JP2001312062A - Image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type image recording material which ensures suppressed ablation in laser scanning in recording, forms a planographic printing plate having high strength of a formed image area and excellent in printing resistance and is adaptable to a heat mode. SOLUTION: The image recording material contains (A) a polyurethane resin insoluble in water and soluble in an aqueous alkali solution, (B) a radical polymerizable compound. (C) a photothermal converting agent and (D) a compound forming a radical when subjected to heat-mode exposure with light of a wavelength which can be absorbed by the photothermal converting agent (C) and can record an image by heat-mode exposure. The polyurethane resin (A) preferably has a structural unit represented by a reaction product of a diisocyanate compound of the formula OCN-X0-NCO and a diol compound of the formula HO-Y0-OH as the basic skeleton.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative type image recording material writable with an infrared laser, and more particularly, to form a lithographic printing plate having a high image portion of a recording layer and excellent printing durability. The present invention relates to a negative type image recording material.

[0002]

2. Description of the Related Art In recent years, the development of lasers has been remarkable, and in particular, solid lasers and semiconductor lasers having a light emitting region in the near infrared to infrared region have been increasing in output and miniaturization. Therefore, these lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like. Using an infrared laser having an emission region in the infrared region as an exposure light source, a negative type lithographic printing plate material for an infrared laser, an infrared absorber, and a polymerization initiator that generates radicals by light or heat,
A lithographic printing plate material having a photosensitive layer containing a polymerizable compound.

Usually, such a negative type image recording material employs a recording system in which a polymerization reaction is caused by using a radical generated by light or heat as an initiator, and a recording layer in an exposed portion is cured to form an image portion. We are using. Such a negative type image forming material has a lower image forming property than a positive type in which the recording layer is solubilized by the energy of infrared laser irradiation, and promotes a curing reaction by polymerization to form a strong image portion. In general, a heat treatment is performed before the development step in order to form. A printing plate having such a light- or heat-polymerized recording layer is disclosed in JP-A-8-108621.
And a technique using a photopolymerizable or thermopolymerizable composition as a photosensitive layer as described in JP-A-9-34110. Although these photosensitive layers are excellent in high-sensitivity image forming properties, when a substrate subjected to hydrophilization treatment is used as a support, adhesion at the interface between the photosensitive layer and the support is low, and printing durability is poor. There was a problem. In order to improve the sensitivity, the use of a high-output infrared laser has been studied. However, there has been a problem that abrasion of the photosensitive layer occurs during laser scanning and the optical system is contaminated.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above problems, and an object of the present invention is to suppress ablation in laser scanning at the time of recording and to reduce the intensity of a formed image portion. An object of the present invention is to provide a negative type image recording material capable of forming a lithographic printing plate which is high and has excellent printing durability.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the use of a polyurethane resin as a low molecular weight compound which is insoluble in water and soluble in an aqueous alkaline solution provides excellent strength in the image area. It has been found that such recording is possible, and the present invention has been completed. That is, the heat mode-compatible negative image recording material of the present invention comprises (A) a polyurethane resin insoluble in water and soluble in an aqueous alkali solution, (B) a radical polymerizable compound, (C) a photothermal conversion agent, and (D) the (C)
It contains a compound that generates a radical by heat mode exposure to light having a wavelength that can be absorbed by the photothermal conversion agent, and is capable of image recording by heat mode exposure.

In the present invention, "corresponding to the heat mode" means that recording by heat mode exposure is possible. The definition of the heat mode exposure in the present invention will be described in detail. Hans-Joachim Tim
pe, IS & Ts NIP 15: 1999 Inte
rational Conference on D
digital printing technology
ies. P. As described in 209, a photoabsorbing substance (for example, a dye) is photoexcited in a photoreceptor material, and undergoes a chemical or physical change to form a chemical or physical change from the photoexcitation of the photoabsorbing substance forming an image. It is known that there are roughly two modes in the above processes. One is that the photo-excited light-absorbing substance deactivates due to some photochemical interaction (eg, energy transfer, electron transfer) with other reactants in the photosensitive material,
As a result, a so-called photon mode in which the activated reactant causes a chemical or physical change required for the above-described image formation, and the other is that the photoexcited light absorbing substance generates heat and deactivates, and the heat is lost. This is a so-called heat mode in which a reactant causes a chemical or physical change required for image formation by utilizing the above-mentioned method. In addition, there are special modes such as ablation in which substances are explosively scattered by the energy of light locally collected and multiphoton absorption in which one molecule absorbs many photons at a time, but these modes are omitted here.

[0007] The exposure processes utilizing the above-described modes are called font mode exposure and heat mode exposure. The technical difference between the font mode exposure and the heat mode exposure is whether or not the energy amount of several photons to be exposed can be added to the energy amount of the target reaction.
For example, consider a case where a certain reaction occurs using n photons. In the font mode exposure, photochemical interaction is used, so that the energy of one photon cannot be added and used due to the requirement of the law of conservation of quantum energy and momentum. That is, in order to cause a certain reaction, the relationship of “energy amount of one photon ≧ energy amount of reaction” is necessary. On the other hand, in heat mode exposure, heat is generated after light excitation, and light energy is converted into heat and used, so that the amount of energy can be added. Therefore, the relationship “energy amount of n photons ≧ energy amount of reaction” is sufficient. However, this energy addition is restricted by thermal diffusion. In other words, if the next photoexcitation-deactivation process occurs and heat is generated before heat escapes from the exposed portion (reaction point) of interest by thermal diffusion, the heat is reliably accumulated and added, and the temperature rises in that portion. Leads to. However, when the next heat is generated slowly, the heat escapes and is not accumulated. In other words, in the heat mode exposure, even if the total exposure energy is the same, the result is different between the case where the high energy light is irradiated for a short time and the case where the low energy light is irradiated for a long time. It becomes advantageous for accumulation of. Of course,
In the font mode exposure, a similar phenomenon may occur due to the influence of the diffusion of the subsequent reactive species, but basically, this does not occur. That is, when viewed as a characteristic of the photosensitive material, the exposure power density (w / cm ² ) in the font mode
The intrinsic sensitivity of the photosensitive material (the amount of energy for the reaction required for image formation) is constant with respect to (= energy density per unit time), but the intrinsic sensitivity of the photosensitive material increases with the exposure power density in the heat mode. Will do. Therefore, if the exposure time is fixed so that the productivity necessary for practical use as an image recording material can be maintained, the font mode exposure is usually about 0.1 m when comparing the modes.
Although a high sensitivity of about J / cm ² can be achieved, the reaction occurs even with any small amount of exposure, so that the problem of low-exposure fog in the unexposed area is likely to occur. In contrast, in the heat mode exposure, no reaction occurs unless the exposure amount exceeds a certain value,
In addition, usually 50 mJ /
cm ^2, but is required, the low exposure fogging problem is avoided. And, in fact heat mode exposure requires exposure power density at the plate surface of the photosensitive material is 5000 W / cm ² or more, preferably it is necessary to 10000 W / cm ² or more. However, although not described in detail here, 5.0
If a high power density laser of × 10 ⁵ / cm ² or more is used, ablation occurs, which is not preferable because of problems such as contamination of the light source.

Although the function of the present invention is not clear, in the image recording material of the present invention, by using (A) a specific polyurethane resin as a polymer compound which can be used in an aqueous alkali solution, hydrogen bonding of a main chain urethane group can be achieved. When this image recording material is used for the photosensitive layer of a lithographic printing plate precursor compatible with heat mode, ablation is suppressed during infrared laser scanning exposure to form a high-strength coating due to its properties. It is considered that the contamination of the optical system such as the spinner mirror is suppressed. Further, since the polyurethane resin has excellent film-forming properties, the amount of dissolved oxygen in the film after the film is formed is low, and the oxygen barrier property from the outside is high, so that the inhibition of polymerization of the radically polymerizable compound by oxygen is suppressed. . Therefore, since a film having a high degree of curing is obtained by polymerization, when used for the photosensitive layer of a lithographic printing plate precursor, the formed image portion is sufficiently cured, and a printing plate with high printing durability can be formed. . Furthermore, since the polyurethane resin used in the present invention has a urethane group which is a polar group in the main chain, it has excellent affinity for a highly polar medium such as water. Therefore, compared to acrylic resins, which are usually alkali-soluble resins used in image recording materials, they are excellent in water dispersibility and, when used in a lithographic printing plate precursor, are less likely to cause development scum that becomes a problem in running suitability. It also has the advantage.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The negative type image recording material of the present invention comprises (A) a polyurethane resin insoluble in water and soluble in an aqueous alkali solution, (B) a radical polymerizable compound, (C) a photothermal conversion agent, and (D)
(C) a compound which generates a radical by heat mode exposure to light having a wavelength that can be absorbed by the photothermal conversion agent. Hereinafter, each compound that can be used in the image recording material of the present invention will be described in order.

(A) Polyurethane resin insoluble in water and soluble in an aqueous alkali solution (hereinafter referred to as a specific polyurethane resin as appropriate). A specific resin used as an essential component in the heat mode-compatible negative image recording material of the present invention. The polyurethane resin has a basic skeleton having a structural unit represented by a reaction product of at least one diisocyanate compound represented by the following general formula (2) and at least one diol compound represented by the following general formula (3). Polyurethane resin.

OCN-X ⁰ -NCO (2) HO-Y ⁰ -OH (3) (where X ⁰ and Y ⁰ represent a divalent organic residue)

The preferred isocyanate compound is a diisocyanate compound represented by the following general formula (4).

OCN-L ¹ -NCO (4)

In the formula, L ¹ represents an optionally substituted 2
And a monovalent aliphatic or aromatic hydrocarbon group. If necessary, L ¹ may have another functional group that does not react with the isocyanate group, for example, an ester, urethane, amide, or ureido group.

A) Diisocyanate compound Specific examples of the diisocyanate compound represented by the general formula (4) include the following. That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate , 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-
Aromatic diisocyanate compounds such as 4,4'-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl) Alicyclic diisocyanate compounds such as isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate A diisocyanate compound which is a reaction product of a diol and a diisocyanate, such as an adduct of a diisocyanate;

(B) Diol compound As the diol compound, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound and the like are broadly mentioned. As the polyether diol compound, the following formulas (5), (6), (7),
Examples include the compounds represented by (8) and (9), and a random copolymer of ethylene oxide and propylene oxide having a hydroxyl group at a terminal.

[0017]

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In the formula, R ¹ is a hydrogen atom or a methyl group, X
Represents the following groups.

[0019]

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A, b, c, d, e, f, and g each represent an integer of 2 or more, preferably an integer of 2 to 100.

Specific examples of the polyether diol compounds represented by formulas (5) and (6) include the following. That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-
1,2-propylene glycol, tri-1,2-propylene glycol, tetra-1,2-propylene glycol, hexa-1,2-propylene glycol, di-1,
3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol,
Di-1,3-butylene glycol, tri-1,3-butylene glycol, hexa-1,3-butylene glycol, polyethylene glycol having a weight average molecular weight of 1,000, polyethylene glycol having a weight average molecular weight of 1500, and polyethylene glycol having a weight average molecular weight of 2,000 Polyethylene glycol having a weight average molecular weight of 3000, polyethylene glycol having a weight average molecular weight of 7,500, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, polypropylene glycol having a weight average molecular weight of 1,000, and polypropylene glycol having a weight average molecular weight of 2,000. And polypropylene glycol having an average molecular weight of 3000, polypropylene glycol having a weight average molecular weight of 4000, and the like.

Specific examples of the polyether diol compound represented by the formula (7) include the following. PTMG65 (trade name) manufactured by Sanyo Chemical Industries, Ltd.
0, PTMG1000, PTMG2000, PTMG3
000 mag.

Specific examples of the polyether diol compound represented by the formula (8) include the following. Sanyo Kasei Kogyo Co., Ltd. (trade name) New Pole P
E-61, New Pole PE-62, New Pole PE
-64, New Pole PE-68, New Pole PE-
71, New Pole PE-74, New Pole PE-7
5, New Pole PE-78, New Pole PE-10
8, New Pole PE-128, New Pole PE-6
First magnitude.

Specific examples of the polyether diol compound represented by the formula (9) include the following. New pole B (trade name) manufactured by Sanyo Chemical Industry Co., Ltd.
PE-20, New Pole BPE-20F, New Pole BPE-20NK, New Pole BPE-20T, New Pole BPE-20G, New Pole BPE-4
0, Newpole BPE-60, Newpole BPE-
100, New Pole BPE-180, New Pole B
PE-2P, Newpole BPE-23P, Newpole BPE-3P, Newpole BPE-5P and the like.

Specific examples of the random copolymer of ethylene oxide having a hydroxyl group at the terminal and propylene oxide include the following. Sanyo Kasei Kogyo Co., Ltd., (trade name) Newpole 50HB-100,
New Pole 50HB-260, New Pole 50HB
-400, New Pole 50HB-660, New Pole 50HB-2000, New Pole 50HB-510
0 magnitude.

Examples of the polyester diol compound include compounds represented by the formulas (10) and (11).

[0027]

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In the formula, L ² , L ³ and L ⁴ may be the same or different and each represents a divalent aliphatic or aromatic hydrocarbon group, and L ⁵ represents a divalent aliphatic hydrocarbon group. . Preferably, L ² , L ³ and L ⁴ each represent an alkylene group, an alkenylene group, an alkynylene group or an arylene group,
L ⁵ represents an alkylene group. In L ² , L ³ , L ⁴ and L ⁵ , other functional groups which do not react with the isocyanate group, for example, ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom are present. You may. nl and n2 are each an integer of 2 or more, and preferably an integer of 2 to 100.

As the polycarbonate diol compound, there is a compound represented by the formula (12).

[0030]

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In the formula, L ⁶ may be the same or different, and represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ⁶ represents an alkylene, alkenylene, alkynylene, or arylene group. The other functional group which does not react with an isocyanate group L ^6, for example an ether,
A carbonyl, ester, cyano, olefin, urethane, amide, ureido group or halogen atom may be present. n3 is an integer of 2 or more, preferably an integer of 2 to 100.

The diol compounds represented by the formulas (10), (11) and (12) specifically include the following (Exemplary Compound No. 1) to (Exemplary Compound No. 18) shown below. N in a specific example is an integer of 2 or more.

[0032]

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[0033]

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[0034]

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The specific polyurethane resin (urethane binder) used when the image recording material of the present invention is used as a photopolymerizable photosensitive layer of a lithographic printing plate precursor is more preferably a polyurethane resin further having a carboxyl group. . Specific polyurethane resins preferably used include structural units represented by at least one of diol compounds of formulas (13), (14) and (15) and / or
A polyurethane resin having a structural unit derived from a compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound is exemplified.

[0036]

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In the above formula, R^TwoIs a hydrogen atom, a substituent (eg,
For example, a cyano group, a nitro group, -F, -Cl, -Br, -I
Halogen atom such as -CONH_Two, -COOR^Three, -OR
^Three, -NHCONHR^Three, -NHCOOR^Three, -NHCO
R^Three, -OCONHR^Three(Where R^ThreeHas 1 to 10 carbon atoms
And an aralkyl group having 7 to 15 carbon atoms.
You. )). A) that may have
Alkyl group, aralkyl group, aryl group, alkoxy group,
An aryloxy group, preferably a hydrogen atom, having 1 carbon atom
~ 8 alkyl groups, 6 ~ 15 carbon aryl groups
Show. L⁷, L⁸, L ⁹Are the same but different
Or a single bond, a substituent (eg, alkyl, aralkyl
, Aryl, alkoxy and halogeno groups are preferred
No. ) A divalent aliphatic or aromatic carbon optionally having
Represents a hydride group, and is preferably an alkyl having 1 to 20 carbon atoms.
Rene group, arylene group having 6 to 15 carbon atoms, more preferably
Or an alkylene group having 1 to 8 carbon atoms. Also necessary
According to L⁷, L⁸, L⁹Reacts with isocyanate groups in
No other functional groups such as carbonyl, ester, urethane
May have an amide, amide, ureide, or ether group.
No. Note that R^Two, L⁷, L⁸, L⁹Two or three of the rings
May be formed. Ar is an optionally substituted three
A valent aromatic hydrocarbon group, preferably having 6 to 1 carbon atoms
Shows 5 aromatic groups.

C) Carboxyl-Containing Diol Compound The carboxyl-containing diol compound represented by the formula (13), (14) or (15) specifically includes the following compounds. That is, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4
-Hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxy Ethyl) -3
-Carboxy-propionamide and the like.

In the present invention, preferred tetracarboxylic dianhydrides used in the synthesis of the specific polyurethane resin include those represented by formulas (16), (17) and (18).

[0040]

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In the formula, L ¹⁰ is a single bond, a substituent (eg, alkyl, aralkyl, aryl, alkoxy, halogeno,
Ester and amide groups are preferred. ) May have a divalent aliphatic or aromatic hydrocarbon group, -CO-,
_{-SO -, - SO 2 -,} - O- or -S- are shown, preferably a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon _{atoms, -CO -, - SO 2 -} , - O- or -S- is shown. R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogeno group, preferably a hydrogen atom, an alkyl having 1 to 8 carbon atoms. Group, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogeno group. Also, two of L ¹⁰ , R ⁴ and R ⁵ may combine to form a ring.

R ⁶ and R ⁷ may be the same or different,
A hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogeno group;
Represents an alkyl group of 8 to 8 or an aryl group having 6 to 15 carbon atoms. Also, two of L ¹⁰ , R ⁶ and R ⁷ may combine to form a ring. L ¹¹ and L ¹² may be the same or different and represent a single bond, a double bond, or a divalent aliphatic hydrocarbon group, preferably a single bond, a double bond, or a methylene group. A represents a mononuclear or polynuclear aromatic ring.
It preferably represents an aromatic ring having 6 to 18 carbon atoms.

Specific examples of the compound represented by the formula (16), (17) or (18) include the following. That is, pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
Propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 ′-[3,3 ′-(alkylphosphoryldiphenylene) -bis (iminocarbonyl)] diphthalic dianhydride,

Aromatic tetracarboxylic dianhydrides such as adducts of hydroquinone diacetate and trimetic anhydride, and adducts of diacetyldiamine and trimetic anhydride;
5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (Dai Nippon Ink Chemical Industry Co., Ltd., Epicron B-4)
400), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride and other alicyclic tetra Carboxylic dianhydride; aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,4,5-pentanetetracarboxylic dianhydride; .

As a method for introducing a structural unit derived from a compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound into a polyurethane resin, for example, the following method is available. a) A method in which an alcohol-terminated compound obtained by ring-opening a tetracarboxylic dianhydride with a diol compound is reacted with a diisocyanate compound. b) A method in which a diisocyanate compound is reacted under the condition of an excess of a diol compound to react an alcohol-terminated urethane compound obtained with tetracarboxylic dianhydride.

The diol compound used at this time specifically includes the following compounds. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6
-Hexanediol, 2-butene-1,4-diol,
2,2,4-trimethyl-1,3-pentanediol,
1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A,
Propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p -Xylylene glycol,
Dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylenedicarbamate, 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate and the like.

D) Other diol compounds Further, in the synthesis of the specific polyurethane resin, other diol compounds which do not have a carboxyl group and may have another substituent which does not react with isocyanate may be used in combination. Can also. Such diol compounds include:
The following are included.

HO-L ¹³ -O-CO-L ¹⁴ -CO-OL ¹³ -OH (19) HO-L ¹⁴ -CO-OL ¹³ -OH (20)

In the formula, L ¹³ and L ¹⁴ may be the same or different and each has a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group,
Each group such as a halogen atom such as —F, —Cl, —Br, and —I is included. A) a divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have If necessary, L ¹³ and L ¹⁴ may have another functional group which does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureide group and the like.
L ¹³ and L ¹⁴ may form a ring.

Specific examples of the compound represented by the above formula (19) or (20) are shown below (exemplary compound N
o.19) to (Exemplary Compound No. 35).

[0051]

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[0052]

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[0053]

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Also, diol compounds represented by the following formulas (21) and (22) can be suitably used.

[0055]

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In the formula, R ⁸ and R ⁹ may be the same or different and each is an alkyl group which may have a substituent, and c represents an integer of 2 or more, preferably an integer of 2 to 100. It is.

Specific examples of the diol compounds represented by formulas (21) and (22) include the following. That is, as the formula (21), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Examples of the formula (22) such as 8-octanediol include the compounds shown below.

[0058]

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Also, diol compounds represented by the following formulas (23) and (24) can be suitably used.

HO-L ¹⁵ -NH-CO-L ¹⁶ -CO-NH-L ¹⁵ -OH (23) HO-L ¹⁶ -CO-NH-L ¹⁵ -OH (24)

In the formula, L ¹⁵ and L ¹⁶ may be the same or different and each has a substituent (eg, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (—F, —Cl, —Br, — A) a divalent aliphatic hydrocarbon group which may have:
It represents an aromatic hydrocarbon group or a heterocyclic group. As needed,
Other functional groups which do not react with isocyanate groups in L ¹⁵ and L ¹⁶ , such as carbonyl, ester, urethane, amide,
It may have a ureido group or the like. L ¹⁵ and L ¹⁶ may form a ring.

Specific examples of the compound represented by the formula (23) or (24) include the following.

[0063]

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[0064]

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Further, diol compounds represented by the following formulas (25) and (26) can also be suitably used.

HO—Ar ² — (L ¹⁷ —Ar ³ ) n—OH (25) HO—Ar ² —L ¹⁷ —OH (26)

In the formula, L ¹⁷ is a substituent (eg, alkyl,
Aralkyl, aryl, alkoxy, aryloxy and halogeno groups are preferred. ) Represents a divalent aliphatic hydrocarbon group which may have If necessary, other functional groups which do not react with isocyanate groups in L ¹⁷ , such as esters,
It may have a urethane, amide, or ureido group. A
r ² and Ar ³ may be the same or different, and represent a divalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms. n is 0 to 10
Indicates an integer.

The diol compound represented by the above formula (25) or (26) specifically includes the following compounds. That is, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcin, 4-ethylresorcin, 4-t-butyl Resorcinol, 4-hexylresorcinol, 4-chlororesorcinol,
4-benzyl resorcinol, 4-acetyl resorcinol, 4
-Carbomethoxy resorcin, 2-methyl resorcin,
5-methylresorcinol, t-butylhydroquinone,
2,5-di-t-butylhydroquinone, 2,5-di-
t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcarbaminohydroquinone, methylureidohydroquinone, methylthiohydroquinone, benzonorbornene-3,6-
Diol, bisphenol A,

Bisphenol S, 3,3'-dichlorobisphenol S, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 4,4'-thiodiphenol, 2,2'-dihydroxydiphenylmethane, 3, 4-bis (p-hydroxyphenyl) hexane, 1,4-bis (2- (p-hydroxyphenyl) propyl) benzene, bis (4-hydroxyphenyl) methylamine, 1,3-dihydroxynaphthalene, 1,4
-Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3,5-di-t-butyl Benzyl alcohol, 4-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxyphenethyl alcohol,
-Hydroxyethyl-4-hydroxybenzoate, 2
-Hydroxyethyl-4-hydroxyphenyl acetate, resorcinol mono-2-hydroxyethyl ether and the like. A diol compound represented by the following formula (27), (28) or (29) can also be suitably used.

[0070]

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Where R^TenIs a hydrogen atom, a substituent (for example,
Cyano, nitro, halogen atom (-F, -Cl, -B
r, -I), -CONH_Two, -COOR^ll, -OR¹¹,
-NHCONHR¹¹, -NHCOOR^ll, -NHCOR
¹¹, -OCONHR¹¹, -CONHR¹¹(Where R¹¹
Represents an alkyl group having 1 to 10 carbon atoms and an ara group having 7 to 15 carbon atoms.
Represents a alkyl group. )). )
Alkyl, aralkyl, aryl, alkoxy
Represents an aryloxy group, preferably a hydrogen atom, carbon
An alkyl group having 1 to 8 carbon atoms and an aryl having 6 to 15 carbon atoms
Represents a group. L¹⁸, L¹⁹, L²⁰Are the same but different
May be a single bond, a substituent (eg, alkyl,
Aralkyl, aryl, alkoxy, and halogen groups are preferred.
Good. Divalent aliphatic or aromatic optionally having
Represents an aromatic hydrocarbon group, and preferably has 1 to 20 carbon atoms.
Alkylene group, arylene group having 6 to 15 carbon atoms, and
It preferably represents an alkylene group having 1 to 8 carbon atoms. necessary
Depending on¹⁸, L¹⁹, L²⁰Isocyanate groups
Other functional groups that do not respond, such as carbonyl, ester,
Even if it has a urethane, amide, ureide or ether group
Good. Note that R^Ten, L ¹⁸, L¹⁹, L²⁰2 of or
Three may form a ring. Ar has a substituent,
Represents a trivalent aromatic hydrocarbon group, preferably a carbon atom
Shows several to 15 aromatic groups. Z₀Represents the following groups
You.

[0072]

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Here, R ¹² and R ¹³ may be the same or different, and each represents a hydrogen atom, sodium, potassium,
Represents an alkyl group or an aryl group, preferably a hydrogen atom,
An alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 15 carbon atoms are shown.

The above formula (27), (28) or (29)
The diol compound having a phosphonic acid, a phosphoric acid and / or an ester group thereof represented by is synthesized by, for example, the following method. The following general formulas (30) and (3)
After protecting the hydroxy group of the halogen compound represented by 1) or (32) as necessary, M represented by the formula (33)
The synthesis is carried out by phosphonate esterification by an Ichaelis-Arbuzov reaction and, if necessary, hydrolysis with hydrogen bromide or the like.

[0075]

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Wherein R ¹⁴ , L ²¹ , L ²² , L ²³ and Ar
Is the same as in the case of the equations (27), (28) and (29). R ¹⁵ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms. R ¹⁶ is represented by the formulas (30), (31), and (32)
A residue obtained by removing the X ^l, X ^l is a halogen atom, preferably denotes Cl, Br, and I.

After the reaction with the phosphorus oxychloride represented by the formula (34), the synthesis is carried out by a hydrolysis method.

[0078]

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In the formula, R ¹⁷ has the same meaning as in formula (33), and M represents a hydrogen atom, sodium or potassium.

When the polyurethane resin of the present invention has a phosphonic acid group, the diisocyanate compound represented by the general formula (4) and the phosphonic acid ester group represented by the general formula (27), (28) or (29) May be synthesized by reacting a diol compound having the following formula to form a polyurethane resin, followed by hydrolysis with hydrogen bromide or the like.

Further, similarly to the diol compound, the following amino group-containing compound may be reacted with the diisocyanate compound represented by the general formula (4) to form a urea structure and be incorporated into the structure of the polyurethane resin. .

[0082]

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In the formula, R ¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen atom, a substituent (for example, alkoxy, a halogen atom (—F, —Cl, —Br, —I), an ester, An alkyl group, an aralkyl group, or an aryl group, which may have a hydrogen atom, and preferably a carbon atom having 1 to 8 carbon atoms which may have a carboxyl group as a substituent. Alkyl represents an aryl group having 6 to 15 carbon atoms. L ²⁴ represents a substituent (eg, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (—F, —Cl, —Br, —
I) and carboxyl groups. A) a divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have If necessary, L ²⁴ may have another functional group that does not react with an isocyanate group, for example, a carbonyl, ester, urethane, or amide group. Two of R ¹⁸ , L ²⁴ and R ¹⁹ may form a ring

Specific examples of the compounds represented by formulas (35) and (36) include the following.
That is, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, dodecamethylenediamine, propane-1,2-diamine, bis (3-aminopropyl) methylamine, , 3-Bis (3-aminopropyl) tetramethylsiloxane, piperazine, 2,5-dimethylpiperazine, N- (2-aminoethyl) piperazine, 4-amino-2,2-6,6-tetramethylpiperidine, N ,
Aliphatic diamine compounds such as N-dimethylethylenediamine, lysine, L-cystine, isophoronediamine;

O-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, benzidine, o-ditoluidine, o-dianisidine, 4-nitro-m-phenylenediamine, 2,5
-Dimethoxy-p-phenylenediamine, bis- (4-
Aminophenyl) sulfone, 4-carboxy-o-phenylenediamine, 3-carboxy-m-phenylenediamine, 4,4′-diaminophenylether, 1,8-
Aromatic diamine compounds such as naphthalenediamine;
2-aminoimidazole, 3-aminotriazole, 5
-Amino-1H-tetrazole, 4-aminopyrazole, 2-aminobenzimidazole, 2-amino-5-
Carboxy-triazole, 2,4-diamino-6-methyl-S-triazine, 2,6-diaminopyridine, L
-Heterocyclic amine compounds such as histidine, DL-tryptophan, adenine and the like;

Ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2
-Propanol, 1-amino-3-propanol, 2-
Aminoethoxyethanol, 2-aminothioethoxyethanol, 2-amino-2-methyl-1-propanol, p-aminophenol, m-aminophenol, o
-Aminophenol, 4-methyl-2-aminophenol, 2-chloro-4-aminophenol, 4-methoxy-3-aminophenol, 4-hydroxybenzylamine, 4-amino-1-naphthol, 4-aminosalicylic acid, 4-hydroxy-N-phenylglycine, 2-aminobenzyl alcohol, 4-aminophenethyl alcohol, 2-carboxy-5-amino-1-naphthol, L
Amino alcohol or aminophenol compounds such as tyrosine and the like.

The specific polyurethane resin that can be used in the present invention is synthesized by adding a known catalyst having an activity corresponding to the reactivity of the above isocyanate compound and diol compound in an aprotic solvent and heating the mixture. The molar ratio of the diisocyanate and the diol compound used is preferably 0.8: 1 to 1.2: 1. When the isocyanate group remains at the polymer terminal, the polymer is treated with alcohols or amines to obtain the final Is synthesized in such a manner that no isocyanate group remains.

As the specific polyurethane resin according to the present invention, those having an unsaturated bond at the polymer terminal, main chain or side chain are preferably used. By having an unsaturated bond, a cross-linking reaction occurs between the polymerizable compound and the polyurethane resin, and as a result, the photocured product strength is increased, and when applied to a lithographic printing plate, a plate material having excellent printing durability is provided. be able to.
As the unsaturated bond, a carbon-carbon double bond is particularly preferable because a crosslinking reaction easily occurs.

As a method for introducing an unsaturated group into the polymer terminal, the following method is available. That is, when an isocyanate group remains at the polymer terminal in the process of synthesizing the polyurethane resin described above, an alcohol or an amine having an unsaturated group may be used in the process of treating with an alcohol or an amine. Specific examples of such compounds include the following.

[0090]

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[0091]

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[0092]

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[0093]

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As a method for introducing an unsaturated group into the main chain or side chain, there is a method in which a diol compound having an unsaturated group is used for synthesizing a polyurethane resin. Specific examples of the diol compound having an unsaturated group include the following compounds. A diol compound represented by the formula (37) or (38). Specific examples include the following.

[0095]

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Specific examples of the diol compound represented by the formula (37) include 2-butene-1,4-diol and the like, and examples of the diol compound represented by the formula (38) include c
is-2-butene-1,4-diol, trans-2
-Butene-1,4-diol and the like.

A diol compound having an unsaturated group in the side chain.
Specific examples include the following compounds.

[0098]

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The specific polyurethane resin according to the present invention preferably contains an aromatic group in a main chain and / or a side chain. More preferably, the content of the aromatic group is in the range of 10 to 80% by weight in the polyurethane resin. Such a specific polyurethane resin is preferably a polyurethane resin having a carboxyl group, and its content is preferably at least 0.4 meq / g, more preferably from 0.4 to 3. 5 meq /
g. The molecular weight of the specific polyurethane resin is preferably 1,000 or more in terms of weight average molecular weight, and more preferably in the range of 10,000 to 300,000.

The specific polyurethane resin according to the present invention may be used alone or in combination of two or more. Further, as long as the effects of the present invention are not impaired, other polymer compounds can be used in combination with the polyurethane resin (A). In this case, the other polymer compound is
(A) 90% of all polymer compounds including polyurethane resin
% By weight or less, more preferably 7% by weight or less.
0% by weight or less.

(A) contained in the image recording material of the present invention.
The content of the specific polyurethane resin is about 5 to 95% by weight, preferably about 10 to 85% by weight in solid content.
When the addition amount is less than 5% by weight, the strength of the image portion is insufficient when an image is formed. When the amount exceeds 95% by weight, no image is formed.

[(B) Radical polymerizable compound] The radical polymerizable compound used in the present invention is a radical polymerizable compound having at least one ethylenically unsaturated double bond, and has a terminal ethylenically unsaturated bond. At least one
, Preferably two or more compounds. Such compounds are widely known in the industrial field, and they can be used in the invention without any particular limitation. These have chemical forms such as, for example, monomers, prepolymers, ie, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, and are preferred. As the ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are used. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, an addition reaction product of an amide with a monofunctional or polyfunctional isocyanate, an epoxy, a monofunctional or A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving group such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene or the like.

Specific examples of the radical polymerizable compound which is an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butane. Diol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, , 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, penta Risuri toll triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate,
Examples include sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, and polyester acrylate oligomer.

Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240 and JP-A-59-5240. 59-524
1, those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Examples of other preferred amide-based monomers include those having a cyclohexylene structure described in JP-B-54-21726.

A urethane-based addition-polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups in one molecule to which a vinyl monomer having a hydroxyl group represented by the following formula (VI) is added. And vinyl urethane compounds containing at least two polymerizable vinyl groups.

Formula (VI) CH ₂ ＣC (R ⁴¹ ) COOCH ₂ CH (R ⁴² ) OH (where R ⁴¹ and R ⁴² represent H or CH ₃ )

Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and JP-B-58-167.
No. 49860, No. 56-17654, No. 62
Urethane compounds having an ethylene oxide skeleton described in JP-B-39417 and JP-B-62-39418 are also suitable.

Further, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909 and JP-A-1-105238 may be used. good.

As another example, see JP-A-48-641.
No. 83, JP-B-49-43191, JP-B-52-30
No. 490, polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in each publication. Also,
JP-B-46-43946, JP-B-1-40337,
Specific unsaturated compounds described in JP-B-1-40336,
Vinyl phosphonic acid compounds described in JP-A-2-25493 can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used.

Even when the radical polymerizable compound is used alone,
More than one species may be used in combination. Details of how to use these radically polymerizable compounds, such as what kind of structure to use, whether to use them alone or in combination, and the amount of addition, are optional according to the performance design of the final recording material. Can be set to Regarding the compounding ratio of the radical polymerizable compound in the image recording material, the larger the ratio, the better the sensitivity. However, if the ratio is too large, undesired phase separation may occur or the production process due to the stickiness of the image recording layer may occur. (For example, poor production resulting from transfer of recording layer components and adhesion) and problems such as precipitation from a developer. From these viewpoints, a preferable compounding ratio of the radical polymerizable compound is, in many cases, from 5 to 80% by weight, and preferably from 20 to 75% by weight, based on all components of the composition. The method of using the radically polymerizable compound can be arbitrarily selected from appropriate structures, blending, and addition amounts based on desired properties, and in some cases, a layer structure and a coating method such as undercoating and overcoating can be performed.

[(C) Photothermal Conversion Agent] Since the image recording material of the present invention performs recording by heat mode exposure, typically a laser emitting infrared rays, it is essential to use a photothermal conversion agent. . The photothermal conversion agent has a function of absorbing light of a predetermined wavelength and converting the light into heat. The heat generated at this time decomposes the component (D), that is, the compound that generates a radical by heat mode exposure to light having a wavelength that can be absorbed by the photothermal conversion agent, thereby generating a radical. The photothermal conversion agent used in the present invention may be any as long as it has a function of converting absorbed light into heat.In general, the wavelength of an infrared laser used for writing, that is,
Having an absorption maximum at a wavelength of 760 nm to 1200 nm,
Dyes or pigments known as so-called infrared absorbers are mentioned.

As the dye, commercially available dyes and known dyes described in literatures such as “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes Is mentioned.

Preferred dyes include, for example, those described in
Cyanine dyes described in JP-A-8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, etc .;
No. 96, JP-A-58-181690, JP-A-58-1
No. 94595, etc., methine dyes described in
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940 and JP-A-60-63744;
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent 434,875 and the like can be mentioned.

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 preferable. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169) described in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
Nos. -84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranyl compounds, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used.

Further, as another preferred example of the dye, US Pat. No. 4,756,993 discloses formula (I):
Near-infrared absorbing dyes described as (II) can be mentioned.

Of these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes. Further, a cyanine dye is preferable, and a cyanine dye represented by the following general formula (I) is most preferable.

[0124]

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In the general formula (I), X ¹ is a halogen atom,
Or an X ² -L ^1. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms. R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of storage stability of a photosensitive layer coating liquid, R ¹ and R ² are preferably a hydrocarbon group having two or more carbon atoms, further, R ¹ and R ²
And particularly preferably combine with each other to form a 5- or 6-membered ring.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Preferred examples of the substituent include a hydrocarbon group having 12 or less carbon atoms, a halogen atom, and an alkoxy group having 12 or less carbon atoms. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different, and represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms,
Examples include a carboxyl group and a sulfo group. R ⁵ , R ⁶ , R
⁷ and R ⁸ may be the same or different,
It represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the viewpoint of availability of raw materials, a hydrogen atom is preferable. Z ^1- represents a counter anion. However, when any of R ^{1 to} R ⁸ is substituted with a sulfo group, Z ^1- is not required. Preferred Z ¹⁻ is, from the storage stability of the photosensitive layer coating solution, a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion,
And sulfonate ions, particularly preferably perchlorate ion, hexafluorophosphate ion and arylsulfonate ion.

In the present invention, specific examples of the cyanine dye represented by the general formula (I) which can be suitably used include paragraph [0] of Japanese Patent Application No. 11-310623.
017] to [0019].

The pigments used in the present invention include:
Commercial Pigment and Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used.

The types of pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing 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. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
If it is less than m, the dispersion is not preferred in terms of stability in the coating solution of the image-sensitive layer.

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner 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, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

These light-to-heat converting agents may be added to the same layer as other components, or may be added to another layer provided. However, when a negative type image forming material is prepared, It is preferable that the optical density of the photosensitive layer at the absorption maximum in the wavelength range of 760 nm to 1200 nm is between 0.1 and 3.0. Outside of this range, sensitivity tends to decrease. Since the optical density is determined by the amount of the photothermal conversion agent added and the thickness of the recording layer, a predetermined optical density can be obtained by controlling both conditions. The optical density of the recording layer can be measured by a conventional method. As a measurement method,
For example, on a transparent or white support, a coating layer having a thickness determined appropriately within a range required for a lithographic printing plate after drying is formed, and a method of measuring with a transmission optical densitometer, aluminum And the like, in which a recording layer is formed on a reflective support such as the above, and the reflection density is measured.

[(D) (C) Compound that generates a radical by heat mode exposure to light having a wavelength that can be absorbed by the photothermal converter] A compound that generates a radical by heat mode exposure (hereinafter referred to as a radical initiator as appropriate) ) Is used in combination with the photothermal conversion agent (C) to generate radicals by light or heat or both energy when irradiating light having a wavelength that the photothermal conversion agent can absorb, for example, an infrared laser; (B) A compound that initiates and promotes polymerization of a radically polymerizable compound having a polymerizable unsaturated group. Here, the “heat mode exposure” follows the definition in the present invention. As the radical initiator, known photopolymerization initiators, thermal polymerization initiators and the like can be selected and used, for example, onium salts, triazine compounds having a trihalomethyl group, peroxides, azo-based polymerization initiators , Azide compounds, quinonediazides, etc., and onium salts are preferred because of their high sensitivity.

An onium salt that can be suitably used as a radical initiator in the present invention will be described. Preferred onium salts include iodonium salts, diazonium salts, and sulfonium salts. In the present invention, these onium salts function not as acid generators but as radical polymerization initiators. Onium salts suitably used in the present invention are onium salts represented by the following general formulas (III) to (V).

[0136]

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In the formula (III), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms which may have a substituent. When the aryl group has a substituent, preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a 12 or less carbon atom. Aryloxy groups. Z ^11- represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and is preferably a perchlorate ion or a hexafluorophosphate. And arylsulfonate ions.

In the formula (IV), Ar^{twenty one}Has a substituent
And represents an aryl group having 20 or less carbon atoms. Good
Preferred substituents include halogen atoms, nitro groups, carbon
Alkyl group with 12 or less atoms, 12 or less carbon atoms
An alkoxy group having 12 or less carbon atoms
Si group, alkylamino group having 12 or less carbon atoms, carbon
Dialkylamino group having 12 or less atoms, 1 carbon atom
2 or less arylamino groups or 12 carbon atoms
The following diarylamino groups are mentioned. Z^{twenty one -}Is Z^11-
Represents a counter ion having the same meaning as

In the formula (V), R ³¹ , R ³² and R ³³ may be the same or different and represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, and an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

In the present invention, specific examples of the onium salt that can be suitably used as a radical generator include:
Paragraph number [003 of Japanese Patent Application No. 11-310623]
0] to [0033].

The general formula (I) described in paragraphs [0012] to [0050] of JP-A-9-34110
-Onium salts represented by formulas (IV) to (IV):
Known polymerization initiators such as the thermal polymerization initiator described in Paragraph No. [0016] of JP-A-1 (1998) are also preferably used. The radical initiator used in the present invention has a maximum absorption wavelength of 4
00 nm or less, preferably 360 nm
The following is preferred. By setting the absorption wavelength in the ultraviolet region, the image recording material can be handled under a white light.

[Other Components] In the image recording material of the present invention, various compounds other than these may be further 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 # 10
3. Oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-50
5 (from Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI4255)
5), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue (CI52015), etc., and JP-A-62-29324
No. 7 can be mentioned. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can be suitably used.

These colorants are preferably added because the image area and the non-image area can be easily distinguished after image formation. The addition amount is based on the total solid content of the photosensitive layer coating solution.
The ratio is 0.01 to 10% by weight.

In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the radically polymerizable compound during preparation or storage of the image recording material. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% by weight based on the weight of the whole composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The added amount of the higher fatty acid derivative is preferably from about 0.1% to about 10% by weight of the whole composition.

The image recording material of the present invention is mainly used for forming an image recording layer of a lithographic printing plate precursor. Kaikai 62-251740
And non-ionic surfactants described in JP-A-3-208514, and amphoteric surfactants described in JP-A-59-121044 and JP-A-4-13149. Can be.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene nonyl phenyl ether and the like.

Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N , N-betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive layer coating solution is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer may be added to the photosensitive layer coating solution according to the present invention, if necessary, in order 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, and the like are used.

In order to produce a lithographic printing plate precursor from the image recording material of the present invention, usually, the components of the image recording material are dissolved in a solvent together with the components necessary for the coating solution, and coated on a suitable support. do it. As the solvent used herein, 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, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene,
Water and the like can be mentioned, but it is not limited thereto. These solvents are 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) of the image recording layer on the support obtained after coating and drying varies depending on the application, but generally ranges from 0.5 to 0.5 for a lithographic printing plate precursor.
5.0 g / m ² is preferred. Various methods can be used as the method of coating, and 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 layer deteriorate.

The coating solution for the image recording layer according to the present invention may contain a surfactant for improving the coating property, for example, a surfactant described in
A fluorinated surfactant as described in JP 170950 can be added. The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the solid content of the material of the entire photosensitive layer.

(Protective Layer) When the image-recording material of the present invention is used for a lithographic printing plate precursor, exposure is usually performed in the air.
It is preferable to provide a protective layer, and the desired properties of such a protective layer include low permeability of low molecular compounds such as oxygen, good transparency of light used for exposure, and adhesion to the recording layer. Water-soluble polymers that are excellent in crystallinity, such as polyvinyl alcohol, polyvinylpyrrolidone, acidic celluloses, gelatin, gum arabic, and polyacrylic acid. It is common to use compounds. In the image recording material of the present invention, as the film-forming resin, the specific polyurethane resin having a low dissolved oxygen content in the film after the film is formed and further having a high oxygen barrier property from the outside is used.
It has the advantage of being able to suppress a decrease in image forming properties due to polymerization inhibition of oxygen and the like, and thus it is not always necessary to provide such a protective layer. The protective layer may be provided for the purpose of enhancing image strength.

(Support) The support used for forming a lithographic printing plate precursor using the image recording material of the present invention is not particularly limited as long as it is a dimensionally stable plate.
For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, 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.). These may be a single-component sheet such as a resin film or a metal plate, or a laminate of two or more materials, for example, a paper or plastic film on which a metal is laminated or vapor-deposited as described above. And laminated sheets of different types of plastic films.

As the support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign elements in the alloy is at most 10% by weight
It is as follows. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate,
About 0.1 to 0.6 mm, preferably 0.15 to
It is 0.4 mm, particularly preferably 0.2 to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like is performed to remove rolling oil on the surface. 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 dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. In addition, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Also,
As disclosed in JP-A-54-63902, a method in which both are combined can also be used. The aluminum plate thus roughened may be subjected to an anodic oxidation treatment through alkali etching treatment and neutralization treatment, if desired, in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte to be used, and thus cannot be specified unconditionally. In general, the concentration of the electrolyte is 1 to 80% by weight, and the solution temperature is 5 to 70 ° C.
Current density 5 to 60 A / dm ^2, voltage 1 to 100 V, which is an electrolyzing time of 10 seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide coating is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image area of the lithographic printing plate is easily damaged, and the ink adheres to the damaged area during printing. "Scratch dirt" is likely to occur. Although such anodizing treatment is performed on a surface used for printing of the support of lithographic printing plates, the back around the electric lines of force, 0.01 to 3 g / m ² on the back surface
Is generally formed.

The hydrophilizing treatment of the surface of the support is performed after the above-described anodic oxidation treatment, and a conventionally known treatment method is used. As such a hydrophilic treatment,
U.S. Pat. Nos. 2,714,066 and 3,181,4
No. 61, No. 3,280,734 and No. 3,902,7
There is an alkali metal silicate (for example, an aqueous solution of sodium silicate) disclosed in Japanese Patent No. 34-34. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, Japanese Patent Publication No. 36-22
No. 063, and potassium fluoride zirconate disclosed in U.S. Pat. Nos. 3,276,868 and 4,15.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in JP-A-3,461 and JP-A-4,689,272 is used. Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

The anodic oxide film of the aluminum plate treated as described above was coated with an alkali metal silicate in an amount of 0.1 to 30% by weight, preferably 0.5 to 10% by weight, and a pH at 25 ° C. of 10 to 10% by weight. Aqueous solution, for example, 15 to 80
Soak at 0.5C for 0.5-120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 10, the solution will gel, and if it is higher than 13.0, the oxide film will be dissolved. As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used to increase the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide and lithium hydroxide. In addition, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned processing solution.
Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. Can be. Alkaline earth metal salt or
The Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.0
1 to 10% by weight, more preferably 0.05 to 10% by weight.
5.0% by weight. Since the silicate treatment further improves the hydrophilicity on the aluminum plate surface, the ink hardly adheres to the non-image area during printing, and the stain performance is improved.

A back coat is provided on the back surface of the support, if necessary. Examples of the back coat include a coating comprising a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. Layers are preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si (OC
_{2 H 5) 4, Si (} OC 3 H 7) 4, Si (OC
Alkoxy compounds of silicon such as ₄ H ₉ ) ₄ are inexpensive and readily available, and a coating layer of a metal oxide provided therefrom is particularly preferred because of its excellent development resistance.

As described above, a lithographic printing plate precursor can be prepared from the image recording material of the present invention. This lithographic printing plate precursor can be recorded with an infrared laser. Also, thermal recording with an ultraviolet lamp or a thermal head is possible. In the present invention, a wavelength of 760 nm to 1200
It is preferable that the image is exposed by a solid-state laser or a semiconductor laser that emits infrared light of nm.

After exposure with an infrared laser, the image recording material of the present invention is preferably developed with water or an aqueous alkaline solution.

When an alkaline aqueous solution is used as the developer, a conventionally known alkaline aqueous solution can be used as the developer and replenisher for the image recording material of the present invention. For example,
Sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, Inorganic alkali salts such as sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Also, monomethylamine, dimethylamine,
Trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc. Organic alkaline agents are also used. These alkali agents are used alone or in combination of two or more.

Further, when developing using an automatic developing machine, the same solution as the developing solution or an aqueous solution having a higher alkali strength than the developing solution (replenishing solution) is added to the developing solution to allow the developing tank to be used for a long time. It is known that a large amount of a lithographic printing plate precursor can be processed without replacing the developer. This replenishment system is also preferably applied in the present invention.

Various surfactants and organic solvents can be added to the developing solution and the replenishing solution, if necessary, for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. . Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof. Further, non-reducing sugars such as arabit, sorbit, and mannitol can also be added.

Further, the developing solution and the replenisher may contain, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcin, sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoaming agent, a hard water Softeners can also be added.

The printing plate developed using the above-described developing solution and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. You. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate material, each processing solution tank, and a spray device. The developing process is performed by spraying each pumped processing liquid from a spray nozzle. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like into a processing liquid tank filled with a processing liquid to perform processing. In such automatic processing,
Processing can be performed while replenishing each processing solution with a replenisher according to the processing amount, operating time, and the like. In addition, the electric conductivity can be detected by a sensor and replenished automatically. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing step after coating with a desensitized gum if desired. However, when a lithographic printing plate having higher printing durability is desired, Is subjected to a burning process.

In the case of burning a lithographic printing plate, prior to burning, JP-B Nos. 61-2518 and 55-280.
No. 62, JP-A-62-131859 and JP-A-61-1596.
It is preferable to treat with a surface-regulating liquid as described in each of the publications No. 55.

[0170] As a method for this, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied onto a lithographic printing plate,
A method in which a printing plate is immersed in a vat filled with a surface conditioning liquid to apply the printing plate, an application using an automatic coater, or the like is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m ^2.
(Dry weight) is appropriate.

The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then burned with a burning processor (for example,
It is heated to a high temperature by a burning processor (BP-1300) sold by Fuji Photo Film Co., Ltd. The heating temperature and time in this case depend on the type of the component forming the image, but may be 1 to 180 ° C. to 300 ° C.
A range of up to 20 minutes is preferred.

The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming if necessary. However, a surface conditioning solution containing a water-soluble polymer compound or the like can be used. When is used, so-called desensitizing treatment such as gumming can be omitted.

The lithographic printing plate obtained from the image recording material of the present invention by such processing is applied to an offset printing machine or the like, and used for printing a large number of sheets.

[0174]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, which should not be construed as limiting the invention thereto. (Synthesis Example 1: Polyurethane resin 1) A 2-ml 500 ml three-necked round bottom flask equipped with a condenser and a stirrer
8.2 g of bis (hydroxymethyl) butanoic acid (0.05
Mol) and 7.8 g (0.05 mol) of trimethylolpropane monoallyl ether were dissolved in 100 ml of N, N-dimethylacetamide. To this, 20.0 g (0.08 mol) of 4,4-diphenylmethane diisocyanate and 3.4 of 1,6-hexamethylene diisocyanate were added.
g (0.02 mol), dibutyltin dilaurate 0. l
g was added and the mixture was heated and stirred at 100 ° C. for 8 hours. Thereafter, the mixture was diluted with 100 ml of N, N-dimethylformamide and 200 ml of methyl alcohol. The reaction solution was poured into 3 liters of water while stirring to precipitate a white polymer. The polymer was separated by filtration, washed with water, and dried under vacuum to obtain 32 g of a polymer. When the molecular weight was measured by gel permeation chromatography (GPC), the weight average molecular weight (polystyrene standard) was 110,000. Further, when the carboxyl group content (acid value) was measured by titration, it was 1.3.
It was 3 meq / g.

(Synthesis Example 2: Polyurethane resin 21) 2,
10.3 g of 2-bis (hydroxymethyl) propionic acid
(0.077 mol) and 23.0 g (0.023 mol) of polypropylene glycol (weight average molecular weight 1000) were dissolved in 100 ml of N, N-dimethylacetamide.
To this, 4,4'-diphenylmethane diisocyanate 2
Using 0.0 g (0.08 mol) and 3.4 g (0.02 mol) of hexamethylenediisocyanate, the reaction and post-treatment were carried out in the same manner as in Synthesis Example 1. White polymer 80
g was obtained. The molecular weight measured by GPC was 100,000 in weight average (polystyrene standard). The content of the carboxyl group (acid value) was measured by titration and found to be 1.35 meq / g.

The polyurethane resins (polyurethane resins 1 to 28) of the present invention were synthesized using the diisocyanate compounds and diol compounds shown in the following Tables 1 to 5 in the same manner as in Synthesis Example 1 or Synthesis Example 2. did. Further, the molecular weight was measured by GPC, and the acid value was measured by titration. Tables 1 to 5 show the measured results.

[0177]

[Table 1]

[0178]

[Table 2]

[0179]

[Table 3]

[0180]

[Table 4]

[0181]

[Table 5]

(Examples 1 to 5, Comparative Example 1) [Preparation of Support] 99.5% or more of aluminum and F
e 0.30%, Si 0.10%, Ti 0.02
% And a melt of JIS A1050 alloy containing 0.013% of Cu were subjected to a cleaning treatment and cast. In the cleaning treatment, a degassing treatment was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter treatment was performed. The casting was performed by DC casting. Solidified plate thickness 50
A 0 mm ingot was chamfered from the surface by 10 mm, and homogenized at 550 ° C. for 10 hours to prevent the intermetallic compound from becoming coarse. Next, after hot rolling at 400 ° C. and intermediate annealing in a continuous annealing furnace at 500 ° C. for 60 seconds, cold rolling was performed to obtain a rolled aluminum sheet having a sheet pressure of 0.30 mm. The center line average surface roughness Ra after cold rolling was controlled to 0.2 μm by controlling the roughness of the rolling roll.
Then, it was subjected to a tension leveler to improve the flatness.

Next, a surface treatment for forming a lithographic printing plate support was performed. First, in order to remove the rolling oil on the surface of the aluminum plate, a degreasing treatment was performed with a 10% aqueous sodium aluminate solution at 50 ° C. for 30 seconds, and a 30% sulfuric acid aqueous solution was neutralized at 50 ° C. for 30 seconds and a smut removal treatment was performed.

Next, in order to improve the adhesion between the support and the recording layer and to impart water retention to the non-image rear portion, a so-called graining treatment was performed to roughen the surface of the support. 1%
Aqueous solution containing 0.5% nitric acid and 0.5% aluminum nitrate
° C while flowing an aluminum web in an aqueous solution, the anode-side electricity quantity 240 C / dm ² with an alternating waveform having a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect feeding cell.
Electrolytic graining was performed by giving ² . Then 10%
Etching was performed with a sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal were performed with a 30% aqueous sulfuric acid solution at 50 ° C. for 30 seconds.

In order to further improve abrasion resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodic oxide film of 2.5 g / m ^{2 is} obtained by performing an electrolytic treatment with a direct current of 14 A / dm ² by an indirect power supply cell while carrying an aluminum web through the electrolyte using a 20% aqueous solution of sulfuric acid at 35 ° C. as an electrolyte. It was created.

Thereafter, the hydrophilicity of the non-image portion of the printing plate was determined.
To secure, silicate treatment was performed. Processing is No.3 silicon
A 1.5% aqueous solution of acid soda is maintained at 70 ° C.
It was transported so that the contact time was 15 seconds, and was further washed with water.
The amount of Si attached is 10 mg / m ^TwoMet. Work
Ra (center line surface roughness) of the formed support is 0.25 μm
Met.

[Formation of photosensitive layer] The following photosensitive layer coating solution (P-
1) was prepared, applied to the aluminum support obtained as described above using a wire bar, and dried at 115 ° C. for 45 seconds with a hot air drier to form a photosensitive layer. I got the original. The coating amount after drying is 1.2 to 1.3 g
/ M ² . In addition, the alkali-soluble resin used in the examples is the specific polyurethane resin (A) obtained in the above-mentioned synthesis example, and the alkali-soluble resin P-1 used in the comparative example is a benzyl methacrylate / methacrylic acid copolymer ( Polymerization molar ratio = 80/20, polymer compound having a weight average molecular weight of 100,000).

<Coating solution for photosensitive layer (P-1)>-Alkali-soluble resin (compounds listed in Table 6, amount described in Table 6)-Dipentaerythritol hexaacrylate (B) 1.00 g-Infrared absorber "IR-6" (C) 0.08 g-Iodonium salt "I-1" (D) 0.30 g-Victoria pure blue naphthalenesulfonic acid 0.04 g-Fluorosurfactant 0.0lg (MegaFac F- 176, manufactured by Dainippon Ink and Chemicals, Inc.)-Methyl ethyl ketone 9.0 g-Methanol 10.0 g-1-methoxy-2-propanol 8.0 g

[0189]

Embedded image

[0190]

[Table 6]

[Exposure] Each of the resulting lithographic printing plate precursors was used as a Cre-mounted 40 W infrared semiconductor laser.
Exposure was performed using Trendsetter 3244 VFS manufactured by O Corporation under the conditions of an output of 6.5 W, an external drum rotation speed of 81 rpm, a plate surface energy of 188 mJ / cm ² , and a resolution of 2400 dpi. After the exposure, the presence or absence of ablation on the plate was visually evaluated. The results are shown in Table 6 above. As is clear from Table 6, the lithographic printing plate of the example using the image recording material of the present invention as a photosensitive layer was able to perform recording without causing ablation at the time of exposure.

(Examples 6 to 10 and Comparative Example 2) The following photosensitive layer coating solution (P-2) was prepared, applied to the above aluminum support using a wire bar, and heated in a hot air drying apparatus.
It was dried at 5 ° C. for 45 seconds to obtain a lithographic printing plate precursor. The coating amount after drying was in the range of 1.2 to 1.3 g / m ^2. <Photosensitive layer coating solution (P-2)>-Alkali-soluble resin (compounds listed in Table 7, amounts described in Table 7)-Dipentaerythritol hexaacrylate (B) 1.00 g-Infrared absorber "IR-6" (C) 0.08 g-Iodonium salt "I-1" (D) 0.30 g-Victoria pure blue naphthalene sulfonic acid 0.04 g-Fluorosurfactant 0.01 g (MegaFac F-176, Dainippon・ Methyl ethyl ketone 9.0g ・ Methanol 10.0g ・ 1-Methoxy-2-propanol 8.0g

[0193]

[Table 7]

[Exposure] The obtained lithographic printing plate precursor was placed in a Creo T-mount equipped with a water-cooled 40 W infrared semiconductor laser.
output 9W at endsetter 3244VFS
External drum rotation speed 210 rpm, plate surface energy 100
Exposure was performed under the conditions of mJ / cm ² and a resolution of 2400 dpi. [Development processing] After exposure, development processing was carried out using an automatic developing machine Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developing solution, a 1: 1 aqueous dilution of DN-3C manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenishing solution. The temperature of the developing greed bath was 30 ° C. The finisher used was a 1: 1 water dilution of FN-6 manufactured by Fuji Photo Film Co., Ltd.

[Evaluation of Printing Durability] Next, printing was performed using a printing machine Lithrone manufactured by Komori Corporation. At this time, how many sheets can be printed while maintaining a sufficient ink density was visually measured to evaluate the printing durability. The results are shown in Table 7 above. From the results shown in Table 7, the lithographic printing plates of Examples using the image recording material of the present invention as the photosensitive layer showed Comparative Example 2 using a known water-insoluble and alkali-soluble resin.
It can be seen that excellent printing durability was achieved as compared with.

(Examples 11 to 13) A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the composition of the photosensitive layer coating solution was changed to the following composition, and laser scanning was performed under the same conditions as in Example 1. Exposure and development were performed to obtain a printing plate. The printing plate was printed in the same manner as in Example 1, and the sensitivity, printing durability, and stain resistance were evaluated. Further, the obtained lithographic printing plate precursor was stored at 60 ° C. for 3 days, respectively, at 45 ° C. and 75% RH.
After storage at H for 3 days and forced aging, the same printing as described above was performed and the results are shown in Table 8.

<Coating solution for photosensitive layer (P-3)> Polyurethane resin (A) (compounds listed in Table 8, amounts described in Table 8) Radical polymerizable compound (B) (compounds listed in Table 8) , The amount described in Table 8)-Infrared absorber "IR-6" (C) 0.08 g-Iodonium salt "I-1" (D) 0.30 g-Victoria pure blue naphthalenesulfonic acid 0.04 g-Fluorine -Based surfactant 0.01 g (MegaFac F-176, manufactured by Dainippon Ink and Chemicals, Inc.)-Methyl ethyl ketone 9.0 g-Methanol 10.0 g-1-methoxy-2-propanol 8.0 g

[0198]

[Table 8]

[0199]

Embedded image

From Table 8, it can be seen that the lithographic printing plate using the image recording material of the present invention as a photosensitive layer has no stain on the non-image area, has excellent printing durability, and has been stored in a high-temperature, high-humidity environment. Also,
It was found that the printing durability and the stain resistance of the non-image area did not decrease, and the stability with time was excellent.

(Examples 14 to 17, Comparative Example 3) [Preparation of Support] The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a water suspension wave of pumicestone of 400 mesh. After that, it was thoroughly washed with water. 10% by weight aqueous sodium hydroxide solution at 70 ° C
After immersion for 2 seconds, etching, washing with running water, neutralization washing with 20% by weight nitric acid, and then washing with water. This is V _A =
Under the condition of 12.7 V, 1
The electrolytic surface-roughening treatment was performed in a weight% aqueous nitric acid solution at an anode charge of 160 coulomb / dm ² . When the surface roughness was measured, it was 0.6 μm (Ra display). Subsequently, after immersing in a 30% by weight aqueous sulfuric acid solution and desmutting at 55 ° C. for 2 minutes, the thickness of the anodic oxide film was 2.7 g in a 20% by weight aqueous sulfuric acid solution at a current density of 2 A / dm ² .
/ M ² for 2 minutes.

[Formation of Undercoat Layer] Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure. <Sol liquid composition>-130 g of methanol-20 g of water-16 g of 85% by weight phosphoric acid-50 g of tetraethoxysilane-60 g of 3-methacryloxypropyltrimethoxysilane The above sol liquid composition was mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the content was transferred to another container, and 3000 g of methanol was added to obtain a sol solution.

This sol was diluted with methanol / ethylene glycol = 9/1 (weight ratio), applied so that the amount of Si on the substrate was 3 mg / m ^2, and dried at 100 ° C. for 1 minute. On the thus treated aluminum support, a photosensitive layer coating solution (P-4) having the composition shown below is applied to the above-mentioned undercoated aluminum support by using a wire bar, and the hot air drying apparatus is used. And dried at 115 ° C. for 45 seconds to obtain a lithographic printing plate precursor. The coating amount after drying is 1.2 to
It was in the range of 1.3 g / m ² .

<Coating solution for photosensitive layer (P-4)> Alkali-soluble resin (compounds listed in Table 9 and amounts described in Table 9) Radical polymerizable compound (B) (compounds listed in Table 9 and Tables 9)-Infrared absorber "IR-1" (C) 0.08 g-Iodonium salt "I-2" (D) 0.30 g-Victoria pure blue naphthalene sulfonic acid 0.04 g-Fluorine-based interface Activator 0.01 g (MegaFac F-176, manufactured by Dainippon Ink and Chemicals, Inc.) 9.0 g of methyl ethyl ketone 10.0 g of methanol 8.0 g of 1-methoxy-2-propanol

[0205]

[Table 9]

[0206]

Embedded image

[Exposure] The obtained lithographic printing plate precursor was subjected to output of 250 mW per beam and rotation speed of the external drum of 800 using a Luxel T-9000CTP manufactured by Fuji Photo Film Co., Ltd. equipped with a multi-channel laser head.
Exposure was performed under the conditions of rpm and resolution of 2400 dpi. [Development processing] After exposure, development processing was carried out using an automatic developing machine Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developing solution, a 1: 8 water dilution of DP-4 manufactured by Fuji Photo Film Co., Ltd. was used for both the charging solution and the replenishing solution. The temperature of the developing greed bath was 30 ° C. As the finisher, a 1: 2 aqueous solution of GU-7 manufactured by Fuji Photo Film Co., Ltd. was used.

[Evaluation of Printing Durability and Stains] Next, printing was performed using a Heidelberg SOR-KZ printing machine. On this occasion,
The printing durability was evaluated by measuring how many sheets can be printed with a sufficient ink density. Further, the obtained printed matter was visually evaluated for the stain property of the non-image portion. Table 9 shows the results. From Table 9, it was found that the lithographic printing plate using the image recording material of the present invention as the photosensitive layer had no stain on the non-image portion and was excellent in printing durability.

(Examples 18 to 21) [Formation of undercoat layer] The following undercoat solution was applied to the aluminum support used in Examples 1 to 5 with a wire bar, and heated at 90 ° C using a hot air drier. Dry for 30 seconds. The coating amount after drying was 10 mg / m ² .

[Undercoat liquid] Copolymer of ethyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt in a molar ratio of 75:15 lg ・ 2-aminoethylphosphonic acid 0.1g ・ methanol 50g ・ ion exchange water 50g

The aluminum plate thus treated was
A lithographic printing plate was prepared by applying a photosensitive layer coating solution (P-5) having the composition shown below to the above-mentioned primed aluminum support using a wire bar, and drying at 115 ° C. for 45 seconds with a hot-air dryer. I got the original. The coating amount after drying is 1.2 to 1.
It was in the range of 3 g / m ² .

<Photosensitive Layer Coating Solution (P-5)> Alkali-soluble resin (compounds listed in Table 10, amounts described in Table 10) Radical polymerizable compound (B) (compounds described in Table 10, tables 10) ・ Infrared absorber “IR-1” (C) 0.08 g ・ Iodonium salt “I-1” (D) 0.30 g ・ Victoria pure blue naphthalenesulfonic acid 0.04 g ・ Fluorine-based interface Activator 0.01 g (MegaFac F-176, manufactured by Dainippon Ink and Chemicals, Inc.) 9.0 g of methyl ethyl ketone 10.0 g of methanol 8.0 g of 1-methoxy-2-propanol

[0213]

[Table 10]

The obtained lithographic printing plate precursor was exposed to light under the same conditions as in Examples 1 to 5 except that a 1: 4 aqueous dilution of CA-1 manufactured by Fuji Photo Film Co., Ltd. was used as a developing solution. ,
Printing was performed by a development process, and printing durability was evaluated. Table 10 shows the results. From Table 10, it was found that a lithographic printing plate using the image recording material of the present invention as a photosensitive layer was excellent in printing durability.

(Examples 22 to 26) Next, Examples 6 to 10
A photosensitive layer is formed on an aluminum support in the same manner as described above, and polyvinyl alcohol (with a saponification degree of 86.5 to 86.5).
A 3% by weight aqueous solution of 89 mol% and a degree of polymerization of 1000) was applied so that the dry application weight was 2 g / m ² ,
For 2 minutes to obtain a lithographic printing plate precursor having a protective layer formed on the photosensitive layer. The obtained lithographic printing plate precursor was exposed and developed under the same conditions as in Examples 6 to 10 to print on a printing plate obtained under the same conditions, and the printing durability was evaluated. Table 11 shows the results.

[0216]

[Table 11]

From Table 11, it can be seen that the lithographic printing plate using the image recording material of the present invention as a photosensitive layer is excellent in printing durability, and the effect of improving printing durability can be seen by forming a protective layer. all right.

According to the present invention, it is possible to directly record digital data from a computer or the like by recording using a solid-state laser or a semiconductor laser that emits infrared light, and it is used for a photosensitive layer for a lithographic printing plate precursor. In this case, it is possible to provide a negative image recording material capable of achieving excellent printing durability without causing ablation.

Continued on front page F-term (reference) 2H025 AA12 AB03 AC08 AD01 BC13 BC34 BC43 BE07 CA00 CA14 CA23 CA41 CB22 CB53 CC12 CC13 FA17 2H114 AA04 AA22 AA23 AA24 BA01 DA04 DA25 DA26 DA35 DA49 DA52 DA73 DA78 EA01 EA34 FA06 GA03 GA05 GA06 GA38

Claims (1)

[Claims] 1. A polyurethane resin which is insoluble in water and soluble in an aqueous alkali solution, (B) a radically polymerizable compound,
(C) It contains a light-to-heat conversion agent and (D) a compound that generates radicals by heat-mode exposure to light having a wavelength that can be absorbed by the light-to-heat conversion agent, and is capable of image recording by heat mode exposure. A heat-mode-compatible negative-type image recording material, characterized in that: