JP2002303983A - Positive type image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type image forming material in which recording with high sensitivity is possible and which is made less liable to a sensitivity change due to moisture in the air and moisture in a system. SOLUTION: The positive type image forming material comprises a polymer matrix containing (A) a compound containing a partial structure of formula (1) and (B) a compound which generates an acid under light or heat. In the formula, R<1> and R<2> are each H, O or an organic group; R<3> and R<4> are each H or an organic residue; R<5> is an organic group; R<6> is a di- or higher valent organic group and may form a double bond with a carbon atom represented by C<1> ; X<1> and X<2> are each -O-, -S- or -N(R)- and may be the same or different; and Nu is a nucleophilic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material, and more particularly, to a positive type image forming material capable of forming an image with high sensitivity and suppressing a change in sensitivity due to the amount of moisture.

[0002]

2. Description of the Related Art As a positive type image forming material for removing an exposed portion by a development process, a system utilizing polarity conversion of naphthoquinonediazide is generally widely used, but there is still room for improvement in terms of sensitivity. Therefore, from the viewpoint of sensitivity, it can be said that a chemical amplification system using a chemical reaction catalyzed by an acid is advantageous. In such a chemically amplified image forming material, the acid generated by exposure functions as a catalyst to amplify the reaction and contribute to the improvement of the solubility of the image forming material in the exposed area, so that the sensitivity is extremely high. System. However, in a system for hydrolyzing acetal, which is widely used as an image forming material of a chemical amplification system, water molecules are required for the reaction, so the reactivity is insufficient, and depending on humidity and the amount of water in the system, There was a problem that the sensitivity fluctuated.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the drawbacks of a positive-type chemically amplified system capable of recording at high sensitivity, and to suppress a change in sensitivity due to humidity and the amount of water in the system. It is to provide a forming material.

[0004]

DISCLOSURE OF THE INVENTION As a result of investigations, the present inventors can solve the above-mentioned problems in the positive-type chemical amplification system by using a compound in which a nucleophilic group is arranged close to an acetal site. That is, the inventors have found that the sensitivity can be improved and the desensitization upon exposure to drying conditions can be eliminated, and the present invention has been completed. That is, the positive image forming material of the present invention contains (A) a compound containing a partial structure represented by the following general formula (1) and (B) a compound that generates an acid by light or heat. It is characterized by comprising a molecular matrix.

[0005]

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Where R¹, R^TwoAre independently hydrogen sources
A hydrogen atom, an oxygen atom or an organic group;^Three, R^FourIs German
Represents a hydrogen atom or an organic residue;^FiveRepresents an organic group
You. These may combine with each other to form a ring. R^Two
Is C¹Is a carbon atom represented by R¹, R⁶Forms a double bond with
When forming, it does not have to be present. Also, R⁶Is divalent
Represents the above organic group,¹And a double bond
A combination may be formed. R¹, R ^Two, R^Three, R^Four, R^Five, R⁶Is
They may combine with each other to form a ring. X¹, X^TwoIs -O
-, -S-, -N (R)-, which are the same or different
May be. Nu represents a nucleophilic group. In addition, the high
Addition of (C) photothermal conversion substance to molecular matrix
High-sensitivity recording by infrared laser
Is possible and is preferable.

In an ordinary chemical amplification system using acetal, the reaction of releasing the interaction by exposure is a two-molecule reaction, and water is essential for the progress of the reaction.
In particular, there is a problem that the sensitivity is lowered when the amount of water is small. The formation is performed, the reaction rate is promoted, and the efficiency of the reaction for releasing the interaction that contributes to the suppression of dissolution in the molecule is increased.In particular, the reaction does not require water, so that regardless of the amount of water, It is considered that sensitivity is achieved. In the light irradiation system,
Since the reaction promoting effect after exposure is high, there is also an advantage that the heating time after exposure for improving sensitivity can be greatly reduced.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The positive image forming material of the present invention comprises (A) a compound having a partial structure represented by the following general formula (1) as an essential component. This compound is characterized in that a nucleophilic group is present close to the acetal site. The acetal moiety having an adjacent nucleophilic group in the present invention refers to a structure represented by the following general formula (1). The following structure may be formed during the matrix formation process, that is, when the image forming material of the present invention is coated with a solvent and dried to form an image forming layer, and a compound having such a structure may be formed in advance. It can be added in advance. In the method of forming the following structure in the system during the matrix formation process, any acetalization reaction such as acetalization with vinyl ether, acetal exchange reaction, acetalization by substitution reaction, etc. can be used, but the method using vinyl ether is a by-product Most preferable because there are few things. In this specification, acetal mainly refers to acetal generally, but also includes one in which an oxygen atom of an acetal is replaced with a hetero atom such as a nitrogen atom or a sulfur atom.

[0009]

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In the formula, R ¹ and R ² each independently represent a hydrogen atom, an oxygen atom or an organic group, R ³ and R ⁴ each independently represent a hydrogen atom or an organic residue, and R ⁵ represents an organic group. Represent. These may combine with each other to form a ring. R ²
May not be present when the carbon atom represented by C ¹ forms a double bond with R ¹ and R ⁶ . R ⁶ represents a divalent or higher valent organic group, and may form a double bond with a carbon atom represented by C ¹ . As one preferred form of R ⁶ ,
A form in which C ¹ and X ¹ are bonded so as to form the following general formula (2), general formula (3) or general formula (4), wherein a nucleophilic atom of Nu and a C ₂ carbon atom However, the general formulas (2) and (4) are located at positions capable of forming a 6-membered ring, and the general formula (3) is located at a position capable of forming a 5-membered ring. Where R ⁷ , R ⁸ , R
⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom or an organic group, and may form a ring with each other. In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ^{4 It} may be bonded to ⁵ to form a ring structure, or may have a polymer structure. Further, from the viewpoint of ease of forming the partial structure (1), at least one of R ⁹ and R ¹⁰ is preferably a hydrogen atom, and more preferably both are hydrogen atoms. R ¹¹ and R ¹² preferably have a cis relationship with each other, and most preferably combine with each other to form an aromatic ring.

[0011]

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Further, among the above, one of the more preferred embodiments of R ⁶ is — (CH ₂ ) _n —. Here, n is preferably 1 or 2, and from the viewpoint of the reaction rate, n is most preferably 1. Also, R
Another more preferred embodiment of ⁶ includes a structure represented by the following general formula (5), wherein R ^{6 ′} is a hydrogen atom or an organic group, and R ¹ and R ^{6 ′} are bonded to each other. The structure forming an aromatic ring is most preferable.

[0013]

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In the general formulas (1) and (2), R
^One of R ³ and R ⁴ is preferably a hydrogen atom from the viewpoint of reactivity, and further, one of them is a methyl group, or one of R ⁵ is R ⁵ from the viewpoint of synthesis suitability.
Is most preferred to form a 6-membered ring by bonding to R ¹ ,
From the viewpoint of solubility of the matrix, at least one of R ² is preferably a polymer chain. R ⁵ is preferably a polymer residue from the viewpoint of solubility change accompanying acetal site decomposition. X ¹ and X ² represent —O—, —S—,
-N (R)-(where R represents a hydrogen atom or an organic group), which may be the same or different. From the viewpoints of stability and synthesis suitability, it is most preferably -O-.

Nu represents a nucleophilic group, and includes, as the nucleophilic atom, an atom having at least one pair of lone electrons on the atom and having at least one hydrogen atom bonded thereto. Refers to a substituent such that the nuclear atom is covalently bonded to the C ¹ carbon atom. Preferably, -OH, -SH, -NHR
(Where R represents a hydrogen atom or an organic group in which the N atom in the structure on the left does not form an amide), and -OH is most preferred from the viewpoint of stability.

The partial structure represented by the general formula (1) is
One or more compounds may be present on the same molecule, and the most preferable form is a compound in which a polymer is crosslinked via a partial structure represented by the general formula (1). be able to. The image forming material of the present invention comprises: (A) a compound having a partial structure represented by the general formula (1); (B) a compound capable of generating an acid by light or heat;
However, it is preferable to use a binder polymer as a material for forming the polymer matrix since it has a film forming ability from the viewpoint of improving the film properties of the image forming material. As the binder polymer that can be used in the formation of the polymer matrix in the present invention, it is possible to use organic polymers in general, but there is a structure in which the partial structure of the general formula (1) is formed in the system during the matrix formation process. In the case of taking, it is preferable to have a partial structure for reacting with an acetalizing reagent to form an acetal structure as shown in the general formula (1). That is, it is preferable to have a functional group that reacts preferentially with the acetalization reagent to form an acetal and a nucleophilic group adjacent thereto.

Any functional group which reacts preferentially with the acetalization reagent to form an acetal may be used, but is preferably -OH from the viewpoint of stability. High primary alcohol (-CH
_2- OH) is most preferred. The functional group forming the acetal and the adjacent nucleophilic group may be the same type of functional group or a different type of functional group, but even in the case of the same type of functional group, both of the adjacent functional groups in the matrix are acetalized. Is low, the partial structure of the present invention (1)
Are formed with priority. The partial structure for forming the acetal structure shown in the partial structure (1) by reacting with the acetalization reagent is not particularly limited as long as it satisfies the above-mentioned conditions. -From the viewpoint of suitability for synthesis, a 1,2-diol structure and a 1,3-diol structure can be cited, and a form in which one hydroxyl group of the diol structure is a primary hydroxyl group has a partial structure (1). Most preferred from the viewpoint of ease of formation.

Reacts with an acetalizing agent to form a partial structure (1)
Is a polymer obtained by polymerizing or copolymerizing a monomer capable of forming a partial structure (1) by reacting with an acetalizing agent, or by reacting with an acetalizing agent by a polymer reaction. A polymer having a partial structure capable of forming the partial structure (1) can be used. There is no particular limitation on the polymer reaction, but it is preferable to use an epoxy ring-opening reaction or an alkylation reaction accompanied by elimination of a leaving group, since the desired structure can be introduced relatively easily. In addition, as the polymer capable of forming the partial structure (1) by reacting with the acetalizing agent, when it is used for a printing plate or a resist, it is often developed using alkaline water. Is preferably soluble in alkaline water. From the viewpoint of image strength, it is most preferable that the compound is water-insoluble and soluble in alkaline water. An example will be given below as a monomer used for a polymer satisfying this condition. This does not limit the monomers that can be used in the present invention, and any monomer that meets the concept of the present invention may be used.

[0019]

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In forming the polymer matrix according to the present invention, other monomers can be used as a copolymerization component in addition to the monomers suitable for acetal formation as described above.

In the present invention, (A) the general formula (1)
The compound having a partial structure represented by the formula (1), forms a ring by an intramolecular reaction with the energy of light exposure, thereby promoting the reaction rate and thereby canceling the interaction that contributes to the suppression of intramolecular dissolution. Is added to realize the chemical conversion. Therefore, even if a small amount, for example, a few weight% or a partial mol% of this partial structure is added to the total solid content of the image forming material, the effects of the present invention such as high sensitivity and suppression of sensitivity fluctuation due to moisture can be obtained. Obtainable. These effects become more remarkable as the added amount increases. However, if the added amount is too large, there is a concern that a problem such as a decrease in film properties may occur, and it is desired as the physical properties of the compound (A) to be used and as an image forming material. The content may be appropriately selected in relation to the performance and the other components used in combination.

The compound constituting the polymer matrix may have a partial structure having no Nu in the general formula (1). In this case, the compound in the compound represented by the general formula (1) may be substituted with Nu. N is the number of moles of the partial structure
₁ , assuming that the number of moles of the partial structure represented by the general formula (1) is n ₂ , n ₂ / (n ₁ + n ₂ )> in the matrix
It is preferably 0.5, and in order to sufficiently exhibit the effects of the present invention, it is preferable that n ₂ / (n ₁ + n ₂ )> 0.7, and n ₂ / (n ₁ + n ₂ ). More preferably> 0.9. When the component (A) is added in advance instead of being formed at the time of preparing the matrix,
In practice, it is most preferred that n ₂ / (n ₁ + n ₂ ) = 1. The compound constituting the polymer matrix includes a partial structure having Nu in the partial structure (1) in one molecule and Nu.
May be a compound having both partial structures having no, or a compound having only one of the partial structures. Based on the total mol number of each partial structure contained in the entire molecular matrix.

When the partial structure (1) is formed at the time of forming the matrix, the molar number of the precursor of the partial structure (1) in the matrix is n ₃ , and the portion having no Nu in the general formula (1) is Assuming that the number of moles of the structural precursor is n ₄ , at least n ₃ / (n ₃ +
n ₄ )> 0.1, and n ₃ / (n ₃ + n ₄ )> 0.
3, preferably n ₃ / (n ₃ + n ₄ )> 0.5
Is more preferable. Here, the partial structure (1)
Is a partial structure containing Nu which can react with the acetalizing agent to form the partial structure (1), and is a precursor of the partial structure having no Nu in the general formula (1). The body is defined as a partial structure that reacts with the acetalizing agent to form an acetal structure but cannot form the partial structure (1).

When an aqueous alkali solution is used as a developer after exposure of the image forming material of the present invention, it is preferable to copolymerize a monomer having an acid group in order to improve the solubility in the aqueous alkali solution. At this time, the ratio of the copolymerizable component is preferably in the range of 5 to 50% by weight. Further, an acid group may be introduced into the polymer by deprotection after the polymerization reaction. As the acid group, those having a pKa <14 are preferable, and more preferable examples include the following.

[0025]

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As the acetalization reagent used when the partial structure of the general formula (1) is formed in the system during the matrix formation process, any commonly used acetalization reagent can be used.
It is preferable to use a compound having a vinyl ether group, a tetrahydropyranyl group, or a 1-haloalkyl ether group. As a more preferred embodiment, there can be mentioned an embodiment in which a crosslinked structure is formed in a binder polymer by using an acetalization reagent having two or more functional groups in a molecule as described above. Examples of such compounds include, for example, those described in paragraphs [0036] to [0051] of JP-A-8-220755, (II-1) to (II-4).
Compounds containing an enol ether group described as the compounds represented by 1) can be mentioned as suitable compounds. By forming a crosslinked structure in the polymer matrix, the binder can be insolubilized in the developer and a strong film can be formed. Examples of the acetalization reagent suitable for the present invention are described below, but may be freely selected within a range not to impair the gist of the present invention.

[0027]

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Another essential component of the image forming material of the present invention is (B) a compound capable of generating an acid by light or heat (hereinafter, appropriately referred to as an acid generator). Since the image forming material according to the present invention utilizes an acetal decomposition reaction using an acid generated by energy ray irradiation as a catalyst, it is necessary to include (B) an acid generator satisfying such a function. As the acid generator (B) that can be used in the present invention, all compounds that generate an acid upon irradiation with energy rays can be used. Here, the acid refers to an acid having a strength capable of acting as a catalyst for acetal hydrolysis, and has a pKa <3.
Are preferred, and the most preferred examples are sulfonic acids. Preferred examples of the acid generator used in the present invention are shown below, but the invention is not limited thereto.

[0029]

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In the present invention, in addition to the above-described acid generators, a compound capable of generating an acid by being decomposed by light or heat, that is, by irradiation with infrared rays or heating at 100 ° C. or more can be arbitrarily selected. Can be used. Other acid generators suitably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. Specifically, US
Compounds described in US Pat. No. 4,708,925 and JP-A-7-20629 can be mentioned. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable. Examples of the diazonium salt include diazonium compounds described in U.S. Pat. No. 3,867,147, diazonium compounds described in U.S. Pat. No. 2,632,703 and JP-A-1-102456 and JP-A-1-102457. The diazo resin described in the gazette is also preferable. US 5,135,83
Benzyl sulfonates described in No. 8 and US Pat. No. 5,200,544 are also preferable. Further, Japanese Patent Laid-Open No. 2-1
00005, JP-A-2-100055 and Japanese Patent Application No. 8
Active sulfonic acid esters and disulfonyl compounds described in No. -9444 are also preferable. In addition, JP-A-7
Also preferred are haloalkyl-substituted S-triazines described in -271029. Further, Japanese Unexamined Patent Application Publication No.
JP-A-2202072, compounds described as "acid precursors" or JP-A-9-171254
In the publication, compounds described as “(a) compounds capable of generating an acid upon irradiation with actinic rays” and the like can also be applied as the acid generator of the present invention.

These acid generators are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 4% by weight, based on the total solid content of the image forming material.
0% by weight, more preferably 0.5 to 30% by weight is added to the layer. If the amount is less than 0.01% by weight, no image can be obtained. If the amount exceeds 50% by weight, the non-image area may be stained during printing.

The image forming material of the present invention can form an image by exposing and heating using various light sources (heat sources) depending on the use. As the light source (heat source) used for image formation, any energy source such as light, heat, and electron beam can be used as long as the acid generator is a light source or a heat source capable of decomposing by exposure or heating to generate an acid. It is possible to In the image forming step using the image forming material of the present invention, a step of promoting the decomposition reaction by heating after exposure may be included.

In a system in which light is used for imagewise writing in image formation, this heating step allows the acetal decomposition reaction to proceed sufficiently to clearly define the discrimination between exposed and unexposed portions. . When a heat source is used for image formation, an acid and heat coexist, so that an acetal decomposition reaction sufficiently proceeds, and a post-heating step after imagewise exposure or heating can be omitted.
In addition, when recording is performed by exposure, by including the photothermal conversion agent (C) in the image forming material, heat is generated in the exposed portion, and the post-heating step is performed in the same manner as when recording is performed by heat. It can be omitted. Further, in the system to which the photothermal conversion agent (C) is added, since a light source such as an infrared laser can be used for recording, there is also an advantage that an image with higher resolution can be formed.

The photothermal conversion agent (C) that can be used in the present invention is not particularly limited as long as it has a function of absorbing light of a predetermined wavelength and converting it into heat. Can be used, but the wavelength of the light source used for writing, generally, the wavelength of the infrared laser, that is,
Having an absorption maximum at a wavelength of 760 nm to 1200 nm,
Dyes or pigments known as so-called infrared absorbers are preferred.

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

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

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

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

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

[0040]

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

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

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

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

The pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing lake pigments,
Azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.
Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

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

When these light-to-heat converting agents are added, the amount of addition is preferably 1 to 20% by weight based on the total solid content of the image forming material.
And more preferably 2 to 10% by weight. If the ratio is out of this range, the sensitivity to exposure with an infrared laser tends to decrease.

[Other Components] As other components of the image recording material of the present invention, various known components of the image recording material recordable with active radiation such as ultraviolet rays and infrared rays can be appropriately selected and used. . In the image forming material of the present invention,
Further, various additives can be added as needed. For example, other onium salts, aromatic sulfone compounds,
It is preferable to add an aromatic sulfonic acid ester compound, a polyfunctional amine compound, or the like, because the function of inhibiting the dissolution of the alkali water-soluble polymer in the developer can be improved.

Examples of the onium salt include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like. The onium salt is preferably added in an amount of 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight, based on the total solids constituting the image forming material. preferable.

Further, in order to further improve the sensitivity,
Cyclic anhydrides, phenols, and organic acids can be used in combination. As the cyclic acid anhydride, US Pat.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride described in US Pat. No. 5,128;
3,6-Endoxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone,
4,4 ', 4 "-trihydroxytriphenylmethane,
4,4 ', 3 ", 4" -tetrahydroxy-3,5
3 ', 5'-tetramethyltriphenylmethane and the like. Further, as the organic acids, JP-A-60-88
No. 942, JP-A-2-96755 and the like, sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, carboxylic acids and the like. The proportion of the above cyclic acid anhydride, phenols and organic acids in the image forming material is,
The content is preferably 0.05 to 20% by weight, more preferably 0.1 to 20% by weight.
It is 1 to 15% by weight, particularly preferably 0.1 to 10% by weight.

Other than these, epoxy compounds,
Vinyl ethers, and further, a crosslinkable compound having an alkali dissolution inhibiting action described in Japanese Patent Application Laid-Open No. 11-160860 previously proposed by the present inventors can be appropriately added according to the purpose.

Further, in the image forming material of the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to widen the stability of processing under development conditions.
Non-ionic surfactants described in JP-A-59-121044, JP-A-4-13149.
An amphoteric surfactant such as that described in JP-A No. 2-211 can be added.

In the image forming material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure,
Dyes and pigments as image colorants can be added.
Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. In particular,
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53-36223, 54-74728, 6
No. 0-3626, No. 61-143748, No. 61-1
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-51644 and JP-A-63-58440 can be exemplified. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the colorant for the image, other dyes can be used in addition to the above-mentioned salt-forming organic dye. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink #
312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), ethyl violet, rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Also, JP-A-62-2932
The dyes described in JP-B-47 are particularly preferred. These dyes are used in an amount of 0.01 to 1 based on the total solid content of the image forming material.
0% by weight, preferably 0.1 to 3% by weight can be added to the image forming material. Further, a plasticizer is added to the image forming material of the present invention, if necessary, in order to impart flexibility and the like to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers are used.

A lithographic printing plate precursor is prepared by dissolving a coating solution for a recording layer containing the image forming material of the present invention or a coating solution component for a desired layer such as a protective layer in a solvent and coating the solution on a suitable support. Can be manufactured. As the solvent used herein, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene,
Water and the like can be mentioned, but it is not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but generally 0.5 to 5.0 g / m ² is preferred for a photosensitive printing plate. As a method of applying, various methods can be used, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Roll coating and the like can be mentioned. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the recording layer deteriorate.

In the coating solution for the recording layer using the image recording material of the present invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950. Surfactants can be added. The preferred addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight of the whole image forming material.

Examples of the support used when the image forming material of the present invention is used as a lithographic printing plate precursor include a dimensionally stable plate-like material. Examples of the support include paper and plastic (eg, polyethylene and polypropylene). , Polystyrene, etc.) laminated paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film on which a metal is laminated or vapor-deposited as described above.

As the support used for the lithographic printing plate precursor, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate having good dimensional stability and relatively low cost is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and 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 the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element.
As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1
mm to 0.6 mm, preferably 0.15 mm to 0.1 mm.
4 mm, particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. The surface roughening treatment of the surface 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. As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment, if desired, in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming 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 cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat. Nos. 2,7,7
No. 14,066, No. 3,181,461, No. 3,2
There is an alkali metal silicate (e.g., sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 80,734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868 and 4,153,46.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in JP-A Nos. 1 and 4,689,272 is used.

The lithographic printing plate precursor is provided with a recording layer containing the image forming material of the present invention on a support. An undercoat layer may be provided between the recording layer and the lithographic printing plate precursor, if necessary. Various organic compounds are used as the undercoat layer component, for example,
Carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, and methylene diphosphonic which may have a substituent Acids and organic phosphonic acids such as ethylene diphosphonic acid, optionally substituted phenylphosphoric acid, naphthyl phosphoric acid, organic phosphoric acids such as alkylphosphoric acid and glycerophosphoric acid, optionally substituted phenylphosphinic acid Organic phosphinic acids such as naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine. Mixed two or more It may be used in. Also, Japanese Patent Application Laid-Open
A polymer compound containing a unit that interacts with an alumina layer and a unit that interacts with a hydrophilic treatment layer described in JP-A-1099641 can also be suitably used.

The lithographic printing plate precursor prepared as described above is usually subjected to image exposure and development processing, and an image is formed to form a lithographic printing plate. Here, as a material used for image formation, a heat source such as a thermal head or a light source for actinic rays can be cited. Examples of the plateau include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp and the like. As radiation,
There are electron beams, X-rays, ion beams, far infrared rays, and the like. In addition, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are also used. Examples of the laser beam include a helium / neon laser, an argon laser, a krypton laser, a helium / cadmium laser, a KrF excimer laser, a solid laser, and a semiconductor laser. When the image forming material of the present invention is a heat mode-compatible material containing a photothermal conversion agent, a solid-state laser or semiconductor laser that emits infrared light having a wavelength of 720 to 1200 nm is preferably used as an exposure light source. Solid-state lasers and semiconductor lasers, which are light sources having emission wavelengths in the infrared region to the infrared region, are particularly preferred.

When preparing a lithographic printing plate, development processing may be performed immediately after exposure, or heat treatment (post-heating) may be performed between the exposure step and the development step. When performing the heat treatment, the conditions are 40 ° C. to 200 ° C., preferably 50 to 1 ° C.
80 ° C, more preferably within the range of 60 to 150 ° C,
It is preferably performed for 2 seconds to 10 minutes, preferably for 5 seconds to 5 minutes. As a heating method, various conventionally known methods can be used. For example, a method of heating while contacting the recording material with a panel heater or a ceramic heater,
And a non-contact heating method using a lamp or warm air. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

As a developer and a replenisher used in the development step after exposing the lithographic printing plate precursor, conventionally known alkaline aqueous solutions can be used. For example,
Sodium silicate, potassium silicate, sodium phosphate tribasic, potassium phosphate tribasic, ammonium phosphate tribasic,
Dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, hydroxide And inorganic alkali salts such as sodium, ammonium hydroxide, potassium hydroxide and lithium hydroxide. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkali agents are used alone or in combination of two or more. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is silicon oxide SiO ₂ and alkali metal oxides are components of the silicate
This is because developability can be adjusted by the ratio and concentration of M ₂ O. For example, JP-A-54-62004 discloses
The alkali metal silicate described in JP-B-57-7427 is effectively used.

Further, when developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of PS plates can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. This replenishment system is also preferably applied in the present invention. To the developing solution and the replenishing solution, various surfactants and organic solvents can be added as necessary for the purpose of promoting or suppressing the developing property, dispersing the developing residue and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, the developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcinol, sulfurous acid, and bisulfite, and an organic carboxylic acid, an antifoaming agent, and a water softener. Can be added. The printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As a post-process when the image recording material of the present invention is used as a printing plate, these processes can be used in various combinations.

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

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired, but when it is desired to obtain a lithographic printing plate having higher printing durability. Is subjected to a burning process. When the lithographic printing plate is subjected to a burning process, before the burning process, Japanese Patent Publication Nos. 61-2518 and 55-28062,
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 62-31859 and 61-159655. As a method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied on a lithographic printing plate, or a method in which the printing plate is immersed in a vat filled with the surface conditioning solution and applied, Application by an automatic coater or the like is applied. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application.

The coating amount of the surface conditioning liquid is generally 0.03 to 0.8.
g / m ² (dry weight) is appropriate. The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then burned (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: "BP-130").
0 "). The heating temperature and time in this case depend on the type of the component forming the image,
The temperature is preferably in the range of 180 to 300 ° C. for 1 to 20 minutes.

The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming if necessary. 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 set on an offset printing machine or the like and used for printing a large number of sheets.

[0073]

EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited to these examples. (Examples 1 and 2 and Comparative Examples 1 and 2) The following coating solution for an image forming layer was coated on an aluminum support using a wire bar and dried at 120 ° C. for 6 minutes to obtain a lithographic printing plate precursor. The coating amount after drying was about 1.3 g / m ² .

(Coating solution for image forming layer) Binder polymer (compound shown in Table 1) 0.67 g Vinyl ether A (structure shown below) 0.05 g Infrared absorbent IR-1 (structure shown below) 0.06 g Acid Generator NSH-1 (structure below) 0.12 g-Fluorosurfactant (Megafac F177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.006 g-Ethyl violet 0.007 g-Methyl ethyl ketone 3.7 g-Methanol 2 3.9 g 1-methoxy-2-propanol 3.9 g

[0075]

[Table 1]

[0076]

Embedded image

[0077]

Embedded image

The lithographic printing plate precursor obtained using the image-forming material of the present invention was exposed to light at an exposure amount shown in Table 1 using Trendsetter 3244 (manufactured by Creo Corporation), and DN-3C was used.
(Developer made by Fuji Photo Film, 1: 2 dilution in water) or DT-1 (Developer made by Fuji Photo Film, 1: 8 dilution in water). The image formed after the development was visually evaluated, and the presence or absence of a residual film was examined. The results are shown in Table 1 above.

As is clear from the results in Table 1, the image forming materials using the binder polymers 1 and 3 having an acetal structure having an adjacent nucleophilic group shown in the present invention are as follows.
As compared with the conventional one using binder polymers 2 and 4 having an acetal structure, a good image with no residual film was formed at the same exposure dose, and it was confirmed that the sensitivity was high.

(Evaluation of Stability Over Time) Further, the obtained lithographic printing plate precursor was stored at 60 ° C. and a humidity of 40% for 3 days, and the same evaluation was performed. At this time, the image forming property was compared with the image forming property immediately after application, and how it changed was visually evaluated. As a result, no change was observed in image formability in the lithographic printing plate precursor using the image forming material of the present invention, but in the lithographic printing plate precursor of Comparative Example, the state of the residual film was further deteriorated. Was observed. As a result, the lithographic printing plate precursor according to the present invention does not fluctuate in sensitivity and image formability even when stored under high temperature and high humidity, does not show a decrease in image formability due to the amount of water, and exhibits stability over time. It turned out to be excellent.

(Example 3, Comparative Example 3: Example of Ultraviolet Exposure Type) On the same aluminum support as used in Example 1,
The following image forming layer coating solution 2 was applied using a wire bar and dried at 100 ° C. for 10 minutes to obtain a lithographic printing plate precursor. (Image forming layer coating solution 2)-Binder polymer (compound shown in Table 2) 2.0 g-Vinyl ether B (the following structure) 0.16 g-Photoacid generator PAG-1 (the following structure) 0.15 g-Victoria Pure Blue naphthalene sulfonate 0.02 g ・ Fluorine surfactant (Megafac F176PF (2% aqueous solution) manufactured by Dainippon Ink and Chemicals, Inc.) 0.165 g ・ Methyl ethyl ketone 8.06 g ・ Methanol 6.34 g ・ 1- 13.1 g of methoxy-2-propanol

The obtained lithographic printing plate precursor was adjusted to a density difference of 0.1
5 with the gray scale in close contact with the eye rotary printer RP-311 (Eye Graphics Co., Ltd.)
For 20 seconds. After exposure, heat treatment was performed at 120 ° C for 3 minutes, and DN-3C manufactured by Fuji Photo Film Co., Ltd.
(1: 2 water dilution) Development was performed using a developer. As the index of the sensitivity, the number of steps at which the exposed portion was cleared in a gray scale was used. In addition, the same lithographic printing plate precursor was placed at 60 ° C and a humidity of 4 ° C.
It was stored for 3 days under 0%, and the sensitivity was evaluated in the same manner. These results are also shown in Table 2 below.

[0083]

[Table 2]

[0084]

Embedded image

As is apparent from Table 2, the image forming material using the binder polymer 1 according to the present invention has higher sensitivity and sensitivity than the conventional one using the binder polymer 2 having an acetal structure. It was confirmed that the aging stability was excellent.

(Example 4, Comparative Example 4) The following image forming layer coating solution 3 was applied to the same aluminum support as used in Example 1 using a wire bar, dried at 120 ° C. for 1 minute, and subjected to lithography. A printing plate was obtained. The coating amount after drying is about 1.3
g / m ² . (Image forming layer coating solution 3)-Binder polymer (compound shown in Table 3) 0.72 g-Acid generator NSH-1 0.1 g-Infrared absorber IR-1 0.06 g-Fluorinated surfactant (mega) FAX F177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g ・ Ethyl violet 0.007 g ・ Methyl ethyl ketone 3.7 g ・ Methanol 2.9 g ・ 1-Methoxy-2-propanol 3.9 g

The obtained image-forming material was exposed to light using a trend setter 3244 (manufactured by Creo Corporation) while changing the amount of exposure, and the amount of exposure capable of forming a good image was measured and used as a measure of sensitivity. Thereafter, development was carried out using a DT-1 1: 8 water dilution solution (developing solution manufactured by Fuji Photo Film), and the obtained images were visually evaluated for residual films. Also, the same lithographic printing plate precursor was stored at 60 ° C. and a humidity of 40% for 3 days,
The sensitivity was evaluated in the same manner. These results are also shown in Table 3 below.

[0088]

[Table 3]

[0089]

Embedded image

As is clear from Table 3, the image forming material using the binder polymer 5 according to the present invention has higher sensitivity and lower sensitivity than the conventional one using the binder polymer 6 having an acetal structure. It was confirmed that the aging stability was excellent. Furthermore, the binder polymer 5 used in the present example is a polymer having the partial structure (1) according to the present invention in advance, and therefore, a chemical reaction is generated as compared with the system that forms the partial structure (1) when forming the matrix. Since there is no need to perform the above, there is an advantage that the same excellent effect can be obtained even if the coating and drying time is shortened.

(Example 5, Comparative Example 5) The following image forming layer coating solution 4 was applied to the same aluminum support as used in Example 1 using a wire bar, dried at 120 ° C. for 6 minutes, and lithographically processed. A printing plate was obtained. The coating amount after drying is about 1.3
g / m ² . (Image forming layer coating solution 4) Novolak resin (m: p = 6: 4 cresol novolak, Mw = 5000) 0.6 g Acetal additive (compound described in Table 4) 0.2 g Acid generator NSH- 2 (the following structure) 0.06 g ・ Infrared absorber IR-1 (the following structure) 0.05 g ・ Fluorine-based surfactant (MegaFac F177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g ・ Ethyl violet 0 0.0007 g-Methyl ethyl ketone 3.7 g-Methanol 2.9 g-1-methoxy-2-propanol 3.9 g

The planographic printing plate precursors were evaluated in the same manner as in Examples 1 and 2. The results are shown in Table 4 below.

[0093]

[Table 4]

[0094]

Embedded image

As is evident from Table 4, similar results were obtained when an image forming material was added with a low molecular weight additive having an acetal structure, and the image forming material had an acetal structure having an adjacent nucleophilic group. It was confirmed that the image forming material using the acetal additive A was higher in sensitivity and more excellent in the aging stability of the sensitivity than the conventional one using the acetal additive B having an acetal structure.

[0096]

According to the present invention, it is possible to provide a positive-type image forming material capable of recording with high sensitivity and suppressing sensitivity fluctuation due to humidity and the amount of water in the system.

Continued on the front page F term (reference) 2H025 AA01 AA11 AB03 AC08 AD03 BE00 BE10 BG00 CB08 CB14 CB41 CC11 CC17 FA17 2H096 AA06 BA11 EA03 EA04 GA08

Claims (2)

[Claims] 1. An image formation comprising a polymer matrix containing (A) a compound having a partial structure represented by the following general formula (1) and (B) a compound which generates an acid by light or heat. material. Embedded image R ¹ and R ² each independently represent a hydrogen atom, an oxygen atom or an organic group, R ³ and R ⁴ each independently represent a hydrogen atom or an organic residue, and R ⁵ represents an organic group. These may combine with each other to form a ring. R ² may not be present when the carbon atom represented by C ¹ forms a double bond with R ¹ and R ⁶ . R ⁶ represents a divalent or higher valent organic group, and may form a double bond with a carbon atom represented by C ¹ . R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may combine with each other to form a ring. X ¹ and X ² represent —O—, —S—, and —N (R) — and may be the same or different. Nu represents a nucleophilic group. 2. The image forming material according to claim 1, wherein the polymer matrix further contains (C) a photothermal conversion substance.