JP2005062478A - Polymerizable composition and recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition which polymerizes with high sensitivity and ensures high strength and excellent storage stability of a formed film, and to provide a recording material using the same. <P>SOLUTION: The polymerizable composition contains (A) a compound having an amino group and a hydroxyl group, (B) an IR absorbent, (C) a radical initiator and (D) a compound having at least one ethylenically unsaturated bond. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymerizable composition used for image recording materials such as three-dimensional stereolithography, holography, planographic printing plates, color proofs, photoresists and color filters, inks, paints, and adhesives. In particular, the present invention relates to a polymerizable composition that can be directly made from a digital signal of a computer or the like using an infrared laser, and can be suitably used as a recording layer of a so-called negative lithographic printing plate precursor capable of direct plate making.

  The development of lasers in recent years has been remarkable, and in particular, solid-state lasers, semiconductor lasers, and gas lasers that emit ultraviolet light, visible light, and infrared light having a wavelength of 300 nm to 1200 nm can be easily obtained with high output and small size. These lasers are very useful as recording light sources when directly making a plate from digital data of a computer or the like in lithographic printing. Various studies have been made on recording materials sensitive to these various laser beams, and acid-catalyst-crosslinked negative recording materials and the like for infrared lasers having a photosensitive wavelength of 760 nm or more are known (see Patent Document 1).

  Usually, a negative recording material that can be recorded by infrared exposure is an infrared absorber that absorbs infrared light energy and converts it into heat, and a radical initiator that generates radicals by heat obtained from this infrared absorber. And a polymerizable compound that polymerizes using the generated radical as an initiator, and a recording method in which the recording layer of the exposed portion is cured and an image is formed by the polymerization reaction of the polymerizable compound occurring and proceeding. We are using. Such a negative recording material has a problem that its sensitivity is lower than that of a positive type in which the recording layer is solubilized by the energy of infrared light.

As a recording material for the purpose of improving sensitivity, for example, a chemically amplified photosensitive material (see Patent Document 2) and a photosensitive material using a polymerization reaction of a compound having an ethylenically unsaturated bond (see Patent Document 3). For example, those containing a component excellent in reactivity to light and heat are known. In particular, in a light-sensitive material using polymerization of a compound having an ethylenically unsaturated bond, a reductive additive is added as a light-sensitive material for further sensitivity improvement (see Patent Document 4), or a dithio compound. And the like (see Patent Document 5) are known. However, none of these recording materials satisfy the sensitivity, and undesired reactions occur due to handling under white light or changes in the environmental temperature, or polymerization inhibition occurs due to oxygen in the air. There were concerns that the sensitivity decreased over time and storage stability was poor.
JP-A-8-276558 Japanese Patent Laid-Open No. 11-65105 JP 2000-89455 A JP 2002-82429 A JP 2002-90985 A

  An object of the present invention, which was made in consideration of the drawbacks of the above-described conventional techniques, is a polymerizable composition that is polymerized with high sensitivity, has a high strength of the formed film, and has excellent storage stability, and a recording material using the same Is to provide.

As a result of intensive studies, the present inventors have found that the above object can be achieved by adding a compound having an amino group and a hydroxyl group to the polymerizable composition, and have solved the present invention.
That is, the polymerizable composition of the present invention comprises (A) a compound having an amino group and a hydroxyl group, (B) an infrared absorber, (C) a radical initiator, and (D) an ethylenically unsaturated bond. And a compound having two.
In the present invention, the compound (A) having an amino group and a hydroxyl group is preferably a compound having in its molecule at least one partial structure represented by the following general formula (I).

In general formula (I), A represents an alkylene group which may have a substituent having 1 to 10 carbon atoms, and R ¹ represents a hydrogen atom or a monovalent organic group.

  Furthermore, in the present invention, the compound having at least one structure represented by the general formula (I) is more preferably a compound represented by the following general formula (II).

In formula (II), A and R ¹ have the same meanings A, and R ¹ in the general formula (I). Ar represents an aromatic group or a heterocyclic group.

  Furthermore, in the present invention, the compound represented by the general formula (II) is most preferably a compound represented by the following general formula (III).

  In general formula (III), A and Ar are synonymous with A and Ar in general formula (II).

  The recording material of the present invention is characterized by having a recording layer containing the polymerizable composition of the present invention on a support.

  Although the action of the present invention is not clear, (A) a compound having an amino group and a hydroxyl group (hereinafter referred to as “specific amino alcohol” as appropriate), which is a characteristic component in the present invention, is added to the polymerizable composition. During exposure, the specific amino alcohol interacts with the infrared absorber to improve the decomposition rate of the radical initiator, and the polymerization initiation radical and polymerization growth radical generated from the radical initiator are radically chained to the specific amino alcohol. It is considered that the polymerization reaction of the compound having migrated and having at least one ethylenically unsaturated bond (hereinafter referred to as “polymerizable compound” as appropriate) is promoted, and a strong film having a high curing density is formed. Therefore, the polymerizable composition to which the specific amino alcohol according to the present invention is added has high sensitivity and the strength of the formed film is high, and the lithographic printing plate precursor in which such a polymerizable composition is applied as a recording layer Is considered to be excellent in printing durability during printing.

  In general, when a compound capable of improving the sensitivity by interacting with such an infrared absorber or radical initiator is added to the polymerizable composition, the storage stability of the polymerizable composition itself is reduced. Although it causes harmful effects, such a harmful effect does not occur when the specific amino alcohol according to the present invention is added, and further, the storage stability of the radically polymerized photosensitive material which is originally insufficient is improved. There is also an effect. This is considered to be because the specific amino alcohol forms a complex with the radical initiator in the polymerizable composition, and the radical initiator is thermally stabilized during raw storage.

  ADVANTAGE OF THE INVENTION According to this invention, the polymeric composition superposed | polymerized with high sensitivity and the intensity | strength of the formed film | membrane is excellent, and the recording material using the same can be obtained which was excellent in storage stability.

[Polymerizable composition]
The polymerizable composition of the present invention has (A) a compound having an amino group and a hydroxyl group, (B) an infrared absorber, (C) a radical initiator, and (D) at least one ethylenically unsaturated bond. And a compound. Hereinafter, each of these components will be described in detail.

[(A) Compound having amino group and hydroxyl group]
The specific amino alcohol used in the present invention is not particularly limited as long as it is a compound having at least one of both an amino group and a hydroxyl group in the molecule. The amino group in the present invention includes structures such as a secondary amine and a tertiary amine in addition to a general amino group (—NH ₂ ) belonging to a primary amine. .
In the present invention, among such specific amino alcohols, a compound having at least one partial structure represented by the following general formula (I) in the molecule is preferable.

In general formula (I), A represents an alkylene group which may have a substituent having 1 to 10 carbon atoms. As such an alkylene group, a C1-C6 thing is preferable from a viewpoint of a sensitivity, and a C2-C4 thing is more preferable. Examples of the substituent that the alkylene group represented by A can have include a group composed of a monovalent non-metallic atomic group excluding a hydrogen atom, and preferably has a substituent described later. And the alkyl group which may be substituted, and those shown as the substituent in the alkyl group which may have a substituent.
R ¹ represents a hydrogen atom or a monovalent organic group. Here, as the monovalent organic group, an alkyl group which may have a substituent described later, or an alkenyl group or an alkynyl group exemplified as a substituent in the alkyl group which may have the substituent. , Aryl groups, heterocyclic groups, and the like. These alkenyl groups, alkynyl groups, aryl groups, and heterocyclic groups may further have a substituent.

  Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t- A butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group can be exemplified. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  As the substituent that such an alkyl group may have, a group consisting of a monovalent non-metallic atomic group excluding a hydrogen atom is used, and preferable examples include halogen atoms (—F, —Br, —Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-aryl Amino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarba Iroxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido Group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-ary Roxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- Diarylcarbamoyl group, N-alkyl-N -Arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group,

Arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkyls Rufiinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N- dialkylsulfamoyl group, N- aryl sulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group (referred to as phosphonato group), dialkylphosphono group (-PO ₃ (alkyl) ₂₎ wherein "alk l = alkyl group, hereinafter the "diarylphosphono group (-PO ₃ (aryl) _2)" aryl = aryl group, hereinafter the "alkylaryl phosphono group _{(-PO 3 (alkyl) (aryl} )), mono Alkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonato group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (arylphosphonate group) ), Phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), diarylphosphonooxy group (—OPO _3). (aryl) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group (-OPO ₃ H (alkyl)) and its conjugated base group (alkyl referred to as phosphonic Hona preparative group), monoarylphosphono group (-OPO ₃ H (aryl)) and its conjugated base group (aryl phosphite Hona DOO Oxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl , It can be exemplified cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, a phosphate Hona preparative phenyl group.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
The R ⁰¹ of the acyl group (R ⁰¹ CO-), include hydrogen atom, and the above-described alkyl group, an aryl group. Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, and an alkenyl group.
Examples of the heterocyclic group include a pyridyl group and a piperidinyl group. Examples of the silyl group include a trimethylsilyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples thereof include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include a benzene ring, a ring in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include: Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
As the substituted aryl group, those having a group consisting of a monovalent nonmetallic atomic group other than a hydrogen atom as a substituent on the ring-forming carbon atom of the above-described aryl group are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, A 2-methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, a 3-butynylphenyl group, and the like can be given.

An alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ ) and —C≡C (R ⁰⁵ )) include R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ may be a group composed of a monovalent nonmetallic atomic group. Preferable examples of R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. More preferred groups of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms.

Preferable specific examples of such alkenyl group, substituted alkenyl group, alkynyl group and substituted alkynyl group include vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group and 1-octenyl group. 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1 -A propynyl group, a 1-butynyl group, and a phenylethynyl group can be mentioned.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁰⁶ O—), a group in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned as the previous example. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

The substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group is a group in which R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atomic groups excluding hydrogen atoms Can be used. R ⁰⁹ and R ⁰¹⁰ may combine to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ⁰⁷ groups definitive acyl group (R ⁰⁷ CO-) are as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

As described above, the sulfonate group (—SO ₃ —) means a conjugate base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds, azinium compounds, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ₂ ⁺ , Zn ₂ ^{+ and the} like).

As the substituted carbonyl group (R ⁰¹³ —CO—), those in which R ⁰¹³ is a group composed of a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), those in which R ⁰¹⁴ is a group composed of a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups, and preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

Phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) as described above and, phosphono group (-PO ₃ H _2), acid first dissociation or conjugate base anion derived from the second dissociation acid Means group. Usually, it is preferable to use it with a counter cation. Such counter cations include those generally known, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ₂ ⁺ , Zn ₂ ^{+ and the} like).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group in the above-described substituted phosphono group. As a specific example, the above-described monoalkylphosphono group (—PO ₃ H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

  Furthermore, in the present invention, the compound having at least one structure represented by the general formula (I) is more preferably a compound represented by the following general formula (II).

In formula (II), A and R ¹ have the same meanings A, and R ¹ in the general formula (I). Ar represents an aromatic group or a heterocyclic group.

Examples of the aromatic group represented by Ar include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
The aromatic group may have a substituent, and the aromatic group having such a substituent is a monovalent group other than a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group. And those having a group consisting of a nonmetallic atomic group. In addition, as an example of the preferable substituent introduce | transduced here, what was shown as a substituent in the above-mentioned alkyl group, a substituted alkyl group, and a substituted alkyl group can be mentioned.

As the heterocyclic group represented by Ar, a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, an isothiazole ring group, Indazole ring group, benzisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, quinoline ring Group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidene ring group, phenanthridine ring group, carbazole ring group, purine ring group, pyran ring Group, piperidine ring group, piperazine ring group, morpholine ring group, indole ring group Indolizine ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, a triazine ring group, and the like.
In addition, the heterocyclic group may have a substituent, and as such a substituent, a monovalent nonmetallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group described above. Those having a group consisting of: Examples of preferred substituents include the alkyl groups, substituted alkyl groups described below, and those shown as substituents in the substituted alkyl group.

  Furthermore, in the present invention, the compound represented by the general formula (II) is most preferably a compound represented by the following general formula (III).

  In general formula (III), A and Ar are synonymous with A and Ar in general formula (II).

  Specific examples of (A) specific amino alcohol according to the present invention will be given below, but the present invention is not limited to these.

  The specific amino alcohol (A) according to the present invention is synthesized by utilizing the method described in “The Chemical Society of Japan, New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds [III]” (Maruzen), page 1342, etc. be able to.

  As for the specific amino alcohol which concerns on this invention demonstrated above, only 1 type may be used and 2 or more types may be used together. As the addition amount of these specific amino alcohols, 0.1 to 70% by mass, preferably 0.5 to 50% by mass, and more preferably 1 to 30% by mass in the total solid content of the polymerizable composition. can do. When the addition amount is within this range, a sufficient sensitivity improvement effect can be obtained, and when this polymerizable composition is used as a recording layer of a lithographic printing plate precursor, the occurrence of smudges in non-image areas during printing. The film physical properties of the recording layer before and after curing are stably maintained.

[(B) Infrared absorber]
The polymerizable composition of the present invention is characterized by containing an infrared absorber that absorbs infrared light and converts it into heat energy. Radiation generation reaction of the radical initiator and polymerization reaction of the polymerizable compound thereby are accelerated by exposure of the wavelength that can be absorbed by the infrared absorber and heat generation at that time. Examples of such infrared absorbers include known spectral sensitizing dyes or dyes or pigments that absorb light and interact with a photo radical initiator.

<Spectral sensitizing dye or dye>
Spectral sensitizing dyes or dyes preferred as infrared absorbers for use in the present invention are polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrins), chlorophylls (eg, chloro I le, chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones, such as (anthraquinone), squaryliums, for example (squarylium), for example, the following compounds.

  More preferable spectral sensitizing dyes or dyes include pyrylium salts described in JP-B-40-28499, for example,

Cyanines described in JP-B-46-42363, for example,

Benzofuran dyes described in JP-A-2-63053, for example,

Conjugated ketone dyes disclosed in JP-A-2-85858 and JP-A-2-216154, for example,

A dye described in JP-A No. 57-10605, an azocinnamylidene derivative described in JP-B-2-30321, for example,

Cyanine dyes described in JP-A-1-287105, for example,

Xanthene dyes described in JP-A-62-31844, JP-A-62-31848, JP-A-62-143043, for example,

Aminostyryl ketone described in JP-B-59-28325, for example,

Etc.
The following infrared absorbers (dyes or pigments) are also preferably used as sensitizing dyes. Preferred examples of the dye include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Examples include cyanine dyes described in Japanese Patent No. 434,875.

  In addition, as cyanine dyes that can be suitably used in the present invention, paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, paragraph numbers [0012] to [0038] of JP-A No. 2002-40638, Those described in paragraph numbers [0012] to [0023] of JP-A-2002-23360 can be mentioned. Moreover, what is illustrated below is mentioned as a specific example.

  Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and further substituted aryl benzoates described in US Pat. No. 3,881,924 are also used. (Thio) pyrylium salt, trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A 58-181051, 58-220143, 59 -41363, 59-84248, 59-84249, 59-146063, 59-146061, pyranyl compounds described in JP-A-59-216146, cyanine dyes described in US The pentamethine thiopyrylium salt described in Japanese Patent No. 4,283,475, and the like described in Japanese Patent Publication Nos. 5-13514 and 5-19702 That pyrylium compounds are also preferably used.

  In addition, near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513A2 are also preferable dyes. Can do.

  Furthermore, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. An anionic infrared absorbing agent refers to an anionic infrared absorbing agent having an anionic structure without a cationic structure in the mother nucleus of a dye that substantially absorbs infrared rays. Examples include (a) anionic metal complexes, (b) anionic carbon black, (c) anionic phthalocyanine, and (d) compounds represented by the following general formula (21). The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

  Here, (a) an anionic metal complex refers to an anion that is an anion of the central metal and the entire ligand of the complex part that substantially absorbs light.

  (B) Examples of the anionic carbon black include carbon black to which anionic groups such as sulfonic acid, carboxylic acid, and phosphonic acid groups are bonded as substituents. In order to introduce these groups into carbon black, as described in Carbon Black Handbook 3rd Edition (Edited by Carbon Black Association, April 5, 1995, published by Carbon Black Association), page 12, What is necessary is just to take means, such as oxidizing carbon black.

  (C) Anionic phthalocyanine refers to a phthalocyanine skeleton having the anion group previously mentioned in the description of (b) as a substituent bonded to form an anion as a whole.

Next, (d) the compound represented by the general formula (21) will be described in detail. In the general formula (21), G ⁹ represents an anionic substituent, and G ¹⁰ represents a neutral substituent. (X ¹⁰ ) ⁺ represents a 1 to m-valent cation containing a proton, and m represents an integer of 1 to 6. M ⁵ represents a conjugated chain, and this conjugated chain M ⁵ may have a substituent or a ring structure. The conjugated chain M ⁵ can be represented by the following formula.

In the formula, R ⁸⁰ , R ⁸¹ and R ⁸² are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy A group and an amino group, which may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

  Of the anionic infrared absorbers represented by the general formula (21), those of the following IRA-1 to IRA-5 are preferably used.

  Moreover, the cationic infrared absorber shown to the following IRC-1-IRC-44 can also be used preferably.

In the structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (BF ₄ ⁻ , PF ₆ ⁻ , SbCl _6). ⁻ , ClO ₄ ⁻ ), an alkyl sulfonate anion, and an aryl sulfonate anion.

  The alkyl of the alkyl sulfonic acid means a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t- A butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group can be exemplified. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  The aryl of the aryl sulfonic acid includes one consisting of one benzene ring, two or three benzene rings forming a condensed ring, and one having a benzene ring and a 5-membered unsaturated ring forming a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Moreover, the nonionic infrared absorber shown to the following IRN-1-IRN-9 can also be used preferably.

  Among the exemplified compounds, IRA-1 is a particularly preferable anionic infrared absorber, and IRC-7, IRC-30, IRC-40, and IRC-42 are nonionic infrared absorbers as cationic infrared absorbers. As IRN-9.

<Pigment>
Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. When the particle size of the pigment is within this range, the stability of the dispersion in the recording layer coating liquid and the uniformity of the recording layer when the polymerizable composition of the present invention is used as the recording layer of the recording material. This is preferable.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

In addition, although the infrared absorber added in order to accelerate | stimulate the hardening reaction of the polymeric composition of this invention may be added directly with another component in a composition, another layer adjacent to this is provided. Even if it is added thereto, the same effect can be obtained.
In particular, when the polymerizable composition of the present invention is used as a negative image recording layer of a lithographic printing plate precursor described later, it may be added to the same layer of the image recording layer, or another layer may be provided. However, when a negative image recording layer is formed, the optical density at the absorption maximum in the wavelength range of 300 nm to 1200 nm of the recording layer may be between 0.1 and 3.0. It is preferable from the viewpoint of sensitivity. Since the optical density is determined by the addition amount of the sensitizing dye and the thickness of the recording layer, the predetermined optical density can be obtained by controlling both conditions. The optical density of the recording layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a recording layer having a thickness appropriately determined in a range where the coating amount after drying is necessary as a lithographic printing plate is formed, and a transmission optical densitometer is used. Examples thereof include a measuring method, a method of forming a recording layer on a reflective support such as aluminum, and measuring a reflection density.

[(C) radical initiator]
The polymerizable composition of the present invention is characterized by containing a radical initiator. The radical initiator refers to a compound that generates radicals by light and / or heat energy and initiates and accelerates a polymerization reaction of a compound (D) having at least one ethylenically unsaturated bond described later.
In the present invention, preferred radical initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, f) Ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, and the like. Specific examples of the above (a) to (k) are given below, but the present invention is not limited to these.

(A) Aromatic ketones (a) Aromatic ketones preferred as the radical initiator used in the present invention include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” P. Fouassier, J. et al. F. Examples include compounds having a benzophenone skeleton or a thioxanthone skeleton described in Rabek (1993), p77-117. For example,

Is mentioned. Among them, examples of particularly preferred (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, for example, the following compounds.

  Examples of the α-substituted benzoin compounds described in JP-B-47-22326 include the following compounds.

  Examples thereof include benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, for example, the following compounds.

  Examples of the benzoin ethers described in JP-B-60-26403 and JP-A-62-181345 include the following compounds.

  Examples of the α-aminobenzophenones described in JP-B-1-34242, US Pat. No. 4,318,791, and European Patent 0284561A1, such as the following compounds.

  P-Di (dimethylaminobenzoyl) benzene described in JP-A-2-211452, for example, the following compounds may be mentioned.

  Examples of the thio-substituted aromatic ketone described in JP-A-61-194062 include the following compounds.

  The acylphosphine sulfide described in JP-B-2-9597, for example, the following compounds may be mentioned.

  Examples of the acylphosphine described in JP-B-2-9596 include the following compounds.

  Further, thioxanthones described in JP-B-63-61950, coumarins described in JP-B-59-42864, and the like can also be mentioned.

(B) Onium salt compound As the radical initiator (b) preferable as the radical initiator used in the present invention, compounds represented by the following general formulas (1) to (3) are exemplified.

In formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a group having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of onium salts that can be suitably used in the present invention include those described in paragraphs [0030] to [0033] of Japanese Patent Application No. 11-310623 previously proposed by the present applicant. And those described in paragraphs [0015] to [0046] of Japanese Patent Application No. 2000-160323, Japanese Patent Application No. 2000-266797, Japanese Patent Application No. 2001-177150, Japanese Patent Application No. 2000-160323, Specific aromatic sulfonium salt compounds described in Japanese Patent Application No. 2000-184603, Japanese Patent Application No. 2000-310808, Japanese Patent Application No. 2002-265467, and Japanese Patent Application No. 2002-366539 may be mentioned.

  The onium salt used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. Thus, by setting the absorption wavelength in the ultraviolet region, the polymerizable composition can be handled under white light.

(C) Organic peroxide Preferred as the radical initiator used in the present invention (c) The organic peroxide includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tertiarybutylperoxy) -3,3,5. -Trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene Idroperoxide, parameter hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl Cumyl peroxide, dicumyl peroxide, bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-xanoyl peroxide, peroxy Succinic oxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydi -Bonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxyneodecanoate, tarsha Tributyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary carbonate, 3,3'4,4'-tetra- (t -Butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3, 3'4 4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumi Ruperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogen diphthalate), and the like.

  Among them, 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3'4 4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (cumylper) Peroxyesters such as (oxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred.

(D) Thio compound (d) Thio compounds preferable as the radical initiator used in the present invention include compounds having a structure represented by the following general formula (4).

(Wherein R ²⁶ represents an alkyl group, an aryl group or a substituted aryl group, R ²⁷ represents a hydrogen atom or an alkyl group, and R ²⁶ and R ²⁷ are bonded to each other to form an oxygen, sulfur and nitrogen atom. (A group of nonmetallic atoms necessary to form a 5-membered to 7-membered ring which may contain a selected heteroatom.)
As an alkyl group in the said General formula (4), a C1-C4 thing is preferable. As the aryl group, those having 6 to 10 carbon atoms such as phenyl and naphthyl are preferable, and as the substituted aryl group, a halogen atom such as a chlorine atom and an alkyl such as a methyl group as described above. And those substituted with an alkoxy group such as a group, a methoxy group, and an ethoxy group. R ²⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the thio compound represented by the general formula (4) include the following compounds.

(E) Hexaarylbiimidazole compound Preferred as the radical initiator used in the present invention (e) Hexaarylbiimidazole compounds include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2 , 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra Phenylbiimidazole, 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'-tetraf Nilbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, Examples include 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

(F) Ketoxime ester compound (f) Ketoxime ester compounds preferable as the radical initiator used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3 -Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, Examples include 3-p-toluenesulfonyloxyiminobutan-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

(G) Borate compound As an example of the (g) borate compound preferable as a radical initiator used for this invention, the compound represented by following General formula (5) can be mentioned.

(Wherein R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, A substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group, R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ may be combined with each other to form a cyclic structure; Provided that at least one of R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ is a substituted or unsubstituted alkyl group (Z ⁵ ) ⁺ represents an alkali metal cation or a quaternary ammonium cation.)
Examples of the alkyl group for R ^{28 to} R ³¹ include straight-chain, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. The substituted alkyl group includes an alkyl group as described above, a halogen atom (for example, —Cl, —Br, etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, —COOR ³² (here R ³² represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —OCOR ³³ or —OR ³⁴ (where R ³³ and R ³⁴ are alkyl groups having 1 to 14 carbon atoms, or aryl. And a group having a substituent represented by the following formula.

(Wherein R ³⁵ and R ³⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group)
The aryl group of R ^{28 to} R ³¹ includes 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group for R ^{28 to} R ³¹ include linear, branched and cyclic groups having 2 to 18 carbon atoms. Examples of the substituent of the substituted alkenyl group include those listed as the substituents of the substituted alkyl group. Examples of the alkynyl group of R ^{28 to} R ³¹ include straight chain or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included. In addition, examples of the heterocyclic group of R ^{28 to} R ³¹ include a 5- or more-membered heterocyclic group containing at least one of N, S, and O, and preferably a 5- to 7-membered heterocyclic group. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula (5) are described in US Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773. Examples include compounds and those shown below.

(H) Azinium compounds Preferred (h) azinium salt compounds as radical initiators used in the present invention include those disclosed in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346, and JP-A-6-142346. Examples thereof include compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

(I) Metallocene compounds (i) Metallocene compounds preferred as the radical initiator used in the present invention include those disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, and JP-A-2 And titanocene compounds described in JP-A No.-249 and JP-A-2-4705, and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopentadi Enyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl] ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bi [2,6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-chloro Benzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium and the like.

(J) Active ester compound Preferred as the radical initiator used in the present invention (j) is an imide sulfonate compound described in JP-B-62-2223, JP-B-63-14340, JP-A-59-174831. Mention may be made of the active sulfonates described.

(K) Compound Having Carbon Halogen Bond Preferred examples of the compound (k) having a carbon halogen bond as the radical initiator used in the present invention include those represented by the following general formulas (6) to (12).

(Wherein X ² represents a halogen atom, and Y ¹ represents —C (X ² ) ₃ , —NH ₂ , —NHR ³⁸ , —NR ³⁸ , —OR ³⁸ , where R ³⁸ represents an alkyl group, substituted An alkyl group, an aryl group, or a substituted aryl group, and R ³⁷ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.

(However, R ³⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group, or a cyano group, and X ³ is a halogen atom. And n is an integer of 1 to 3.)

(However, R ⁴⁰ is an aryl group or a substituted aryl group, R ⁴¹ is a group or halogen shown below, and Z ⁶ is —C (═O) —, —C (═S) — or —SO _2- , X ³ is a halogen atom, and m is 1 or 2.)

(R ⁴² and R ⁴³ are an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, and R ⁴⁴ is the same as R ³⁸ in the general formula (6).)

Wherein R ⁴⁵ is an optionally substituted aryl group or heterocyclic group, R ⁴⁶ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, p is 1, 2 or 3.)

(Equation (10), .L ⁷ which represents a carbonylmethylene heterocyclic compound having a trihalogenomethyl group is a hydrogen atom or the ^{formula: CO- (R 47) q (} C (X 4) 3) at r substituent Q ² is a sulfur, selenium or oxygen atom, dialkylmethylene group, alkene-1,2-ylene group, 1,2-phenylene group or N—R group, and M ⁴ is a substituted or unsubstituted alkylene group or An alkenylene group or a 1,2-arylene group; R ⁴⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group; and R ⁴⁷ is a carbocyclic or heterocyclic divalent aromatic group. X ⁴ is a chlorine, bromine or iodine atom, and q = 0 and r = 1, or q = 1 and r = 1 or 2.)

(Formula (11) represents a 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative. X ⁵ is a halogen atom, t is an integer of 1 to 3, and s is an integer of 1 to 4. in and, R ⁴⁹ is a hydrogen atom or a CH _3-t X ⁵ _t group, R ⁵⁰ is s-valent optionally substituted unsaturated organic group.)

(Formula (12) represents a 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative. X ⁶ is a halogen atom, v is an integer of 1 to 3, and u is an integer of 1 to 4. R ⁵¹ is a hydrogen atom or a CH _3-v X ⁶ _v group, and R ⁵² is an u-valent unsaturated organic group which may be substituted.)

  Specific examples of such a compound having a carbon-halogen bond include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), such as 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2 -(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6 -Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6 Bis (trichloromethyl) -S- triazine. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho) 1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trick Rumethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples include compounds described in German Patent No. 3333724, such as bis-trichloromethyl-S-triazine, and the like.

  F.F. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), such as 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4 , 6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, etc. Can do. Furthermore, for example, the following compounds described in JP-A-62-258241 can be exemplified.

  Furthermore, for example, the following compounds described in JP-A-5-281728 can be mentioned.

  Or even more P. Hutt, E .; F. Elslager and L.L. M.M. The following compounds that can be easily synthesized by those skilled in the art according to the synthesis method described in “Journalof Heterocyclic Chemistry”, Volume 7 (No. 3) by Herbel, page 511 et seq. (1970) Examples of the group include the following compounds.

(L) Azo-based compound Preferred as the radical initiator used in the present invention (i) As the azo-based compound, 2,2′-azobisisobutyronitrile, 2,2′-azobispropionitrile, 1, 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamide oxime) ), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxy Til] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 '-Azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (2,4,4- Trimethylpentane) and the like.

  Still more preferred examples of the radical initiator in the present invention include the above-mentioned (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (e) hexaarylbiimidazole compounds, (i) ) Metallocene compounds, (k) compounds having a carbon halogen bond, and the most preferred examples include aromatic iodonium salts, aromatic sulfonium salts, titanocene compounds, and trihalomethyl represented by the general formula (6) -S-triazine compounds can be mentioned.

These radical initiators are 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 5 to 20% by mass, based on the total solid content of the polymerizable composition. It can be added to the composition.
The radical initiator in the present invention is preferably used alone or in combination of two or more.

[(D) Compound having at least one ethylenically unsaturated bond]
The polymerizable compound used in the polymerizable composition of the present invention is selected from compounds having at least one ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, 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. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. And vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups. It is done.

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

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, In addition, a polymerizable composition excellent in photosensitive speed can be obtained.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  For these polymerizable compounds, the structure, whether used alone or in combination, and details of usage such as the amount added, the purpose of use, for example, when the polymerizable composition of the present invention is used as a recording layer of a lithographic printing plate precursor Can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and intensity by using a compound) is also effective. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in photosensitive speed and film strength, but is not preferable in terms of development speed and precipitation in a developer. Further, the selection / use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components (for example, binder polymer, initiator, colorant, etc.) in the recording layer. The compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the substrate and an overcoat layer described later. Regarding the compounding ratio of the polymerizable compound in the recording layer, a larger amount is advantageous in terms of sensitivity, but if it is too much, an undesirable phase separation occurs or a problem in the production process due to the adhesiveness of the recording layer ( For example, problems such as transfer of recording layer components and manufacturing defects due to adhesion) and precipitation from the developer may occur. From these viewpoints, the polymerizable compound is preferably used in the range of 5 to 80% by mass, and more preferably 25 to 75% by mass with respect to the nonvolatile component in the polymerizable composition. These may be used alone or in combination of two or more. In addition, the usage of the polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. The layer construction and coating method such as undercoating and overcoating can also be carried out.

[(E) Binder polymer]
In the polymerizable composition of the present invention, a binder polymer (E) can be used as needed for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder polymer. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent for the image recording layer but also according to its use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP 54-92723, JP 59-53836, JP 59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer. Examples thereof include a polymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  Among these, in particular, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxy group in the side chain, and Japanese Patent Application Laid-Open Nos. 2000-187322, 2002-62648, 2001-253217, and Japanese Patent Application Alkali-soluble resins having a double bond in the side chain described in JP-A-2002-287920, JP-A-2002-62648 and the like are excellent in balance of film strength, sensitivity, and developability, and are preferable.

  In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane-based binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength, and are advantageous in terms of printing durability and suitability for low exposure.

  In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer used in the present invention is preferably 5000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1000 or more, more preferably 2000. It is in the range of ~ 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These polymers may be random polymers, block polymers, graft polymers or the like, but are preferably random polymers.

The binder polymer used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
As the radical initiator used in synthesizing the binder polymer used in the present invention, known compounds such as azo initiators and peroxide initiators can be used.

The binder polymer used in the present invention may be used alone or in combination. When the polymerizable composition of the present invention is used as an image recording layer of a lithographic printing plate precursor, the amount of the binder polymer added is 20 to 95% by weight, preferably 30 to 30% by weight based on the total solid content of the polymerizable composition. 90% by mass is added. Within this range, the lithographic printing plate precursor according to the present invention is excellent in image forming properties and sufficiently improves the strength of the image area. The compound having at least one ethylenically unsaturated double bond and the linear organic polymer are preferably in the range of 1/9 to 7/3 by mass ratio.
The polymerizable composition of the present invention obtained as described above is polymerized with high sensitivity, the strength of the formed film is high, and the storage stability is excellent. In particular, three-dimensional stereolithography, holography, lithographic printing It is suitably used as an image recording material such as a printing plate material, a color proof, a photoresist and a color filter.

[Recording material]
The recording material of the present invention is characterized by having a recording layer containing the polymerizable composition on a support.
Such a recording layer can be provided by, for example, dissolving the polymerizable composition in an appropriate solvent to form a recording layer coating solution and coating the solution on a support. Depending on the purpose, various additives, backcoat layers, intermediate layers, protective layers and the like described later can be formed in the same manner.

  In the recording material of the present invention, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Manufactured by Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc., and JP-A-62-2 And dyes described in No. 293247. In addition, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can also be suitably used.

  These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. The added amount is 0.01 to 10% by mass with respect to the total solid content of the recording layer coating solution.

  In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during preparation of the recording layer coating solution or during storage. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen and may be unevenly distributed on the surface of the recording layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.1% by mass to about 10% by mass of the total composition.

  In the recording material of the present invention, nonionic surfactants as described in JP-A-62-251740 and JP-A-3-208514 are used in order to broaden the processing stability of the recording layer with respect to the development conditions. , Amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149 can be added.

  Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like.

Specific examples of amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N, N- Examples include betaine type (for example, trade name Amorgen K, manufactured by Dai-ichi Kogyo Co., Ltd.).
The proportion of the nonionic surfactant and the amphoteric surfactant in the recording layer coating solution is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

  Furthermore, a plasticizer is added to the recording layer coating solution according to the present invention as needed to impart flexibility and the like of the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and the like are used.

  In the recording material of the present invention, the solvent used for preparing the recording layer coating solution includes ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2- Methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, Examples thereof include, but are not limited to, γ-butyrolactone, toluene, and water. These solvents are used alone or in combination. The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.

Further, the coating amount (solid content) of the recording layer on the support obtained after coating and drying varies depending on the application, but generally speaking, it is preferably 0.5 to 5.0 g / m ² for a lithographic printing plate precursor. As the coating amount decreases, the apparent sensitivity increases, but the film properties of the recording layer decrease.
Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

  In the recording layer coating liquid according to the present invention, a surfactant for improving the coating property, for example, a fluorosurfactant described in JP-A-62-170950 can be added. . A preferable addition amount is 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the material solid content of the entire recording layer.

(Support)
The support used in the recording material of the present invention is not particularly limited as long as it is a dimensionally stable plate-like material. For example, paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) is laminated. Paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene , Polycarbonate, polyvinyl acetal, etc.). These may be a single component sheet such as a resin film or a metal plate, or may be a laminate of two or more materials. For example, a paper or plastic film on which a metal as described above is laminated or vapor-deposited. And laminated sheets of different plastic films.

As the support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of different elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and used aluminum plates can be appropriately used.
The aluminum plate has a thickness of about 0.1 to 0.6 mm, preferably 0.15 to 0.4 mm, and particularly preferably 0.2 to 0.3 mm.

Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing rolling oil on the surface is performed as desired.
The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

  The aluminum plate roughened in this way can be subjected to an anodizing treatment to enhance the water retention and wear resistance of the surface through an alkali etching treatment and a neutralization treatment, if desired. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. However, in general, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / day. dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are suitable.
The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide coating is less than 1.0 g / m ² , the printing durability is insufficient, or the non-image part of the lithographic printing plate is easily scratched, so that the ink adheres to the scratched part during printing. “Scratches and dirt” are likely to occur.
Such anodizing treatment is applied to the surface used for printing the support of the lithographic printing plate, but an anodized film of 0.01 to 3 g / m ² is also formed on the back surface due to the back of the lines of electric force. It is common to form.

The hydrophilic treatment of the support surface is performed after the anodizing treatment, and conventionally known treatment methods are used. Such hydrophilization treatment is disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There are various alkali metal silicate methods (for example, sodium silicate aqueous solution). In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, disclosed in Japanese Patent Publication No. 36-22063 is potassium fluoride zirconate and U.S. Pat. Nos. 3,276,868, 4,153,461, and 4,689,272. A method of treating with polyvinylphosphonic acid as described above is used.
Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

The anodized film of the aluminum plate subjected to the treatment as described above has an alkali metal silicate content of 0.1 to 30% by mass, preferably 0.5 to 10% by mass, and a pH at 25 ° C. of 10 to 13. It is immersed in a certain aqueous solution at 15 to 80 ° C. for 0.5 to 120 seconds, for example. If the pH of the alkali metal silicate aqueous solution is lower than 10, the solution will gel, and if it is higher than 13.0, the oxide film will be dissolved. Examples of the alkali metal silicate used in the present invention include sodium silicate, potassium silicate, and lithium silicate. Examples of the hydroxide used to increase the pH of the alkali metal silicate aqueous solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. In addition, you may mix | blend alkaline-earth metal salt or a group IVB metal salt with said process liquid. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate, and borate. Can be mentioned. Examples of Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, potassium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc. Can do. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. A preferable range of these metal salts is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5.0% by mass.
Since the hydrophilicity on the surface of the aluminum plate is further improved by the silicate treatment, the ink hardly adheres to the non-image area during printing, and the stain performance is improved.

Hereinafter, the case where the recording material of the present invention is used as a lithographic printing plate precursor which is a particularly preferred embodiment will be described.
(Back coat layer)
When the recording material of the present invention is used as a lithographic printing plate precursor, a back coat may be provided on the back surface of the support, if necessary. As such a backcoat, a coating comprising a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 A layer is preferably used.
Among these coating layers, silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , and Si (OC ₄ H ₉ ) ₄ are available at a low price. The coating layer of the metal oxide provided therefrom is particularly preferred because of its excellent development resistance.

(Middle layer)
When the recording material of the present invention is used as a lithographic printing plate precursor, an intermediate layer may be provided for the purpose of improving adhesion between the recording layer and the substrate and soiling. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, Japanese Patent Application No. 8-225335, Japanese Patent Application No. 8-270098, Japanese Patent Application No. 9-195863, Japanese Patent Application No. 9-195864, Japanese Patent Application No. 9-89646, Japanese Patent Application No. 9-106068, Japanese Patent Application No. 9-183834, Japanese Patent Application No. 9-264411, Japanese Patent Application No. 9 -127232, Japanese Patent Application No. 9-245419, Japanese Patent Application No. 10-127602, Japanese Patent Application No. 10-170202, Japanese Patent Application No. 11-36377, Japanese Patent Application No. 11-165661, Japanese Patent Application No. 11-284091 No., Japanese Patent Application No. 2000-14697, and the like.

(Protective layer)
When the recording material of the present invention is used as a lithographic printing plate precursor, it is preferable to further provide a protective layer on the above-mentioned recording layer because exposure is usually performed in the air. The protective layer prevents exposure of low molecular weight compounds such as oxygen and basic substances present in the atmosphere that hinder the image formation reaction caused by exposure in the recording layer, and enables exposure in the air. To do. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, and further, transmission of light used for exposure is not substantially inhibited, and excellent adhesion to the recording layer. And it is desirable that it can be easily removed in the development process after exposure. Such a device for the protective layer has been conventionally devised, which is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, the use of polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on an oleophilic recording layer, film peeling due to insufficient adhesive force is likely to occur, and the peeled portion causes defects such as poor film hardening due to inhibition of oxygen polymerization. On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, in US Pat. No. 292,501 and US Pat. No. 44,563, an acrylic emulsion or a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer is contained in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesion can be obtained by mixing by mass% and laminating on a recording layer.
Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.

(Exposure, development and printing)
The planographic printing plate precursor according to the invention can be recorded with an infrared laser. Thermal recording with an ultraviolet lamp or a thermal head is also possible. In the present invention, image exposure is preferably performed by a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 760 nm to 1200 nm.

  After exposure with an infrared laser, the polymerizable composition of the present invention is preferably developed with water or an alkaline aqueous solution.

When an alkaline aqueous solution is used as the developer, a conventionally known alkaline aqueous solution can be used as the developer and replenisher for the polymerizable composition of the present invention. For example, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, Examples include inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used.
These alkali agents are used alone or in combination of two or more.

  Furthermore, when developing using an automatic developing machine, the developer in the developing tank for a long time is added to the developer by adding an aqueous solution (replenisher) that is the same as the developer or higher in alkali strength than the developer. It is known that a large amount of a lithographic printing plate precursor can be processed without replacing the plate. This replenishment method is also preferably applied in the present invention.

  Various surfactants, organic solvents, and the like can be added to the developer and the replenisher as necessary for the purpose of promoting and suppressing developability, dispersing development residue, and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol. Moreover, addition of polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof is also preferable. In addition, non-reducing sugars such as arabit, sorbit and mannitol can be added.

  In addition, the developer and replenisher may contain inorganic quinone reducing agents such as hydroquinone, resorcin, sodium sulfite or sodium bisulfite, and organic carboxylic acids, antifoaming agents, and hard water softeners as necessary. It can also be added.

  The printing plate developed using the developer and replenisher described above is post-treated with a desensitizing solution containing washing water, a rinsing solution containing a surfactant and the like, gum arabic and starch derivatives. As the post-treatment when the polymerizable composition of the present invention is used as a printing plate material, these treatments can be used in various combinations.

In recent years, automatic developing machines for printing plate materials have been widely used in the plate making and printing industries in order to rationalize and standardize plate making operations. This automatic developing machine is generally composed of a developing unit and a post-processing unit, and includes an apparatus for conveying a printing plate material, processing liquid tanks and a spray device. Each processing liquid pumped up is sprayed from a spray nozzle for development processing. In addition, recently, a method is also known in which a printing plate material is immersed and conveyed in a processing liquid tank filled with a processing liquid by a submerged guide roll or the like. In such automatic processing, each processing solution can be processed while being supplemented with a replenisher according to the processing amount, operating time, and the like. In addition, the electrical conductivity can be detected by a sensor and replenished automatically.
In addition, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing process after applying a desensitized gum if desired. However, if it is desired to obtain a lithographic printing plate with a higher printing durability, a burning treatment is performed. Is given.
In the case of burning a lithographic printing plate, before burning, an adjustment as described in JP-B-61-2518, JP-A-55-28062, JP-A-62-31859, JP-A-61-159655 is used. It is preferable to treat with a surface liquid.

As its method, with a sponge or absorbent cotton soaked with the surface-adjusting liquid, it is applied onto a lithographic printing plate, or a method in which the printing plate is immersed and applied in a vat filled with the surface-adjusting liquid, Application by an automatic coater is applied. Further, it is more preferable to make the coating amount uniform with a squeegee or a squeegee roller after coating.
In general, the amount of surface-adjusting solution applied is suitably 0.03 to 0.8 g / m ² (dry mass).
The lithographic printing plate coated with the surface-adjusting liquid is dried if necessary, and then heated to a high temperature with a burning processor (for example, burning processor BP-1300 sold by Fuji Photo Film Co., Ltd.). . In this case, the heating temperature and time are in the range of 180 to 300 ° C. and preferably in the range of 1 to 20 minutes, although depending on the type of components forming the image.

  The burned lithographic printing plate can be subjected to conventional treatments such as washing and gumming as needed, but a surface-conditioning solution containing a water-soluble polymer compound or the like is used. In such a case, a so-called desensitizing treatment such as gumming can be omitted.

  The lithographic printing plate obtained by such processing is applied to an offset printing machine or the like and used for printing a large number of sheets.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In Examples of the present application, evaluation is performed on a lithographic printing plate using the polymerizable composition of the present invention as a recording layer, and the evaluation is regarded as evaluation of the polymerizable composition of the present invention and the recording material.

(Production of support)
A molten metal of JIS A1050 alloy containing 99.5% or more of aluminum and Fe 0.30%, Si 0.10%, Ti 0.02%, and Cu 0.013% was subjected to cleaning treatment and cast. In the cleaning process, a degassing process was performed to remove unnecessary gases such as hydrogen in the molten metal, and a ceramic tube filter process was performed. The casting method was a DC casting method. The solidified 500 mm thick ingot was chamfered 10 mm from the surface and homogenized at 550 ° C. for 10 hours so as not to coarsen the intermetallic compound.
Next, after hot rolling at 400 ° C. and intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, cold rolling was performed to obtain an aluminum rolled plate having a plate pressure of 0.30 mm. By controlling the roughness of the rolling roll, the centerline average surface roughness Ra after cold rolling was controlled to 0.2 μm. Then, it applied to the tension leveler in order to improve planarity.

Next, the surface treatment for making a lithographic printing plate support was performed.
First, in order to remove the rolling oil on the surface of the aluminum plate, degreasing treatment was carried out with a 10% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal treatment were carried out with a 30% sulfuric acid aqueous solution at 50 ° C. for 30 seconds.
Next, in order to improve the adhesion between the support and the recording layer and to provide water retention to the non-image area, a so-called graining treatment was performed to roughen the surface of the support. While maintaining an aqueous solution containing 1% nitric acid and 0.5% aluminum nitrate at 45 ° C. and flowing an aluminum web through the aqueous solution, an alternating waveform with a current density of 20 A / dm ² and a duty ratio of 1: 1 by an indirect power supply cell Then, electrolytic graining was performed by giving an anode side electric quantity of 240 C / dm ² . Thereafter, etching treatment was performed with a 10% sodium aluminate aqueous solution at 50 ° C. for 30 seconds, and neutralization and smut removal treatment were performed with a 30% sulfuric acid aqueous solution at 50 ° C. for 30 seconds.

Furthermore, in order to improve wear resistance, chemical resistance and water retention, an oxide film was formed on the support by anodic oxidation. An anodized film of 2.5 g / m ² by using a 20% sulfuric acid aqueous solution as an electrolyte at 35 ° C. and carrying out an electrolytic treatment with a direct current of 14 A / dm ² by an indirect power feeding cell while carrying an aluminum web into the electrolyte. It was created.

[Examples 1 to 14, Comparative Examples 1 and 2]
(Formation of recording layer)
A recording layer coating solution 1 having the following composition was prepared, applied to the aluminum support obtained as described above using a wire bar, and dried at 115 ° C. for 45 seconds in a hot air drying apparatus to form a recording layer. Formed. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² . Furthermore, an overcoat layer coating solution having the following composition was applied using a slide hopper and dried at 120 ° C. for 75 seconds with a hot air dryer to obtain a lithographic printing plate precursor according to the present invention. The coating amount of the overcoat layer was 2.3 g / m ² .

<Recording layer coating solution 1>
-(A) component: additive (compound and amount described in Table 1)
-(B) component: Infrared absorber “IR-1” (the following structure) 0.08 g
-Component (C): radical initiator (compound described in Table 1) 0.35 g
Component (D): polymerizable compound “M-1” (the following structure) 2.00 g
-(E) component: Binder polymer (compound described in Table 1) 2.00 g
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Fluorine-based surfactant 0.01g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ Methanol 10.0g
1-methoxy-2-propanol 8.0g

<Overcoat layer coating solution>
・ Polyvinyl alcohol 2.5g
(Saponification degree 98.5 mol%, polymerization degree 500)
・ Polyvinylpyrrolidone 0.5g
(K30, Tokyo Chemical Industry Co., Ltd. molecular weight 40,000)
・ Nonionic surfactant 0.05g
(EMAREX NP-10 manufactured by Nippon Emulsion Co., Ltd.)
・ Ion-exchanged water 96.95g

  The additive of the component (A) used in the examples of the present invention is the specific amino alcohol (A) mentioned in the above specific example, and the additive used in the comparative example has the structure shown below. And additives (C-1) to (C-3) outside the scope of the present invention.

  The structures of the infrared absorbers (IR-1) to (IR-3) used in Examples and Comparative Examples of the present invention are shown below.

  The structures of the radical initiators (S-1) to (S-6) used in the examples and comparative examples of the present invention are shown below.

  The structures of the polymerizable compounds (M-1) to (M-3) used in Examples and Comparative Examples of the present invention are shown below.

  The structures of binder polymers (P-1) to (P-3) used in Examples and Comparative Examples of the present invention are shown below.

(exposure)
The obtained negative lithographic printing plate precursor is exposed with a Trend setter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an output of 9 W, an outer drum rotation speed of 210 rpm, a plate surface energy of 100 mJ / cm ² , and a resolution of 2400 dpi. did.

(Development processing)
After the exposure, the film was developed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water diluted solution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the feed solution and the replenisher solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

[Evaluation of printing durability]
The obtained lithographic printing plate was printed with a GEOS-G (N) ink manufactured by Dainippon Ink with a R201 printer manufactured by Roland. The printed matter in the solid image portion was observed, and the printing durability was examined based on the number of sheets on which the image began to fade. The larger the number, the better the printing durability. The results are also shown in Table 1.

[Evaluation of sensitivity]
The amount of energy necessary for recording was calculated based on the line width and laser output of the image obtained by the above exposure (with an infrared laser having a wavelength of about 830 to 850 nm) and development, the loss in the optical system, and the scanning speed. The smaller the value, the higher the sensitivity. The results are also shown in Table 1.

  As is apparent from Table 1, the planographic printing plates of Examples 1 to 14 to which the specific amino alcohol according to the present invention was added were the planographic printing plates of Comparative Examples 1 and 2 to which the specific amino alcohol according to the present invention was not added. It was found that the printing durability and sensitivity were excellent compared to.

[Examples 15 to 25, Comparative Examples 3 and 4]
(Formation of undercoat layer)
An undercoat liquid having the following composition was applied to the same aluminum support as in Example 1 with a wire bar, and dried at 90 ° C. for 30 seconds using a hot air dryer. The coating amount after drying was 10 mg / m ² .

<Undercoat liquid>
・ Β-Alanine 0.1g
・ Phenylphosphonic acid 0.1g
・ Methanol 40g
・ Pure water 60g

(Formation of recording layer)
Next, the recording layer coating solution 2 having the following composition is prepared, applied to the above-mentioned undercoated aluminum plate using a wire bar, and dried at 115 ° C. for 45 seconds with a hot air drying apparatus to form a recording layer. did. The coverage of the recording layer after drying was in the range of 1.2 to 1.3 g / m ² . Further, the same overcoat layer coating solution as in Example 1 was applied using a slide hopper, and dried at 120 ° C. for 75 seconds with a hot air drying apparatus to obtain a lithographic printing plate precursor. The coating amount of the overcoat layer was 2.3 g / m ² .

<Recording layer coating solution 2>
-(A) component: Additive (compound and amount described in Table 2)
-(B) component: Infrared absorber "IR-1" (the said structure) 0.08g
Component (C): radical initiator “S-1” (the above structure) 0.35 g
-Component (D): polymerizable compound (compound described in Table 2) 2.00 g
-(E) component: Binder polymer (compound of Table 2) 2.00g
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Fluorine-based surfactant 0.01g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ Methanol 10.0g
1-methoxy-2-propanol 8.0g

(Exposure and development processing)
The obtained negative planographic printing plate precursor was subjected to infrared laser exposure and development in the same manner as in Example 1 to obtain a planographic printing plate.

[Evaluation of printing durability, stain resistance of non-image area and storage stability]
The obtained lithographic printing plate was printed with a Lithrone printing machine manufactured by Komori Corporation using DIC-GEOS (N) black ink manufactured by Dainippon Ink and Chemicals. At this time, the number of sheets that can be printed while maintaining a sufficient ink density was measured by visual observation, and the printing durability and the stain resistance of the non-image area were evaluated.
The obtained lithographic printing plate precursor was stored for 3 days at 60 ° C. and stored for 3 days at 45 ° C. and a humidity of 75% RH, followed by forced aging. The dirtiness (storage stability) of the non-image area was evaluated. The results are also shown in Table 2.

  As is apparent from Table 2, the planographic printing plates of Examples 15 to 25 to which the specific amino alcohol according to the present invention was added were the planographic printing plates of Comparative Examples 3 and 4 to which the specific amino alcohol according to the present invention was not added. Compared to the above, it was confirmed that the printing durability was excellent and the storage stability was excellent because no stain was observed in the non-image area even after forced aging.

[Examples 26 to 34, Comparative Examples 5 to 8]
(Formation of undercoat layer)
On the same aluminum support as in Example 1, a SG composition liquid composition (sol solution) was prepared by the following procedure to provide an undercoat layer.
<Sol solution composition>
・ Methanol 130g
・ Water 20g
・ 85% phosphoric acid 16g
・ Tetraethoxysilane 50g
・ 60 g of 3-methacryloxypropyltrimethoxysilane

The sol composition was mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the contents were transferred to another container, and 3000 g of methanol was added to obtain a sol solution.
This sol solution was diluted with methanol / ethylene glycol = 9/1 (mass ratio) and applied to the same support as in Example 1 so that the amount of Si on the support was 30 mg / m ² . An undercoat layer was formed by drying at 100 ° C. for 1 minute.

(Formation of recording layer)
A recording layer coating solution 3 having the following composition was applied to the above-mentioned undercoated aluminum support using a wire bar, and dried at 115 ° C. for 45 seconds with a hot air dryer to form a recording layer. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² . Further, the same overcoat layer coating solution as in Example 1 was applied using a slide hopper, and dried at 120 ° C. for 75 seconds with a hot air drying apparatus to obtain a lithographic printing plate precursor. The coating amount of the overcoat layer was 2.3 g / m ² .

<Recording layer coating solution 3>
-(A) component: Additive (compound and amount described in Table 3)
-(B) component: Infrared absorber (compound described in Table 3) 0.08 g
-Component (C): radical initiator (compound described in Table 3) 0.35 g
Component (D): polymerizable compound “M-1” (the above structure) 2.00 g
-(E) component: Binder polymer "P-1" 2.00g
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Fluorine-based surfactant 0.01g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ Methanol 10.0g
1-methoxy-2-propanol 8.0g

(Exposure and development processing)
The obtained negative planographic printing plate precursor was subjected to infrared laser exposure and development in the same manner as in Example 1 to obtain a planographic printing plate.

[Evaluation of sensitivity, dirtiness of non-image area and storage stability]
The obtained lithographic printing plate was evaluated for sensitivity in the same manner as in Example 1.
In addition, the obtained lithographic printing plate precursor was evaluated in the same manner as in Example 15 for stainability (storage stability) of non-image areas. The results are also shown in Table 3.

  As is apparent from Table 3, the planographic printing plates of Examples 26 to 34 to which the specific amino alcohol according to the present invention was added were the lithographic printing plates of Comparative Examples 5 to 8 to which the specific amino alcohol according to the present invention was not added. Compared to the above, the sensitivity was excellent, and no stain was observed in the non-image area even after forced aging. Thus, it was confirmed that the storage stability was excellent.

[Examples 35 to 40, Comparative Examples 9 and 10]
(Formation of undercoat layer)
A silicate treatment was performed on the same aluminum support as in Example 1 in order to ensure hydrophilicity as a non-image portion of the printing plate. The treatment was carried with a 1.5% aqueous solution of sodium silicate 3 maintained at 70 ° C. so that the contact time of the aluminum web was 15 seconds, and further washed with water. The adhesion amount of Si was 10 mg / m ² . Ra (center line surface roughness) of the support prepared as described above was 0.25 μm.

(Formation of recording layer)
The recording layer coating solution 4 having the following composition was applied to the undercoated aluminum support using a wire bar, and dried at 115 ° C. for 45 seconds with a hot air dryer to form a recording layer. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² . Further, the same overcoat layer coating solution as in Example 1 was applied using a slide hopper, and dried at 120 ° C. for 75 seconds with a hot air drying apparatus to obtain a lithographic printing plate precursor. The coating amount of the overcoat layer was 2.3 g / m ² .

<Recording layer coating solution 4>
-(A) component: Additive (compound and amount described in Table 4)
-(B) component: Infrared absorber "IR-1" (the said structure) 0.06g
-Component (C): radical initiator “S-1” (the above structure) 0.40 g
Component (D): polymerizable compound “M-1” (the above structure) 1.80 g
-(E) component: Binder polymer "P-1" (the said structure) 2.20g
・ Victoria Pure Blue Naphthalenesulfonate 0.04g
・ Fluorine-based surfactant 0.01g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 9.0g
・ Methanol 10.0g
1-methoxy-2-propanol 8.0g

(Exposure and development processing)
The obtained negative planographic printing plate precursor was subjected to infrared laser exposure and development in the same manner as in Example 1 to obtain a planographic printing plate.

[Evaluation of printing durability and sensitivity]
The lithographic printing plate thus obtained was evaluated for printing durability and sensitivity in the same manner as in Example 1. The results are also shown in Table 4.

As is clear from Table 4, the planographic printing plates of Examples 35 to 40 to which the specific amino alcohol according to the present invention was added were the planographic printing plates of Comparative Examples 9 and 10 to which the specific amino alcohol according to the present invention was not added. It was found that the printing durability and sensitivity were excellent compared to.
As described above, according to this example, the polymerizable composition of the present invention to which a specific amino alcohol is added is excellent in sensitivity, printing durability and storage stability, and is useful as an image recording layer of a lithographic printing plate precursor. all right.

Claims (3)

(A) a compound having an amino group and a hydroxyl group;
(B) an infrared absorber;
(C) a radical initiator;
(D) a compound having at least one ethylenically unsaturated bond;
A polymerizable composition containing (A) The polymerizable compound according to claim 1, wherein the compound having an amino group and a hydroxyl group is a compound having at least one partial structure represented by the following general formula (I) in the molecule. Composition.
In the following general formula (I), A represents an alkylene group which may have a substituent having 1 to 10 carbon atoms, and R ¹ represents a hydrogen atom or a monovalent organic group.

A recording material comprising a recording layer containing the polymerizable composition according to claim 1 on a support.