JP2006306031A - Hydrophilic film, lithographic printing material using the same, antifouling component, anticlouding component and method for manufacturing lithographic printing plate using lithographic printing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrophilic film having hydrophilic property and its retention performance, a lithographic printing material equipped with the hydrophilic film, an antifouling component, an anticlouding component, and a method for manufacturing a lithographic printing plate having a non-image area excellent in hydrophilic property and life using the same. <P>SOLUTION: (A) In a molecule, two or more pieces of ring structures to be selected from a five-membered ring structure and a six-membered ring structure are provided. And, the hydrophilic film is composed of a composition containing a compound of which the ring structure has a hydrophilic group, and is obtained by curing the film by heat and/or light. Further, (B) a crosslinking agent should be preferably contained in the composition. The hydrophilic film is useful as an image recording layer of the lithographic printing plate and a hydrophilic component having an antifouling property and an anticlouding property. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hydrophilic film, a lithographic printing material provided with the hydrophilic film, an antifouling member, an antifogging member, and a method for producing a lithographic printing plate using the lithographic printing material.

  Lithographic printing is a printing method that uses a plate material that has an oleophilic area that accepts ink and an ink-repellent area (hydrophilic area) that does not accept ink and accepts dampening water. A lithographic printing plate precursor (PS plate) is used. A PS plate having a photosensitive layer provided on a support such as an aluminum plate has been put into practical use and widely used. Such a PS plate is printed by removing the photosensitive layer in the non-image area by image exposure and development, and utilizing the hydrophilicity of the substrate surface and the oleophilicity of the photosensitive layer in the image area. Such a plate material is required to have high hydrophilicity on the substrate surface in order to prevent non-image areas from being stained.

  On the other hand, many studies have been made on printing plates for computer-to-plate systems that have made remarkable progress in recent years. Among them, as an aim to further streamline the process and solve the waste liquid treatment problem, development-free planographic printing plate precursors that can be mounted on a printing press and printed without being developed after exposure have been studied, A method has been proposed. One method of eliminating the processing step is to remove the non-image area of the printing plate by mounting the exposed printing plate on the cylinder of the printing press and supplying dampening water and ink while rotating the cylinder. There is a method called on-press development. In other words, after the printing master is exposed, it is mounted on a printing machine as it is, and the processing is completed in a normal printing process.

  A lithographic printing plate precursor suitable for such on-press development has a photosensitive layer soluble in dampening water or an ink solvent, and is suitable for development on a printing press placed in a bright room. It is necessary to have light room handling. As a printing plate that does not require a development step, a non-processed printing plate is described in which a crosslinked hydrophilic layer is provided on a substrate and a microcapsulated hot-melt material is contained therein (for example, Patent Document 1). reference). In this printing plate, the microcapsules are collapsed by the action of heat generated in the exposure area of the laser, the lipophilic substance in the capsules is dissolved, and the hydrophilic layer surface is hydrophobized. This printing plate precursor does not require development processing, but the hydrophilicity and durability of the hydrophilic layer provided on the substrate are insufficient, and the non-image area is gradually soiled as it is printed. was there.

  Hydrophilic layer (for example, see Patent Document 2), gelatin or polyvinyl alcohol obtained by curing a copolymer of acrylamide-hydroxyethyl acrylate with a methylol melamine cross-linking agent for the purpose of improving hydrophilicity and durability There have been proposed a hydrophilic layer (for example, see Patent Document 3) and a hydrophilic layer made of a quaternary ammonium salt polymer (for example, see Patent Document 4). These improve the hydrophilicity and cross-linked structure of the polymer used, and some improvements have been achieved, but practically lack hydrophilicity for use as a printing plate, At present, no satisfactory product has been obtained in terms of payability. In view of such a current situation, a support in which a hydrophilic polymer is directly bonded to the surface has been proposed (for example, see Patent Document 5). The hydrophilic layer on the surface of the support has certainly achieved high hydrophilicity, and although it has good performance as a general lithographic printing plate support, it is used for the purpose of containing a hydrophobic material such as a microcapsule. In some cases, there is a problem that handling is difficult, for example, preparation of film formation becomes difficult.

Moreover, as a member for which high surface hydrophilicity and its durability are desired, a hydrophilic member having antifouling property and antifogging property can be mentioned. For example, various techniques for preventing oily dirt from adhering to the member surface have been proposed. In particular, optical members such as antireflection films, optical filters, optical lenses, spectacle lenses, mirrors, etc., when used by humans, are contaminated with fingerprints, sebum, sweat, cosmetics, etc. Since removal of dirt is complicated, it is desired to perform effective dirt prevention treatment. In recent years, with the spread of mobile devices, displays are often used outdoors. When used in an environment where external light is incident, the incident light is regularly reflected on the display surface. As a result, the reflected light is mixed with the display light to cause problems such as difficulty in viewing the display image. For this reason, an antireflection optical member is often disposed on the display surface.
As such an antireflection optical member, for example, a layer of a high refractive index layer and a low refractive index layer made of a metal oxide or the like are laminated on the surface of a transparent substrate, and an inorganic or organic fluoride compound on the surface of the transparent substrate. Known are those in which a low refractive index layer such as a single layer is formed, or a coating layer containing transparent fine particles is formed on the surface of a transparent plastic film base material, and external light is irregularly reflected by an uneven surface. ing. These anti-reflective optical member surfaces, like the optical members described above, can easily be contaminated with fingerprints, sebum, and other dirt when used by humans. In addition to the problem, the surface of the antireflection film usually has fine irregularities, and there is a problem that it is difficult to remove dirt.

Various techniques have been proposed for forming on the surface an anti-smudge function having the performance of making it difficult to get dirt on the surface of a solid member or making it easier to remove attached dirt. In particular, as a combination of an antireflection member and an antifouling member, for example, an antireflection film made mainly of silicon dioxide and an antifouling and friction resistant material treated with a compound containing an organosilicon substituent (for example, Patent Document 6), and an antifouling and friction resistant CRT filter (for example, see Patent Document 7) in which the surface of the substrate is coated with a terminal silanol organopolysiloxane has been proposed. Further, an antireflection film containing a silane compound including a silane compound containing a polyfluoroalkyl group (see, for example, Patent Document 8), an optical thin film mainly composed of silicon dioxide, a perfluoroalkyl acrylate, and an alkoxysilane group. A combination with a copolymer with a monomer having a hydrogen atom (see, for example, Patent Document 9) has been proposed.
However, the antifouling layer formed by the conventional method has insufficient antifouling property, and in particular, it is difficult to wipe off dirt such as fingerprints, sebum, sweat, cosmetics, etc., and the surface energy such as fluorine and silicon is low. The surface treatment with a material is concerned with a decrease in antifouling performance over time, and therefore, development of an antifouling member having excellent antifouling properties and durability is desired.

  In general, a resin film generally used for the surface of an optical member or the like or an inorganic material such as glass or metal has a hydrophobic surface or a weak hydrophilic surface. When the surface of a substrate using resin film or inorganic material is made hydrophilic, the adhered water droplets spread uniformly on the substrate surface to form a uniform water film. It is useful for preventing devitrification due to moisture and ensuring visibility in rainy weather. In addition, combustion products such as carbon black contained in exhaust gas from automobile dust, automobiles, etc., and hydrophobic pollutants such as oil and fat and sealant elution components are difficult to adhere. Therefore, it is useful for various applications.

  Conventionally proposed surface treatment methods for hydrophilization, such as etching treatment and plasma treatment, are highly hydrophilized, but their effects are temporary and maintain the hydrophilized state for a long time. I can't. Further, a surface hydrophilic coating film using a hydrophilic graft polymer as one of hydrophilic resins has also been proposed (see, for example, Non-Patent Document 1), although this coating film has a certain degree of hydrophilicity, It cannot be said that the affinity with the substrate is sufficient, and higher durability is required.

Further, as a film having excellent surface hydrophilicity, a film using titanium oxide has been conventionally known. For example, a photocatalyst-containing layer is formed on the surface of a substrate, and the surface is highly hydrophilized according to photoexcitation of the photocatalyst. Technology has been disclosed, and it has been reported that if this technology is applied to various composite materials such as glass, lenses, mirrors, exterior materials, and water circulation members, excellent antifouling properties can be imparted to these composite materials. (For example, refer to Patent Document 10). However, the hydrophilic film using titanium oxide does not have sufficient film strength, and since there is a problem that the use site is limited because the hydrophilization effect is not manifested unless photoexcited, it is durable, and There is a demand for antifouling members having good wear resistance.
International application WO94 / 23954 Japanese Patent Laid-Open No. 2002-370467 JP-A-11-95417 Special table 2003-527978 gazette JP 2003-63166 A JP-A 64-86101 JP-A-4-338901 Japanese Patent Publication No. 6-29332 JP-A-7-16940, International Application Publication PTC / JP96 / 00733 Pamphlet Newspaper "Chemical Industry Daily" article dated January 30, 1995

  The present invention has been made for the purpose of solving the above-mentioned conventional problems, and an object of the present invention is to provide a hydrophilic film excellent in surface hydrophilicity and its sustainability. Another object of the present invention is to provide a lithographic printing material provided with the hydrophilic film, and a method for producing a lithographic printing plate excellent in hydrophilicity and durability of a non-image area using the lithographic printing material. It is in. A further object of the present invention is to provide an antifouling member and an antifogging member provided with the hydrophilic film.

As a result of intensive studies, the present inventor has found that the above problem can be solved by a film obtained by crosslinking and curing a compound having a plurality of ring structures having a specific hydrophilic group with a specific alkoxide compound. Completed the invention. Further, it has been found that an excellent lithographic printing material, antifouling member, and antifogging member can be obtained by applying a hydrophilic film having hydrophilicity and durability.
That is, the hydrophilic film of the present invention has (A) two or more ring structures selected from a 5-membered ring structure and a 6-membered ring structure in the molecule, and the ring structure has a hydrophilic group. A compound (hereinafter referred to as (A) a specific hydrophilic compound as appropriate) and (B) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al (hereinafter referred to as (B) a specific alkoxide as appropriate) And a film made of a composition containing the above, and obtained by curing with heat and / or light.
The composition for forming such a hydrophilic film contains (C) a hydrophilic polymer in addition to (A) the hydrophilic compound having a specific ring structure. From the viewpoint of improving durability.

  Examples of the specific hydrophilic compound (A) in the present invention include hydrophilic saccharides, starch derivatives, and cellulose derivatives having a 5-membered ring structure having a hydrophilic group and / or a 6-membered ring structure having a hydrophilic group. Can be mentioned. The mechanism for obtaining a highly hydrophilic and high-strength film by using a specific hydrophilic compound (A) typified by such a hydrophilic saccharide is not clear, but saccharides, cellulose derivatives, etc. Since one unit has many hydrophilic groups and forms a ring structure, the hydrophilic group exists toward the outside of the ring structure. When formed, it is considered that the coating surface shows high hydrophilicity. In addition, the hydrophilic groups in such saccharides often show structures such as alcohols and carboxylic acids. For this reason, when (B) a specific alkoxide is present as a crosslinking component, these hydrophilic groups are formed during film formation. A group, preferably a hydroxyl group, and the (B) specific crosslinking component exhibit high reactivity, and (A) and (B) are crosslinked, and (B) hydrolysis of the specific alkoxide, The components (B) are also cross-linked by condensation polymerization, and a high-density cross-linked structure is formed. Therefore, the cured film is considered to exhibit excellent strength and durability.

The hydrophilic film according to the present invention has high surface hydrophilicity, high strength, and excellent durability, and therefore can be used for various applications that require surface hydrophilicity. Useful for forming sex regions.
That is, as described in claim 3 of the present invention, by incorporating a material that changes from hydrophilic to hydrophobic by energy rays in the hydrophilic film, only the energy irradiation region is made a hydrophobic region. It is possible to obtain a hydrophilic film capable of forming a hydrophobic region in an arbitrary region. Accordingly, it is possible to obtain a lithographic printing plate by forming a hydrophilic / hydrophobic region like an image using such a hydrophilic film.

The lithographic printing material according to claim 4 of the present invention is characterized by having the hydrophilic film of the present invention on a support. Since such a lithographic printing material gives an excellent hydrophilic surface property on the support, a lithographic printing plate can be produced by forming a hydrophobic ink-receptive region on the surface by some means.
The method for producing a lithographic printing plate according to claim 5 of the present invention shows an example thereof, and the lithographic printing material formed by forming the hydrophilic film of the present invention on a support by an inkjet recording method. The ink receiving region is formed by applying a hydrophobic material.
As one of the ink jet recording methods, there is a recording method using an ink for ink jet recording that can be cured by irradiation of radiation. For example, the ultraviolet curable ink jet method has been attracting attention in recent years because it has a relatively low odor, can be quickly dried, and can be recorded on a hydrophilic film having low ink absorbability.
Such an ink for ink jet recording is applied imagewise to the lithographic printing material using the highly hydrophilic film of the present invention and cured to form an image portion, whereby the hydrophobicity of the UV curable ink and the hydrophilic film Due to the high hydrophilicity, it is possible to easily produce a lithographic printing plate capable of forming an excellent printed image.

Further, examples of applications utilizing the characteristics of the hydrophilic film of the present invention include antifouling members and antifogging members that require high hydrophilicity and surface characteristics having durability.
That is, the antifouling member according to claim 8 of the present invention is characterized by having the hydrophilic film of the present invention on a substrate. Moreover, the antifogging member which concerns on Claim 9 of this invention has the hydrophilic film | membrane of the said this invention on a base material, It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to this invention, the hydrophilic film excellent in surface hydrophilicity and its sustainability can be provided.
Since the hydrophilic film is excellent in surface hydrophilicity, it becomes an excellent lithographic printing material by forming the hydrophilic film on the support, and further excellent by forming the hydrophilic film on an appropriate substrate. It becomes an antifouling member and an antifogging member.
Further, by using the lithographic printing material, it is possible to provide a method for preparing a lithographic printing plate excellent in the hydrophilicity of the non-image area and its durability.

  The hydrophilic film of the present invention comprises (A) a compound having two or more specific hydrophilic ring structures in the molecule, and (B) an alkoxide compound containing an element selected from Si, Ti, Zr, and Al. It is characterized by being obtained by curing a film comprising the composition to be contained by heat and / or light. Hereinafter, the constituent components of the hydrophilic film of the present invention will be sequentially described.

<(A) Compound having two or more ring structures selected from a 5-membered ring structure and a 6-membered ring structure in the molecule, and the ring structure has a hydrophilic group>
The 5-membered ring and the 6-membered ring constituting the main structure of the specific hydrophilic compound (A) can be formed of atoms arbitrarily selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. The plurality of 5-membered rings and 6-membered rings are bonded to each other by a linking group formed by combining a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrogen atom.

(A) The specific hydrophilic compound used in the present invention (A) The molecule has two or more ring structures selected from a 5-membered ring structure and a 6-membered ring structure, and the ring structure is hydrophilic. Examples of the compound having a functional group include glucose, fructose, mannose, galactose, gulose, allose, idose, xylose, ribose, arabinose, lyxose, monosaccharides such as maltose, cellobiose, lactose, sucrose, sucrose, etc. Two or more compounds having a ring structure such as saccharides and gentianose are bonded with a linking group having a methylene group, an ether group, an ester group, an amide group, an amino group, a thioether group, an aryl group, a urethane group, a urea group, or the like. Can be obtained.
Further, the saccharide is an alkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, amino group, ethyleneoxy group, sulfonic acid group, phosphoric acid group, urethane group, urea group. , A thiol group, an acetal group or the like, or a combination of these.
In addition, a polymer compound in which a large number of ring structures having a hydrophilic group are linked, such as a cellulose derivative and a starch derivative, can also be used as the (A) specific hydrophilic compound of the present invention.

(A) The specific hydrophilic compound needs to have a hydrophilic group in its ring structure. Examples of such a hydrophilic group include a hydroxyl group, a carboxyl group, an amino group, an ethyleneoxy group, a sulfonic acid group, Examples thereof include a phosphoric acid group, a urethane group, a urea group, a thiol group, and a sulfuric acid group. These may be directly bonded to a 5-membered ring or a 6-membered ring, and may be bonded to a ring structure through a linking group such as a methylene group, a methyleneoxy group, or an aryl group as necessary. Of the hydrophilic groups described above, hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, thiol groups, sulfuric acid groups and the like can be used either in the proton form or neutralized with a base.
The amino group may be an ammonium group neutralized with an acid.

Specific examples of the specific hydrophilic compound (A) that can be used in the present invention are shown below, but the present invention is not limited thereto.
Hydroxymethylcellulose, hydroxypropylcellulose, carboxymethylcellulose or salts thereof, methylcellulose, carrageenan, maltoheptanose, maltohexanose, nystose, raffinose, panose, chitin, chitosan, pectinic acid, pentosan, pentose, cellulose triacetate, hydroxypropylmethylcellulose phthalate, Dextrin, cellulose nitrate, cellulose acetate, cellulose carbamate, cyanoethyl cellulose, ethyl hydroxyethyl cellulose, copolymer of glucuronic acid and N-acetylglucosamine, chondroitin 6-sulfate hexasaccharide, heparin, dextran sulfate, carotene sulfate, maltodextrin sulfate , Hemicellulose sulfate, alginic acid, sodium alginate, N -Dicarboxyethylaminoethylcellulose, diethylaminoethylcellulose ethylsulfonate, N- (o-carboxyphenyl) aminodeoxycellulose, s- (o-carboxyphenyl) mercaptodeoxycellulose, hydrazinodeoxycellulose, amylose, methylamylose, starch, carboxymethyl Examples include starch, phosphate starch, starch acetate, hydroxypropyl starch, acrylic acid grafted starch, pullulan, curdlan, xanthan gum, duran gum, guar gum, gum arabic, carrageenan, heparan sulfate and the like.

From the viewpoint of hydrophilicity, a preferred form of the compound having two or more 5-membered ring and / or 6-membered ring structures that can be used in the present invention and having a hydrophilic group is at least a hydroxyl group in the ring structure. It preferably has a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfuric acid group or a salt thereof. Most preferred is a compound having a sugar structure having a —SO ₃ ^— structure and a —OSO ₃ ^— structure. These hydrophilic groups may have at least one in the ring structure, but may have a plurality. In that case, a plurality of the same kind of hydrophilic groups may be included in the 5-membered ring and / or 6-membered ring structure. It may have a group, and may have a plurality of different hydrophilic groups. From the viewpoint of the effect, it is preferable that the ring structure has a plurality of hydrophilic groups in combination of a hydroxyl group and a carboxylic acid group, a hydroxyl group and a phosphate group, a hydroxyl group and a sulfate group, and the like.

(A) The specific hydrophilic compound may be used alone or in combination of two or more.
(A) The specific hydrophilic compound is preferably used in the composition for forming a hydrophilic film according to the present invention as a nonvolatile component in the range of 10 to 80% by mass, more preferably 25 to 50% by mass. The Within this range, good film strength and coating properties can be obtained, and there is no concern of cracks in the film, which is preferable.

<(B) Alkoxide Compound Containing Element Selected from Si, Ti, Zr, Al>
In the present invention, the composition for forming a hydrophilic film contains (B) a specific alkoxide as a crosslinking component in addition to the (A) specific hydrophilic compound, thereby improving hydrophilicity and durability. An excellent high-strength film is formed.
(B) The alkoxide compound containing an element selected from Si, Ti, Zr, and Al is preferably a compound represented by the general formula (2), and forms a crosslinked structure in order to cure the hydrophilic film. In doing so, it is preferable that the specific hydrophilic compound and a crosslinking component represented by the following general formula (2) are mixed and applied to the surface of the support and dried.
The crosslinking component represented by the following general formula (2) is a compound having a polymerizable functional group in its structure and serving as a crosslinking agent, and (A) the specific hydrophilic compound, or (B) A crosslinked structure is formed by condensation polymerization between components. Moreover, it is preferable to further contain the hydrophilic polymer (C) mentioned later from a viewpoint of the further improvement of film property and hydrophilic property.

In the general formula (2), R ^a represents a hydrogen atom, an alkyl group or an aryl group, R ^b represents an alkyl group or an aryl group, X represents Si, Al, Ti or Zr, and m is 0 to 2. Represents an integer.
When R ^a and R ^b represent an alkyl group, the alkyl group preferably has 1 to 4 carbon atoms. The alkyl group or aryl group may have a substituent, and examples of the substituent that can be introduced include a halogen atom, an amino group, and a mercapto group.
This compound is a low molecular compound and preferably has a molecular weight of 1000 or less.

Specific examples of the crosslinking component represented by the general formula (2) are given below, but the present invention is not limited thereto.
When X is Si, that is, the hydrolyzable compound containing silicon includes, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxy Silane, ethyltriethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diph Alkenyl dimethoxysilane, mention may be made of diphenyl diethoxy silane.
Among these, tetramethoxysilane, tetraethoxysilane, methyltolumethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxy are particularly preferable. Examples include silane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

In addition, when X is Al, that is, examples of the hydrolyzable compound containing aluminum include, for example, trimethoxy aluminate, triethoxy aluminate, tripropoxy aluminate, tetraethoxy aluminate and the like. it can.
When X is Ti, i.e., those containing titanium include, for example, trimethoxy titanate, tetramethoxy titanate, triethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, chlorotrimethoxy titanate, chlorotriethoxy titanate, ethyl triethoxy titanate. 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, the one containing zirconium can include, for example, a zirconate corresponding to the compound exemplified as containing titanium.

  (B) The specific alkoxide is preferably used in the range of 5 to 80% by mass, more preferably 20 to 70% by mass, as a non-volatile component in the composition for forming a hydrophilic film according to the present invention. Moreover, (B) specific alkoxide may be used independently or may be used together 2 or more types.

<Other cross-linking agents>
In the present invention, in addition to the (B) specific alkoxide, as long as the effects of the present invention are not impaired, crosslinking with a known heat, acid or radical other than the (B) specific alkoxide is performed in order to improve the properties of the hydrophilic film. A cross-linking agent that forms can be used in combination.
Examples of “other crosslinking agents” that can be used in the present invention include those described in “Crosslinking agent handbook”, Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981). The number of functional groups of the crosslinking agent that can be used in the present invention is not particularly limited as long as it is 2 or more and can be effectively crosslinked with the (A) specific hydrophilic compound and / or the component (B). However, aldehyde ketone can be used as a crosslinking agent according to the present invention as long as it has at least one functional group.
Specific thermal crosslinking agents include α, ω-alkanes such as 1,2-ethanedicarboxylic acid and adipic acid or alkenedicarboxylic acids, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetra. Polycarboxylic acids such as carboxylic acid, trimellitic acid, polyacrylic acid, polyamine compounds such as 1,2-ethanediamine, diethylenediamine, diethylenetriamine, polyethyleneimine, ethylene or propylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether , Nonaethylene tylene glycol diglycidyl ether, polyethylene or polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylo Polyepoxy compounds such as lepropane triglycidyl ether and sorbitol polyglycidyl ether,

  Oligoalkylene or polyalkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol, and tetraethylene glycol, polyhydroxy compounds such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, and polyvinyl alcohol, glyoxal, terephthalaldehyde, acetaldehyde, benzaldehyde, etc. Polyaldehyde compounds, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane isocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate , Polyisocyanate compounds such as polypropylene glycol / tolylene diisocyanate addition reaction products, block polyisocyanate compounds, silane coupling agents such as tetraalkoxysilane, and metal cross-linking agents such as acetylacetonate of aluminum, copper and iron (III) And polymethylol compounds such as trimethylol melamine and pentaerythritol, and polythiol compounds such as dithioerythritol, 1,2,6-hexanetriol trithioglycolate, pentaerythritol tetrakis (2-mercaptoacetate), and the like. Among these thermal crosslinking agents, a water-soluble crosslinking agent is preferable from the viewpoint of easy preparation of the coating solution and prevention of a decrease in hydrophilicity of the produced hydrophilic film.

  The other crosslinking agent is preferably used in the range of 0 to 30% by mass, more preferably 0 to 15% by mass as a nonvolatile component in the composition used for forming the hydrophilic film in the present invention. Moreover, although such a crosslinking agent may be used independently or may be used together 2 or more types, it is 50 mass% or less with respect to (B) specific alkoxide which is the main crosslinking component of this invention. preferable.

<(C) hydrophilic polymer>
The hydrophilic film-forming composition of the present invention preferably further contains (C) a hydrophilic polymer from the viewpoint of improving the crosslinking density.
Examples of hydrophilic polymers that can be used in the present invention include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyls or hydrolysates thereof, styrenes, acrylic acid or salts thereof, methacrylic acids or salts thereof. , Acrylonitrile, maleic anhydrides, maleic imides, and other polymers as raw materials.
Among these monomers, monomers having an amino group, ammonium group, hydroxyl group, sulfonamide group, carboxyl group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof, ether group, particularly ethyleneoxy group are preferable.
In addition to the above, hydrophilic polymers having a urethane bond, an amide bond, or a urea bond in the main chain can also be used.

  Specific examples of acrylic esters include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, hydroxybenzyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate , Tetrahydrofurfuryl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl acrylate, diethylene glycol ethyl ether acrylate, 2-ethoxyethyl acrylate and the like.

  Specific examples of methacrylic acid esters include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl. Examples include methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate, diethylene glycol ethyl ether methacrylate, 2-ethoxyethyl methacrylate, and methoxytetraethylene glycol monomethacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N, N-dimethylacrylamide, N- Examples include methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-hydroxyethylmethacrylamide, N- (sulfamoylphenyl). ) Methacrylamide, N- (phenylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyls include vinyl acetate and vinyl pyrrolidone.
Specific examples of styrenes include trimethoxy styrene, carboxy styrene, styrene sulfone or a salt thereof.

In the present invention, from the viewpoint of further improving the properties of the hydrophilic membrane, at least a specific hydrophilic polymer having a structure represented by the following general formula (1) [hereinafter referred to as “(C-1) specific” It is preferable to contain a “hydrophilic polymer”. (C-1) The specific hydrophilic polymer has a silane coupling group at the terminal.
By the combined use of the (C-1) specific hydrophilic polymer having a silane coupling group at such a terminal, the interaction between the silane coupling group of the hydrophilic polymer and the crosslinking component, and further, between the silane coupling groups It is presumed that a cross-linked structure formed of Si (OR) _{4 is} formed by the interaction, and the strength and durability of the hydrophilic film are improved by the strong cross-linked structure.

The hydrophilic polymer compound having the structure represented by the general formula (1) is represented by the structural unit (iii) at at least one of both ends of the polymer unit represented by the structural units (i) and (ii). As long as it has a silane coupling group, the other terminal may have this functional group, and may have a hydrogen atom or a functional group having a polymerization initiating ability.
In the general formula (1), m represents 0, 1 or 2, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon having 8 or less carbon atoms. Represents a group. Examples of the hydrocarbon group include an alkyl group and an aryl group, and a linear, branched or cyclic alkyl group having 8 or less carbon atoms is preferable. Specifically, 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, cyclopentyl group and the like.
R ^{1 to} R ⁶ are preferably a hydrogen atom, a methyl group, or an ethyl group from the viewpoints of effects and availability.

These hydrocarbon groups may further have a substituent.
When the alkyl group has a substituent, the substituted alkyl group is constituted by a bond between a substituent and an alkylene group, and here, a monovalent nonmetallic atomic group excluding hydrogen is used as the substituent. Preferred examples include halogen atoms (-F, -Br, -Cl, -I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, amino groups, N-alkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-aryl Acylamino group, ureido group, N ′ -Alkyl ureido group, N ', N'-dialkyl ureido group, N'-aryl ureido group, N', N'-diaryl ureido group, N'-alkyl-N'-aryl ureido group, N-alkyl ureido 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-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl -N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- Alkoxycarbonyl amino group, N- aryl -N- aryloxycarbonylamino group, a formyl group, an acyl group, a carboxyl group,

Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate 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 N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group (—PO ₃ (aryl) ₂ ), alkyl An arylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base group thereof (hereinafter referred to as an alkylphosphonate group), a monoarylphosphono Group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphono Xyl group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonatooxy group”), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ ( aryl) ₂ ), an alkylarylphosphonooxy group (—OPO (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as alkylphosphonatooxy group). Monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonatooxy group), morpholino group, cyano group, nitro group, aryl group, alkenyl group , An alkynyl group.

Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl 2 group, xylyl group, mesityl group, cumenyl group. Group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methyl Aminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl , It can be exemplified cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl 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. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO ⁻ ) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkyls. Amino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfamoy Group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group Group, phosphonooxy group, phosphonatooxy group, aryl group, and alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can be a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyl group. Oxymethyl group, phenoxymethyl group, methylthiomethyl, 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 Carbonyl butyl group,

  Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoyl Methyl 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, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Torilho Phonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

L ¹ and L ² represent a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a nonmetallic atom, and specifically includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 carbon atoms. It consists of up to 1 oxygen atom, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specific examples of the linking group include the following structural units or those formed by combining them.

L ³ represents a single bond or an organic linking group. Here, the organic linking group refers to a polyvalent linking group composed of a non-metal atom, and specific examples thereof include those similar to L ¹ and L ² described above. Among them, a particularly preferable structure is — (CH ₂ ) _n —S— (n is an integer of 1 to 8).

Y ¹ and Y ² represent —NHCOR ⁷ , —CONH ₂ , —CON (R ⁷ ) (R ⁸ ), —COR ⁷ , —OH, —CO ₂ M, or —SO ₃ M, R ⁷ and R ⁸ each independently represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. ^{Further, -CON (R 7) R 7} , R 8 for ^{(R 8)} is may have to each other to form a ring, and the formed ring is an oxygen atom, a hetero such as sulfur atom, a nitrogen atom Heterocycle containing an atom may be sufficient. R ⁷ and R ⁸ may further have a substituent, and the substituents that can be introduced here are the same as those exemplified as the substituents that can be introduced when R ^{1 to} R ⁶ are alkyl groups. Can be listed.

Specific examples of R ⁷ and R ⁸ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, s-butyl group, and t-butyl. Preferred examples include a group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
Examples of M include a hydrogen atom; an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as calcium and barium; or an onium such as ammonium, iodonium and sulfonium.
^Further, specifically as _{^{Y 1, Y 2, -NHCOCH 3}} , -CONH 2, -COOH, -SO 3 - NMe 4 +, a morpholino group, etc. are preferable.

  x and y represent a composition ratio when x + y = 100, x: y represents a range of 100: 0 to 1:99, and a range of 100: 0 to 5:95 is more preferable.

  (C-1) The molecular weight of the specific hydrophilic polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and most preferably 1,000 to 30,000.

  Specific examples (1-1) to (1-23) of the specific hydrophilic polymer (C-1) that can be suitably used in the present invention are shown below, but the present invention is not limited thereto.

<Synthesis method>
The (C-1) specific hydrophilic polymer used in combination according to the present invention in the present invention is represented by a radically polymerizable monomer represented by the following structural units (i) and (ii) and the following structural unit (iii): It can be synthesized by radical polymerization using a silane coupling agent having chain transfer ability in radical polymerization. Since the silane coupling agent has chain transfer ability, it is possible to synthesize a polymer in which a silane coupling group is introduced at the end of the polymer main chain in radical polymerization.
Although this reaction mode is not particularly limited, bulk reaction, solution reaction, suspension reaction, etc. may be performed in the presence of a radical polymerization initiator or irradiation with a high-pressure mercury lamp.

In addition, in the polymerization reaction, the amount of the structural unit represented by (iii) is controlled, and the homopolymerization of the structural unit with the structural unit (i) or (ii) is effectively suppressed. It is preferable to perform the same polymerization method using an addition method, a sequential addition method, or the like.
The reaction ratio of the structural units (i) and (ii) with respect to the structural unit (iii) is not particularly limited, but the structural units (i) and (ii) are 0 with respect to 1 mol of the structural unit (iii). From the viewpoint of suppressing side reactions and improving the yield of the hydrolyzable silane compound, the range of 1 to 45 mol is more preferable, and the range of 5 to 40 mol is preferable. Most preferred.

In the structural units (i), (ii), and (iii), R ^{1 to} R ⁶ , L ^{1 to} L ³ , Y ¹ , Y ² , and m are as defined in the general formula (1). These compounds are commercially available and can be easily synthesized.

  (C-1) As a radical polymerization method for synthesizing the specific hydrophilic polymer, any conventionally known method can be used. Specifically, general radical polymerization methods include, for example, New Polymer Experimental Science 3, Polymer Synthesis and Reaction 1 (Edited by the Society of Polymer Science, Kyoritsu Shuppan), New Experimental Chemistry Course 19, Polymer Chemistry (I) (The Chemical Society of Japan, Maruzen), Materials Engineering, Synthetic Polymer Chemistry (Tokyo Denki University Press), etc., can be applied.

  The (C-1) specific hydrophilic polymer may be a copolymer of each structural unit described above and another monomer as described later. Examples of other monomers used include acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic imide and the like. A well-known monomer is also mentioned. By copolymerizing such monomers, various physical properties such as film forming property, film strength, hydrophilicity, hydrophobicity, solubility, reactivity, and stability can be improved.

  Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, Dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, chloro Benzyl acrylate, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

  Specific examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, chloro Benzyl methacrylate, hydroxybenzyl methacrylate, hydroxyphene Chill methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, 2- (hydroxyphenyl carbonyloxy) ethyl methacrylate.

  Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, and N-tolylacrylamide. N- (hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide , N-hydroxyethyl-N-methylacrylamide and the like.

  Specific examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-butylmethacrylamide, N-benzylmethacrylamide, N-hydroxyethylmethacrylamide, N -Phenylmethacrylamide, N-tolylmethacrylamide, N- (hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N- (tolylsulfonyl) methacrylamide, N , N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like.
Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, dimethoxy styrene. Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene, and the like.

  The proportion of these other monomers used in the synthesis of the copolymer must be sufficient to improve various physical properties, but if the proportion is too large, the function as a hydrophilic film is insufficient. Therefore, there is a concern that the advantage of adding the (C-1) hydrophilic polymer cannot be sufficiently obtained. Accordingly, the preferred total proportion of other monomers in the (C-1) specific hydrophilic polymer is 80% by weight or less, and more preferably 50% by weight or less.

(C) A hydrophilic polymer may be used independently or may be used together 2 or more types. Considering that the most preferred embodiment of this (C) hydrophilic polymer is (C-1) a specific hydrophilic polymer, all of the (C) hydrophilic polymers used are such (C-1) specific It may be a hydrophilic polymer.
The hydrophilic polymer (C) used in combination is preferably 0 as a non-volatile component in the composition used for forming the hydrophilic film in the present invention from the viewpoint of balancing the film property and hydrophilicity. It is used in a range of ˜50 mass%, more preferably 0 to 20 mass%.

<Surfactant>
In the present invention, it is preferable to use a surfactant in order to improve the coated surface state of the hydrophilic film-forming composition. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants. Surfactant may be used independently and may be used in combination of 2 or more type.

  The nonionic surfactant used for this invention is not specifically limited, A conventionally well-known thing can be used. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol Fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N N- bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, copolymers of polyethylene glycol and polypropylene glycol.

  The anionic surfactant used in the present invention is not particularly limited, and conventionally known anionic surfactants can be used. For example, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinate esters, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl phenoxy poly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, fatty acid alkyl esters Sulfates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alcohol Ruphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / maleic anhydride Examples thereof include partial saponification products of polymers, partial saponification products of olefin / maleic anhydride copolymers, and naphthalene sulfonate formalin condensates.

The cationic surfactant used in the present invention is not particularly limited, and conventionally known cationic surfactants can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
The amphoteric surfactant used in the present invention is not particularly limited, and conventionally known amphoteric surfactants can be used. Examples thereof include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

  Of the above surfactants, the term “polyoxyethylene” can be read as “polyoxyalkylene” such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. These surfactants can also be used.

  More preferable surfactants include fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Examples of such fluorosurfactants include anionic types such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and perfluoroalkyl phosphates; amphoteric types such as perfluoroalkyl betaines; Cation type such as trimethylammonium salt; perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, perfluoroalkyl Nonionic types such as an oligomer containing a group, a hydrophilic group and a lipophilic group, and a urethane containing a perfluoroalkyl group and a lipophilic group. Moreover, the fluorine-type surfactant described in each gazette of Unexamined-Japanese-Patent No. 62-170950, 62-226143, and 60-168144 is also mentioned suitably.

Surfactant can be used individually or in combination of 2 or more types.
The content of the surfactant is preferably 0.001 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the composition.

<Inorganic fine particles>
The composition for forming a hydrophilic film of the present invention may contain inorganic fine particles in order to improve the cured film strength of the hydrophilic film and to improve hydrophilicity and water retention.
As the inorganic fine particles, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate or a mixture thereof can be preferably mentioned. Even if they are not photothermally convertible, they can be used for strengthening the film, enhancing interfacial adhesion by surface roughening, and the like.
The inorganic fine particles preferably have an average particle size of 5 nm to 10 μm, and more preferably 0.5 μm to 3 μm. Within the above range, it is possible to form a non-image portion having excellent hydrophilicity that is stably dispersed in the image recording layer, sufficiently retains the film strength of the image recording layer, and hardly causes stains during printing.
The inorganic fine particles as described above can be easily obtained as a commercial product such as a colloidal silica dispersion.
The content of the inorganic fine particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the hydrophilic film forming composition.

<Formation of hydrophilic film>
The hydrophilic film of the present invention is prepared by dispersing or dissolving the necessary components described above in a solvent to prepare a coating solution, and curing the coating film formed on an appropriate support by heat and / or light. Can be formed.

  Moreover, in preparing the hydrophilic film coating liquid composition which is a preferred embodiment, (B) the specific alkoxide is in a mass ratio of 0.1 to 4 with respect to the mass 1 of the specific hydrophilic compound (A). It is preferable to be used. The upper limit of the amount of crosslinking component added is not particularly limited as long as it can be sufficiently crosslinked with the hydrophilic polymer, but when added excessively, the produced hydrophilic surface becomes sticky due to the crosslinking component not involved in crosslinking. there is a possibility.

  Among (C) hydrophilic polymers used as desired, in particular, when (C-1) a specific hydrophilic polymer having a silane coupling group at the terminal is used, (C-1) hydrophilicity having a silane coupling group at the terminal A polymer, (A) a compound having at least a 5-membered ring and / or a 6-membered ring structure, wherein the ring structure contains a hydrophilic group, and (B) a crosslinking component such as a specific alkoxide in a solvent, By stirring well, these components are hydrolyzed and polycondensed to form an organic-inorganic composite sol solution, which becomes the coating solution for forming a hydrophilic film according to the present invention. A surface hydrophilic layer having hydrophilicity and high film strength is formed. In the preparation of the organic-inorganic composite sol solution, it is preferable to use an acidic catalyst or a basic catalyst in combination in order to promote hydrolysis and polycondensation reaction. It 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 and a basic catalyst, respectively). The concentration at the time of dissolving in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound to be used, the desired content of the catalyst, etc. The polymerization rate tends to increase. However, when a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution. Therefore, when a basic catalyst is used, the concentration is preferably 1 N or less in terms of concentration in an aqueous solution.

The type of the acidic catalyst or the basic catalyst is not particularly limited. However, 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 or acetic acid, and its RCOOH. Examples thereof include substituted carboxylic acids in which R in the structural formula is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, etc., and basic catalysts include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline Etc. Other catalysts include metal compounds such as Ti acetylacetone complex, SuCl ₄ , and Zr (OR).

  The hydrophilic film coating solution is prepared by (A) a specific hydrophilic compound, (B) a crosslinking component such as a specific alkoxide, and preferably (C-1) a hydrophilic polymer having a silane coupling group at the end. After dissolving in a solvent such as ethanol, the catalyst can be added as desired and stirred. The reaction temperature is from room temperature to 80 ° C., and the reaction time, that is, the time during which stirring is continued, is preferably in the range of 1 to 72 hours. A composite sol solution can be obtained.

  The solvent used in preparing the hydrophilic film coating solution composition is not particularly limited as long as it can uniformly dissolve and disperse these, and examples thereof include aqueous solvents such as methanol, ethanol, and water. preferable.

  As described above, the preparation of the organic-inorganic composite sol liquid (hydrophilic coating liquid composition) for forming the hydrophilic film of the present invention utilizes the sol-gel method. For the sol-gel method, Sakuo Sakuo “Science of Sol-Gel Method”, Agne Jofusha (published) (1988), Satoshi Hirashima “Functional Thin Film Formation Technology by the Latest Sol-Gel Method” General Technology Center (Published) (1992) and the like, and the methods described therein can be applied to the preparation of the hydrophilic film coating liquid composition according to the present invention.

  As described above, various additives can be used in the hydrophilic film coating solution composition according to the present invention depending on the purpose as long as the effects of the present invention are not impaired. For example, as detailed above, a surfactant can be added to improve the uniformity of the coating solution.

A hydrophilic surface can be formed by applying and drying the hydrophilic film coating solution composition prepared as described above on a substrate of a support.
The hydrophilic film of the present invention can be formed by preparing a plurality of coating solutions in which the same or different components are dispersed or dissolved in the same or different solvents, and repeating a plurality of coatings and dryings.
The film thickness of the hydrophilic surface can be selected according to the purpose, but generally the coating amount after drying is in the range of 0.2 to 5.0 g / m ² , preferably 0.5 to 3.0 g / m 2. ² range. When the coating amount is in the above range, excellent hydrophilic effect and good film strength can be obtained. As described in detail below, even when an image recording component is added, good recording sensitivity can be achieved.

  Various methods can be used as a coating method. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

<Support>
The hydrophilic film of the present invention can be formed on an arbitrary substrate, but a lithographic printing plate material can be obtained by forming the hydrophilic film on an appropriate support. Further, as will be described later, a lithographic printing plate precursor can be obtained by containing a material that changes from hydrophilic to hydrophobic by energy application, as will be described later.
The support used here is not particularly limited as long as it is a dimensionally stable plate. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or deposited. Preferable supports include a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

The thickness of the support is preferably 0.05 to 1.0 mm, more preferably 0.07 to 0.7 mm, and still more preferably 0.1 to 0.5 mm.
Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment.

<Curing method>
The hydrophilic film of the present invention can be cured by drying after coating on a support, but it can also be cured by light and / or heat after coating and drying. That is, heating and / or light irradiation may be performed to cure the film formed by coating, and the crosslinking reaction further proceeds by heating and / or light irradiation after coating, and the coating strength of the hydrophilic film is increased. improves.
Of these, it is preferable to cure with heat for suitability for production. There are no particular limitations on the temperature conditions when the composition relating to the formation of the hydrophilic film of the present invention is cured and formed with heat, but it is preferably 60 ° C to 300 ° C and contains a crosslinking agent. The range of 80 ° C. to 250 ° C. is more preferable from the viewpoints of stability and production stability. After coating, the hydrophilic film may be dried and cured as it is under the above temperature conditions, or after drying the hydrophilic film, it may be heated in a separate step to cure the film.
Moreover, when making it harden | cure by light, a light source does not have a restriction | limiting in particular, You may use any wavelength of ultraviolet light, visible light, infrared rays, and white light.

When the composition for forming a hydrophilic film contains another cross-linking agent, the cross-linked structure is formed by forming a covalent bond by heat, light, etc., or forming a covalent bond by acid and / or radical generated by heat, light, etc. Alternatively, any of ionic crosslink formation by acid and base may be used. If a large amount of radicals can be generated and cured, the curing reaction may be carried out in the atmosphere under nitrogen or argon.
In the present invention, in order to improve curability, a known crosslinking reaction accelerator suitable for the crosslinking reaction used for curing can be used as necessary. In particular, when the film-forming composition is cured using a radical polymerization reaction, a heat or photo radical generator such as an azo compound, a peroxy compound, an organic halogen compound, an oxime ester compound, an onium salt compound, or a transition metal compound is used. be able to.

<Material that changes from hydrophilic to hydrophobic by heat or light>
By adding a compound having an image forming function to the hydrophilic film of the present invention, that is, a compound capable of forming a hydrophobic region by heating or radiation exposure, the hydrophilic film of the present invention is heated or irradiated with radiation. The material can form a hydrophobic region by applying energy such as irradiation. By using such a compound, for example, a hydrophobic region is formed in the hydrophilic film by exposure and can be used as it is as a lithographic printing plate.
As a material that changes from hydrophilic to hydrophobic by heat or light, a compound that changes its physical properties from hydrophilic to hydrophobic, or a substance that forms a hydrophobic region by adhesion, such as polymer particles And so on.
As a compound that changes from hydrophilic to hydrophobic, a polymer having a functional group that changes from hydrophilic to hydrophobic by decarboxylation by heat described in JP-A No. 2000-122272 (Japanese Patent Application No. 10-229783). Specifically, the polymer compounds shown below are preferably exemplified. As a preferred physical property, it is particularly preferable that the contact angle of the water droplets on the coating surface when the polymer itself is applied is 20 ° or less before heating and changes to 65 ° or more after heating. However, it is not limited to these.

  The polymer particles preferably used in the present invention are particles capable of converting a hydrophilic image recording layer to hydrophobic when heat is applied. The particles are preferably at least one polymer particle selected from thermoplastic polymer particles, heat-reactive polymer particles, and microcapsules encapsulating a hydrophobic compound.

  Examples of the thermoplastic polymer particles used in the image recording layer of the present invention include Research Disclosure No. 1 of January 1992. 33303, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250, and EP931647, and the like. it can. Specific examples of the polymer constituting such polymer particles include homopolymers of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, or the like. Mention may be made of copolymers or mixtures thereof. Among them, more preferred are polystyrene and polymethyl methacrylate.

  The average particle size of the thermoplastic polymer particles used in the present invention is preferably 0.01 to 2.0 μm. As a method for synthesizing such thermoplastic polymer particles, in addition to emulsion polymerization and suspension polymerization, these compounds are dissolved in a water-insoluble organic solvent, and this is mixed and emulsified with an aqueous solution containing a dispersant. Further, there is a method (solution dispersion method) in which heat is further applied to solidify the organic solvent into particles while evaporating.

  Examples of the thermoreactive polymer particles used in the present invention include thermosetting polymer particles and polymer particles having a thermoreactive group.

  Examples of the thermosetting polymer include a resin having a phenol skeleton, a urea resin (for example, a urea derivative such as urea or methoxymethylated urea resinized with an aldehyde such as formaldehyde), a melamine resin (for example, melamine or Examples thereof include those obtained by converting the derivatives into resins with aldehydes such as formaldehyde, alkyd resins, unsaturated polyester resins, polyurethane resins, and epoxy resins. Among these, resins having a phenol skeleton, melamine resins, urea resins and epoxy resins are particularly preferable.

  Suitable resins having a phenol skeleton include, for example, phenol resins obtained by resinizing phenol, cresol, etc. with aldehydes such as formaldehyde, hydroxystyrene resins, N- (p-hydroxyphenyl) methacrylamide, and p-hydroxyphenyl methacrylate. Examples thereof include a polymer or copolymer of methacrylamide or acrylamide or methacrylate or acrylate having a phenol skeleton.

  As for the average particle diameter of the thermosetting polymer particle used for this invention, 0.01-2.0 micrometers is preferable. Such thermosetting polymer particles can be easily obtained by a solution dispersion method, but may be formed into particles when the thermosetting polymer is synthesized. However, it is not restricted to these methods.

  The thermally reactive group of the polymer particles having a thermally reactive group used in the present invention may be any functional group that undergoes a reaction as long as a chemical bond is formed, but is an ethylenically unsaturated group that undergoes a radical polymerization reaction. Group (for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.), cationically polymerizable group (for example, vinyl group, vinyloxy group, etc.), isocyanate group that performs addition reaction or its block, epoxy group, vinyloxy group And a functional group having an active hydrogen atom as a reaction partner (for example, an amino group, a hydroxyl group, a carboxyl group, etc.), a carboxyl group for performing a condensation reaction, a hydroxyl group or an amino group as a reaction partner, a ring-opening addition reaction Examples of suitable acid anhydrides and amino or hydroxyl groups that are reaction partners That.

  Introduction of these functional groups into the polymer particles may be performed at the time of polymerization, or may be performed using a polymer reaction after the polymerization.

  When introduced at the time of polymerization, it is preferable to carry out emulsion polymerization or suspension polymerization of the monomer having the above functional group. Specific examples of the monomer having the above functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, 2- (vinyloxy) ethyl methacrylate, p-vinyloxystyrene, p- {2- (vinyloxy) ethyl} styrene, Block isocyanate with glycidyl methacrylate, glycidyl acrylate, 2-isocyanatoethyl methacrylate or alcohol thereof, block isocyanate with 2-isocyanate ethyl acrylate or alcohol thereof, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, 2 officers Methacrylate, and the like, but not limited thereto.

  In the present invention, a copolymer of these monomers and a monomer that is copolymerizable with these monomers and does not have a thermally reactive group can also be used. Examples of the copolymer monomer having no heat-reactive group include styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, vinyl acetate, and the like. It is not limited to.

  Examples of the polymer reaction used when the introduction of the thermally reactive group is carried out after the polymerization include the polymer reaction described in International Publication No. 96/34316 pamphlet.

  Among the above polymer particles having a thermoreactive group, those in which polymer fine particles are coalesced by heat are preferable, and those having a hydrophilic surface and being dispersed in water are particularly preferable. The contact angle (airborne droplets) of the film prepared by applying only polymer particles and drying at a temperature lower than the solidification temperature is higher than the contact angle (airborne droplets) of the film prepared by drying at a temperature higher than the solidification temperature. It is preferable to lower. In order to make the surface of the polymer fine particles hydrophilic in this way, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol or a hydrophilic low molecular weight compound may be adsorbed on the surface of the polymer fine particles. However, the surface hydrophilization method is not limited to this.

  The solidification temperature of the polymer particles having these heat-reactive groups is preferably 70 ° C. or higher, but more preferably 100 ° C. or higher in view of stability over time. The average particle size of the polymer fine particles is preferably 0.01 to 2.0 μm, more preferably 0.05 to 2.0 μm, and most preferably 0.1 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.

  The microcapsule used in the present invention contains a hydrophobic compound. This hydrophobic compound is preferably a compound having a thermally reactive group. As the heat-reactive group, the same heat-reactive group as that used for the polymer particles having the heat-reactive group can be mentioned as a preferable one. Hereinafter, the compound having a thermally reactive group will be described in more detail.

  As the compound having a radically polymerizable unsaturated group, a compound having at least one, preferably two or more ethylenically unsaturated bonds such as acryloyl group, methacryloyl group, vinyl group, allyl group, styryl group and the like is suitable. As mentioned. Such a group of compounds is widely known as a monomer or a crosslinking agent for the polymerizable composition in the industrial field, and these can be used in the present invention without any particular limitation. The chemical form is a monomer, a prepolymer, that is, a dimer, a trimer, an oligomer, a polymer or a copolymer, or a mixture thereof.

  Specific examples include compounds described in JP-A-2001-277740 as compounds having a polymerizable unsaturated group. Typical compound examples include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Examples include pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and adducts of trimethylolpropane diacrylate and xylylene diisocyanate. However, it is not limited to these.

Examples of the polymer or copolymer having an ethylenically polymerizable unsaturated group include an allyl methacrylate copolymer. For example, allyl methacrylate / methacrylic acid copolymer, allyl methacrylate / ethyl methacrylate copolymer, allyl methacrylate / butyl methacrylate copolymer and the like can be mentioned.
Examples of the styryl compound that can be used in the present invention include compounds described in Japanese Patent Application No. 2004-045114.

  Examples of the compound having a vinyloxy group suitable for the present invention include compounds described in JP-A-2002-29162. Specific examples include tetramethylene glycol divinyl ether, trimethylolpropane trivinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, 1,4-bis {2- (vinyloxy) ethyloxy} Benzene, 1,2-bis {2- (vinyloxy) ethyloxy} benzene, 1,3-bis {2- (vinyloxy) ethyloxy} benzene, 1,3,5-tris {2- (vinyloxy) ethyloxy} benzene, 4 , 4′-bis {2- (vinyloxy) ethyloxy} biphenyl, 4,4′-bis {2- (vinyloxy) ethyloxy} diphenyl ether, 4,4′-bis {2- (vinyloxy) ester Ruoxy} diphenylmethane, 1,4-bis {2- (vinyloxy) ethyloxy} naphthalene, 2,5-bis {2- (vinyloxy) ethyloxy} furan, 2,5-bis {2- (vinyloxy) ethyloxy} thiophene, , 5-bis {2- (vinyloxy) ethyloxy} imidazole, 2,2-bis [4- {2- (vinyloxy) ethyloxy} phenyl] propane {bis (vinyloxyethyl) ether of bisphenol A}, 2,2- Examples include, but are not limited to, bis {4- (vinyloxymethyloxy) phenyl} propane, 2,2-bis {4- (vinyloxy) phenyl} propane, and the like.

  As the compound having an epoxy group suitable for the present invention, a compound having two or more epoxy groups is preferable, and a glycidyl ether compound obtained by reaction of a polyhydric alcohol or a polyhydric phenol with epichlorohydrin or a prepolymer thereof. Furthermore, a polymer or copolymer of glycidyl acrylate or glycidyl methacrylate can be used.

  Specific examples include propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, hydroquinone diglycidyl. Ether, resorcinol diglycidyl ether, diglycidyl ether or epichlorohydrin polyadduct of bisphenol A, diglycidyl ether or epichlorohydrin polyadduct of bisphenol F, diglycidyl ether or epichlorohydride of halogenated bisphenol A Phosphorus polyadduct, diglycidyl ether of biphenyl type bisphenol or epichlorohydrin polyadduct, novolak tree Etc. glycidyl ethers, furthermore, methyl methacrylate / glycidyl methacrylate copolymer, methacrylic acid ethyl / glycidyl methacrylate copolymer, and the like.

  Commercially available products of the above compounds include, for example, Epicoat 1001 (molecular weight: about 900, epoxy equivalent: 450 to 500), Epicoat 1002 (molecular weight: about 1600, epoxy equivalent: 600 to 700), Epicoat 1004 (about) manufactured by Japan Epoxy Resin Co., Ltd. 1060, epoxy equivalent 875-975), Epicoat 1007 (molecular weight about 2900, epoxy equivalent 2000), Epicoat 1009 (molecular weight about 3750, epoxy equivalent 3000), Epicoat 1010 (molecular weight about 5500, epoxy equivalent 4000), Epicoat 1100L (epoxy equivalent) 4000), Epicoat YX31575 (epoxy equivalent 1200), Sumitomo Chemical Co., Ltd. Sumiepoxy ESCN-195XHN, ESCN-195XL, ESCN-195XF, and the like.

  Suitable isocyanate compounds for the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate, cyclohexanephenylene diisocyanate, isophorone diisocyanate, Examples include hexamethylene diisocyanate, cyclohexyl diisocyanate, and compounds obtained by blocking these with alcohol or amine.

  Suitable amine compounds for the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, propylenediamine, polyethyleneimine and the like.

  Examples of the compound having a hydroxyl group suitable for the present invention include a compound having a terminal methylol group, a polyhydric alcohol such as pentaerythritol, and bisphenol / polyphenols.

  Examples of the compound having a carboxyl group suitable for the present invention include aromatic polyvalent carboxylic acids such as pyromellitic acid, trimellitic acid and phthalic acid, and aliphatic polyvalent carboxylic acids such as adipic acid.

  Suitable acid anhydrides for the present invention include pyromellitic acid anhydride and benzophenone tetracarboxylic acid anhydride.

As a method for microencapsulating the above compound having a thermoreactive group, a known method can be applied. For example, as a method for producing microcapsules, a method using coacervation found in U.S. Pat. Nos. 2,800,047 and 2,800,498, British Patent No. 990443, U.S. Pat. No. 3,287,154, Japanese Patent Publication No. 38-19574, 42-446, 42-711, a method by an interfacial polymerization method, U.S. Pat. Nos. 3,418,250 and 3,660,304, a method by precipitation of a polymer, US Pat. No. 3,796,669, a method using an isocyanate polyol wall material, US Pat. No. 3,914,511, a method using an isocyanate wall material, US Pat. Nos. 4,001,140, 4,087,376, 4,089,802 -Formaldehyde found in each specification of No. Or a method using a urea formaldehyde-resorcinol-based wall forming material, a method using a wall material such as melamine-formaldehyde resin or hydroxycellulose, as described in US Pat. No. 4,025,445, JP-B-36-9163, 51-9079 In-situ method by monomer polymerization, as seen in each of the publications of U.S. Pat. No. 9,304,422, spray drying method in U.S. Pat. No. 3,111,407, and U.S. Pat. Nos. 952807 and 967074. However, it is not limited to these.
A water-soluble polymer can be used as a dispersant for stably dispersing the microcapsules in an aqueous medium. Water-soluble polymers include polyvinyl alcohol and modified products thereof, polyacrylic acid amide and derivatives thereof, ethylene / vinyl acetate copolymer, styrene / maleic anhydride copolymer, ethylene / maleic anhydride copolymer, and isobutylene / anhydrous. Mention may be made of maleic acid copolymers, polyvinylpyrrolidone, ethylene / acrylic acid copolymers, vinyl acetate / acrylic acid copolymers, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivatives, arabic gum and sodium alginate. These water-soluble polymers are preferably those that do not react with isocyanate compounds or those that are extremely difficult to react. For example, those having a reactive amino group in the molecular chain, such as gelatin, are made inactive beforehand. It is preferable.

  A preferable microcapsule wall used in the present invention has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, and a mixture thereof, and particularly preferably polyurea and polyurethane. A compound having a thermally reactive group may be introduced into the microcapsule wall.

  In the present invention, a polyfunctional isocyanate compound having two or more isocyanate groups as described in Japanese Patent Application No. 2004-222932 previously proposed by the applicant of the present application is dissolved in a solvent immiscible with water. This solution is emulsified and dispersed in an aqueous solution containing a hydrophilic polymer having at least one active hydrogen group capable of reacting with an isocyanate group at one end, and then the microcapsule particles for removing the solvent from the oil droplets have improved dirtiness. From the viewpoint of After emulsifying and dispersing in an aqueous solution containing one or more hydrophilic polymers at one end, the microcapsule particles for removing the solvent from the oil droplets can include the reactive compound.

  The average particle size of the microcapsules is preferably 0.01 to 3.0 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.10 to 1.0 μm. Within this range, good resolution and stability over time can be obtained.

  Such microcapsules may be combined with each other by heat or may not be combined. In short, among the microcapsule inclusions, the one that oozes out of the capsule surface or outside the microcapsule at the time of application, or the one that enters the microcapsule wall may cause a chemical reaction by heat. You may react with the added hydrophilic resin or the added low molecular weight compound. Alternatively, two or more types of microcapsules may be reacted with each other by providing functional groups that can thermally react with different functional groups. Therefore, it is preferable for image formation that the microcapsules are fused and united by heat, but it is not essential.

  The amount of the polymer particles and microcapsules added to the image recording layer is preferably 50% by mass or more and more preferably 70 to 98% by mass in terms of solid content in any particle. Within this range, a good image can be formed and good printing durability can be obtained.

  When the microcapsules are contained in the image recording layer of the present invention, a solvent capable of dissolving the inclusion and swelling the wall material can be added to the microcapsule dispersion medium. By such a solvent, diffusion of the encapsulated compound having a thermally reactive group to the outside of the microcapsule is promoted. Such a solvent depends on the microcapsule dispersion medium, the material of the microcapsule wall, the wall thickness, and the inclusion, but can be easily selected from many commercially available solvents. For example, in the case of a water-dispersible microcapsule comprising a crosslinked polyurea or polyurethane wall, alcohols, ethers, acetals, esters, ketones, polyhydric alcohols, amides, amines, fatty acids and the like are preferable.

  Specific compounds include methanol, ethanol, tertiary butanol, n-propanol, tetrahydrofuran, methyl lactate, ethyl lactate, methyl ethyl ketone, propylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, γ-butyl lactone, N, There are N-dimethylformamide, N, N-dimethylacetamide, and the like, but not limited thereto. Two or more of these solvents may be used. A solvent that does not dissolve in the microcapsule dispersion but dissolves when the solvent is mixed can also be used.

  The amount of the solvent added is determined by the combination of materials, but usually 5 to 95% by mass of the coating solution is effective, and a preferable range is 10 to 90% by mass, and a more preferable range is 15 to 85%. % By mass.

<Infrared absorber>
When the hydrophilic film of the present invention is used as a lithographic printing material, an infrared absorber is used in combination in order to form a hydrophobic region with a material that changes from hydrophilic to hydrophobic by heat or light. It is preferable. That is, when a lithographic printing material is produced by forming an image of a lithographic printing material with a laser beam that emits infrared rays of 760 to 1200 nm using a light source, it is usually essential to use an infrared absorber. The infrared absorber has a function of converting absorbed infrared rays into heat. The hydrophobized region is formed by the thermal decomposition of the compound capable of forming the hydrophobized region, the thermal fusion of the polymer particles, and the phase change by the generated heat. The infrared absorber used in the present invention may be any substance that absorbs at a wavelength of 760 to 1200 nm, and various known pigments, dyes or pigments, and metal particles can be used.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.
Examples of preferable dyes include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-60-78787, JP-A-58-173696, 58-181690, JP-A-58-194595, etc., methine dyes, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59- No. 73996, JP-A-60-52940, JP-A-60-63744 and the like, Naphthoquinone dyes described in JP-A-58-112792, etc., British Patent 434,875 And cyanine dyes.

Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, cyanine dyes described in JP-A-59-216146, U.S. Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Another example of a preferable dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formulas (I) and (II).
Other preferred examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferable, and one particularly preferable example is a cyanine dye represented by the following general formula (i).

In formula (i), ^{X 1} represents a hydrogen atom, a halogen _atom, -NPh ^2, X 2 -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom including a hetero atom. 12 hydrocarbon groups are shown. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. Xa ^- the Za described later ^- is defined as for, R ^a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (i) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, a hexagonal salt, in view of the storage stability of the recording layer coating solution. Fluorophosphate ions and aryl sulfonate ions.

Specific examples of cyanine dyes represented by formula (i) that can be suitably used in the present invention include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. Can do.
Further, other particularly preferable examples include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 described above.

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

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

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

  The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. Within this range, good stability of the pigment dispersion in the image recording layer coating solution and good uniformity of the image recording layer can be obtained.

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

The metal particles used in the present invention include transition metal oxides, sulfides of group 2-12 metal elements of the periodic table, and nitrides of group 3-12 metals of the periodic table, 2 of the periodic table. It is a simple substance or an alloy of a metal of ~ 12 group.
Transition metal oxides include oxides such as iron, cobalt, chromium, manganese, nickel, molybdenum, tellurium, niobium, yttrium, zirconium, bismuth, ruthenium, and vanadium. Although there are classification methods that are not necessarily included in the transition metal, oxides of zinc, mercury, cadmium, silver, and copper can also be used in the present invention. Among these, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO, Cr ₂ O ₃ , MnO ₂ , ZrO ₂ , Bi ₂ O ₃ , CuO, CuO ₂ , AgO, PbO, PbO ₂ , VO _x ( x = 1 to 5) are examples of particularly preferred metal oxides. Examples of VO _x include black VO, V ₂ O ₃ , VO ₂ , and brown V ₂ O ₅ .

Preferred inorganic metal oxides include TiO _x (x = 1.0 to 2.0), SiO _x (x = 0.6 to 2.0), and AlO _x (x = 1.0 to 2.0). Can be mentioned. TiO _x (x = 1.0 to 2.0) includes black TiO, black-purple Ti ₂ O ₃ , and TiO ₂ that exhibits various colors depending on crystal forms and impurities. The _{SiO x (x = 0.6~2.0),} SiO, Si 3 O 2, purple by colorless or coexisting substances, blue include SiO ₂ showing the color such as red. Further, AlO _x (x = 1.5) includes corundum that is colorless or colored in red, blue, green, etc. by coexisting substances.

  When the metal oxide is a low-order oxide of a polyvalent metal, it may be a photothermal conversion agent and a self-heating type air oxidation reaction substance. In that case, the heat energy generated as a result of the self-exothermic reaction can be used in addition to the light-absorbed energy, which is preferable. Examples of the low-order oxides of these polyvalent metals include low-order oxides such as Fe, Co, and Ni. Specific examples include ferrous oxide, triiron tetroxide, titanium monoxide, stannous oxide, and chromium oxide. Of these, ferrous oxide, triiron tetroxide, and titanium monoxide are preferable.

  Whether a self-exothermic reaction occurs can be easily confirmed by a differential thermobalance (TG / DTA). When a self-exothermic reactant is inserted into the differential thermobalance and the temperature is increased at a constant rate, an exothermic peak appears at a certain temperature, and an exothermic reaction occurs. When an oxidation reaction of a metal or a low-order metal oxide is used as a self-exothermic reaction, an exothermic peak appears and an increase in weight is also observed in the thermobalance. Again, by using self-heating reaction energy in addition to the light-heat conversion mechanism, more heat energy per unit radiation dose than before can be used continuously and for that purpose. Sensitivity can be improved.

  When the photothermal conversion fine particles are made of a metal sulfide, a preferred metal sulfide is a heavy metal sulfide such as a transition metal. Among them, preferable sulfides include sulfides of iron, cobalt, chromium, manganese, nickel, molybdenum, tellurium, strontium, tin, copper, silver, lead, and cadmium, and in particular, silver sulfide, ferrous sulfide, and cobalt sulfide. Is preferred.

When the photothermal conversion fine particles are made of a metal nitride, a preferred metal nitride is a metal azide compound. In particular, azides of copper, silver and tin are preferred. These azide compounds are also self-heating compounds that generate heat by photolysis. Other preferable inorganic metal nitrides include TiN _x (x = 1.0 to 2.0), SiN _x (x = 1.0 to 2.0), AlN _x (x = 1.0 to 2.0). ). Examples of TiN _x (x = 1.0 to 2.0) include bronze TiN and brown TiN _x (x = 1.3). Examples of SiN _x (x = 1.0 to 2.0) include Si ₂ N ₃ , SiN, and Si ₃ N ₄ . AlN _x (x = 1.0 to 2.0) includes AlN.

  Each of the above metal oxides, sulfides and nitrides can be obtained by a known production method. Many of them are also marketed under names such as titanium black, iron black, molybdenum red, emerald green, cadmium red, cobalt blue, bitumen, and ultramarine.

  The particle size of these hydrophilic metal compounds varies depending on the refractive index and absorption coefficient of the substance constituting the particles, but is generally 0.005 to 5 μm, preferably 0.01 to 3 μm. If the particle size is too small, light scattering is caused by light scattering, and if the particle size is too coarse, light reflection becomes inefficient due to particle interface reflection.

  Many of the metal particles are light-to-heat convertible and self-heating, and generate heat by light absorption, and supply a larger amount of heat by an exothermic reaction triggered by the heat.

  As particles, Mg, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Fine particles such as In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Pb are included. These metal fine particles are not only heat-convertible but also self-heating. Among these, those that easily cause an exothermic reaction such as an oxidation reaction by thermal energy obtained by photothermal conversion of absorbed light are preferable. Specifically, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ag, In, Sn, and W are preferable. Among them, Fe, Co, Ni, Cr, Ti, and Zr are preferable as those having particularly high absorbance of radiation and large self-exothermic reaction heat energy.

  These metals may be composed of not only single particles but also alloys of two or more components, or particles composed of metals and the above-mentioned metal oxides, nitrides, sulfides and carbides. Good. Although the metal alone has a higher heat energy for self-heating reaction such as oxidation, there are some cases where handling in air is complicated and there is a risk of spontaneous ignition when exposed to air. Such metal powder is preferably covered with a metal oxide, nitride, sulfide, carbide or the like with a thickness of several nm from the surface. The particle diameter of these particles is 10 μm or less, preferably 0.005 to 5 μm, and more preferably 0.01 to 3 μm. When the particle size is 0.01 μm or less, it is difficult to disperse the particles, and when the particle size is 10 μm or more, the resolution of the printed matter is deteriorated.

These infrared absorbers may be added to particles such as microcapsules in the same manner as other components, or may be added to the hydrophilic film, and added to another layer by providing another layer. However, when the hydrophilic film is formed as the image recording layer, the absorbance at the maximum absorption wavelength in the wavelength range of 760 nm to 1200 nm of the image recording layer is 0.3 to 1.2 by the reflection measurement method. Add to be in range. Preferably, it is the range of 0.4-1.1. Within this range, the hydrophobic region is efficiently formed in the image recording layer.
The absorbance of the image recording layer can be adjusted by the amount of infrared absorber added to the image recording layer and the thickness of the image recording layer. The absorbance can be measured by a conventional method. As a measuring method, for example, on a reflective support such as aluminum, an image recording layer having a thickness appropriately determined in a range in which the coating amount after drying is necessary as a lithographic printing plate is formed, and the reflection density is set to the optical density. And a method of measuring with a spectrophotometer by a reflection method using an integrating sphere.
The addition amount with respect to the hydrophilic film (image recording layer) is preferably in the range of 0.5 to 30% by mass, and more preferably in the range of 1 to 15% by mass.

<Colorant>
In the present invention, various compounds other than these may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as an image colorant. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orientated chemistry) Kogyo Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), etc. And dyes described in No. 293247. Also, pigments such as phthalocyanine pigments, azo pigments, carbon black, titanium oxide, etc. can be suitably used.
These colorants are preferably added since it is easy to distinguish an image area from a non-image area after image formation. In addition, the addition amount is a ratio of 0.01 to 10% by mass with respect to the total solid content of the composition for forming a hydrophilic film.

<Bakeout agent>
When the hydrophilic film according to the present invention is used as an image recording layer of a lithographic printing plate, a compound that is discolored by an acid or a radical can be added to produce a printout image. As such a compound, for example, various dyes such as diphenylmethane, triphenylmethane, thiazine, oxazine, xanthene, anthraquinone, iminoquinone, azo, and azomethine are effectively used.

Specific examples include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachide Green, Parafuchsin, Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Kogyo Co., Ltd.], Oil Pink # 312 [Orient Chemical Co., Ltd.], Oil Red 5B [Orient Chemical Co., Ltd.], Oil Scarlet # 308 [Orient Gaku Kogyo Co., Ltd.], Oil Red OG [Orient Chemical Co., Ltd.], Oil Red RR [Orient Chemical Co., Ltd.], Oil Green # 502 [Orient Chemical Co., Ltd.], Spiron Red BEH Special [made by Hodogaya Chemical Co., Ltd.], m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p- Diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-pN, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4- - dyes and p of diethylamino phenyl imino-5-pyrazolone, p ', p "- hexamethyl triamnotriphenylmethane (leuco crystal violet), and a leuco dye such as Pergascript Blue SRB (manufactured by Ciba-Geigy).

  In addition to the above, a leuco dye known as a material for thermal paper or pressure-sensitive paper is also suitable. Specific examples include crystal violet lactone, malachite green lactone, benzoylleucomethylene blue, 2- (N-phenyl-N-methylamino) -6- (Np-tolyl-N-ethyl) amino-fluorane, 2-anilino. -3-methyl-6- (N-ethyl-p-toluidino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) ) -Fluorane, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3 -(N, N-diethylamino) -6-methyl-7-xylidinofluorane, 3- (N, N-diethylamino) -6-methyl-7-chloro Fluorane, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (4-chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-diethylamino) -7,8-benzofluorane, 3- (N, N-dibutyl) Amino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7-xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl- -Methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl- 2-methylindol-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, and the like.

  A suitable addition amount of the dye that changes color by acid or radical is a ratio of 0.01 to 10% by mass with respect to the total solid content of the composition for forming a hydrophilic film.

Thus, a lithographic printing plate precursor can be obtained by incorporating a material that changes from hydrophilic to hydrophobic upon application of energy to the hydrophilic film of the present invention.
In image writing, energy is applied imagewise by heat and / or light, etc., so that only the energy application region of the material that changes from hydrophilic to hydrophobic changes to hydrophobic, and the image area of the ink receiving property. In general, an image is formed by heat. Specifically, direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, infrared lamp exposure, and the like are used, but a semiconductor that emits infrared light having a wavelength of 700 to 1200 nm. Exposure by a solid high-power infrared laser such as a laser or a YAG laser is suitable.

An image-exposed lithographic printing plate becomes an image area in which the exposed area is a hydrophobic ink-receiving area, and the unexposed area becomes a non-image area that is dampening water-accepting. It can be installed in a printing press and printed in the normal procedure using ink and fountain solution.
Here, in order to clarify the difference between the hydrophilic region and the hydrophobic region and to improve the durability of the hydrophilic region, it is also a preferable aspect to perform energy application such as post-heating treatment. The post-heating treatment is preferably performed at 80 to 200 ° C. for 15 seconds to 10 minutes by a non-contact heating means such as a panel heater or a Wisconsin oven. Specifically, the method etc. which heat-process at 100-160 degreeC for 1 to 8 minutes with a panel heater etc. are mentioned, for example.

In addition, as described in Japanese Patent No. 2938398, the lithographic printing plate precursor according to the present invention is mounted on a printing machine cylinder, exposed to a laser mounted on the printing machine, and then dampening water and / or Alternatively, on-press development can be performed with ink.
The lithographic printing plate precursor of the present invention thus obtained can be printed by supplying ink and fountain solution as it is without undergoing any development processing after image exposure, and has a hydrophilic property constituting a non-image part. Since the hydrophilic property of the light-sensitive region and its durability are excellent, it is possible to obtain a large number of high-quality printed materials that are free from stains in the non-image area.

<Inkjet recording method and inkjet recording apparatus>
A lithographic printing plate to which an inkjet recording method is applied as another lithographic printing plate preparation method for obtaining a lithographic printing plate by forming a hydrophobic region on a lithographic printing material obtained by forming the hydrophilic film of the present invention on a support. Can be mentioned.
That is, the hydrophobic film is directly applied to the hydrophilic film by the ink jet recording method without containing a material that changes from hydrophilic to hydrophobic by applying energy to the hydrophilic film of the present invention. Is formed into a lithographic printing plate having a hydrophilic / hydrophobic region.
Hereinafter, an ink jet recording method and an ink jet recording apparatus that can be suitably employed in the method of preparing a lithographic printing plate according to the present invention will be described.

  As an ink composition used in the ink jet recording method, a so-called solid ink mainly composed of wax, which is liquid when ink is ejected and is immediately cured on a recording medium, a polymerizable monomer, a polymerization initiator, and a coloring material. And an ink composition that cures on the surface without penetrating the recording medium, such as a UV curable ink that is polymerized and cured by ultraviolet irradiation after the ink has adhered to the recording medium.

In the ink jet recording method, it is preferable that the ink composition is heated to 40 to 80 ° C. to lower the viscosity of the ink composition to 7 to 30 mPa · s and then ejected. Stability can be achieved. In general, radiation curable ink compositions generally have a higher viscosity than aqueous inks, so that the viscosity fluctuation range due to temperature fluctuations during printing is large.
This viscosity variation of the ink composition directly affects the droplet size and droplet ejection speed as it is, which causes image quality deterioration. Therefore, it is necessary to keep the ink composition temperature as constant as possible during printing. is there. The control range of the ink composition temperature is preferably set temperature ± 5 ° C., more preferably set temperature ± 2 ° C., and further preferably set temperature ± 1 ° C.
One characteristic of the ink jet recording apparatus is that it includes a means for stabilizing the temperature of the ink composition, and all the piping systems and members from the ink tank to the nozzle ejection surface are targeted for the constant temperature.
The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping site and perform heating control according to the ink composition flow rate and the environmental temperature.
Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature of the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

Next, radiation conditions will be described. The basic irradiation method is disclosed in JP-A-60-132767. Specifically, a light source is provided on both sides of the head unit, and the head and the light source are scanned by a shuttle method. Irradiation is performed after a certain period of time after ink landing.
Further, the curing is completed by another light source that is not driven. In WO99 / 54415, as an irradiation method, a method using an optical fiber or a method in which a collimated light source is applied to a mirror surface provided on the side surface of the head unit to irradiate the recording unit with UV light is disclosed. In the present invention, these irradiation methods can be used.
In the present invention, the ink composition is heated to a constant temperature, and the time from landing to irradiation is desirably 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, and more preferably Preferably, radiation is applied after 0.01 to 0.15 seconds. Thus, by controlling the time from landing to irradiation to an extremely short time, it is possible to prevent the landing ink from bleeding before curing. In addition, since the ink composition can be exposed to a porous recording medium before it penetrates deeper than the light source reaches, residual unreacted monomer can be suppressed, and as a result, odor can be reduced. Can do.

According to the method for preparing a lithographic printing plate of the present invention, a lithographic printing plate can be easily obtained by forming a hydrophobic region on the surface of the lithographic printing material of the present invention according to the resolution of the ink jet recording apparatus. That is, the lithographic printing plate obtained by the production method of the present invention can be printed by supplying ink and dampening water as it is without any development processing.
Since the lithographic printing material of the present invention has an excellent hydrophilic surface, the lithographic printing plate in which a hydrophobic region is formed with a hydrophobic material such as a solid ink or an ultraviolet curable ink has a hydrophilicity in a non-image area. It is possible to obtain a large number of high-quality printed materials that are excellent in durability and have no stain on non-image areas.

<Anti-fouling member>
Since the hydrophilic film of the present invention has high hydrophilicity and its durability, it can be suitably used for an antifouling member that prevents oily dirt from adhering to the surface of the member. That is, by providing the hydrophilic film of the present invention on the surface of the substrate that requires surface antifouling property, due to its high surface hydrophilicity, oily dirt, for example, fingerprints attached by human use, Dirt such as sebum, sweat, cosmetics, etc., or oily dirt in factories and cooking facilities is difficult to adhere to the surface, or even if it adheres, it can be easily removed by wiping or washing with water.
As a general application example of such an antifouling member, use on the surface of an optical member such as an antireflection film, an optical filter, an optical lens, an eyeglass lens, a mirror, and the like can be given.

There is no restriction | limiting in the base material used for an antifouling member here, What kind of material can be used if the hydrophilic film | membrane of this invention is formed.
For example, when used for an optical member in particular, a transparent base material is preferable, and the material thereof is glass, a metal oxide such as titanium oxide or ITO (Indium Tin Oxide); a metal such as magnesium fluoride or calcium fluoride. Inorganic base materials such as glass plates provided with inorganic compound layers formed of halides, etc., polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins, or polystyrene Visible light transmissive plastics such as polyvinyl chloride, polyimide, polyvinyl alcohol, ethylene vinyl alcohol, acrylic resins, cellulose resins such as triacetyl cellulose, diacetyl cellulose, cellophane, etc. Transparent plastic plate or the like having the same inorganic compound layer can be suitably used.
The base material applicable to the antifouling member is described in detail in paragraphs [0029] to [0036] of JP-A-2003-206472 previously proposed by the applicant of the present application. It can be used as a substrate for forming the hydrophilic membrane of the invention.

  Applicable applications include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors, spectacle lenses, optical lenses, camera lenses, endoscope lenses, lighting lenses, Lenses for semiconductors, lenses for photocopiers; prisms, cathode ray tubes, etc., and applications other than optical components include window glass for buildings and monitoring towers; automobiles, railway vehicles, aircraft, ships, submersibles, snow Cars, ropeway gondola, amusement park gondola, spacecraft vehicle windows; automobiles, rail vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, motorcycles, ropeway gondola, amusement park gondola, Windshields for spacecraft vehicles; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet seal De, glass frozen food display cases; cover glass measuring instruments, and the like films for attached to the article surface and the like.

When applying the antifouling member to a base material that does not require transparency, in addition to the above transparent base material, for example, metal, ceramics, wood, stone, cement, concrete, fiber, fabric, those Combinations, laminates thereof and the like can be suitably used.
Applicable applications include building materials, building exteriors, building interiors, window frames, window glass, structural members, exterior and painting of vehicles, exteriors of machinery and equipment, dust covers and coatings, traffic signs, various display devices, advertisements Tower, road noise barrier, railway noise barrier, bridge, guardrail exterior and paint, tunnel interior and paint, insulator, solar battery cover, solar water heater heat collection cover, plastic house, vehicle lighting cover, housing equipment , Toilets, bathtubs, washstands, lighting fixtures, lighting covers, kitchenware, tableware, dishwashers, tableware dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, and films to be applied to the surfaces of the articles, household Examples include housings, parts, exteriors, and coatings for electrical products, housings, parts, exteriors, and paintings for OA equipment products, and films for application to the surface of the article. .

<Anti-fogging member>
Since the hydrophilic film of the present invention has high hydrophilicity and its durability, it can be suitably used for an antifogging member that prevents adhesion of water droplets due to condensation on the surface of the member. That is, the surface having high hydrophilicity due to the hydrophilic film diffuses quickly without forming water droplets on the surface even when water vapor in the atmosphere is condensed due to the influence of temperature and humidity. , Surface fogging can be suppressed.
Therefore, it can be suitably used on the surface of an optical member such as an antireflection film, an optical filter, an optical lens, a spectacle lens, or a mirror, or the surface of a window glass or vehicle glass that requires visibility.
The base materials applicable to the antifogging member are the same as those mentioned above for the antifouling member, and the uses are also the same. In the aspect mentioned as the use of the antifouling member, the present invention can be suitably used for a member that requires not only the adhesion of oily dirt but also prevention of condensation due to high hydrophilicity.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.
<Example 1>
[Production of hydrophilic film]
The following components were uniformly mixed and hydrolyzed by stirring for 2 hours at room temperature to obtain a sol-like hydrophilic film coating liquid composition 1.
(Hydrophilic film coating composition 1)
・ (A) Carrageenan 12g
・ (B) Tetramethoxysilane [Crosslinking component] 30g
・ Ethanol 250g
・ 750g of water
・ Nitric acid aqueous solution (1N) 10g

The hydrophilic film coating solution composition 1 was applied to an aluminum support obtained by the method described below so that the coating amount after drying was 1.0 g / m ^2, and dried by heating at 100 ° C. for 10 minutes. Thus, a hydrophilic film was formed on the support.

[Evaluation of hydrophilicity]
The obtained hydrophilic membrane surface was rubbed 100 times with a non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.) wetted with water, and the contact angle before and after that (contact angle of water droplets in the air) was manufactured by Kyowa Interface Science Co., Ltd., CA- Measured using Z. After rubbing, the surface of the member was observed, but even after rubbing, the hydrophilic film on the surface was not peeled off or scratches that could be visually confirmed were observed, and the hydrophilic film of Example 1 was resistant to wear. It was found to have sufficient strength.
The contact angle was 8.6 ° before rubbing and 8.1 ° after rubbing. Sufficient hydrophilicity was exhibited even after rubbing, and it was confirmed that the hydrophilic film of Example 1 of the present invention had good wear resistance.

<Example 2>
[Production of hydrophilic film]
The following components were mixed uniformly, followed by hydrolysis at room temperature for 2 hours to obtain a sol-like hydrophilic film coating liquid composition 2.
(Hydrophilic film coating composition 2)
・ (A) Carboxymethylcellulose 12g
・ (B) Tetramethoxysilane [Crosslinking component] 30g
・ (C-1) 4 g of the following hydrophilic polymer
・ Ethanol 250g
・ 750g of water
・ Nitric acid aqueous solution (1N) 10g

A hydrophilic film was formed on a support in the same manner as in Example 1 except that the hydrophilic film coating liquid composition 1 used in Example 1 was replaced with the hydrophilic film coating liquid composition 2. Evaluated. As a result, it was found that the hydrophilic film of Example 2 also has sufficient strength against abrasion.
The contact angle was 7.8 ° before rubbing and 7.6 ° after rubbing. Even after rubbing, sufficient hydrophilicity was exhibited, and it was confirmed that the hydrophilic film of Example 2 also had good wear resistance.
<Examples 3 to 6>
[Preparation of lithographic printing plate precursor]
(1) Preparation of support <aluminum plate>
Al: 99.5% by mass or more, Fe: 0.30% by mass, Si: 0.10% by mass, Ti: 0.02% by mass, Cu: 0.013% by mass, the balance being JIS of inevitable impurities The molten A1050 aluminum alloy was subjected to a cleaning treatment and cast. As the cleaning treatment, degassing treatment was performed to remove unnecessary gas such as hydrogen in the molten metal, and further ceramic tube filter treatment was performed. The casting method was a DC casting method. The surface of the ingot having a thickness of 500 mm was chamfered by 10 mm, and homogenized at 550 ° C. for 10 hours so that the intermetallic compound would not become coarse. Subsequently, it was hot-rolled at 400 ° C., subjected to intermediate annealing at 500 ° C. for 60 seconds in a continuous annealing furnace, and then cold-rolled to obtain an aluminum rolled plate having a thickness of 0.30 mm. By controlling the roughness of the rolling roll, to control the center line average roughness R _a after cold rolling to 0.2 [mu] m. Then, it applied to the tension leveler in order to improve planarity. The obtained aluminum plate was subjected to the following surface treatment.

First, in order to remove the rolling oil on the surface of the aluminum plate, a degreasing treatment is performed at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, and then, at 30 ° C. for 30 seconds using a 30 mass% nitric acid aqueous solution. Then, neutralization and smut removal treatment were performed.
Next, a surface roughening treatment was performed in order to improve the adhesion between the image recording layer and the support and to provide water retention to the non-image area. Specifically, a current density of 20 A is passed through an aqueous solution (liquid temperature: 45 ° C.) containing 1% by mass of nitric acid and 0.5% by mass of aluminum nitrate supplied to the indirect power supply cell through a web of an aluminum plate. Electrolytic surface roughening treatment was performed by electrolysis so that the amount of electricity when the aluminum plate was an anode was 240 C / dm ² with an alternating waveform of / dm ² and a duty ratio of 1: 1.
Further, an etching treatment was performed at 35 ° C. for 30 seconds using a 10 mass% sodium hydroxide aqueous solution, and then neutralization and smut removal treatment were performed at 50 ° C. for 30 seconds using a 30 mass% sulfuric acid aqueous solution.

Thereafter, an anodizing treatment was performed to improve wear resistance, chemical resistance and water retention. Specifically, electrolysis is performed with a direct current having a current density of 14 A / dm ² while passing through a web of an aluminum plate through a 20% by mass sulfuric acid aqueous solution (liquid temperature: 35 ° C.) supplied to the indirect power feeding cell. An anodized film of 0.5 g / m ² was prepared.
Then, in order to ensure the hydrophilic property of a non-image part, the silicate process was performed for 15 second at 70 degreeC using the 1.5 mass% No. 3 sodium silicate aqueous solution. The adhesion amount of Si was 10 mg / m ² . Then, it washed with water and the support body was obtained. Center line average roughness _{R a} of the support obtained was 0.25 [mu] m.

(2) Formation of image recording layer An image recording layer coating solution 3 having the following composition was bar-coated on the support, followed by oven drying at 140 ° C. for 2 minutes, and an image having a dry coating amount of 0.9 g / m ² . A recording layer was formed to prepare a lithographic printing plate precursor.

(Image recording layer coating solution 3)
-(A) Specific hydrophilic compound (compound described in Table 1) 1.0 g
・ (B) Tetraethoxysilane 1.4g
・ Water 90g
・ Methanol 25g
・ Microcapsule (described in Table 1 (1) or (2)) (in terms of solid content) 1.6 g
・ Surfactant (diethylhexyl sulfosuccinate sodium salt) 0.01g
・ 1N hydrochloric acid 10g

(Synthesis of microcapsule (1))
As oil phase components, trimethylolpropane and xylene diisocyanate adduct (Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., SR444) 3.15 g, 0.35 g of the following infrared absorbent (1), 1 g of 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane (ODB manufactured by Yamamoto Kasei), the following polymerization initiator (1) 0. 75 g and 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) were dissolved in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by mass aqueous solution of carboxylic acid-modified polyvinyl alcohol (KL-506, manufactured by Kuraray Co., Ltd.) was prepared. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 40 ° C. for 3 hours. The microcapsule liquid (1) thus obtained was diluted with distilled water so that the solid content concentration became 20% by mass. The average particle size was 0.4 μm.

(Synthesis of microcapsule (2))
[Synthesis example of hydrophilic polymer (1) having one or more active hydrogen groups that react with isocyanate groups at one end]
Acrylamide: 50 g, 2-mercaptoethylamine hydrochloride: 5 g dissolved in ethanol: 100 g, heated to 60 ° C. in a nitrogen atmosphere, thermal polymerization initiator 2,2-azobisisobutylnitrile (AIBN): 0.5 g In addition, it reacted for 6 hours. After the reaction, the white precipitate was filtered and thoroughly washed with methanol to obtain 48 g of a hydrophilic polymer (1) of terminal amine hydrochloride. (Molecular weight 2.2 × 10 ³ ).

(Production example 1 of microcapsule particles)
As oil phase components, trimethylolpropane and xylene diisocyanate adduct (Mitsui Takeda Chemical Co., Ltd., Takenate D-110N) 10 g, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd., SR444) 4.5 g, 1.5 g of the following infrared absorber (1), 0.5 g of 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane (ODB manufactured by Yamamoto Kasei Co., Ltd.), the following polymerization initiator (1) 0.75 g and 0.1 g of Pionein A-41C (manufactured by Takemoto Yushi Co., Ltd.) were dissolved in 17 g of ethyl acetate. As an aqueous phase component, 33 g of water was prepared by adding 1.5 g of the hydrophilic polymer (1) prepared in Synthesis Example 1 and 0.7 g of a 1N sodium hydroxide aqueous solution. The oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12000 rpm using a homogenizer. The obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 60 ° C. for 2 hours. The microcapsule solution thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass. Microcapsules (2) having an average particle size of 0.3 μm were prepared.

<Example 7>
[Preparation of lithographic printing plate precursor]
A lithographic printing plate precursor of Example 7 was prepared in the same manner except that the image recording layer coating solution 3 used in Examples 3 to 6 was replaced with the following image recording layer coating solution.

(Image recording layer coating solution 4)
・ (A) Carboxymethylcellulose 0.8g
・ (B) Tetraethoxysilane 1.4g
-(C-1) Specific hydrophilic polymer (compound used in Example 2) 0.2 g
・ Water 90g
・ Methanol 25g
・ Microcapsule (1) (solid content conversion) 1.8g
・ Surfactant (diethylhexyl sulfosuccinate sodium salt) 0.01g
・ 1N hydrochloric acid 10g

<Comparative Example 1>
The lithographic printing plate of Comparative Example 1 was prepared in the same manner as in Example 3 except that poly (hydroxymethyl methacrylate) was used instead of (A) the specific hydrophilic compound in the image recording layer coating solution 3 used in Example 3. An original plate was prepared.

(3) Exposure and printing The obtained planographic printing plate precursors of Examples 3 to 7 and Comparative Example 1 were output by a Creo Trendsetter 3244VX equipped with a water-cooled 40 W infrared semiconductor laser, output 9 W, outer drum rotation speed 210 rpm, resolution 2400 dpi. The exposure was performed under the following conditions. The exposure image includes a thin line chart. The obtained exposed original plate was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg without developing. Dampening water (EU-3 (etch solution manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G (N) black ink (Dainippon Ink & Chemicals, Inc.) After supplying dampening water, 500 sheets were printed at a printing speed of 6000 sheets per hour. Thereafter, the ink was once deposited on the plate surface, and dampening water was supplied to measure the number of sheets where the ink disappeared from the plate surface and no scumming occurred in the non-image area of the printed material. Thereafter, printing was performed until scumming occurred.

<Example 8>
[Preparation and printing of planographic printing plate using inkjet recording method]
The same aluminum substrate as used in Examples 3 to 7 was used as a support, and the following hydrophilic film coating solution composition 5 was coated thereon so that the coating amount after drying was 0.7 g / m ^2. The film was dried by heating at 130 ° C. for 4 minutes to form a hydrophilic film on the support to obtain a lithographic printing material.
(Hydrophilic film coating composition 5)
・ (A) Carboxymethylcellulose 11.5g
・ (B) Tetramethoxysilane 30g
・ (C-1) 4.5 g of the following specified hydrophilic polymer
・ Ethanol 250g
・ Water 850g
・ Nitric acid aqueous solution (1N) 10g

An image portion (hydrophobic ink receiving area) is formed on the hydrophilic support using an ink jet printer (manufactured by Epson Corporation, PM-9000) and solid ink jet black ink mainly composed of wax, and lithographic printing is performed. A plate was made.
The obtained lithographic printing plate was attached to a cylinder of a printing machine SOR-M manufactured by Heidelberg. Dampening solution (EU-3 (Etch solution manufactured by Fuji Photo Film Co., Ltd.) / Water / isopropyl alcohol = 1/89/10 (volume ratio)) and TRANS-G (N) black ink (Dainippon Ink and Chemicals, Inc.) After the fountain solution was supplied, 500 sheets were printed at a printing speed of 6000 sheets per hour. Thereafter, the ink was once adhered to the plate surface, and dampening water was supplied to measure the number of sheets where the ink disappeared from the plate surface and no scumming occurred on the non-image portion of the printed matter.
<Comparative Example 2>
A lithographic printing plate of Comparative Example 2 was prepared in the same manner as in Example 8 except that the carboxymethyl cellulose in the hydrophilic film coating solution composition 5 used in Example 8 was changed to polyvinyl alcohol, and the same printing was performed.

[Evaluation of planographic printing plates]
In the printing of the planographic printing plates of Examples 2 to 8 and Comparative Examples 1 and 2, the background stain and the ink removal were evaluated as follows. The results are shown in Table 2 below.
(1) Soil stain At the time of starting printing 500 sheets, the ink adhesion amount in the non-image area on the printed matter was visually evaluated. The state in which no ink was adhered and the background was not soiled was indicated as “◯”, and the state where ink was adhered even a little was designated as “X”.
(2) Ink wiping Printing was performed by the method described above, and the number of ink wiping was measured. The hydrophilic layer with superior hydrophilicity has a smaller number of inks.

  As is apparent from Table 2, the lithographic printing plate produced using the hydrophilic film of the present invention uses a lithographic printing material comprising a material that changes from hydrophilic to hydrophobic by applying energy to the hydrophilic film. Examples 2 to 7 were both excellent in the hydrophilicity and durability of the non-image area, using the lithographic printing material that does not contain the compound in the hydrophilic film, and forming the image area by the inkjet recording method. It was found that there was no scumming and excellent ink repellency.

<Examples 9 to 13>
[Production of surface hydrophilic member]
Using the following hydrophilic coating liquid composition B-1 to hydrophilic coating liquid composition B-5, sol-like hydrophilic film coating liquid B-1 to hydrophilic film coating liquid B-5 are prepared as follows. Then, it is applied to a glass plate (made by Endo Kagaku) as a base material so that the coating amount after drying is 2 g / m ² and dried by heating at 100 ° C. for 10 minutes to form a hydrophilic film on the base material. And the surface hydrophilic member of Examples 9-13 was obtained.

The following components (Hydrophilic film coating liquid composition B-1) to (Hydrophilic film coating liquid composition B-5) are uniformly mixed, and stirred at room temperature for 2 hours for hydrolysis to give a sol-like hydrophilic The hydrophilic film coating liquid B-1 to hydrophilic film coating liquid B-5 were obtained.
(Hydrophilic film coating liquid composition B-1)
・ (A) Carboxymethylcellulose 12g
・ (B) Tetramethoxysilane [Crosslinking component] 30g
・ (C-1) 4 g of the following hydrophilic polymer
・ Ethanol 250g
・ 750g of water
・ Nitric acid aqueous solution (1N) 10g

(Hydrophilic film coating liquid composition B-2)
・ (A) Carrageenan 15g
・ (B) Tetramethoxysilane [Crosslinking component] 31g
・ Ethanol 250g
・ 750g of water
-Hydrochloric acid (1N) 10g

(Hydrophilic film coating liquid composition B-3)
・ (A) Alginate 12g
・ (B) Tetramethoxytitanium [crosslinking component] 30g
・ (C-1) 4 g of the following hydrophilic polymer
・ Ethanol 250g
・ 750g of water
-Hydrochloric acid (1N) 10g

(Hydrophilic film coating liquid composition B-4)
・ (A) Carboxymethylcellulose 12g
・ (B) Tetraethoxyzirconium [Crosslinking component] 30g
・ (C-1) 4 g of the following hydrophilic polymer
・ Ethanol 250g
・ 750g of water
-Hydrochloric acid (1N) 10g

(Hydrophilic film coating liquid composition B-5)
・ (A) Carboxymethylcellulose 12g
・ (B) Tetraethoxysilane [Crosslinking component] 30g
・ (C-1) 4 g of the following hydrophilic polymer
・ Ethanol 250g
・ 750g of water
・ Titanium acetylacetonate 1g

<Comparative Example 3>
In the said hydrophilic film | membrane coating liquid composition B-1, it replaced with (A) carboxymethylcellulose and obtained the hydrophilic film | membrane coating liquid B-6 similarly except having used the equivalent amount of polyvinyl alcohol, and using it. A hydrophilic film was formed, and the surface hydrophilic member of Comparative Example 3 was obtained.

[Evaluation of surface hydrophilic member]
[Evaluation of friction resistance]
The hydrophilic member surfaces of Examples 9 to 13 and Comparative Example 3 thus obtained were rubbed 100 times with a non-woven fabric (BEMCOT, manufactured by Asahi Chemical Fiber Co., Ltd.), and the contact angle before and after that (aerial water droplet contact angle) was determined as Kyowa Interface Science. Measurement was performed using a DropMaster 500 manufactured by Co., Ltd., and evaluation was performed according to the following criteria. The results are shown in Table 3 below. As the following evaluation criteria, it is evaluated that the smaller the change in the contact angle before and after rubbing, the better the durability without lowering the hydrophilicity.
○: Change in contact angle before and after rubbing is 1 °
Δ: greater than 1 ° and less than 2 ° ×: greater than 2 °

[Evaluation of anti-fogging property]
The hydrophilic member obtained above was exposed to water vapor for 1 minute in the daytime under an indoor fluorescent lamp, separated from the water vapor, and then placed in an environment of 25 ° C. and RH 10%. The degree of fogging and its change under a fluorescent lamp were sensory evaluated in three stages according to the following criteria. The results are shown in Table 3 below.
○: No cloudiness is observed Δ: Cloudy, but recovers within 10 seconds, no cloudiness is observed ×: Cloudy, no cloudiness is recovered even after 10 seconds

[Evaluation of antifouling properties]
A line was written on the surface of the hydrophilic member obtained above with oil-based ink (an oil-based marker manufactured by Mitsubishi Pencil Co., Ltd.), and water was poured on, and sensory evaluation was performed in three stages. The results are shown in Table 3 below.
○: Ink can be taken within 1 minute. Δ: Ink can be taken after 1 minute. ×: Ink cannot be removed even if it is performed over 2 minutes for 10 minutes.

  As is apparent from Table 3, the surface hydrophilic member having a hydrophilic film formed using the hydrophilic composition of the present invention on the substrate surface is excellent in antifouling property and antifogging property, and the friction resistance of the hydrophilic film. The property was good. For this reason, it turns out that it is useful as an antifouling member and an antifogging member. On the other hand, the hydrophilic member of Comparative Example 3 having a hydrophilic film that did not use the specific hydrophilic compound according to the present invention was insufficient in antifouling property and antifogging property, and had a practically problematic level. .

Claims (9)

  (A) a compound having two or more ring structures selected from a 5-membered ring structure and a 6-membered ring structure in the molecule, and the ring structure has a hydrophilic group; and (B) Si, Ti, A hydrophilic film obtained by curing a film made of a composition containing an alkoxide compound containing an element selected from Zr and Al with heat and / or light. The hydrophilic film according to claim 1, wherein the hydrophilic film is formed by hydrolysis or polycondensation of a compound contained in the composition. The hydrophilic film according to claim 1, wherein the composition further contains (C) a hydrophilic polymer. The hydrophilic film according to any one of claims 1 to 3, wherein the (C) hydrophilic polymer is a compound having a structure represented by at least the following general formula (1).

The hydrophilic polymer having the structure represented by the general formula (1) is a silane coupling group represented by the structural unit (iii) at the terminal of the polymer unit represented by the structural units (i) and (ii). Have
In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m is 0, 1 or 2 X and y represent the composition ratio when x + y = 100, and x: y represents a range of 100: 0 to 1:99. L ¹ , L ² and L ³ each independently represents a single bond or an organic linking group, and Y ¹ and Y ² each independently represent —N (R ⁷ ) (R ⁸ ), —OH, —NHCOR ⁷ and —COR. ⁷ , —CO ₂ M or —SO ₃ M, wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and M represents a hydrogen atom, an alkali metal, or an alkaline earth. Represents a similar metal or onium.
And R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 8 or less carbon atoms. The hydrophilic film according to any one of claims 1 to 4, wherein the hydrophilic film contains a material that changes from hydrophilic to hydrophobic by energy application. A lithographic printing material having the hydrophilic film according to any one of claims 1 to 5 on a support. Applying a hydrophobic material to the lithographic printing material having the hydrophilic film according to any one of claims 1 to 5 on a support by an inkjet recording method to form an ink receiving region. A method for producing a lithographic printing plate as a feature. An antifouling member having the hydrophilic film according to any one of claims 1 to 4 on a substrate. The anti-fogging member which has a hydrophilic film of any one of Claims 1 thru | or 4 on a board | substrate.