JP4397191B2 - Image forming composition and photosensitive lithographic printing plate using the same - Google Patents

Description

  The present invention relates to a novel image forming composition and further relates to a lithographic printing plate using the same. In particular, the present invention relates to an image forming composition for a negative lithographic printing plate for direct plate making which can be directly made from a digital signal such as a computer.

In recent years, there has been a demand for a lithographic printing plate capable of directly making a plate from a digital signal of a computer or the like using an infrared laser. As such an image recording material that can be recorded with an infrared laser, there is a recording material described in Patent Document 1 composed of an onium salt, a resole resin, a novolac resin, and an infrared absorber. However, plate materials using these image recording materials have the problem that stains occur in non-image areas when image formation and printing are performed after long-term storage, particularly storage at high temperatures and high humidity. Yes. As a result, development defects are likely to occur, and an immediate improvement is desired. Further, when the above materials are used, there is no difference in solubility in the developer in the image area and the non-image area, that is, there is no developer stability (development latitude), and the film strength of the image area is insufficient. There were many problems, such as the ease of scratching during development (scratch resistance) and insufficient printing durability during printing.
Japanese Patent No. 3362078

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an image forming composition having high storage stability at high temperature and high humidity and excellent sensitivity to the infrared region, and a photosensitive lithographic printing plate using the same. More preferably, the object of the present invention is that the difference in solubility in the developing solution between the exposed portion and the unexposed portion is large, that is, the stability to the developing solution (developing latitude) is excellent, and the treatment m ^{2 is performed on the} developing solution. Another object of the present invention is to provide a negative type image-forming composition having a large scratch resistance and high printing durability and a negative photosensitive lithographic printing plate using the same.

According to the present invention, (A) an alkali-soluble copolymer containing a monomer unit represented by the following general formula (I) and / or (II), (B) an acid generator, (C) an infrared absorber, (D) an alkali-soluble novolak resin, and (E) a diamine compound represented by the general formula (III), methylene bis (2-chloroaniline), methylene bis (2-ethyl 6-methylaniline), methylene bis (2,3-dichloro) Aniline), 5,5′-methylenebis (anthranilic acid), 2,2′-dimethyl-4,4′-diaminobiphenyl, or 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl , good Mashiku further (F) the general formula (IV), the image-forming composition containing represented by the polymer compound (V), and photosensitive lithographic printing on a support formed by providing an image forming composition Edition It is provided.

[In the general formula (I), R ¹ represents a hydrogen atom, a methyl group, a chlorine atom or a cyano group. R ² represents an alkyl group or an aryl group.
In general formula (II), R ³ represents a hydrogen atom, a methyl group, a chlorine atom or a cyano group. R ⁴ and R ⁵ each independently represents an alkyl group or an aryl group. k is an integer of 1 or more.
In the general formula (III), R ^{6 to} R ¹³ are each independently hydrogen, a C _{1 to} C ₁₂ alkyl group, a halogen atom, OH, COOH , or C _m F _{2m + 1} (m is 1 to It is an integer of 12.) n is an integer of 0 or more. T represents —COO—, —SO ₂ — , or —O—. ]

(In the general formula (IV), Polym represents a polymer in which Polym-OH is a resin having a phenolic hydroxyl group. G ¹ represents O or COO. R ¹⁴ and R ¹⁵ independently represent a hydrogen atom or methoxy. R ¹⁴ and R ¹⁵ may be bonded to form an alkylenedioxy group to form a ring, and R ¹⁶ represents a side chain of the hydrocarbon group. A represents an m-ethylene group which may have, wherein a is an integer of 3 or more, R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a methyl group or an ethyl group;
In the general formula (V), Polym represents a polymer in which Polym-OH is a resin having a phenolic hydroxyl group. G ² represents O or COO. R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group. R ¹⁸ represents b methylene groups which may have a hydrocarbon group side chain. Here, b is an integer of 3 or more. R ²¹ and R ²² independently represent a methyl group, a hydroxyl group or a chlorine atom. )

As will be described in detail below, the lithographic printing plate provided with the image forming composition according to the present invention has no stain on the non-image area even when stored at high temperature and high humidity, has excellent storage stability, and infrared rays. It is an excellent printing plate for direct plate making with high sensitivity to the area. Furthermore, the negative type image forming composition according to the present invention and the negative type photosensitive lithographic printing plate using the same include a polymer compound represented by the general formulas (IV) and (V), thereby developing latitude. The process m ² for the developer, scratch resistance, and printing durability are also excellent.

Hereinafter, the present invention will be described in more detail. The image forming composition according to the present invention comprises (A) an alkali-soluble copolymer containing a monomer unit represented by the following general formula (I) and / or (II), (B) an acid generator, (C ) An infrared absorber, (D) an alkali-soluble novolak resin, and (E) a diamine compound . The components of the image-forming composition of the present invention will be described in detail later. The alkali-soluble copolymer (A) containing the monomer unit represented by the general formula (I) and / or (II) of the present invention (A) It has been revealed that the image-forming composition containing) has high water resistance and good storage properties.

Further, the scope of the present invention should not be limited by theory, but the present invention is considered to have excellent development latitude by the following mechanism. That is, when the image forming composition is irradiated with infrared rays such as a semiconductor laser, the infrared absorbent can instantaneously generate heat of, for example, several hundred degrees by absorbing this light. The acid generator can be decomposed to generate an acid by the generated heat or the like. The alkali-soluble copolymer (A) of the present invention is represented by the general formula (I) (II) by the heat from the infrared absorber (C) thus generated and the acid from the acid generator (B). Decomposes at the isocyanate group. Furthermore, between the decomposition product of the alkali-soluble copolymer (A) containing the polymer main chain and the diamine compound (E) and / or the alkali-soluble novolak resin (D), a portion of the decomposed isocyanate group A cross-linking reaction occurs. Thereby, the alkali-soluble copolymer (A) is considered to be insoluble in an alkaline developer or the like. On the other hand, the unexposed area is easily dissolved in the developer due to the effect of these alkali-soluble copolymers, and as a result, the difference in solubility widens.

Further, preferably, by containing the polymer compound (F) of the general formula (IV) and / or (V), the processing m ² number for the developer is also improved, and the stability (development latitude) for the developer is improved. The present invention has been found by remarkably spreading and improving scratch resistance and printing durability.

  In the present invention, the copolymer used as the component (A) is an alkali-soluble copolymer containing a monomer unit represented by the general formula (I) and / or (II). Here, alkali-soluble means that when this copolymer is used as the component (A) of the image-forming composition, the copolymer in the unexposed area can be substantially completely dissolved in the alkaline developer. Say. Specifically, for example, at room temperature, it is preferable that 0.5 g or more of a copolymer can be dissolved in a 0.2 M potassium hydroxide aqueous solution, and it is more preferable that 1.0 g or more of a copolymer can be dissolved. .

Although not particularly limited, in the general formula (I), when R ² is an alkyl group, examples of R ² include groups having 2 to 12 carbon atoms such as ethyl, n-butyl, and n-hexyl. When R ² is an aryl group, examples of R ² include groups having 6 to 15 carbon atoms such as phenyl, 3-methoxyphenyl, chlorophenyl, and p-toluenesulfonyl.

  Examples of the compound giving the monomer unit represented by the general formula (I) include ethyl (carb) ethylcarbamate (meth) acrylate, ethyl n-butylcarbamate (meth) acrylate, and ethyl n-dodecylcarbamate (meth). Acrylate, ethyl laurylcarbamate (meth) acrylate, ethyl n-hexylcarbamate (meth) acrylate, ethyl cyclohexylcarbamate (meth) acrylate, ethyl phenylcarbamate (meth) acrylate, ethyl 4-chlorophenylcarbamate ( (Meth) acrylate, ethyl m-chlorophenylcarbamate (meth) acrylate, ethyl 3-methoxyphenylcarbamate (meth) acrylate, ethyl p-toluenesulfonylcarbamate (meth) acrylate, p-tolylfe , And the like Rukarubamin ethyl (meth) acrylate. As the compound giving the monomer unit represented by the general formula (I), commercially available compounds can be used, or they can be synthesized by methods known to those skilled in the art. In addition, in this specification, (meth) acrylate shall represent an acrylate and / or a methacrylate. Similarly, (meth) acrylamide shall represent acrylamide and / or methacrylamide.

Further, although not particularly limited, in the general formula (II), when R ⁴ and R ⁵ are alkyl groups, R ⁴ and R ⁵ may be methyl, ethyl, n-butyl, n-hexyl, etc. It includes groups having 1 to 12 carbon atoms, when R ^4, R ⁵ is an aryl group, as R ^4, R ^5, phenyl, 3-methoxyphenyl, chlorophenyl, such as p- toluenesulfonyl number 6 to 15 carbon Groups. Preferably, k is 1 to 12, more preferably 1 to 10.

  As a compound which gives the monomer unit represented by the general formula (II), for example, 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 2- (O— [methacrylate] 1'-ethylpropylideneamino] carboxyamino) ethyl, 2- (O- [1'-butylpropylideneamino] carboxyamino) ethyl methacrylate, 2- (O- [1'-methylpropylideneamino] methacrylate Carboxyamino) methyl and the like. In addition, the compound which gives the monomer unit represented by these general formula (II) can use a commercially available thing, or can also synthesize | combine by a method well-known to those skilled in the art.

The alkali-soluble copolymer used as the component (A) in the present invention is exemplified by the monomer represented by the general formula (I) and / or (II) and the following (1) to (9). A copolymer with another monomer may be sufficient and it can also be set as the alkali-soluble copolymer which has a phenolic hydroxyl group.
(1) Monomers having a phenolic hydroxyl group, such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, N- (p-hydroxyphenyl) maleimide, p-isopropenylphenol, o -, M- or p-hydroxystyrene, o-, m- or p-hydroxyphenyl acrylate, or o-, m- or p-hydroxyphenyl methacrylate.
(2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, or 2-hydroxy-3-phenoxypropyl methacrylate.
(3) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride.
(4) Monomers having an allyl group such as allyl methacrylate and N-allylmethacrylamide.
(5) Alkyl acrylates or alkyl methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, and glycidyl acrylate.
(6) Acrylamides or methacrylamides, for example, (meth) acrylamide, N-methylol (meth) acrylamide, N-ethyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-cyclohexyl (meth) Acrylamide, N-hydroxyethyl (meth) acrylamide, or N-phenyl (meth) acrylamide.
(7) Styrenes such as styrene, α-methylstyrene, chloromethylstyrene.
(8) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.
(9) Urethane (meth) acrylate, for example, polyether type urethane (meth) acrylate, polyester type urethane (meth) acrylate. Commercially available products include Aronix M-305, M-1310, M-315, M-360, M-1600 (manufactured by Toa Gosei Co., Ltd.), UA-7100, UA-7200, UA-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) And UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.).

  Furthermore, the alkali-soluble copolymer is composed of the above monomers (monomers represented by the general formulas (I) and / or (II) and other monomers exemplified in the above (1) to (9)). It may be a copolymer with a monomer other than those mentioned above that can be copolymerized with (A). Moreover, the alkali-soluble copolymer may be obtained by modifying an alkali-soluble copolymer obtained by copolymerization of the above monomers with, for example, glycidyl methacrylate.

  In the alkali-soluble copolymer (A) used in the composition of the present invention, the monomer represented by the general formula (I) and / or (II) may be used alone, or two or more types may be used. You may use it in combination. In addition, the alkali-soluble copolymer preferably includes a monomer represented by the general formula (I) and / or (II) in a total range of 5 to 100 mol%, and is preferably 20 to 100 mol%. Those included in the range are more preferable. When the content is 5 mol% or more, particularly 20 mol% or more, the effect of improving scratch resistance and printing durability according to the present invention is particularly high. When the content is 100 mol% or less, alkali developability is good and practical.

  There is no restriction | limiting in particular about the manufacturing method of the said alkali-soluble copolymer, It can manufacture similarly to the manufacturing method of a normal acrylic copolymer. For example, a desired alkali-soluble copolymer can be obtained by dissolving each monomer component in a suitable solvent, adding a conventionally used radical polymerization initiator, heating as necessary, and performing polymerization. it can. The alkali-soluble copolymer thus obtained has a polystyrene calculated weight average molecular weight of preferably 10,000 to 200,000, more preferably 20,000 to 150,000, as measured by gel permeation chromatography (GPC). Are used. When the weight average molecular weight is 10,000 or more, particularly 20,000 or more, swelling of the image portion or insufficient mechanical strength is not particularly likely to occur, and when it is 200,000 or less, particularly 150,000 or less, contamination due to poor development is particularly difficult to occur. Therefore, it is preferable.

  Although not particularly limited, the solvent used for the polymerization of the alkali-soluble copolymer includes methyl cellosolve, propylene glycol monomethyl ether, dioxane, methyl ethyl ketone, N, N-dimethylformamide, N, N- Examples include dimethylacetamide. Examples of the radical polymerization initiator used for the polymerization of the copolymer include azobisisobutyronitrile and benzoyl peroxide. Although not particularly limited, the amount of the solvent is preferably 2 to 10 g with respect to 1 g of the monomer. Moreover, the addition amount of the radical polymerization initiator is preferably 0.1 to 1.0% by weight with respect to the total amount of monomers. When heating at the time of superposition | polymerization, about 60-120 degreeC is generally preferable for heating temperature.

  The alkali-soluble copolymer (A) of the present invention may be used alone or in combination of two or more. The addition amount of the alkali-soluble copolymer is preferably 1 to 99% by weight, more preferably 5 to 98% by weight, based on the total solid content of the image forming composition. When the addition amount is 1% by weight or more, particularly 5% by weight or more, the printing durability is particularly good, and when it is 99% by weight or less, particularly 98% by weight or less, the sensitivity is particularly high.

As described above, the image forming composition having the alkali-soluble copolymer (A) containing the monomer unit represented by the general formula (I) and / or (II) has high water resistance and storage stability. good. This is presumably because high water resistance is exhibited by protecting highly reactive isocyanate groups, and external factors such as moisture are also prevented. In addition, as described above, the alkali-soluble copolymer (A) of the present invention comprises the heat from the infrared absorbent (C) and the acid from the acid generator (B) generated by irradiation with near infrared or infrared light. As a result, in the general formulas (I) and (II), the isocyanate group is decomposed. It is considered that the alkali-soluble copolymer (A) becomes insoluble in an alkaline developer by causing a crosslinking reaction between the decomposed portion and the diamine compound (E) and / or the alkali-soluble novolak resin (D). . On the other hand, the alkali-soluble copolymer in the unexposed area is easily dissolved in an alkali developer. As a result, an image forming composition having an alkali-soluble copolymer (A) containing a monomer unit represented by the general formula (I) and / or (II) is provided between an exposed area and an unexposed area. The difference in solubility in alkali spreads.

  The acid generator used as the component (B) in the present invention is a compound capable of generating an acid when the composition of the present invention is irradiated with near infrared or infrared light. That is, as described above, when the image forming composition is irradiated with near-infrared light or infrared light, the infrared absorbent can instantaneously generate heat of, for example, several hundred degrees by absorbing this light. An acid generator is a compound that can be decomposed by the heat generated to generate an acid. Examples of such an acid generator include various known compounds and mixtures thereof. For example, an organic halogen compound can be preferably used from the viewpoints of sensitivity in image formation by near-infrared and infrared exposure and storage stability of the image-forming composition. As the organic halogen compound, triazines having a halogen-substituted alkyl group and oxadiazoles having a halogen-substituted alkyl group are preferable, and s-triazines having a halogen-substituted alkyl group are particularly preferable. Although not particularly limited, specifically, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like can be mentioned.

  In the present invention, the amount of the acid generator added is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight, based on the total solid content of the image forming composition. When the addition amount is 0.1% by weight or more, particularly 0.2% by weight or more, the sensitivity is particularly high, and when it is 20% by weight or less, particularly 15% by weight or less, it is particularly easily dissolved in a solvent that dissolves the image forming composition. . These acid generators may be commercially available or synthesized by methods known to those skilled in the art.

In the present invention, the infrared absorbent used as the component (C) is irradiated with near infrared or infrared light (preferably light having a wavelength of 700 nm to 2500 nm, more preferably light having a wavelength of 700 nm to 1300 nm, such as an infrared laser). A substance having a light-to-heat conversion function that generates heat, and the generated heat quickly decomposes the isocyanate group part and the acid generator in the above general formulas (I) and (II) of the alkali-soluble copolymer. , Used to facilitate the generation of acid. As the infrared absorber used in the present invention, an infrared absorbing dye having absorption at a wavelength of 700 nm or more, carbon black, magnetic powder, and the like can be used. A particularly preferred infrared absorber is an infrared absorbing dye having an absorption peak at 700 nm to 850 nm, and preferably having a peak molar absorption coefficient ε of 10 ⁵ or more.

  Examples of the infrared absorbing dye include a cyanine dye, a squalium dye, a croconium dye, an azurenium dye, a phthalocyanine dye, a naphthalocyanine dye, a polymethine dye, a naphthoquinone dye, a thiopyrylium dye, and a dithiol metal complex dye. Anthraquinone dyes, indoaniline metal complex dyes, intermolecular CT dyes and the like are preferable.

Although these pigment | dyes can be synthesize | combined by a well-known method, the following commercial items can also be used.
Nippon Kayaku Co., Ltd .: IR750 (anthraquinone); IR002, IR003 (aluminum); IR820 (polymethine); IRG022, IRG033 (diimonium); CY-2, CY-4, CY-9, CY-10, CY-20
Dainippon Ink & Chemicals, Inc .: Fastogen blue 8120
Midori Chemical Co., Ltd .: MIR-101,1011,1021
In addition, the above dyes are also commercially available from various companies such as Nippon Photosensitive Co., Ltd., Sumitomo Chemical Co., Ltd., and Fuji Photo Film Co., Ltd.

  In the present invention, the amount of the infrared absorber added is preferably 0.5 to 15% by weight, more preferably 0.6 to 10% by weight, based on the total solid content of the image forming composition. When the addition amount is 0.5% by weight or less, particularly 0.6% by weight or less, the sensitivity is particularly fast, and when it is 15% by weight or less, particularly 10% by weight or less, the developability of the non-image area (unexposed part) is particularly high. Since it improves, it is preferable.

  The alkali-soluble novolak resin used as the component (D) in the present invention is used for a crosslinking reaction with the alkali-soluble copolymer of the present invention. That is, as described above, a crosslinking reaction occurs between the decomposition portion of the alkali-soluble copolymer (A) by irradiation with near infrared or infrared light and the hydroxyl group of the alkali-soluble novolak resin (D). As described above, the alkali-soluble copolymer (A) becomes insoluble in alkali by this crosslinking reaction, thereby improving the development latitude. Here, alkali-soluble means that when this novolak resin is used as the component (D) of the image forming composition, the novolak resin in the unexposed area can be substantially completely dissolved in the alkaline developer. . Specifically, for example, it is preferable that 0.5 g or more of a novolak resin can be dissolved in a 0.2 M potassium hydroxide aqueous solution at room temperature, and it is more preferable that 1.0 g or more of a novolak resin can be dissolved.

  Examples of the alkali-soluble novolak resin (D) include phenol / formaldehyde resins, cresol / novolak resins, cresol / formaldehyde resins, and phenol / cresol / formaldehyde copolycondensates as described in JP-A No. 55-57841. Preferred are resins, copolycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde, as described in JP-A No. 55-127553. Preferably, those having a weight average molecular weight of 1000 to 15000, particularly preferably 1500 to 10,000 are used. Note that these alkali-soluble novolak resins may be commercially available or may be synthesized by methods known to those skilled in the art.

  Commercially available products of alkali-soluble novolac resins include, for example, PSF-2803, PSF-2807, PSF-2808 (manufactured by Gunei Chemical Industry Co., Ltd.), EP4020GS, EP5020G, EP6020G (manufactured by Asahi Organic Materials Co., Ltd.), Hitachiol 1501 (Hitachi) Kasei Kogyo Co., Ltd.), BRM-565 (Showa Polymer Co., Ltd.), RV-95, RT-95 (Gifu Shellac Co., Ltd.) and the like can be used.

  The alkali-soluble novolak resin used in the present invention is more preferable in terms of development latitude when mixed with the alkali-soluble copolymer of the present invention. Since the alkali-soluble novolak resin has more crosslinking points (hydroxyl groups) than the isocyanate group portion which is a crosslinking point in the alkali-soluble copolymer (A), it is preferable to mix the alkali-soluble novolak resin. By this reaction, the alkali-soluble copolymer and the novolak resin are cross-linked with the alkali-soluble copolymer and the novolak resin while containing the novolak resin that is easily soluble in the alkali developer, and the alkali-soluble copolymer alone is obtained. The development latitude is wider than the addition. The addition amount of the alkali-soluble novolak resin is preferably 5 to 90% by weight, more preferably 5 to 70% by weight, based on the total solid content of the image forming composition. When the addition amount is 5% by weight or more, the developability is particularly improved, and when it is 90% by weight or less, particularly 70% by weight, the image strength is particularly improved.

In the present invention, the diamine compound of the following general formula (III) used as the component (E), methylene bis (2-chloroaniline), methylene bis (2-ethyl 6-methylaniline), methylene bis (2,3-dichloroaniline), 5,5'-methylenebis (anthranilic acid), 2,2'-dimethyl-4,4'-diamino biphenyl or 2,2'-bis (trifluoromethyl) -4,4'-diamino biphenyl, is present Used for crosslinking reaction with the alkali-soluble copolymer of the invention. That is, as described above, a crosslinking reaction occurs between the decomposition portion of the alkali-soluble copolymer (A) by irradiation with near infrared or infrared light and the amine of the component (E). As described above, the alkali-soluble copolymer (A) becomes insoluble in alkali by this crosslinking reaction, thereby improving the development latitude. The following general formula (III) is mentioned as a diamine compound used for this invention.

(In the formula, R ^{6 to} R ¹³ are each independently hydrogen, a C _{1 to} C ₁₂ alkyl group, a halogen atom, OH, COOH , or C _m F _{2m + 1} (m is an integer of 1 to 12). . there) .n representing the is an integer of 0 or more .T is -COO- (the carbonyl group in the ester group is bonded to the benzene ring), - SO ₂ -, or an -O-).

Preferred examples of the diamine compound represented by the general formula (III) include trimethylenebis (4-aminobenzoate) and polytetramethylene oxide-di-p-aminobenzoate. Examples of the diamine compound of component E include methylene bis (2-chloroaniline), methylene bis (2-ethyl 6-methylaniline), methylene bis (2,3-dichloroaniline), 5,5′-methylene bis (anthranilic acid), 2,2'-dimethyl-4,4'-diamino biphenyl, or 2,2'-bis include (trifluoromethyl) -4,4'-diaminodiphenyl biphenyl. These diamine compounds may be commercially available or may be synthesized by methods known to those skilled in the art.

  Commercially available diamine compounds include, for example, Iharacamine MT, CUA-4, Cure Hard-MED, Iharacamine ML-520, -530, -100, -150 (Ihara Chemical Industry Co., Ltd.) D-230, D -400, XTJ-500, XTJ-504 (manufactured by Sun Techno Chemical Co., Ltd.) can be used.

  The amount of these diamine compounds added is preferably 0.01 to 50% by weight, more preferably 0.01 to 30% by weight, based on the total solid content of the image forming composition. When it is 0.01% by weight or more, image formation is particularly good, and when it is 50% by weight or less, particularly 30% by weight or less, development failure is particularly unlikely to occur.

The image-forming composition of the present invention can preferably further contain a component (F). The compounds represented by the general formulas (IV) and (V) used as the component (F) are used for the purpose of improving the processing m ² number and developing latitude for the developer. That is, the polymer represented by the general formulas (IV) and (V) is decomposed at the silyl group by an acid generated from the acid generator upon irradiation with near infrared or infrared light, and has a phenolic hydroxyl group. And produces silanol compounds. There is a possibility that heat further contributes to the decomposition of the compounds represented by the general formulas (IV) and (V). Both the polymer having a phenolic hydroxyl group produced by decomposition and the silanol compound have high solubility in an alkaline developer or the like. On the other hand, the unexposed area has high alkali resistance due to the effect of addition of these polymer compounds, and is hardly affected by the developer. Therefore, by further adding the compounds represented by the general formulas (IV) and (V), the difference in solubility in an alkaline developer between the exposed area and the non-exposed area is wide, and the stability to the developer is increased. An image forming composition having a more excellent (development latitude) is provided. Further, the compounds represented by the general formulas (IV) and (V) are good in terms of ink loading, and the image forming composition has more excellent printing durability. In addition, the image portion is obtained by decomposing the isocyanate group of the alkali-soluble copolymer (A) by acid and heat, and crosslinking the OH (hydroxyl group) bonded to Si in the compound (F) in the decomposed portion. , The alkali-soluble copolymer becomes insoluble in the alkali developer. On the other hand, in the non-image area, a hydrogen bond is formed by the alkali-soluble copolymer (A) that is not decomposed and the OH (hydroxyl group) moiety bonded to Si in the compound (F). When heated at 100 ° C. to 200 ° C., the hydrogen bond is broken and it becomes soluble in an alkali developer.

(In the general formula (IV), Polym represents a resin polymer in which Polym-OH has a phenolic hydroxyl group. G ¹ represents O or COO. R ¹⁴ and R ¹⁵ independently represent a hydrogen atom or a methoxy group. Both of them are not simultaneously hydrogen atoms, and R ¹⁴ and R ¹⁵ may combine to form a ring, and R ¹⁶ may have a hydrocarbon side chain. Where a is an integer of 3 or more, wherein a is preferably 3 to 15, more preferably 3 to 10. R ¹⁹ and R ²⁰ are independently Represents a hydrogen atom, a methyl group or an ethyl group.
In the general formula (V), Polym represents a resin polymer in which Polym-OH has a phenolic hydroxyl group. G ² represents O or COO. R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group. In addition, carbon number of this alkyl group becomes like this. Preferably it is 1-10, More preferably, it is 1-5. R ¹⁸ represents b methylene groups which may have a hydrocarbon group side chain. Here, b is an integer of 3 or more. In addition, b becomes like this. Preferably it is 3-15, More preferably, it is 3-10. R ²¹ and R ²² independently represent a methyl group, a hydroxyl group or a chlorine atom. )

The general formulas (IV) and (V) used in the present invention can be synthesized by addition reaction of a resin polymer having a phenolic hydroxyl group and a silane coupling agent represented by the following general formulas (1) and (2). it can. This reaction is preferably carried out under the following conditions. That is, as a solvent, hexane, cyclohexane, benzene and the like are preferable. As for the quantity of a solvent, 0.5-100 mol is preferable per mol of hydroxyl groups which a resin polymer has. It is considered that the amount of the silane coupling agent does not depend on the number of OCH ₃ , OC ₂ H ₅ and Cl which are reactive groups bonded to silicon due to steric factors and the like. Moreover, 50-150 degreeC of reaction temperature is preferable. The (IV) and (V) thus obtained can be purified, for example, by fractional distillation of the solvent. In addition, the weight average molecular weights of (IV) and (V) are preferably 1000 or more, and more preferably in the range of 1500 to 300,000. In general, the compounds (IV) and (V) are characterized by absorbing ultraviolet light having a wavelength of, for example, 200 to 450 nm and decomposing at G ¹ or G ² .

(In the above formula (1), X ¹ represents a trimethoxysilyl group or a triethoxysilyl group. G ¹ represents O or COO. R ¹⁴ and R ¹⁵ independently represent a hydrogen atom or a methoxy group. R ¹⁴ and R ¹⁵ may combine to form a ring, and R ¹⁶ represents a methylene group which may have a side chain of a hydrocarbon group. Where a is an integer greater than or equal to 3. In addition, a is preferably 3-15, More preferably, it is 3-10.
In the above formula (2), X ² represents a trimethoxysilyl group, a triethoxysilyl group, a chlorodimethylsilyl group, a dichloromethylsilyl group or a trichlorosilyl group. G ² represents O or COO, and R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group. In addition, carbon number of this alkyl group becomes like this. Preferably it is 1-10, More preferably, it is 1-5. R ¹⁸ represents b methylene groups which may have a hydrocarbon group side chain. Here, b is an integer of 3 or more. In addition, b becomes like this. Preferably it is 3-15, More preferably, it is 3-10. )

In the addition reaction of the silane coupling agent to the resin polymer, OCH ₃ , OC ₂ H ₅ and Cl bonded to silicon in X ¹ and X ² of the silane coupling agent are stable in an anhydrous state, It may be hydrolyzed by water naturally contained therein to become OH. By the addition reaction with the silane coupling agent, for example, the polymer compound represented by the general formula (IV) or (V) is obtained. Here, Polym-OH represents a resin polymer having a phenolic hydroxyl group. R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a methyl group or an ethyl group, and R ²¹ and R ²² independently represent a methyl group, a hydroxyl group or a chlorine atom.

In addition, when the silicon of this silane coupling agent has a plurality of reactive groups (OCH ₃ , OC ₂ H ₅ or Cl), it may react with a plurality of phenolic hydroxyl groups, but this is rare. Conceivable. In addition, self-condensation between silane coupling agents is possible, but this is considered to be kept low due to steric hindrance of the nitro group bonded to the benzene ring.

  The compounds of the general formulas (1) and (2) are preferably compounds represented by the following general formulas (1ET), (1ES), (2ET) and (2ES).

(In the above formula, X ¹ represents a trimethoxysilyl group or a triethoxysilyl group. X ² represents a trimethoxysilyl group, a triethoxysilyl group, a chlorodimethylsilyl group, a dichloromethylsilyl group, or a trichlorosilyl group. A and b independently represent an integer of 3 or more, wherein a is preferably 3 to 15, and more preferably 3 to 10. Here, a methylene groups or b The methylene group may have a side chain of one or more hydrocarbon groups, and in the synthesis, the position of the side chain is from the carbon atom to which X ¹ or X ² is bonded to the methylene chain. The hydrocarbon group is preferably 3 to 15 and more preferably an integer of 3 to 10. Carbon atom C to which X ¹ is bonded two methylene Kusarijo from _p The distant carbon _{^{atoms, X 1 -C p -C q -C}} r -. The size of the a C _r side chain hydrocarbon group preferably has a carbon number 3 to 15, more preferably The number of carbon atoms is 3 to 10. In the compounds of general formula (1ET) and general formula (1ES), R ¹⁴ and R ¹⁵ independently represent a hydrogen atom or a methoxy group, (R ¹⁴ and R ¹⁵ may combine to form a ring.)

  The compound of the general formula (1ET) is preferably 2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether, 2-nitrobenzyl 10- (trimethoxy Silyl) decyl ether, 4-methoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 4-methoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether, 4-methoxy-2-nitrobenzyl 10 -(Trimethoxysilyl) decyl ether, 5-methoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 5-methoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether, 5-methoxy-2 -Nitrobenzyl 10- (g Methoxysilyl) decyl ether, 4,5-dimethoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 4,5-dimethoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether, 4,5- Dimethoxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether, 4,5-methylenedioxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 4,5-methylenedioxy-2-nitrobenzyl Examples include 6- (trimethoxysilyl) hexyl ether and 4,5-methylenedioxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether. More preferably, 4,5-dimethoxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 4,5-dimethoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether, 4,5-dimethoxy- 2-nitrobenzyl 10- (trimethoxysilyl) decyl ether, 4,5-methylenedioxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 4,5-methylenedioxy-2-nitrobenzyl 6- (Trimethoxysilyl) hexyl ether, 4,5-methylenedioxy-2-nitrobenzyl 10- (trimethoxysilyl) decyl ether.

In the compound of the general formula (1ET), an example of R ¹⁴ and R ¹⁵ forming a ring includes an alkylenedioxy group. Carbon number of alkylene dioxy group becomes like this. Preferably it is 1-10, More preferably, it is 1-5. Specifically, 4,5-methylenedioxy-2-nitrobenzyl 3- (trimethoxysilyl) propyl ether, 4,5-methylenedioxy-2-nitrobenzyl 3- (triethoxysilyl) propyl ether, 4 , 5-methylenedioxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether, 4,5-methylenedioxy-2-nitrobenzyl 6- (triethoxysilyl) hexyl ether, 4,5-methylenedioxy 2-nitrobenzyl 10- (trimethoxysilyl) decyl ether, 4,5-methylenedioxy-2-nitrobenzyl 10- (triethoxysilyl) propyl ether, and the like.

  Preferred examples of the compound of the general formula (2ET) include 3- (chlorodimethylsilyl) propyl 1- (2-nitrophenyl) ethyl ether and 3- (dichloromethylsilyl) propyl 1- (2-nitrophenyl) ethyl. Ether, 3- (trichlorosilyl) propyl 1- (2-nitrophenyl) ethyl ether, 6- (chlorodimethylsilyl) hexyl 1- (2-nitrophenyl) ethyl ether, 6- (dichloromethylsilyl) hexyl 1- ( 2-Nitrophenyl) ethyl ether, 6- (trichlorosilyl) hexyl 1- (2-nitrophenyl) ethyl ether, 3- (chlorodimethylsilyl) propyl o-nitrobenzyl ether, 3- (dichloromethylsilyl) propyl o- Nitrobenzyl ether, 3- (trichlorosilyl) propyl Pyro-nitrobenzyl ether, 6- (chlorodimethylsilyl) hexyl o-nitrobenzyl ether, 6- (dichloromethylsilyl) hexyl o-nitrobenzyl ether, 6- (trichlorosilyl) hexyl o-nitrobenzyl ether, 3- (Trimethoxysilyl) propyl 1- (2-nitrophenyl) ethyl ether, 3- (triethoxysilyl) propyl 1- (2-nitrophenyl) ethyl ether, 6- (trimethoxysilyl) hexyl 1- (2-nitro Phenyl) ethyl ether, 6- (triethoxysilyl) hexyl 1- (2-nitrophenyl) ethyl ether, 3- (trimethoxy) propyl o-nitrobenzyl ether, 3- (triethoxysilyl) propyl o-nitrobenzyl ether, 6- (Trimethoxysilyl ) Hexyl o- nitrobenzyl ether, 6- (triethoxysilyl) hexyl o- nitrobenzyl ether, and the like.

  As the compound of the general formula (1ES), 5- (trimethoxysilyl) -pentanoic acid 1- (4,5-dimethoxy-2-nitrophenyl) methyl, 5- (triethoxysilyl) -pentanoic acid is particularly preferable. 1- (4,5-dimethoxy-2-nitrophenyl) methyl, 5- (trimethoxysilyl) -undecanoic acid 1- (4,5-dimethoxy-2-nitrophenyl) methyl, 5- (triethoxysilyl)- Examples include 1- (4,5-dimethoxy-2-nitrophenyl) methyl undecanoate.

  As the compound of the general formula (2ES), particularly preferred is 5- (chlorodimethylsilyl) pentanoic acid 1- (2-nitrophenyl) ethyl, 5- (dichloromethylsilyl) pentanoic acid 1- (2-nitrophenyl). Ethyl, 1- (2-nitrophenyl) ethyl 5- (trichlorosilyl) pentanoate, 1- (2-nitrophenyl) ethyl 11- (chlorodimethylsilyl) undecanoate, 1- (dichloromethylsilyl) undecanoic acid 1- (2-nitrophenyl) ethyl, 11- (trichlorosilyl) undecanoic acid 1- (2-nitrophenyl) ethyl, 5- (chlorodimethylsilyl) pentanoic acid o-nitrobenzyl, 5- (dichloromethylsilyl) pentanoic acid o -Nitrobenzyl, 5- (trichlorosilyl) pentanoic acid o-nitrobenzyl, 11- (c (Rodimethylsilyl) undecanoic acid o-nitrobenzyl, 11- (dichloromethylsilyl) undecanoic acid o-nitrobenzyl, 11- (trichlorosilyl) undecanoic acid o-nitrobenzyl, 5- (trimethoxysilyl) pentanoic acid 1- ( 2-nitrophenyl) ethyl, 5- (triethoxysilyl) pentanoic acid 1- (2-nitrophenyl) ethyl, 11- (trimethoxysilyl) undecanoic acid 1- (2-nitrophenyl) ethyl, 11- (triethoxy Silyl) undecanoic acid 1- (2-nitrophenyl) ethyl, 5- (trimethoxysilyl) pentanoic acid o-nitrobenzyl, 5- (triethoxysilyl) pentanoic acid o-nitrobenzyl, 11- (trimethoxysilyl) undecane Acid o-nitrobenzyl, 11- (triethoxysilyl) unde Phosphate o- nitrobenzyl and the like.

  The compounds represented by the general formulas (1ET), (1ES), (2ET) and (2ES) can be synthesized by the methods described below.

  An example of a method for producing the compounds of the general formula (1ET) and the general formula (2ET) is shown below.

The compound of the general formula (1ET) is obtained by reacting, for example, 2-nitrobenzaldehyde (3) having R ¹⁴ and R ¹⁵ at the 4-position and 5-position with hydrazine and oxidizing with manganese dioxide to obtain a diazo compound (5). After reacting with alcohol (6) having a double bond in the presence of perchloric acid to obtain ether (7), the double bond of ether (7) is converted to platinum (IV) chloride hexahydrate (H ₂ PtCl ₆ · 6H ₂ O) is used as a catalyst to react with trimethoxysilane or triethoxysilane. A compound of the general formula (2ET) is obtained in the same manner, and the corresponding chlorodimethylsilane, dichloromethylsilane and trichlorosilane can be used for introduction of the chlorodimethylsilyl group, dichloromethylsilyl group and trichlorosilyl group, respectively. it can.
The manufacturing method of the compound of general formula (1ET) and general formula (2ET) is not restricted to this, The other well-known method can be utilized. In addition, (1ET) and (2ET) in which a m methylene groups have a hydrocarbon group side chain can be synthesized using a corresponding alcohol.

  An example of a method for producing the compounds of general formula (1ES) and general formula (2ES) is shown below.

The compound of the general formula (1ES) is produced, for example, by reacting a carboxylic acid (8) having a double bond with an o-nitrobenzyl alcohol derivative (9) to produce an ester (10). (IV) It can be obtained by reacting acid hexahydrate (H ₂ PtCl ₆ .6H ₂ O) with a compound selected from trimethoxysilane, chlorodimethylsilane, dichloromethylsilane and trichlorosilane. For example, WSC · HCl [WSC is an abbreviation for water-soluble carbodiimide, and WSC · HCl includes 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride. And DMAP (4-dimethylaminopyridine). Further, the ester (10) is converted into an acid chloride by a known method using thionyl chloride (SOCl ₂ ) or the like, and the carboxylic acid (8) having a double bond is converted into an o-nitrobenzyl alcohol derivative (9) and DMAP. It can also be obtained by reacting in the presence of a tertiary amine. The compound of the general formula (9) can be synthesized by a known method such as reduction of the carbonyl group of 2-nitrobenzaldehyde having an alkoxy group at the 4th and 5th positions with sodium borohydride.

  The compound of the general formula (2ES) can be synthesized by the same method, and the corresponding chlorodimethylsilane, dichloromethylsilane and trichlorosilane should be used for introduction of the chlorodimethylsilyl group, dichloromethylsilyl group and trichlorosilyl group, respectively. Can do.

  The manufacturing method of the ester compound of General formula (1ES) and General formula (2ES) is not restricted to this, A well-known method can be utilized. In addition, the ester compound (1ES) of the general formula (1) and the ester compound (2ES) of the general formula (2) in which b methylene groups have a hydrocarbon side chain should be synthesized using corresponding alcohols. Can do.

  The compounds represented by the general formulas (2ET) and (2ES) can be synthesized by the method described in JP-A No. 2002-80481 (for example, Examples [0022] and [0033]).

  Regarding the resin polymer having a phenolic hydroxyl group, the position of the hydroxyl group is not particularly limited, and may be a part of the side chain. The weight average molecular weight of the resin polymer is preferably 1000 or more, and more preferably 1500 to 300,000. Specifically, the resin polymer is a cresol formaldehyde resin {for example, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, a mixture of m-cresol formaldehyde resin and p-cresol formaldehyde resin, phenol / cresol. (Examples of cresol include m-cresol, p-cresol, o-cresol, a mixture of m-cresol and p-cresol, or a mixture of m-cresol and o-cresol) mixed formaldehyde resin, etc.}, Resol type phenol resins, pyrogallol / acetone resin, polyvinyl phenol, a copolymer of vinyl phenol and styrene, t-butyl substituted polyvinyl phenol resin and the like are preferable.

  The introduction ratio of the compounds represented by the general formulas (1ET), (1ES), (2ET) and (2ES) to the resin polymer is preferably 5 to 100%. When the introduction rate is 5% or more, the difference in solubility (contrast) in the developer between the exposed area and the unexposed area is good. The introduction rate refers to the ratio of the hydroxyl group of the resin polymer to the compound bonded with the compound represented by the formula (1ET) or the like.

The polymer compounds (IV) and (V) used in the present invention may be used alone or in combination. The amount of these polymer compounds added is preferably 0.01 to 30% by weight, more preferably 0.01 to 20% by weight, based on the total solid content of the image forming composition. When the addition amount is 0.01% by weight or more, the treatment m ² for the developer is particularly good, and when it is 30% by weight or less, particularly 20% by weight or less, the sensitivity is particularly high.

  A dye can be added for the purpose of coloring the image-forming composition of the present invention. Examples of the dye include oil-soluble dyes, basic dyes, and leuco dyes. Specifically, Crystal Violet, Malachite Green, Victoria Blue, Methylene Blue, Ethyl Violet, Rhodamine B, Victoria Pure Blue BOH (Hodogaya Chemical Industries), Oil Blue 613 (Orient Chemical Industries), Oil Green, etc. Can be mentioned. Examples of leuco dyes include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole) -3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (4-diethylamino-2-ethoxy) Phenyl) -4-azaphthalide, 3,6,6'-tris (dimethyl-amino) spiro [fluorene-9,3'-phthalide], 3,3-bis (1-n-butyl-2-methyl-indole- 3-yl) phthalide and the like are preferred. The amount of these dyes added is preferably 0.01 to 5.0% by weight, more preferably 0.01 to 4.0% by weight, based on the total solid content of the image forming composition. When the content is 0.01% by weight or more, the coloring of the image forming layer is particularly good and the image is easy to see. When the content is 5.0% by weight or less, particularly 4.0% by weight or less, a dye is formed on the non-image area after development. This is preferable because the remainder of the film becomes difficult to remain.

  Furthermore, an oleophilic resin can be added to the photosensitive layer formed from the image forming composition of the present invention in order to improve the sensitivity of the photosensitive layer. Examples of the lipophilic resin include condensates of phenols and aldehydes substituted with an alkyl group having 3 to 15 carbon atoms, or t-butylphenol as described in JP-A-50-125806. Formaldehyde resin or the like can be used.

  A blocked isocyanate can be added to the image forming composition of the present invention, if necessary, for the purpose of improving sensitivity. Blocked isocyanate is a compound in which an isocyanate group is chemically protected, and the protecting group is preferably a compound that dissociates at 80 ° C. or higher. For example, when the protecting group is phenol, RNHCOOPh, which is a blocked isocyanate, is decomposed by heat to become RNCO. Protecting groups include phenolic compounds, caprolactam, oximes and the like. The blocked isocyanate may be liquid or solid.

  As phenolic compounds as protecting groups, phenol, p-chlorophenol, p-nitrophenol, o-nitrophenol, m-methylphenol, p-methylphenol, p-tert-butylphenol, p-octylphenol, methoxyphenol, p -Phenylphenol, thymol, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, 1- Bis (p-hydroxyphenyl) propane, 2,2-bis (p-hydroxyphenyl) propane, 1,1-bis (p-hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 4,4-chi Examples include bis (p-hydroxyphenol), 4,4-thiobis (6-tert-butyl-m-cresol), 2,2-bis (p-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, and the like. .

  Examples of the oximes include diethyl oxime, methyl butyl ketone oxime, diethyl ketone oxime, dibutyl ketone oxime, acetophenol oxime, ethyl phenol ketone oxime, propyl aldehyde oxime, butyraldehyde oxime, and the like.

  As isocyanate compounds, phenyl isocyanate, p-bromophenyl isocyanate, p-chlorophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, m-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dimethylphenyl isocyanate, 2,5- Dichlorophenyl isocyanate, o-methoxyphenyl isocyanate, p-methoxyphenyl isocyanate, o-ethoxyphenyl isocyanate, p-ethoxyphenyl isocyanate, m-nitrophenyl isocyanate, p-nitrophenyl isocyanate, o-tolyl isocyanate, m-tolyl isocyanate, p -Tolyl isocyanate, diphenylmethane diisocyanate, 3,3 ' -Dimethyl-4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, p-bromophenyl isocyanate and the like.

  The addition amount of these blocked isocyanate compounds is preferably 0.01 to 5.0% by weight, more preferably 0.01 to 4.0% by weight, based on the total solid content of the image forming composition. . If it is 0.01% by weight or more, curing of the image forming layer is particularly good, and if it is 5.0% by weight or less, particularly 4.0% by weight or less, it is particularly difficult to remain in the non-image area after development.

  A plasticizer can be added to the photosensitive layer of the present invention in order to impart flexibility and the like of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, trioctyl phosphate, tributyl phosphate and the like are used.

  Further, the image forming composition of the present invention has a nonionic surfactant as described in JP-A-62-251740 and JP-A-3-208514 in order to broaden the processing stability against development conditions. , Amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, and N-tetradecyl-N, N- Examples include betaine type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the total solid content of the image forming material is preferably 0.005 to 15% by weight, and more preferably 0.01 to 10% by weight. When it is 0.005% by weight or more, particularly 0.01% by weight or more, developability is particularly good, and when it is 15% by weight or less, particularly 10% by weight or less, ink deposition is particularly good.

  A photosensitive lithographic printing plate can be produced by dissolving each component of the image-forming composition of the present invention in a suitable solvent, applying the solution on a support and drying it.

  Examples of the solvent include methanol, ethanol, propanol, methylene chloride, ethyl acetate, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, methyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone. , Trichlorethylene, methyl ethyl ketone and the like. These solvents can be used alone or in admixture of two or more.

As a coating method, conventionally known methods such as spin coating, extrusion coating, wire bar coating, roll coating, air knife coating, dip coating and curtain coating can be used. The coating amount varies depending on the application, but is preferably 0.5 to 5.0 g / m ² as a solid content.

  As a support used in the present invention, a metal plate such as aluminum, zinc, copper, steel, etc., a metal plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic film, glass Examples thereof include a plate, a paper coated with a resin, and a hydrophilic plastic film.

  When the present invention is applied to a photosensitive lithographic printing plate, a brush or ball-polished aluminum plate, brush-polished, anodized aluminum plate, electropolished, anodized aluminum plate, or An aluminum plate that has been subjected to a treatment combining these is particularly preferred.

  The aluminum plate thus pretreated is further subjected to a chemical conversion treatment with an alkali silicate, sodium phosphate, sodium fluoride, zirconium fluoride, alkyl titanate, trihydroxybenzoic acid or the like alone or in a mixed solution, or to a hot aqueous solution. Sealing with water immersion or steam bath, coating treatment with aqueous solution of strontium acetate, zinc acetate, magnesium acetate, calcium benzoate, polyvinylpyrrolidone, polyaminesulfonic acid, polyvinylphosphonic acid, polyacrylic acid, polymethacrylic acid A surface or back surface coating treatment with an acid or the like can also be performed as a post-treatment.

  Furthermore, as the above-mentioned support, an aluminum support subjected to the surface treatment described in JP-A-10-297130 can also be used.

  As the laser light source for irradiating the image forming composition of the present invention with actinic rays, a solid or semiconductor laser beam having an oscillation wavelength in the near infrared to infrared region is preferable.

  In the present invention, development treatment may be performed immediately after laser irradiation, but it is preferable to perform heat treatment (preheating) between the laser irradiation step and the development step. The heat treatment is preferably performed in the range of 100 ° C. to 200 ° C. for 10 seconds to 3 minutes. This heat treatment can reduce the laser energy required for image formation when irradiating a laser with a semiconductor laser, and can extend the life of an expensive semiconductor laser.

  As the developer used for developing the image forming composition of the present invention, an aqueous alkaline developer is suitable. As an aqueous alkaline developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, tribasic sodium phosphate, etc. An aqueous solution of an alkali metal salt of

  An activator can be added to the alkaline aqueous solution as necessary. As the above-mentioned active agent, an anionic surfactant or an amphoteric surfactant can be used.

  Examples of the ionic surfactant include sulfates of alcohols having 8 to 22 carbon atoms (for example, polyoxyethylene alkyl sulfate soda salt), alkyl aryl sulfonates (for example, sodium dodecylbenzenesulfonate, polyoxyethylene dodecylphenyl sulfate). Soda salt, alkyl naphthalene sulfonic acid soda, naphthalene sulfone soda, formalin condensate of naphthalene sulfone soda), sodium dialkyl sulfonate, alkyl ether phosphate, alkyl phosphate, and the like can be used. In addition, as the amphoteric surfactant, for example, alkylbetaine type and alkylimidazoline type surfactants are preferable. Furthermore, for example, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite can be added to the alkaline aqueous solution.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

[Synthesis Example 1 (alkali-soluble copolymer a)]
In a 500 ml four-necked flask equipped with a stirrer and a condenser tube, 20.0 g of p-isopropenylphenol, 5.3 g of acrylonitrile, 12.5 g of phenylcarbamic acid ethyl methacrylate, 2- (O- [1'-methacrylic acid) Methylpropylideneamino] carboxyamino) ethyl (54.5 g) and dimethylacetamide (125.4 g) were added and the atmosphere was replaced with nitrogen for about 30 minutes. Next, after heating to 73 ° C. in an oil bath, 0.25 g of 2,2′-azobis (2-methylbutyronitrile) was added and stirred for 2 hours. Further to this reaction mixture, 20.0 g of p-isopropenylphenol, 5.3 g of acrylonitrile, 12.5 g of (phenylcarbamic acid ethyl methacrylate), 2- (O- [1′-methylpropylideneamino] carboxyamino methacrylate) ) A mixture of 54.5 g of ethyl, 125.4 g of dimethylacetamide and 0.25 g of 2,2′-azobis (2-methylbutyronitrile) was added dropwise by a dropping funnel over 2 hours. After completion of the dropping, the mixture was further stirred at 73 ° C. for about 2 hours to obtain an alkali-soluble copolymer a having a concentration of 30% by weight.

[Synthesis Example 2 (alkali-soluble copolymer b)]
In a 500 ml four-necked flask equipped with a stirrer and a condenser tube, 10.7 g of N- (p-hydroxyphenyl) maleimide, 8.5 g of acrylonitrile, 5 g of ethyl phenylcarbamate, 2- (O- [1 '-Methylpropylideneamino] carboxyamino) ethyl (29.04 g), methacrylic acid (4.8 g) and dimethylacetamide (125.4 g) were added, and the atmosphere was replaced with nitrogen for about 30 minutes. Next, after heating to 73 ° C. in an oil bath, 0.25 g of 2,2′-azobis (2-methylbutyronitrile) was added and stirred for 2 hours. This reaction mixture was further mixed with 10.7 g of N- (p-hydroxyphenyl) maleimide, 8.5 g of acrylonitrile, 29.04 g of 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, methacrylic acid A mixture of 4.8 g and 125.4 g of dimethylacetamide and 0.25 g of 2,2′-azobis (2-methylbutyronitrile) was added dropwise by a dropping funnel over 2 hours. After completion of dropping, the mixture was further stirred at 73 ° C. for about 2 hours to obtain an alkali-soluble copolymer b having a concentration of 30% by weight.

[Synthesis Example 3 (alkali-soluble copolymer c)]
In a 500 ml four-necked flask equipped with a stirrer and a condenser tube, 14.9 g of p-isopropenylphenol, 9.0 g of acrylonitrile, 4.9 g of methacrylic acid, 2- (O- [1′-methylpropylideneamino methacrylate) Carboxyamino) methyl 33.9 g, bifunctional urethane acrylate M-1600 (manufactured by Toagosei Co., Ltd.) 5.0 g, hydroxyethyl methacrylate 3.25 g, and dimethylacetamide 165.5 g were added and the atmosphere was replaced with nitrogen for about 30 minutes. Next, after heating to 73 ° C. in an oil bath, 0.25 g of 2,2′-azobis (2-methylbutyronitrile) was added and stirred for 2 hours. The reaction mixture was further mixed with 14.9 g of p-isopropenylphenol, 9.0 g of acrylonitrile, 4.9 g of methacrylic acid, 33.9 g of 2- (O- [1′-methylpropylideneamino] carboxyamino) methyl methacrylate, A mixture of 5.0 g of M-1600, 3.25 g of hydroxyethyl methacrylate and 165.5 g of dimethylacetamide and 0.25 g of 2,2′-azobis (2-methylbutyronitrile) was dropped by a dropping funnel over 2 hours. . After completion of dropping, the mixture was further stirred at 73 ° C. for about 2 hours to obtain an alkali-soluble copolymer c having a concentration of 30% by weight.

[Synthesis of Polymer Compound A Represented by General Formula (IV)]
As a resin polymer containing a phenolic hydroxyl group, pyrogallol-acetone resin (0.173 g) and as a silane coupling agent, 4,5-dimethoxy-2-nitrobenzyl-6- (trimethoxysilyl) hexyl ether (0.52 g) : Theoretical introduction rate 100%) was mixed in hexane (6 ml), heated and stirred at 70 ° C. for 1 hour, and then hexane was fractionated to obtain polymer compound A. Note that a new peak due to -O-Si- appeared in the IR spectrum. The theoretical introduction rate of 100% means that the amount of the silane coupling agent is stoichiometrically equivalent to the hydroxyl group of the polymer. 4,5-dimethoxy-2-nitrobenzyl-6- (trimethoxysilyl) hexyl ether was synthesized as follows.

[Synthesis of 4,5-dimethoxy-2-nitrobenzyl 6- (trimethoxysilyl) hexyl ether]
The 20 ml eggplant flask was replaced with nitrogen, and 5-hexenyl 4,5-dimethoxy-2-nitrobenzyl ether 2.95 g (10.0 mmol), trimethoxysilane 1.47 g (12 mmol), hydrogen hexachloroplatinate (IV) hexahydrate A very small amount of Japanese product H ₂ PtCl ₆ .6H ₂ O was added and stirred at 37 ° C. for 30 minutes, and then the bath temperature was raised to 100 ° C. and the reaction was completed in 2 hours. Purification by silica gel column chromatography was performed using an intermediate pressure column. Hexane: ethyl acetate: tetramethoxysilane = 100: 20: 1 (volume ratio) was used as an eluent to obtain 1.4 g (3.35 mmol) of the desired product. Yield 1.4 g, yield 34%. R _f value (eluent above) 0.1.
¹ H-NMR (400MHz, CDCl ₃ / TMS): δ7.71 (s, 1H, Ar), 7,31 (s, 1H, Ar), 4.89 (s, 2H, Ar-C H ₂ -O-) , 3.96-3.99 (s, 6H, Ar-OC H ₃ ) 3.58-3.61 (s, 2H, -OC H ₂ -CH _2- ), 3.57 (s, 9H, -Si (OC H ₃ ) ₃ ), 1.4 -1.7 (m, 8H, -CH _2- (C H ₂ ) ₄ -CH _2- ), 0.63-0.67 (m, 2H, -C H ₂ -Si-). FT-IR (NaCl): 2936 cm ⁻¹ (CH), 2843 (CH), 1520 (NO ₂ ), 1328 (NO ₂ ), 1276 (COC).

[Synthesis of Polymer Compound B Represented by General Formula (V)]
As a resin polymer containing a phenolic hydroxyl group, Marcalinker CST50 (vinylphenol: styrene = 5: 5) (manufactured by Maruzen Petrochemical Co., Ltd.) (0.215 g) and as a silane coupling agent, 2-nitrobenzyl-6- ( Trimethoxysilyl) hexyl ether (0.34 g: theoretical introduction rate 100%) was mixed with hexane (6 ml), heated and stirred at 70 ° C. for 1 hour, and then the hexane was fractionated to obtain a polymer. Compound B was obtained. This compound was assigned in the same manner as the synthesis of polymer compound A. Note that 2-nitrobenzyl-6- (trimethoxysilyl) hexyl ether was synthesized as follows.

[Synthesis of 2-nitrobenzyl-6- (trimethoxysilyl) hexyl ether]
The 20 ml eggplant flask was purged with nitrogen, 2.5 g (10.7 mmol) of 5-hexyl-2-nitrobenzyl ether, 1.56 g (12.8 mmol) of trimethoxysilane, and hexachloroplatinic (IV) acid hexahydrate were added. A small amount was added, and the mixture was stirred at 37 ° C for 30 minutes, and then reacted at 100 ° C for 2 hours. The mixture was returned to room temperature and purified by distillation under reduced pressure using a short path. From the second fraction (0.2 mmHg / 123-125 ° C./1.98 g), 1.98 g (yield 52%) of the desired product was obtained.
¹ H-NMR (400MHz, CDCl ₃ / TMS): δ7.4-8.1 (m, 4H, Ar), 4.9 (s, 2H, Ar-C H ₂ -O-), 3.6 (m, 9H, -OC H ₂ -CH _2- ), 3.58 (s, 2H, Si- (OC H ₃ ) ₃ ), 1.7 (m, 2H, -CH ₂ -C H ₂ -CH _2- ), 1.4 (m, 6H,- _{CH 2 -CH 2 -CH 2 -)} , 0.70 (t, 2H, -C H 2 -Si-).
FT-IR (NaCl): 2935 cm ⁻¹ (CH), 2844 (CH), 1528 (NO ₂ ), 1344 (NO ₂ ), 1191 (COC).

(Production of support)
After 0.24 mm thick aluminum (material 1050) was alkali degreased, the surface was polished with a nylon brush while applying a water suspension of permiston and washed thoroughly with water. Next, a 15 wt% sodium hydroxide aqueous solution was poured for 5 seconds at 70 ° C., the surface was etched by 3 g / m ² , then further washed with water, and then electro-roughened at 200 coulomb / dm ² in a 1N hydrochloric acid bath. Processed. Subsequently, after washing with water, the surface was etched again with a 15% by weight aqueous sodium hydroxide solution, washed with water, then immersed in a 20% by weight aqueous nitric acid solution and desmutted. Next, an anodizing treatment was performed in a 15% by weight sulfuric acid aqueous solution to form an oxide film of 1.8 g / m ² , and after water washing, after-treatment with a 2% by weight potassium fluoride solution at 50 ° C. and water washing. , Dried.

[Example 1]
The following photosensitive solution 1 was applied onto the obtained aluminum support using a spin coater so that the film thickness after drying was 1.6 g / m ^2, and dried at 100 ° C. for 10 minutes in a thermostatic bath. A lithographic printing plate was obtained.
(Photosensitive solution 1)
Alkali-soluble copolymer a (0.4 g)
Alkali-soluble copolymer c (0.6 g)
Acid generator: 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine (0.1 g)
Infrared absorber: Cyanine compound A (0.2 g) shown below
Alkali-soluble resin: novolak resin (PSF-2803) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.5 g), novolak resin (PSF-2807) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.15 g)
Iharacamine MT (manufactured by Ihara Chemical) (0.05g)
Polymer compound A (0.1 g)
Dye: Oil blue 613 (0.01 g)
Solvent: propylene glycol monomethyl ether / methyl cellosolve acetate = 45 ml / 5 ml

[Example 2]
The following photosensitive solution 2 was applied on the same support as in Example 1 using a spin coater so that the film thickness after drying was 1.6 g / m ^2, and dried at 100 ° C. for 10 minutes in a thermostatic bath. A lithographic printing plate was obtained.
(Photosensitive solution 2)
Alkali-soluble copolymer a (0.4 g)
Alkali-soluble copolymer c (0.6 g)
Acid generator: 2- (p-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine (0.1 g)
Infrared absorber: Cyanine compound A (0.2 g)
Alkali-soluble resin: novolak resin (PSF-2803) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.5 g), novolak resin (PSF-2807) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.2 g)
Erasmer 1000 (Ihara Chemical Co., Ltd.) (0.05g)
Polymer compound B (0.1 g)
Dye: Crystal violet (0.01 g)
Solvent: propylene glycol monomethyl ether / methyl cellosolve acetate = 45 ml / 5 ml

[Example 3]
The following photosensitive solution 3 was applied on the same support as in Example 1 using a spin coater so that the film thickness after drying was 1.6 g / m ^2, and dried at 100 ° C. for 10 minutes in a thermostatic bath. A lithographic printing plate was obtained.
(Photosensitive solution 3)
Alkali-soluble copolymer b (1.0 g)
Acid generator: 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine (0.1 g)
Infrared absorber: Cyanine compound A (0.2 g)
Alkali-soluble resin: novolak resin (PSF-2803) (manufactured by Gunei Chemical Industry Co., Ltd.) (0.8 g), novolak resin (PSF-2807) (manufactured by Gunei Chemical Industry Co., Ltd.) (0.2 g)
Erasmer 1000 (Ihara Chemical Co., Ltd.) (0.05g)
Dye: Crystal violet (0.01 g)
Solvent: propylene glycol monomethyl ether / methyl cellosolve acetate = 45 ml / 5 ml

[Comparative Example 1]
The following image forming composition was applied onto the same support as in Example 1 and dried in the same manner as in Example 1 to obtain a lithographic printing plate.
(Photosensitive solution 4)
Alkali-soluble copolymer a (0.4 g)
Alkali-soluble copolymer c (0.6 g)
Acid generator: 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine (0.1 g)
Infrared absorber: Cyanine compound A (0.2 g)
Alkali-soluble resin: novolak resin (PSF-2803) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.5 g), novolak resin (PSF-2807) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.15 g)
Dye: Crystal violet (0.01 g)
Solvent: propylene glycol monomethyl ether / methyl cellosolve acetate = 45 ml / 5 ml

[Comparative Example 2]
The following image forming composition was applied on the same support as in Example 1 and dried in the same manner as in Example 1 to obtain a lithographic printing plate.
(Photosensitive solution 5)
Cross-linking agent: resole resin (bisphenol A type) (1.0 g)
Acid generator: 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine (0.1 g)
Infrared absorber: Cyanine compound A (0.2 g)
Alkali-soluble resin: novolak resin (PSF-2803) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.5 g), novolak resin (PSF-2807) (manufactured by Gunei Chemical Industry Co., Ltd.) (1.15 g)
Dye: Crystal violet (0.01 g)
Solvent: propylene glycol monomethyl ether / methyl cellosolve acetate = 45 ml / 5 ml

  Each lithographic printing plate obtained was image-exposed with a semiconductor laser having a wavelength of 830 nm (manufactured by Creo: Trendsetter 400QTM) with various exposure energies at 175 lines and 1-99% halftone dot lines at 135 ° C. 30 seconds in an automatic developing machine (PK-1310 II) charged with a 14-fold diluted solution of an alkaline developer (No. 4 developer for positive type lithographic plate manufactured by Okamoto Chemical Co., Ltd.) having the following composition: Developed at 20 ° C. for 20 seconds.

Next, the following evaluations were performed, and the results are shown in Table 1. As an evaluation of sensitivity (minimum exposure energy), a printing plate developed with the above developer was measured at a halftone dot density meter (X-RITE) of 50% as a minimum exposure amount. Further, as an evaluation of the development latitude, the exposed printing plate was immersed in the developer, and the time until the image portion (exposed portion) disappeared was measured. Further, as a further evaluation of the development latitude, the number of processed sheets (number of processed m ² / L) until undeveloped under the developing conditions of the developer was measured. For evaluation of printing durability, each printing plate developed under the developing conditions of the developer was printed on high-quality paper with a commercial ink using a Ryobi 480D machine, and the number of sheets until the image was faded was counted. Further, as an evaluation of scratch resistance, the scratch was intentionally determined with a pen wound with a cloth, exposed as it was, and developed for 5 seconds longer than usual (25 seconds), and the scratch property was judged from the scratch occurrence state.

  Furthermore, as an evaluation of soiling property during printing, after storing the planographic printing plate naked for 5 days under the conditions of a high temperature of 45 ° C., a high humidity of 75% and a high humidity, each of the printing plates was subjected to a semiconductor laser having a wavelength of 830 nm. 175 lines and 1-99% halftone dot lines were image-exposed using various exposure energies, and heated at 135 ° C. for 20 seconds. Development was performed at 30 ° C. for 20 seconds with an automatic processor (PK-1310 II) charged with a 14-fold diluted solution of 4 developers. Each printing plate was printed on high-quality paper with a commercially available ink using a Ryobi 480D machine, and it was evaluated whether smear occurred in the non-image area.

<Evaluation criteria>
* Scratch resistance: ◎ Does not damage the image area. ○ Scratches can be confirmed. X Image part completely peels off.
* Dirty property: ◎ Non-image area is not stained. X Ink remains in the non-image area.

As is apparent from Table 1, the lithographic printing plate provided with the image forming composition according to the present invention has no stain in the non-image area even when stored at high temperature and high humidity, has excellent storage stability, and has an infrared region. It is an excellent printing plate for direct plate making that has a high sensitivity to. Furthermore, the negative type image forming composition according to the present invention and the negative type photosensitive lithographic printing plate using the same include a polymer compound represented by the general formulas (IV) and (V), thereby developing latitude. The process m ² for the developer, scratch resistance, and printing durability are also excellent.

Claims (3)

(A) an alkali-soluble copolymer containing a monomer unit represented by the following general formula (I) and / or (II):
(B) an acid generator,
(C) an infrared absorber,
(D) an alkali-soluble novolak resin, and (E) a diamine compound represented by the following general formula (III), methylene bis (2-chloroaniline), methylene bis (2-ethyl 6-methylaniline), methylene bis (2,3- Dichloroaniline), 5,5′-methylenebis (anthranilic acid), 2,2′-dimethyl-4,4′-diaminobiphenyl, or 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl An imaging composition containing ru .
[In the general formula (I), R ¹ represents a hydrogen atom, a methyl group, a chlorine atom or a cyano group. R ² represents an alkyl group or an aryl group.
In general formula (II), R ³ represents a hydrogen atom, a methyl group, a chlorine atom or a cyano group. R ⁴ and R ⁵ each independently represents an alkyl group or an aryl group. k is an integer of 1 or more.
In general formula (III), R ^{6 to} R ¹³ are each independently hydrogen, a C _{1 to} C ₁₂ alkyl group, a halogen atom, OH, COOH, or C _m F _{2m + 1} (m is 1 to 12). It is an integer. n is an integer of 0 or more. T represents —COO— (the carbonyl group in the ester group is bonded to the benzene ring), —SO ₂ —, or —O—. ] (F) The image forming composition according to claim 1, further comprising a polymer compound represented by the following general formula (IV) and / or (V).
(In the general formula (IV), Polym represents a polymer in which Polym-OH is a resin having a phenolic hydroxyl group. G ¹ represents O or COO. R ¹⁴ and R ¹⁵ independently represent a hydrogen atom or methoxy. R ¹⁴ and R ¹⁵ may be bonded to form an alkylenedioxy group to form a ring, and R ¹⁶ represents a side chain of the hydrocarbon group. A represents an m-ethylene group which may have, wherein a is an integer of 3 or more, R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a methyl group or an ethyl group;
In the general formula (V), Polym represents a polymer in which Polym-OH is a resin having a phenolic hydroxyl group. G ² represents O or COO. R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group. R ¹⁸ represents b methylene groups which may have a hydrocarbon group side chain. Here, b is an integer of 3 or more. R ²¹ and R ²² independently represent a methyl group, a hydroxyl group or a chlorine atom. ) A photosensitive lithographic printing plate comprising a support and a layer of the image-forming composition according to claim 1 or 2 provided thereon.