each being a single group or a plurality of groups. Alternatively, polyhydric phenol compounds having an arbitrary combination of a single group and a plurality of groups may be mentioned.

X represents S (thioether bond)
For example, monohydric phenol to R¹ As the -S group
Dodecylthiophenol having decylthio group, etc.
R ¹ -S group, etc. and a hydroxyl group at an arbitrary position of the cyclic group, an integer
Within the range of n and m, a single group or multiple groups, or a single group
Group and polyhydric phenols with any combination of groups
Compounds and the like can be mentioned.

Examples of those in which X represents COO (ester bond) include, for example, dodecyloxycarbonylphenol having a dodecyloxycarbonyl group or a dodecanoyloxy group as R ¹ -COO group in monohydric phenol,
Dodecanoyloxyphenol, etc., such as R ¹ -COO
Examples thereof include a polyhydric phenol compound having a group or the like and a hydroxyl group at arbitrary positions in the cyclic group within a range of integers n and m, respectively, in a single group or a plurality of groups, or in an arbitrary combination of a single group and a plurality of groups.

Examples of those in which X represents CONH (amide bond) include, for example, dodecylaminocarbonylphenol having dodecylaminocarbonyl group, dodecanoylamino group or oleoylamino group as R ¹ -CONH group in monohydric phenol, Dodecanoylaminophenol, oleoylaminophenol, etc., such as R ¹ -CO
A polyhydric phenol compound having an NH group or the like and a hydroxyl group at any position of the cyclic group within the range of integers n and m, respectively, in a single group or a plurality of groups, or in an arbitrary combination of a single group and a plurality of groups, or a monovalent (4- or 5-) dodecanoylamino-1 having a dodecanoylamino group as R ^{1 in} naphthol
-Naphthol and the like, the R ¹ -CONH group and the like and a hydroxyl group at any position of the cyclic group, within the range of integers n and m, respectively, in a single group or a plurality of groups, or in any combination of a single group and a plurality of groups. Examples include valence naphthols.

The compound (E) in which Ar in the general formula (a) is an alicyclic hydrocarbon group is, for example, 2-hexylcyclohexanol, 2-dodecyloxycyclohexanol, 4-dodecanoylaminocyclohexanol. Alicyclic alcohol compounds such as
Examples of the compound (E) in which r is a heterocyclic group include, for example, N
-Octyl-2-hydroxynicotinic acid amide, 1-S
Heterocyclic alcohol compounds such as -octyl-β-D-thioglucopyranoside, sorbitan monolaurate, and N-dodecanoyl-3-pyrrolidinol.

Of the above, the cyclic group represented by Ar in the general formula (a) is preferably an aromatic hydrocarbon group from the viewpoint of easy availability, and is further a phenyl group or a naphthyl group. Is particularly preferable. In addition, it is particularly preferable that n and m in the formula are independently 1 or 2 from the viewpoint of easy availability.

The addition amount of the compound represented by the general formula (a) is 0.5 to the total solid content of the image recording material.
The range is preferably 10% by weight, more preferably 1 to 6% by weight. If the addition amount of the compound represented by the general formula (a) is less than 0.5% by weight, the wax film formed on the surface of the image recording material becomes thin and the fingerprint resistance is deteriorated, which is not preferable. On the other hand, the effect is saturated at 10% by weight, so that it is not necessary to add more.

The constituent components other than the component (E) of the negative image recording material of the present invention will be described below. [(A) Compound that decomposes to generate acid when exposed to light or heat]
In the present invention, the compound that decomposes by light or heat to generate an acid (hereinafter, appropriately referred to as “acid generator”) is 20
It refers to a compound that generates an acid by irradiation with light having a wavelength of 0 to 500 nm or heating at 100° C. or higher. As the acid generator preferably used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes,
A known compound that thermally decomposes to generate an acid, such as a photochromic agent or a known acid generator used for a micro resist, and a mixture 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), the diazonium salt, U.S. Pat. Nos. 4,069,055 and 4,06.
9,056, Re27,992, 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, Macromol
ecules, 10(6), 1307(1977), C
hem. & Eng. News, Nov. 28, p31
(1988), European Patent No. 104,143, U.S. Patent Nos. 339,049, 410,201, and Japanese Patent Laid-Open No. Hei 2
-150848, 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.I. R. W
att et al. Polymer Sci. ，
Polymer Chem. Ed. , 22, 1789
(1984), J. V. Crivello et a
l, Polymer

Bull. , 14, 279 (1985),
J. V. Crivello et al, Macrom
olecules, 14(5), 1141 (198).
1), J. V. Crivello et al. P
polymer Sci. , Polymer Chem.
Ed. , 17, 2877 (1979), European Patent No. 37.
0,693, 390,214, 233,567
No. 297,443, No. 297,442, and U.S. Pat. Nos. 4,933,377, 161,811 and 4
10,201, 339,049, 4,760,
013, 4,734,444, 2,833,8
27, German Patents 2,904,626 and 3,60
Sulfonium salts described in 4,580, and 3,604,581,

J. V. Crivello et al,
Macromolecules, 10(6), 1307
(1977), J. V. Crivello et a
1, J.I. 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.
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.
JP-A-62-212401, JP-A-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 et
al, J.; Polymer Sci. , 25,753
(1987), E.I. Reichmanis et a
1, J.I. Polymer Sci. , Polymer
Chem. Ed. 23, 1 (1985), Q.I. Q. Z
hu et al, J Photochem. , 36,
85, 39, 317 (1987), B.I. Amitet
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, Tetrahed
ron Lett. , (17), 1445 (197)
5), J. W. Walker et al. Am.
Chem. Soc. , 110, 7170 (1988),
S. C. Busman et al. Imagin
g Technol. , 11(4), 191 (198
5), H. M. Houlihan et al, Mac
romolecules, 21, 2001 (198
8), P. M. Collins et al. Ch
em. Soc. Chem. Commun. 532
(1972), S.H. Hayase et al, Mac
romolecules, 18, 1799 (198
5), E. Reichmanis et al. E
retrochem. Soc. , SolidStat
e Sci. Technol. 130(6), F.I.
M. Houlihan et al, Macromol
ecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083 and 15
No. 6,535, No. 271,851, No. 0,388,3
43, US Pat. Nos. 3,901,710 and 4,18.
1,531, JP-A-60-198538, JP-A-5
No. 3-133022, a photo-acid generator having an o-nitrobenzyl type protecting group, M.K. Tsunoka et a
1, Polymer Preprints Japan
n, 38(8), G.I. Berner et al.
Rad. Curing, 13(4), W.W. J. Mijs
et al, Coating Technology. , 5
5 (697), 45 (1983), Akzo, H.; Ad
achi et al, Polymer Prepri
nts, Japan, 37(3), European Patent No. 019.
No. 9,672, No. 84515, No. 199,672,
044,115, 0101,122, U.S. Pat. Nos. 4,618,564, 4,371,605, 4,431,774, JP-A-64-18143 and JP-A-2- No. 245756, Japanese Patent Application No. 3-140109, and other compounds which generate sulfonic acid upon photolysis, represented by iminosulfonates, and JP-A-61-1665.
The disulfone compound described in No. 44 can be mentioned.

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.
Am. Chem. Soc. , 104, 5586 (198
2), S. P. Pappase et al. Imag
ing Sci. , 30(5), 218(1986),
S. Kondo et al. Makromol. C
hem. , Rapid Commun. , 9,625
(1988), Y. Yamada et al, Mak
romol. Chem. , 152, 153, 163(1
972), J. et al. V. Crivello et al.
J. Polymer Sci. , Polymer Ch
em. Ed. , 17,3845 (1979), U.S. Pat. No. 3,849,137, German Patent No. 3,914,40.
7, JP-A-63-26653, JP-A-55-1648
24, JP-A-62-69263, JP-A-63-14.
6037, JP-A-63-163452, JP-A-62-
The compounds described in JP-A-153853 and JP-A-63-146029 can be used.

Further, V. N. R. Pillai, Syn
these, (1), 1 (1980), A.S. Abad
et al, Tetrahedron Lett. ，
(47) 4555 (1971), D.I. H. R. Bart
on et al, J. et al. Chem, Soc,. (C),
329 (1970), U.S. Pat. No. 3,779,778.
The compounds which generate an acid by light described in JP-A No. 126,712 and the like can also be used. Among these, as the acid generator particularly preferably used in the present invention,
The compound represented by the following general formula (I)-(V) is mentioned.

[0028]

[Chemical 1]

[In the formula, R ¹ , R ² , R ⁴ and R ⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. R ³ represents a halogen atom, an optionally substituted hydrocarbon group having 10 or less carbon atoms or an alkoxy group having 10 or less carbon atoms. Ar ¹ and Ar ² may be the same or different,
The aryl group having 20 or less carbon atoms which may have a substituent is shown. R ⁶ has 2 carbon atoms which may have a substituent.
It represents 0 or less divalent hydrocarbon groups. n shows the integer of 0-4. ]

In the above general formulas (I) to (V), R
¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrocarbon group having 20 or less carbon atoms, which may have a substituent, and preferably a hydrocarbon group having 1 to 14 carbon atoms. .. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-
Propyl group, i-propyl group, n-butyl group, sec-
Butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, undecyl group, dodecyl group and other alkyl groups, allyl group, vinyl group,
Alkenyl groups such as 1-methylvinyl group and 2-phenylvinyl group, aralkyl groups such as benzyl group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group, anthracenyl group. And aryl groups such as groups. These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group and a carboxy group. Specific examples of the hydrocarbon group having a substituent include trifluoromethyl group, chloroethyl group, 2-methoxyethyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, phenoxyphenyl group, Examples thereof include a methoxyphenylvinyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, and a 9,10-dimethoxyanthracenyl group.

R ³ is a halogen atom, a hydrocarbon group having 10 or less carbon atoms which may have a substituent (for example, an alkyl group, an alkenyl group, an aralkyl group, an aryl group) or a C 10 or less carbon atom. Indicates an alkoxy group. Specifically, halogen atoms of fluorine, chlorine, bromine, iodine, methyl group, ethyl group, n-propyl group, i-propyl group, allyl group, n-butyl group, sec-butyl group, t-butyl group, Hydrocarbon groups such as hexyl group, cyclohexyl group, benzyl group, phenyl group, tolyl group, 2-methoxyethyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group and other substituents An alkoxy group such as a hydrogen group, a methoxy group or an ethoxy group can be used. When n is 2 or more,
Two adjacent R ³ 's may combine with each other to form a condensed ring.

Ar ¹ and Ar ^{2, which} may be the same or different, each represents an aryl group having 20 or less carbon atoms, which may have a substituent, preferably an aryl group having 6 to 14 carbon atoms. Show. Specifically, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, chloronaphthyl group, Examples thereof include a methoxyphenyl group, a phenoxyphenyl group, an ethoxynaphthyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, a nitronaphthyl group and an anthracenyl group.

R ⁶ is a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent (eg, alkylene group, alkenylene group, aralkylene group, arylene group).
Indicates. Specifically, ethynylene group, 1,2-cyclohexenylene group, 1,2-phenylene group, 4-chloro-
1,2-phenylene group, 4-nitro-1,2-phenylene group, 4-methyl-1,2-phenylene group, 4-methoxy-1,2-phenylene group, 4-carboxy-1,2-
Examples thereof include a phenylene group and a 1,8-naphthalenylene group. n shows the integer of 0-4. Here, when n is 0, it means that there is no R ₃ , that is, it is a hydrogen atom.

Among the compounds represented by the general formulas (I) to (V), preferred ones are listed below. Incidentally, these compounds are disclosed in, for example, JP-A Nos. 2-100054 and 2-1
It can be synthesized by the method described in No. 00005.

[0035]

[Chemical 2]

[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]

[0045]

[Chemical formula 12]

As the acid generator (A), an onium salt having a counter ion such as halide or sulfonic acid, preferably an iodonium salt, a sulfonium salt or a diazonium salt represented by the following general formulas (VI) to (VIII) is used. Those having any of the structures can be preferably mentioned.

[0047]

[Chemical 13]

[Wherein X^-Is a halide ion, C
10_Four ^-, PF₆ ^-, SbF₆ ^-, BF_Four ^-Or R⁷
-SO₃ ^-, Where R⁷ Has a substituent
Optionally represents a hydrocarbon group having 20 or less carbon atoms. Ar
³ , Ar^Four Is an optionally substituted carbon
An aryl group of 20 or less is shown. R⁸ , R⁹ , And R ^Ten
Is a hydrocarbon having 18 or less carbon atoms which may have a substituent
Indicates a group. ]

In the above general formulas (VI) to (VIII), X
^{As -} , R ⁷ -SO ₃ ^- is particularly preferably used,
Here, R ⁷ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Specific examples of the hydrocarbon group represented by R ⁷ include methyl group, ethyl group, n-propyl group, i-propyl group, allyl group, n-butyl group and s.
ec-butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, alkyl groups such as dodecyl group, vinyl group, 1-methylvinyl group,
Alkenyl group such as 2-phenylvinyl group, benzyl group,
Examples thereof include an aralkyl group such as a phenethyl group, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a dodecylphenyl group, a phenylphenyl group, an aryl group such as a naphthyl group and an anthracenyl group.

These hydrocarbon groups are, for example, halogen atom, hydroxy group, alkoxy group, allyloxy group,
Nitro group, cyano group, carbonyl group, carboxyl group,
It may have a substituent such as an alkoxycarbonyl group, anilino group, and acetamide group. Specific examples of the hydrocarbon group having a substituent include trifluoromethyl group, 2-methoxyethyl group, 10-camphanyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group and hydroxy. Examples thereof include a phenyl group, a phenoxyphenyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, a methoxynaphthyl group, a dimethoxyanthracenyl group, a diethoxyanthracenyl group and an anthraquinonyl group.

Ar ³ and Ar ⁴ each represent an aryl group having a carbon number of 20 or less, which may have a substituent. Specifically, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, Dodecylphenyl group, phenylphenyl group, naphthyl group, anthracenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, hydroxyphenyl group, phenoxyphenyl group, nitrophenyl group, cyanophenyl group, carboxy Phenyl group, anilinophenyl group, anilinocarbonylphenyl group, morpholinophenyl group, phenylazophenyl group, methoxynaphthyl group,
Examples thereof include a hydroxynaphthyl group, a nitronaphthyl group and an anthraquinonyl group.

R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent, and more specifically, a methyl group, an ethyl group, n -Propyl group, i-propyl group, allyl group, n-butyl group,
sec-butyl group, t-butyl group, hexyl group, cyclohexyl group, benzyl group, phenyl group, tolyl group, t-
Hydrocarbon groups such as butylphenyl group, naphthyl group, anthracenyl group, 2-methoxyethyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, hydroxyphenyl group, phenylthiophenyl group, Hydroxynaphthyl group,
Examples thereof include a hydrocarbon group having a substituent such as a methoxynaphthyl group, a benzoylmethyl group and a naphthoylmethyl group.
Further, R ⁸ and R ⁹ may combine with each other to form a ring.

Examples of the cation moiety of the onium salt represented by the general formulas (VI) to (VIII) include iodonium ion, sulfonium ion and diazonium ion. Specific structures of the cation moieties of these onium salts are shown below, but the invention is not limited thereto.

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

On the other hand, among the counter anions of these onium salts, examples of sulfonate ions which are particularly preferably used are: 1) methane sulfonate, 2) ethane sulfonate, 3) 1-propane sulfonate, 4) 2-propane sulfonate. , 5) n-butane sulfonate, 6) allyl sulfonate, 7) 10-camphor sulfonate, 8) trifluoromethane sulfonate, 9) pentafluoroethane sulfonate, 10) benzene sulfonate, 11) p-toluene sulfonate, 12) 3-methoxy. Benzene sulfonate, 13) 4-methoxybenzene sulfonate, 14) 4-hydroxybenzene sulfonate, 15) 4-chlorobenzene sulfonate, 16) 3-nitrobenzene sulfonate, 17) 4-nitrobenzene sulfonate, 18) 4-acetylbenzene sulfonate, 19) Pentafluorobenzene sulfonate, 20) 4-dodecylbenzene sulfonate, 21) mesitylene sulfonate, 22) 2,4,6-triisopropylbenzene sulfonate, 23) 2-hydroxy-4-methoxybenzophenone-
5-sulfonate, 24) dimethyl-5-sulfonate isophthalate, 25) diphenylamine-4-sulfonate, 26) 1-naphthalene sulfonate, 27) 2-naphthalene sulfonate, 28) 2-naphthol-6-sulfonate, 29) 2- Naphthol-7-sulfonate, 30) Anthraquinone-1-sulfonate, 31) Anthraquinone-2-sulfonate, 32) 9,10-Dimethoxyanthracene-2-sulfonate, 33) 9,10-Diethoxyanthracene-2-sulfonate, 34 ) Quinoline-8-sulfonate, 35) 8-hydroxyquinoline-5-sulfonate, 36) 8-anilino-naphthalene-1-sulfonate and the like.

Further, 41) m-benzenedisulfonate, 42) benzaldehyde-2,4-disulfonate, 43) 1,5-naphthalenedisulfonate, 44) 2,6-naphthalenedisulfonate, 45) 2,7- Naphthalene disulfonate, 46) anthraquinone-1,5-disulfonate, 47) anthraquinone-1,8-disulfonate, 48) anthraquinone-2,6-disulfonate, 49) 9,10-dimethoxyanthracene-2,6- Salts of disulfonates such as disulfonate, 50)9,10-diethoxyanthracene-2,6-disulfonate, and 2 equivalents of the onium salt cation can also be used.

The onium salt sulfonates that are preferably used in the present invention are prepared by adding the corresponding Cl ^- salt or the like to a sulfonic acid or sodium or potassium sulfonate salt in water, or in a mixed solvent of a hydrophilic solvent such as alcohol and water. It can be obtained by mixing and salt exchange. The onium compound can be synthesized by a known method, for example, Maruzen and Shin Jikken Kagaku Koza 14-I, Chapters 2 and 3 (p. 4).
48), Chapters 8-16 of Volume 14-III (p. 1838),
Chapter 7-14 (p. 1564), J. W. Knapcz
Yk et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 91, 14
5 (1969), A.A. L. Maycok et al., Journal of Organic Chemistry (J. Org. Ch.
em. ) 35, 2532 (1970), J. V. Cr
ivello et al., Polymer Chemistry Edition (Polym. Chem. Ed.) Vol. 18, 2677
(1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101331,
It can be synthesized by the method described in JP-B-5-53166. Preferred specific examples of onium salt sulfonates that are favorably used as an acid generator in the present invention are shown below.

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[0071]

[Chemical 28]

[0072]

[Chemical 29]

[0073]

[Chemical 30]

These acid generators 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 is added to the image recording material in a proportion of 5% by weight, more preferably 0.5 to 20% by weight. 0.01% by weight
If the amount is less than the above range, an image cannot be obtained, and if the amount added exceeds 50% by weight, stains are generated on the non-image area during printing, which is not preferable. These compounds may be used alone or in combination of two or more.

[(B) Acid-Crosslinking Crosslinking Agent] An acid-crosslinking crosslinking agent that can be used in the present invention (hereinafter appropriately referred to as “acid crosslinking agent” or simply “crosslinking agent”)
Will be described. The following are preferable examples of the crosslinking agent used in the present invention. (I) An aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group (ii) A compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group (iii) Epoxy compound

These cross-linking agents will be described in detail below. (I) Examples of the aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group include aromatic compounds and heterocyclic compounds polysubstituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. Be done. However, it does not include a resinous compound known as a resole resin, which is obtained by polycondensing phenols and aldehydes under basic conditions. Although the resole resin has excellent crosslinkability, it does not have sufficient thermal stability. Especially when it is contained in a photosensitive material and stored at high temperature for a long time,
It is not preferable because uniform development becomes difficult.

Among aromatic compounds and heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, a compound having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group may be mentioned as a preferred example. it can. In the case of an alkoxymethyl group, the alkoxymethyl group is preferably a compound having 18 or less carbon atoms. Particularly preferred examples include compounds represented by the following general formulas (1) to (4).

[0078]

[Chemical 31]

[0079]

[Chemical 32]

In each of the above formulas, L _{1 to} L ₈ each independently have 1 carbon atom such as methoxymethyl and ethoxymethyl.
A hydroxymethyl group or an alkoxymethyl group substituted with 8 or less alkoxy groups is shown. These are preferred because they have high crosslinking efficiency and can improve printing durability. The above-exemplified crosslinkable compounds may be used alone or in combination of two or more.

(Ii) Compounds having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group are described in European Patent Publication (hereinafter referred to as "EP-
A)) No. 0,133,216, West German Patent Nos. 3,634,671 and 3,711,264, wherein the monomer and oligomer-melamine-formaldehyde condensate and urea- Formaldehyde condensate, E
Examples thereof include alkoxy-substituted compounds disclosed in PA No. 0,212,482. As a more preferable example,
Examples thereof include melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups, and among them, N-alkoxymethyl derivatives are particularly preferable.

(Iii) Examples of epoxy compounds include monomer, dimer, oligomer and polymer epoxy compounds containing one or more epoxy groups. Examples thereof include a reaction product of bisphenol A and epichlorohydrin, a reaction product of low molecular weight phenol-formaldehyde resin and epichlorohydrin, and the like. Other examples include the epoxy resins described and used in US Pat. No. 4,026,705 and British Patent No. 1,539,192.

The cross-linking agents (i) to (iii) that can be used in the present invention are 5 parts by weight based on the total solid content of the image recording material.
The range is from -80% by weight, preferably from 10-75% by weight, particularly preferably from 20-70% by weight. If the amount of the crosslinking agent added is less than 5% by weight, the durability of the photosensitive layer of the resulting image recording material is deteriorated, and if it exceeds 80% by weight, it is not preferable from the viewpoint of stability during storage.

(Iv) In the present invention, it is also preferable to use a phenol derivative represented by the following general formula (5) as a crosslinking agent.

[0085]

[Chemical 33]

In the above general formula (5), Ar¹ Is a substituent
The aromatic hydrocarbon ring which may have is shown. Obtaining raw materials
Therefore, benzene ring, naphtho ring
A tarene ring or an anthracene ring is preferable. Also preferred
Examples of the substituent include a halogen atom and a C 12 or less
Hydrocarbon group, alkoxy group having 12 or less carbon atoms, carbon number
Up to 12 alkylthio groups, cyano groups, nitro groups,
Examples thereof include a Rifluoromethyl group. High sensitivity
Because of Ar¹ As a benze without a substituent
Ring and naphthalene ring, or halogen atom, carbon number 6
Hydrocarbon groups of not more than 6 or alkoxy groups of 6 or less carbon atoms,
Substituents such as alkylthio groups and nitro groups with 6 or less carbon atoms
Especially preferred are benzene ring and naphthalene ring
Yes. R¹ And R² Are the same or different
Well, a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms is shown.
You R is because it is easy to synthesize.¹ And R ²
Is particularly preferably a hydrogen atom or a methyl group.
R³ Is a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms
Show. R because of its high sensitivity³ Is, for example, methyl
Group, ethyl group, propyl group, cyclohexyl group, benzyl
In particular, it is a hydrocarbon group having 7 or less carbon atoms such as
preferable. m represents an integer of 2 to 4. n is 1 to 3
Indicates an integer.

Specific examples of the phenol derivative represented by the above general formula (5) which is preferably used in the present invention are shown below (crosslinking agents [KZ-1] to [KZ-8]). Is not limited to.

[0088]

[Chemical 34]

[0089]

[Chemical 35]

These phenol derivatives can be synthesized by a conventionally known method. For example, [KZ-1] is reacted with phenol, formaldehyde, and a secondary amine such as dimethylamine or morpholine to give tri(dialkylaminomethyl)phenol, and then with acetic anhydride.
Further, by reacting with ethanol in the presence of a weak alkali such as potassium carbonate, the compound can be synthesized by the route represented by the following reaction formula [1].

[0091]

[Chemical 36]

Further, it can be synthesized by another method. For example, [KZ-1] is prepared by reacting phenol with formaldehyde or paraformaldehyde in the presence of an alkali such as KOH to give 2,4,6-trihydroxymethylphenol, and subsequently reacting with ethanol in the presence of an acid such as sulfuric acid. Thus, the compound can be synthesized by the route represented by the following reaction formula [2].

[0093]

[Chemical 37]

These phenol derivatives may be used alone or in combination of two or more kinds. Further, when these phenol derivatives are synthesized, the phenol derivatives may be condensed with each other to produce by-products such as dimers and trimers, but these impurities may be used as they are. Even in this case, the impurities are 3
It is preferably 0% or less, and more preferably 20% or less.

In the present invention, the phenol derivative is 5 to 70% by weight, preferably 10% by weight based on the total solid content of the image recording material.
Used in an amount of up to 50% by weight. Here, if the addition amount of the phenol derivative as the crosslinking agent is less than 5% by weight, the film strength of the image portion at the time of image recording is deteriorated.
If it exceeds 0% by weight, it is not preferable in terms of stability during storage.

[(C) Alkali-Soluble Resin] Examples of the alkali-soluble resin used in the present invention include novolac resins and polymers having a hydroxyaryl group in the side chain. The novolak resin that can be used as the alkali-soluble resin in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions. Preferred novolac resins include, for example, novolac resins obtained from phenol and formaldehyde, novolac resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, and novolac resins obtained from o-cresol and formaldehyde. Novolak resin, novolak resin obtained from octylphenol and formaldehyde, m-/
Novolac resin obtained from p-mixed cresol and formaldehyde, phenol/cresol (m-,p
-, o- or m-/p-, m-/o-, o-/p- mixture) and a novolak resin obtained from formaldehyde. These novolak resins have a weight average molecular weight of 800 to 200,00.
It is preferably 0 and has a number average molecular weight of 400 to 60,000.

Further, as the alkali-soluble resin in the present invention, a polymer having a hydroxyaryl group in its side chain can be preferably mentioned. In this polymer, the hydroxyaryl group means an aryl group in which one or more —OH groups are bonded. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and the like, and a phenyl group or a naphthyl group is preferable from the viewpoint of easy availability and physical properties. Therefore, the hydroxyaryl group is preferably a hydroxyphenyl group, a dihydroxyphenyl group, a trihydroxyphenyl group, a tetrahydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group and the like. These hydroxyaryl groups may further have a substituent such as a halogen atom, a hydrocarbon group having 20 or less carbon atoms, an alkoxy group having 20 or less carbon atoms and an aryloxy group having 20 or less carbon atoms. Good. These hydroxyaryl groups are pendantly bonded to the polymer main chain as side chains of the polymer, but may have a linking group between them and the main chain.

The polymer having a hydroxyaryl group in its side chain, which is preferably used in the present invention, is a polymer containing any one of the structural units represented by the following general formulas (IX) to (XII). ..

[0099]

[Chemical 38]

[In the formula, R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ may be the same or different,
Hydrogen atom, halogen atom, hydrocarbon group having 10 or less carbon atoms, alkoxy group having 10 or less carbon atoms, or 10 carbon atoms
The number of or less aryloxy groups is shown. In addition, R ¹² and R ¹³ may combine to form a condensed benzene ring or cyclohexane ring. R ¹⁴ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁵ is a single bond or
A divalent hydrocarbon group having 20 or less carbon atoms is shown. R ¹⁶ is
A single bond or a divalent hydrocarbon group having 10 or less carbon atoms is shown. X ¹ represents a single bond, an ether bond, a thioether bond, an ester bond, or an amide bond. p is 1 to 4
Indicates an integer. q and r each represent an integer of 0 to 3. ]

Among the structural units represented by the general formulas (IX) to (XII), examples of specific structural units preferably used in the present invention are shown below.

[0102]

[Chemical Formula 39]

[0103]

[Chemical 40]

[0104]

[Chemical 41]

[0105]

[Chemical 42]

[0106]

[Chemical 43]

These polymers can be synthesized by a conventionally known method. For example, a polymer having a constitutional unit represented by the general formula (IX) has a hydroxy group protected as an acetic acid ester or t-butyl ether. It is obtained by doing. Further, polymers having a constitutional unit represented by the general formula (X) are disclosed in JP-A-64-32256 and JP-A-64-25625.
It can be synthesized by the method described in No. 35436 or the like. Further, a polymer having a constitutional unit represented by the general formula (XI) can be obtained by reacting a hydroxyl group-containing amine compound with maleic anhydride to obtain a corresponding monomer, and then radical polymerizing the polymer. .. Further, a polymer having a structural unit represented by the general formula (XII) is derived from a styrene having a functional group useful for synthesis such as chloromethylstyrene or carboxystyrene as a raw material to obtain a monomer corresponding to the general formula (XII). It is also obtained by radical polymerization to obtain a polymer.

In the present invention, it may be a homopolymer consisting only of the constitutional units represented by the general formulas (IX) to (XII), but it may also be a copolymer containing other constitutional units. Other structural units that are preferably used include, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, and maleic acid. A structural unit introduced from a known monomer such as acid imide may be mentioned.

Specific examples of acrylic acid esters that can be used include methyl acrylate, ethyl acrylate, (n- or i-)propyl acrylate, and (n
-, i-, sec- or t-)butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate,
Dodecyl acrylate, chloroethyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, 2- (P-Hydroxyphenyl)ethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate and the like can be mentioned.

Specific examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate,
(N- or i-)propyl methacrylate, (n-, i
-, sec- or t-)butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate,
Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,
Examples thereof include glycidyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, 2-(p-hydroxyphenyl)ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, chlorophenyl methacrylate and sulfamoylphenyl methacrylate.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-.
Hydroxyethyl acrylamide, N-phenyl acrylamide, N-tolyl acrylamide, N-(p-hydroxyphenyl) acrylamide, N-(sulfamoylphenyl) acrylamide, N-(phenylsulfonyl) acrylamide, N-(tolyl sulfonyl) acrylamide, Examples thereof include N,N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like.

Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, and N-hydroxyethylmethacrylamide. Amide,
N-phenylmethacrylamide, N-tolylmethacrylamide, N-(p-hydroxyphenyl)methacrylamide, N-(sulfamoylphenyl)methacrylamide, N-(phenylsulfonyl)methacrylamide, N
Examples include -(tolylsulfonyl)methacrylamide, N,N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, dimethoxystyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

Among these monomers, acrylic acid esters having 20 or less carbon atoms, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, styrenes and acrylic acid are particularly preferably used. Methacrylic acid and acrylonitrile.

The proportion of the constitutional units represented by the general formulas (IX) to (XII) contained in the copolymer using them is 5 to 1
It is preferably 00% by weight, more preferably 10%.
~100% by weight. The molecular weight of the polymer used in the present invention is preferably 4000 in terms of weight average molecular weight.
Or more, more preferably in the range of 10,000 to 300,000, preferably in the number average molecular weight of 1,000 or more, and more preferably in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10. These polymers are random polymers, block polymers,
Any graft polymer or the like may be used, but a random polymer is preferable.

The alkali-soluble resin used in the present invention may be used alone or in combination of two or more kinds. The amount of alkali-soluble resin added is 5 to 95% by weight based on the total solid content of the image recording material.
Preferably 10 to 95% by weight, particularly preferably 20 to 9
Used at 0% by weight. If the amount of the alkali-soluble resin added is less than 5% by weight, the durability of the recording layer deteriorates.
If the addition amount exceeds 95% by weight, no image is formed.

[(D) Infrared Absorber] The infrared absorber used in the present invention is a dye or pigment that effectively absorbs infrared rays having a wavelength of 760 to 1200 nm. A dye or pigment having an absorption maximum at a wavelength of 760 to 1200 nm is preferable. As the dye, commercially available dyes and literatures (for example, "Handbook of Dyes" edited by the Society of Organic Synthetic Chemistry, Showa 45)
The well-known thing described in the annual publication can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes,
Examples include dyes such as methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.
Preferred dyes are, for example, JP-A-58-125246.
No. 59-84356 and 59-2028.
29, JP-A-60-78787, and other cyanine dyes, JP-A-58-173696, and JP-A-5-173696.
8-181690, methine dyes described in JP-A-58-194595, JP-A-58-112793.
JP-A-58-224793, JP-A-59-481
87, JP-A-59-73996, JP-A-60-52.
940, naphthoquinone dyes described in JP-A-60-63744, etc., squarylium dyes described in JP-A-58-112792, UK Patent 434, etc.
Examples thereof include cyanine dyes described in No. 875.

Further, the near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted arylbenzo(thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
Trimethine thiapyrylium salt described in U.S. Pat. No. 4,327,169, JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
-84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-13
Pyrylium compounds disclosed in Japanese Patent Nos. 514 and 5-19702 are also preferably used. Further, as another preferable example of the dye, US Pat. No. 4,756,99
The near-infrared absorbing dyes described as formulas (I) and (II) in the specification No. 3 can be mentioned. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes:
Commercial pigment and color index (CI) handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technology Association, published in 1977), "Latest pigment application technology" (published by CMC, published in 1986), "printing ink technology" published by CMC, published in 1984)
The pigments described in 1. can be used. The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments,
Red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment,
Examples include metal powder pigments and 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, quinacridone pigments, dioxazine pigments, isoindolinone pigments. Further, 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. Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above surface treatment method is "property and application of metallic soap" (Koushobo),
"Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986)
It is described in.

The particle diameter of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. When the particle size of the pigment is less than 0.01 μm, the stability of the dispersion in the coating solution for the photosensitive layer is not preferable, and when it exceeds 10 μm, the uniformity of the image recording layer is not preferable. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader. For details, see "Latest Pigment Application Technology" (CMC
Publication, published in 1986).

These dyes or pigments are contained in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the image recording material.
5 to 10% by weight, in the case of a pigment, particularly preferably 1.0 to
It can be added to the image recording material in a proportion of 10% by weight. If the amount of the pigment or dye added is less than 0.01% by weight, the sensitivity will be low, and if it exceeds 50% by weight, stains will be generated on the non-image area during printing. These dyes or pigments may be added to the same layer as other components or may be added to another layer provided separately.

[Other Components] In the present invention, the above five components are essential, but various compounds other than these may be added if necessary. For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (above Orient Chem. Industrial Co., Ltd., Victoria Pure Blue, Crystal Violet (CI
42555), methyl violet (CI4253
5), ethyl violet, rhodamine B (CI145
170B), malachite green (CI42000),
Examples thereof include methylene blue (CI52015) and the like, or dyes described in JP-A-62-293247. It is preferable to add these dyes because the image area and the non-image area can be easily distinguished after the image formation. The addition amount is based on the total solid content of the image recording material.
The ratio is 0.01 to 10% by weight.

Further, in the image recording material of the present invention, in order to broaden the stability of the process against the developing conditions, JP-A-62-251740 and JP-A-3-208514 are used.
Nonionic surfactants as described in JP-A-59-121044 and JP-A-4-13149.
Amphoteric surfactants such as those described in the publication can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include:
Alkyldi(aminoethyl)glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N,N-betaine type (for example, brand name Amogen K, Daiichi Kogyo Co., Ltd. etc. are mentioned. The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is 0.05 to 15% by weight.
Is preferable, and more preferably 0.1 to 5% by weight.

Further, if necessary, a plasticizer is added to the image recording material of the present invention to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid. And polymers are used. In addition to these, epoxy compounds, vinyl ethers and the like may be added.

The image recording material of the present invention can be usually prepared by dissolving each of the above components in a solvent and coating the solution on a suitable support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy. Ethane, methyl lactate, ethyl lactate, N,N-dimethylacetamide, N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyl lactone, toluene,
Examples thereof include water, but are not limited to these. These solvents may be used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.5 to 5.0 g/m ² for the planographic printing plate material. As a method of applying, various methods can be used, for example,
Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image recording film deteriorate.

In the image-recording layer according to the invention, a surfactant for improving the coatability, such as JP-A-62-17 is used.
A fluorinated surfactant as described in 0950 can be added. The preferable addition amount is 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight based on the total solid content of the image recording material.

The support used in the present invention is a dimensionally stable plate-like material such as paper, paper laminated with plastic (eg polyethylene, polypropylene, polystyrene etc.), metal plate ( For example, aluminum, zinc, copper, etc., plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper laminated with the above-mentioned metals, or vapor-deposited, or a plastic film. As the support of the present invention,
Polyester film or aluminum plate is preferable,
Among them, an aluminum plate, which has good dimensional stability and is relatively inexpensive, is particularly preferable. The preferred aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a slight amount of a foreign element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy are silicon,
Examples include iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of foreign elements in the alloy is at most 10% by weight. Aluminum which is particularly preferred in the present invention is pure aluminum, but completely pure aluminum is difficult to produce due to refining technology, and thus may contain a slight amount of a foreign element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly known aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 to 0.6 m.
It is about m, preferably 0.15 to 0.4 mm, and particularly preferably 0.2 to 0.3 mm.

Prior to roughening the aluminum plate, if desired, a degreasing treatment for removing the rolling oil on the surface is carried out, for example, with a surfactant, an organic solvent or an alkaline aqueous solution. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically melting and roughening the surface, and a method of chemically selecting the surface. It is carried out by a method of dissolving. As the mechanical method, known methods such as a ball polishing method, a brush polishing method, a blast polishing method and a buff polishing method can be used. As an electrochemical graining method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution. Further, as disclosed in Japanese Patent Laid-Open No. 54-63902, a method in which both are combined can be used. The thus roughened aluminum plate is optionally subjected to alkali etching treatment and neutralization treatment, and then subjected to anodization treatment if desired in order to enhance water retention and abrasion resistance of the surface. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used, and sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is generally used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

[0130] The treatment conditions for anodic oxidation cannot be unconditionally specified because it varies depending on the electrolyte used, but generally, the concentration of the electrolyte is 1 to 80% by weight solution, the liquid temperature is 5 to 70°C, and the current density is 5 to 5. A range of 60 A/dm ² , a voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes is suitable. If the amount of the anodic oxide film is less than 1.0 g/m ² , printing durability is insufficient, or the non-image area of the planographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. So-called "scratch stains" tend to occur. After the anodizing treatment, the aluminum surface is optionally subjected to a hydrophilic treatment. Examples of the hydrophilic treatment used in the present invention include US Pat.
No. 714,066, No. 3,181,461, No. 3,
280,734 and 3,902,734, which are alkali metal silicate (eg, aqueous sodium silicate) processes. In this way,
The support is immersed in an aqueous solution of sodium silicate or electrolyzed. Besides, potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and US Pat. Nos. 3,276,868 and 4,153,461.
No. 4,689,272, a method of treating with polyvinylphosphonic acid and the like are used.

In the image recording material of the present invention, an undercoat layer may be provided on the support, if desired. As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, 2-
Amino group-containing phosphonic acids such as aminoethylphosphonic acid, optionally substituted phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid Acid, organic phosphoric acid such as optionally substituted phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycero An organic phosphinic acid such as phosphinic acid,
It is selected from amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as triethanolamine hydrochloride, but two or more kinds may be mixed and used. The coating amount of the organic undercoat layer is appropriately ² to 200 mg/m ² .

As described above, a lithographic printing plate material using the image recording material of the present invention can be prepared. This lithographic printing plate material is imagewise exposed by a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 760 to 1200 nm. In the present invention, the development treatment may be carried out immediately after the laser irradiation, but it is preferable to carry out the heat treatment between the laser irradiation step and the development step. The condition of heat treatment is 8
It is preferable to perform the heating in the range of 0 to 150° C. for 10 seconds to 5 minutes. This heat treatment can reduce the laser energy required for recording during laser irradiation.

After the heat treatment, if necessary, the image recording material of the present invention is developed with an alkaline aqueous solution. 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, sodium triphosphate, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, Examples thereof include inorganic alkali salts such as sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium borate, potassium borate, and lithium borate. Also, monomethylamine, dimethylamine,
Trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc. Organic alkaline agents are also used. These alkaline agents may be used alone or in combination of two or more. Among these alkaline agents, a particularly preferable developer is an aqueous silicate solution such as sodium silicate or potassium silicate. The reason is that the developability can be controlled by the ratio and concentration of silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide M ₂ O. For example, JP-A-54-62004. Alkali metal silicates such as those described in JP-B No. 57-7427 are effectively used.

Further, in the case of developing using an automatic processor, an aqueous solution (replenisher) having a higher alkaline strength than the developing solution is used.
It is known that a large amount of lithographic printing plate material can be processed by replacing the developing solution in the developing tank for a long period of time without adding the developing solution to the developing solution. Also in the present invention, this replenishment method is preferably applied. For developer and replenisher,
Various surfactants and organic solvents can be added, if necessary, for the purpose of promoting or suppressing the developability, dispersing the development residue, and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, in the developing solution and the replenishing solution, if necessary, a reducing agent such as sodium salt and potassium salt of inorganic acids such as hydroquinone, resorcin, sulfurous acid, and bisulfite, an organic carboxylic acid, a defoaming agent, and a water softener. It can also be added. The printing plate developed using the above-mentioned developing solution and replenishing solution is post-treated with washing water, a rinse solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-treatment when the image recording material of the present invention is used as a printing plate material, various combinations of these treatments can be used.

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 material, each processing liquid tank, and a spray device.The exposed printing plate is conveyed horizontally while being pumped up by a pump. Each processing solution is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate material 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 the treatment while supplementing the replenisher with each treatment solution according to the treatment amount, operating time, and the like. Further, a so-called disposable treatment method in which treatment is performed with a substantially unused treatment liquid can be applied.

The lithographic printing plate obtained as described above,
After applying the desensitizing gum, if desired, it can be subjected to a printing step, but if it is desired to obtain a lithographic printing plate having a higher printing durability, a burning treatment is applied. When burning a lithographic printing plate, before the burning
No. 2518, No. 55-28062, JP-A-62-3
It is preferable to treat with a surface-adjusting solution as described in each of the publications of 1859 and 61-159655. As the method, with a sponge or absorbent cotton soaked with the surface-adjusting solution, it is applied on the lithographic printing plate, or by immersing the printing plate in a vat filled with the surface-adjusting solution, Application by an automatic coater is applied. Further, making the coating amount uniform with a squeegee or a squeegee roller after coating gives more preferable results. In general, a suitable amount of the surface-adjusting solution is 0.03 to 0.8 g/m ² (dry weight).

The planographic printing plate coated with the surface-adjusting solution is dried if necessary, and then burned with a burning processor (for example,
It is heated to a high temperature with a burning processor: BP-1300) sold by Fuji Photo Film Co., Ltd. The heating temperature and time in this case depend on the kinds of the components forming the image, but are 1 to 100° C. to 300° C.
The range of up to 20 minutes is preferred. The lithographic printing plate that has been subjected to the burning treatment can be subjected to conventional treatments such as washing with water and gumming, if necessary, but a surface-adjusting solution containing a water-soluble polymer compound or the like is used. In that case, so-called desensitizing treatment such as gumming can be omitted. The planographic printing plate obtained by such treatment is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0138]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto. <Synthesis of Crosslinking Agent [KZ-9]> 1-[α-methyl-α-
(4-Hydroxyphenyl)ethyl]-4-[α,α-
Bis(4-hydroxyphenyl)ethyl]benzene,
It was reacted with formalin in an aqueous solution of potassium hydroxide.
The reaction solution was acidified with sulfuric acid, crystallized, and recrystallized from methanol to give a crosslinking agent [KZ-
9] was obtained. The purity was 92% as measured by reverse phase HPLC.

[0139]

[Chemical 44]

<Obtaining Binder Polymer [BP-1]> Poly(p-hydroxystyrene), Maruka Linker MS-4P (trade name) manufactured by Maruzen Petrochemical Co., Ltd. was obtained and named as [BP-1]. did.

Examples 1 to 4 Al having a thickness of 0.30 mm
Cleaning the minium plate (material 1050) with trichlorethylene
And degrease it, then use a nylon brush and a 400 mesh pad.
Using a mistone-water suspension, grain the surface and
It was washed with water. This plate is put in 25% sodium hydroxide at 45°C.
After immersing in an aqueous solution of um for 9 seconds to perform etching and washing with water,
2% HNO ₃ It was soaked in water for 20 seconds and washed with water. At this time
The etching amount of the grained surface is about 3g/m² And
It was Next, this plate is 7% H₂ SO_Four Current as electrolyte
Density 15A/dm² At 3 g/m² DC anodized film of
After providing, it was washed with water and dried. Next, on this aluminum plate
The undercoat liquid described below was applied and dried at 80° C. for 30 seconds. Dry
The coating amount after drying is 10 mg/m² Met.

<Undercoating liquid> β-alanine ・・・0.1 g Phenylphosphonic acid ・・・0.05 g Methanol ・・・40 g Pure water ・・・60 g

Next, the following solution [P] was prepared, and this solution was applied to the above-mentioned undercoated aluminum plate and 10
Negative lithographic printing plate material [P-1] after drying at 0°C for 1 minute
~ [P-4] were obtained. The coating amount after drying is 1.5 g/m ²
Met.

<Solution [P]> Compound of General Formula (a): 0.05 g Acid Generator [SH-1]: 0.3 g Crosslinking Agent [KZ-9]: 0.5 g Binder polymer [BP-1]... 1.5 g Infrared absorber [IK-1]... 0.07 g AIZEN SPILON BLUE C-RH... 0.035 g (manufactured by Hodogaya Chemical Co., Ltd.) Mega Fuck F-177: 0.01 g (Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) Methyl ethyl ketone: 12 g Methyl alcohol: 10 g 1-Methoxy-2-propanol: 8 g

Table 1 shows the compound (E) represented by the general formula (a) used in the solutions [P-1] to [P-4]. Also,
Acid generator [SH-1] (exemplified compound of general formula (VIII))
And the structures of the infrared absorbent [IK-1] are shown below.

[0146]

[Chemical 45]

(Development stability against external damage) The obtained negative type planographic printing plate materials [P-1] to [P-4] were continuously loaded with a scratch strength tester "SB62 type" (Shinto Kagaku (Shinto Kagaku) Co., Ltd.)
Adhesive "No. 5C" filter paper made by Advantech Toyo Co., Ltd. is attached to the square flat surface of 1 cm square that hits the plate of the scratching jig, a load of 100 g is placed, and scratching is performed at a speed of 6 cm/sec. After exposure with a semiconductor laser having a wavelength of 830 nm and a beam diameter of 17 μm (1/e ² ) at 500 mW at a main scanning speed of 5 m/sec, a panel heater was used to perform heat treatment at 110° C. for 30 seconds, and then Fuji Photo Film Co., Ltd. ) Developer, DP-4 (1:8 water dilution) 30
Developed for seconds. The evaluation was performed based on the following criteria, and the results are shown in Table 1. ◯: The photosensitive film in the scratched part is not completely dissolved Δ: The photosensitive film in the scratched part is partially dissolved ×: The photosensitive film in the scratched part is completely dissolved

(Comparative Example 1) The solution used in Example 1 [P-
[1] was prepared in the same manner as in Example 1 except that nonylphenol was not used. This solution was applied to the undercoated aluminum plate used in Example 1 and dried at 100° C. for 1 minute to obtain a negative lithographic printing plate material [Q-1]. Weight after drying is 1.5
It was g/m ² . The obtained planographic printing plate material [Q-1]
The development stability against external damage was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 2) The solution used in Example 1 [P-
1] except that p-cresol was used instead of nonylphenol to prepare a solution [R-1] in the same manner as in Example 1. This solution was applied to the undercoated aluminum plate used in Example 1, and the solution was applied at 100° C. for 1 hour.
After drying for a minute, a negative lithographic printing plate material [R-1] was obtained.
The weight after drying was 1.5 g/m ² . The obtained lithographic printing plate material [R-1] was evaluated for development stability against external damage in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 3) The solution used in Example 1 [P-
1] except that 5-pentyl resorcinol (manufactured by Aldrich) was used instead of nonylphenol in the same manner as in Example 1 to prepare a solution [S-1]. This solution was applied to the undercoated aluminum plate used in Example 1 and dried at 100° C. for 1 minute to obtain a negative lithographic printing plate material [S-1]. The weight after drying was 1.5 g/m ² . The obtained planographic printing plate material [S
-1] was evaluated for development stability against external damage in the same manner as in Example 1, and the results are shown in Table 1.

[0151]

[Table 1]

From the results shown in Table 1, the negative type lithographic printing plate material of the present invention has significantly improved stability against external scratches due to the addition of the compound represented by the general formula (a), and the plate surface It can be seen that even if scratches are formed, the development can be stably carried out without inhibiting the hardening of the part. On the other hand, when the compound represented by the general formula (a) of Comparative Example 1 was not added, the photosensitive film in the scratched portion was not cured and was dissolved in the developer, so-called image loss. It turns out that In addition, as in Comparative Examples 2 and 3,
Even when the compound represented by the general formula (a) is added, when R ¹ in the general formula (a) has a small carbon number, it is the same as when the compound represented by the general formula (a) is not added. The surface of the plate material cannot be obtained with resistance to external damage and is dissolved. Further, even when a compound of R ¹ having 5 carbon atoms is used, the resistance against external damage is not sufficient, and the photosensitive film in the damaged part is It can be seen that the toner is dissolved in the developer and an image dropout occurs.

[0153]

INDUSTRIAL APPLICABILITY The negative lithographic printing plate material of the present invention can be directly plate-formed from digital data of a computer or the like by recording using a solid-state laser emitting infrared rays and a semiconductor laser, and further fingerprints and the like. Even if it’s scratched
There is an effect that stable development is possible without causing image dropout, that is, excellent scratch resistance.

Claims (1)

[Claims] 1. A negative image recording material containing the following (A) to (E): (A) a compound that decomposes to generate an acid when exposed to light or heat, (B) a crosslinking agent that crosslinks with an acid, (C) at least one alkali-soluble resin, (D) an infrared absorbing agent, (E) the following general formula A compound represented by (a). _{^{(R 1 -X) n -Ar- (}} OH) m Formula (a) wherein, X represents single bond, O, S, and COO or CONH, R ¹ is an alkyl group having from 6 to 32 carbon atoms The alkenyl group and Ar represent an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group. In addition, n and m each independently represent an integer of 1 to 3. ]