JP2002148790A - Heat sensitive composition, lithographic printing master plate which uses the same and sulfonium salt compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat sensitive composition which can cause irreversible changes of physical properties with high sensitivity by heating, to provide a negative lithographic printing master plate responding to a heat mode and having high sensitivity and excellent printing durability by using the above composition, and to provide onium salt compounds useful for the above composition. SOLUTION: The heat sensitive composition contains (I) compounds expressed by general formulae (A) to (C) which generate acids or radicals by heat and (II) compounds which irreversibly change physical and chemical properties by acids or radicals. In formulae, each of R1 to R8 is a monovalent nonmetal atom, M+ is a monovalent cation selected from sulfonium, iodonium or the like, X represents the following groups or halogen atoms, Y is same as X or represents -OH, -CN, -NO2, -Si(R5)(R6)(R7), and each of Ar1 and Ar2 is an aryl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive composition which can be widely applied as a heat-sensitive recording material, a high-sensitivity writable by an infrared laser using the heat-sensitive composition, and an alkali developing resistance in an image portion of a recording layer. The present invention relates to a lithographic printing plate precursor having a negative recording layer having excellent printing durability, and a novel sulfonium salt compound which can be suitably used for the lithographic printing plate precursor.

[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. 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, a photothermal conversion agent,
The lithographic printing plate material has a photosensitive layer containing a polymerization initiator that generates a radical by light or heat and 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. As a negative type image recording material to be subjected to such a post-heating treatment, for example, US Pat. No. 5,340,699
And a recording material comprising a resol resin and a novolak resin described in the above item. In particular, when an aluminum support is used, the energy from the infrared laser irradiation diffuses into the support having high thermal conductivity, and is not used for initiating or accelerating a polymerization reaction for image formation, and sufficient sensitivity is obtained. There was no problem.

[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 provide a heat-sensitive composition capable of irreversibly changing physical properties by heating. High sensitivity using the heat-sensitive composition, no heat treatment before development is required or the heat treatment can be simplified, and in the image area, alkali development resistance is good, An object of the present invention is to provide a negative type lithographic printing plate precursor excellent in printability and recordable by a heat mode, and a novel onium salt compound that can be suitably used for the lithographic printing plate precursor.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an acid / radical generation represented by the following general formula (A), general formula (B) or general formula (C) is formed on a support. Agent and a compound whose physical properties are irreversibly changed by an acid or a radical, whereby a composition excellent in curability by heat and color development is obtained, and a recording layer containing such a composition The present inventors have found that the provision of a lithographic printing plate can achieve higher recording sensitivity and improved printing durability of a lithographic printing plate, and completed the present invention. That is, the heat-sensitive composition of the present invention comprises (I) a compound that generates an acid or a radical by heat represented by the following general formula (A), general formula (B) or general formula (C) (hereinafter, appropriately, (Referred to as an acid / radical generator) and (II) a compound whose physical or chemical properties are irreversibly changed by an acid or a radical.

[0006]

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In the formula, X represents a group shown below or a halogen atom. M ⁺ represents a monovalent cation. In the following groups, R ¹ and R ² represent the same or different monovalent nonmetallic atoms.

[0008]

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[0009]

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In the formula, Y has the same meaning as X in the general formula (A) or —OH, —CN, —NO ₂ , —Si (R ⁵ ) (R
⁶ ) represents (R ⁷ ). R ^{3 to} R ⁷ represent monovalent nonmetal atoms which may be the same or different. M ⁺ represents a monovalent cation.

[0011]

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In the formula, R ⁸ represents a monovalent nonmetal atom. A
r ^l and Ar ² represent an aryl group which may be the same or different. M ⁺ represents a monovalent cation.

The composition further contains (III) a light-to-heat conversion agent, and (III) a compound represented by the following general formulas (A) to (C) upon exposure to the absorption wavelength of the light-to-heat conversion agent. The acid or radical of the compound that generates an acid or a radical by the heat is generated, (II) by the acid or the radical,
For compounds whose physical or chemical properties change irreversibly,
The physical or chemical properties change, and recording by exposure becomes possible. Further, the lithographic printing plate precursor of the present invention according to claim 3 can be recorded by heat mode exposure, and can be formed on a support by (I) the following general formula (A), general formula (B) or general formula ( Acid / radical polymerization initiator represented by C), (III)
A photosensitive layer containing a photothermal conversion agent, (II-1) a radically polymerizable compound having an unsaturated bond, and (IV) a binder polymer is provided.

[0014]

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In the formula, X represents a group shown below or a halogen atom. M ⁺ represents a monovalent cation. In the following groups, R ¹ and R ² represent the same or different monovalent nonmetallic atoms.

[0016]

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[0017]

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In the formula, Y has the same meaning as X in formula (A), or —OH, —CN, —NO ₂ , —Si (R ⁵ ) (R
⁶ ) represents (R ⁷ ). R ^{3 to} R ⁷ represent monovalent nonmetal atoms which may be the same or different. M ⁺ represents a monovalent cation.

[0019]

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In the formula, R ⁸ represents a monovalent nonmetal atom. A
r ^l and Ar ² represent an aryl group which may be the same or different. M ⁺ represents a monovalent cation.

Further, the present inventors have found that the above-mentioned general formula (A)
Among the acid / radical polymerization initiators represented by the following, a sulfonium salt compound represented by the following general formula (A-1), and a sulfonium salt compound represented by the following general formula (A-2) which is a more preferred embodiment, It has been found that the compound is a novel compound and is particularly useful as an acid / radical polymerization initiator in the composition. That is, claim 4 of the present invention relates to a sulfonium salt compound represented by the following general formula (A-1).

[0022]

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In the formula, Ar ^a-1 , Ar ^a-2 and Ar ^a-3 each independently represent an aryl group, and R ⁹ represents an alkyl group or an aryl group. Further, claim 5 relates to a sulfonium salt compound represented by the following general formula (A-2), which is a further preferred embodiment thereof.

[0024]

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Where R^TenIs a phenyl group or 1 carbon atom
Represents an alkyl group of 4 to 4. R¹¹, R ¹², R¹³Are each
Independently represents hydrogen, chlorine, methyl or butyl
You.

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 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 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 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 processes using the above modes are 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 is caused by using n photons. In photon mode exposure, photochemical interaction is used, so that the energy of one photon cannot be added together 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, a relationship of “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 (the energy required for the reaction required for image formation) is compared with 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 unexposed areas 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
It is necessary to be 0 w / cm ² or more, preferably 10,000 w / cm ² or more. 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 staining the light source.

Although the operation of the present invention is not clear,
(I) General formula (A) to general formula contained in the heat-sensitive composition
The acid / radical generator represented by (C) has an onium salt structure
With carboxylate as counter anion
Compound, generally used as a radical polymerization initiator.
Sulfonate (-SO_Three ^-) And inorganic salts (PF₆ ^-, Sb
F₆ ^-, BF_Four ^-) As a compound having a counter anion
In comparison, the pyrolysis temperature is lower and the sensitivity is higher. Also, anti
The reaction mechanism is unknown, but the acid / radical generator decomposes
Carboxylic acid as a counter anion is removed by heat
Causes carbonic acid, causing not only the sulfonium salt
An acid or radical is also generated from the union
Is considered to be highly sensitive. Cause decarboxylation.
The pan structure is R-COO^-Carboxyl group and R
When the bond dissociation energy of the group is low, or R-COO
^-P-Ka of RH which is a hydrogen form of the R portion of the structure of
That is, for example, pKa is a hydrogen form of methane (CH _Three−
H). In addition, decarboxylation
The temperature is preferably 250 ° C. or less, preferably 230 ° C.
C. or lower, more preferably 215.degree.
Is preferred. In addition, the acid generated during decomposition
Are also carboxylic acids or carbon dioxide, that is, relatively weak acids.
Is effective in initiating and promoting polymerization,
Immersion in alkaline water compared to compounds that generate strong acids
Due to low permeability, this composition is used as a recording layer for a lithographic printing plate precursor.
When used as an alkaline developer during development
Damage due to this, the film strength of the image area increases,
As a result, it is considered that the printing durability is improved. The above
By action, (I) represented by general formulas (A) to (C)
Acid / radical generator and (II) acid or radical
Compounds whose physical or chemical properties change irreversibly
And high sensitivity to heat or exposure.
It turns out that a composition with excellent thermosetting properties can be obtained.
Was.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The heat-sensitive composition of the present invention has irreversible physical and chemical properties due to (I) an acid / radical generator represented by the general formulas (A) to (C) and (II) an acid or a radical. To contain a compound that changes over time,
(I) The acid / radical generator represented by the general formulas (A) to (C) decomposes to generate an acid or a radical, and (II) the acid or the radical by the acid or the radical, The physical or chemical properties of the compound whose chemical properties change irreversibly change, causing a curing reaction, a color development, a decoloring reaction, etc. due to radical polymerization. Further, the heat-sensitive composition further contains (III) a light-to-heat conversion agent, so that light having an absorption wavelength of the light-to-heat conversion agent, for example, by irradiating an infrared laser or the like, makes the (III) light-to-heat conversion agent Generates heat, the heat of the infrared laser light itself, or (II
I) The heat generated by the photothermal conversion agent decomposes (I) the acid / radical generator represented by the general formulas (A) to (C) to generate an acid or radical, and (II) the acid or radical The radicals cause a change in the properties of the compound whose physical and chemical properties change irreversibly.

(I) Compounds of general formulas (A) to (C) which generate an acid or a radical by heat The acid / radical generator used in the present invention includes the following general formulas (A) to (C) It is represented by equation (C).

[0032]

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In the general formula (A), X represents the aforementioned substituent or a halogen atom, wherein R ¹ and R ² represent the same or different monovalent nonmetallic atoms. R ^l , R ²
Is preferably hydrogen, an alkyl group, an alkenyl group or an alkynyl group having 1 to 20 carbon atoms, or an aryl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group or an alkoxy group having 1 to 10 carbon atoms, and these are halogen. Atom, carbonyl group, alkoxy group, ester group, thioether group, amide group, imide group, hydroxyl group, nitro group, cyano group, thiocarbonyl group, amino group, sulfonic ester group, sulfoxide group, aryl group, silyl group, etc. It may be substituted with one or more functional groups. From the viewpoint of sensitivity, an alkyl group, an alkenyl group and an aryl group having 1 to 12 carbon atoms are preferred. Further, preferred aryl groups include phenyl, naphthalene, anthracene, imidazole, indole, carbazole, furan, benzofuran, benzimidazole, oxazole, benzoxazole, benzothiazole, hydrolysine triazole, pyrazole, and thiophene, and more preferably. , Phenyl, naphthalene, anthracene, and indole.

M ⁺ represents a monovalent cation, specifically, Li ⁺ , Na ⁺ , K ⁺ , phosphonium, selenonium, oxonium, siliconium, carbonium, sulfonium, iodonium, diazonium, ammonium, azinium Is mentioned. 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 is condensed with an azine ring 1
It contains one or more aromatic rings and includes, for example, quinolinium, isoquinolinium, benzoazinium, naphthoazinium and the like. Specifically, for example, USP
4,743,528, JP-A-63-138345,
Nos. 63-142345, 63-142346, and JP-B-46-42363.
Counter cations forming 1-methoxy-4-phenylpyridinium tetrafluoroborate, N-alkoxypyridinium salts and the like are exemplified. Among these cations, Li ⁺ , Na ⁺ , K ⁺ ,
Ammonium, iodonium or sulfonium is preferable, and a compound having a diaryliodonium or triarylsulfonium skeleton represented by the following general formula (MI) or (M-II) is more preferable in terms of stability and sensitivity.

[0035]

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The general formula (MI) or the general formula (MI)
In I), R ^{M1 to} R ^M25 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 —S—R ^M26.
Represents a group. Here, R ^M26 represents a linear, branched, or cyclic alkyl group or an aryl group.

In the general formula (MI) or the general formula (M-II), the straight-chain or branched alkyl group of R ^{M1 to} R ^M25 may be a methyl group, an ethyl group, Examples thereof include those having 1 to 4 carbon atoms such as a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. The alkoxy group represented by R ^{M1 to} R ^M25 has 2 to 4 carbon atoms such as 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. R ^{M1 to} R ^M25
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. ^Examples of the aryl group for R ^M26 include those having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. The aryl group may have a substituent. R ^{M1 to} R
Preferred substituents that the group of ^M25 may have are those having 1 carbon atom
~ 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl groups 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.

[0038]

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In the general formula (B), Y has the same meaning as X in the general formula (A) or —OH, —CN, —NO ₂ , —Si
(R ⁵ ) (R ⁶ ) (R ⁷ ), and R ^{3 to} R ⁷ represent monovalent non-metallic atoms which may be the same or different. M ⁺ represents a monovalent cation, and specific examples are preferably the same as those exemplified in formula (A). Specifically, R ^{3 to} R ⁷ have the same meanings as those exemplified for R ¹ and R ² in the general formula (A), and R ³ and R ⁴ are preferably a hydrogen atom, an alkyl having 1 to 6 carbon atoms. Group or carbon number 6-10
Is an aryl group. R ³ and R ⁴ may be bonded to each other to form a ring. R ^{5 to} R ⁷ are preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

[0040]

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In the formula, R ⁸ represents a monovalent nonmetal atom. A
r ^l and Ar ² represent an aryl group which may be the same or different. M ⁺ represents a monovalent cation, and specific examples are preferably the same as those exemplified in formula (A). Specifically, R ⁸ has the same meaning as that exemplified for R ¹ and R ² in the general formula (A), and R ⁸ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon atom having 6 to 6 carbon atoms. 10 aryl groups or hydroxyl groups. Ar ¹ , Ar ²
Specific examples thereof include phenyl, naphthalene, anthracene, imidazole, indole, carbazole, furan, benzofuran, benzimidazole, oxazole, benzoxazole, benzothiazole, pyridinetriazole, pyrazole, and thiophene, preferably a phenyl group. , Naphthalene, anthracene, and indole.

Among these, as the acid / radical generator suitably used in the present invention, those in which X has the following structure in the general formula (A) from the viewpoint of stability and thermal reactivity:

[0043]

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In addition, those represented by the general formula (C) and those having the following structure in the general formula (B) are exemplified.

[0045]

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Among these, the most preferred acid / radical generators are those in which X in the general formula (A) has the following structure.

[0047]

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Among the above compounds, the following general formula (A)
-1) and a sulfonium salt compound represented by the following general formula (A-2), which is a more preferred embodiment thereof, are novel compounds,
It is also particularly useful as a radical generator. Compared with the conventional sulfonium-sulfonate and sulfonium-inorganic salt, this compound uses the anion having a COCOO 2 ^- structure as the counter anion of the sulfonium salt, so that thermal decomposition occurs more efficiently and high sensitivity can be obtained. It is possible, and has the advantage of being more stable than a simple sulfonium-carboxylate.

[0049]

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In the formula (A-1), Ar ^a-1 , Ar ^a-2 , Ar
^a-3 each independently represents an aryl group, and R ⁹ represents an alkyl group or an aryl group. Here, Ar ^a-1 , Ar ^a-2 ,
The aryl group represented by Ar ^a-3 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, a s-position group,
It may have a substituent selected from a halogen atom, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, a carbonyl group, and an amide group. Ar ^a-1 , Ar ^a-2 and Ar ^a-3 are preferably a phenyl group, an alkyl group having 1 to 4 carbon atoms, or a phenyl group substituted with a halogen atom. Also, R ⁹
Represents an alkyl group or an aryl group having 1 to 12 carbon atoms,
This aryl group has the same meaning as Ar ^a-1 , Ar ^a-2 , and Ar ^a-3 . Further, among such sulfonium salt compounds, a sulfonium salt compound represented by the following general formula (A-2) is particularly preferable.

[0051]

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In the formula (A-2), R ¹⁰ represents a phenyl group or an alkyl group having 1 to 4 carbon atoms. R ¹¹ , R ¹² , R ¹³
Each independently represents a hydrogen atom, a chlorine atom, a methyl group or a butyl group. Among them, those in which R ¹⁰ is a phenyl group or a methyl group, those in which all of R ¹¹ , R ¹² , and R ¹³ are a hydrogen atom or a butyl group, two of R ¹¹ , R ¹² , and R ¹³ are methyl What is a group or a chlorine atom is preferable from a viewpoint of sensitivity.

Hereinafter, specific examples of the acid / radical generators represented by the general formulas (A) to (C) are shown in combination with an anion portion corresponding to a preferable counter cation. It is not limited to. First, specific examples of the acid / radical generator represented by Formula (A) [Exemplified Compound (I-1) to Exemplified Compound (I-28)] are illustrated.

[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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Hereinafter, specific examples of the acid / radical generator represented by the formula (B) [exemplified compounds (II-1) to (II-47)] will be described.

[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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Hereinafter, specific examples of the acid / radical generator represented by the general formula (C) [exemplified compounds (III-1) to (III-17)] are shown.

[0069]

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[0070]

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[0071]

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[0072]

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Examples of carboxylic acids suitable for forming the radical polymerization initiator according to the present invention are shown below.

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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As a typical example, a synthesis example of triphenylsulfonium-benzoylformic acid [exemplified compound (I-1)] is shown. a-1) Synthesis of triphenylsulfonium iodide 76 g of diphenylsulfoxide was added to 1200 ml of benzene
And 300 g of aluminum chloride is added thereto.
Refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water under ice cooling, and 500 ml of concentrated hydrochloric acid was added thereto.
Heated for a minute. This aqueous solution was washed with 800 ml of ethyl acetate, filtered, and then 300 g of ammonium iodide was added to 60 ml of water.
A solution dissolved in 0 ml was added. The precipitated powder is collected by filtration,
After washing with water, washing with ethyl acetate and drying yielded 98 g of triphenylsulfonium iodide. a-2) Synthesis of triphenylsulfonium-benzoylformic acid (I-1) 78 g of triphenylsulfonium iodide was dissolved in 1000 ml of methanol, and 48.7 g of silver oxide was added to this solution.
Was added and stirred at room temperature for 4 hours. The solution was filtered and to this was added an excess of 34.0 g of benzoylformic acid. The reaction solution was concentrated, and the concentrated solutions were respectively 200 ml of ethyl acetate, 100 ml of hexane, 100 ml of acetone, and
The slurry was reslurried with 0 ml, the supernatant liquid was decanted, and vacuum drying was performed to obtain 75 g of benzoyl formate (I-1) of triphenylsulfonium (yield:
91%).

The compound (I-1) was prepared by NMR (Va
rian 300 MHz) N measured in CDCl ₃
This shows the peak determined from the MR spectrum. H ¹ -NMR (300 MHz): 7.38 (m, 2
H), 7.48 (m, 1H), 7.61-7.74
(M, 9H), 7.82 (m, 6H), 8.06 (m,
2H)

B) Synthesis of Exemplified Compound (I-2) The above-mentioned triphenylsulfonium-benzoylformic acid (I-
Exemplified compound (I-2) was obtained in the same manner as in the synthesis of 1), except that an excess amount of pyruvic acid was added instead of benzoylformic acid as the carboxylic acid. The peaks obtained from the NMR (300 MHz: CDCl ₃ ) spectrum of the exemplified compound (I-2) are shown below. H ¹ -NMR (300 MHz): 2.29 (s, 3
H), 7.67-7.80 (m, 15H)

C) Synthesis of Exemplified Compound (I-12) The above-mentioned triphenylsulfonium-benzoylformic acid (I-
In the synthesis of 1), instead of triphenylsulfonium iodide as a starting material in a-2), tri (4
Except that (-t-butylphenyl) sulfonium iodide was used, Exemplified compound (I-12) was obtained. The NMR (300 MHz: CD) of the compound (I-12) is described below.
Cl ₃ ) shows the peak determined from the spectrum. H ¹ -NMR (300 MHz): 1.32 (s, 9
H), 7.38 (m, 2H), 7.47 (m, 1H),
7.63 (m, 6H), 7.74 (m, 6H), 8.0
9 (m, 2H)

D) Synthesis of Exemplified Compound (I-27) The above-mentioned triphenylsulfonium-benzoylformic acid (I-
In the synthesis of 1), di-p-tolyloxide is used as a raw material of a-1) instead of diphenylsulfoxide,
Exemplified compound (I-27) was obtained in the same manner as in a-2) except that di (4-methylphenyl) sulfonium iodide was obtained as the starting material in a-2). less than,
NMR of compound (I-27) (300 MHz: CDCl
₃ ) Indicates the peak determined from the spectrum. H ¹ -NMR (300 MHz): 2.42 (s, 6
H), 7.33-7.49 (m, 7H), 7.59-
7.76 (m, 7H), 7.73-7.76 (m, 2
H), 8.04-8.07 (m, 2H)

E) Synthesis of exemplified compound (I-28) The above-mentioned triphenylsulfonium-benzoylformic acid (I-
In the synthesis of 1), di (4-chlorosulfoxide) was used as a starting material for a-1) instead of diphenylsulfoxide to obtain di (4-chlorophenyl) sulfonium iodide as a starting material in a-2), and In the same manner except that was used, Exemplified Compound (I-28) was obtained. The NMR (300 MHz: CD) of the compound (I-28) is described below.
Cl ₃ ) shows the peak determined from the spectrum. H ¹ -NMR (300MHz): 7.36-7.41
(M, 2H), 7.45-7.52 (m, 1H), 7.
56-7.87 (m, 13H)

Other sulfonium salts and iodonium salts can be similarly synthesized by appropriately selecting the starting material and the carboxylic acid to be added.

Another method for obtaining iodonium iodide is described in Bull. Chem. Soc. Jpn. 7
0, 219-224 (1997), Bull. Che
m. Soc. Jpn. 70, 1665-1669 (19
97), Bull. Chem. Soc. Jpn. 70,
115-120 (1999); Amer. Che
m. Soc; 82; 1960,725-731, J. A
mer. Chem. Soc; 81; 1959, 342.
346 can be used.

Another method for obtaining sulfonium iodide is described in J. Am. Amer. Chem. Soc; 91; 196
9; 145-150, etc. can be used. Other methods for obtaining sulfonium carboxylate are described in J. Am. Org. Chem 35; 197
0 2539-2543.

In the heat-sensitive composition of the present invention, the acid / radical generator represented by the general formulas (A) to (C) is used in an amount of 0.5 to 0.5% of the total solid content of the composition. 30% by weight
It is preferable to be contained.

In the present invention, in addition to the specific acid / radical generator, other known photopolymerization initiators, thermal polymerization initiators and the like may be selected and used in combination as long as the effects of the present invention are not impaired. Can be. Examples of these polymerization initiators that can be used in combination include, for example, known onium salts having no carboxylic acid structure in the counter cation portion, triazine compounds having a trihalomethyl group, peroxides, azo-based polymerization initiators, azide compounds, quinonediazides And the like.

Specific examples of onium salts that can be suitably used as a radical generator that can be used in combination include paragraphs [0030] to [0030] of Japanese Patent Application No. 11-310623.
Examples described in [0033] can be given.

The general formula (I) described in paragraphs [0012] to [0050] of JP-A-9-34110 is also disclosed.
-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. When other polymerization initiators are used in combination, the content thereof is preferably not more than 50% by weight of the specific acid / radical generator. The acid / radical generator used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. By setting the absorption wavelength in the ultraviolet region, the image forming material can be handled under a white light.

(II) A compound whose physical and chemical properties are irreversibly changed by an acid or a radical The second essential component in the heat-sensitive composition of the present invention (I)
I) Compounds whose physical and chemical properties are irreversibly changed by acids or radicals are described. This compound
A compound whose physical properties or chemical properties are changed by the action of an acid or a radical generated by the heat of the acid / radical generator, and the changed state is maintained;
There is no particular limitation as long as it is a compound having such properties,
Any compound can be used. For example, the compounds listed in (I) the acid / radical generator itself often have such properties. The characteristics of the compound (II) that is changed by an acid or a radical generated from an acid / radical generator include, for example, an absorption spectrum (color), a chemical structure,
Examples include molecular properties such as polarizability, and material properties such as solubility, strength, refractive index, fluidity, and adhesiveness.

When a compound whose absorption spectrum is changed by oxidation / reduction or nucleophilic addition reaction is used as the compound (II), it causes oxidation or reduction by an acid or radical generated from an acid / radical generator, resulting in an image. Formation is possible. Such an example is described, for example, in J. Am. Chem. Soc., 1
08, 128 (1986), J. Imaging. Soc., 30,
215 (1986), Israel. J. Chem., 25, 264.
(1986).

Further, as the compound (II), addition polymerization,
Alternatively, a thermosetting resin or a negative type photopolymer can be formed by using a compound capable of polycondensation and combining it with (I) an acid / radical generator.

As the content of the compound (II), an optimum amount is appropriately selected depending on the intended property change or the compound to be used, but in general, the absorption spectrum is changed by oxidation / reduction or nucleophilic addition reaction. When the compound is used, it is about 0.5 to 40% by weight based on the total solid content of the composition. When a compound capable of addition polymerization or polycondensation is used, the content is 0.5% by weight based on the total solid content of the composition. About 30% by weight.

One of the objects of the present invention, as a compound (II) suitable for producing a highly sensitive lithographic printing plate precursor, is (II-
1) A radically polymerizable compound having an unsaturated bond is exemplified. Hereinafter, this compound will be described in detail. (II-1) Radical polymerizable compound having unsaturated bond The radical polymerizable compound used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is preferably And at least one, preferably at least two, terminal ethylenically unsaturated bonds. Such compounds are widely known in the industrial field, and they can be used in the present invention without any particular limitation. These include those having 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 preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds. 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 dehydration condensation product with a monofunctional or polyfunctional carboxylic acid is also preferably used.

Further, an isocyanate group, an epoxy group,
Having an electrophilic substituent such as an unsaturated carboxylic acid ester, an amide and a monofunctional or polyfunctional alcohol,
Amines, addition products with thiols, halogen groups,
Substitution products of unsaturated carboxylic acid esters and amides having a leaving substituent such as a tosyloxy group and the like with monofunctional or polyfunctional alcohols, amines and thiols are 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, vinyl ether or the like.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol Tetraacrylate, SO Bito one Le pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate 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.

Examples of crotonates 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, and JP-A-57-196231, and 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. Further, the above-mentioned ester monomers can be used as a mixture.

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 and a hydroxyl-containing vinyl monomer represented by the following general formula (2) added to one molecule. Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups.

[0106]

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In the general formula (2), R and R ′ represent H or CH ₃ . Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and
Urethane compounds having an ethylene oxide skeleton described in JP-A-8-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.

Further, by using addition 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. Can obtain a photosensitive composition having an extremely high photosensitive speed.

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. Further, the Journal of the Adhesion Society of Japan, vol. 20, no. 7, pages 300 to 308 (1
984) as photocurable monomers and oligomers.

Regarding these addition-polymerizable compounds, what kind of structure is used, whether they are used alone or in combination,
Details of the method of use, such as the amount of addition, can be arbitrarily set in accordance with the final performance design of the light-sensitive material. For example, it is selected from the following viewpoints. From the viewpoint of the photosensitive speed, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or more functional structure is preferable. In order to increase the strength of the image area, that is, the cured film, those having three or more functional groups are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylates, methacrylates, styrene compounds, vinyl ethers) It is also effective to adjust both the photosensitivity and the intensity by using the compound (1) in combination. A compound having a large molecular weight or a compound having a high hydrophobicity is excellent in photosensitive speed and film strength, but may not be preferable in terms of developing speed and precipitation in a developing solution.

Further, compatibility with other components (eg, binder polymer, initiator, colorant, etc.) in the heat-sensitive composition,
The selection and use of the addition polymerization compound is also an important factor for the dispersibility. For example, the use of a low-purity compound or the combination of two or more compounds may improve the compatibility.

The heat-sensitive composition of the present invention is characterized by exhibiting an irreversible change in properties due to heat. By adding a photothermal conversion agent in addition to the above components, heat mode exposure, typically The above-mentioned property change can be caused by a laser emitting infrared rays, that is, a composition having photosensitivity can be obtained. This (II
I) The photothermal conversion agent will be described. (III) Light-to-heat conversion agent As the light-to-heat conversion agent used in the present invention, any material can be used without particular limitation in the absorption wavelength range, as long as it is a substance that absorbs light energy used for recording and generates heat. An infrared absorbing dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm is preferably used from the viewpoint of compatibility with a readily available high-output laser.

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, 1970) can be used. Specifically, azo dye, metal complex salt azo dye, pyrazolone azo dye, naphthoquinone dye, anthraquinone dye, phthalocyanine dye, carbonium dye, quinone imine dye, methine dye, cyanine dye, squarylium dye, pyrylium salt, metal thiolate complex, oxonol dye 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 and JP-A-60-78787;
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.

Further, a near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a 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), trimethinethiapyrylium salts described in JP-A-58-181051, 58-220143, 59-41363, and 59.
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.

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.

[0118]

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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.

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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 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.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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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 those exemplified below.

[0131]

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[0132]

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In the 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, 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.

[0135]

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[0136]

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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
And may combine 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. X^TwoAnd X^ThreeIs German
In addition, a hydrogen atom, an alkyl group, or an aryl group,
X^TwoAnd X^ThreeAt least one is a hydrogen atom or an alkyl group
Is shown. Q is 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.

[0139]

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[0140]

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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.

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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 the Japan Pigment Technical Association, 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 being subjected to a surface treatment, or may be used after being subjected to a 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 photothermal conversion agents are preferably added to the heat-sensitive composition in an amount of 0.1 to 30% by weight of the total solids. If the amount is less than this range, the sensitivity of the property change due to exposure is low, and the photosensitivity tends to be insufficient.If the amount is too large, the uniformity and strength of the film tend to decrease. Is also not preferred.

Next, the lithographic printing plate precursor of the present invention using the above heat-sensitive composition will be described. In the lithographic printing plate precursor according to the invention, the heat-sensitive composition is used for a recording layer. (Recording Layer) First, the recording layer (photosensitive layer) having an image forming function in the lithographic printing plate precursor according to the invention will be described.
The photosensitive layer of the lithographic printing plate precursor according to the invention comprises (I) an acid / radical polymerization initiator represented by the following general formula (A), (III) a photothermal conversion agent, and (II-1) a polymerizable unsaturated group. And (IV) a binder polymer, but the (III) photothermal conversion agent generates heat by infrared laser irradiation, and the (III) photothermal conversion agent is generated by infrared laser light or infrared laser irradiation. Due to the heat, (I) the acid / radical generator represented by the general formula (A) is decomposed to generate an acid or a radical, and (II-1) a curing reaction of the compound having a polymerizable unsaturated group is performed. Acceleration causes the exposed area to cure to form an image area, forming a negative image.

In forming the recording layer of the lithographic printing plate precursor according to the present invention, the (I) acid represented by the general formula (A)
The radical generator is contained in an amount of 0.1% of the total solid content of the photosensitive layer.
It is preferably contained in an amount of 5 to 15% by weight. This acid / radical generator is used in combination with a photothermal conversion agent (III) described below, and generates an acid or a radical by the energy of light or heat or both when irradiated with an infrared laser, and (II-1) It has the function of initiating and accelerating the polymerization of a compound having an unsaturated group.

Used for the recording layer of the lithographic printing plate precursor (II-
1) The compound having a polymerizable unsaturated group is as described in the above (II)
The compound as described in detail in the description of the compound is used, but what kind of compound is used, in addition to the requirements described above, a support described later, a specific structure for the purpose of improving the adhesion of the overcoat layer and the like. May be selected.
Regarding the compounding ratio of the (II-1) addition polymerizable compound in the heat-sensitive composition, the larger the ratio, the better the sensitivity. However, if the ratio is too large, undesired phase separation may occur or the heat-sensitive composition In the case of a lithographic printing plate precursor, there may be problems in the production process (for example, poor transfer due to transfer of photosensitive material components and adhesion) due to the adhesiveness, and problems such as precipitation from a developer. From these viewpoints, the preferable compounding ratio is, in many cases, 5 to 8 with respect to the total solid content of the composition constituting the recording layer.
0% by weight, preferably 25 to 75% by weight. Also,
These may be used alone or in combination of two or more. In addition, the method of using the addition polymerizable compound can be arbitrarily selected from the viewpoints of the degree of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, etc. Depending on the case, a layer structure and a coating method such as undercoating and overcoating may be performed.

In the lithographic printing plate precursor according to the present invention, the photothermal conversion agent (III) may be added to the same layer as other components or may be added to another layer provided separately. When a negative-type image forming material was prepared, the wavelength of the photosensitive layer was 760 n.
It is preferable that the optical density at the absorption maximum in the range of m 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 addition amount of the photothermal conversion agent (III) 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 measuring method, for example, on a transparent or white support, a coating layer after drying is formed on a recording layer having a thickness appropriately determined in a range required as a lithographic printing plate, and a transmission type optical densitometer is used. Examples include a method of measuring, a method of forming a recording layer on a reflective support such as aluminum, and measuring a reflection density.

(IV) Water-insoluble and alkaline aqueous solution-soluble binder In the lithographic printing plate precursor according to the invention, it is preferable to further use a binder polymer in the recording layer. It is preferable to include a linear organic high molecular polymer as the binder. Any of such “linear organic high molecular polymers” may be used. Preferably, a water-soluble or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is selected and used not only as a film forming agent of the composition but also as a water, weakly alkaline water or organic solvent developing agent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, Japanese Unexamined Patent Publication No.
Nos. 9-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048. Those described, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers as needed) copolymer,
It is suitable because it has an excellent balance of film strength, sensitivity and developability.

Further, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No.
JP-A-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, JP-A-1-271174,
The urethane-based binder polymer containing an acid group described in Japanese Patent Application No. 10-116232 is very excellent in strength, and is advantageous in terms of printing durability and low exposure suitability.
Further, a binder having an amide group described in JP-A-11-171907 is suitable because it has excellent developability and film strength.

Further, as the water-soluble linear organic polymer, polyvinyl pyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be incorporated in any amount into the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 30 to 85
% By weight. In addition, the compound having an ethylenically unsaturated double bond and the linear organic high molecular weight are 1/9 to 7 by weight ratio.
/ 3 is preferable.

The binder polymer of the present invention is substantially insoluble in water and soluble in an aqueous alkali solution. For this reason, an organic solvent which is not environmentally unfavorable is not used or the amount used is extremely small as a developer.
The acid value (acid content per gram of polymer expressed by chemical equivalent number) and molecular weight of such a binder polymer are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 0.4 to 3.0 meq / g, and the preferred molecular weight is in the range of 3,000 to 500,000. More preferably, the acid value is 0.6 to 2.0, and the molecular weight is 10,000 to 300,000. Range.

(V) Other Components In the composition constituting the recording layer of the lithographic printing plate of the present invention,
Further, other components suitable for the use, the production method and the like can be appropriately added. Hereinafter, preferred additives will be exemplified. (V-1) Co-sensitizer The sensitivity can be further improved by using a certain additive (hereinafter referred to as a co-sensitizer). Although their mechanism of action is not clear, most are thought to be based on the following chemical processes. That is, the co-sensitizer reacts with a photoreaction initiated by the thermal polymerization initiator and various intermediate active species (radicals, cations) generated in the course of the subsequent addition polymerization reaction to generate a new active radical. It is estimated that These are largely (a) those that can be reduced to form active radicals, (b) those that can be oxidized to form active radicals, and (c) those that react with less active radicals and are more active radicals. Or acting as a chain transfer agent, but there is often no myth as to which of these compounds each belongs to.

(A) Compound that generates an active radical by being reduced Compound having a carbon-halogen bond: It is considered that the carbon-halogen bond is reductively cleaved to generate an active radical. Specifically, for example, trihalomethyl-s-
Triazines, trihalomethyloxadiazoles and the like can be suitably used. Compound having a nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used. Compound having an oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides and the like are preferably used. Onium compound: a carbon-hetero bond or an oxygen-
It is thought that the nitrogen bond is cleaved to generate an active radical. Specifically, for example, diaryliodonium salts,
Triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used. Ferrocene, iron arene complexes: can generate active radicals reductively.

(B) Compound which is oxidized to generate an active radical Alkyl ate complex: It is considered that the carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, for example, triarylalkyl borates are preferably used. Alkylamine compound: It is considered that the CX bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group, or the like.
Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines and the like. Sulfur- and tin-containing compounds: Compounds in which the nitrogen atom of the above-mentioned amines is replaced with a sulfur atom or a tin atom can generate an active radical by the same action. Compounds having an SS bond are also known to be sensitized by SS cleavage.

Α-Substituted methylcarbonyl compound: An active radical can be generated by the cleavage of the carbonyl-α carbon bond by oxidation. In addition, those obtained by converting carbonyl to oxime ether also show the same action. In particular,
2-alkyl-1- [4- (alkylthio) phenyl]
-2-morpholinopronones-1 and oxime ethers obtained by reacting these with hydroxyamines and then etherifying N-OH. Sulfinates: Active radicals can be generated reductively. Specific examples include sodium arylsulfin sodium.

(C) Compounds that react with radicals to convert them into highly active radicals or act as chain transfer agents: For example, compounds having SH, PH, SiH, and GeH in the molecule are used. These can generate a radical by donating hydrogen to a low-activity radical species, or can generate a radical by being oxidized and then deprotonated. Specific examples include 2-mercaptobenzimidazoles.

More specific examples of these co-sensitizers are described in, for example, JP-A-9-236913 as additives for the purpose of improving sensitivity. Can also be applied. These co-sensitizers can be used alone or in combination of two or more. The amount is suitably in the range of 0.05 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the compound having an ethylenically unsaturated double bond.

(V-2) Polymerization Inhibitor In the present invention, in addition to the above basic components, there is no need for a compound having an ethylenically unsaturated double bond which can be polymerized during the production or storage of the photosensitive composition. It is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent a thermal polymerization. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, and the like. The amount of the thermal polymerization inhibitor added is about 0.01 to the weight of the whole composition.
% By weight to about 5% by weight is preferred. In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition by oxygen, and when used as a lithographic printing plate precursor, after application to a support or the like, During the drying process, it may be unevenly distributed on the surface of the photosensitive layer. The amount of the higher fatty acid derivative to be added ranges from about 0.5% by weight to about 10% by weight of the total composition.
% By weight is preferred.

(V-3) Colorant, etc. When the photosensitive composition of the present invention is used for a lithographic printing plate precursor, a dye or pigment may be added for the purpose of coloring the photosensitive layer. As a result, as a printing plate,
It is possible to improve so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring device. As a coloring agent, since many dyes cause a decrease in the sensitivity of the photopolymerizable photosensitive layer,
As the colorant, use of a pigment is particularly preferable. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. Dyes and pigments may be added in an amount of about 0.5% to about 5% by weight of the total composition.
% By weight is preferred.

(V-4) Other Additives When the photosensitive composition of the present invention is used in a lithographic printing plate precursor, inorganic fillers, other plasticizers, photosensitive materials, and the like may be used to improve the physical properties of the cured film. A known additive such as a sensitizer capable of improving the ink inking property of the layer surface may be added.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. A binder was used. In this case, it can be added in an amount of 10% by weight or less based on the total weight of the compound having an ethylenically unsaturated double bond and the binder.

Further, a UV initiator, a mature cross-linking agent or the like can be added to enhance the effect of heating and exposure after development for the purpose of improving the film strength (printing durability) described later. In addition, it is possible to provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support and for improving the development and removability of the unexposed photosensitive layer. For example, a compound having a diazonium structure or a phosphone compound, such as a compound having a relatively strong interaction with the substrate or an undercoat, the adhesion is improved,
The printing durability can be increased, while the addition or undercoating of a hydrophilic polymer such as polyacrylic acid or polysulfonic acid improves the developability of the non-image area and improves the stain resistance.

When the photosensitive composition of the present invention is coated on a support to provide a lithographic printing plate, it is used after being dissolved in various organic solvents. As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,
N-dimethylformamide, dimethyl sulfoxide, γ
-Butyrolactone, methyl lactate, ethyl lactate, etc. These solvents can be used alone or as a mixture. And the concentration of solids in the coating solution is 2
~ 50% by weight is suitable.

The amount of the photosensitive layer to be applied to the support is desirably appropriately selected depending on the application in consideration of the effects of the sensitivity and developability of the photosensitive layer and the strength and printing durability of the exposed film. When the coating amount is too small, the printing durability becomes insufficient. On the other hand, if the amount is too large, the sensitivity is lowered, the exposure takes time, and the developing process requires a longer time, which is not preferable. The coating amount of the lithographic printing plate precursor according to the invention is generally about 0. lg / m ² to about 10 g / m ²
Is appropriate. More preferably 0.5 to 5 g / m
²

"Protective layer" In the lithographic printing plate precursor according to the invention,
A protective layer can be provided on the recording layer containing the photopolymerizable compound, if necessary. Such lithographic printing plate precursors are usually exposed in the air, but the protective layer is a low-molecular-weight substance such as oxygen or a basic substance present in the atmosphere that inhibits an image forming reaction caused by exposure in the photosensitive layer. The compound is prevented from being mixed into the photosensitive layer, and the image formation reaction due to exposure in the air is prevented. Therefore, the desired property of such a protective layer is that the permeability of low molecular compounds such as oxygen is low,
Furthermore, it is desirable that the light used for exposure has good transparency, excellent adhesion to the photosensitive layer, and that it can be easily removed in the development step after exposure.

Such a device for the protective layer has been conventionally devised, which is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, it is preferable to use a water-soluble polymer compound having relatively excellent crystallinity. Although water-soluble polymers such as acrylic acid are known, use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, or an acetal as long as it contains an unsubstituted vinyl alcohol unit for obtaining necessary oxygen barrier properties and water solubility. Similarly, a part thereof may have another copolymer component.

Specific examples of polyvinyl alcohol include 7
1-100% hydrolyzed, molecular weight 300-240
A range of 0 can be given. Specifically, Kuraray's PVA-105, PVA-110, PVA
A-117, PVA-117H, PVA-120, PV
A-124, PVA-124H, PVA-CS, PVA
-CST, PVA-HC, PVA-203, PVA-2
04, PVA-205, PVA-210, PVA-21
7, PVA-220, PVA-224, PVA-217
EE, PVA-217E, PVA-220E, PVA-
224E, PVA-405, PVA-420, PVA-
613, L-8 and the like.

The components of the protective layer (selection of PVA, use of additives), the amount of coating and the like are selected in consideration of fogging properties, adhesion and scratch resistance in addition to oxygen barrier properties and development removal properties. Generally, the higher the hydrolysis rate of the PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer) and the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen-barrier property is extremely increased, there arises a problem that an unnecessary polymerization reaction occurs during production or raw storage, and unnecessary fogging and thickening of an image occur during image exposure. Further, the adhesion to the image area and the scratch resistance are also extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling due to insufficient adhesive force is likely to occur, and the peeled portion causes defects such as poor film curing due to inhibition of oxygen polymerization.

On the other hand, various proposals have been made to improve the adhesiveness between these two layers. For example, US Patent No. 2
No. 92,501 and U.S. Pat. No. 44,563, an acrylic emulsion or a water-insoluble vinylpyrrolidone-vinyl acetate copolymer or the like is mixed at 20 to 60% by weight in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesiveness can be obtained by laminating on a polymer layer. Any of these known techniques can be applied to the protective layer in the present invention. Regarding the method of applying such a protective layer,
For example, U.S. Pat. No. 3,458,311;
No. 49729.

Further, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye), which has excellent transmittance for light used for exposure (for example, a wavelength of 760 to 1200 nm for an infrared laser) and can efficiently absorb light having a wavelength not related to exposure. Further, the suitability for safelight can be further increased without lowering the sensitivity.

(Support) The support used in the lithographic printing plate precursor according to the invention is not particularly limited as long as it is a dimensionally stable plate-like material. For example, paper, plastic (for example,
Paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate) laminated with polyethylene, polypropylene, polystyrene, etc. Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.). These are single component sheets such as resin films and metal plates,
The laminate may be a laminate of two or more materials, for example, such as the above-described metal-laminated or vapor-deposited paper or plastic film, or a laminated sheet 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, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing the rolling oil on the surface is performed. 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 can 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
No. 34 discloses an alkali metal silicate (for example, an aqueous solution of sodium silicate). 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 Japanese Patent Nos. 3,461 and 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.
Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. No. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium titanium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, and the like. Can be. Alkaline earth metal salt or
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 such a 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 and 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.

(Exposure) As described above, the planographic printing plate precursor of the invention can be prepared. This lithographic printing plate precursor is image-exposed by a solid-state laser and a semiconductor laser that emit infrared light having a wavelength of 760 nm to 1200 nm. In the present invention, the developing treatment may be performed immediately after the laser irradiation, or the heat treatment may be performed between the laser irradiation step and the developing step. The condition of the heat treatment is 80 ° C. to 15 ° C.
It is preferable to carry out for 10 seconds to 5 minutes within the range of 0 ° C. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

(Developer) When a photosensitive material using the photosensitive composition of the present invention is used as an image forming material, it is usually
After image exposure, an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Preferred developers when these photopolymerizable compositions are used for preparing a lithographic printing plate include those described in JP-B-57-7427, such as sodium silicate and potassium silicate. Like sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of a suitable inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. The alkaline solution is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Also, such an alkaline aqueous solution includes:
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol can be contained. For example, those described in U.S. Pat. Nos. 3,375,171 and 3,615,480 can be mentioned. Further, Japanese Unexamined Patent Publication No.
No. 0-26601, No. 58-54341, Tokubo Sho56
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

The lithographic printing plate obtained as described above can be subjected to a printing step after coating with a desensitizing gum as required. 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 the method, a method of applying the printing solution on a lithographic printing plate with a sponge or absorbent cotton impregnated with the surface conditioning solution, or immersing the printing plate in a vat filled with the surface conditioning solution, Application by an automatic coater is applied. Further, it is more preferable to make the amount of the coating uniform with a squeegee or a squeegee roller after the coating.

The burned lithographic printing plate can be subjected to a conventional treatment such as washing with water or gumming, if necessary, but the surface preparation containing a water-soluble polymer compound or the like can be performed. When a liquid is used, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0190]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Examples 1 to 20, Comparative Examples 1 to 4) [Preparation of Substrate] An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene and degreased, and then a nylon brush and a 400 mesh pumice were used. The surface was grained with a water suspension and washed well with water. This plate was etched by immersing it in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, washed with water, further immersed in 20% nitric acid for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Then this board is 7%
3 g / m ² at a current density of 15 A / dm ^{2 using} sulfuric acid as an electrolyte
Was provided, and then washed with water and dried to produce a substrate [A]. The substrate [A] was treated with a 2% by weight aqueous solution of sodium silicate at 25 ° C. for 15 seconds, and washed with water to prepare a substrate [B].

[Formation of Intermediate Layer] Next, S
A liquid composition (sol solution) of Method G was prepared. <Sol solution composition>-130 g of methanol-20 g of water-16 g of 85 wt% phosphoric acid-50 g of tetraethoxysilane-60 g of 3-methacryloxypropyltrimethoxysilane The above compounds were 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 solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio) so that the amount of Si on the substrate [A] prepared as described above was 3 mg / m ^2. It was applied and dried at 100 ° C. for 1 minute to obtain a substrate [C].

[Formation of Lithographic Printing Plate Precursor] One of the substrates [A] to [C] prepared as described above was used as a support, and the following photosensitive layer coating solution was applied to the surface of the substrate in an amount of 1%. .5
g / m ² to obtain the lithographic printing plate precursors of Examples 1 to 20. Substrate used, (I) acid / radical generator (denoted as polymerization initiator), (II) photothermal conversion agent,
(III) The compound having a polymerizable unsaturated group (denoted as an addition polymerizable compound) and (IV) the binder are as shown in Tables 1 and 2 below.

(Coating solution for photosensitive layer) Addition polymerizable compound (compound described in Table 1 or Table 2) 1.5 g Binder (compound described in Table 1 or Table 2) 2.0 g Photothermal conversion agent (Table 1 or Table 2) Compounds described in Table 2) 0.1 g Polymerization initiator (compounds described in Table 1 or Table 2) 0.2 g Fluorinated nonionic surfactant (Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g ・ Dye in which the counter anion of Victoria Pure Blue BOH is changed to 1-naphthalene sulfonic acid anion 0.04 g ・ Methyl ethyl ketone 10 g ・ Methanol 7 g ・ 2-methoxy-1-propanol 10 g

[0195]

[Table 1]

[0196]

[Table 2]

[0197]

Embedded image

(Addition polymerizable compound in Table 1 or 2) (M-1) pentaerythritol tetraacrylate (M-2) glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer

(Binders in Tables 1 and 2) (B-1) Allyl methacrylate / methacrylic acid / N-isopropylamide copolymer (copolymerization molar ratio: 67/13/20) Acid value (actually measured by NaOH titration) 1.15 meq / g Polymerization average molecular weight 130,000 (B-2) Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio: 83/17) Acid value (actually measured by NaOH titration) 1.55 meq / g Polymerization average molecular weight (B-3) Polyurethane resin which is a condensate of the following diisocyanate and diol: (a) 4,4'-diphenylmethane diisocyanate (b) hexamethylene diisocyanate (c) polypropylene glycol (weight average molecular weight: 10
00) (d) 2,2-bis (hydroxymethyl) propionic acid ((a) / (b) / (c) / (d) copolymer molar ratio: 40/10/1)
5/35) Acid value (actually measured by NaOH titration) 1.05 meq / g Polymerization average molecular weight 45,000

(Comparative Examples 1-4) For comparison, the substrate [A]
Or a known radical having an onium salt structure as a counter anion, for example, sulfonate (—SO ₃ ⁻ ) as a counter anion, other than that represented by the general formula (A) on any surface of the substrate [C]. Polymerization initiator H-
1, H-2, H-3, and H-4 (the structures are as shown below), and the other layers were formed using a photosensitive layer coating solution having the composition shown in Table 2 to form a lithographic printing plate. Master plates were obtained (Comparative Examples 1 to 4).

[0201]

Embedded image

[Exposure and Development] The obtained lithographic printing plate precursor was output at a power of 500 mW, a wavelength of 830 nm, and a beam diameter of 17 μm.
After exposure at a main scanning speed of 5 m / sec using a semiconductor laser of (l / e ² ), a DN3C developer manufactured by Fuji Film Co., Ltd., or a DP-4 developer and a rinse FR-3 (1:
7) Automatic developing machine (Fuji Photo Film Co., Ltd.)
(Manufactured by PS Processor 900VR) and the following evaluation was performed. In addition, which developing solution was used in the developing process is shown in Table 1 or Table 2 above.

[Printing endurance test] R201 manufactured by Roland was used as a printing machine, and G was manufactured by Dainippon Ink Co., Ltd.
EOS-G (N) was used. The printed matter in the solid image area was observed, and the printing durability was examined based on the number of sheets at which the image began to fade. It was represented by a relative ratio where the numerical value (number of sheets) in Comparative Example 1 was 100. The greater the number, the better the printing durability.

[Evaluation of Sensitivity] The lithographic printing plate precursor was set to a wavelength of 83
Exposure was performed with a semiconductor laser emitting infrared light of about 0 to 850 nm. After exposure, developer D from Fuji Photo Film Co., Ltd.
The film was developed with N-3C (diluted with water at a ratio of 1: 2) or Developer DP-4 (diluted with water at a ratio of 1: 8) manufactured by Fuji Photo Film Co., Ltd., and washed with water. The amount of energy required for recording was calculated based on the line width and laser output of the images obtained at these times, the loss in the optical system, and the scanning speed. The smaller the value, the higher the sensitivity. These evaluation results are also shown in Table 1 or Table 2.

From the results shown in Tables 1 and 2, it can be seen that the lithographic printing plate precursor according to the present invention has a high resistance to an alkaline developer in an image area, has excellent printing durability, and has high sensitivity. On the other hand, the lithographic printing plate precursors of Comparative Examples 1, 3, and 4 using a known radical polymerization initiator were compared with each of Examples 1, 8, and 11 obtained under the same conditions except for the polymerization initiator. It was found that both printing durability and sensitivity were poor. Comparative Example 2 using a compound having a carboxylate having a structure not belonging to the scope of the present invention as the counter anion did not form an image.

(Examples 21 to 40, Comparative Examples 5 to 8) Polyvinyl alcohol (degree of saponification: 98) was formed on the photosensitive layers of the lithographic printing plate precursors obtained in Examples 1 to 20 and Comparative Examples 1 to 4.
Mol%, degree of polymerization: 550) in an amount of 2 g / m ² after drying.
After drying for 5 minutes, a lithographic printing plate precursor having a protective layer provided on the photosensitive layer was obtained, and Examples 21 to 40 and Comparative Examples 5 to 8, respectively. The resulting lithographic printing plate precursor was exposed and developed under the same conditions as in Examples 1 to 20 and Comparative Examples 1 to 4 to make a lithographic printing plate. The adhesion and printing durability were evaluated. The results are shown in Table 1 or Table 2 above.

From the results shown in Tables 1 and 2, even when a protective layer was provided on the photosensitive layer, the same tendency as in Examples 1 to 20 having no protective layer was observed. The original plate has high resistance to the alkaline developer in the image area,
It can be seen that the printing durability was excellent and the sensitivity was high, and that the provision of the protective layer further improved both the sensitivity and the printing durability.

(Example 41) The following recording layer coating solution was coated on a polyethylene terephthalate film (0.1 mm thick) as a support so that the coating amount after drying was 2.0 g / m ² , Was obtained. (Recording layer coating solution)-Addition polymerizable compound (M-1) 2.0 g-Binder (B-1) 1.6 g-Acid / radical generator (I-1) 0.4 g-Methyl ethyl ketone 10 g-Methanol 5 g- 10 g of 2-methoxy-1-propanol

The recording material was placed in a 200 ° C. oven for 1 hour.
The recording layer on the heating support was cured by heating for 5 seconds. Thereafter, the recording layer was immersed in dimethyl sulfoxide for 5 minutes, and the insolubilization rate of the recording layer was determined from the amount of the remaining recording layer.
The insolubilization rate was 97%. From this, it was confirmed that the recording layer composed of the heat-sensitive composition of the present invention containing the acid / radical generator represented by the general formulas (A) to (C) was successfully cured by heating. Was done.

[0210] (Comparative Example 9) The recording layer radical generator in the coating solution (I-1): a counter cation Ph-COCOO ^-)
Instead of the pair SbF ₆ as a cation ^- with those containing a radical generating agent having, cured by heating the recording layer in the same manner as in Example 41, was measured insolubilization rate, 1
It showed an insolubilization rate of 4%. It was confirmed that the heat-sensitive composition of the present invention was excellent in sensitivity in comparison with a radical generator having a similar anion moiety.

Example 42 A coating solution for the following recording layer was applied on a polyethylene terephthalate film (thickness: 0.1 mm) as a support so that the coating amount after drying was 2.0 g / m ^2. A yellow transparent recording material was obtained. (Recording layer coating solution)-Oxidizing color dye (leuco crystal violet) 0.2 g-Binder (polymethyl methacrylate) 2.7 g-Acid / radical generator (III-1) 0.3 g-Methyl ethyl ketone 10 g-Methanol 8 g-2 -Methoxy-1-propanol 8g

This recording material was placed in an oven at 200 ° C. for 15 minutes.
The recording layer on the heated support was heated for 2 seconds to develop a color. The recording layer developed a bright blue color. From this, the recording layer comprising the heat-sensitive composition of the present invention containing the acid / radical generator represented by the general formulas (A) to (C) shows that the leuco dye is oxidized and colored by the generation of radicals. It is estimated that

[0213]

According to the heat-sensitive composition of the present invention, irreversible changes in physical properties with high sensitivity can be obtained by heating. In addition, a negative type lithographic printing plate precursor using this heat-sensitive composition can be written by an infrared laser, has a good alkali developing solution resistance in an image area, has excellent printing durability, and has high sensitivity. It works.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA04 AA12 AB03 AC08 AD01 BE07 CA30 CA34 CA48 CB00 CC11 CC20 FA17 4H006 AA01 AA03 AB76 TA04 4J002 AA001 EG016 EV006 EV046 EV206 EV216 EW016 EW026 EZ006 FD146

Claims (5)

[Claims] (I) The following general formulas (A) and (B)
Or a compound that generates an acid or a radical by heat represented by the general formula (C), and (II) an acid or a radical,
A heat-sensitive composition containing a compound whose physical and chemical properties change irreversibly. Embedded image In the formula, X represents a group or a halogen atom shown below. M
⁺ Represents a monovalent cation. Embedded image In the formula, R ¹ and R ² represent a monovalent nonmetal atom which may be the same or different. Embedded image In the formula, Y has the same meaning as X in formula (A), or —O
H, —CN, —NO ₂ , and —Si (R ⁵ ) (R ⁶ ) (R ⁷ ). R ^{3 to} R ⁷ represent monovalent nonmetal atoms which may be the same or different. M ⁺ represents a monovalent cation. Embedded image In the formula, R ⁸ represents a monovalent nonmetal atom. Ar ¹ and Ar ² represent an aryl group which may be the same or different. M ⁺ represents a monovalent cation. 2. The composition further comprises (III) a light-to-heat conversion agent, and (I) by exposure to light having an absorption wavelength of the light-to-heat conversion agent, (I) heat generated by the general formulas (A) to (C). An acid or radical of a compound that generates an acid or radical is generated,
(II) The heat-sensitive composition according to claim 1, wherein the physical or chemical properties of the compound whose physical or chemical properties are irreversibly changed by an acid or a radical are changed. 3. On a support, (I) the following general formula (A):
An acid / radical polymerization initiator represented by the general formula (B) or (C), (III) a photothermal conversion agent, (II-1) a radical polymerizable compound having an unsaturated bond, and (IV) A lithographic printing plate precursor for heat mode, comprising a photosensitive layer containing a binder polymer. Embedded image In the formula, X represents a group or a halogen atom shown below. M
⁺ Represents a monovalent cation. Embedded image In the formula, R ¹ and R ² represent a monovalent nonmetal atom which may be the same or different. Embedded image In the formula, Y has the same meaning as X in formula (A), or —O
Represents _{H, -CN, -NO 2, -Si} (R 5) (R 6) a (R ^7). R ^{3 to} R ⁷ represent monovalent nonmetal atoms which may be the same or different. M ⁺ represents a monovalent cation. Embedded image In the formula, R ⁸ represents a monovalent nonmetal atom. Ar ¹ and Ar ² represent an aryl group which may be the same or different. M ⁺ represents a monovalent cation. 4. A sulfonium salt compound represented by the following general formula (A-1). Embedded image In the formula, Ar ^a-1 , Ar ^a-2 and Ar ^a-3 each independently represent an aryl group, and R ⁹ represents an alkyl group or an aryl group. 5. A sulfo represented by the following general formula (A-2)
Nium salt compounds. Embedded imageWhere R^TenIs a phenyl group or an alkyl having 1 to 4 carbon atoms
Represents a hydroxyl group. R¹¹, R ¹², R¹³Are independently hydrogen sources
, A chlorine atom, a methyl group or a butyl group.