JP2003175683A - Original planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original planographic printing plate which allows to obtain a number of unblotted printed matter under severe printing conditions by achieving improvement in the avoidance of blot, enables production of plates by scanning exposure based on digital signals, and has an excellent developing property on machine. <P>SOLUTION: The original planographic printing plate is provided with a hydrophilic graft on its support, and a hydrophilic layer having a bridge structure which is formed by hydrolysis and condensation polymerization of an alkoxide compound comprising elements selected from Si, Ti, Zr and Al. Also, the plate comprises water dispersible particles which enable formation of a hydrophobic region on the surface through heating of or radiant ray irradiation on the hydrophilic layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel lithographic printing plate precursor, and more particularly to a lithographic printing plate capable of scanning and exposing an image with a laser beam based on a digital signal and having excellent sensitivity and stain resistance. Regarding the original printing plate.

[0002]

2. Description of the Related Art Lithographic printing is a printing method which utilizes a plate material having an oleophilic region for receiving ink and an ink repellent region (hydrophilic region) for receiving dampening water without receiving ink. In general, a photosensitive lithographic printing plate precursor (PS plate) is used. As the PS plate, one having a photosensitive layer provided on a support such as an aluminum plate has been put into practical use and widely used. In such a PS plate, the photosensitive layer in the non-image area is removed by imagewise exposure and development, and printing is performed by utilizing the hydrophilicity of the substrate surface and the lipophilicity of the photosensitive layer in the image area.
In such a plate material, the substrate surface is required to have high hydrophilicity in order to prevent stains on the non-image area.

Conventionally, as a hydrophilic substrate or hydrophilic layer used for a lithographic printing plate, an anodized aluminum substrate,
Alternatively, in order to further increase the hydrophilicity, it is common practice to subject the anodized aluminum substrate to a silicate treatment. Furthermore, researches on hydrophilic substrates or hydrophilic layers using these aluminum supports have been actively conducted. For example, Japanese Patent Laid-Open No. 7-1853 discloses a substrate treated with polyvinylphosphonic acid as an undercoating agent. Further, JP-A-59-101651 discloses a technique of using a polymer having a sulfonic acid group as an undercoat layer of a photosensitive layer.
A technique of using polyvinyl benzoic acid or the like as an undercoating agent has also been proposed.

On the other hand, the hydrophilic layer when a flexible support such as PET (polyethylene phthalate) or cellulose acetate is used without using a metal support such as aluminum is described in JP-A-8-292558. A swollen hydrophilic layer composed of a hydrophilic polymer and a hydrophobic polymer, a PET support having a microporous hydrophilic crosslinked silicate surface described in EP 0709228, and described in JP-A-8-272087 and JP-A-8-507727. Various techniques have been proposed, such as a hydrophilic layer containing the hydrophilic polymer described above and cured with a hydrolyzed tetraalkyl orthosilicate.

These hydrophilic layers provide a lithographic printing plate which has improved hydrophilicity as compared with the conventional ones and gives a printed matter free from stains at the start of printing. Even if the printing conditions are more severe, the hydrophilic layer does not peel off from the support or the hydrophilicity of the surface does not decrease, and a number of stain-free printed products can be obtained. A planographic printing plate precursor to be used was desired. In addition, from the practical viewpoint, it is the current situation that further improvement in hydrophilicity is required.

[0006] On the other hand, many studies have been conducted on printing plates for computer-to-plate systems, which have made remarkable progress in recent years. Among them, in order to further rationalize the process and solve the problem of waste liquid treatment, a development-free planographic printing plate precursor that can be mounted on a printing machine and printed without being subjected to development processing after exposure has been studied and various A method has been proposed. One of the methods to eliminate the processing step is to mount the exposed printing original plate on the cylinder of the printing machine and supply the dampening water and ink while rotating the cylinder to remove the non-image area of the printing original plate. There is a method called on-press development. That is, this is a method in which the printing original plate is exposed and then mounted on a printing machine as it is, and the processing is completed in a normal printing process.

Such a lithographic printing plate precursor suitable for on-press development has a photosensitive layer soluble in fountain solution and ink solvent, and is developed on a printing machine placed in a bright room. It is necessary to have a light room handling property suitable for. As a printing plate which does not require a developing step, WO94 / 23954 describes an untreated printing plate in which a crosslinked hydrophilic layer is provided on a substrate and a micro-encapsulated heat-melting substance is contained therein. In this printing plate, the microcapsules collapse due to the action of heat generated in the exposed area of the laser, the lipophilic substance in the capsules dissolves, and the surface of the hydrophilic layer becomes hydrophobic. This printing plate precursor does not require a developing treatment, but the hydrophilicity and durability of the hydrophilic layer provided on the substrate are insufficient, and there is a problem that the non-image area gradually becomes dirty as it is printed. there were.

[0008]

SUMMARY OF THE INVENTION An object of the present invention, which has been made to solve the above-mentioned problems of the prior art, is to provide a hydrophilic layer having high hydrophilicity and excellent durability, and in particular, printing stains. It is an object of the present invention to provide a lithographic printing plate precursor which has improved properties and is capable of obtaining a large number of printed materials which are free from stains even under severe printing conditions. A further object of the present invention is to enable plate making by scanning exposure based on a digital signal, and to perform printing as it is without performing plate making by a simple water development processing operation after image formation or performing special development processing. It is to provide a lithographic printing plate precursor that can be mounted on and printed.

[0009]

Means for Solving the Problems As a result of studies to achieve the above object, the present inventors have found that a hydrophilic layer in which a crosslinked structure composed of an organic-inorganic composite containing a specific hydrophilic polymer is formed. We have found that the problem can be solved by incorporating a compound capable of forming a surface-hydrophobicized region into, and have completed the present invention.

That is, the lithographic printing plate precursor of the present invention has a hydrophilic graft chain on a support, and has Si, T
a hydrophilic layer having a crosslinked structure formed by hydrolysis and condensation polymerization of an alkoxide compound containing an element selected from i, Zr and Al, and the surface of the hydrophilic layer is hydrophobized by heating or irradiation with radiation. And water-dispersible particles capable of forming Such a hydrophilic layer is
For example, it is preferable that a hydrophilic coating liquid composition containing a hydrophilic polymer compound represented by the following general formula (IV) is prepared and obtained by coating, and further when forming this hydrophilic layer: By adding the cross-linking component, the cross-linked structure is formed at a higher density, which contributes to the improvement of the film strength.

[0011]

[Chemical 4]

In the formula (IV), R ⁸ , R ⁹ , R ¹⁰ and R
¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ¹¹ represents an alkoxy group having 1 to 40 carbon atoms or an acyloxy group, k is an integer of 0 to 2, and m is 0.
Is an integer of 3 and k + m is 3 or less, and X represents a monovalent metal or hydrogen atom. L represents a single bond or an organic linking group, Y ² is —NHCOR ¹² , —
^{_{CONH 2, -CON (R 12)}} 2, -COR 12, -OH,
-CO ₂ M ^2, or an -SO ₃ M ^2. Wherein, R ^{1 2} represents an alkyl group having 1 to 8 carbon atoms, M ² represents a hydrogen atom, an alkali metal, alkaline earth metal or an onium, n
Represents an integer of 1 to 8.

As the water-dispersible particles which are compounds capable of forming a surface-hydrophobicized region by heating or irradiation with radiation, a hydrophobic polymer having a structural unit represented by the following general formula (I) is immiscible with water. Water-soluble resin having a structural unit represented by the following general formula (II) or (III) and / or oxide particles of at least one element selected from elements of Groups 2 to 15 of the periodic table Dispersed in an aqueous phase containing
It is preferably obtained by forming the oil droplets and then removing the solvent from the oil droplets.

[0014]

[Chemical 5]

[0015] ^{(wherein, R 1, R 2, R} 3 and R ⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ⁴ is alkoxy or acyloxy group having 1 to 40 carbon atoms , K is an integer of 0 to 2, m is an integer of 0 to 3, and k + m is 3 or less,
X represents a monovalent metal or a hydrogen atom, and Z represents a group selected from the following. )

[0016]

[Chemical 6]

(Here, R ⁵ is a hydrogen atom or a carbon number 1
Represents a hydrocarbon group of 8 to 8, R ⁶ represents an alkylene group having 5 or less carbon atoms or a divalent organic residue in which a plurality of chain carbon atom groups are bonded to each other by a carbon atom or a nitrogen atom, and n is 0 to 4 Represents the integer. )

[0018]

[Chemical 7]

(Where R ^{1 to} R ⁴ , X, Z, k and m
Is the same as in the general formula (I), Y ¹ is —NHCOR ⁷ , —
^{_{CONH 2, -CON (R 7)}} 2, -COR 7, -OH, -
CO ₂ M ^1, or an -SO ₃ M ^1. Wherein, R ⁷ represents an alkyl group having 1 to 8 carbon atoms, M ¹ is a hydrogen atom, an alkali metal, alkaline earth metal or an onium, n represents an integer of 1-8. )

Although the function of the present invention is not clear, Si, Ti, Z having a hydrophilic graft chain on the support,
The hydrophilic layer having a crosslinked structure formed by hydrolysis and polycondensation of an alkoxide compound containing an element selected from r and Al has a hydrophilic functional group introduced in a graft chain state on the surface. In addition, the organic-inorganic composite film having a high-density crosslinked structure is formed by the hydrolysis and polycondensation of the alkoxide compound, resulting in a high-strength film having high hydrophilicity. Specifically, when a hydrophilic coating liquid composition containing a hydrophilic polymer compound represented by the following general formula (IV) is prepared and applied to form a hydrophilic layer, the hydrophilic polymer compound is Since the silane coupling group has a crosslinked structure formed of Si (OR) ₄ due to the interaction between the silane coupling groups, high printing durability due to the strong crosslinked structure can be realized, and the hydrophilic group of the hydrophilic polymer compound can be realized. Since the part having is located at the other end of the linear trunk part, it has high motility, the dampening water supply / drain rate supplied at the time of printing is high, and the high hydrophilic property prevents stains on non-image areas. It is presumed that it is possible to effectively suppress and form a high-quality image. Further, by adding a cross-linking component represented by the following general formula (V) to the hydrophilic coating liquid composition, the cross-linking structure is formed at a higher density due to the interaction between the silane coupling group and the cross-linking component, High printing durability is expected due to further improvement in film strength.

[0021]

[Chemical 8]

In the formula (IV), R ⁸ , R ⁹ , R ¹⁰ and R
¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ¹¹ represents an alkoxy group having 1 to 40 carbon atoms or an acyloxy group, k is an integer of 0 to 2, and m is 0.
Is an integer of 3 and k + m is 3 or less, and X represents a monovalent metal or hydrogen atom. L represents a single bond or an organic linking group, Y ² is —NHCOR ¹² , —
^{_{CONH 2, -CON (R 12)}} 2, -COR 12, -OH,
-CO ₂ M ^2, or an -SO ₃ M ^2. Wherein, R ^{1 2} represents an alkyl group having 1 to 8 carbon atoms, M ² represents a hydrogen atom, an alkali metal, alkaline earth metal or an onium, n
Represents an integer of 1 to 8.

In the formula (V), R ¹³ and R ¹⁴ each independently represent an alkyl group or an aryl group, and X is Si, Al,
Represents Ti or Zr, and m represents an integer of 0 to 2.

Furthermore, in the present invention, by incorporating water-dispersible particles capable of forming a surface-hydrophobicized region into the hydrophilic layer, the water-dispersible particles are contained in a matrix composed of a hydrophilic polymer compound. In a heating or radiation irradiation area, they are fused with each other to form a hydrophobic area, and an image can be formed by scanning exposure with a laser beam or the like in a short time, which functions as an image forming layer. The non-image part region contains water-dispersible particles capable of forming a surface-hydrophobicized region in the hydrophilic layer, but the water-dispersible particles are water-soluble resin,
And / or since the surface is made hydrophilic by oxide particles of at least one element selected from elements of Groups 2 to 15 of the periodic table, it is less likely to cause stains and high hydrophilicity is maintained. For this reason, even a small amount of water is easily dispersed and removed, and plate making by a simple water development processing operation, or high on-press developability that is directly mounted on a printing machine to make a plate without requiring development processing It became possible to do. The water-dispersible particles of the present invention have an organic silicon group capable of forming an interaction with the atoms such as silicon constituting the alkoxide compound in the hydrophilic layer in the structure of the hydrophobic polymer, and therefore, are It is considered that it also has an advantage that high adhesiveness can be achieved and high printing durability can be realized.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The planographic printing plate precursor of the invention is described in detail below. The lithographic printing plate precursor according to the invention has, on a support, a hydrophilic layer having a specific hydrophilic polymer and a crosslinked structure composed of an organic-inorganic composite, and the hydrophilic layer is heated or radiated. The hydrophilic layer itself has an image forming function because it has a structure containing water-dispersible particles capable of forming a surface-hydrophobicized region by irradiation with rays. Hereinafter, each constitution of the planographic printing plate precursor of the invention will be described in detail.

[Hydrophilic layer] The hydrophilic layer in the invention is
It has a hydrophilic graft chain and contains Si, Ti, Zr, A
The alkoxide compound containing an element selected from 1 has a crosslinked structure formed by hydrolysis and polycondensation, and the hydrophilic layer having such a crosslinked structure has the structure of the alkoxide compound exemplified above. And a compound having a hydrophilic functional group capable of forming a hydrophilic graft chain, can be appropriately formed. Among the alkoxide compounds, Si alkoxides are preferable from the viewpoint of reactivity and easy availability, and specifically, the compounds used for the silane coupling agent can be preferably used.

The crosslinked structure formed by hydrolysis and polycondensation of the alkoxide compound as described above will be appropriately referred to as a sol-gel crosslinked structure in the present invention. The hydrophilic layer having such a free hydrophilic graft chain and the sol-gel crosslinked structure preferably contains the hydrophilic polymer described in detail below. Hereinafter, each component in the preferred embodiment of the hydrophilic layer according to the present invention and the method for forming the hydrophilic layer will be described in detail.

(Polymer compound represented by general formula (IV))
The polymer compound represented by the general formula (IV) is a hydrophilic polymer having a silane coupling group at the terminal, and is hereinafter referred to as a specific hydrophilic polymer as appropriate. In the above general formula (IV), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m represents 0, 1 or 2, and n Represents an integer of 1 to 8. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is preferable. Specifically, a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group,
s-Butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-
Examples thereof include an ethylhexyl group, a 2-methylhexyl group and a cyclopentyl group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are
From the viewpoint of effect and availability, preferably a hydrogen atom,
It is a methyl group or an ethyl group.

These hydrocarbon groups may further have a substituent. When the alkyl group has a substituent, the substituted alkyl group is composed of a bond between the substituent and an alkylene group, and as the substituent, a monovalent non-metal atomic group except hydrogen is used. Preferred examples are 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-
Diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, Ν-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyl Oxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group,
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-alkylureate group, N', N '-Dialkyl-N-arylureido group, N'-aryl-α-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, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino 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-aryl. Rucarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-
SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N
-Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N
- arylsulfamoyl group, N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group) , dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl))
And a conjugate base group thereof (hereinafter referred to as an alkylphosphonate group), a monoarylphosphono group (—PO ₃ H (ar
yl)) and a conjugated base group (hereinafter referred to as aryl phosphonophenyl group), phosphonooxy group (-OPO ₃ H ₂₎
And its conjugate base group (hereinafter referred to as a phosphonatoxy group), a dialkylphosphonooxy group (-OPO ₃ (a
lkyl) ₂ ), diarylphosphonooxy group (-O
PO ₃ (aryl) _2), alkylaryl phosphonooxy group (-OPO (alkyl) (aryl) ), monoalkyl phosphonooxy group (-OPO ₃ H (alky
l)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group ), A morpholino group, a cyano group, a nitro group, an aryl group, an alkenyl group, and an alkynyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl 2 group, xylyl group and mesityl group. 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, phenoxycarbonyl group Examples thereof include a phenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group and phosphonatophenyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like, and examples of alkynyl group include ethynyl group, 1- A propynyl group,
Examples thereof include 1-butynyl group and trimethylsilylethynyl group. Examples of G ¹ in the acyl group (G ¹ CO-),
Examples thereof include hydrogen, and the above-mentioned alkyl group and aryl group.

Of these substituents, more preferred are halogen atoms (-F, -Br, -Cl, -I),
Alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcapamoyloxy group, acylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-
Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonato group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl-N
-Arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group, Examples thereof include a phosphonatoxy group, an aryl group, and an alkenyl group.

On the other hand, examples of the alkylene group in the substituted alkyl group include a divalent organic residue obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Examples thereof include linear alkylene groups having 1 to 12 carbon atoms, branched alkylene groups having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferred specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, and allyl. Oxymethyl group, phenoxymethyl group, methylthiomethyl and tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N- Phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxyethyl group, 2-oxypropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxy group Carbonyl butyl group,

Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N-
(Methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbavamoylmethyl group,
Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N
-Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonathexyl group, diethylphosphonobutyl group, Diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methyl group Benzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2
-Methylpropenylmethyl group, 2-propynyl group, 2-
Examples include butynyl group and 3-butynyl group.

L represents a single bond or an organic linking group. Here, when L represents an organic linking group, L represents a polyvalent linking group consisting of a non-metal atom, and specifically, 1 to 60 carbon atoms, 0 to 10 nitrogens. It is composed of atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Examples of more specific linking groups include the following structural units or those formed by combining these.

[0037]

[Chemical 9]

Y ² is --NHCOR ¹² , --CON
^{_{H 2, -CON (R 12)}} 2, -COR 12, -OH, -CO
₂ M ² or —SO ₃ M ² is represented. Here, R ¹² represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Moreover, when it has a plurality of R ¹² such as —CON (R ¹² ) ₂ , R ¹² may combine with each other to form a ring, and the formed ring is an oxygen atom, a sulfur atom or a nitrogen atom. It may be a heterocycle containing heteroatoms such as atoms. R ¹² may further have a substituent, and examples of the substituent which can be introduced here are the substituents which can be introduced when R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are alkyl groups. The same can be mentioned.

Specific examples of R ¹² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, t- Butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group,
A cyclopentyl group and the like are preferred. Examples of M ² include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; and an onium such as ammonium, iodonium and sulfonium. Specific examples of Y ² include —NHCOCH ₃ , —CONH ₂ , —COOH,
-SO ₃ ^- NMe ₄ ^+, a morpholino group, etc. are preferable.

Specific examples (Exemplified Compound 1 to Exemplified Compound 12) of the specific hydrophilic polymer which can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 10]

The specific hydrophilic polymer according to the present invention comprises a radically polymerizable monomer represented by the following general formula (iv) and a silane cup having a chain transfer ability in the radical polymerization represented by the following general formula (v). It can be synthesized by radical polymerization using a ring agent. Since the silane coupling agent (v) has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the terminal of the polymer main chain in radical polymerization.

[0043]

[Chemical 11]

In the above formulas (iv) and (v), R ⁸
R ¹¹ , L, Y ² , n and m have the same meaning as in the above formula (IV). In addition, these compounds are commercially available and can be easily synthesized.

As the radical polymerization method for synthesizing the hydrophilic polymer represented by the general formula (IV), any conventionally known method can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experiments 3, Polymer Synthesis and Reactions 1 (edited by The Polymer Society of Japan, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I). (Edited by The Chemical Society of Japan, Maruzen), Material Engineering Course, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., and these can be applied.

(Crosslinking Component Represented by General Formula (V))
The crosslinking component represented by the general formula (V) used in
It has a polymerizable functional group in its structure and functions as a crosslinking agent.
It is a compound that fulfills its function and is condensed with the specific hydrophilic polymer.
Polymerizes to form a strong film with a crosslinked structure
It In the general formula (V), R¹³Is a hydrogen atom or an alkyl group
Or represents an aryl group, R ¹⁴Is an alkyl group or aryl
Represents a group, X represents Si, Al, Ti or Zr, and m represents
It represents an integer of 0 to 2. R¹³And R¹⁴Represents an alkyl group
The carbon number in this case is preferably 1 to 4. Alkyl group
Or, the aryl group may have a substituent and can be introduced.
Examples of such substituents include halogen atom, amino group, mercap
Group and the like. This compound is a low molecular compound.
It is a substance and preferably has a molecular weight of 1,000 or less.

Specific examples of the crosslinking component represented by the general formula (V) are shown below, but the invention is not limited thereto. When X is Si, that is, when the hydrolyzable compound contains silicon, examples thereof include trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and methyltrimethoxy. Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane,
Diethyldiethoxysilane, γ-chloroprepyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
-Aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane,
Examples thereof include diphenyldiethoxysilane.
Among these, particularly preferable are tetramethoxysilane, tetraethoxysilane, methyltoluymethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, and phenyltriethoxy. Examples thereof include silane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like.

When X is Al, that is, when the hydrolyzable compound contains aluminum, for example, trimethoxyaluminate, triethoxyaluminate, tripropoxyaluminate, tetraethoxyaluminate, etc. Can be mentioned. When X is Ti, that is, as titanium, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl trititanate. Examples thereof include methoxy titanate, methyl triethoxy titanate, ethyl triethoxy titanate, diethyl diethoxy titanate, phenyl trimethoxy titanate and phenyl triethoxy titanate. When X is Zr, that is, as a material containing zirconium, for example, a zirconate corresponding to the compounds exemplified as the material containing titanium can be mentioned.

(Formation of Hydrophilic Layer) In the present invention, the hydrophilic layer is prepared by preparing a hydrophilic coating solution composition containing the above-mentioned specific hydrophilic polymer, coating the composition on a suitable support, and drying. It can be formed. In preparing the hydrophilic coating liquid composition, the content of the specific hydrophilic polymer is preferably 10% by mass or more and less than 50% by mass in terms of solid content. When the content is 50% by mass or more, the film strength tends to decrease, and when the content is less than 10% by mass, the film properties are deteriorated and the possibility of cracks in the film increases, and both are preferable. Absent.

When the crosslinking component is added in the preparation of the hydrophilic coating liquid composition which is a preferred embodiment, the addition amount of the crosslinking component is 5 mol% or more with respect to the silane coupling group in the specific hydrophilic polymer. Further, the amount is preferably 10 mol% or more. The upper limit of the amount of the cross-linking component added is not particularly limited as long as it is sufficiently cross-linkable with the hydrophilic polymer, but when added in a large excess, the cross-linking component not involved in the cross-linking causes a problem such as stickiness of the prepared hydrophilic surface. there is a possibility.

A specific hydrophilic polymer having a silane coupling group at its terminal, preferably a crosslinking component, is dissolved in a solvent and stirred well to hydrolyze these components for polycondensation. The organic-inorganic composite sol liquid according to the present invention serves as the hydrophilic coating liquid according to the present invention, whereby a surface hydrophilic layer having high hydrophilicity and high film strength is formed. In the preparation of the organic-inorganic composite sol liquid, in order to promote the hydrolysis and polycondensation reactions, it is preferable to use an acidic catalyst or a basic catalyst in combination, and a catalyst is essential in order to obtain a practically preferable reaction efficiency. Is.

As the catalyst, an acid or a basic compound is used as it is, or a catalyst dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst) is used. The concentration when dissolved in a solvent is not particularly limited, and may be appropriately selected depending on the properties of the acid or basic compound used, the desired content of the catalyst, etc. The condensation rate tends to increase. However, when a basic catalyst having a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when the basic catalyst is used, its concentration is preferably 1N or less in terms of concentration in an aqueous solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the coating film after drying is preferable. Specifically, the acidic catalyst is represented by hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid and acetic acid, and RCOOH thereof. Substituted carboxylic acids obtained by substituting R of the structural formula with other elements or substituents, sulfonic acids such as benzene sulfonic acid, and the like can be cited. As the basic catalyst, ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline can be used. And so on.

The hydrophilic coating solution can be prepared by dissolving a hydrophilic polymer having a silane coupling group at the terminal, preferably a crosslinking component, in a solvent such as ethanol, and then adding the above catalyst if desired and stirring. . The reaction temperature is room temperature to 80 ° C., and the reaction time, that is, the time for which stirring is continued is preferably in the range of 1 to 72 hours. By this stirring, hydrolysis and polycondensation of both components are advanced, and A composite sol liquid can be obtained.

The solvent used in preparing the hydrophilic coating liquid composition containing the hydrophilic polymer and preferably the crosslinking component is not particularly limited as long as it can dissolve and disperse these uniformly. However, for example, an aqueous solvent such as methanol, ethanol or water is preferable.

As described above, the sol-gel method is used for the preparation of the organic-inorganic composite sol liquid (hydrophilic coating liquid composition) for forming the hydrophilic surface according to the present invention. For the sol-gel method, see Sakuhana "Sol-gel method science"
It is described in detail in publications such as Agne Jofusha (published) (1988), Shira Hirashima "Technology for functional thin film formation by the latest sol-gel method" General Technology Center (published) (1992). The methods described therein can be applied to the preparation of the hydrophilic coating liquid composition according to the present invention.

Various additives can be used in the hydrophilic coating liquid composition according to the present invention depending on the purpose, as long as the effects of the present invention are not impaired. For example, a surfactant can be added to improve the uniformity of the coating liquid.

A hydrophilic layer can be formed by coating the hydrophilic coating liquid composition prepared as described above on the surface of a support and drying. The film thickness of the hydrophilic layer can be selected depending on the purpose, but generally, the coating amount after drying is 0.5 to 5.
The range is 0 g / m ² , preferably 1.0 to 3.0 g
The range is / m ² . If the coating amount is less than 0.5 g / m ² , the hydrophilic effect is less likely to be exhibited and 5.0 g / m ²
If it exceeds, there is a tendency that the sensitivity and the film strength are deteriorated, which is not preferable.

[Water-Dispersible Particles] Water-dispersible particles capable of forming a surface-hydrophobicized region by heating or irradiation of radiation used as an image recording component in the present invention are adjacent particles by heating or irradiation of radiation. Are hydrophobic polymer particles that can be fused with each other to form a surface-hydrophobicized region, and have high water dispersibility because the surface is hydrophilized. (Hydrophobic Polymer) The hydrophobic polymer used as an image recording component in the present invention is a hydrophobic polymer that is soluble in a solvent immiscible with water, and has a structural unit containing an organosilicon group represented by the general formula (I). It is a polymer having.

The organic silicon group-containing polymer can be obtained by polymerizing an unsaturated double bond-forming monomer which can be converted into the structural unit of the above-mentioned general formula (I) alone or with the monomer. It is obtained by copolymerizing with a monomer such as styrene, an acrylic type, a vinyl type, an olefin type. Further, the organic silicon group-containing polymer in the present invention may be one in which the structural unit containing an organic silicon group is randomly introduced into the polymer molecule, or may be one introduced at the molecular end of the polymer.

Specific examples of the unsaturated double bond-forming monomer which can be converted into the structural unit containing an organosilicon group represented by the general formula (I) include styrylethyltrimethoxysilane and 4-
Trimethoxysilylstyrene, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, vinyltrimethoxysilane, vinyltris- (β
-Methoxyethoxy) silane, allyltrimethoxysilane, vinyltriacetoxysilane, allyltriacetoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane,
Vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltrihexyloxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyoctyloxysilane , Vinylmethoxydioctyloxysilane, vinyltrioctyloxysilane, vinylmethoxydilauryloxysilane, vinyldimethoxylauryloxysilane, vinylmethoxydioleyloxysilane, vinyldimethoxyoleyloxysilane,
3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide-
Propyltriethoxysilane,

3- (meth) acrylamido-propyltri (β-methoxyethoxy) silane, 2- (meth) acrylamido-2-methylpropyltrimethoxysilane,
2- (meth) acrylamido-2-methylethyltrimethoxysilane, N- (2- (meth) acrylamido-ethyl) -aminopropyltrimethoxysilane, 3- (meth) acrylamide-propyltriacetoxysilane,
2- (meth) acrylamide-ethyltrimethoxysilane, 1- (meth) acrylamide-methyltrimethoxysilane, 3- (meth) acrylamide-propylmethyldimethoxysilane, 3- (meth) acrylamide-propyldimethylmethoxysilane, 3- (N-methyl- (meth) acrylamide) -propyltrimethoxysilane,
3-((meth) acrylamide-methoxy) -3-hydroxypropyltrimethoxysilane, 3-((meth)
Acrylamide-methoxy) -propyltrimethoxysilane, dimethyl-3- (meth) acrylamido-propyl-3- (trimethoxysilyl) -propylammonium chloride, dimethyl-2- (meth) acrylamido-2-methylpropyl-3- ( Trimethoxysilyl)-
Propyl ammonium chloride and the like can be mentioned.

It can be used as a copolymerization component which constitutes the hydrophobic polymer according to the present invention together with the unsaturated double bond-forming monomer which can be converted into the structural unit containing the organosilicon group of the above general formula (I). As the monomer, the following (A) to (K)
The monomer (monomer) shown in can be mentioned.

(A) Acrylic acid esters. Examples of this monomer include methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, 4-acrylic acid acrylate Examples thereof include acrylic acid esters which may have a substituent, such as hydroxybutyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, o-, m- and p-hydroxyphenyl acrylate.

(B) Methacrylic acid esters. Examples of this monomer group include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid-
Having a substituent such as 2-chloroethyl, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, o-, m- and p-hydroxyphenyl methacrylate. Methacrylic acid esters may be mentioned.

(C) Acrylamide and methacrylamide. Examples of this monomer group include acrylamide, methacrylamide, N-methylol acrylamide, N-
Methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N-hydroxyethyl acrylamide, N-
Hydroxyethyl acrylamide, N-phenyl acrylamide, N-phenyl methacrylamide, N-benzyl acrylamide, N-benzyl methacrylamide, N
-Nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide, N- (4-hydroxyphenyl) acrylamide,
Examples thereof include acrylamide or methacrylamide such as N- (4-hydroxyphenyl) methacrylamide.

(D) Vinyl ethers. Examples of this monomer group include ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(E) Vinyl esters. Examples of this monomer group include vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like. (F) Styrenes. Examples of this monomer group include styrene, methylstyrene, chloromethylstyrene, o-, and m.
And p-hydroxystyrene and the like.

(G) Vinyl ketones. Examples of this monomer group include methyl vinyl ketone, ethyl vinyl ketone,
Examples include propyl vinyl ketone and phenyl vinyl ketone. (H) Olefins. Examples of this monomer group include ethylene, propylene, isobutylene, butadiene, isoprene and the like. (I) N-containing monomer. An example of this monomer group is N
-Vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like can be mentioned.

(J) Unsaturated sulfonamide. Examples of this monomer group include N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3 -Aminosulfonyl) naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- ( p-aminosulfonylphenyl)
Methacrylamides such as methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate, m-aminosulfonylphenyl. Acrylate, p
-Aminosulfonylphenyl acrylate, 1- (3-
Unsaturated sulfonamides such as acrylic acid esters such as aminosulfonylphenylnaphthyl) acrylate,
Examples thereof include o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate and 1- (3-aminosulfonylphenylnaphthyl) methacrylate.

(K) Unsaturated acid anhydride. Examples of this monomer group include itaconic anhydride, maleic anhydride, and 2,3-
Examples thereof include dimethyl maleic anhydride and 2-chloromaleic anhydride.

The content of the organic silicon group-containing structural unit of the general formula (I) in the hydrophobic polymer used in the present invention is preferably 0.01 to 100 mol%, 0.0
5 to 90 mol% is more preferable, and 0.1 to 80 mol% is particularly preferable. When the content of the organic silicon group-containing structural unit is less than 0.01 mol%, the effect of the present invention is poor.

The organic polymer compound obtained from these monomers preferably has a mass average molecular weight of 500 to 500,000 and a number average molecular weight of 200 to 60,000.
Specific examples of preferred organic silicon group-containing polymers as the hydrophobic polymer used in the present invention are shown below, but the invention is not limited thereto.

[0074]

[Chemical 12]

[0075]

[Chemical 13]

(Water-Immiscible Solvent) In the present invention,
Specific examples of water-immiscible solvents that can be used to prepare the hydrophobic polymer include chloromethane, dichloromethane, ethyl acetate, methyl ethyl ketone (MEK), trichloromethane, carbon tetrachloride, ethylene chloride, trichloroethane, toluene, xylene. , Cyclohexanone, 2-
Examples thereof include, but are not limited to, nitropropane, and any suitable solvent can be applied to the present invention as long as it can dissolve a hydrophobic polymer and is immiscible with water. Among the exemplified solvents, particularly useful ones include dichloromethane and MEK. These are in the preparation of hydrophobic polymers,
It can be suitably used in the step of removing the solvent from the oil layer particles by evaporation and rapidly curing the polymer particles.

(Water-Soluble Resin) In the present invention, the hydrophobic polymer must be water-dispersible, that is, the surface must be hydrophilic. When oil droplets are dispersed in the aqueous phase as described above, it is preferable that the aqueous phase contains a water-soluble resin. Further, in the present invention, S is used as the hydrophilic layer.
i, Ti, Zr, and Alkoxide compounds containing an element selected from Al are used to have a cross-linking structure formed by hydrolysis and polycondensation of an alkoxide compound. For this reason, an interaction with the hydrophilic layer is formed. It is more preferable to use the water-soluble resin obtained. From the viewpoint of the surface hydrophilicity of the hydrophobic polymer and the formation of the interaction with the hydrophilic layer, the water-soluble resin used in the present invention is a water-soluble resin having a structural unit represented by the general formula (II) or (III). Is preferred. These are water-soluble resins having an organic silicon group at the terminal or the side chain. In addition, in the water-soluble resin having the structural unit represented by the general formula (III), the content of the structural unit having an organic silicon group in the side chain among the two types of structural units is about 0.01 to 20 mol%. Is preferably from the viewpoint of water solubility, and more preferably in the range of 1 to 15 mol%. Specific examples of the water-soluble resin having a structural unit represented by the general formula (II) or (III) that can be used in the present invention are shown below, but the invention is not limited thereto.

[0078]

[Chemical 14]

[0079]

[Chemical 15]

The content of the water-soluble resin used in the preparation of the water-dispersible particles is appropriately 1 to 25% by mass, preferably 2 to 15% by mass, based on the water phase component.

(Catalyst) In the method for producing water-dispersible particles according to the present invention, the general formula (I), which is a structural unit contained in the hydrophobic polymer, or the general formula (II), which is contained in the aqueous phase as the hydrophilic resin, is used. Alternatively, an acidic catalyst or a basic catalyst can be used to accelerate the hydrolysis and polycondensation reaction of the organic silicon group present in the structural unit represented by the general formula (III). The type of acidic catalyst or basic catalyst is not particularly limited, but when it is necessary to use a high-concentration catalyst, a catalyst composed of an element that hardly remains after the preparation of fine particles is preferable.

Specifically, as the acidic catalyst, hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acid such as formic acid and acetic acid, and RCOOH thereof can be used. Examples thereof include substituted carboxylic acids in which R in the structural formula shown is substituted, sulfonic acids such as benzenesulfonic acid, and the like. Examples of the base catalyst include ammonia and amines such as ethylamine and aniline. The catalyst is added to the aqueous phase as it is or in the state of being dissolved in a solvent such as water or alcohol.
The concentration of the catalyst to be added is not particularly limited, but if the concentration is high, the hydrolysis or polycondensation rate tends to increase. However, when a high-concentration basic catalyst is used, a precipitate may be generated in the dispersion solution, which may adversely affect the dispersion stability of oil droplets. Therefore, the basic catalyst concentration is preferably 1N or less. .

(Surfactant) In the process of producing the water-dispersible particles in the present invention, it is preferable to add a surfactant to the aqueous phase in order to improve the dispersion stability of oil droplets. Examples of the surfactant used here include nonionic and anionic surfactants, and JP-A-2-1953.
Japanese Patent Application Laid-Open No. 59-12104.
Examples thereof include amphoteric surfactants described in JP-A No. 4 and JP-A-4-13149.

Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene nonylphenyl. Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, and further polyoxyethylene / polyoxypropylene block copolymers have terminal hydroxyl groups with an ether bond of an aliphatic group having 5 to 24 carbon atoms. Complex polyoxyalkylene alkyl ethers, also complex polyoxyalkylene alkyl aryl ethers in which an alkyl-substituted aryl group is ether-bonded, sorbi Emissions monolaurate, sorbitan monostearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan trioleate,
Examples include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan trioleate, and other polyoxyethylene sorbitan fatty acid esters. To be

Specific examples of the anionic activator include alkyl sulfonic acids, aryl sulfonic acids, aliphatic carboxylic acids, alkyl naphthalene sulfonic acids, alkyl naphthalene sulfonic acids or condensation type of naphthalene sulfonic acid and formaldehyde, carbon number 9 To aliphatic sulfonic acids, alkylbenzene sulfonic acids, lauryl polyoxyethylene sulfuric acid, cetyl polyoxyethylene sulfonic acid, oleyl polyoxyethylene phosphonic acid, and other polyoxyethylene-containing sulfuric acid and polyoxyethylene-containing phosphoric acid.

Specific examples of the cationic surfactant include lauryl amine acetate, lauryl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, alkylbenzyl dimethyl ammonium chloride and the like. Specific examples of the fluorine-based surfactant include perfluoroalkylcarboxylic acid salts, perfluoroalkylphosphoric acid esters, perfluoroalkyltrimethylammonium salts, perfluoroalkylbetaines, perfluoroalkylaminexides, perfluoroalkylEO adducts, and the like. Is mentioned.

Specific examples of the amphoteric surfactant include alkylcarboxybetaines, alkylaminocarboxylic acids, alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl. Examples thereof include imidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.).

Among these, anionic, nonionic and amphoteric types are preferable, and specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene / polyoxypropylene block copolymers, alkyl sulfonic acids. , Aliphatic carboxylic acids, alkylbenzene sulfonic acids, polyoxyethylene-containing sulfuric acid, alkylnaphthalenesulfonic acid or a condensation type of naphthalenesulfonic acid and formaldehyde, alkylcarboxybetaines, alkylaminocarboxylic acids and the like.

As described above, good water-dispersible particles can be obtained by using a polymer having a specific organosilicon group as the hydrophobic polymer and the water-soluble polymer, and the thermal reactivity of the organosilicon group can be improved. In the case of combination with a resin that forms the resin, for example, a binder resin of a sol-gel conversion system, it is possible to form a chemical bond directly with the binder resin matrix, so that a film having excellent mechanical strength and good wear resistance can be formed. Even in the irradiated area which has been converted to hydrophobic by being irradiated with the laser beam of the photosensitive layer, a uniform layer can be formed while being chemically bonded to the binder resin, so that an image area having excellent abrasion resistance is formed. .

(Oxide or hydroxide fine particles) In the production of the water-dispersible particles in the present invention, in order to improve the surface physical properties of the hydrophobic polymer, instead of the water-soluble resin, or in the above water-soluble resin, In addition, the water phase is added to the periodic table group 2 to 15
Oxide or hydroxide fine particles of at least one element selected from the group elements can be added. These fine particles are adsorbed on the surface of the hydrophobic particles and contribute to the surface hydrophilicity and the improvement of water dispersibility. Specific examples of suitable elements include magnesium, titanium, zirconium, vanadium, chromium, zinc, aluminum, silicon, tin and iron. Among them, preferable elements include silicon, titanium, aluminum and tin.
The oxide fine particles or hydroxide fine particles of the above elements can be used as an oxide colloid or hydroxide colloid, and the particle diameter of the fine particles is generally about 0.001 to 1 μm.
Preferably 5-40 nm, most preferably 10-30 n
m. For the dispersion liquid of these colloids, commercially available products such as Nissan Chemical Industries, Ltd. can be purchased. By the addition of these compounds, the surface hydrophilicity of the resulting hydrophobic polymer is improved, water-dispersible particles having better dispersion stability in water are obtained, and as a result, as a recording layer component of the lithographic printing plate precursor. When used, the stain resistance of the non-image area is improved.

The production of water-dispersible particles using the above raw materials can be carried out by a well-known operation. That is,
Oil phase solution in which a hydrophobic polymer is dissolved in a water-immiscible solvent, and water-soluble resin and / or oxide or hydroxide of at least one element selected from elements of Groups 2 to 15 of the periodic table After preparing an aqueous phase solution containing fine particles and, if necessary, an optional component such as a surfactant, an acidic or basic catalyst, the both are mixed and then, using an emulsifying disperser such as a homogenizer, for example, 12 The oil droplets are emulsified and dispersed in the aqueous phase by vigorously stirring and mixing for 10 to 15 minutes under conditions of about 1,000 rpm. Then, the obtained emulsified dispersion is heated and stirred to evaporate the solvent, whereby an intended aqueous dispersion of water-dispersible particles is obtained. The water dispersion of the water-dispersible particles may be added in the state of being dispersed in the water phase when it is added to the hydrophilic layer, or may be added in the state of particles after removing the water phase.

[Image-Recording Layer] The lithographic printing plate precursor according to the invention uses the water-dispersible particles contained in the hydrophilic layer as an image-recording component, and the water-dispersible particles are fused to each other in the exposed area. To form a hydrophobic region. In this hydrophilic layer, the sensitivity is improved, the physical strength of the recording layer is improved, the dispersibility of the constituents of the recording layer is improved, the coatability is improved, and the printing is performed within a range that does not impair the effects of the present invention. For various purposes such as improving suitability and convenience of plate making work,
Known additives, for example, photothermal conversion agents that absorb light and generate heat, inorganic fine particles, hydrophilic polymer compounds, surfactants, colorants, and other compounds can be added. These will be described below.

(Photothermal Conversion Agent) As the photothermal conversion agent, metals, metal oxides, nitrides or sulfides, pigments and dyes are preferable. As the metal and the metal compound, Al,
Si, Ti, V, Cr, Mn, Fe, Co, Ni, C
u, Zn, Y, Zr, Mo, Ag, Au, Pt, Pd,
A metal selected from the metals selected from the group consisting of Rh, In, Sn, and W or a metal compound that can be made into particles and dispersed in the hydrophilic layer can be used. Of these, fine metal particles of iron, silver, platinum, gold, and palladium are preferable. In addition, TiOx (x = 1.0 to 2.0),
SiOx (x = 0.6 to 2.0), AlOx (x = 1.
0 to 2.0), and metal azide compounds such as copper, silver and tin azides are also preferable. Each of the above metal oxides, nitrides and sulfides can be obtained by a known manufacturing method. In addition, many are commercially available under the names such as titanium black, iron black, molybdenum red, emerald green, cadmium red, cobalt blue, navy blue, and ultramarine.

In the present invention, as the pigment contained in the hydrophilic layer, in addition to the above metal compounds and metals, non-metal simple particles such as carbon black, graphite (bone graphite) and bone charcoal (bone black), and various organic substances. Inorganic pigments can also be used. From the viewpoint of the effect, it is preferable to use those pigments and various fine particles that have a hydrophilic surface that can be easily dispersed in water.

Further, a photothermal conversion dye (dye) can also be used. As such a dye, those having a light absorption region in the spectral wavelength region of irradiation light used for image formation and easily soluble in water are preferable. Preferred solid fine particle, dyeing and molecular disperse dyes are those known as infrared absorbers, and specifically, polymethine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, diimmonium dyes, phthalocyanine compounds. , A triarylmethane dye, and a metal dithiolene. Of these, more preferred are polymethine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, diimmonium dyes and phthalocyanine compounds, and among them, polymethine dyes, cyanine dyes and phthalocyanine compounds are most preferred from the viewpoint of suitability for synthesis. From the viewpoint of on-press developability, it is preferable that the above-mentioned dye is a water-soluble dye having a water-soluble group such as a sulfonic acid group, a carboxyl group and a phosphonic acid group in the molecule. Specific examples of the dye (infrared absorber) used as the photothermal conversion agent in the present invention are shown below, but the invention is not limited thereto.

[0096]

[Chemical 16]

[0097]

[Chemical 17]

The light-heat converting agent may be added to the hydrophilic layer in the coating solution when the hydrophilic layer is formed, but it may be added in the water-dispersible particles. You can also do it. That is, it can be contained in the water-dispersible particles by adding it to the oil phase at the time of producing the water-dispersible particles. In that case, the above-mentioned photothermal conversion agent may be used, but it is preferable to use a lipophilic photothermal conversion agent having a good affinity with the hydrophobic polymer. Examples of such lipophilic light-heat converting agents are shown below, but the invention is not limited thereto.

[0099]

[Chemical 18]

[0100]

[Chemical 19]

The content of the photothermal conversion agent may be an amount sufficient to cause heat fusion in the vicinity of the water-dispersible particles by the heat generated by the light absorption of the photothermal conversion agent to make it hydrophobic, and the solid constitution. A wide selection can be made between 2 and 50% by weight of the components. If it is 2% by mass or less, the heat generation amount is insufficient and the sensitivity is lowered, and if it is 50% by mass or more, the film strength is lowered.

(Surfactant) As the surfactant used in the hydrophilic layer, the same surfactants as those which can be used in the production of water-dispersible particles can be used. When used to disperse the recording layer components, in addition to the above-mentioned surfactant,
Further, specifically, a surfactant having a perfluoroalkyl group is preferable, and an anionic surfactant having any of a carboxylic acid, a sulfonic acid, a sulfuric acid ester and a phosphoric acid ester, or an aliphatic amine, Cationic surfactants such as primary ammonium salts, or betaine amphoteric surfactants, or nonionic surfactants such as aliphatic esters of polyoxy compounds, polyalkylene oxide condensation types, and polyethyleneimine condensation types. Is mentioned. The ratio of the above surfactant in the total solid content of the recording layer is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

(Coloring Agent) In the image recording layer of the present invention, a dye having a large absorption in the visible light region is added to the image recording layer in order to make it easy to distinguish the image area from the non-image area after the image formation. Can be used as Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY,
Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000). , Methylene blue (CI5
2015) and the like, and dyes described in JP-A No. 62-293247. Further, pigments such as phthalocyanine pigments, azo pigments, and titanium oxide can also be preferably used. The addition amount is 0.01 to 10 mass% with respect to the total solid content of the image recording layer.

[Heat Insulating Layer] In the lithographic printing plate precursor according to the invention, it is preferable to provide a heat insulating layer between the support and the image recording layer. The heat insulating layer will be described below. The heat insulating layer provided as a lower layer of the image recording layer is a layer having a low thermal conductivity and a function of suppressing heat diffusion to the support.
Further, this heat insulating layer may contain a photothermal conversion agent, and in this case, it is heated by light irradiation to contribute to the improvement of the recording sensitivity of the image recording layer. Such a heat insulating layer contains an organic or inorganic resin.

The organic or inorganic resin that can be used for the heat insulating layer can be widely selected from hydrophilic and hydrophobic resins. For example, as the hydrophobic resin, polyethylene, polypropylene, polyester, polyamide, acrylic resin, vinyl chloride resin, pinylidene chloride resin, polyvinyl butyral resin, nitrocellulose, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polystyrene, vinyl chloride resin- Vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-resin vinyl-maleic acid copolymer, vinyl chloride-acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, etc. Is mentioned.

In this heat insulating layer, the hydrophobic resin having a form of an aqueous emulsion can also be used. The aqueous emulsion is a hydrophobic polymer suspension aqueous solution in which particles comprising fine resin particles and, if necessary, a protective agent for dispersing and stabilizing the particles are dispersed in water. Specific examples of the aqueous emulsion used include vinyl-based polymer latexes (polyacrylate-based, vinyl acetate-based, ethylene-vinyl acetate-based, etc.), conjugated siene-based polymer latexes (methyl methacrylate-butadiene-based, styrene-butadiene-based, agglomerates). Ronitrile-p-butadiene type, chloroprene type, etc.) and polyurethane resin.

Specific examples of the hydrophilic resin include polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, starch and its derivatives, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, ammonium alginate, and polyacrylic acid. , Polyacrylate, polyethylene oxide, water-soluble urethane resin, water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol diacrylate polymer, N-vinylcarboxylic acid amide polymer, casein, gelatin, polyvinylpyrrolidone,
Examples thereof include water-soluble resins such as vinyl acetate-crotonic acid copolymer and styrene-maleic acid copolymer.

When the above hydrophilic resin is used for the heat insulating layer, it is preferable to use it after crosslinking and curing, from the viewpoint of improving the film property, and as the crosslinking agent, a known crosslinking agent compatible with the hydrophilic resin used It can be used as appropriate.

The inorganic resin used for the heat insulating layer is preferably an inorganic matrix formed by sol-gel conversion. The system capable of sol-gel conversion which can be preferably applied to the present invention, a bonding group bonded to a polyvalent element forms a network structure through an oxygen atom, and at the same time, the polyvalent metal also has an unbonded hydroxyl group or an alkoxy group. However, it is a polymer having a resin-like structure in which these are mixed, and is in a sol state at the stage where there are many alkoxy groups and hydroxyl groups, and the network resin structure becomes firm as the dehydration condensation proceeds. Become. In addition to the property of changing the hydrophilicity of the resin structure, it also has a function of modifying the surface of the solid fine particles by binding some of the hydroxyl groups to the solid fine particles to change the hydrophilicity. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that undergoes sol-gel conversion is aluminum, silicon, titanium, zirconium, or the like, and any of these can be used in the present invention.

From the viewpoint of adhesiveness to the image recording layer, a hydrophilic resin is particularly preferable as the resin constituting the heat insulating layer. When a light-heat converting agent is contained in the heat insulating layer, the same material as the light-heat converting agent used in the image recording layer can be used as the light-heat converting agent. The content of the photothermal conversion agent contained in the heat insulating layer is 2 to 95% of the solid constituent components.
Widely selectable between mass%. If it is 2 mass% or less, the calorific value is insufficient and the effect of the addition is not remarkable, and if it is 95 mass% or more, the film strength decreases.

In the heat insulating layer, in addition to the above-mentioned resin and photothermal conversion agent, the physical strength of the heat insulating layer is improved, the dispersibility of the constituents of the layers is improved, the coatability is improved, and the image recording layer is formed. For the purpose of, for example, improving the adhesiveness with, it is possible to add various objective compounds such as inorganic fine particles and a surfactant. (Inorganic fine particles) Examples of suitable inorganic fine particles that can be added to the heat insulating layer include silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate, and mixtures thereof. These are not photothermal convertible. Even so, it contributes to strengthening the film and strengthening the interfacial adhesion by roughening the surface.

The average particle size of the inorganic fine particles is 5 nm to 10 μm.
Those having a thickness of 10 nm to 1 μm are more preferable. When the particle size is within this range, the water-dispersible particles and the metal fine particles of the photothermal conversion agent are stably dispersed in the binder resin, the film strength of the image recording layer is sufficiently maintained, and the hydrophilic property is less likely to cause printing stains. An excellent non-image area can be formed. Such inorganic fine particles are easily available as a commercial product such as a colloidal silica dispersion. The content of the inorganic fine particles in the heat insulating layer is preferably 1.0 to 70 mass% of the total solid content of the heat insulating layer, and more preferably 5.0 to 50 mass%.

[Water-Soluble Protective Layer] Since the surface of the image recording layer of the lithographic printing original plate of the invention is hydrophilic, when the original plate is transported or stored in the form of a product, or when it is handled before use, It is apt to be hydrophobic due to the influence of the environment atmosphere, to be affected by temperature and humidity, or to be susceptible to mechanical scratches or dirt. In order to prevent this, the lithographic printing plate precursor according to the invention is preferably provided with a water-soluble surface protective layer containing a water-soluble polymer as a main component.
Since the water-soluble protective layer is dissolved and removed by dampening water in the initial stage of printing, no particular removing step is required and the on-press developability is not deteriorated.

The components contained in the water-soluble protective layer will be described below. The water-soluble protective layer contains a water-soluble polymer, which functions as a binder resin (layer forming component) of the water-soluble protective layer. As the water-soluble polymer, for example, a hydroxyl group,
Polymers having sufficient hydrophilic functional groups such as carboxyl groups and basic nitrogen-containing groups are mentioned.

Specifically, polyvinyl alcohol (PV
A), modified PVA such as carboxy-modified PVA, gum arabic, water-soluble soybean polysaccharide, polyacrylamide and copolymers thereof, acrylic acid copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride Such as acid copolymers, styrene / maleic anhydride copolymers, roasted dextrins, oxygen-degraded dextrins, enzyme-decomposed etherified dextrins, starch and its derivatives, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, hydroxyethylcellulose. Cellulose derivatives, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymers, styrene-maleic acid copolymers, alginic acid and its alkali metal salts, alkaline earth metal salts or ammonium salts, polyacrylic acid, poly (ethyl ether). Emissions oxide), water-soluble urethane resins, water-soluble polyester resins, polyhydroxyethyl acrylate, polyethylene glycol, polypropylene glycol, N- vinylcarboxamide polymers. Among them, polyvinyl alcohol (PV
A), modified PVA such as carboxy-modified PVA, gum arabic, polyacrylamide, polyacrylic acid, acrylic acid copolymer, polyvinylpyrrolidone, alginic acid and alkali metal salts thereof are preferably used, and these may be used alone. Well, two or more kinds may be mixed and used depending on the purpose. The content of the water-soluble polymer in the coating solution for the water-soluble protective layer is appropriately 3 to 25% by mass, and the preferable range is 1
It is 0 to 25 mass%.

The water-soluble protective layer may contain various surfactants in addition to the above water-soluble polymer. Examples of the surfactant that can be used include anionic surfactants and nonionic surfactants. As the surfactant used, the same surfactants as those used for the image recording layer can be used. The surfactant is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the total solid content of the water-soluble protective layer.

In addition to the above-mentioned components, a lower polyhydric alcohol such as glycerin, ethylene glycol or triethylene glycol can be used as a wetting agent in the protective layer coating liquid, if necessary. An appropriate amount of these wetting agents is 0.1 to 5.0% by mass in the protective layer, and a preferable range is 0.5 to 3.0% by mass. Further, a preservative and the like can be added to the coating solution for protective layer. For example, benzoic acid and its derivatives, phenol, formalin, sodium dehydroacetate, etc.
It can be added in the range of 05 to 2.0 mass%. An antifoaming agent can be added to the coating liquid. A preferable defoaming agent contains an organic silicone compound, and the addition amount thereof is 0.0001.
The range of 0.1 mass% is preferable.

A photothermal conversion agent may be added to the water-soluble protective layer. In this case, the sensitivity of heat fusion of the image recording layer due to light irradiation is further enhanced, and a preferable result is obtained. As the light-heat converting agent, those mentioned as the light-heat converting agent that can be added to the heat insulating layer can be used, and the preferable addition amount is also the same.

[Support] Next, the support on which the image recording layer is coated will be described. As the support, a dimensionally stable plate-like material is used. The support that can be used in the present invention includes paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, nickel, stainless steel, etc.), plastic Films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film laminated or vapor-deposited with the above metals, and the like.

The preferred support is polyester film, aluminum, or SUS which is resistant to corrosion on printing plates.
A steel plate is preferable, and an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable. The preferred aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a slight amount of a foreign element, and may be a plastic film in which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy are
There are silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of foreign elements in the alloy is at most 10% by mass. Aluminum which is particularly preferred in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in terms of refining technology, and thus may contain a slightly different element.
As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly known aluminum plates can be appropriately used. The thickness of the support used in the present invention is approximately 0.05 mm-
About 0.6 mm, preferably 0.1 mm to 0.4 mm,
Particularly preferably, it is 0.15 mm to 0.3 mm.

Prior to the roughening of the aluminum plate, if desired, a degreasing treatment for removing rolling oil on the surface is carried out, for example, with a surfactant, an organic solvent or an alkaline aqueous solution. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically melting the surface and a method of selectively melting the surface chemically. It is performed by the method. As the mechanical method, known methods such as a ball polishing method, a brush polishing method, a blast polishing method and a buff polishing method can be used. As a chemical method, JP-A-54-
A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Japanese Patent No. 31187 is suitable. Further, as an electrochemical graining method, there is a method of performing alternating current or direct current in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Also, an electrolytic surface roughening method using a mixed acid as disclosed in JP-A-54-63902 can be used. Among such roughening methods, especially Japanese Patent Laid-Open No.
A surface-roughening method combining mechanical surface-roughening and electrochemical surface-roughening as described in JP-A-5-137993 is preferable because the adhesion of the oil-sensitive image to the support is strong. The surface roughening by the method as described above is preferably performed in a range such that the center line surface roughness (Ra) of the surface of the aluminum plate is 0.3 to 1.0 μm. The roughened aluminum plate is optionally subjected to alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide, etc., and further neutralized, and then anodized to enhance abrasion resistance if desired. Processing is performed.

As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes which form a porous oxide film can be used. Generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. To be The concentration of these electrolytes is appropriately determined depending on the type of electrolyte. The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally the concentration of electrolyte is 1
~ 80 mass% solution, liquid temperature 5 ~ 70 ° C, current density 5 ~ 6
0 A / dm ² , voltage 1 to 100 V, electrolysis time 10 seconds to 5
A range of minutes is suitable. The amount of oxide film formed is 1.0 to 5.0 g / m ² , particularly 1.5 to 4.0 g / m ² .
It is preferably m ² . The amount of anodized film is 1.0
When it is less than g / m ² , printing durability is insufficient or scratches are likely to occur.

Among these anodizing treatments, a method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768 and US Pat. No. 3,511,661 are particularly mentioned. The method of anodic oxidation using phosphoric acid as an electrolytic bath described in 1) is preferable.

[Plate Making and Printing] The planographic printing plate precursor of the invention is image-formed by heat. Specifically, direct image-like recording with a thermal recording head, scanning exposure with an infrared laser, high-illuminance flash exposure with a xenon discharge lamp, infrared lamp exposure, or the like is used.
Exposure with a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser that emits 0 nm infrared is suitable.
The lithographic printing plate precursor of the invention has a laser output of 0.1 to 3.
Irradiation can be performed with a 00 W laser. When using a pulsed laser, the peak output is 1000
It is preferable to irradiate the laser with W, preferably 2000 W. The exposure amount in this case is preferably in the range of 0.1 to 10 J / cm ² of surface exposure intensity before being modulated by the printing image, and more preferably in the range of 0.3 to 1 J / cm ^2. preferable. When the support is transparent, it can also be exposed through the support from the back side of the support.

In the exposed area, the water-dispersible particles dispersed in the hydrophilic layer fuse with each other to form a hydrophobized area. The surface of the water-dispersible particles is hydrophilic, and in a preferred embodiment, the water-dispersible particles have an organosilicon group that forms an interaction with an element in the alkoxide compound such as silicon in the hydrophilic layer. It adheres to the layer to form an ink receptive area, i.e. an image area. Further, in the unexposed area, the water-dispersible particles are easily removed by even a small amount of water, and the hydrophilic layer having a crosslinked structure serves as a dampening water receiving area having high hydrophilicity, forming a non-image area. To do. The imagewise exposed lithographic printing plate precursor according to the invention can be mounted on a printing machine without further treatment and can be printed by a usual procedure using ink and fountain solution. Further, these lithographic printing plate precursors can be mounted on a cylinder of a printing machine and then exposed by a laser mounted on the printing machine, and can be directly printed with an ink and a fountain solution by a usual procedure. Since the lithographic printing plate precursor according to the invention has a hydrophilic layer excellent in durability and hydrophilicity, it is possible to obtain a large number of printed matters having excellent image quality without stains on non-image areas even under severe printing conditions. .

[0126]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these. [Synthesis of Specific Hydrophilic Polymer (1)] 50 g of acrylamide, 3.4 g of mercaptopropyltrimethoxysilane and 220 g of dimethylacetamide were placed in a 500 ml three-necked flask, and 2,2-azobis (2,4-azobis (2,4-) 0.5 g of dimethylvaleronitrile) was added. After maintaining the same temperature for 6 hours with stirring, the mixture was cooled to room temperature. It was put into 2 liters of ethyl acetate, and the precipitated solid was collected by filtration and washed with water to obtain a hydrophilic polymer (1). The mass after drying was 52.4 g. Polymer having a structure of Exemplified Compound 1, which is a polymer having a mass average molecular weight of 3000 by GPC (polystyrene standard) and a trimethoxysilyl group (50.0 ppm) introduced at the end by ¹³ C-NMR (DMSO-d6). It was confirmed to be (1).

[Synthesis of Water-Dispersible Particles 1 to 10] (Synthesis Example 1) As an oil phase component, 30.0 g of a hydrophobic polymer (PI-1 described in the present specification), 45.0 g of MEK, anion surfactant pioneine A41C (Takemoto Yushi Co., Ltd.)
0.5 g) was prepared, and as an aqueous phase component, 4.2 g of a water-soluble resin (WII-1 described in this specification), water 259.
8 g of a solution was prepared, and both were mixed and then vigorously stirred and mixed with a homogenizer at 12,000 rpm for 10 minutes to obtain an emulsified dispersion in which oil droplets were dispersed in the aqueous phase. next,
Put the emulsified dispersion in a stainless steel pot and keep at 40 ° C for 3
By stirring for a period of time to remove the solvent component, water-dispersible particles 1 having a particle diameter of 0.24 μm were obtained.

(Synthesis Example 2) As an oil phase component, 30.0 g of a hydrophobic polymer (PI-1 described in this specification), MEK4
A solution of 5.0 g and 0.5 g of the anionic surfactant Pionin A41C (manufactured by Takemoto Yushi Co., Ltd.) was prepared, and as an aqueous phase component, Snowtex C 60 g manufactured by Nissan Chemical Industries, Ltd.,
A solution of 259.8 g of water was prepared, both were mixed, and then vigorously stirred and mixed with a homogenizer at 12,000 rpm for 10 minutes to obtain an emulsified dispersion in which oil droplets were dispersed in the aqueous phase. Next, put the emulsified dispersion in a stainless steel pot,
By stirring at 40 ° C. for 3 hours to remove the solvent component, water-dispersible particles 2 having a particle diameter of 0.21 μm were obtained.

(Synthesis Examples 3 to 10) Synthesis Examples 1 and 2 except that the hydrophobic polymer, water-soluble resin, oxide particles and surfactant used in Synthesis Examples 1 and 2 were replaced with the materials shown in Table 1, respectively. Water-dispersible particles 3 to 10 were synthesized in the same manner as in.
The results are shown in Table 1.

[0130]

[Table 1]

The abbreviations and product names in the table are as follows. Titania sol: Ishihara Sangyo Co., Ltd. STS-01 Alumina sol: Nissan Chemical Industry Co., Ltd. Alumina sol 5
20 Emal NC: Kao Co., Ltd. anionic surfactant

Example 1 (Preparation of Support) A 0.30 mm thick aluminum plate (material 1050) was washed with trichlorethylene to degrease it, and then a nylon brush and 400 mesh pumice stone were used.
The surface was grained using a water suspension and washed thoroughly with water. This plate was immersed in a 25% by mass aqueous solution of sodium hydroxide at 45 ° C for 9 seconds for etching, washed with water, and further immersed in 2% by mass nitric acid for 20 seconds and washed with water. At this time,
The amount of etching of the grained surface was about 3 g / m ² .
Next, the current density of this plate was set to 1% by using 7 mass% sulfuric acid as an electrolyte.
In 5A / dm ^2, so that the thickness of the anodic oxide film is 2.4 g / m ^2, to provide a DC anodic oxide film, to obtain a washed with water and dried to support.

(Formation of hydrophilic layer) The following components were uniformly mixed and stirred at room temperature for 2 hours for hydrolysis to obtain a sol-like hydrophilic coating liquid composition 1. (Hydrophilic coating liquid composition 1) -Specific hydrophilic polymer (1) 21 g-Tetramethoxysilane [crosslinking component] 62 g-Ethanol 470 g-Water 470 g-Nitric acid aqueous solution (1N) 10 g

Then, using the above hydrophilic coating liquid composition 1,
Preparation of hydrophilic layer-forming coating liquid 1 having the following image forming ability
The coating amount after drying on the aluminum support is 3 g.
/ M ²To 100 ° C and heat dry for 10 minutes
It was dried to obtain a lithographic printing plate precursor 1. (Coating liquid 1 for forming hydrophilic layer) ・ Hydrophilic coating composition 1 66 g ・ Water-dispersible particles 1 (10% by mass) 400 g ・ Infrared absorbing dye I (compound below) 10 g ・ Water 374g

[0135]

[Chemical 20]

[Evaluation of planographic printing plate] Contact angle (water droplet in the air) on the surface of the hydrophilic layer having image forming ability on the obtained support.
Was measured using CA-Z manufactured by Kyowa Interface Science Co., Ltd., it was found to be 6.0 °, and it was confirmed to have excellent hydrophilicity.

The lithographic printing plate precursor 1 thus obtained was water-cooled 40
Cleo's trend setter 3244VFS equipped with W infrared semiconductor laser, outer drum rotation speed 100r
pm, plate energy 200 mJ / cm ² , resolution 24
Exposure was carried out under the condition of 00 dpi to form an image area on the exposed surface. The contact angle of water droplets on the surface of the infrared laser irradiation area of this printing plate was 110 °, which changed to hydrophobic, indicating that a hydrophobic area (ink-accepting area) was formed. After the exposure, it was mounted on the following printing machine and used for printing without developing. As a printing machine, Heidelberg SOR-
IF201 (2.5%), IF20 in fountain solution using M
2 (0.75%) (manufactured by Fuji Photo Film Co., Ltd.) and GEOS-G ink (manufactured by Dainippon Ink and Chemicals, Inc.) were used as ink. High quality printed matter was immediately obtained at the beginning of the printing process. When printing was continued continuously after that, a good printed matter with no stain on the non-image area was obtained even after printing 30,000 sheets, and excellent hydrophilicity was maintained in the non-image area. It turned out to be excellent in sex.

Example 2 (Formation of Hydrophilic Layer) The following components were uniformly mixed and hydrolyzed by stirring at room temperature for 2 hours to obtain a sol-like hydrophilic coating liquid composition 2. (Hydrophilic coating liquid composition 2) -Hydrophilic polymer (5) 21g-Tetramethoxysilane [crosslinking component] 62g-Ethanol 470g-Water 470g-Nitric acid aqueous solution (1N) 10g

Thereafter, the hydrophilic coating liquid composition 2 was used to prepare a coating liquid 2 for forming a hydrophilic layer having the following image forming ability, and the coating after drying was performed on a corona-treated polyethylene terephthalate film support. The amount was 3 g / m ^2, and the mixture was heated and dried at 100 ° C. for 10 minutes to obtain a lithographic printing plate precursor 2. (Coating liquid 2 for forming hydrophilic layer) -66 g of hydrophilic coating liquid composition-400 g of water-dispersible particles 2 (10% by mass) -Infrared absorbing dye I (described in Example 1) 10 g-374 g of water

[Evaluation] The contact angle (water droplets in the air) on the surface of the hydrophilic layer having image forming ability on the obtained support was measured using CA-Z manufactured by Kyowa Interface Science Co., Ltd. 5
It was confirmed to have excellent hydrophilicity.

Further, the lithographic printing plate precursor 2 thus obtained was subjected to a trend setter 3244VFS manufactured by Creo Co. equipped with a water-cooled 40 W infrared semiconductor laser under the conditions of an outer drum rotation speed of 100 rpm, a plate surface energy of 200 mJ / cm ² and a resolution of 2400 dpi. It was exposed to light to form an image area on the surface of the exposed portion. The contact angle of water droplets on the surface of the infrared laser irradiation area of this printing plate was 102 °, which changed to hydrophobic, indicating that a hydrophobic area (ink-accepting area) was formed. After the exposure, it was mounted on the following printing machine without developing and used for printing. As a printing machine, SOR-M manufactured by Heidelberg was used, and IF201 (2.5
%), IF202 (0.75%) (manufactured by Fuji Photo Film Co., Ltd.), and GEOS-G ink (manufactured by Dainippon Ink and Chemicals, Inc.) was used as the ink. High quality printed matter was immediately obtained at the beginning of the printing process. When printing was continued continuously after that, a good printed matter with no stain on the non-image area was obtained even after printing 30,000 sheets, and excellent hydrophilicity was maintained in the non-image area. It turned out to be excellent in sex.

[Examples 3 to 10] Instead of the water-dispersible particles 2 used in Example 2, the above-mentioned water-dispersible particles 3 to 10 were used in correspondence with Examples 3 to 10, respectively. ,
A printing original plate was prepared in the same manner as in Example 2, and image irradiation and printing by laser exposure were performed and evaluated. As a result, in any of the lithographic printing plate precursors, the hydrophilicity of the surface of the printing plate was very high, the degree of hydrophobicity of the surface of the irradiation region was sufficiently large, and the ink-jetting property was excellent and up to 30,000 sheets. ,
It was found that an excellent printed matter having no stain on the non-image area was obtained and the printing durability was also excellent.

[0143]

INDUSTRIAL APPLICABILITY The lithographic printing plate precursor according to the invention retains high hydrophilicity even under severe printing conditions, has good printing durability, and is capable of obtaining a large number of high-quality printed matters without stains on non-image areas. To be Further, it is possible to make a plate by scanning exposure based on a digital signal, and it is possible to make a plate by a simple water development processing operation, or it is possible to print on a printing machine without performing a development process. It is possible to provide a lithographic printing plate precursor exhibiting on-press developability.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Satoshi Hoshi             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. F-term (reference) 2H025 AA01 AA12 AB03 AC08 AD01                       BH03 BJ03 CB54 CC20 DA36                       DA40                 2H096 AA06 BA01 CA03 CA05 EA04                 2H114 AA04 AA23 BA01 DA03 DA04                       DA08 DA38 DA54 EA01 EA03                       EA04

Claims (2)

[Claims] 1. A support having a hydrophilic graft chain,
Also, a hydrophilic layer having a crosslinked structure formed by hydrolysis and polycondensation of an alkoxide compound containing an element selected from Si, Ti, Zr and Al is provided, and the hydrophilic layer is heated or irradiated with radiation. A lithographic printing plate precursor comprising water-dispersible particles capable of forming a surface-hydrophobicized region. 2. The water-dispersible particles have the following general formula (I):
The hydrophobic polymer having the structural unit of is dissolved in a solvent immiscible with water, and the solution is converted to the following general formula (II) or (II
Water-soluble resin having structural unit I) and / or Periodic Table 2
It is obtained by dispersing in a water phase containing oxide particles of at least one element selected from Group 15 elements to form oil droplets, and then removing the solvent from the oil droplets. The planographic printing plate precursor described in 1. [Chemical 1] ^{(Wherein, R 1, R 2, R} 3 and R ⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ⁴ represents an alkoxy group or acyloxy group of 1 to 40 carbon atoms,
k is an integer of 0 to 2, m is an integer of 0 to 3,
And k + m represents 3 or less, X represents a monovalent metal or hydrogen atom, and Z represents a group selected from the following. ) [Chemical 2] (Here, R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁶ represents an alkylene group having 5 or less carbon atoms or a plurality of chain carbon atom groups bonded to each other by a carbon atom or a nitrogen atom. Represents a valent organic residue, and n represents an integer of 0 to 4.) (Here, R ^{1 to} R ⁴ , X, Z, k and m are the same as those in formula (I), and Y ¹ is —NHCOR ⁷ , —CONH.
_{^{2, -CON (R 7) 2}} , -COR 7, -OH, -CO
_{It represents 2} M ¹ or —SO ₃ M ¹ . Here, R ⁷ represents an alkyl group having 1 to 8 carbon atoms, M ¹ represents a hydrogen atom, an alkali metal, an alkaline earth metal or onium, and n is 1 to 1
Represents an integer of 8. )