JP3825453B2 - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Description

  The present invention relates to a photosensitive composition suitable for the production of lithographic printing plates, IC circuits and photomasks. More specifically, the present invention relates to a photosensitive composition that gives a coating film excellent in solvent resistance and abrasion resistance and a photosensitive lithographic printing plate excellent in printing durability.

  JP-A-63-89864, JP-A-1-35436, and JP-A-1-52139 disclose a photosensitive substance composed of ο-naphthoquinonediazide sulfonic acid ester and the side chain as shown below. A photosensitive composition containing, as an essential component, a binder resin composed of a resin having an atomic group having a structure and a positive photosensitive lithographic printing plate provided thereon on an aluminum support are described.

  Japanese Patent Application Laid-Open No. 63-261350 discloses a photosensitive composition characterized by containing a polyurethane resin containing a sulfonylureido group (—SO 2 —NH—CO—NH—).

  On the other hand, Japanese Patent Application Laid-Open No. 54-98614 describes a negative photosensitive composition characterized by containing a diazo resin and a polymer compound having an aromatic hydroxyl group as shown in Chemical Formula 3 as essential components. ing.

  However, any of the coating films obtained from the photosensitive composition described in the above-mentioned publication and containing a binder resin made of a resin having an atomic group having the specific structure in the side chain has insufficient solvent resistance. There was a drawback. In particular, the cleaning agent containing a solvent used in UV ink printing has poor resistance and large wear, resulting in insufficient printing durability.

  Further, the polyurethane resin having a sulfonylureido group described in JP-A-63-261350 has a drawback that the development characteristics are further deteriorated when used in a photosensitive composition. Furthermore, this polyurethane resin is easily gelled during synthesis, and it has been difficult to use it as a photosensitive composition.

［式中、Ｒ ₁ 及びＲ ₂ はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基、又はカルボキシル基、もしくはその塩を表し、Ｒ ₃ は水素原子、ハロゲン原子、アルキル基またはアリール基を表し、Ｘは２価の連結基を表し、Ｙは置換基を有してもよい２価の芳香族基を表す］

［式中、Ｒ ₁ 及びＲ ₂ はそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基、又はカルボキシル基、もしくはその塩を表し、Ｒ ₃ は水素原子、ハロゲン原子、アルキル基またはアリール基を表し、Ｘは２価の連結基を表し、Ｙは置換基を有してもよい２価の芳香族基を表す］
で示される構造単位を含むアルカリ可溶性アクリル系樹脂（Ａ）からなるバインダー樹脂を含む感光性組成物が、上記した公知の側鎖に上記特定構造の原子団を有する樹脂からなるバインダー樹脂を含んだ感光性組成物に比べて、耐溶剤性に優れたものとなることを見い出し、本発明を完成するに至った。 Accordingly, the present inventors synthesized various resins having an atomic group having a specific structure in the side chain, prepared a photosensitive composition and evaluated the physical properties. As a result, the following general formula (Ia) having a urea bond in the side chain was obtained. Or (Ic):

[Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.

[Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.
A photosensitive composition containing a binder resin made of an alkali-soluble acrylic resin (A) containing a structural unit represented by the formula (1) contains a binder resin made of a resin having an atomic group having the specific structure in the above-mentioned known side chain. It has been found that the solvent composition is superior to the photosensitive composition, and the present invention has been completed.

That is, the present invention provides a photosensitive composition comprising the alkali-soluble acrylic resin having a urea bond in the side chain and a photosensitive compound, and a photosensitive layer having a photosensitive layer comprising the composition. Provide lithographic printing plates.

  The coating film obtained from the photosensitive resin composition of the present invention has excellent solvent resistance and development characteristics, and exhibits excellent solvent resistance and printing durability even when used as a lithographic printing plate. In particular, even in UV ink printing, good printing durability was exhibited due to its excellent solvent resistance.

Hereinafter, the alkali-soluble acrylic resin having a urea bond in the side chain used in the composition of the present invention and the method for producing the same and other components, the method for preparing the photosensitive composition used in the present invention, and the method of the present invention. A method for producing a lithographic printing plate will be described in detail.

  Accordingly, the resin (A) having a urea bond in the side chain does not act as an alkali-soluble group, and therefore, for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, an active imide It is preferable to have an alkali-soluble group such as a group separately in the resin skeleton, and it is more preferable to use a phenolic hydroxyl group in order to further improve the development characteristics. However, when the sensitivity of the photosensitive composition is increased, or when development is possible even with a developer having significantly reduced activity, a carboxyl group or a sulfonamide group may be included in the resin skeleton.

  The urea bond itself can be made into an alkali-soluble group by making the urea bond adjacent to a strong electron-withdrawing functional group such as a sulfonyl group, but it has a phenolic hydroxyl group as an alkali-soluble group and has a side chain. Development characteristics are more favorable when a resin having a urea bond is used.

The photosensitive compound (B) used in the photosensitive composition of the present invention may be appropriately selected from known ones depending on whether a positive or negative composition is prepared. A photosensitive compound selected from the following 1), 2), 3) or 4) can be used.
1) ο-naphthoquinonediazide compound 2) photosensitive diazonium compound 3) combination of compound having ethylenically unsaturated group and photopolymerization initiator 4) photosensitive diazonium compound, compound having ethylenically unsaturated group and photopolymerization initiator Combination

  Specific examples of the positive photosensitive compound include an o-naphthoquinonediazide compound. The o-naphthoquinonediazide compound used in the present invention is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403.

  Other suitable orthoquinonediazide compounds include 1,2-diazonaphthoquinonesulfonic acid chloride and phenol-formaldehyde resin described in US Pat. Nos. 3,046,120 and 3,188,210. There is an ester with.

  Other useful o-naphthoquinone diazide compounds are described and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, JP-B-37-18015. No. 4, No. 41-11222, No. 45-9610, No. 49-17481, and the like.

  A particularly preferred o-naphthoquinonediazide compound in the present invention is a compound obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less and 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds include JP-A Nos. 51-139402, 58-150948, 58-203434, 59-165053, 60-112445, 60-134235, and 60-. No. 163043, 61-118744, 62-10645, 62-10646, 62-153950, 62-178562 and the like.

  When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound. It is more preferable to react 1.0 equivalent.

  The resulting ο-naphthoquinone diazide compound is a mixture of different positions and introduction amounts of 1,2 diazonaphthoquinonesulfonic acid ester groups, but all hydroxyl groups are converted with 1,2-diazonaphthoquinonesulfonic acid esters. The proportion of the compound in the mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 100 mol%.

  Examples of positive photosensitive compounds other than ο-naphthoquinonediazide compounds include, for example, Japanese Patent Publication Nos. 56-2696, 48-89003, 51-120714, 53-133429, As described in JP-A-55-12995, JP-A-55-126236, JP-A-56-17345, JP-A-60-10247, JP-A-60-37549, JP-A-60-112446, etc. Can be mentioned.

  Moreover, as a photosensitive compound used for a negative photosensitive composition, although there exists a thing of said 2) -4), the following can be mentioned specifically.

  Examples of the photosensitive diazonium compound include a diazo resin represented by a salt of a condensate of a diazodiarylamine and an active carbonyl compound, and a photosensitive, water-insoluble and organic solvent-soluble one is preferable.

  Particularly suitable diazo resins are, for example, 4-diazodiphenylamine, 4-diazo-3-methyldiphenylamine, 4-diazo-4′-methyldiphenylamine, 4-diazo-3′-methyldiphenylamine, 4-diazo-4′-methoxy. At least one compound selected from diphenylamine, 4-diazo-3-methyl-4'-ethoxydiphenylamine, 4-diazo-3-methoxydiphenylamine, and the like, and formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, 4,4'- Organic acid salt or inorganic acid salt of a condensate with at least one compound selected from bis-methoxymethyldiphenyl ether and the like.

  Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, mesitylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, propylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, Examples include 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,4-dihydroxybenzophenone, and benzenephosphinic acid. As the inorganic acid, hexafluorophosphoric acid , Tetrafluoroboric acid, thiocyanic acid and the like.

  Further, a diazo resin whose main chain is a polyester group described in JP-A No. 54-30121; a polymer having a carboxylic anhydride residue described in JP-A No. 61-273538; and a diazo resin having a hydroxyl group A diazo resin obtained by reacting a compound; a diazo resin obtained by reacting a polyisocyanate compound and a diazo compound having a hydroxyl group: a diazo resin having a carboxyl group: a diazo resin having a phenolic hydroxyl group can be used.

  The amount of these diazo resins used is preferably in the range of 0 to 40% by weight with respect to the solid content of the composition, and if necessary, two or more diazo resins may be used in combination.

  The compound having an ethylenically unsaturated group is a monomer or oligomer having a boiling point of 100 ° C. or higher at normal pressure and at least one, preferably two or more ethylenically unsaturated groups capable of addition polymerization in one molecule. is there. Examples of such a monomer or oligomer include polyethylene glycol mono (meth) acrylate [hereinafter, methacrylate and acrylate are collectively referred to as (meth) acrylate. ], Monofunctional (meth) acrylates such as polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, tri (acryloyloxyethyl) isocyanurate , (Meth) acrylates of polyhydric alcohol / alxylene oxide adducts, (meth) acrylates of polyhydric phenol / alkylene oxide adducts Relate, urethane acrylates described in JP-B 48-41708, JP-B 50-6034, JP-B 51-37193, JP-A 48-64183, JP-B 49-43191, JP-B Examples thereof include polyfunctional (meth) acrylates such as polyester acrylates and epoxy acrylates obtained by adding an epoxy resin and (meth) acrylic acid, which are described in each publication of Japanese Patent No. 52-30490.

  As the resin (A), for example, a resin having both a urea bond and an ethylenically unsaturated group in the side chain can be used. As an example, a resin (D) having a structure represented by the general formula (I) of the present invention and an ethylenically unsaturated group can be mentioned. The resin having both a urea bond and an ethylenically unsaturated group in the side chain is particularly preferably used in combination with the above-described compound having an ethylenically unsaturated group alone or in combination with a photopolymerization initiator. If the photosensitive diazonium compound is further combined, the adhesion to the substrate is further improved, and an excellent printing durability negative photosensitive lithographic printing plate can be obtained.

  When the resin (A) contains the structure represented by the general formula (I), aqueous alkali development is possible, and developability when used as a lithographic printing plate is also improved. In addition, as the content of ethylenically unsaturated groups in the resin increases, a photosensitive composition with higher sensitivity is obtained, and the printing durability when used as a lithographic printing plate is improved.

  Examples of such a resin (D) include an isocyanate represented by the general formula (III) in a polymer of a compound represented by the general formula (II) and a compound having one vinyl group and one or more hydroxyl groups in one molecule. The thing which added the compound is mentioned. When the compound represented by the general formula (IIa) having a phenolic hydroxyl group among the compounds represented by the general formula (II) is used, the ink inking property when used as a lithographic printing plate is remarkably improved. And can be used more suitably.

  Examples of the compound having one vinyl group and one or more hydroxyl groups in one molecule include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and N-methylol. Examples include acrylamide derivatives such as acrylamide, compounds of general formula (IIa), and the like.

  One specific example of the resin (D) that can be particularly preferably used in the present invention is a polymer of 2- (N ′-(4-hydroxyphenyl) ureido) ethyl methacrylate and 2-hydroxyethyl methacrylate and methacryloyloxyethyl. An isocyanate is added. The resin (D) can be used as a compound having an ethylenically unsaturated group alone or in combination with the above-described compound having a known ethylenically unsaturated group.

  The amount of the compound having an ethylenically unsaturated group capable of addition polymerization is preferably in the range of 5 to 70% by weight based on the solid content of the composition.

  Examples of the photopolymerization initiator include α-carbonyl compounds described in US Pat. No. 2,367,661, acyloin ethers described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512. Α-hydrocarbon substituted aromatic acyloin compounds described, polycyclic quinone compounds described in US Pat. No. 3,046,127, triarylbiimidazole compounds described in US Pat. No. 3,549,367, Combination of p-aminophenyl ketone, trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, oxadiazole compound described in US Pat. No. 4,221,970, US Pat. Acridine and phena described in US Pat. No. 3,751,259 Examples thereof include gin compounds and benzothiazole compounds described in JP-B 51-48516, and the amount used is preferably in the range of 0.5 to 20% by weight based on the solid content of the composition.

Hereinafter, the present invention will be described by taking a positive photosensitive composition as an example. When the photosensitive composition of the present invention contains the alkali-soluble acrylic resin having a urea bond in the side chain and an o-naphthoquinonediazide compound, the photosensitive composition acts as a positive photosensitive composition and is developed with an alkaline developer. The development characteristics at the time are improved.

The alkali-soluble acrylic resin having a urea bond in the side chain used in the present invention may contain various structures, but the structural unit represented by the general formula (I) [the following formula (Ia) or (Ic)] Can be mentioned as a resin that is particularly preferably used.

About the said formula (Ia) and (Ic), all are as follows. [ Wherein , R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent. ]

  X represents, for example, an optionally substituted alkylene group or an optionally substituted phenylene group, and Y represents, for example, an optionally substituted phenylene group or substituent. A good naphthylene group is mentioned.

  A photosensitive composition using a resin containing a structural unit represented by the general formula (I) as a binder resin exhibits excellent performance in solvent resistance, abrasion resistance, and development characteristics.

  Of the resins containing the structural unit represented by the general formula (I), those suitably used in the present invention include 10 to 80 parts by weight of the structural unit represented by the general formula (I) per 100 parts by weight of the resin. When it is used as a binder resin, it exhibits further superior performance in solvent resistance, abrasion resistance, and development characteristics.

  In addition to this, a known alkali-soluble resin can be contained in the positive photosensitive composition of the present invention. For example, phenol-formaldehyde resin, m-cresol-formaldehyde resin, p-cresol-formaldehyde resin, m- / p-mixed cresol-formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed Any of these may be used. Examples include mixed-formaldehyde resins, phenol-formaldehyde resins, novolak resins such as resorcinol-formaldehyde resins, resole resins, and polyhydroxystyrene. The photosensitive composition of the present invention is characterized in that the development latitude is further widened by using these known resins in combination, and in combination with the o-quinonediazide compound (B), a novolak other than the resin (A) The resin is particularly preferably used. These alkali-soluble resins preferably have a number average molecular weight of 200 to 20,000 and a weight average molecular weight of 300 to 60,000.

  Furthermore, as described in U.S. Pat. No. 4,123,279, a phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol-formaldehyde resin and octylphenol novolak resin; It is preferable to use a condensate with formaldehyde in order to improve the oil sensitivity of the image.

The photosensitive composition of the present invention is 10 to 50 parts by weight per 100 parts by weight of the binder resin comprising the alkali-soluble acrylic resin (A) having a urea bond in the side chain and the novolak resin (C). -By using the naphthoquinonediazide compound (B) and using 5 to 95 parts by weight of the resin (A) per 100 parts by weight of the binder resin, it can be suitably used as a photosensitive composition for a lithographic printing plate. .

  The resin containing the structure of the general formula (I) used in the present invention can be synthesized by various methods. For example, one or more urea bonds and one or more polymerizations per molecule. It can be obtained by polymerizing a polymerizable monomer having a possible unsaturated bond in a suitable solvent using a known polymerization initiator.

  These polymerizable monomers having one or more urea bonds and one or more polymerizable unsaturated bonds in one molecule can be produced, for example, by the following method.

  An isocyanate compound represented by the following general formula [III] and an amine compound represented by the general formula [IV] are reacted to form one or more urea bonds and one or more polymerizable unsaturated bonds in one molecule. A polymerizable monomer can be obtained.

[Wherein, R represents a hydrogen atom or an alkyl group, and X represents a divalent linking group] X is, for example, an alkylene group which may have a substituent or a phenylene group which may have a substituent. Is mentioned.

[R ′ represents a hydrogen atom or an alkyl group which may have a substituent, Y represents a divalent aromatic group which may have a substituent, and Z represents a hydroxyl group or a sulfonamide group]

  Examples of Y include a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

  In the compound represented by the general formula [III] and the compound represented by the general formula [IV], X is an alkylene group, Y is a phenylene group or naphthylene group which may have a substituent, Z is a hydroxyl group, and R When the above reaction is carried out using a hydrogen atom having a hydrogen atom, a polymerizable monomer represented by the general formula [IIa] is obtained.

  In addition, since an amino group has relatively higher activity with respect to an isocyanate group than a hydroxyl group, a carboxyl group, or a —NH—CO— group, a monomer represented by the structure [II] can be easily obtained. For example, a method of performing the above reaction within a range of about 0 to 40 ° C. or adding the isocyanate compound [III] little by little to an excess of the amine compound [IV] is also effective.

  In carrying out the above reaction, among known organic solvents which will be described later, those having no active hydrogen atom can be suitably used. The reaction time may be carried out until there is no isocyanate group or the amount of urea bonds is constant. The usual reaction time is 15 minutes to 24 hours.

  The reaction mixture thus obtained can be used as the monomer [II] as it is, but if necessary, the unreacted raw material obtained when the reaction mixture is reacted with an excess of the compound [IV] For the purpose of removing by-products, neutralization with an acidic compound such as dilute hydrochloric acid to convert the compound [IV] into a salt, followed by washing with water, filtration, and vacuum drying, the high-purity monomer [II] is obtained. Obtainable.

  The monomer [II] thus obtained has characteristic absorption at 1600 to 1700 cm −1 in the infrared absorption spectrum based on the urea bond, and the same substance can be identified by measuring it. In addition, identification by melting point, proton NMR, etc. is also possible.

  In the present invention, such a polymerizable monomer that is preferably used includes a compound represented by the general formula (IIa).

[Wherein, R represents a hydrogen atom or an alkyl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.]

  Specific examples of X and Y include those described above.

  Examples of such polymerizable monomers include 1- (N ′-(4-hydroxyphenyl) ureido) methyl acrylate, 1- (N ′-(3-hydroxyphenyl) ureido) methyl acrylate, 1- ( N ′-(2-hydroxyphenyl) ureido) methyl acrylate, 1- (N ′-(3-hydroxy-4-methylphenyl) ureido) methyl acrylate, 1- (N ′-(2-hydroxy-5-methylphenyl) ) Ureido) methyl acrylate, 1- (N '-(5-hydroxynaphthyl) ureido) methyl acrylate, 1- (N'-(2-hydroxy-5-phenylphenyl) ureido) methyl acrylate, 2- (N'- (4-Hydroxyphenyl) ureido) ethyl acrylate, 2- (N ′-(3-hydroxyphenyl) urei ) Ethyl acrylate, 2- (N ′-(2-hydroxyphenyl) ureido) ethyl acrylate, 2- (N ′-(3-hydroxy-4-methylphenyl) ureido) ethyl acrylate, 2- (N ′-(2 -Hydroxy-5-methylphenyl) ureido) ethyl acrylate, 2- (N '-(5-hydroxynaphthyl) ureido) ethyl acrylate, 2- (N'-(2-hydroxy-5-phenylphenyl) ureido) ethyl acrylate 4- (N ′-(4-hydroxyphenyl) ureido) butyl acrylate, 4- (N ′-(3-hydroxyphenyl) ureido) butyl acrylate, 4- (N ′-(2-hydroxyphenyl) ureido) butyl Acrylate, 4- (N ′-(3-hydroxy-4-methylphenyl) ureido) Tyl acrylate, 4- (N ′-(2-hydroxy-5-methylphenyl) ureido) butyl acrylate, 4- (N ′-(5-hydroxynaphthyl) ureido) butyl acrylate, 4- (N ′-(2- Acrylate derivatives such as hydroxy-5-phenylphenyl) ureido) butyl acrylate: 1- (N ′-(4-hydroxyphenyl) ureido) methyl methacrylate, 1- (N ′-(3-hydroxyphenyl) ureido) methyl methacrylate, 1- (N ′-(2-hydroxyphenyl) ureido) methyl methacrylate, 1- (N ′-(3-hydroxy-4-methylphenyl) ureido) methyl methacrylate, 1- (N ′-(2-hydroxy-5) -Methylphenyl) ureido) methyl methacrylate, 1- (N '-(5- Droxynaphthyl) ureido) methyl methacrylate, 1- (N ′-(2-hydroxy-5-phenylphenyl) ureido) methyl methacrylate, 2- (N ′-(4-hydroxyphenyl) ureido) ethyl methacrylate, 2- ( N ′-(3-hydroxyphenyl) ureido) ethyl methacrylate, 2- (N ′-(2-hydroxyphenyl) ureido) ethyl methacrylate, 2- (N ′-(3-hydroxy-4-methylphenyl) ureido) ethyl Methacrylate, 2- (N ′-(2-hydroxy-5-methylphenyl) ureido) ethyl methacrylate, 2- (N ′-(5-hydroxynaphthyl) ureido) ethyl methacrylate, 2- (N ′-(2-hydroxy) -5-phenylphenyl) ureido) ethyl methacrylate, 4- (N ′-(4-hydroxyphenyl) ureido) butyl methacrylate, 4- (N ′-(3-hydroxyphenyl) ureido) butyl methacrylate, 4- (N ′-(2-hydroxyphenyl) ureido) butyl methacrylate, 4 -(N '-(3-hydroxy-4-methylphenyl) ureido) butyl methacrylate, 4- (N'-(2-hydroxy-5-methylphenyl) ureido) butyl methacrylate, 4- (N '-(5- And methacrylate derivatives such as hydroxynaphthyl) ureido) butyl methacrylate and 4- (N ′-(2-hydroxy-5-phenylphenyl) ureido) butyl methacrylate.

  Incidentally, 2- (N ′-(4-hydroxyphenyl) ureido) ethyl methacrylate has a melting point of 131 to 133 ° C. and can be identified from the absorption of IR spectrum based on the hydroxyl group and the urea bond.

  Another example of a polymerizable monomer having a polymerizable unsaturated bond and a urea bond that is preferably used in the present invention is, for example, 2- (N ′-(4-sulfamoylphenyl) Acrylates having an acidic group such as ureido) ethyl acrylate, 2- (N ′-(4-sulfophenyl) ureido) ethyl acrylate, 2- (N ′-(4-phosphonophenyl) ureido) ethyl acrylate: (N ′-(4-sulfamoylphenyl) ureido) ethyl methacrylate, 2- (N ′-(4-sulfophenyl) ureido) ethyl methacrylate, 2- (N ′-(4-phosphonophenyl) ureido) ethyl Methacrylates having an acidic group such as methacrylate: 2- (N′-methylureido) ethyl acrylate, 2- (N′-propylureido) Tyl acrylate, 2- (N'-phenylureido) ethyl acrylate, 2- (N '-(4-methylphenyl) ureido) ethyl acrylate, 2- (N'-(2-methylphenyl) ureido) ethyl acrylate, 2 Acrylates having no acidic group such as-(N'-naphthylureido) ethyl acrylate and 2- (N '-(2-phenylphenyl) ureido) ethyl acrylate: 2- (N'-methylureido) ethyl methacrylate 2- (N′-propylureido) ethyl methacrylate, 2- (N′-phenylureido) ethyl methacrylate, 2- (N ′-(4-methylphenyl) ureido) ethyl methacrylate, 2- (N ′-(2 -Methylphenyl) ureido) ethyl methacrylate, 2- (N'-naphthylurei) ) Ethyl methacrylate, 2- (N '- (2- phenylphenyl) ureido) do not have such an acidic group methacrylate methacrylates, and the like.

The alkali-soluble acrylic resin (A) having a urea bond in the side chain, preferably used in the present invention, is a homopolymer of a polymerizable monomer having a polymerizable unsaturated bond and a urea bond, or two or more thereof. However, it is preferably a copolymer with one or more compounds containing one or more polymerizable unsaturated bonds and no urea bonds.

  Specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethyl Acrylic esters such as hydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, tetrahydroacrylate: aryl acrylates such as phenyl acrylate and furfuryl acrylate Class: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Mil methacrylate hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol Methacrylic acid esters such as monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate: aryl methacrylates such as phenyl methacrylate, cresyl methacrylate, and naphthyl methacrylate: N-methylacrylamide, N-ethyl as acrylamide or derivatives thereof Acrylic N-alkyl acrylamides such as amide, N-propyl acrylamide, N-butyl acrylamide, Nt-butyl acrylamide, N-heptyl acrylamide, N-octyl acrylamide, N-cyclohexyl acrylamide, N-benzyl acrylamide: N-phenyl acrylamide N-arylacrylamides such as N-tolylacrylamide, N-nitrophenylacrylamide, N-naphthylacrylamide, N-hydroxyphenylacrylamide: N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide N, N-dibutylacrylamide, N, N-diisobutylacrylamide, N, N-diethylhexylacrylamide, N, N-dicyclohexylacrylic N, N-dialkylacrylamides such as amide: N, N-arylacrylamides such as N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide : Methacrylamide or derivatives thereof include N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, Nt-butylmethacrylamide, N-ethylhexylmethacrylamide, N-hydroxy N-alkyl methacrylamides such as ethyl methacrylamide and N-cyclohexyl methacrylamide: N-aryl methacrylamides such as N-phenyl methacrylamide and N-naphthyl methacrylamide: N, N- N, N-dialkylmethacrylamides such as ethyl methacrylamide, N, N-dipropylmethacrylamide, N, N-dibutylmethacrylamide: N, N-diarylmethacrylamides such as N, N-diphenylmethacrylamide: N Methacrylamide derivatives such as -hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide: allyl acetate, allyl caproate, allyl caprylate, allyl laurate, Allyl compounds such as allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, allyloxyethanol: hexyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, ethylhexyl vinyl ester Ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylamino Vinyl ethers such as ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether: vinyl butyrate, vinyl iso Butyrate, vinyltrimethyla Tate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl cyclohexyl carboxylate, Vinyl esters such as vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate: methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene , Cyclohexyl styrene, dodecyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, etho Ximethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluoro Styrenes such as styrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene: crotonates such as butyl crotonic acid, hexyl crotonic acid, crotonic acid, glycerol monocrotonate: Dialkyl itaconates such as dimethyl itaconate, diethyl itaconate, and dibutyl itaconate: maleic acids such as dimethyl malate and dibutyl fumarate or dialkyls of fumaric acid Maleimides such as maleimide, N-phenylmaleimide, N-2-methylphenylmaleimide, N-2,6-diethylphenylmaleimide, N-2-chlorophenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-hydroxyphenylmaleimide Class: Others include N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

  Among these compounds having a polymerizable unsaturated bond, (meth) acrylic acid esters, (meth) acrylamides, maleimides, and (meth) acrylonitriles are preferably used.

  As the alkali-soluble acrylic resin binder, a copolymer of a monomer mixture containing (meth) acrylonitrile in excess of 60 mol% and 90 mol% and also containing (meth) acrylamide is solvent resistant. Are better.

  (Meth) acrylic acid can be used in combination with these suitably used compounds.

  In the present invention, when referred to as (meth) acrylate or (meth) acrylic acid, it includes not only acrylate but also methacrylate, and includes not only acrylic acid but also methacrylic acid. (Meth) acrylonitrile includes acrylonitrile and methacrylonitrile, and (meth) acrylamide includes acrylamide and methacrylamide.

  One or more of these compounds having a polymerizable unsaturated bond and one or more copolymers of a compound having a urea bond and having a polymerizable unsaturated bond may be any of block, random, graft, etc. This structure can also be used.

The alkali-soluble acrylic resin (A) having a urea bond suitably used in the present invention is composed of the polymerizable monomer represented by the general formula [II] and the other polymerizable monomers other than the polymerizable monomer. The copolymer obtained by copolymerization with the monomer and using the former 10 to 80 parts by weight per 100 parts by weight of the total can be more preferably used in the present invention.

  As the latter component, it is preferable to use at least one selected from the group consisting of polymerizable maleimides, polymerizable (meth) acrylamides, polymerizable (meth) acrylates, and polymerizable (meth) acrylonitriles. It is.

  The copolymer thus obtained preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 1,000 or more. More preferably, the weight average molecular weight is in the range of 3,000 to 500,000, and the number average molecular weight is in the range of 2,000 to 400,000.

  Examples of the solvent used for synthesizing such a resin include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl glycol, 2-methoxyethyl acetate, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, 1-methoxy-2-propyl acetate, 1-ethoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl -2-pyrrolidone, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These solvents are used alone or in combination of two or more.

  The resin (A) having a urea bond in the side chain used in the photosensitive composition of the present invention may be mixed with other resins or used alone, and these resins contained in the photosensitive composition may be used. The resin content is preferably 5 to 95%.

  In the photosensitive composition of the present invention, any known and commonly used photosensitive compounds (B) having various structures can be used. In the case of a positive photosensitive composition, it is a ο-naphthoquinonediazide compound. Preferably, in the case of a negative photosensitive composition, it is preferably a diazo compound. As the photosensitive compound (B), for example, a photosensitive compound having a urea bond in the side chain can be used.

  Examples of the photosensitive compound having a urea bond in the side chain used in the positive photosensitive composition of the present invention include ο-naphthoquinonediazide sulfonic acid ester of acrylic resin containing a structural unit represented by the general formula (I) Can be preferably used. The structural unit represented by the general formula (I) is preferably 10 to 100% by weight in the resin, and the higher the ratio of converting it to o-naphthoquinonediazide sulfonic acid ester, the better the solvent resistance. Since the solubility to the solvent used at the time of application falls, the esterification rate is preferably 1 to 80%. Such o-naphthoquinonediazide sulfonic acid ester can be easily synthesized by the above-mentioned known synthesis method.

  In addition, the photosensitive compound having a urea bond in the side chain that can be used in the present invention, when used in combination with the binder resin (A) having a urea bond in the side chain of the present invention, is further superior in solvent resistance. A composition is obtained. When the o-naphthoquinonediazide sulfonic acid ester of a binder resin having a urea bond in the side chain is used, a photosensitive composition having particularly excellent solvent resistance can be obtained.

  The photosensitive composition of the present invention can be used as a positive lithographic printing plate and a negative lithographic printing plate by coating on an aluminum support.

  In the case of a positive planographic printing plate, various additives can be added depending on the purpose. For example, a surfactant to improve coatability, a plasticizer to improve the physical properties of the coating film, a fat sensitizer having a hydrophobic group to improve ink fillability in the image area, and a sensitivity In addition, a cyclic acid anhydride, a print-out agent for obtaining a visible image immediately after exposure, and a dye or other filler as an image colorant can be added.

  In the case of a negative lithographic printing plate, an organic polymer binder can be used in addition to the negative photosensitive compound and the alkali-soluble resin having a urea bond. Examples of such organic polymer binders include acrylic resins, polyamide resins, polyurethane resins, phenoxy resins, epoxy resins, polyacetal resins, polystyrene resins, novolac resins, and the like. Furthermore, known additives such as thermal polymerization inhibitors, dyes, surfactants, plasticizers, and stability improvers can be added to improve performance.

  Examples of the surfactant include fluorine-based surfactants described in JP-A Nos. 62-36657 and 62-226143. Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, tributyl citrate and the like.

  Examples of the sensitizer include novolak resins having a hydrophobic group such as p-octylphenol novolak and pt-butylphenol novolak. As cyclic acid anhydrides, as described in US Pat. No. 4,115,128, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydroanhydride Examples include phthalic acid, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride, and the like. By including these cyclic acid anhydrides in an amount of 1 to 15% by weight in the total photosensitive composition, the sensitivity can be increased up to about 3 times.

  Typical examples of the print-out agent for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, combinations of ο-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, Nos. 36223, 54-74728, 60-3626, 61-143748, 61-151644, 63-58440 and combinations of salt-forming organic dyes Can be mentioned.

  In addition to the salt-forming organic dyes described above, other dyes can also be used as the image colorant. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, oil yellow # 101, oil yellow # 130, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (or more, Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI 42555), Methyl Violet (CI 42535), Rhodamine B (CI 45170B), Malachite Green (CI 42000), Methylene Blue (CI 522015), and the like.

  Examples of known stability improvers include phosphoric acid, phosphorous acid, succinic acid, tartaric acid, malic acid, citric acid, dipicolinic acid, polyacrylic acid, benzenesulfonic acid, and toluenesulfonic acid.

  Although the addition amount of these various additives changes with the objectives, generally the range of 0-30 weight% of solid content of the photosensitive composition is preferable.

  The photosensitive composition can be dissolved in various solvents and coated on a support as necessary. Examples of the solvent include halogenated solvents such as methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and carbon tetrachloride: aliphatic or alicyclic such as hexane, heptane, cyclohesan, benzene, toluene, and xylene. Aromatic or aromatic hydrocarbon solvents: ether solvents such as tetrahydrofuran, dioxane, diethyl ether: ester solvents such as methyl acetate, butyl acetate, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate: acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone, methanol, ethanol, butanol, benzyl alcohol, diacetone alcohol, methyl cellosolve Alcohol solvents such as ethyl cellosolve and cyclohexanol: nitrogen-containing solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone: dimethyl sulfoxide and the like. A mixture of two or more types can be used, and in some cases, a mixed solvent with water can also be used.

  The photosensitive composition thus produced is applied to a support by a known application method such as dip coating, curtain coating, roll coating, spray coating, whirler coating, spinner coating, air knife coating, doctor knife coating and the like. The

  Examples of the support include metal plates such as aluminum, zinc, copper, stainless steel, and iron: plastic films such as polyethylene terephthalate, polycarbonate, polyvinyl acetal, and polyethylene: paper, plastic coated with a synthetic resin or a synthetic resin solution Composite materials in which a metal layer is provided on a film by a technique such as vacuum deposition or lamination: In addition, various materials used as a support for a printing plate can be mentioned.

  In the case of a support having a surface of metal, particularly aluminum, it is preferable that surface treatment such as graining treatment, anodizing treatment, hydrophilization treatment or the like is performed. The coating amount of the photosensitive composition is usually about 0.5 to 5 g / m @ 2 by dry weight.

  After coating, the photosensitive lithographic printing plate having a photosensitive layer provided on the support is obtained by drying by a known method.

  The photosensitive lithographic printing plate thus obtained can be used by a known method. For example, a positive type film is brought into close contact with this photosensitive lithographic printing plate, exposed with an ultra-high pressure mercury lamp, a metal halide lamp, etc., and developed with an alkaline aqueous solution such as sodium metasilicate, potassium metasilicate, sodium phosphate, caustic soda, etc. Used as.

  When the lithographic printing plate thus obtained is subjected to a thermosetting process (called a burning process or a baking process), the printing durability is further improved, and there is also an effect that stains are hardly generated in the non-image area. .

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

(Synthesis Example 1)
2- (N ′-(4-carboxyphenyl) ureido) ethyl methacrylate was obtained by adding methacryloyloxyethyl isocyanate and 4-aminobenzoic acid to a dioxane solvent and dissolving the mixture and stirring for 2 hours.

(Synthesis Example 2)
2- (N ′-(4-hydroxyphenyl) ureido) ethyl methacrylate was obtained by adding methacryloyloxyethyl isocyanate and 4-aminophenol to the dioxane solvent and stirring for 2 hours.

(Synthesis Examples 3 to 7)
The compound obtained in Synthesis Example 1 and the other monomer having a polymerizable unsaturated bond were polymerized at the ratio shown in Table 1 to obtain an alkali-soluble resin having a urea bond in the side chain used in the present invention.

(Synthesis Example 8)
4- (N′-phenylureido) phenol was obtained by adding phenyl isocyanate and 4-aminophenol to the dioxane solvent and stirring for 2 hours.

(Synthesis Example 9)
4- (N′-phenylureido) phenol, an aqueous formaldehyde solution, and oxalic acid are heated to 100 ° C. with stirring, and an alkali-soluble resin having a urea bond in the side chain, which is mainly composed of a resin having the following structure used in the present invention. Got. The weight average molecular weight of the obtained resin was 2,000.

［但し、ｎは１〜１５であり、（ ）内のＰｈは、ベンゼン環（Ｃ6Ｈ2）であり、ＮＨに結合するＰｈは、フェニル基である。］

[However, n is 1-15, Ph in () is a benzene ring (C6H2), and Ph bonded to NH is a phenyl group. ]

Then, for Reference Examples 1-2, Examples 2-4 and Comparative Example 1, the photosensitive solutions (photosensitive compositions) having the composition ratios shown in Table 2 below, and for Examples 5 and Comparative Examples 2, the composition ratios shown in Table 4 below. The photosensitive solution (photosensitive composition), Example 6 and Comparative Example 3 were each prepared as a photosensitive solution (photosensitive composition) having the composition ratio shown in Table 5 below.

Note 1: 90% esterification rate Note 2: A mixture of m-cresol (100 g), p-cresol (66.8 g), phenol (36.0 g), 37% aqueous formaldehyde solution (105 g) and oxalic acid (2.5 g) is heated. The mixture was stirred at 105 ° C. for 3 hours. Thereafter, the temperature was raised to 175 ° C. to distill off water, and the residual monomer was distilled off at 200 ° C./100 mmHg. The weight average molecular weight of the resin obtained by the above production method was 4000.
Note 3: Basic oil-soluble dye manufactured by Hodogaya Chemical Co., Ltd.

Reference Examples 1-2 and Examples 1-4
An aluminum plate having a thickness of 0.24 mm was degreased with an aqueous sodium hydroxide solution and subjected to electrolytic polishing in a 20% hydrochloric acid bath to obtain a grained plate having a center line average roughness (Ra) of 0.6 μm. . Subsequently, it was anodized in a 20% sulfuric acid bath at a current density of 2 A / dm 2 to form an oxide film of 2.7 g / m 2, washed with water and dried to obtain an aluminum support. A photosensitive solution (photosensitive composition) having the above composition was applied onto the aluminum support thus obtained using a roll coater and dried at 100 ° C. for 3 minutes to obtain a photosensitive lithographic printing plate. The amount of the dried coating film was 2.0 g / m2.

  An image film was brought into close contact with each of the obtained positive photosensitive lithographic printing plates, and was exposed from a distance of 1 m with a 3 kW metal halide lamp. Using an automatic developing machine PD-912 manufactured by Dainippon Screen Co., Ltd., and using a developer PD-1 (9-fold dilution) manufactured by Polychrome Japan Co., Ltd. sold by Dainippon Ink & Chemicals, Inc. And developed at 30 ° C. for 12 seconds.

  The lithographic printing plate thus prepared was evaluated for solvent resistance and printing durability. The solvent resistance was evaluated based on the degree of erosion of the photosensitive layer by immersing the lithographic printing plate exposed with the above apparatus in various solvents for 30 minutes.

  For printing durability, a lithographic printing plate was mounted on a Roland Fabry printing press, UV ink "Dicure Scepter Ink" (Dainippon Ink Chemical Co., Ltd.), dampening water "NA-108W" (Dainippon Ink). Printing was performed using a 100-fold diluted solution (manufactured by Chemical Industry Co., Ltd.).

  The results are shown in Table 3.

A and B in the solvent resistance column represent the following mixed solvents, respectively.
A: Light oil (60%) + Butyl cellosolve (40%)
B: Xylene (30%) + light oil (50%) + butyl cellosolve (20%) The evaluation criteria are as follows.

○: No erosion, △: Some erosion, ×: Complete erosion

(Comparative Synthesis Example 1)
Hydroquinone (350 g) was dissolved in acetone (2.5 kg) and pyridine (500 ml). After cooling to 0 ° C., methacrylic acid chloride (313.5 g) was added dropwise. At this time, the reaction temperature was kept at 0 to 5 ° C., and then stirred at the same temperature for 3 hours. After further stirring for 1 hour at room temperature, acetone was distilled off. Water was added thereto, acidified with hydrochloric acid (pH 4), and extracted with ether. The ether layer was washed with 5% aqueous sodium hydrogen carbonate solution, washed with water and dried (anhydrous sodium carbonate), and then the ether was distilled off to obtain a white solid. This was recrystallized with water to obtain colorless needle-like crystals (420 g) of hydroquinone monomethacrylate having a melting point of 120.5 to 121.5 ° C.

  A copolymer was synthesized in the same manner as in Synthesis Example 4 except that the hydroquinone monomethacrylate was used instead of the monomer of Synthesis Example 2 used in Synthesis Example 4. Its weight average molecular weight was 18,000.

Comparative Example 1
In the composition of Table 2, using the resin synthesized in Comparative Synthesis Example 1 instead of the resin of Synthesis Example (3-7), a lithographic printing plate was prepared by the same method as in Example, and its solvent resistance was The results of comparing printing durability are also shown in Table 3.

As a result, the lithographic printing plate of Example 3 is superior to the lithographic printing plate of Comparative Example 1 in both solvent resistance and printing durability, and the resin having a urea bond in the side chain improves the solvent resistance. It has been found. Reference Example 1 and Examples 1, 2 and 4 were obtained by changing the copolymer composition of the acrylic resin used, and Reference Example 2 was a novolac resin, both of which had excellent resistance to resistance. It was found to have solvent resistance and printing durability. Further, from the comparison between Reference Example 1 and Example 1 , it can be seen that the end group is more excellent in printing durability when it is a hydroxyl group than a carboxyl group. The development characteristics were evaluated from the fact that an image can be formed by the above-described development processing, and that the grayscale halftone portion does not turn brown or black during development. Reference Examples 1 and 2 and Example 1 were evaluated. ~ 4 and Comparative Example 1 were good.

(Synthesis Example 10)
The compound of Synthesis Example 2 (50 parts by weight), methyl methacrylate (20 parts by weight) and 2-hydroxyethyl methacrylate (30 parts by weight) were added to N, N-dimethylacetamide solution as a catalyst using AIBN at 80 ° C. Stir for hours. The precipitate produced by pouring this into water was filtered and dried to obtain an alkali-soluble resin having a urea bond in the side chain used in the present invention. (Weight average molecular weight: 100,000, yield: 95%)

(Comparative Synthesis Example 2)
A resin was synthesized in the same manner as in Synthesis Example 10 except that the compound of Comparative Synthesis Example 1 was used instead of the compound of Synthesis Example 2 used in Synthesis Example 10. (Weight average molecular weight: 100,000, yield: 95%)

Example 5
Except that the photosensitive composition shown in Table 4 was prepared, the same operation as in the above example was performed to obtain a negative photosensitive lithographic printing plate. Each of these printing plates was developed at 30 ° C. for 19 seconds using a developer ND-1 (4-fold dilution) manufactured by Polychrome Japan Co., Ltd. sold by Dainippon Ink & Chemicals, Inc. The results of comparing the printing durability and solvent resistance are shown in Table 6.

Comparative Example 2
In the composition of Table 4, a photosensitive composition was prepared using the resin synthesized in Comparative Synthesis Example 2 instead of the resin in Synthesis Example 10, and a lithographic printing plate was prepared in the same manner as in Example 5 . . The results of comparing the printing durability and solvent resistance are also shown in Table 6.

Note 1: Basic oil-soluble dye manufactured by Hodogaya Chemical Co., Ltd.

(Synthesis Example 11)
The compound of Synthesis Example 2 (50 parts by weight), methyl methacrylate (20 parts by weight) and 2-hydroxyethyl methacrylate (30 parts by weight) were added to N, N-dimethylacetamide solution as a catalyst using AIBN at 80 ° C. Stir for hours. After cooling this to 25 ° C., methacryloyloxyethyl isocyanate (35.7 parts by weight, equimolar amount with 2-hydroxyethyl methacrylate) was added while thoroughly blowing dry air into the reaction solution, and the mixture was further stirred at room temperature for 5 hours. did. The reaction solution was poured into water and the resulting precipitate was filtered and dried to obtain an alkali-soluble resin having a urea bond in the side chain used in the present invention. (Weight average molecular weight: 120,000, yield 95%)

(Comparative Synthesis Example 3)
A resin was synthesized in the same manner as in Synthesis Example 11 except that the compound of Comparative Synthesis Example 1 was used instead of the compound of Synthesis Example 2 used in Synthesis Example 11. (Weight average molecular weight: 120,000, yield: 95%)

Example 6
Except that the photosensitive composition shown in Table 5 was prepared, the same operation as in the above example was performed to obtain a negative photosensitive lithographic printing plate. Each of these printing plates was developed at 30 ° C. for 19 seconds using a developer ND-1 (4-fold dilution) manufactured by Polychrome Japan Co., Ltd. sold by Dainippon Ink & Chemicals, Inc. The results of comparing the printing durability and solvent resistance are shown in Table 6.

Comparative Example 3
In the composition of Table 5, a photosensitive composition was prepared using the resin synthesized in Comparative Synthesis Example 3 instead of the resin in Synthesis Example 11, and a lithographic printing plate was prepared in the same manner as in Example 6 . . The results of comparing the printing durability and solvent resistance are also shown in Table 6.

Note 1: Basic oil-soluble dye manufactured by Hodogaya Chemical Co., Ltd.

Example 5 and Comparative Example 2 using a resin having a urea bond in a side chain, and a resin having a urea bond and a polymerizable unsaturated double bond in a side chain for a negative photosensitive lithographic printing plate The evaluation results of Example 6 and Comparative Example 3 are as follows.

Note 1: Evaluation was performed by immersing in butyl cellosolve for 1 hour. The evaluation criteria are as follows. ◯: No erosion, Δ: Slightly eroded, X: Erosion mark clearly remains Note 2: Printed using UV ink, showing the number of printed sheets until a normal printed matter cannot be obtained.

Example 5 showed better solvent resistance and superior printing durability compared to Comparative Example 2. On the other hand, Example 6 also showed good solvent resistance as compared with Comparative Example 3, and was excellent in printing durability. The negative photosensitive lithographic printing plate (Example 5 ) in which a resin having a urea bond in the side chain of the present invention is used in combination with a photosensitive diazonium compound exhibits good solvent resistance and printing durability, stability over time, Excellent safety light.

When the resin having a urea bond in the side chain of the present invention has an ethylenically unsaturated group (Example 6 ), a photosensitive diazonium compound, a photopolymerization initiator, and a monomer having an ethylenically unsaturated group are used. When combined, further excellent solvent resistance and printing durability were obtained, and a highly sensitive negative photosensitive lithographic printing plate was obtained. Moreover, all of Examples 5 and 6 had good ink inking properties.

Claims (8)

The following general formula (Ia) or (Ic):

[Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.

[Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.
A photosensitive composition comprising an alkali-soluble acrylic resin (A) containing a structural unit represented by formula (B) and a photosensitive compound (B). The photosensitive composition according to claim 1, which acts positively, wherein the photosensitive compound (B) is an o-naphthoquinonediazide compound. The following general formula (IIa) or (IIc):

[Wherein, R represents a hydrogen atom or an alkyl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.]

[Wherein, R represents a hydrogen atom or an alkyl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.]
The positive photosensitive composition according to claim 2, comprising an alkali-soluble acrylic resin (A) obtained by polymerizing the polymerizable monomer represented by formula (I) as an essential component and an o-naphthoquinonediazide compound. A positive photosensitive lithographic printing plate in which a metal support layer and a photosensitive layer are laminated, wherein the photosensitive layer has the following general formula (Ia) or (Ic):

[Wherein R ₁ And R ₂ Each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; _Three Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.

[Wherein R ₁ And R ₂ Each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; _Three Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.
A positive photosensitive lithographic printing plate comprising a photosensitive layer containing, as essential components, an alkali-soluble acrylic resin (A) containing the structural unit represented by formula (I) and ο-naphthoquinonediazide sulfonic acid ester. A negative photosensitive lithographic printing plate in which a metal support layer and a photosensitive layer are laminated, wherein the photosensitive layer has the following general formula (Ia) or (Ic):

[Wherein R ₁ And R ₂ Each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; _Three Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.

[Wherein R ₁ And R ₂ Each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof; _Three Represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent.
A negative photosensitive lithographic printing plate comprising a photosensitive layer containing, as an essential component, an alkali-soluble acrylic resin (A) containing the structural unit represented by formula (I) and a negative photosensitive compound. 6. The negative photosensitive lithographic printing plate according to claim 5, wherein the negative photosensitive compound is a photosensitive diazonium compound. 6. The negative photosensitive lithographic printing plate according to claim 5, wherein the alkali-soluble acrylic resin (A) is a resin (D) having a structure represented by the general formula (Ia) and an ethylenically unsaturated group. The negative photosensitive lithographic printing according to claim 5, wherein the negative photosensitive compound is a combination of a photosensitive diazonium compound, a photopolymerization initiator, and a monomer or oligomer having an ethylenically unsaturated group other than the resin (D). Edition.