JP5690671B2 - NOVEL POLYMERIZABLE COMPOSITION, POLYMERIZABLE COMPOUND USED FOR THE SAME, IMAGE-FORMING MATERIAL USING NOVEL POLYMERIZABLE COMPOSITION, AND lithographic printing plate precursor - Google Patents

Description

  The present invention relates to a polymerizable composition and a polymerizable compound used therefor. The polymerizable composition of the present invention is particularly suitably used as a so-called lithographic printing plate material capable of direct plate making, which can be directly made by using various lasers from a digital signal such as a computer.

In general, a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water. Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area, and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). In this method, a difference in ink adhesion is caused on the surface of the lithographic printing plate, and after ink is applied only to the image area, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, conventionally, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support has been widely used. Usually, the lithographic printing plate precursor is exposed through an original image such as a lithographic film, then the image recording layer that becomes the image portion remains, and the alkaline development that dissolves and removes the unnecessary image recording layer corresponding to the non-image portion A lithographic printing plate was obtained by developing with a liquid or the like.

  Due to recent advances in this field, lithographic printing plates are now available with CTP (computer to plate) technology. That is, a lithographic printing plate can be obtained by scanning and exposing a lithographic printing plate precursor directly using a laser or a laser diode without a lith film, and developing it.

Under such circumstances, development issues related to the lithographic printing plate precursor are concentrated on improvements in image formation characteristics, printing characteristics, physical characteristics and the like corresponding to the CTP.
Another development issue related to lithographic printing plate precursors is an environmental issue related to waste liquids associated with wet processing such as development processing, which has become a major concern of the industry in recent years due to consideration for the global environment. .

For the environmental problems described above, simplification and no processing of development or plate making are directed. As one simple plate making method, a method called “on-press development” is performed. That is, after the exposure of the lithographic printing plate precursor, conventional development is not performed, but it is mounted on a printing machine as it is, and unnecessary portions of the image recording layer are removed at the initial stage of a normal printing process.
Further, as a simple development method, the unnecessary portion of the image recording layer is removed by a finisher or gum solution having a pH close to neutrality used in the post-development processing instead of the conventional highly alkaline developer. A method called “gum development” is also performed.

  In the simplification of the plate making operation as described above, a system using an image recording layer and a light source that can be handled in a bright room or under a yellow light is preferable from the viewpoint of ease of work, and such a light source has a wavelength of 760. A solid-state laser such as a semiconductor laser that emits infrared light of up to 1200 nm and a YAG laser is used. A UV laser can also be used.

  As a lithographic printing plate precursor that can be developed on the machine, for example, in Patent Document 1, an image recording layer (photosensitive layer) containing an infrared absorber, a radical polymerization initiator, and a polymerizable compound is provided on a support. A planographic printing plate precursor is described. Further, as a lithographic printing plate precursor capable of gum development, for example, a lithographic printing plate precursor of a type in which development is performed with a finisher or gum solution having a pH close to neutral as in Patent Documents 2 and 3 is known.

  As a lithographic printing plate precursor capable of on-machine development, for example, in Patent Documents 1 and 2, a lithographic printing plate having an image recording layer (thermosensitive layer) containing a microcapsule containing a polymerizable compound on a hydrophilic support. The original edition is listed. Patent Document 3 describes a lithographic printing plate precursor in which an image recording layer (photosensitive layer) containing an infrared absorber, a radical polymerization initiator, and a polymerizable compound is provided on a support. Further, in Patent Document 4, on-press development is possible in which an image recording layer containing a polymerizable compound and a graft polymer having a polyethylene oxide chain in the side chain or a block polymer having a polyethylene oxide block is provided on a support. A planographic printing plate precursor is described.

  However, these simple processing type lithographic printing plate precursors are conventionally hydrophilic in the image recording layer in order to enable development with a low pH developer or a dampening solution (usually almost neutral) on a printing press. There is a problem that it is difficult to achieve both coexistence of using a high component, so that the printing durability becomes insufficient, and conversely, if the hydrophilicity is lowered to improve the printing durability, the developing property deteriorates.

  Various studies have been made to improve this problem. For example, Patent Document 5 describes that an image recording layer contains a low molecular weight hydrophilic compound, polyols, organic sulfates, organic sulfonates, or betaines. Patent Document 6 describes a composition containing a polymerizable monomer having a sulfobetaine structure. However, even if these techniques are used, the compatibility between developability and printing durability is not yet sufficient, and further improvements have been desired.

JP 2001-277740 A JP 2001-277742 A JP 2002-287334 A US Patent Application Publication No. 2003/0064318 JP 2009-172790 A JP-A-5-179155

  An object of the present invention is to provide a polymerizable composition capable of forming a good polymerized cured film having good developability and no film loss. When used for the image recording layer of a lithographic printing plate precursor, the developability and stain resistance are good and sufficient printing durability can be maintained. In particular, an object of the present invention is to provide an on-press development type lithographic printing plate precursor having good on-press developability, stain resistance and printing durability.

（一般式（１）中、Ｒ _１ 、Ｒ _２ は各々独立に置換基を有してもよい炭素原子数１〜６のアルキル基、アルケニル基、アルキニル基、シクロアルキル基又はアリール基を表す。Ｒ _３ は水素原子又はメチル基を表す。Ｚ _１ は２価の連結基を表し、Ｙ _１ は置換基を有してもよい炭素原子数１〜６のアルキレン基を表す。ｘは１〜５の整数、ｙは２〜５の整数を表し、Ｗ _１ は３〜１０価の非金属原子から構成される有機基を表す。また、任意のＲ _１ 、Ｒ _２ 、Ｗ _１ のうち２以上が互いに結合して複素環を形成してもよい。）
＜２＞ 前記重合性ベタイン化合物が、下記の一般式（２）又は（３）で表される構造を有することを特徴とする＜１＞に記載の重合性組成物。

（一般式（２）中、Ｒ _４ 〜Ｒ _７ は各々独立に置換基を有してもよい炭素原子数１〜６のアルキル基、アルケニル基、アルキニル基、シクロアルキル基又はアリール基を表す。あるいはＲ _４ 、Ｒ _５ 、Ｒ _６ 、Ｒ _７ の任意の２つが互いに結合して複素環を形成してもよい。Ｒ _８ は水素原子又はメチル基を表し、Ｚ _２ は−ＣＯ−、−Ｏ−、−ＣＨ _２ Ｏ−又は置換基を有してもよいフェニレン基を表す。Ｗ _２ は炭素原子数１０以下の３価の連結基を表し、Ｙ _２ 、Ｙ _３ は独立に置換基を有してもよい炭素原子数１〜６のアルキレン基を表す。
一般式（３）中、Ｒ _９ 〜Ｒ _１１ は各々独立に置換基を有してもよい炭素原子数１〜６のアルキル基、アルケニル基、アルキニル基、シクロアルキル基又はアリール基を表す。あるいはＲ _９ 、Ｒ _１０ 、Ｒ _１１ の任意の２つが互いに結合して複素環を形成してもよい。Ｒ _１２ は水素原子又はメチル基を表し、Ｚ _３ は−ＣＯ−、−Ｏ−、−ＣＨ _２ Ｏ−又は置換基を有してもよいフェニレン基を表す。Ｘ _１ 、Ｘ _２ は独立に炭素原子数１０以下の２価の連結基を表し、Ｙ _４ 、Ｙ _５ は独立に置換基を有してもよい炭素原子数１〜６のアルキレン基を表す。）
＜３＞ 前記重合性ベタイン化合物が、前記一般式（２）又は（３）において、Ｒ _４ 〜Ｒ _７ 、Ｒ _９ 〜Ｒ _１１ は各々独立にメチル基、エチル基、又は（Ｒ _４ 、Ｒ _５ 、Ｒ _６ 、Ｒ _７ ）若しくは（Ｒ _９ 、Ｒ _１０ 、Ｒ _１１ ）の群の任意の２つが互いに結合した５員若しくは６員の複素環を含有する基を表し、Ｚ _２ 、Ｚ _３ は−ＣＯ−又は置換基を有してもよいフェニレン基を表し、Ｗ _２ は炭素原子数１０以下の３価の連結基を表し、Ｘ _１ 、Ｘ _２ は炭素原子数１０以下の２価の連結基を表し、Ｙ _２ 〜Ｙ _５ は独立に炭素原子数２〜５のアルキレン基を表すことを特徴とする＜２＞に記載の重合性組成物。
＜４＞ 前記重合性ベタイン化合物が、下記の一般式（４）で表される構造を有することを特徴とする＜１＞〜＜３＞のいずれか１項に記載の重合性組成物。

（式中、Ｒ _１３ 〜Ｒ _１６ は各々独立にメチル基又はエチル基を表し、Ｒ _１７ は水素原子又はメチル基を表し、Ｌ _１ 、Ｌ _２ は各々独立に炭素原子数５以下の２価の連結基を表す。Ｙ _６ 、Ｙ _７ は各々独立に炭素原子数２〜５のアルキレン基を表す。）
＜５＞ ＜１＞〜＜４＞のいずれか１項に記載の重合性組成物を含有することを特徴とする画像形成材料。
＜６＞ 支持体上に、＜１＞〜＜４＞のいずれか１項に記載の重合性組成物を含有する画像記録層を有することを特徴とする平版印刷版原版。
＜７＞ 前記平版印刷版原版の画像記録層が、更に（ｃ）増感色素、（ｄ）重合性化合物及び（ｅ）バインダーポリマーを含有することを特徴とする＜６＞に記載の平版印刷版原版。
＜８＞ 前記平版印刷版原版の画像記録層が、印刷インキ及び湿し水の少なくともいずれかにより除去可能であることを特徴とする＜６＞又は＜７＞に記載の平版印刷版原版。
＜９＞ 前記平版印刷版原版の画像記録層が、ｐＨ２〜１４の水溶液により除去可能であることを特徴とする請求項＜６＞又は＜７＞に記載の平版印刷版原版。
＜１０＞ 下記の一般式（５）で表される構造を有することを特徴とする重合性ベタイン化合物。

（式中、Ｒ _１３ 〜Ｒ _１６ は各々独立にメチル基又はエチル基を表し、Ｒ _１７ は水素原子又はメチル基を表し、Ｌ _１ 、Ｌ _２ は各々独立に炭素原子数５以下の２価の連結基を表す。Ｙ _６ 、Ｙ _７ は各々独立に炭素原子数２〜５のアルキレン基を表す。）
本発明は、上記＜１＞〜＜１０＞に記載の重合性組成物、画像形成材料、平版印刷版原版及び重合性ベタイン化合物に関するものであるが、その他の事項についても参考のために記載する。
１．（ａ）１分子中に、スルホベタイン構造を少なくとも２つ有し、かつエチレン性不飽
和結合を少なくとも１つ有する重合性ベタイン化合物、及び（ｂ）重合開始剤を含有する
重合性組成物。
２．前記重合性ベタイン化合物が、下記一般式（１）で表される構造を有することを特徴
とする前記１記載の重合性組成物。 <1> A polymerizable composition comprising (a) a polymerizable betaine compound having a structure represented by the following general formula (1), and (b) a polymerization initiator.

(In general formula (1), R < ₁ > , R < ₂ > represents the C1-C6 alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group which may have a substituent each independently. R ₃ represents a hydrogen atom or a methyl group, Z ₁ represents a divalent linking group, Y ₁ represents an optionally substituted alkylene group having 1 to 6 carbon atoms, x is 1 to 5 Y represents an integer of 2 to 5, and W ₁ represents an organic group composed of a trivalent to 10-valent non-metallic atom, and two or more of any R ₁ , R ₂ , and W ₁ are They may combine with each other to form a heterocyclic ring.)
<2> The polymerizable composition according to <1>, wherein the polymerizable betaine compound has a structure represented by the following general formula (2) or (3).

(In the general formula (2), R _{4 to} R ₇ each independently represents a C 1-6 alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group which may have a substituent. Alternatively , any two of R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a heterocyclic ring, R ₈ represents a hydrogen atom or a methyl group, and Z ₂ represents —CO—, —O. —, —CH ₂ O— or an optionally substituted phenylene group, W ₂ represents a trivalent linking group having 10 or less carbon atoms, and Y ₂ and Y ₃ independently have a substituent. Represents an alkylene group having 1 to 6 carbon atoms.
In general formula (3), R _{9 to} R ₁₁ each independently represents an alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group having 1 to 6 carbon atoms which may have a substituent. Alternatively , any two of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other to form a heterocyclic ring. R ₁₂ represents a hydrogen atom or a methyl group, and Z ₃ represents —CO—, —O— , —CH ₂ O— or a phenylene group which may have a substituent. X ₁ and X ₂ independently represent a divalent linking group having 10 or less carbon atoms, and Y ₄ and Y ₅ independently represent an alkylene group having 1 to 6 carbon atoms which may have a substituent. )
<3> In the general formula (2) or (3), the polymerizable betaine compound is independently a methyl group, an ethyl group, or (R ₄ , R ₅ ), wherein R _{4 to} R ₇ and R _{9 to} R ₁₁ are each independently. , R ₆ , R ₇ ) or (R ₉ , R ₁₀ , R ₁₁ ) represent a group containing a 5- or 6-membered heterocyclic ring in which any two of them are bonded to each other, Z ₂ and Z ₃ are — CO— represents an optionally substituted phenylene group, W ₂ represents a trivalent linking group having 10 or less carbon atoms , and X ₁ and X ₂ are divalent linking groups having 10 or less carbon atoms. the stands, Y ₂ to Y ₅ is characterized in that an alkylene group having 2 to 5 carbon atoms independently polymerizable composition according to <2>.
<4> The polymerizable composition according to any one of <1> to <3>, wherein the polymerizable betaine compound has a structure represented by the following general formula (4).

(Wherein R _{13 to} R ₁₆ each independently represents a methyl group or an ethyl group, R ₁₇ represents a hydrogen atom or a methyl group, and L ₁ and L ₂ each independently represents a divalent group having 5 or less carbon atoms. Y ₆ and Y ₇ each independently represent an alkylene group having 2 to 5 carbon atoms.
<5> An image forming material comprising the polymerizable composition according to any one of <1> to <4>.
<6> A lithographic printing plate precursor comprising an image recording layer containing the polymerizable composition according to any one of <1> to <4> on a support.
<7> The lithographic printing according to <6>, wherein the image recording layer of the lithographic printing plate precursor further comprises (c) a sensitizing dye, (d) a polymerizable compound, and (e) a binder polymer. Version original edition.
<8> The lithographic printing plate precursor as described in <6> or <7>, wherein the image recording layer of the lithographic printing plate precursor can be removed with at least one of printing ink and fountain solution.
<9> The lithographic printing plate precursor as described in <6> or <7>, wherein the image recording layer of the lithographic printing plate precursor can be removed with an aqueous solution having a pH of 2 to 14.
<10> A polymerizable betaine compound having a structure represented by the following general formula (5).

(Wherein R _{13 to} R ₁₆ each independently represents a methyl group or an ethyl group, R ₁₇ represents a hydrogen atom or a methyl group, and L ₁ and L ₂ each independently represents a divalent group having 5 or less carbon atoms. Y ₆ and Y ₇ each independently represent an alkylene group having 2 to 5 carbon atoms.
The present invention relates to the polymerizable composition, the image forming material, the lithographic printing plate precursor and the polymerizable betaine compound described in <1> to <10> above, but other matters are also described for reference. .
1. (A) A polymerizable composition containing a polymerizable betaine compound having at least two sulfobetaine structures and at least one ethylenically unsaturated bond in one molecule, and (b) a polymerization initiator.
2. 2. The polymerizable composition as described in 1 above, wherein the polymerizable betaine compound has a structure represented by the following general formula (1).

In general formula (1), R ₁ and R ₂ each independently represents an alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group having 1 to 6 carbon atoms which may have a substituent. R ₃ represents a hydrogen atom or a methyl group. Z ₁ represents a divalent linking group, and Y ₁ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent. x represents an integer of 1 to 5, y represents an integer of 2 to 5, and W ₁ represents an organic group composed of 3 to 10 valent nonmetallic atoms. Two or more of R ₁ , R ₂ and W ₁ may be bonded to each other to form a heterocyclic ring.

3. 3. The polymerizable composition as described in 1 or 2 above, wherein the polymerizable betaine compound has a structure represented by the following general formula (2) or (3).

In General Formula (2), R _{4 to} R ₇ each independently represents an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group having 1 to 6 carbon atoms that may have a substituent. Alternatively, any two of R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a heterocyclic ring. R ₈ represents a hydrogen atom or a methyl group, and Z ₂ represents —CO—, —O—, —CH ₂ O— or a phenylene group which may have a substituent. W ₂ represents a trivalent linking group having 10 or less carbon atoms, and Y ₂ and Y ₃ independently represent an alkylene group having 1 to 6 carbon atoms which may have a substituent.
In general formula (3), R _{9 to} R ₁₁ each independently represents an alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group having 1 to 6 carbon atoms which may have a substituent. Alternatively, any two of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other to form a heterocyclic ring. R ₁₂ represents a hydrogen atom or a methyl group, and Z ₃ represents —CO—, —O—, —CH ₂ O— or a phenylene group which may have a substituent. X ₁ and X ₂ independently represent a divalent linking group having 10 or less carbon atoms, and Y ₄ and Y ₅ independently represent an alkylene group having 1 to 6 carbon atoms which may have a substituent.

4). In the general formula (2) or (3), R _{4 to} R ₇ and R _{9 to} R ₁₁ are each independently a methyl group, an ethyl group, or (R ₄ , R ₅ , R _6). , R ₇ ) or (R ₉ , R ₁₀ , R ₁₁ ) represents a group containing a 5-membered or 6-membered heterocyclic ring bonded to each other, and Z ₂ , Z ₃ are —CO— or Represents a phenylene group which may have a substituent, W ₂ represents a trivalent linking group having 10 or less carbon atoms, X ₁ and X ₂ represent a divalent linking group having 10 or less carbon atoms, Y < ₂ > -Y < ₅ > represents a C2-C5 alkylene group independently, The polymeric composition of any one of said 1-3 characterized by the above-mentioned.
5. 5. The polymerizable composition according to any one of 1 to 4, wherein the polymerizable betaine compound has a structure represented by the following general formula (4).

In the formula, R _{13 to} R ₁₆ each independently represent a methyl group or an ethyl group, R ₁₇ represents a hydrogen atom or a methyl group, and L ₁ and L ₂ each independently represent a divalent linkage having 5 or less carbon atoms. Represents a group. Y ₆ and Y ₇ each independently represents an alkylene group having 2 to 5 carbon atoms.

6). 6. An image forming material comprising the polymerizable composition as described in any one of 1 to 5 above.
7). A lithographic printing plate precursor having an image recording layer containing the polymerizable composition according to any one of 1 to 5 above on a support.
8). 8. The lithographic printing plate precursor as described in 7 above, wherein the image recording layer of the lithographic printing plate precursor further comprises (c) a sensitizing dye, (d) a polymerizable compound and (e) a binder polymer.
9. 9. The lithographic printing plate precursor as described in 7 or 8 above, wherein the image recording layer of the lithographic printing plate precursor can be removed by at least one of printing ink and fountain solution.
10. 9. The lithographic printing plate precursor as described in 7 or 8 above, wherein the image recording layer of the lithographic printing plate precursor can be removed with an aqueous solution having a pH of 2 to 14.
11. The polymeric betaine compound which has a structure represented by following General formula (5).

In the formula, R _{13 to} R ₁₆ each independently represent a methyl group or an ethyl group, R ₁₇ represents a hydrogen atom or a methyl group, and L ₁ and L ₂ each independently represent a divalent linkage having 5 or less carbon atoms. Represents a group. Y ₆ and Y ₇ each independently represents an alkylene group having 2 to 5 carbon atoms.

In the present invention, (a) a polymerizable betaine compound having at least two sulfobetaine structures and at least one ethylenically unsaturated bond in one molecule, and (b) a polymerization property containing a polymerization initiator By using the composition, it has become possible to obtain a lithographic printing plate precursor having good printing durability in addition to developability.
Although the mechanism of action of the present invention is not clear, the following is presumed. In the unexposed area, it is estimated that the compound of the present invention having a plurality of highly hydrophilic sulfobetaine structures improves the fountain solution permeability and exhibits good on-press developability. In addition, the printing durability was unexpectedly improved by adopting a monomer structure having two sulfobetaine structures, but this is because the monomer unit having the sulfobetaine structure is thermally decomposed and hydrophobized in the exposed area. It is presumed that the permeability of the fountain solution is lowered and the thermal decomposition product contains radical chemical species to promote radical polymerization, thereby further increasing the curability of the image.

  According to the present invention, there are provided a polymerizable composition having good developability and capable of forming a good polymer film, and a lithographic printing plate precursor having good developability and stain resistance and sufficient printing durability. Can be provided. In particular, an on-press development type lithographic printing plate precursor having good on-press developability, stain resistance and printing durability can be provided.

It is a schematic block diagram of an automatic processor.

<< (a) Polymerizable betaine compound having at least two sulfobetaine structures and at least one ethylenically unsaturated bond in one molecule >>
The polymerizable betaine compound of the present invention is a compound having at least two sulfobetaine structures and at least one ethylenically unsaturated bond in one molecule.
The structure of the polymerizable betaine compound is represented, for example, by the following general formula (1).

In the general formula _{(1), R 1, R} 2 each independently represent a substituent having also an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group or an aryl group, introduced Possible substituents include, for example, halogen atoms, hydroxy groups, carboxy groups, sulfonate groups, nitro groups, cyano groups, amide groups, amino groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, substituted oxy groups, and substituted groups. Examples include a sulfonyl group, a substituted carbonyl group, a substituted sulfinyl group, a sulfo group, a phosphono group, a phosphonate group, a silyl group, and a heterocyclic group. R ₃ represents a hydrogen atom or a methyl group. Z ₁ represents a divalent linking group. Specific examples include —CO—O—, —CO—NH—, —CO—NR— (R represents a substituent), —O—, —CH ₂ O—, or phenylene which may have a substituent. Groups. Here, the substituent is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, and these groups include a halogen atom, a hydroxy group, Carboxy group, sulfonate group, nitro group, cyano group, amide group, amino group, alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono Group, phosphonato group, silyl group, and heterocyclic group may be contained. Y ₁ represents an optionally substituted alkylene group having 1 to 6 carbon atoms, and examples of the substituent that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, and a cyano group. Amide group, amino group, alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonato group, silyl group, heterocyclic group , Etc. x represents an integer of 1 to 5, and y represents an integer of 2 to 5. W ₁ is an organic group composed of 3 to 10 non-metallic atoms, for example, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms. Examples thereof include organic groups composed of at least one element selected from 1 to 100 hydrogen atoms and 0 to 20 sulfur atoms. More specific examples include organic groups composed of the following structures singly or in combination.

The organic group represented by W ₁ may further have a substituent, and examples of the substituent that can be introduced include a halogen atom, a hydroxy group, a carboxy group, a sulfonate group, a nitro group, a cyano group, and an amide group. Amino group, alkyl group, alkenyl group, alkynyl group, aryl group, substituted oxy group, substituted sulfonyl group, substituted carbonyl group, substituted sulfinyl group, sulfo group, phosphono group, phosphonato group, silyl group, heterocyclic group, etc. Can be mentioned. The organic group represented by W ₁ may contain an ether bond, an ester bond, or a ureido bond.
Two or more of R ₁ , R ₂ and W ₁ may be bonded to each other to form a heterocyclic ring.

  More preferably, the structure of the polymerizable betaine compound is represented by the following general formula (2) or (3).

In General Formula (2), R _{4 to} R ₇ each independently represents an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group having 1 to 6 carbon atoms that may have a substituent. Alternatively, any two of R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a heterocyclic ring. R ₈ represents a hydrogen atom or a methyl group, and Z ₂ represents —CO—, —O—, —CH ₂ O— or a phenylene group which may have a substituent. W ₂ represents a trivalent linking group having 10 or less carbon atoms, and Y ₂ and Y ₃ independently represent an alkylene group having 1 to 6 carbon atoms which may have a substituent.
In formula (3), R _{9 to} R ₁₁ each independently represent an alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group having 1 to 6 carbon atoms which may have a substituent. Alternatively, any two of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other to form a heterocyclic ring. R ₁₂ represents a hydrogen atom or a methyl group, and Z ₃ represents —CO—, —O—, —CH ₂ O— or a phenylene group which may have a substituent. X ₁ and X ₂ independently represent a divalent linking group having 10 or less carbon atoms, and Y ₄ and Y ₅ independently represent an alkylene group having 1 to 6 carbon atoms which may have a substituent.
Examples of the substituent include alkyl group, aryl group, heteroaryl group, alkenyl group, alkynyl group, aralkyl group, halogen atom, hydroxy group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, Amino group, acyloxy group, carbamoyloxy group, sulfoxy group, ureido group, oxycarbonylamino group, formyl group, acyl group, carbonyl group, oxycarbonyl group, carbamoyl group, sulfinyl group, sulfonyl group, sulfo group (—SO ₃ H ) And conjugated base groups (hereinafter referred to as sulfonate groups), sulfinamoyl groups, phosphono groups (—PO ₃ H ₂ ) and conjugated base groups (hereinafter referred to as phosphonate groups), phosphonooxy groups (—OPO ₃ H). ₂₎ and its conjugated base group (hereinafter, phosphonato Referred to as carboxymethyl group), a cyano group, a nitro group, and the like.

Preferred forms in the above formula are shown below.
R ₄ , R ₅ , R ₆ , R ₇ , R ₉ , R ₁₀ , R ₁₁ are each independently a methyl group or an ethyl group, or each of (R _{4 to} R ₇ ) and (R _{9 to} R ₁₁ ) Any two members in the group are preferably groups containing 5-membered or 6-membered heterocycles bonded to each other, more preferably a methyl group or an ethyl group, and most preferably a methyl group.
Z ₂ and Z ₃ are preferably —CO— or a phenylene group which may have a substituent, and more preferably —CO—.
W ₂ is preferably a trivalent linking group having 8 or less carbon atoms, and more preferably a linking group having 6 or less carbon atoms. Further, when Z ₂ is —CO—, W ₂ is particularly preferably a linking group capable of forming an amide bond with Z ₂ .
Specific examples of W ₂ include the following structures.

X ₁ and X ₂ are preferably independently a divalent linking group having 8 or less carbon atoms, more preferably a divalent linking group having 6 or less carbon atoms, and more preferably 4 or less carbon atoms. Most preferred is an alkylene group.
Y _{2 to} Y ₅ are preferably independently an alkylene group having 2 to 5 carbon atoms, more preferably an alkylene group having 3 to 5 carbon atoms, and an alkylene group having 3 or 4 carbon atoms. Most preferably it is.

Specific examples of the polymerizable betaine compound of the present invention are shown below. Compound groups are shown by structural formulas (A) to (T), and specific compound examples of each group are shown in the table. The first column of each table represents a compound number, and A to T at the beginning of the compound number correspond to structural formulas (A) to (T).
The present invention is not limited to these compounds.

When the polymerizable composition of the present invention is used as an image recording layer of a lithographic printing plate precursor, the polymerizable betaine compound of the present invention may be 0.5% by mass or more and 20% by mass or less of the total solid content of the image recording layer. preferable. More preferably, they are 1 mass% or more and 15 mass% or less, More preferably, they are 2 mass% or more and 10 mass% or less. In this range, good on-press developability and printing durability can be obtained.
Moreover, these compounds may be used independently and may mix and use 2 or more types.

<< (b) Polymerization initiator >>
As the polymerization initiator used in the present invention, a radical polymerization initiator is preferably used.
As the radical polymerization initiator, those known to those skilled in the art can be used without limitation, and specifically include, for example, trihalomethyl compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, hexaarynes. Examples include rubiimidazole compounds, organic boron compounds, disulfone compounds, oxime ester compounds, onium salts, and iron arene complexes. Among these, at least one selected from the group consisting of hexaarylbiimidazole compounds, onium salts, trihalomethyl compounds and metallocene compounds is preferable, and hexaarylbiimidazole compounds and onium salts are particularly preferable. Two or more polymerization initiators may be used in combination as appropriate.

  Examples of the hexaarylbiimidazole compound include lophine dimers described in the specifications of European Patent No. 24629, European Patent No. 107792, and US Pat. No. 4,410,621, such as 2,2′-bis (o- Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m -Methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) Nil) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Bis (o-trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like. The hexaarylbiimidazole compound is particularly preferably used in combination with a sensitizing dye having a maximum absorption in a wavelength region of 300 to 450 nm.

  Examples of onium salts include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230, ammonium described in US Pat. No. 4,069,055, JP-A-4-365049, and the like. Salt, phosphonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, EP 104,143, U.S. Patent Application Publication No. 2008/0311520 JP-A-2-150848, JP-A-2008-195018, or J.P. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), iodonium salts, European Patent Nos. 370,693, 233,567, 297,443, 297,442, US Patent 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patents 2,904,626, 3,604,580, Sulfonium salts described in each specification of JP-A-3,604,581; V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), azinium salts described in JP-A-2008-195018, and the like.

  Of these, more preferred are iodonium salts, sulfonium salts, and azinium salts. Although the specific example of these compounds is shown below, it is not limited to this.

  As an example of the iodonium salt, a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt substituted with an electron donating group such as an alkyl group or an alkoxyl group is particularly preferable, and an asymmetric diphenyl iodonium salt is more preferable. Specific examples include diphenyliodonium = hexafluorophosphate, 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium = hexafluorophosphate, 4- (2-methylpropyl) phenyl-p-tolyliodonium = hexa. Fluorophosphate, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium = tetrafluoroborate, 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium = 1-perfluorobutanesulfonate, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, bis ( -t- butylphenyl) iodonium tetraphenylborate and the like.

  Examples of sulfonium salts include triphenylsulfonium = hexafluorophosphate, triphenylsulfonium = benzoylformate, bis (4-chlorophenyl) phenylsulfonium = benzoylformate, bis (4-chlorophenyl) -4-methylphenylsulfonium = Examples thereof include tetrafluoroborate, tris (4-chlorophenyl) sulfonium = 3,5-bis (methoxycarbonyl) benzenesulfonate, and tris (4-chlorophenyl) sulfonium = hexafluorophosphate.

Examples of azinium salts include 1-cyclohexylmethyloxypyridinium = hexafluorophosphate, 1-cyclohexyloxy-4-phenylpyridinium = hexafluorophosphate, 1-ethoxy-4-phenylpyridinium = hexafluorophosphate, 1-cyclohexyl (2-ethylhexyloxy) -4-phenylpyridinium = hexafluorophosphate, 4-chloro-1-cyclohexylmethyloxypyridinium = hexafluorophosphate, 1-ethoxy-4-cyanopyridinium = hexafluorophosphate, 3,4 -Dichloro-1- (2-ethylhexyloxy) pyridinium = hexafluorophosphate, 1-benzyloxy-4-phenylpyridinium = hexafluorophosphate, 1-phenethylo Ci-4-phenylpyridinium = hexafluorophosphate, 1- (2-ethylhexyloxy) -4-phenylpyridinium = p-toluenesulfonate, 1- (2-ethylhexyloxy) -4-phenylpyridinium = perfluorobutanesulfonate 1- (2-ethylhexyloxy) -4-phenylpyridinium bromide, 1- (2-ethylhexyloxy) -4-phenylpyridinium tetrafluoroborate.
The onium salt is particularly preferably used in combination with an infrared absorber having a maximum absorption in a wavelength range of 750 to 1400 nm.

  In addition, polymerization initiators described in paragraph numbers [0071] to [0129] of JP-A-2007-206217 can also be preferably used.

  When the polymerizable composition of the present invention is used as an image recording layer of a lithographic printing plate precursor, the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0, based on the total solid content constituting the image recording layer. 0.5 to 30% by mass, particularly preferably 0.8 to 20% by mass. Within this range, good sensitivity and good stain resistance of the non-image area during printing can be obtained.

(Image recording layer)
Next, when the polymerizable composition of the present invention is used for a lithographic printing plate precursor, components other than those described above constituting the image recording layer of the lithographic printing plate will be described in detail.
The image recording layer used in the present invention may contain (c) a sensitizing dye, (d) a polymerizable compound, (e) a binder polymer, and (f) a hydrophobized precursor. Below, each component which can be contained in an image recording layer is demonstrated one by one.

(C) Sensitizing dye The sensitizing dye used in the image recording layer absorbs light at the time of image exposure to be in an excited state, supplies energy to the polymerization initiator by electron transfer, energy transfer or heat generation, and starts polymerization. Any device that improves the function can be used without particular limitation. In particular, a sensitizing dye having a maximum absorption in a wavelength range of 300 to 450 nm or 750 to 1400 nm is preferably used.

  Examples of the sensitizing dye having the maximum absorption in the wavelength range of 350 to 450 nm include merocyanines, benzopyrans, coumarins, aromatic ketones, anthracenes, styryls, and oxazoles.

  Of the sensitizing dyes having an absorption maximum in the wavelength range of 350 to 450 nm, a dye more preferable from the viewpoint of high sensitivity is a dye represented by the following general formula (I).

In general formula (I), A represents an aryl group or heteroaryl group which may have a substituent, and X represents an oxygen atom, a sulfur atom or N (R ₃ ). R ₁ , R ₂ and R ₃ each independently represents a monovalent non-metallic atomic group, and A and R ₁ or R ₂ and R ₃ are bonded to each other to form an aliphatic or aromatic group. A ring may be formed.

The general formula (I) will be described in more detail. The monovalent nonmetallic atomic group represented by R ₁ , R ₂ or R ₃ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group. Represents a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxy group, or a halogen atom.

The aryl group and heteroaryl group which may have a substituent represented by A are each a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group represented by R ₁ , R ₂ and R ₃ , respectively. It is the same.

  As specific examples of such a sensitizing dye, compounds described in paragraph numbers [0047] to [0053] of JP-A-2007-58170 are preferably used.

  Furthermore, sensitizing dyes represented by the following general formula (II) or (III) can also be used.

In formula (II), R ^{1 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, or a halogen atom. However, at least one of R ^{1 to} R ¹⁰ represents an alkoxy group having 2 or more carbon atoms.
In the formula (III), R ^{15 to} R ³² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a cyano group, or a halogen atom. However, at least one of R ^{15 to} R ²⁴ represents an alkoxy group having 2 or more carbon atoms.

  As specific examples of such sensitizing dyes, compounds described in European Patent Application Publication No. 1349006 and International Publication No. 2005/029187 are preferably used.

  JP-A-2006-189604, JP-A-2007-171406, JP-A-2007-206216, JP-A-2007-206217, JP-A-2007-225701, JP-A-2007-225702, JP-A-2007-316582 The sensitizing dyes described in JP-A-2007-328243 are also preferably used.

  Then, it describes about the sensitizing dye (henceforth an infrared absorber) which has maximum absorption in the wavelength range of 750-1400 nm. As the infrared absorber, a dye or a pigment is preferably used.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned.
Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).

In general formula (a), X ¹ represents a hydrogen atom, a halogen atom, —N (R ⁹ ) (R ¹⁰ ), —X ² -L ¹ or a group shown below. Here, R ⁹ and R ¹⁰ may be the same or different, and may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Represents a hydrogen atom, and R ⁹ and R ¹⁰ may be bonded to each other to form a ring. Of these, a phenyl group is preferred. X ² represents an oxygen atom or a sulfur atom, and L ¹ includes a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom (N, S, O, halogen atom, Se), or a hetero atom. A hydrocarbon group having 1 to 12 carbon atoms is shown. It is Z _a to be described later ^{- -} formula X _a of the same definition, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ^{2 in} the general formula (a) each independently represent a hydrocarbon group having 1 to 12 carbon atoms. In view of storage stability of the image recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms. R ¹ and R ² may be connected to each other to form a ring, and when a ring is formed, it is particularly preferable to form a 5-membered ring or a 6-membered ring.

Ar ¹ and Ar ² may be the same or different and each represents an aryl group which may have a substituent. Preferred aryl groups include a benzene ring group and a naphthalene ring group. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxy group, and a sulfo group. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of easy availability of the raw material, a hydrogen atom is preferred. Z _a ⁻ represents a counter anion. However, when the cyanine dye represented by formula (a) has an anionic substituent in the structure thereof, Z _a is does not require charge neutralization ^- is not necessary. Preferred Z _a ⁻ is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the image recording layer coating solution. , Hexafluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by the general formula (a) include compounds described in paragraph Nos. [0017] to [0019] of JP-A No. 2001-133969, paragraph Nos. [0016] of JP-A No. 2002-023360. ] To [0021], compounds described in paragraphs [0012] to [0037] of JP 2002-040638 A, preferably paragraphs [0034] to [0041] of JP 2002-278057 A, JP The compounds described in paragraphs [0080] to [0086] of 2008-195018, particularly preferably the compounds described in paragraphs [0035] to [0043] of JP-A-2007-90850 are exemplified.

  In addition, compounds described in paragraph Nos. [0008] to [0009] of JP-A No. 5-5005 and paragraph numbers [0022] to [0025] of JP-A No. 2001-222101 can also be preferably used.

  Only 1 type may be used for an infrared absorption dye, 2 or more types may be used together, and infrared absorbers other than infrared absorption dyes, such as a pigment, may be used together. As the pigment, the compounds described in JP-A-2008-195018, paragraphs [0072] to [0076] are preferable.

  The content of the sensitizing dye is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. Part by mass

(D) Polymerizable compound In the image recording layer of the present invention, an addition polymerizable compound having at least one ethylenically unsaturated double bond, particularly a terminal ethylenic compound, in addition to the polymerizable betaine compound listed in (a). It is preferable to contain a polymerizable compound having at least one, preferably two or more unsaturated bonds. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof. Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. Esters of an acid and a polyhydric alcohol compound and amides of an unsaturated carboxylic acid and a polyamine compound are used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group, addition products of monofunctional or polyfunctional alcohols, amines, thiols, halogen groups, A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like. These are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP-A-9-179298, JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in Japanese Laid-Open Patent Publication No. 10-333321.

  Specific examples of the monomer of the ester of a polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like. Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  In addition, urethane-based addition-polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxy group are also suitable, and specific examples thereof include, for example, one molecule described in Japanese Patent Publication No. 48-41708. A vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following general formula (b) to a polyisocyanate compound having two or more isocyanate groups. A urethane compound etc. are mentioned.

_{CH 2 = C (R 4)} COOCH 2 CH (R 5) OH (b)
(However, R ₄ and R ₅ represent H or CH _3. )

  Also, photo-oxidizable polymerizable compounds described in JP-T-2007-506125 are suitable, and polymerizable compounds containing at least one urea group and / or tertiary amino group are particularly preferred. Specific examples include the following compounds.

  Also, urethanes described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, and JP-A-2006-65210. Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide skeleton described in the publication, US Pat. No. 7,153,632, JP-T 8-505958, JP-A 2007-293221, and JP-A 2007-293223. Urethane compounds having a hydrophilic group described in (2) are also suitable.

  Among the above, in the case of a lithographic printing plate precursor to which on-press development is applied, tris (acryloyloxyethyl) isocyanate is excellent in that it has a good balance of hydrophilicity involved in on-press developability and polymerization ability involved in printing durability. Isocyanuric acid ethylene oxide-modified acrylates such as nurate and bis (acryloyloxyethyl) hydroxyethyl isocyanurate are particularly preferred.

  Details of the method of use, such as the structure of the polymerizable compound, whether it is used alone or in combination, and the amount added, can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. The polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass with respect to the total solid content of the image recording layer.

<(E) Binder polymer>
The photosensitive layer of the present invention has a binder polymer. Hereinafter, the binder that can be removed by the developer and the binder that can be removed by at least one of the printing ink and the fountain solution on the printing press will be described in order.

<Binder polymer removable by developer>
As the binder polymer that can be removed by the developer, those that can carry the photosensitive layer component on the support and can be removed by the developer are used. As the binder polymer, (meth) acrylic polymer, polyurethane resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyester resin, epoxy resin and the like are used. In particular, vinyl copolymers such as (meth) acrylic polymers, polyvinyl alcohol resins, polyvinyl butyral resins, and polyvinyl formal resins, and polyurethane resins are preferably used.

In the present invention, “(meth) acrylic polymer” means (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide, and (meth). A copolymer having a (meth) acrylic acid derivative such as an acrylamide derivative as a polymerization component. “Polyurethane resin” refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups.
“Polyvinyl butyral resin” refers to a polymer synthesized by reacting polyvinyl alcohol obtained by saponifying part or all of polyvinyl acetate and butyraldehyde under acidic conditions (acetalization reaction), Polymers having an acid group or the like introduced by a method of reacting a compound having a remaining hydroxy group and an acid group or the like are also included.
A suitable example of the binder polymer in the present invention includes a copolymer having a repeating unit containing an acid group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group, but a carboxylic acid group is particularly preferable, and a repeating unit derived from (meth) acrylic acid or the following general formula Those represented by (c) are preferably used.

(In general formula (c), R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an n + 1 valent linking group, A represents an oxygen atom or NR ³ —, and R ³ represents a hydrogen atom or Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5.)

The linking group represented by R ² in the general formula (c) is composed of at least one of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms is preferably 1-80. Specific examples include alkylene, substituted alkylene, arylene, substituted arylene, and the like, and a structure in which a plurality of these divalent groups are linked by an amide bond or an ester bond may be used. R ² is preferably a single bond, alkylene, or substituted alkylene, particularly preferably a single bond, alkylene having 1 to 5 carbons, or substituted alkylene having 1 to 5 carbons. Most preferably, it is an alkylene having 1 to 3 or a substituted alkylene having 1 to 3 carbon atoms.
Examples of the substituent include a monovalent non-metallic atomic group excluding a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, An acyl group, a carboxyl group and its conjugate base group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aryl group, an alkenyl group, an alkynyl group and the like can be mentioned.

R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. n is preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.

  From the viewpoint of developability, the proportion (mol%) of the copolymer component having a carboxylic acid group in the total copolymer components of the binder polymer is preferably 1 to 70%. Considering compatibility between developability and printing durability, 1 to 50% is more preferable, and 1 to 30% is particularly preferable.

  Moreover, for example, polyvinyl butyral resins into which acid groups as described below are introduced are also preferably used.

  In the general formula (d), a preferable ratio of each repeating unit is in the range of p / q / r / s = 50 to 78 mol% / 1 to 5 mol% / 5 to 28 mol% / 5 to 20 mol%. . Ra, Rb, Rc, Rd, Re, and Rf are each independently a monovalent substituent or a single bond that may have a substituent, and m is 0 or 1. Preferable substituents for Ra, Rb, Rc, Rd, Re, and Rf include a hydrogen atom, an alkyl group that may have a substituent, a halogen atom, and an aryl group that may have a substituent. More preferably, a straight-chain alkyl group such as a hydrogen atom, a methyl group, an ethyl group or a propyl group, an alkyl group substituted with a carboxylic acid, a halogen atom, a phenyl group or a phenyl group substituted with a carboxylic acid can be mentioned. Rc and Rd, Re and Rf can each form a ring structure. The bond between the carbon atom to which Rc and Re are bonded and the carbon atom to which Rd and Rf are bonded is a single bond, a double bond or an aromatic double bond, and in the case of a double bond or an aromatic double bond , Rc and Rd, Re and Rf, Rc and Rf, or Re and Rd are combined to form a single bond.

  Preferable specific examples of the carboxylic acid group-containing unit include the following examples.

  Furthermore, the acid group of the polymer containing an acid group, which is a preferred example of the binder polymer in the present invention, may be neutralized with a basic compound, and in particular, a base such as an amino group, an amidine group, or a guanidine group. It is preferably neutralized with a compound containing basic nitrogen. Furthermore, it is also preferred that the compound containing basic nitrogen has an ethylenically unsaturated group. Specific examples of the compound include compounds described in WO2007 / 057442.

  The binder polymer used in the present invention preferably further has a crosslinkable group. Here, the crosslinkable group is a group that crosslinks the binder polymer in the process of radical polymerization reaction that occurs in the photosensitive layer when the lithographic printing plate precursor is exposed. Although it will not specifically limit if it is a group of such a function, For example, an ethylenically unsaturated bond group, an amino group, an epoxy group etc. are mentioned as a functional group which can be addition-polymerized. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, etc. are mentioned, for example. Of these, an ethylenically unsaturated bond group is preferable. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable.

  In the binder polymer, for example, free radicals (polymerization initiating radicals or growth radicals in the polymerization process of the polymerizable compound) are added to the crosslinkable functional group, and the addition polymerization is performed directly between the polymers or through the polymerization chain of the polymerizable compound. As a result, a cross-link is formed between the polymer molecules and cured. Alternatively, atoms in the polymer (eg, hydrogen atoms on carbon atoms adjacent to the functional bridging group) are abstracted by free radicals to form polymer radicals that are bonded together, thereby causing cross-linking between polymer molecules. Forms and cures.

  The content of the crosslinkable group in the binder polymer (content of unsaturated double bond capable of radical polymerization by iodometric titration) is preferably 0.01 to 10.0 mmol, more preferably 0.05, per 1 g of the binder polymer. -5.0 mmol, most preferably 0.1-2.0 mmol.

  The binder polymer used in the present invention may have a polymer unit of an alkyl (meth) acrylate or an aralkyl ester in addition to the polymer unit having an acid group and a polymer unit having a crosslinkable group. The alkyl group of the (meth) acrylic acid alkyl ester is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate.

The binder polymer preferably has a mass average molecular weight of 5,000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2000 to 250,000. More preferred. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1.1 to 10.
A binder polymer may be used independently or may be used in mixture of 2 or more types. The content of the binder polymer is preferably from 5 to 75 mass%, more preferably from 10 to 70 mass%, more preferably from 10 to 70 mass%, based on the total solid content of the photosensitive layer, from the viewpoint of good image area strength and image formability. More preferably, it is 60 mass%.
The total content of the polymerizable compound and the binder polymer is preferably 80% by mass or less based on the total solid content of the photosensitive layer. If it exceeds 80% by mass, the sensitivity and developability may be lowered. More preferably, it is 35-75 mass%.

  In the present invention, by adjusting the ratio of the polymerizable compound and the binder polymer in the photosensitive layer of the lithographic printing plate precursor, the permeability of the developer into the photosensitive layer is further improved, and the developability is further improved. That is, the mass ratio of the polymerizable compound / binder polymer in the photosensitive layer is preferably 1.2 or more, more preferably 1.25 to 4.5, and most preferably 2 to 4.

<Binder polymer that can be removed by printing ink and / or fountain solution on printing press>
In order to improve the film strength of the image recording layer, a binder polymer can be used for the image recording layer removable by at least one of the printing ink and the fountain solution of the present invention. As the binder polymer that can be used in the present invention, conventionally known binder polymers can be used without limitation, and polymers having film properties are preferred. Of these, acrylic resins, polyvinyl acetal resins, and polyurethane resins are preferable.

  Among them, as a binder polymer suitable for the present invention, as described in JP-A-2008-195018, a crosslinkable functional group for improving the film strength of the image portion is a main chain or a side chain, preferably a side chain. Have the following. Crosslinking is formed between the polymer molecules by the crosslinkable group, and curing is accelerated.

  The crosslinkable functional group is preferably an ethylenically unsaturated group such as a (meth) acryl group, vinyl group, allyl group, or styryl group, or an epoxy group, and these groups are introduced into the polymer by polymer reaction or copolymerization. be able to. For example, a reaction between an acrylic polymer or polyurethane having a carboxy group in the side chain and polyurethane and glycidyl methacrylate, or a reaction between a polymer having an epoxy group and an ethylenically unsaturated group-containing carboxylic acid such as methacrylic acid can be used.

  The content of the crosslinkable group in the binder polymer is preferably 0.1 to 10.0 mmol, more preferably 0.25 to 7.0 mmol, and most preferably 0.5 to 5.5 mmol per 1 g of the binder polymer. .

  Moreover, it is preferable that the binder polymer of this invention has a hydrophilic group further. The hydrophilic group contributes to imparting on-press developability to the image recording layer. In particular, the coexistence of the crosslinkable group and the hydrophilic group makes it possible to achieve both printing durability and developability.

  Examples of the hydrophilic group include a hydroxy group, a carboxy group, an alkylene oxide structure, an amino group, an ammonium group, an amide group, a sulfo group, and a phosphoric acid group. Among them, an alkylene oxide unit having 2 or 3 carbon atoms An alkylene oxide structure having 1 to 9 is preferable. In order to impart a hydrophilic group to the binder polymer, a monomer having a hydrophilic group may be copolymerized.

  In addition, in the binder polymer of the present invention, an oleophilic group such as an alkyl group, an aryl group, an aralkyl group, or an alkenyl group can be introduced in order to control the inking property. Specifically, a lipophilic group-containing monomer such as an alkyl methacrylate may be copolymerized.

  Specific examples (1) to (11) of the binder polymer used in the present invention are shown below, but the present invention is not limited thereto.

  The binder polymer in the present invention preferably has a mass average molar mass (Mw) of 2000 or more, more preferably 5000 or more, and still more preferably 10,000 to 300,000.

  In the present invention, if necessary, hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used. Further, a lipophilic binder polymer and a hydrophilic binder polymer can be used in combination.

  The content of the binder polymer is preferably 5 to 90% by mass, more preferably 5 to 80% by mass, and further preferably 10 to 70% by mass with respect to the total solid content of the image recording layer. preferable.

(F) Hydrophobized precursor In the lithographic printing plate precursor according to the invention, particularly a lithographic printing plate precursor to which on-press development is applied, a hydrophobized precursor can be used in order to improve on-press developability. The hydrophobized precursor in the present invention means fine particles capable of converting the image recording layer to hydrophobic when heat is applied. The fine particles are at least one selected from hydrophobic thermoplastic polymer fine particles, thermally reactive polymer fine particles, polymer fine particles having a polymerizable group, microcapsules enclosing a hydrophobic compound, and microgel (crosslinked polymer fine particles). It is preferable. Among these, polymer fine particles and microgels having a polymerizable group are preferable.

Hydrophobic thermoplastic polymer fine particles include Research Disclosure No. 1 of January 1992. 331,003, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are suitable. Can be cited as
Specific examples of polymers constituting such polymer fine particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures. Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Among them, more preferable examples include a copolymer containing polystyrene, styrene and acrylonitrile, and polymethyl methacrylate.

  The average particle diameter of the hydrophobic thermoplastic polymer fine particles used in the present invention is preferably 0.01 to 2.0 μm.

  Examples of the heat-reactive polymer fine particles used in the present invention include polymer fine particles having a heat-reactive group, and these form a hydrophobized region by cross-linking by a heat reaction and a functional group change at that time.

  The thermoreactive group in the polymer fine particles having a thermoreactive group used in the present invention may be any functional group that performs any reaction as long as a chemical bond is formed, but is preferably a polymerizable group, Examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups, etc.) ), An isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), and a condensation reaction Carboxy group and reaction partner hydroxy group or amino group, acid anhydride and reaction phase for ring-opening addition reaction , And the like as a preferable amino group or a hydroxy group is.

  As the microcapsules used in the present invention, for example, as described in JP-A Nos. 2001-277740 and 2001-277742, all or part of the constituent components of the image recording layer are encapsulated in the microcapsules. Is. The constituent components of the image recording layer can also be contained outside the microcapsules. Furthermore, it is preferable that the image recording layer containing the microcapsule includes a hydrophobic constituent component in the microcapsule and a hydrophilic constituent component outside the microcapsule.

  In this invention, the aspect containing a crosslinked resin particle, ie, a microgel, may be sufficient. This microgel can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof, and in particular, an embodiment in which a reactive microgel is formed by having a radical polymerizable group on the surface thereof, This is particularly preferable from the viewpoint of image formation sensitivity and printing durability.

  As a method for microencapsulating or microgelling the constituent components of the image recording layer, known methods can be applied.

  The average particle size of the microcapsules or microgel is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is still more preferable, and 0.10-1.0 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.

  The content of the hydrophobizing precursor is preferably in the range of 5 to 90% by mass of the total solid content of the image recording layer.

(G) Other components The image recording layer in the invention may further contain other components as required.

(1) Low molecular weight hydrophilic compound The image-recording layer in the invention may contain a low molecular weight hydrophilic compound in order to improve the on-press developability without reducing the printing durability.
As the low molecular weight hydrophilic compound, for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, and the like.

  Among these, in the present invention, it is preferable to contain at least one selected from the group of polyols, organic sulfates, and organic sulfonates.

  Specific examples of organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, and sodium n-octyl sulfonate. Sodium 5,8,11-trioxapentadecane-1-sulfonate, sodium 5,8,11-trioxaheptadecane-1-sulfonate, 13-ethyl-5,8,11-trioxaheptadecane-1; Alkyl sulfonates containing ethylene oxide chains such as sodium sulfonate, 5,8,11,14-tetraoxatetradecosane-1-sodium sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxy Benzenesulfo Acid sodium, sodium p-styrenesulfonate, sodium dimethyl-5-sulfonate isophthalate, sodium 1-naphthylsulfonate, sodium 4-hydroxynaphthylsulfonate, disodium 1,5-naphthalenedisulfonate, 1,3,6 -Aryl sulfonates such as trisodium naphthalene trisulfonate, compounds described in JP-A 2007-276454 [0026] to [0031], JP-A 2009-154525 [0020] to [0047], and the like. The salt may be a potassium salt or a lithium salt.

  Organic sulfates include sulfates of alkyl, alkenyl, alkynyl, aryl or heterocyclic monoethers of polyethylene oxide. The number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples thereof include compounds described in JP-A-2007-276454 [0034] to [0038].

  The above low molecular weight hydrophilic compound has a small hydrophobic part structure and almost no surface-active action, so that dampening water penetrates into the exposed part of the image recording layer (image part) and the hydrophobicity and film strength of the image part. Ink acceptability and printing durability of the image recording layer can be maintained satisfactorily.

The addition amount of these low molecular weight hydrophilic compounds to the image recording layer is 0.5% by mass or more and 20% by mass or less of the total solid content of the image recording layer, together with the addition amount of the polymerizable betaine compound (a) of the present invention. It is preferable that More preferably, they are 1 mass% or more and 15 mass% or less, More preferably, they are 2 mass% or more and 10 mass% or less. In this range, good on-press developability and printing durability can be obtained.
These compounds may be used alone or in combination of two or more.

(2) Grease Sensitizer In the image recording layer of the present invention, a lipid sensitizer such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer is used for the image recording layer in order to improve the inking property. be able to. In particular, when an inorganic layered compound is contained in the protective layer, these compounds function as a surface coating agent for the inorganic layered compound, and prevent a decrease in the inking property during printing by the inorganic layered compound.

  Suitable phosphonium compounds include phosphonium compounds described in JP-A-2006-297907 and JP-A-2007-50660. Specific examples include tetrabutylphosphonium iodide, butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 1,4-bis (triphenylphosphonio) butanedi (hexafluorophosphate), 1,7-bis (tri Phenylphosphonio) heptane sulfate, 1,9-bis (triphenylphosphonio) nonane = naphthalene-2,7-disulfonate, and the like.

  Examples of the nitrogen-containing low molecular weight compound include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzoimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferable. Specific examples include tetramethylammonium = hexafluorophosphate, tetrabutylammonium = hexafluorophosphate, dodecyltrimethylammonium = p-toluenesulfonate, benzyltriethylammonium = hexafluorophosphate, benzyldimethyloctylammonium = hexafluorophosphate. And the compounds described in JP-A 2008-284858 [0021] to [0037], JP-A 2009-90645 [0030] to [0057], and the like.

  The ammonium group-containing polymer may be any polymer as long as it has an ammonium group in its structure, but a polymer containing 5 to 80 mol% of a (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable. . Specific examples include polymers described in JP2009-208458 [0089] to [0105].

  The ammonium salt-containing polymer has a reduced specific viscosity (unit: ml / g) determined by the following measurement method, preferably in the range of 5 to 120, more preferably in the range of 10 to 110, 15 Those in the range of ~ 100 are particularly preferred. When the said reduced specific viscosity is converted into a mass mean molar mass (Mw), 10,000-150,000 are preferable, 17000-140000 are more preferable, 20000-130000 are especially preferable.

<Measurement method of reduced specific viscosity>
1 g of polymer solid content was weighed into a 20 ml volumetric flask and diluted with N-methylpyrrolidone.
This solution is allowed to stand for 30 minutes in a constant temperature bath at 30 ° C., placed in an Ubbelohde reduced specific viscosity tube (viscosity constant = 0.010 cSt / s), and the time for flowing down at 30 ° C. is measured. The measurement is performed twice with the same sample, and the average value is calculated. Similarly, in the case of a blank (only N-methylpyrrolidone), the reduced specific viscosity (ml / g) was calculated from the following formula.

Specific examples of the ammonium group-containing polymer are shown below.
(1) 2- (Trimethylammonio) ethyl methacrylate = p-toluenesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 10/90 mass average molar mass (Mw) 45,000)
(2) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 Mw: 60,000)
(3) 2- (Ethyldimethylammonio) ethyl methacrylate = p-toluenesulfonate / hexyl methacrylate copolymer (molar ratio 30/70 Mw: 45,000)
(4) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 2-ethylhexyl methacrylate copolymer (molar ratio 20/80 Mw: 60,000)
(5) 2- (Trimethylammonio) ethyl methacrylate = methyl sulfate / hexyl methacrylate copolymer (molar ratio 40/60 Mw: 7 million)
(6) 2- (butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 25/75 Mw: 65,000)
(7) 2- (Butyldimethylammonio) ethyl acrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 Mw: 65,000)
(8) 2- (butyldimethylammonio) ethyl methacrylate = 13-ethyl-5,8,11-trioxa-1-heptadecanesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 (Mw: 75,000)
(9) 2- (butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate / 2-hydroxy-3-methacryloyloxypropyl methacrylate copolymer (molar ratio 15/80/5 (Mw: 65,000)

  The content of the sensitizer is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass and 1 to 10% by mass with respect to the total solid content of the image recording layer. Is more preferable.

(3) Others Further, as other components, surfactants, colorants, print-out agents, polymerization inhibitors, higher fatty acid derivatives, plasticizers, inorganic fine particles, inorganic layered compounds, co-sensitizers or chain transfer agents, etc. Can be added. Specifically, paragraph numbers [0114] to [0159] of Japanese Patent Application Laid-Open No. 2008-284817, paragraph numbers [0023] to [0027] of Japanese Patent Application Laid-Open No. 2006-091479, and US Patent Publication No. 2008/0311520. [0060] The compounds and addition amounts described in [0060] are preferred.

(G) Formation of Image Recording Layer The image recording layer in the present invention may be prepared by using the necessary components described above as described in paragraphs [0142] to [0143] of JP-A-2008-195018, for example. A coating solution is prepared by dispersing or dissolving in a coating solution, which is formed by applying the coating solution on a support by a known method such as bar coater coating and drying. The image recording layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but is generally preferably 0.3 to 3.0 g / m ² . Within this range, good sensitivity and good film characteristics of the image recording layer can be obtained.

(Undercoat layer)
In the lithographic printing plate precursor according to the invention, an undercoat layer (sometimes referred to as an intermediate layer) is preferably provided between the image recording layer and the support. The undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. Contributes to improvement. In the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, thereby preventing the heat generated by the exposure from diffusing to the support and reducing the sensitivity.

As the compound used for the undercoat layer, those having an adsorptive group capable of being adsorbed on the surface of the support and a crosslinkable group for improving the adhesion to the image recording layer are preferable. Furthermore, compounds having a hydrophilicity-imparting group such as a sulfo group can also be mentioned as suitable compounds. These compounds may be low molecular weight or high molecular weight polymers. Moreover, you may use these compounds in mixture of 2 or more types as needed.
In the case of a high molecular polymer, a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable. The adsorbable adsorptive group to the surface of the support, a phenolic hydroxy group, a carboxy _{group, -PO 3 H 2, -OPO 3} H 2, -CONHSO 2 -, - SO 2 NHSO 2 -, - COCH 2 COCH 3 Is preferred. As the hydrophilic group, a sulfo group is preferable. The crosslinkable group is preferably a methacryl group or an allyl group.
This polymer may have a crosslinkable group introduced by salt formation between the polar substituent of the polymer, a substituent having a counter charge and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.
Specifically, a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679 and an ethylenic compound described in JP-A-2-304441. The phosphorus compound which has a heavy bond reactive group is mentioned suitably. JP-A 2005-238816, JP-A 2005-12549, JP-A 2006-239867, JP-A 2006-215263, cross-linkable group (preferably ethylenically unsaturated bond group), functional group interacting with support surface And those containing a low molecular or high molecular compound having a hydrophilic group are also preferably used. More preferable are polymer polymers having an adsorbable group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the support surface described in JP-A Nos. 2005-125749 and 2006-188038.

The content of unsaturated double bonds in the polymer resin for the undercoat layer is preferably 0.1 to 10.0 mmol, and most preferably 0.2 to 5.5 mmol per 1 g of the polymer.
The polymer for the undercoat layer preferably has a mass average molar mass of 5000 or more, more preferably 10,000 to 300,000.

  The undercoat layer of the present invention comprises, in addition to the above undercoat compound, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibiting ability, in order to prevent contamination over time. Compounds having a group that interacts with the surface of an aluminum support (for example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil , Sulfophthalic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like.

The undercoat layer is applied by a known method. The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m ^2, and more preferably 1 to 30 mg / m ^2.

(Support)
As the support used in the lithographic printing plate precursor according to the invention, a known support is used. Of these, an aluminum plate that has been roughened and anodized by a known method is preferred.
In addition, the above aluminum plate is optionally subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A Nos. 2001-253181 and 2001-322365, and US Pat. 714,066, 3,181,461, 3,280,734 and 3,902,734, or alkali metal silicates as described in U.S. Pat. Surface hydrophilization treatment with polyvinylphosphonic acid or the like as described in each specification of 3,276,868, 4,153,461 and 4,689,272 is appropriately performed and performed. be able to.
The support preferably has a center line average roughness of 0.10 to 1.2 μm.

  If necessary, the support of the present invention includes an organic polymer compound described in JP-A-5-45885 and a silicon alkoxy compound described in JP-A-6-35174 on the back surface. A backcoat layer can be provided.

(Protective layer)
In the lithographic printing plate precursor according to the invention, a protective layer (overcoat layer) is preferably provided on the image recording layer. In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.

The protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. As the low oxygen permeability polymer used for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as necessary. it can. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
As the modified polyvinyl alcohol, acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specifically, modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 are preferable.

Further, in order to enhance the oxygen barrier property, the protective layer preferably contains an inorganic layered compound such as natural mica and synthetic mica as described in JP-A-2005-119273.
Further, the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling surface slipperiness. Further, the protective layer can contain the sensitizer described in the description of the image recording layer.

The protective layer is applied by a known method. The coating amount of the protective layer, the coating amount after drying is preferably in the range of 0.01 to 10 g / ^{m 2,} more preferably in the range of 0.02 to 3 g / ^{m 2,} and most preferably 0. in the range of 02~1g / ^{m 2.}

[Preparation method of lithographic printing plate]
A lithographic printing plate can be produced by subjecting the lithographic printing plate precursor according to the invention to image exposure and development.

<Image exposure>
The lithographic printing plate precursor is imagewise exposed by laser exposure through a transparent original image having a line image, a halftone dot image or the like, or by laser beam scanning by digital data.
The wavelength of the light source is preferably 300 to 450 nm or 750 to 1400 nm. In the case of a light source of 300 to 450 nm, a lithographic printing plate precursor having a sensitizing dye having an absorption maximum in this wavelength region in the image recording layer is preferably used, and in the case of a light source of 750 to 1400 nm, absorption is performed in this wavelength region. A lithographic printing plate precursor containing an infrared absorbing agent, which is a sensitizing dye, in the image recording layer is preferably used. As the light source of 300 to 450 nm, a semiconductor laser is suitable. As a light source of 750 to 1400 nm, a solid laser and a semiconductor laser emitting infrared rays are suitable. Regarding the infrared laser, the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy amount is preferably 10 to 300 mJ / cm ² . In order to shorten the exposure time, it is preferable to use a multi-beam laser device. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
Image exposure can be performed by a conventional method using a plate setter or the like. In the case of on-press development, the lithographic printing plate precursor may be mounted on a printing press and then image exposure may be performed on the printing press.

<Development processing>
Development processing is (1) a method of developing with a developer having a pH of 2 to 14 (developer processing method), or (2) a method of developing while adding dampening water and / or ink on a printing press. (On-press development method).

<Developer processing method>
In the developer processing method, the lithographic printing plate precursor subjected to image exposure is processed with a developer having a pH of 2 to 14, and the image recording layer in the non-exposed portion is removed to prepare a lithographic printing plate.
In the development processing using a highly alkaline developer (pH 12 or more), usually, the protective layer is removed by a pre-water washing step, then alkali development is performed, the alkali is washed away by water in the post-water washing step, gum solution treatment is performed, and drying is performed. A lithographic printing plate is produced by drying in the process.
According to a preferred embodiment of the present invention, a developer having a pH of 2 to 14 is used. In this embodiment, it is preferable that a surfactant or a water-soluble polymer compound is contained in the developer, whereby the development and the gum solution treatment can be performed simultaneously. Therefore, the post-water washing step is not particularly required, and the development-gum solution treatment can be performed with one solution. Further, no pre-water washing step is required, and the protective layer can be removed simultaneously with the development-gum solution treatment. After the development-gum treatment, for example, it is preferable to perform drying after removing excess developer using a squeeze roller.

  The developer treatment of the lithographic printing plate precursor according to the invention is carried out in accordance with a conventional method at a temperature of 0 to 60 ° C., preferably 15 to 40 ° C. It can be carried out by a method of rubbing with a brush, a method of spraying a developer by spraying and rubbing with a brush.

  In the present invention, the development treatment with a developer having a pH of 2 to 14 can be preferably carried out by an automatic development processor equipped with a developer supply means and a rubbing member. An automatic developing processor using a rotating brush roll as the rubbing member is particularly preferable. Further, the automatic processor preferably includes a means for removing excess developer such as a squeeze roller and a drying means such as a warm air device after the development processing means. Further, the automatic development processor may be provided with a preheating means for heat-treating the lithographic printing plate precursor after image exposure before the development processing means.

  In the present invention, the developer used for the developer processing is an aqueous solution having a pH of 2 to 14. An aqueous solution containing water as a main component (containing 60% by mass or more of water) is preferable. In particular, an aqueous solution containing a surfactant (anionic, nonionic, cationic, amphoteric ion, etc.) or a water-soluble polymer compound. An aqueous solution containing is preferred. An aqueous solution containing both a surfactant and a water-soluble polymer compound is also preferred. The pH of the developer is more preferably 3.5 to 13, further preferably 6 to 13, and particularly preferably 6.5 to 10.5.

  The anionic surfactant used in the developer of the present invention is not particularly limited, but fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic acid salts, linear alkylbenzenesulfonic acid salts. Branched alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether (di) sulfonates, alkylphenoxy polyoxyethylene alkyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl-N-oleyl taurine Sodium, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salt, alkyl Acid ester salts, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates Ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, saponified saponified styrene-maleic anhydride copolymers, partially saponified olefin-maleic anhydride copolymers, naphthalene sulfonate formalin condensates, etc. Is mentioned. Of these, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and alkyl diphenyl ether (di) sulfonates are particularly preferably used.

  Although it does not specifically limit as a cationic surfactant used for the developing solution of this invention, A conventionally well-known thing can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkyl imidazolinium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

  The nonionic surfactant used in the developer of the present invention is not particularly limited, but is a polyethylene glycol type higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, phenol ethylene oxide adduct. , Naphthol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, fat and oil ethylene oxide adduct, polypropylene glycol ethylene oxide addition Dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) Id) block copolymer, fatty acid ester of polyhydric alcohol type glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, alkyl ether of polyhydric alcohol, fatty acid amide of alkanolamines, etc. It is done. Among these, those having an aromatic ring and an ethylene oxide chain are preferable, and an alkyl-substituted or unsubstituted phenol ethylene oxide adduct or an alkyl-substituted or unsubstituted naphthol ethylene oxide adduct is more preferable.

  The zwitterionic surfactant used in the developer of the present invention is not particularly limited, and examples thereof include amine oxides such as alkyldimethylamine oxide, betaines such as alkylbetaine, and amino acids such as sodium alkylamino fatty acid. . In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, a compound represented by the formula (2) in paragraph No. [0256] of JP-A-2008-203359, a formula (I), a formula (II) in paragraph No. [0028] of JP-A-2008-276166, A compound represented by the formula (VI) or a compound represented by paragraph numbers [0022] to [0029] of JP-A-2009-47927 can be used.

  Two or more surfactants may be used in the developer. 0.01-20 mass% is preferable and, as for the quantity of surfactant contained in a developing solution, 0.1-10 mass% is more preferable.

  Examples of the water-soluble polymer compound used in the developer of the present invention include soybean polysaccharide, modified starch, gum arabic, dextrin, fiber derivatives (eg, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, pullulan, polyvinyl Alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and acrylamide copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / maleic anhydride copolymer, polyvinyl sulfonic acid and The salt, polystyrene sulfonic acid, its salt, etc. are mentioned.

  A well-known thing can be used for the said soybean polysaccharide, for example, there exists a brand name Soya Five (made by Fuji Oil Co., Ltd.) as a commercial item, and the thing of various grades can be used. What can be preferably used is one in which the viscosity of a 10% by mass aqueous solution is in the range of 10 to 100 mPa / sec.

  As the modified starch, known ones can be used. For example, starch such as corn, potato, tapioca, rice, wheat etc. is decomposed with acid or enzyme in the range of 5-30 glucose residues per molecule, and further alkali It can be made by a method of adding oxypropylene in the inside.

  Two or more water-soluble polymer compounds may be used in combination in the developer. The content of the water-soluble polymer compound in the developer is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass.

  The developer used in the present invention may contain a pH buffer. The developer of the present invention can be used without particular limitation as long as it is a buffering agent that exhibits a buffering action at a pH of 2 to 14. In the present invention, weakly alkaline buffering agents are preferably used. For example, (a) carbonate ions and hydrogen carbonate ions, (b) borate ions, (c) water-soluble amine compounds and ions of the amine compounds, and their Combination use etc. are mentioned. That is, for example, a combination of (a) carbonate ion-bicarbonate ion, (b) borate ion, or (c) water-soluble amine compound-amine compound ion exhibits pH buffering action in the developer. Even when the developer is used for a long period of time, fluctuations in pH can be suppressed, and therefore, development loss due to fluctuations in pH, development debris generation, and the like can be suppressed. Particularly preferred is a combination of carbonate ions and bicarbonate ions.

  In order for carbonate ions and bicarbonate ions to be present in the developer, carbonate and bicarbonate may be added to the developer, or by adjusting the pH after adding carbonate or bicarbonate, Ions and bicarbonate ions may be generated. The carbonate and bicarbonate are not particularly limited, but are preferably alkali metal salts. Examples of the alkali metal include lithium, sodium, and potassium, and sodium is particularly preferable. Alkali metals may be used alone or in combination of two or more.

  The total amount of carbonate ions and bicarbonate ions is preferably 0.05 to 5 mol / L, more preferably 0.07 to 2 mol / L, and particularly preferably 0.1 to 1 mol / L with respect to the developer.

  The developer of the present invention may contain an organic solvent. Examples of the organic solvent that can be contained include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd.)), aromatic hydrocarbons (toluene, xylene, etc.), halogens, and the like. Hydrocarbons (methylene dichloride, ethylene dichloride, trichlene, monochlorobenzene, etc.) and polar solvents. Examples of polar solvents include alcohols (methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1 -Nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl Ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether Ter, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, 2-butanone, ethyl butyl ketone, methyl) Isobutyl ketone, cyclohexanone, etc.) Esters (ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, levulin Acid butyl, etc.), other (triethyl phosphate, tricresyl phosphate, N-phenylethanolamine, N Phenyl diethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, 4- (2-hydroxyethyl) morpholine, N, N- dimethylacetamide, N- methylpyrrolidone and the like) and the like.

  Two or more organic solvents can be used in combination in the developer. When the organic solvent is insoluble in water, it can be used after being solubilized in water using a surfactant or the like. When the developer contains an organic solvent, the concentration of the organic solvent is preferably less than 40% by mass from the viewpoint of safety and flammability.

  In addition to the above components, the developer of the present invention may contain preservatives, chelate compounds, antifoaming agents, organic acids, inorganic acids, inorganic salts, and the like. Specifically, compounds described in paragraph numbers [0266] to [0270] of JP-A-2007-206217 can be preferably used.

  The developer of the present invention can be used as a developer and a development replenisher for an exposed lithographic printing plate precursor. Further, the present invention can be preferably applied to the automatic developing processor as described above. When developing using an automatic developing processor, the developing solution becomes fatigued according to the amount of processing, so that the processing capability may be restored by using a replenishing solution or a fresh developing solution.

<On-press development method>
In the on-press development system, an image-exposed lithographic printing plate precursor is supplied with oil-based ink and an aqueous component on a printing machine, and an unexposed image recording layer is removed to produce a lithographic printing plate.
In other words, after image exposure of the lithographic printing plate precursor, it is mounted on the printing machine without any development processing, or after the lithographic printing plate precursor is mounted on the printing machine, image exposure is performed on the printing machine. When printing is performed by supplying the oil-based ink and the aqueous component, the uncured image recording layer is dissolved or dispersed by the supplied oil-based ink and / or the aqueous component in the unexposed area at an early stage of printing. And a hydrophilic surface is exposed at the portion. On the other hand, in the exposed portion, the image recording layer cured by exposure forms an oil-based ink receiving portion having a lipophilic surface. Oil-based ink or water-based component may be first supplied to the plate surface, but oil-based ink is supplied first in order to prevent the water-based component from being contaminated by the removed image recording layer component. Is preferred. In this way, the lithographic printing plate precursor is subjected to on-press development on a printing machine and used as it is for printing a large number of sheets. As the oil-based ink and the aqueous component, ordinary lithographic printing ink and fountain solution are preferably used.

  In the method of preparing a lithographic printing plate from the lithographic printing plate precursor according to the present invention, the entire lithographic printing plate precursor is exposed before exposure, during exposure, and from exposure to development, regardless of the development method. You may heat. By such heating, an image forming reaction in the image recording layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. In the case of the developer processing method, it is also effective to perform whole surface post-heating or whole surface exposure on the image after the development processing for the purpose of improving the image strength and printing durability. Usually, heating before development is preferably performed under a mild condition of 150 ° C. or less. If the temperature is too high, problems such as curing of the unexposed area may occur. Very strong conditions are used for heating after development. Usually, it is the range of 100-500 degreeC. If the temperature is low, sufficient image reinforcing action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area may occur.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In the polymer compound, the molecular weight is a mass average molar mass (Mw), and the ratio of repeating units is a mole percentage, except for those specifically defined.

[Synthesis example of polymerizable betaine compound]

[Synthesis of Compound (E-7)]
Step1
In a 300 ml three-necked flask equipped with a stirrer and a thermometer, weigh 25.10 g of 3,3′-iminobis (N, N-dimethylisopropylamine), 31.02 g of potassium carbonate, 100 g of ethyl acetate and 50 g of water, and put them in an ice bath. Then, 11.76 g of acrylic acid chloride was added dropwise over 30 minutes. The mixture was further stirred at 0 ° C. for 30 minutes, and the resulting white precipitate was filtered off. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow crude product was purified by alumina column chromatography (development with ethyl acetate / methanol) to obtain 7.73 g of N, N-bis (3- (dimethylamino) propyl) acrylamide.

Step2
In a 200 ml three-necked flask equipped with a stirrer, a thermometer and a reflux tube, 7.73 g of N, N-bis (3- (dimethylamino) propyl) acrylamide obtained in Step 1, 3.0 mg of p-methoxyphenol, and 40 g of acetonitrile were added. Weighed. 8.77 g of 1,4-butane sultone was added dropwise at room temperature, and the mixture was heated to 80 ° C. and reacted for 4 hours. After allowing to cool, the supernatant was removed by decantation, and the purified white precipitate was reslurried with 20 ml of methanol / 800 ml of ethyl acetate, and then the precipitate was collected by suction filtration under a nitrogen atmosphere. The solid was dried in a vacuum oven at 40 ° C. to obtain 15.30 g of a white solid compound (E-7).
The NMR measurement results of the white solid compound are shown below.

1H-NMR (400 MHz, D2O): δ = 6.62 ppm (a: 1H, t), 6.16 ppm, 5.79 ppm (b, c: 2H, 2d), 3.40-3.15 ppm (d + e + f: 12H, m), 2.96 ppm (g: 12H, s), 2.84 ppm (h: 4H, t), 1.96-1.69 ppm (i + j + k: 12H, m)

[Preparation of lithographic printing plate precursor]
The following lithographic printing plate combining the aluminum support (1-3), the undercoat layer, the image recording layer (1-5) and the protective layer (1-2) as shown in Table 2-1 and Table 2-2 Original plates A-1 to A-56 and B-1 to B-17 were prepared.

[Preparation of Aluminum Support 1]
In order to remove rolling oil on the surface of an aluminum plate (material: JIS A1050) having a thickness of 0.3 mm, after degreasing at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, the hair diameter is 0.3 mm. The aluminum surface was grained using 3 bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and washed thoroughly with water. This plate was etched by being immersed in a 25 mass% aqueous sodium hydroxide solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying. The plate was provided with a DC anodized film of 2.5 g / m ² at a current density of 15 A / dm ² using a 15% by mass sulfuric acid aqueous solution (containing 0.5% by mass of aluminum ions) as an electrolyte, then washed with water and dried. An aluminum support 1 was prepared.
The center line average roughness (Ra indication according to JIS B0601) of the support thus obtained was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

[Preparation of aluminum support 2]
The aluminum support 1 was treated with a 1% by mass aqueous solution of sodium silicate at 20 ° C. for 10 seconds to produce an aluminum support 2. The centerline surface roughness (Ra) was measured and found to be 0.54 μm.

[Preparation of Aluminum Support 3]
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% by mass aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. The aluminum plate was neutralized by immersing it in a 10% by mass hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute, and then washed with water. Subsequently, this aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3 mass% hydrochloric acid aqueous solution, and then kept at 60 ° C. In addition, the desmut treatment was performed for 10 seconds in a 5% by mass aqueous sodium hydroxide solution. This aluminum plate was anodized in a 15 mass% sulfuric acid aqueous solution at 25 ° C., a current density of 10 A / dm ² , and a voltage of 15 V for 1 minute to produce an aluminum support 3. The centerline surface roughness (Ra) was measured and found to be 0.44 μm.

(Formation of undercoat layer)
An undercoat layer coating solution having the following composition was applied with a bar coater and dried at 100 ° C. for 1 minute to form an undercoat layer. The dry coating amount of the undercoat layer was 20 mg / m ² .

<Coating liquid for undercoat layer (1)>
-Undercoat layer compound (1) having the following structure: 0.18 g
・ Hydroxyethyliminodiacetic acid 0.10g
・ Methanol 55.24g
・ Water 6.15g

[Formation of Image Recording Layer 1]
The image recording layer coating solution 1 having the following composition was bar coated and then oven dried at 90 ° C. for 60 seconds to form an image recording layer 1 having a dry coating amount of 1.3 g / m ² .

<Image recording layer coating solution 1>
-The following binder polymer (1) (Mw: 80,000) 0.34 g
・ The following polymerizable compound (1) 0.58 g
(PLEX6661-O, manufactured by Degussa Japan)
Polymerizable betaine compound or comparative compound (described in Table 2) 0.10 g
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following chain transfer agent (1) 0.02 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (Mw: 60,000, copolymer molar ratio: 83/17)):
(10 parts by mass, cyclohexanone: 15 parts by mass)
-Thermal polymerization inhibitor N-nitrosophenylhydroxylamine aluminum salt 0.01 g
-The following fluorosurfactant (1) (Mw: 10,000) 0.001 g
・ Polyoxyethylene-polyoxypropylene condensate 0.02g
(Pluronic L44, manufactured by ADEKA Corporation)
・ Dispersion of yellow pigment 0.04g
(Yellow pigment Novoperm Yellow H2G (manufactured by Clariant): 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (Mw: 60,000, copolymer molar ratio 83/17)): 10 parts by mass, cyclohexanone: 15 parts by mass Part)
・ 3.5 g of 1-methoxy-2-propanol
・ 2-butanone 8.0g

[Formation of Image Recording Layer 2]
An image recording layer coating solution 2 having the following composition was bar coated and then oven dried at 90 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.3 g / m ² .

<Image recording layer coating solution 2>
・ The above binder polymer (1) (Mw: 50,000) 0.04 g
・ The following binder polymer (2) (Mw: 80,000) 0.30 g
・ Polymerizable compound (1) 0.17 g
(PLEX6661-O, manufactured by Degussa Japan)
-0.41 g of the following polymerizable compound (2)
Polymerizable betaine compound or comparative compound (described in Table 2) 0.10 g
・ The following sensitizing dye (2) 0.03 g
・ The following sensitizing dye (3) 0.015 g
・ The following sensitizing dye (4) 0.015 g
・ The above polymerization initiator (1) 0.13 g
・ Chain transfer agent: Mercaptobenzothiazole 0.01g
・ 0.40 g of ε-phthalocyanine pigment dispersion
[Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (Mw: 60,000, copolymer molar ratio: 83/17)): 10 parts by mass,
Cyclohexanone: 15 parts by mass]
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt / Fluorosurfactant (1) (Mw: 10,000) 0.001 g
・ 3.5 g of 1-methoxy-2-propanol
・ 2-butanone 8.0g

[Formation of Image Recording Layer 3]
The image recording layer coating solution 3 having the following composition was bar coated, and then oven-dried at 100 ° C. for 60 seconds to form an image recording layer 3 having a dry coating amount of 1.0 g / m ² . The image recording layer coating solution 3 was prepared by mixing and stirring the following photosensitive solution (1) and hydrophobized precursor solution (1) immediately before coating.

<Photosensitive solution (1)>
・ The following binder polymer (3) 0.162 g
・ The following infrared absorbing dye (1) 0.030 g
-The following polymerization initiator (3) 0.162g
・ Polymerizable compound (Aronix M215, manufactured by Toagosei Co., Ltd.) 0.285 g
・ Pionine A-20 (Takemoto Yushi Co., Ltd.) 0.055g
Polymerizable betaine compound or comparative compound (described in Table 2) 0.10 g
・ The following oil sensitizer (1) 0.044 g
・ 0.008 g of the above-mentioned fluorosurfactant (1)
・ 2-butanone 1.091g
・ 1-methoxy-2-propanol 8.609g

<Hydrophobic precursor liquid (1)>
-Hydrophobic precursor aqueous dispersion (1) below 2.640 g
・ Distilled water 2.425g

(Production of hydrophobized precursor aqueous dispersion (1))
A stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser is applied to a 1000 ml four-necked flask, and 350 mL of distilled water is added while deoxygenating by introducing nitrogen gas, and the internal temperature becomes 80 ° C. Until heated. 1.5 g of sodium dodecyl sulfate was added as a dispersant, 0.45 g of ammonium persulfide was added as an initiator, and then a mixture of 45.0 g of glycidyl methacrylate and 45.0 g of styrene was added from the dropping funnel over about 1 hour. It was dripped. After the completion of the dropwise addition, the reaction was continued as it was for 5 hours, and then the unreacted monomer was removed by steam distillation. Thereafter, the mixture was cooled and adjusted to pH 6 with ammonia water, and finally purified water was added so that the nonvolatile content was 15% by mass to obtain a hydrophobized precursor aqueous dispersion (1) composed of polymer fine particles. The particle size distribution of the polymer fine particles had a maximum value at a particle size of 60 nm.

  The particle size distribution is obtained by taking an electron micrograph of polymer fine particles, measuring the total particle size of 5000 particles on the photograph, and dividing the obtained particle size measurement value from the maximum value to 0 on a logarithmic scale by 50. Then, the appearance frequency of each particle size was plotted and determined. For non-spherical particles, the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.

[Formation of Image Recording Layer 4]
The image recording layer coating solution 4 having the following composition was bar-coated and then oven-dried at 70 ° C. for 60 seconds to prepare an image recording layer 4 having a dry coating amount of 0.6 g / m ² .

<Image recording layer coating solution 4>
-Polymer fine particle aqueous dispersion (1) 20.0 g
・ Infrared absorbing dye (2) [The following structure] 0.2g
・ Polymerization initiator Irgacure250 (Ciba Specialty Chemicals) 0.5g
-Polymerizable betaine compound or comparative compound (described in Table 2) 0.50 g
-Polymerizable compound SR-399 (Sartomer) 1.50 g
・ Mercapto-3-triazole 0.2g
・ Byk336 (Byk Chimie) 0.4g
・ KlucelM (Hercules) 4.8g
・ ELVACITE4026 (Ineos Acrylica) 2.5g
・ N-propanol 55.0g
・ 2-butanone 17.0g

In addition, the compounds described by trade names in the above composition are as follows.
Irgacure 250: (4-methoxyphenyl) [4- (2-methylpropyl) phenyl] iodonium = hexafluorophosphate (75% by mass propylene carbonate solution)
SR-399: Dipentaerythritol pentaacrylate Byk336: Modified dimethylpolysiloxane copolymer (25% by mass xylene / methoxypropyl acetate solution)
・ KlucelM: Hydroxypropyl cellulose (2 mass% aqueous solution)
ELVACITE 4026: Hyperbranched polymethyl methacrylate (10% by mass 2-butanone solution)

(Production of polymer fine particle aqueous dispersion (1))
A 1000 ml four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, and nitrogen gas is introduced to perform deoxygenation, while polyethylene glycol methyl ether methacrylate (average of PEGMA ethylene glycol) The repeating unit was 50) 10 g, distilled water 200 g and n-propanol 200 g were added and heated until the internal temperature reached 70 ° C. Next, a premixed mixture of 10 g of styrene (St), 80 g of acrylonitrile (AN) and 0.8 g of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was continued for 5 hours, and then 0.4 g of 2,2′-azobisisobutyronitrile was added to raise the internal temperature to 80 ° C. Subsequently, 0.5 g of 2,2′-azobisisobutyronitrile was added over 6 hours. Polymerization progressed 98% or more at the stage of reaction for a total of 20 hours, and a polymer fine particle water dispersion (1) having a mass ratio of PEGMA / St / AN = 10/10/80 was obtained. The particle size distribution of the polymer fine particles had a maximum value at a particle size of 150 nm.

  Here, the particle size distribution is obtained by taking an electron micrograph of polymer fine particles, measuring a total of 5000 fine particle sizes on the photograph, and a logarithmic scale between 0 and the maximum value of the obtained particle size measurement values. And the frequency of appearance of each particle size was plotted and obtained. For non-spherical particles, the particle size of spherical particles having the same particle area as that on the photograph was used as the particle size.

[Formation of Image Recording Layer 5]
The image recording layer coating solution 5 having the following composition was bar-coated and then oven-dried at 70 ° C. for 60 seconds to produce an image recording layer 5 having a dry coating amount of 0.6 g / m ² .

<Image recording layer coating solution 5>
・ Polymer fine particle aqueous dispersion (2) 33.0 g
Infrared absorbing dye (3) [following structure] 1.0 g
-Polymerizable betaine compound or comparative compound (described in Table 2) 0.50 g
・ Polyacrylic acid (mass average molar mass 20000) 0.4 g
・ 1,5-Naphthalenedisulfonic acid disodium 0.1g
・ Methanol 16.0g

(Production of polymer fine particle aqueous dispersion (2))
A stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser is applied to a 1000 ml four-necked flask, and 350 mL of distilled water is added while deoxygenating by introducing nitrogen gas, and the internal temperature becomes 80 ° C. Until heated. 1.5 g of sodium dodecyl sulfate was added as a dispersant, 0.45 g of ammonium persulfide was added as an initiator, and then 45.0 g of styrene was dropped from the dropping funnel over about 1 hour. After the completion of the dropwise addition, the reaction was continued as it was for 5 hours, and then the unreacted monomer was removed by steam distillation. Thereafter, the mixture was cooled and adjusted to pH 6 with ammonia water, and finally pure water was added so that the nonvolatile content was 15% by mass to obtain a polymer fine particle water dispersion (2). The particle size distribution of the polymer particles measured in the same manner as in the case of the polymer particle aqueous dispersion (1) had a maximum value at a particle size of 60 nm.

[Formation of Protective Layer 1]
A protective layer coating solution 1 having the following composition was applied using a bar so that the dry coating amount was 0.75 g / m ^2, and then dried at 125 ° C. for 70 seconds to form a protective layer.

<Protective layer coating solution 1>
・ Polyvinyl alcohol PVA105
(Kuraray Co., Ltd., saponification degree 98.5 mol%, polymerization degree 500) 40 g
・ Polyvinylpyrrolidone K30 (Mw: 50,000)
(Tokyo Chemical Industry Co., Ltd., Mw = 40,000) 5g
・ Poly [vinyl pyrrolidone / vinyl acetate] LUVITEC VA64W
(Manufactured by ISP, copolymerization ratio = 6/4) 0.5 g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.5g
・ 950g of water

[Formation of Protective Layer 2]
A protective layer coating solution 2 having the following composition was applied using a bar so that the dry coating amount was 0.75 g / m ^2, and then dried at 125 ° C. for 70 seconds to form a protective layer.

<Protective layer coating solution 2>
-1.5 g of the following inorganic layered compound dispersion (1)
・ 0.55 g of 6% by weight aqueous solution of sulfonic acid-modified polyvinyl alcohol
(Nippon Synthetic Chemical Co., Ltd. CKS50, saponification degree 99 mol% or more, polymerization degree 300)
・ Polyvinyl alcohol 6 mass% aqueous solution 0.03g
(Kuraray Co., Ltd. PVA-405, saponification degree 81.5 mol%, polymerization degree 500)
-1% by weight aqueous solution of surfactant (Emulex 710, manufactured by Nippon Emulsion Co., Ltd.) 8.60 g
・ Ion-exchanged water 6.0g

(Preparation of inorganic layered compound dispersion (1))
6.4 g of synthetic mica Somasif ME-100 (manufactured by Coop Chemical Co., Ltd.) is added to 193.6 g of ion-exchanged water, and the mixture is dispersed using a homogenizer until the average particle size (laser scattering method) is 3 μm. An inorganic layered compound dispersion (1) was prepared. The aspect ratio of the obtained dispersed particles was 100 or more.

[Comparative compound]

[Examples 1 to 18 and Comparative Examples 1 to 10] Evaluation of planographic printing plate precursor (Part 1)

[Exposure, development and printing]
The lithographic printing plate precursors (A-1) to (A-12) and (B-1) to (B-6) were obtained from FUJIFILM Electronic Imaging Ltd. Image exposure was performed with a Violet semiconductor laser plate setter Vx9600 (InGaN-based semiconductor laser (with an emission wavelength of 405 nm ± 10 nm / output 30 mW) mounted) manufactured by (FFEI). Image exposure was performed at a resolution of 2,438 dpi, using an FM screen (TAFFETA 20) manufactured by Fuji Film Co., Ltd., with a plate surface exposure of 0.05 mJ / cm ² so that the dot area ratio was 50%.
Next, after preheating at 100 ° C. for 30 seconds, development processing was carried out using an automatic developing processor having a structure as shown in FIG. The automatic processor has one brush roll with an outer diameter of 50 mm in which fibers made of polybutylene terephthalate (hair diameter 200 μm, hair length 17 mm) are implanted, and rotates 200 times per minute in the same direction as the conveying direction ( The peripheral speed of the brush tip was 0.52 m / sec). The temperature of the developer was 30 ° C. The planographic printing plate precursor was transported at a transport speed of 100 cm / min. After the development processing, drying was performed in a drying section. The drying temperature was 80 ° C. However, when the developer 2 was used, it was washed with water before the post-development drying step.

  Below, the composition of developer 1-4 is shown. In the following composition, New Coal B13 (manufactured by Nippon Emulsifier Co., Ltd.) is polyoxyethylene β-naphthyl ether (oxyethylene average number n = 13), and gum arabic has Mw of 200,000.

<Developer 1>
・ 13.0 g of sodium carbonate
・ Sodium bicarbonate 7.0g
・ New Coal B13 (Nippon Emulsifier Co., Ltd.) 50.0g
・ Ammonium phosphate 2.0g
2-bromo-2-nitropropane-1,3-diol 0.01 g
・ 2-methyl-4-isothiazolin-3-one 0.01 g
・ Trisodium citrate 15.0g
・ 913.98 g of distilled water

The pH of this developer was 9.9.

<Developer 2>
・ Potassium hydroxide 0.15g
・ New Coal B13 (Nippon Emulsifier Co., Ltd.) 5.0g
・ Kirest 400 (chelating agent) 0.1g
・ 94.75g of distilled water

The pH of this developer was 11.5.

<Developer 3>
・ Arabic gum 25.0g
・ Enzyme-modified potato starch 70.0g
・ Sodium salt of dioctylsulfosuccinate 5.0g
・ Primary ammonium phosphate 1.0g
・ Citric acid 1.0g
・ 2-bromo-2-nitropropane-1,3-diol 0.01 g
・ 0.01 g of 2-methyl-4-isothiazolin-3-one
・ The following surfactant (W-1) 2.5g
・ The following surfactant (AN-1) 2.5g
・ 824.98 g of distilled water
(Phosphoric acid and sodium hydroxide are added to adjust the pH to 4.5)

<Developer 4>
・ Water 88.6g
-2.4 g of the following nonionic surfactant (W-2)
-2.4 g of the following nonionic surfactant (W-3)
・ Nonionic surfactant 1.0g
(Emalex 710, manufactured by Nippon Emulsion Co., Ltd.)
・ Phenoxypropanol 1.0g
・ Octanol 0.6g
-N- (2-hydroxyethyl) morpholine 1.0 g
・ Triethanolamine 0.5g
・ Sodium gluconate 1.0g
・ Trisodium citrate 0.5g
・ Ethylenediaminetetraacetate tetrasodium 0.05g
・ 1.0 g of polystyrene sulfonic acid
(Versa TL77 (30% solution), manufactured by Alco Chemical)
(Add phosphoric acid and adjust pH to 7.0)

  The obtained lithographic printing plate is attached to a printing machine SOR-M manufactured by Heidelberg, and fountain solution (EU-3 (etch solution manufactured by FUJIFILM Corporation) / water / isopropyl alcohol = 1/89/10 (volume ratio). )) And TRANS-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.), printing was performed at a printing speed of 6000 sheets per hour.

[Evaluation]
Each lithographic printing plate precursor was evaluated for printing durability, stain resistance, and developability as follows. The results are shown in Table 3.

<Print durability>
As the number of printed sheets increased, the image recording layer was gradually worn out and the ink acceptance decreased, so that the ink density in the printing paper decreased. In the printing plate exposed with the same exposure amount, the printing durability was evaluated by the number of printed sheets when the ink density (reflection density) was reduced by 0.1 from the start of printing.

<Stain resistance>
The printed material on the 20th sheet was taken out after the start of printing, and the stain resistance was evaluated based on the ink density adhered to the non-image area. In visual evaluation, a score of 10 was assigned. The higher the score, the better the stain resistance.

<Developability>
Development processing was performed at various transport speeds, and the cyan density of the non-image area of the obtained lithographic printing plate was measured with a Macbeth densitometer. The transport speed at which the cyan density of the non-image area was equal to the cyan density of the aluminum support was determined and used as developability. The evaluation of developability is shown in Table 3 as relative developability defined as follows, with Comparative Example 2 as the reference (1.0). The larger the value of the relative developability, the higher the developability and the better the performance.
Relative developability = (transport speed of target lithographic printing plate precursor) / (transport speed of reference lithographic printing plate precursor)

[Examples 19 to 62 and Comparative Examples 11 to 21] Evaluation of planographic printing plate precursor (Part 2)

[Exposure, on-press development and printing]
The lithographic printing plate precursors (A-13) to (A-56) and (B-7) to (B-17) were placed on an outer drum with a Luxel PLANETSETTER T-6000III manufactured by Fuji Film Co., Ltd. equipped with an infrared semiconductor laser. The exposure was performed under the conditions of a rotational speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi. The exposure image included a solid image and a 50% halftone dot chart of a 20 μm dot FM screen.
The obtained exposed original plate was attached to a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing. Equality-2 (manufactured by FUJIFILM Corporation) / tap water = 2/98 (volume ratio) dampening water and Values-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) After fountain solution and ink were supplied by the standard automatic printing start method of LITHRONE26 and developed on the machine, printing was performed using Tokuhishi Art (76.5 kg) paper at a printing speed of 10,000 sheets per hour.

[Evaluation]
Each lithographic printing plate precursor was evaluated for on-press developability, stain resistance, and printing durability as follows. The results are shown in Table 4.

(1) On-press developability Necessary to start printing as described above, complete on-press development on the printing press in the unexposed area of the image recording layer, and no ink is transferred to the non-image area. The number of printed sheets was measured as on-press developability.

(2) Printing durability After the above-described evaluation of on-press developability, the printing was further continued. As the number of printed sheets was increased, the image recording layer was gradually worn out, so that the ink density on the printed material decreased. Printing durability was evaluated using the number of printed copies when the value measured by the Gretag densitometer for the 50% halftone dot area ratio of the FM screen in the printed material was 5% lower than the measured value for the 100th printed sheet. .

(3) Stain resistance After the on-press development was completed, the printed material on the 20th sheet was taken out, and the stain resistance was evaluated based on the ink concentration adhered to the non-image area. In visual evaluation, a score of 10 was assigned. The higher the score, the better the stain resistance.

  As can be seen from Tables 3 and 4, according to the present invention, it is possible to provide a lithographic printing plate precursor exhibiting good stain resistance and having both good developability and printing durability.

[Production and evaluation of hydrophilic image forming materials]
The polymerizable composition of the present invention can be suitably used not only as a lithographic printing plate precursor but also as other image forming materials. An example is shown below.

[Example 63]
20 parts by mass of urethane acrylate oligomer ("Unidic V-4263" manufactured by Dainippon Ink & Chemicals, Inc.) having an average of 3 acryloyl groups in one molecule (hereinafter, all parts are shown in parts by mass) , 30 parts of dicyclopentanyl diacrylate (“Kayarad R-684” manufactured by Nippon Kayaku Co., Ltd.), binder polymer (1) as a polymer binder containing a crosslinkable group, and 1-hydroxycyclohexyl phenyl ketone (5.0 parts of photopolymerization initiator “Irgacure 184” manufactured by Ciba Geigy Co., Ltd.) was uniformly mixed to obtain a photopolymerizable composition (X-1).

  Also, 15 parts of the polymerizable betaine compound (E-7) of the present invention, 85 parts of distilled water, 5 parts of polyethylene glycol mono-4-nonylphenyl ether (surfactant, manufactured by Tokyo Chemical Industry Co., Ltd.), and Irgacure 184 3.0 parts was mixed uniformly and the photopolymerizable composition (Y-1) was obtained.

  Next, after applying and drying the photopolymerizable composition (X-1) on the surface of the glass plate to a film thickness of 10 μm, the photopolymerizable composition (Y-1) is formed to a film thickness of 1 μm. Applied and dried. Subsequently, this was exposed through a mask with a high-pressure mercury lamp. By developing this unexposed portion with pure water and examining the pattern formability, a 5 μm line width relief image was formed without any problems, and no film loss or defects were observed.

[Example 64]
The same operation as in Example 63 except that the polymerizable betaine compound (E-8) was used in place of the polymerizable betaine compound (E-7) in the photopolymerizable composition (Y-1) of Example 63. Went. Further, when the pattern formability was examined, a relief image having a line width of 5 μm was formed without any problem, and no film reduction or defects were observed.

[Comparative Example 22]
The same operation as in Example 63 was performed, except that the polymerizable betaine compound (E-7) was removed from the photopolymerizable composition (Y-1) of Example 63. Regarding pattern formability, a residual film in the unexposed area was observed, and a relief image having a line width of 5 μm was not formed.

[Comparative Example 23]
The same operation as in Example 63 was performed, except that the comparative compound (Z-4) was used instead of the polymerizable betaine compound (E-7) in the photopolymerizable composition (Y-1) of Example 63. It was. Regarding pattern formability, a residual film in the unexposed area was observed, and a relief image having a line width of 5 μm was not formed.

[Comparative Example 24]
The same operation as in Example 63 was performed, except that the comparative compound (Z-5) was used instead of the polymerizable betaine compound (E-7) in the photopolymerizable composition (Y-1) of Example 63. It was. When the pattern formability was examined, a relief image having a line width of 5 μm was formed, but film reduction was observed.

  From the above results, it has been clarified that the image forming material using the polymerizable composition of the present invention exhibits good pattern forming properties.

4 Planographic printing plate precursor (PS version)
6 Developing Unit 10 Drying Unit 16 Loading Roller 20 Developing Tank 22 Transporting Roller 24 Brush Roller 26 Squeeze Roller (Unloading Roller)
28 Backup roller 36 Guide roller 38 Skewer roller

Claims (10)

(A) Polymerizable betaine compound having the structure represented by the following general formula (1), and (b) a polymerizable composition characterized by containing a polymerization initiator.

(In general formula (1), R < ₁ >, R < ₂ > represents the C1-C6 alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group which may have a substituent each independently. R ₃ represents a hydrogen atom or a methyl group, Z ₁ represents a divalent linking group, Y ₁ represents an optionally substituted alkylene group having 1 to 6 carbon atoms, x is 1 to 5 Y represents an integer of 2 to 5, and W ₁ represents an organic group composed of a trivalent to 10-valent non-metallic atom, and two or more of any R ₁ , R ₂ , and W ₁ are They may combine with each other to form a heterocyclic ring.) The polymerizable composition according to claim 1 , wherein the polymerizable betaine compound has a structure represented by the following general formula (2) or (3).

(In the general formula (2), R _{4 to} R ₇ each independently represents a C 1-6 alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group which may have a substituent. Alternatively, any two of R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a heterocyclic ring, R ₈ represents a hydrogen atom or a methyl group, and Z ₂ represents —CO—, —O. —, —CH ₂ O— or an optionally substituted phenylene group, W ₂ represents a trivalent linking group having 10 or less carbon atoms, and Y ₂ and Y ₃ independently have a substituent. Represents an alkylene group having 1 to 6 carbon atoms.
In general formula (3), R _{9 to} R ₁₁ each independently represents an alkyl group, alkenyl group, alkynyl group, cycloalkyl group or aryl group having 1 to 6 carbon atoms which may have a substituent. Alternatively, any two of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other to form a heterocyclic ring. R ₁₂ represents a hydrogen atom or a methyl group, and Z ₃ represents —CO—, —O—, —CH ₂ O— or a phenylene group which may have a substituent. X ₁ and X ₂ independently represent a divalent linking group having 10 or less carbon atoms, and Y ₄ and Y ₅ independently represent an alkylene group having 1 to 6 carbon atoms which may have a substituent. ) In the general formula (2) or (3), R _{4 to} R ₇ and R _{9 to} R ₁₁ are each independently a methyl group, an ethyl group, or (R ₄ , R ₅ , R _6). , R ₇ ) or (R ₉ , R ₁₀ , R ₁₁ ) represents a group containing a 5-membered or 6-membered heterocyclic ring bonded to each other, and Z ₂ , Z ₃ are —CO— or Represents a phenylene group which may have a substituent, W ₂ represents a trivalent linking group having 10 or less carbon atoms, X ₁ and X ₂ represent a divalent linking group having 10 or less carbon atoms, Y ₂ to Y ₅ are independently a polymerizable composition according to 請 Motomeko 2 you, characterized in that represents an alkylene group having 2 to 5 carbon atoms. The polymerizable composition according to any one of claims 1 to 3 , wherein the polymerizable betaine compound has a structure represented by the following general formula (4).

(Wherein R _{13 to} R ₁₆ each independently represents a methyl group or an ethyl group, R ₁₇ represents a hydrogen atom or a methyl group, and L ₁ and L ₂ each independently represents a divalent group having 5 or less carbon atoms. Y ₆ and Y ₇ each independently represent an alkylene group having 2 to 5 carbon atoms. Image forming material characterized by containing the polymerizable composition according to any one of claims 1-4. A lithographic printing plate precursor comprising an image recording layer containing the polymerizable composition according to any one of claims 1 to 4 on a support. The lithographic printing plate precursor as claimed in claim 6, wherein the image recording layer of the lithographic printing plate precursor further comprises (c) a sensitizing dye, (d) a polymerizable compound, and (e) a binder polymer. The lithographic printing plate precursor as claimed in claim 6 or 7, wherein the image recording layer of the lithographic printing plate precursor can be removed with at least one of printing ink and fountain solution. The lithographic printing plate precursor as claimed in claim 6 or 7, wherein the image recording layer of the lithographic printing plate precursor can be removed with an aqueous solution having a pH of 2 to 14. A polymerizable betaine compound having a structure represented by the following general formula (5):

(Wherein R _{13 to} R ₁₆ each independently represents a methyl group or an ethyl group, R ₁₇ represents a hydrogen atom or a methyl group, and L ₁ and L ₂ each independently represents a divalent group having 5 or less carbon atoms. Y ₆ and Y ₇ each independently represent an alkylene group having 2 to 5 carbon atoms.

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