JP2002278050A - Positive type image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type image forming material capable of high sensitivity recording, excellent in development latitude and printing resistance and adaptable to a heat mode. SOLUTION: The positive type image forming material contains (1) a water- insoluble and alkali-soluble high molecular compound, (2) a compound which absorbs IR and generates heat and (3) a compound of the formula X<-> M<+> (A) which lowers the solubility of (1) the water-insoluble and alkali-soluble high molecular compound in an alkali developing solution when mixed with the high molecular compound on the base. In the formula (A), X<-> is an anion of a compound of formula (B) or the formula R<c> -COO<-> M<+> (C) and M<+> is a counter cation selected from sulfonium, iodonium, diazonium, ammonium and azinium. In the formula (B), Y is a single bond, -CO- or -SO2 -. In the formula (C), R<c> is alkyl or aryl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material having a positive recording layer writable by an infrared laser, and more particularly, to an image forming material having excellent development latitude, excellent recording layer film properties and excellent scratch resistance. The present invention relates to a positive image forming material.

[0002]

2. Description of the Related Art In recent years, the development of lasers has been remarkable. In particular, solid-state lasers and semiconductor lasers having a light-emitting region from the near infrared to the infrared 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. As a system generally used in the heat mode positive type image forming using the infrared laser for writing, a system utilizing the interaction of a novolak resin can be exemplified. The details of the mechanism of image formation using novolak resin are not clear, but the photothermal conversion agent generates heat due to infrared laser exposure, and the heat breaks hydrogen bonds between novolak molecules and improves solubility, resulting in positive images. Is believed to be obtained. As described above, in the positive type image forming material for an infrared laser, the photothermal conversion agent only functions as a dissolution inhibitor for the unexposed portion (image portion), and promotes the dissolution of the exposed portion (non-image portion). However, there is a problem that a difference in solubility between an unexposed portion and an exposed portion is hardly obtained.

On the other hand, a conventional type positive PS plate which forms an image by UV exposure or visible light exposure uses an excellent technique for controlling the solubility of novolak. The most common naphthoquinonediazides (hereinafter,
In the positive PS plate using NQD), NQD functions as a novolak resin dissolution inhibiting (inhibition) component in the unexposed area, and NQD is chemically changed in the exposed area to form carboxylic acid. Occurs, and functions as a dissolution accelerating (promotion) component, so that there is a large difference in the solubility between exposed and unexposed portions, and this is a mechanism for developing excellent discrimination.

[0004] Various attempts have been made to introduce a mechanism for developing such excellent discrimination into a thermal positive system.
No. 75 discloses a technique of adding an onium salt compound which functions as a dissolution inhibitor for a film-forming resin of a recording layer in an unexposed portion, although the recording layer is rapidly decomposed by heat supplied from a photothermal conversion agent. Since then, various attempts have been made, and have greatly contributed to the expansion of discrimination of exposed / unexposed portions. In recent years, with the development of the thermal exposure system due to the development of the infrared laser as described above, a demand for higher sensitivity of the image forming material itself has been increased. For example, if a resin having a weak interaction is used to increase the sensitivity and improve the solubility of the exposed area, the strength of the image area decreases, for example,
There is a tendency for problems with scratch resistance such as scratches to occur when a strong developer is used, while, when the dissolution suppressing ability is too strong, poor development occurs when a weak developer is used. There is also a problem that the sensitivity is reduced, the function of the dissolution inhibitor added to the recording layer is not only the dissolution suppression ability,
Higher sensitivity is also required to release the dissolution inhibiting ability, and further improvement is currently desired.

[0005]

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 enable recording with high sensitivity, latitude during alkaline development,
Another object of the present invention is to provide a heat-mode recordable positive image forming material having excellent scratch resistance.

[0006]

Means for Solving the Problems The present inventors have conducted various studies on compounds having a dissolving bath performance, and have found that by using an onium salt having a specific counter anion as a dissolution inhibitor, It has been found that an image-forming material capable of forming an image with a low exposure amount and achieving a sufficient latitude can be obtained, and the present invention has been completed. That is, the heat-mode-compatible positive image forming material of the present invention comprises (1) an alkali-soluble and water-insoluble polymer compound on a support, (2) a compound that absorbs infrared rays and generates heat, and (3) And a compound represented by the following general formula (A). This compound comprises the component (1)
Has a function of lowering the solubility of the polymer compound in water or an alkali developing solution by mixing with the polymer compound.

[0007] Formula (A) X ^- M ⁺ wherein, X ^- represents an anion moiety of the compound represented by anionic or formula of the compound represented by the following general formula (B) (C), M + is a sulfonium , Iodonium, diazonium, ammonium, azinium.

[0008]

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In the general formula (B), Y represents a single bond, —CO— or —SO ₂ —, and R ^a and R ^b are each independently a linear, branched or cyclic alkyl group, aryl group, Represents an aralkyl group and a camphor group. R ^a and R ^b may be bonded via an alkylene group, an arylene group, or an aralkyl group to form a ring. When Y is a —CO— group, R ^b may be a hydroxyl group or an alkoxy group.

Formula (C) R ^C -COO ^- M ^{+ In} Formula (C), R ^C represents an alkyl group or an aryl group, and M ⁺ has the same meaning as in Formula (A).

In the present invention, "corresponding to a 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 two modes roughly divided into the above processes. One is that the photoexcited light absorbing substance is deactivated by 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 the above-mentioned chemical or physical change required for image formation, and the other is that the photo-excited light-absorbing substance generates heat and deactivates, This is a so-called heat mode in which a reactant causes a chemical or physical change required for image formation using the above-described 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.

The exposure process using each of the above modes is called photon mode exposure and heat mode exposure. The technical difference between photon mode exposure and 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 photon mode exposure, since photochemical interaction is used, 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 the 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. That is, if the next photoexcitation-deactivation process occurs and heat is generated before the 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, the result is different between the case of irradiating a high energy light for a short time and the case of irradiating a low energy light for a long time even at the same total exposure energy. It becomes advantageous for accumulation of.

Of course, in the photon 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, in terms of the characteristics of the photosensitive material, in the photon mode, the intrinsic sensitivity of the photosensitive material (energy for the reaction required for image formation) with respect to the exposure power density (w / cm ² ) (= energy density per unit time). Amount) is constant, but in the heat mode, the intrinsic sensitivity of the photosensitive material increases with respect to the exposure power density. Therefore, if the exposure time is fixed such that the productivity necessary for practical use as an image recording material can be maintained, the photon mode exposure usually has a high sensitivity of about 0.1 mJ / cm ² when comparing the modes. Reaction can be achieved at any low exposure, although
The problem of low-exposure fog in the unexposed area is likely to occur. On the other hand, in the heat mode exposure, a reaction does not occur unless the exposure amount exceeds a certain value, and usually about 50 mJ / cm ² is required in relation to the thermal stability of the photosensitive material. Is avoided. In fact, in heat mode exposure, the exposure power density on the plate surface of the photosensitive material is 500
0 w / cm ² or more, preferably 10,000
w / cm ² or more is required. However, although not described in detail here, if a high power density laser of 5.0 × 10 ⁵ w / cm ² or more is used, ablation occurs, which is not preferable because of problems such as soiling the light source.

Although the function of the present invention is not clear, the addition of the dissolution inhibitor represented by the general formula (A) according to the present invention enhances the resistance of the image area to a developing solution,
The image area is less likely to be damaged by a more active developer. On the other hand, since the compound uses a compound having a sulfonamide structure in the general formula (B) and a carboxylate in the general formula (C) as a counter anion, it generally uses a sulfonate (—SO ₃ ^−). )
Thermal decomposition temperature is lower than compounds having a counter anion or an inorganic salt (PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ )
In each case, the thermal decomposability is improved, and a decomposition reaction occurs effectively by infrared laser exposure, so that the dissolution suppressing action of the exposed portion can be sufficiently released with high sensitivity. As a result, the image area has high resistance to a highly active developer,
It is considered that excellent development latitude, in which the developability of the non-image area hardly decreases, can be achieved. Further, by adding the dissolution inhibitor according to the present invention, the interaction of the binder polymer was strengthened, and an effect of improving the film strength was obtained.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The image forming material of the present invention is represented by (1) a water-insoluble and alkali-soluble polymer compound in a recording layer, (2) a compound that absorbs infrared rays and generates heat, and (3) a compound represented by the following general formula (A). And the component (1), which is required to contain a compound which lowers the solubility of the polymer compound in water or an alkali developer by mixing with a polymer compound which is soluble in water and alkali-soluble. Hereinafter, components constituting the recording layer will be sequentially described.

[(3) Compound represented by the following general formula (A)] wherein X ^- is an anion of the compound represented by the general formula (B) or X ^- M ⁺ ) Represents the anion of the compound represented by
M ⁺ represents a counter cation selected from sulfonium, iodonium, diazonium, ammonium and azinium. First, the case where X ⁻ is an anion of a compound represented by the following general formula (B) will be described.

[0017]

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In the general formula (B), Y is a single bond, -CO-,
Or -SO ₂ - represents a. From the viewpoint of sensitivity and stability, Y
Is preferably -CO-, and the compound represented by the general formula (B)
In a more preferred embodiment, the compound represented by the formula (1) has a pKa of 0 to 6. R ^a and R ^b each independently represent a linear, branched or cyclic alkyl group, aryl group, aralkyl group, or camphor group. ^Ra and ^Rb may be bonded via an alkylene group, an arylene group, or an aralkylene group to form a ring. When Y is a -CO- group, ^Rb may be a hydroxyl group or an alkoxy group. R ^a and R ^b are preferably 1 carbon atom
Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms or an aralkyl group having 1 to 20 carbon atoms. These alkyl group, aryl group or aralkyl group may have a substituent, and examples of the substituent that can be introduced include, for example, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an alkynyl group, Amino group, cyano group,
Examples thereof include a hydroxyl group, a halogen atom, an amide group, an ester group, a carbonyl group, a carboxyl group, a sulfonic acid group, a sulfonamide group, and a nitro group. These may further have the above-mentioned substituents. Further, two or more substituents may be bonded to each other to form a ring,
Further, the ring structure may be a heterocyclic structure containing a nitrogen atom, a sulfur atom, or the like.

The compound (A) is prepared by mixing the component (1) with a water-insoluble and alkali-soluble polymer to lower the solubility of the polymer in water or an alkali developing solution. Functions as an inhibitor. Hereinafter, compounds having a structure of the following general formula (B) capable of forming a counter anion of the compound (A) will be exemplified, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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In the image forming material of the present invention, among the components (3) contained in the recording layer, the compound having the general formula (B) in the anion part is more preferably the following general formulas (II) and (III) The compound represented by these is mentioned. Thereby, the sensitivity and the scratch resistance are further improved. By heating this compound or, in the case of an embodiment containing an infrared absorber as in the present invention, irradiating infrared rays to generate heat, the compounds represented by the general formulas (II) and (III)
Of X ^- a compound having the structure of the corresponding general formula (B) in the, etc. occur decomposed to acid, so that the dissolution suppressing ability is released.

[0025]

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In the above formula, R ^{1 to} R ²⁵ represent a hydrogen atom, a straight-chain, branched or cyclic alkyl group, a straight-chain, branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or a —S—R ²⁶ group. . Here, R ²⁶ represents a linear, branched, or cyclic alkyl group or an aryl group. X ^- is an anion of a compound having a structure of the general formula (B).

In the general formula (II) or (III), the linear or branched alkyl group of R ^{1 to} R ²⁵ may be a methyl group, an ethyl group, a propyl group, which may have a substituent.
Those having 1 to 4 carbon atoms such as n-butyl group, sec-butyl group and t-butyl group are exemplified. As the cyclic alkyl group, a cyclopropyl group which may have a substituent,
3 carbon atoms such as cyclopentyl and cyclohexyl
To 8 items. Examples of the alkoxy group represented by R ^{1 to} R ²⁵ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. One. Examples of the halogen atom for R ^{1 to} R ²⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The aryl group of R ^26, a phenyl group, a tolyl group, methoxyphenyl group include those having 6 to 14 carbon atoms such as naphthyl group. The aryl group may have a substituent. Preferred substituents that the groups R ^{1 to} R ²⁵ may have are an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, and an iodine atom), an aryl group having 6 to 10 carbon atoms, Examples thereof include an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

M ⁺ represents a counter cation selected from sulfonium, iodonium, diazonium, ammonium and azinium. Here, azinium has a azine ring which is a six-membered ring containing a nitrogen atom in its structure, and includes pyridinium, diazinium, and triazinium. Azinium contains one or more aromatic rings fused to an azine ring and includes, for example, quinolinium, isoquinolinium, benzoazinium, naphthoazinium and the like. Specifically, for example, USP 4,743,5
No. 28, JP-A-63-138345, JP-A-63-142
No. 345, No. 63-142346, JP-B-46-42
No. 363, and 1-methoxy-
4-phenylpyridinium tetrafluoroborate, N
-Counter cations forming alkoxypyridinium salts and the like.

Among these counter cations, stability,
From the viewpoint of sensitivity, a compound having iodonium or sulfonium as a counter cation is preferable, and a compound having a diaryliodonium or triarylsulfonium skeleton is more preferable. Hereinafter, among the compounds represented by the general formula (A), specific examples of the compound having the anion part of the compound represented by the general formula (B) in the anion part will be described with a cation part corresponding to a preferable counter cation. Although shown in combination, the present invention is not limited to this.

The preferred structure of the sulfonium skeleton is a triarylsulfonium skeleton from the viewpoint of sensitivity and stability, and the aryl group may be substituted in the same manner as the above-mentioned aryl group. Preferred sulfonium salts, namely, the dissolution inhibitors represented by the general formula (II) include the following exemplified compounds (II-1) to (II-28).

[0031]

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[0032]

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[0033]

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[0034]

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The preferred structure of the iodonium skeleton is preferably a diaryliodonium skeleton from the viewpoint of stability, and the aryl group may be substituted in the same manner as the above-mentioned aryl group. Preferred iodonium salts, that is, the dissolution inhibitors represented by the general formula (III) include the following exemplified compounds (III-1) to (III-15).

[0036]

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[0037]

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[0038]

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[0039]

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A typical example of the synthesis of the compound represented by the general formula (A) and having an anion moiety in the general formula (B) is described in Japanese Patent Application No. 2000-18, previously proposed by the present applicant.
No. 4603, paragraphs [0039] to [004]
3].

Next, X^-Is represented by the following general formula (C)
Portion of the compound (R^C-COO ^-)
I will describe. General formula (C) R^C-COO^- M⁺ In the general formula (C), R^CPreferably has 1 to 20 carbon atoms
Represents an alkyl group or an aryl group having 1 to 20 carbon atoms.
You. R^CMay have a ring structure. In addition,
The alkyl group or the aryl group may have a substituent,
Specific examples of the substituent which can be introduced include, for example,
A kill group, an alkoxy group, an alkenyl group, an alkynyl group,
Amino group, cyano group, hydroxyl group, halogen atom, amide
Groups, ester groups, carbonyl groups, carboxyl groups, etc.
These further have substituents as described above.
It may be. Further, two or more substituents
May form a ring, and the ring structure is a nitrogen atom.
It may have a heterocyclic structure containing an atom or a sulfur atom.
The polymerization initiator according to the present invention has a pKa in water of 2 or more.
It is preferable that the pKa is 3 or more.
preferable. When the pKa in water is 2 or more, a dissolution inhibitor
Tends to decrease the thermal decomposition temperature of
It is thought to contribute.

M ⁺ has the same meaning as described above, and preferred embodiments include the same. Hereinafter, a specific example of the dissolution inhibitor having the anion portion of the compound represented by the general formula (C) represented by the general formula (A) as a counter anion is described in combination with a cation portion corresponding to a preferable counter cation. However, the present invention is not limited to this. As a preferable structure of the iodonium skeleton, a diarylsulfonium skeleton is preferable from the viewpoint of stability, and the aryl group may be substituted in the same manner as the above-mentioned aryl group. First, preferred iodonium salts (iodonium as a counter cation) compounds [exemplified compounds (IA-1) to (IJ-8)] are exemplified below.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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As a preferred structure of the sulfonium skeleton, a triarylsulfonium skeleton is preferable in terms of sensitivity and stability, and the aryl group may be substituted in the same manner as the above-mentioned aryl group. Next, a preferred sulfonium salt (having sulfonium as a counter cation) compound [exemplary compound (S
A-1) to Exemplified Compound (SJ-12)].

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075] In dissolution inhibitor according to the present invention, the cation portion ^- shows an example of a suitable carboxylic acids for forming the (R-COOH) the following (R-COO).

[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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A typical example of the synthesis of the compound represented by the general formula (A) and having an anion moiety in the general formula (C) is described in Japanese Patent Application No. 2000-16, which was previously proposed by the present applicant.
No. 0323, paragraph numbers [0057] to [006]
0].

In the recording layer of the image forming material of the present invention, the dissolution inhibitor represented by the general formula (A) is contained at 0.5 to 20% by weight based on the total solids constituting the recording layer. Is preferred. If the content is too large, the film properties and sensitivity of the recording layer tend to decrease, and if the content is too small, the effect of improving dissolution suppression is reduced.

[(1) Water-Insoluble and Alkali-Soluble Polymer Compound] The water-insoluble and alkali-soluble polymer compound (hereinafter, appropriately referred to as an alkali-soluble polymer) used in the present invention may be selected from the main compounds in the polymer. It includes homopolymers containing an acidic group in the chain and / or side chain, copolymers thereof, or mixtures thereof. Among them, the following (1)-
Those having an acidic group described in (6) in the main chain and / or side chain of the polymer are preferable in terms of solubility in an alkaline developer and development of dissolution inhibiting ability.

(1) Phenol group (—Ar—OH) (2) Sulfonamide group (—SO ₂ NH—R) (3) Substituted sulfonamide acid group (hereinafter referred to as “active imide group”) SO ₂ NHCOR, -SO ₂ NHSO ₂ R, -CO
NHSO ₂ R] (4) Carboxylic acid group (—CO ₂ H) (5) Sulfonic acid group (—SO ₃ H) (6) Phosphate group (—OPO ₃ H ₂ )

In the above (1) to (6), Ar represents a divalent aryl linking group which may have a substituent, and R represents a hydrocarbon group which may have a substituent. .

Among the alkali-soluble polymers having an acidic group selected from the above (1) to (6), among the alkali-soluble polymers having (1) a phenol group, (2) a sulfonamide group and (3) an active imide group, Is preferred, and in particular,
An alkali-soluble polymer having (1) a phenol group or (2) a sulfonamide group is most preferable from the viewpoint of ensuring sufficient solubility in an alkaline developer, development latitude, and film strength.

Examples of the alkali-soluble polymer having an acidic group selected from the above (1) to (6) include the following. (1) Examples of the alkali-soluble polymer having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, a condensation polymer of p-cresol and formaldehyde,
Condensed polymer of m- / p-mixed cresol and formaldehyde, phenol and cresol (m-, p- or m
-/ P- mixture) and a novolak resin such as a condensation polymer of formaldehyde, and a condensation polymer of pyrogallol and acetone. further,
Copolymers obtained by copolymerizing a compound having a phenol group in the side chain can also be used. Alternatively, a copolymer obtained by copolymerizing a compound having a phenol group in the side chain can be used.

Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylate, methacrylate, and hydroxystyrene having a phenol group.

(2) Examples of the alkali-soluble polymer having a sulfonamide group include a polymer having, as a main constituent, a minimum structural unit derived from a compound having a sulfonamide group. Examples of the compound as described above include a compound having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and at least one polymerizable unsaturated group in the molecule. Among them, a low molecular weight compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group in a molecule is preferable. For example, the following general formulas (a) to ( Compounds represented by e) are mentioned.

[0095]

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In the formula, X ¹ and X ² each represent —O— or —NR ⁷ —. R ¹ and R ⁴ each represent a hydrogen atom or —CH ₃ . R ² , R ⁵ , R ⁹ , R ¹² and R ¹⁶ each represent an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group. R ³ , R ⁷ and R ¹³ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group, an aryl group or an aralkyl group. R ⁶ and R ¹⁷ each represent an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. R ⁸ ,
R ¹⁰ and R ¹⁴ represent a hydrogen atom or —CH ₃ . R ¹¹ and R ¹⁵ each represent a single bond or an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group. Y ¹ and Y ² each represent a single bond or —CO—. Specifically, m-aminosulfonylphenyl methacrylate, N
-(P-Aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

(3) The alkali-soluble polymer having an active imide group is preferably one having an active imide group represented by the following formula in the molecule.
In the molecule, an active imide group represented by the following formula and a polymerizable monomer composed of a low-molecular compound having at least one polymerizable unsaturated bond are homopolymerized, or another polymerizable monomer is copolymerized with the monomer. And a polymer compound obtained by the reaction.

[0098]

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Specific examples of such a compound include:
N- (p-toluenesulfonyl) methacrylamide, N
-(P-Toluenesulfonyl) acrylamide and the like can be suitably used.

(4) As the alkali-soluble polymer having a carboxylic acid group, for example, a minimum structural unit derived from a compound having at least one carboxylic acid group and at least one polymerizable unsaturated group in the molecule is mainly used. Examples of the polymer include constituent polymers. (5) Examples of the alkali-soluble polymer having a sulfonic acid group include, as a main structural unit, a minimum structural unit derived from a compound having one or more sulfonic acid groups and one or more polymerizable unsaturated groups in a molecule. Polymer. (6) Examples of the alkali-soluble polymer having a phosphate group include, as a main component, a minimum constituent unit derived from a compound having at least one phosphate group and at least one polymerizable unsaturated group in a molecule. Polymer.

The minimum structural unit having an acidic group selected from the above (1) to (6), which constitutes the alkali-soluble polymer used in the positive recording layer, need not be only one kind, but may be the same acidic structural unit. Two or more types of minimum structural units having a group,
Alternatively, those obtained by copolymerizing two or more kinds of the minimum constituent units having different acidic groups can be used.

The copolymers are copolymerized (1) to
It is preferred that the compound having an acidic group selected from (6) is contained in the copolymer in an amount of at least 10 mol%, more preferably at least 20 mol%. 10 mol%
If it is less than 3, the developing latitude tends to be insufficiently improved.

The alkali-soluble polymer of the present invention includes
Novolak resins are preferred. Further, a polymer compound obtained by polymerizing two or more of the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, and the polymerizable monomer having an active imide group, or a polymer compound of these two or more types It is preferable to use a polymer compound obtained by copolymerizing a polymerizable monomer with another polymerizable monomer. When a polymerizable monomer having a sulfonamide group and / or a polymerizable monomer having an active imide group is copolymerized with a polymerizable monomer having a phenolic hydroxyl group, the mixing weight ratio of these components is from 50:50 to 5: It is preferably in the range of 95, particularly preferably in the range of 40:60 to 10:90.

In the present invention, the alkali-soluble polymer is a copolymer of a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group, with another polymerizable monomer. In the case of a polymer, the content of the monomer for imparting alkali solubility is preferably at least 10 mol%, more preferably at least 20 mol%. When the amount of the copolymer component is less than 10 mol%, the alkali solubility tends to be insufficient, and the effect of improving the development latitude may not be sufficiently achieved.

Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group include the following (m1) to (m1
The monomers described in 2) can be used, but are not limited thereto. (M1) For example, acrylates and methacrylates having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (M2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Alkyl acrylates such as hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate; (M3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2-
Alkyl methacrylates such as chloroethyl, glycidyl methacrylate and N-dimethylaminoethyl methacrylate; (M4) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N
Acrylamide or methacrylamide such as -phenylacrylamide, N-nitrophenylacrylamide, and N-ethyl-N-phenylacrylamide. (M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate. (M7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. (M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (M10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide. (M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

The alkali-soluble polymer preferably has a weight average molecular weight of 500 or more from the viewpoint of image forming properties, and more preferably from 1,000 to 700,000. Further, the number average molecular weight is preferably 500 or more, and more preferably 750 to 650,000. The degree of dispersion (weight average molecular weight / number average molecular weight) is preferably from 1.1 to 10.

These alkali-soluble polymers may be used alone or in combination of two or more. If combined, see US Pat.
Phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a condensation polymer of t-butylphenol and formaldehyde or a condensation polymer of octylphenol and formaldehyde as described in JP-A-3279. And a formaldehyde and a polycondensate, an alkali-soluble polymer having a phenol structure having an electron-withdrawing group on an aromatic ring described in Japanese Patent Application Laid-Open No. 2000-241972 previously submitted by the present inventors. Is also good.

In the present invention, the alkali-soluble polymer is
The total content is preferably 30 to 98% by weight, more preferably 40 to 95% by weight, based on the total solid content of the recording layer. If the content is less than 30% by weight, the durability tends to deteriorate, and if it exceeds 98% by weight, sensitivity and image forming properties tend to decrease, which is not preferable.

[(2) Compound that absorbs infrared rays and generates heat] The compound that absorbs infrared rays and generates heat (hereinafter, appropriately referred to as an infrared absorbent) used in the present invention includes light used for recording. Any substance that absorbs energy radiation and generates heat can be used without any particular limitation on the absorption wavelength range. However, from the viewpoint of compatibility with an easily available high-power laser, the absorption maximum is increased from a wavelength of 760 nm to 1200 nm. Preferred are those having an infrared absorbing dye or pigment.

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

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 and the like,
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 aryl benzo (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, pentamethine thiopyrylium 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.

Among these dyes, particularly preferred are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Further, dyes represented by the following general formulas (a) to (e) are preferred because of their excellent light-to-heat conversion efficiency. Particularly, cyanine dyes represented by the following general formula (a) are used in the polymerizable composition of the present invention. This is most preferable because it gives high polymerization activity and is excellent in stability and economy.

[0116]

[Of 60]

In the general formula (a), X ¹ represents a hydrogen atom, a halogen atom, -NPh ₂ , X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹
Represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom. Here, the hetero atom is N,
S, O, a halogen atom and Se are shown.

[0118]

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R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of storage stability of the coating solution for the photosensitive layer, R ¹ and R ² are preferably a hydrocarbon group having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable to form a 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 substituents include a hydrocarbon group having 12 or less carbon atoms,
Examples include 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 an alkoxy group having 12 or less carbon atoms, a carboxyl group, and a sulfo group. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represent 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. In addition, Za ^-
Represents a counter anion. However, if the sulfo group in any of R ¹ to R ⁸ is substituted, Za ^- is not necessary. Preferred Za ^- is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion from the storage stability of the photosensitive layer coating solution, and particularly preferably, a perchlorate ion,
Hexafluorophosphate ion and arylsulfonate ion.

In the present invention, specific examples of the cyanine dye represented by the general formula (a) which can be suitably used include, in addition to those exemplified below, Japanese Patent Application No. 11-31062.
Paragraph Nos. [0017] to [0019] of the specification of No. 3 and paragraph number [001] of the specification of Japanese Patent Application No. 2000-224031.
2] to [0038], and those described in paragraphs [0012] to [0023] of Japanese Patent Application No. 2000-21147.

[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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In the general formula (b), L represents a methine chain having 7 or more conjugated carbon atoms, and the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. It may be. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Ni ⁺ , K ⁺ , Li ⁺ ). R ^{9 to} R
¹⁴ and R ^{15 to} R ²⁰ are each independently a hydrogen atom or a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group Or a substituent obtained by combining two or three of these, and may be bonded to each other to form a ring structure. Here, in the general formula (b), those in which L represents a methine chain having 7 conjugated carbon atoms and those in which R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms are readily available. And from the viewpoint of effects.

In the present invention, specific examples of the dye represented by formula (b) which can be suitably used include the following.

[0129]

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[0130]

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In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. M represents a methine chain having 5 or more conjugated carbon atoms.
R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thiol group. Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. In the formula, Z
a ^- represents a counter anion, Za in the general formula (a) ^-
Is synonymous with

In the present invention, specific examples of the dye represented by formula (c) which can be suitably used include the following.

[0133]

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[0134]

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In the general formula (d), R²⁹Or R³¹Is each
Each independently represents a hydrogen atom, an alkyl group, or an aryl group;
You. R³³And R³⁴Are each independently an alkyl group,
Represents a silyl group or a halogen atom. n and m are each independently
Indicates an integer of 0 to 4. R ²⁹And R³⁰Or R³¹And R³²
May be bonded to each other to form a ring;²⁹as well as
/ Or R³⁰Is R³³And R³¹And / or R³²Is R³⁴When
May be combined with each other to form a ring;³³Or R³⁴
When there are a plurality of³³Each other or R³⁴Each other
They may combine together to form a ring. X¹And X^TwoIs German
In addition, a hydrogen atom, an alkyl group, or an aryl group,
X¹And X^TwoAt least one is a hydrogen atom or an alkyl group
Is shown. Q represents a trimethine group which may have a substituent or
Is a pentamethine group, which has a ring structure with a divalent organic group
May be formed. Zc^-Represents a counter anion;
Za in the equation (a)^-Is synonymous with

In the present invention, specific examples of the dye represented by formula (d) which can be suitably used include the following.

[0137]

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[0138]

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In the general formula (e), R ^{35 to} R ⁵⁰ each independently represent a hydrogen atom which may have a substituent, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, Shows a hydroxyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy group, amino group, and onium salt structure. M represents two hydrogen atoms or metal atoms, a halometal group, or an oxymetal group, and the metal atoms contained therein include IA, IIA and II in the periodic table.
IB, group IVB atoms, first, second and third period transition metals,
Lanthanoid elements are mentioned, and among them, copper, magnesium, iron, zinc, cobalt, aluminum, titanium and vanadium are preferable.

In the present invention, specific examples of the dye represented by formula (e) which can be suitably used include those exemplified below.

[0141]

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Examples of the pigment used as an infrared absorber in the present invention include commercially available pigments and Color Index (CI) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, published in 1977), "Latest Pigment" Application Technology ”(CMC
Publishing, 1986) and "Printing Ink Technology", CMC Publishing, 1984).

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
When it is less than m, it is not preferable in terms of stability of the dispersion in the coating solution of the image-sensitive layer, and when it exceeds 10 μm, it is not preferable in terms of uniformity 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 pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solids constituting the recording layer.
5 to 10% by weight, particularly preferably 0.1 to 1 in the case of pigments
0% by weight can be added. If the amount of the pigment or dye is less than 0.01% by weight, the sensitivity is lowered. If the amount exceeds 50% by weight, the uniformity of the photosensitive layer is lost and the durability of the recording layer is deteriorated.

[Other Components] In forming the positive recording layer of the present invention, various additives may be used in combination, if necessary, as long as the effects of the present invention are not impaired. For example, a general-purpose onium salt, an o-quinonediazide compound, an aromatic sulfone compound, a substance that is thermally decomposable, such as an aromatic sulfonate compound, and substantially reduces the solubility of an alkali-soluble polymer in a state where it is not decomposed It is preferable to use them together in order to improve the dissolution inhibiting property of the image area in the developing solution. Examples of the onium salt used as an additive include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like, which are generally widely used.

Preferred quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and can be a compound having various structures. In other words, o-quinonediazide assists the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder by thermal decomposition and the fact that o-quinonediazide itself changes to an alkali-soluble substance. The amount of the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 3% by weight, based on the total solids of the printing plate material.
0% by weight, particularly preferably in the range of 10 to 30% by weight. These compounds can be used alone, but may be used as a mixture of several kinds.

For the purpose of further improving the sensitivity, cyclic acid anhydrides, phenols and organic acids can be used in combination. The proportion of the cyclic acid anhydride, phenols and organic acids in the printing plate material is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0.1 to 15% by weight. 10% by weight.

The recording layer coating solution according to the present invention contains:
Japanese Patent Application Laid-Open No.
Nonionic surfactants as described in JP-A-2-251740 and JP-A-3-208514, and amphoteric as described in JP-A-59-121044 and JP-A-4-13149. Surfactant, EP950
It is possible to add a siloxane compound as described in JP-A-517, and a fluorine-containing monomer copolymer as described in JP-A-11-288093. The proportion of the nonionic surfactant and amphoteric surfactant in the printing plate material is preferably from 0.05 to 15% by weight, and more preferably from 0.1 to 5% by weight.

In the recording layer according to the invention, a printing-out agent for obtaining a visible image immediately after heating by exposure, and a dye or pigment as an image coloring agent can be added. Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128,
3-36223, 54-74728, 60-3
No. 626, No. 61-143748, No. 61-1516
Nos. 44 and 63-58440, and combinations of trihalomethyl compounds and salt-forming organic dyes. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink #
312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, Japanese Patent Application Laid-Open No.
The dyes described in JP 93247 A are particularly preferred. These dyes are used in an amount of 0.1 to the total solid content of the printing plate material.
It can be added to the printing plate material in a proportion of from 01 to 10% by weight, preferably from 0.1 to 3% by weight. Further, a plasticizer is added to the printing plate material of the present invention, if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers are used.

In addition to these, epoxy compounds,
Vinyl ethers, and furthermore, JP-A-8-276558
Phenolic compound having a hydroxymethyl group, a phenolic compound having an alkoxymethyl group, and JP-A-11-16 previously proposed by the present inventors.
A crosslinkable compound having an alkali dissolution inhibiting action described in JP-A-0860 may be appropriately added according to the purpose.

The image forming material of the present invention is prepared by dissolving a coating solution component for a desired layer such as a recording layer coating solution or a protective layer in a solvent.
It can be produced by coating on a suitable support. In addition, depending on the purpose, a protective layer, a resin intermediate layer, a back coat layer, and the like can be similarly formed. 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-butyrolactone, toluene and the like can be mentioned. It is not limited. 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.
Further, the coating amount (solid content) of the recording layer on the support obtained after coating and drying varies depending on the application, but is generally preferably 0.5 to 5.0 g / m ² for a lithographic printing plate. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate. As a method of applying, various methods can be used, for example,
Examples include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating, and the like. In the recording layer of the present invention, a surfactant for improving coating properties,
For example, a fluorine-based surfactant as described in JP-A-62-170950 can be added.
A preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight based on the total solid content of the recording layer.

[Support] The support used in 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.), and paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited. As the support of the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate having good dimensional stability and relatively low cost is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing 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 used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.1 mm to 0.4 mm.
It is 2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing rolling oil on the surface is performed. The surface roughening treatment of the aluminum plate
The method is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. 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.
Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus surface-roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation 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. 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 anodizing treatment conditions vary depending on the electrolyte to be used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat. Nos. 2,7,7
No. 14,066, No. 3,181,461, No. 3,2
There is an alkali metal silicate (e.g., sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 80,734 and 3,902,734. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. Further, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 are disclosed. A method of treating with polyvinyl phosphonic acid as described above is used.

The image-forming material of the present invention has a positive recording layer provided on a support. An undercoat layer may be provided between the recording layers as needed. As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenylphosphonic acid optionally having a substituent , Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloric acid of triethanolamine Has hydroxy groups such as salts -Alanine, and hydrochlorides of amines that may be used in combination of two or more.

The organic undercoat layer can be provided by the following method. That is, water or methanol, ethanol,
A method in which a solution obtained by dissolving the above organic compound in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof is applied to an aluminum plate and dried, and an organic solvent such as water or methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof is used. In this method, an aluminum plate is immersed in a solution in which the above-mentioned organic compound is dissolved to adsorb the above-mentioned compound, and then washed with water or the like and dried to form an organic undercoat layer. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight.
The immersion temperature is 20 to 90 ° C., preferably 25 to 5 ° C.
0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is ammonia,
The pH can be adjusted to a range of 1 to 12 with a basic substance such as triethylamine or potassium hydroxide or an acidic substance such as hydrochloric acid or phosphoric acid. Further, a yellow dye can be added for improving the tone reproducibility of the image recording material. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² , and preferably from 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

The positive image forming material prepared as described above is useful as a lithographic printing plate precursor and is usually subjected to image exposure and development processing. As the light source of the light beam used for image exposure, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser and a semiconductor laser are particularly preferable.

As the developer and replenisher for the lithographic printing plate of the present invention, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium, sodium hydroxide,
And inorganic alkali salts such as ammonium, potassium and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Organic alkaline agents such as diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. Can be These alkaline agents can be used alone or
Used in combination of more than one species. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and the concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are the components of the silicate. For example, JP-A-54-62004 discloses An alkali metal silicate described in JP-B-57-7427 is effectively used.

In the case of developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is used.
It has been known that a large amount of PS plates can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. 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 as needed 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. Further, the developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcinol, sulfurous acid, and bisulfite, and further include an organic carboxylic acid, an antifoaming agent, and a water softener. Can be added. The printing plate developed using the above developer 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. As a post-process when the image recording material of the present invention is used as a printing plate, these processes can be used in various combinations.

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

When the image forming material of the present invention is used as a lithographic printing plate precursor, an unnecessary portion of the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming is used. If there is an image portion (for example, a film edge mark of the original film), the unnecessary image portion is erased. Such erasing is preferably carried out by applying an erasing liquid as described in, for example, Japanese Patent Publication No. 2-129393 to an unnecessary image portion, leaving it for a predetermined time, and then washing it with water. A method described in JP-A-59-174842, in which active light guided by an optical fiber is applied to an unnecessary image portion and then developed, can be used.

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 a higher printing durability is desired to be obtained, Is subjected to a burning process. When burning a lithographic printing plate, before burning,
No. 2518, No. 55-28062, JP-A-62-3
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 1859 and 61-159655. As a method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied on a lithographic printing plate, or a method in which the printing plate is immersed in a vat filled with the surface conditioning solution and applied, Application by an automatic coater or the like is applied. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application.

The coating 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 (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: "BP-130").
0 "). The heating temperature and time in this case depend on the type of the component forming the image,
The temperature is preferably in the range of 180 to 300 ° C. for 1 to 20 minutes.

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 by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0169]

Hereinafter, the present invention will be described with reference to Examples.
The scope of the present invention is not limited to these examples. (Examples 1 to 4 and Comparative Examples 1 to 5) [Preparation of Support] An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased.
The surface was grained using a water suspension and washed well with water. This aluminum plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds to perform etching and washing with water.
Further, it was immersed in 2% HNO ₃ for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, this plate was provided with a 3 g / m ² DC anodic oxide coating at a current density of 15 A / dm ² using 7% H ₂ SO ₄ as an electrolyte, and then washed and dried. Next, the undercoat liquid 1 described below was applied to this aluminum plate, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 10 mg / m ² . <Undercoat liquid 1> • β-alanine: 0.10 g • Phenylphosphonic acid: 0.05 g • Methanol: 40 g • Pure water: 60 g

[Formation of Recording Layer] The following coating solution 1 for a positive recording layer was applied to the surface of the undercoated aluminum support with a wire bar, and dried at 120 ° C. for 1 minute to form a recording layer. The material was obtained. The coating amount after drying is 1.3
was g / cm ^2. <Coating liquid 1 for positive recording layer> Novolak resin 1 1.0 g (cresol novolak with m-, p- = 6: 4) Dissolution inhibitor (compound shown in Table 1) 0.12 g Infrared absorber 1 (The following structure) 0.1 g ・ Dye in which the counter anion of Victoria Pure Blue BOH is converted to 1-naphthalenesulfonic acid anion 0.01 g ・ Fluorinated surfactant (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) ) 0.05 g-? -Butyrolactone 3.0 g-methyl ethyl ketone 8.0 g-1-methoxy-2-propanol 7.0 g

[0171]

[Table 1]

[0172]

Embedded image

[0173]

[Of 75]

[Evaluation] (1. Sensitivity) The obtained lithographic printing plate precursor was exposed using a trend setter 3244 (manufactured by Creo Corporation), and DT-1 was obtained.
(1: 8 dilution with water). At this time, exposure was performed while changing the exposure amount, and the minimum exposure amount at which the exposed portion was sufficiently developed under the same developing conditions was defined as sensitivity, and is shown in Table 1 together with the following evaluation results of scratch resistance and development latitude. (2. Scratch resistance) The scratch resistance of the photosensitive layer was evaluated by a rubbing test using absorbent cotton. The rubbing test is a test in which the surface of the photosensitive material is rubbed with a certain force using absorbent cotton, and the scratch resistance is determined by the number of rubs at which the unexposed portion subjected to the absorbent cotton rubbing is removed. In this evaluation, five samples were tested, and the average number of times of rubbing was adopted. (3. Development latitude) Trend setter 3244
A lithographic printing plate precursor exposed with an exposure amount of 188 mJ / cm ² using (manufactured by Creo Corporation) was developed by adjusting the conductivity (mS: milliSiemens) by appropriately diluting the stock solution of the DT-1 developer. When developed by the method, the conductivity where the exposed portion is sufficiently removed and the conductivity where the unexposed portion is thin enough to measure the film loss are measured, and the difference in the conductivity (conductivity width) is measured.
Is used as a guideline of the development latitude, and the larger the difference, the better the development latitude.

As shown in Table 1, the dissolution inhibitors (I-3), (I-4), (I-7), and (I-
It can be seen that the planographic printing plate precursors of Examples 1 to 4 using 8) achieved both sensitivity and scratch resistance, and were also excellent in developing latitude. Comparative Examples 1 to 4 using compounds having an anion moiety outside the scope of the present invention as a dissolution inhibitor
In Comparative Example 5, although an improvement effect on the scratch resistance was observed as compared with Comparative Example 5 in which no dissolution inhibitor was used, it was found that the sensitivity was liable to decrease.

(Examples 6 to 8 and Comparative Examples 6 to 10) [Synthesis of Copolymer 1] After stirring, methacrylic acid was placed in a 500 ml three-necked flask equipped with a cooling tube and a dropping funnel.
0 g (0.36 mol), 39.1 g of ethyl chloroformate
(0.36 mol) and 200 ml of acetonitrile were added, and the mixture was stirred while cooling in an ice-water bath. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped by a dropping funnel over about 1 hour. After dropping,
The ice water bath was removed and the mixture was stirred at room temperature for 30 minutes.

To this reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. This mixture was filtered to remove a precipitate, which was then washed with 500 m of water.
Then, the slurry was filtered and the obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
92 mol), 2.58 g of ethyl methacrylate (0.02 g)
58 mol), 0.80 g (0.015 g) of acrylonitrile
Mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. This mixture was mixed with “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.).
0.15 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. N- (p-
Aminosulfonylphenyl) methacrylamide 4.61
g, 2.58 g of methyl methacrylate, 0.80 g of acrylonitrile, N, N-dimethylacetamide and "V-
65 "and a mixture of 0.15 g was added dropwise with a dropping funnel over 2 hours. After the addition was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, methanol (40 g) was added to the mixture, and the mixture was cooled. The obtained mixture was added to 2 liters of water while stirring the water. The mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried. 15 g of a white solid was obtained. The weight average molecular weight (polystyrene standard) of this specific copolymer 1 was measured by gel permeation chromatography and found to be 54,000.
It was 0.

[Preparation of Substrate] Aluminum 0.3 mm thick
Plate (material 1050) is washed with trichlorethylene
After degreasing, use a nylon brush and 400 mesh
Use a water suspension to grain this surface and wash well with water.
Was cleaned. This plate is heated at 45 ° C in 25% aqueous sodium hydroxide
Immerse in the solution for 9 seconds to perform etching, and after washing with water,
It was immersed in 20% nitric acid for 20 seconds and washed with water. Grain at this time
The amount of etching on the standing surface is about 3 g / m ^TwoMet. next
This plate was subjected to a current density of 15 A / dm using 7% sulfuric acid as an electrolyte.
^Two3g / m^TwoAfter providing a direct current anodic oxide coating of
Dried, and further with a 2.5% by weight aqueous solution of sodium silicate
Treated at 30 ° C for 10 seconds, apply the following undercoat liquid 2,
Was dried at 80 ° C. for 15 seconds to obtain a substrate. Of the dried coating
15 mg / m coating amount^TwoMet.

<Undercoat liquid 2>-0.3 g of the following copolymer having a molecular weight of 28,000-100 g of methanol-1 g of water

[0181]

Embedded image

The following recording layer coating solution 2 was prepared. This recording layer coating liquid 2 was applied to the obtained undercoated substrate so that the coating amount was 1.2 g / m ² , to obtain a lithographic printing plate precursor. <Recording layer coating liquid 2>-Fluorine-containing polymer (the following structure) 0.03 g-Copolymer 1 0.75 g-Novolak resin 1 0.20 g-Dissolution inhibitor (compound shown in Table 2) 0.05 g-Tetrahydroanhydride Phthalic acid 0.03 g ・ Pyrylium dye B (the following structure) 0.017 g ・ Dye with the counter ion of Victoria Pure Blue BOH converted to 1-naphthalene sulfonic acid anion 0.015 g ・ 3-Methoxy-4-diazodiphenylaminehexafluorophosphate 0.02 g of salt 0.03 g of n-dodecyl stearate 0.05 g of fluorinated surfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 10 g of γ-butyrolactone 10 g of methyl ethyl ketone 1- 8 g of methoxy-2-propanol

[0183]

[Table 2]

[0184]

Embedded image

The lithographic printing plate precursors thus obtained were evaluated for sensitivity and scratch resistance in the same manner as in Example 1. The results are shown in Table 2 above.
It was also described in. As shown in Table 2, the same tendency was observed in the case of a phase separation type recording layer in which two kinds of binders were used in combination, and the dissolution inhibitor according to the present invention (I-3),
Example 5 using (I-4), (I-7), and (I-8)
It can be seen that the planographic printing plate precursors Nos. To 8 achieved both sensitivity and scratch resistance. Comparative Example 6 using a compound having an anion moiety outside the scope of the present invention as a dissolution inhibitor
In Nos. To 9, it can be seen that although the effect of improving the scratch resistance is seen as compared with Comparative Example 10 in which the dissolution inhibitor was not used, the sensitivity tends to decrease.

(Examples 9 to 12, Comparative Examples 11 to 15) [Preparation of Substrate] An aluminum plate having a thickness of 0.3 mm (material
1050) was degreased by washing with trichloroethylene.
After, nylon brush and 400 mesh pumice-water suspension
The surface was grained using a liquid and washed well with water. This
The plate in a 25% aqueous solution of sodium hydroxide at 45 ° C for 9 seconds
Etching by immersion, washing with water, and then 20% nitric acid
For 20 seconds and washed with water. At this time,
Etching amount is about 3g / m ^TwoMet. Next, this plate
% Sulfuric acid as electrolyte and current density 15A / dm^Two3g /
m^TwoAfter providing a direct current anodic oxide coating of
Further, the undercoat liquid 2 was applied, and the coating film was heated at 90 ° C. for 1 minute.
Dried. The coating amount of the dried coating film is 10 mg / m^TwoIn
Was. The following recording layer coating solution 3-A is applied to the obtained substrate.
Then, the resultant was dried at 130 ° C. for 1 minute to form a layer (A).
The coating amount after drying is 1.3 g / m^TwoMet. After that,
Apply the lower recording layer coating solution 3-B and dry at 110 ° C for 1 minute.
After drying, the (B) layer (upper layer) is formed, and the lithographic printing plate precursor is
Obtained. The total coating amount of the photosensitive solution after drying is 1.8 g / m^Twoso
there were.

<Recording Layer Coating Solution 3-A> Copolymer 1 0.75 g Infrared absorber 1 0.02 g p-Toluenesulfonic acid 0.002 g Tetrahydrophthalic anhydride 0.05 g Victoria Pure Blue BOH 0.015 g of a dye having a counter anion of 1-naphthalene sulfonic acid anion as a fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g ・ γ-butyrolactone 8 g ・ Methyl ethyl ketone 7 g -1-methoxy-2-propanol 7g

<Recording Layer Coating Solution 3-B>-Novolak resin 1 0.25 g-Infrared absorber 1 0.03 g-Dissolution inhibitor (compound described in Table 3) 0.03 g-n-dodecyl stearate 0.02 g -Fluorinated surfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.01 g-Methyl ethyl ketone 7 g-1-methoxy-2-propanol 7 g

[0189]

[Table 3]

The lithographic printing plate precursors thus obtained were evaluated for sensitivity and scratch resistance in the same manner as in Example 1. The results are shown in Table 3 above.
It was also described in. As shown in Table 3, the same tendency was observed in the case of the recording layer having a multilayer structure, and the dissolution inhibitors (I-3), (I-4), and (I-7) according to the present invention were used. ,
It can be seen that the lithographic printing plate precursors of Examples 9 to 12 using (I-8) achieved both sensitivity and scratch resistance.
Further, in Comparative Examples 10 to 14 using a compound having an anion moiety out of the range of the present invention as a dissolution inhibitor,
It can be seen that although the effect of improving the scratch resistance is seen as compared with Comparative Example 15 in which no dissolution inhibitor is used, the sensitivity tends to decrease.

[0191]

The positive-type image-forming material capable of recording in the heat mode according to the present invention is capable of recording with high sensitivity, and has the effect of being excellent in latitude and scratch resistance during alkali development.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA04 AA12 AA13 AB03 AC08 AD03 CC11 CC20 FA10 FA17 2H096 AA06 BA11 EA04 GA08 2H114 AA04 AA22 AA23 BA01 EA02 GA03 GA04 GA09 GA27 GA34 GA35 GA36

Claims (1)

[Claims] 1. A water-insoluble and alkali-soluble polymer compound, (2) a compound that absorbs infrared rays and generates heat, and (3) a compound represented by the following general formula (A) on a support: And a heat-mode compatible positive image forming material containing: In the formula (A) X ⁻ M ⁺ , X ⁻ represents an anion of a compound represented by the following formula (B) or an anion part of a compound represented by the following formula (C), and M ⁺ represents sulfonium, iodonium, Represents a counter cation selected from diazonium, ammonium and azinium. Embedded image In the general formula (B), Y is a single bond, -CO- or -SO ₂
And R ^a and R ^b each independently represent a linear, branched or cyclic alkyl group, aryl group, aralkyl group, or camphor group. R ^a and R ^b are an alkylene group, an arylene group,
They may be bonded via an aralkyl group to form a ring. Y
Is a —CO— group, R ^b may be a hydroxyl group or an alkoxy group. Formula ^(C) R ^C -COO ^- of M ⁺ wherein, R ^C represents an alkyl group or an aryl group, M ⁺ is the same as in the general formula (A).