JP2001315452A - Lithographic printing original film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-mode type lithographic printing original film, which necessitates, no development treatment, from which a die can be easily made, the die making from which is possible under the state directly being installed on a printing machine, which is excellent in recognizabilty between an image part and a non-image part and the printing scumming on a printing surface of which excellent in plate wear and inking properties is small. SOLUTION: In this lithographic printing original film, at least 2 kinds of fine particle polymers, the particle sizes of which are different from each other, are included in a hydrophilic resin polymer formed on a support by three- dimensional cross-linking.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing original plate which does not require development and has excellent printing durability. More specifically, a lithographic plate that can make a plate by heat mode image recording, and can also record an image by scanning exposure based on a digital signal, and that can be mounted on a printing machine without development to make a plate and print. It relates to an original plate for printing.

[0002]

2. Description of the Related Art In general, a lithographic printing plate comprises an oleophilic image area for receiving ink during a printing process and a hydrophilic non-image area for receiving fountain solution. As such a lithographic printing plate precursor, a PS plate in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used.

On the other hand, with the widespread use of digitization techniques for electronically processing, storing, and outputting image information using a computer, various new image output methods corresponding to such digitization techniques have become practical. It is becoming. Along with this, a computer that carries digitized image information in high-convergent radiation such as laser light, scans and exposes the original plate with this light, and directly manufactures a printing plate without passing through a lith film. Attention has been focused on to-plate technology. Therefore, obtaining an original plate for a printing plate adapted to this purpose is an important technical problem.

Recently, since high-power solid-state lasers such as a semiconductor laser and a YAG laser have become available at a low cost, a plate-making method of a scanning exposure system using these lasers as image recording means has been developed. It is promising as a printing plate manufacturing method that can be easily incorporated into chemical technology. In the conventional plate-making method, image recording is performed by applying imagewise exposure of the photosensitive original plate at low to medium illuminance and changing the image-like physical properties of the original plate surface by a photochemical reaction. In the method using density exposure, a large amount of light energy is intensively irradiated onto an exposure area during an instantaneous exposure time, the light energy is efficiently converted into heat energy, and the heat causes chemical change, phase change, A thermal change such as a change in form or structure is caused, and the change is used for image recording. That is, image information is input by light energy such as laser light, while image recording is recorded by a reaction by heat energy. Usually, a recording method utilizing heat generated by such high power density exposure is called heat mode recording, and converting light energy into heat energy is called photothermal conversion.

A major advantage of the plate making method using the heat mode recording means is that the plate making method is insensitive to light having a normal illuminance level such as indoor lighting, and that an image recorded by high illuminance exposure does not necessarily require fixing. . That is, if a heat mode photosensitive material is used for image recording, it is safe against room light before exposure, and image fixation is not essential after exposure. Therefore, if heat mode recording is used, it is expected that it is possible to obtain a lithographic printing plate precursor that can be easily developed in the computer-to-plate system.

[0006] As one of the preferred methods for producing a lithographic printing plate based on heat mode recording, a hydrophobic image recording layer is provided on a hydrophilic substrate, and is subjected to heat mode exposure in the form of an image. A method has been proposed in which the dispersibility is changed and the non-image portion is removed by wet development as needed. As an example of such an original plate, for example, Japanese Patent Publication No. 46-279
JP-A No. 19 discloses an original plate in which a recording layer having a so-called positive action in which solubility is improved by heat, specifically a recording layer having a specific composition such as a saccharide or a melamine formaldehyde resin, is provided on a hydrophilic support. A method of obtaining a printing plate by recording in a heat mode is disclosed. The disclosed simple plate making technology of heat mode recording, including this disclosed technology, generally has insufficient sensitivity to heat mode scanning exposure because of insufficient heat sensitivity. The hydrophobic / hydrophilic discrimination of the parts, that is, the discriminability was small, and these were practical restrictions. If discrimination is poor, it is practically difficult to make an on-press development plate.

As a means for solving the problem, a method of scattering and removing the image layer of the irradiated portion by the action of heat by irradiating a high-power laser beam (called ablation) is also described in, for example, WO98 / 40212 and WO98 / 347.
No. 96 and JP-A-6-199064, a multilayer structure layer having a hydrophilic layer containing a transition metal oxide colloid as an upper layer and a lipophilic image recording layer as a lower layer is provided on a substrate without developing. A lithographic printing plate which can be used for plate making is disclosed. Although this method certainly has a high discriminability between the irradiated area and the non-irradiated area where heat scattering is completely performed, dirt on the apparatus due to scattered objects, dirt on the printing surface impairs the operation and print quality of the apparatus, Often, the heat of the irradiating light does not reach the deep part of the image recording layer, and there is a phenomenon that the bottom of the image layer close to the support remains without being scattered. Lower.

For this reason, a simple plate-making method utilizing a change in the degree of hydrophilicity / hydrophobicity of the surface due to heat, that is, a change in polarity, without relying on ablation even in image formation by light irradiation in a heat mode, has been proposed. It is disclosed as a method without disadvantages. For example, a method in which a polymer such as a hydrophobic wax or a polymer latex is added to a hydrophilic layer, and the surface is phase-separated by heat to hydrophobize the hydrophilic layer is disclosed in Japanese Patent Publication No. Sho.
No. 22957, JP-A-58-199153, US Pat.
No. 3,168,864, WO99 / 4974, EP9
No. 25916 proposes one direction of the discriminability improving means. However, these disclosed technologies are desired to be improved due to insufficient discriminability, insufficient heat fusion sensitivity, and lack of hydrophilicity, which may cause print stains. Further, a method of making hydrophobic by monodisperse or hydrophobic polymer particles having a narrow particle size distribution is proposed in Japanese Patent Application Laid-Open No. Hei 10-186646. There is a problem with the nature, and improvement is desired.

[0009]

[0006] Sufficient discrimination between an image portion and a non-image portion is a fundamental important characteristic directly linked to improvement of both printing quality such as printing stains and inking property and printing durability. Therefore, a plate making method having both discriminability and simplicity of plate making work, particularly, high discrimination, sufficient sensitivity, no development processing required, and plate making in a heat mode, printing durability during printing, and inking It is desired to develop a method that is excellent in performance.

Further, according to the study of the present inventors, in the case of image formation utilizing the above-mentioned heat mode light irradiation, in particular, the polarity change by laser light irradiation, if heat diffusion to the support is fast, hydrophobicity is increased. The layer is not formed sufficiently, and when the light irradiation amount is increased to avoid this, undesired phenomena such as contamination of the device and the printing plate due to heat scattering of the image layer occur, and therefore, image formation can be performed with less energy. To improve discrimination and enlarge the latitude,
At the same time, improvements in printing durability and inking properties are desired.

An object of the present invention is to improve the performance by solving the above-mentioned defects of the plate making method in the heat mode.
In other words, an object of the present invention is to make plate making easy without requiring a development process, with a high sensitivity and a wide exposure amount latitude, and it is also possible to directly mount a plate on a printing machine and make plate making, and on the printing surface An object of the present invention is to provide a heat-mode type lithographic printing original plate that causes less printing stain. In particular, an object of the present invention is to make a plate easily by a scanning type image exposure method using a laser beam, to be excellent in discrimination between an image part and a non-image part, and to be excellent in printing durability and inking property at the time of printing. To provide a heat-mode type lithographic printing plate.

[0012]

The present inventors have solved the above-mentioned problems by providing a three-dimensionally crosslinked hydrophilic resin layer containing at least two kinds of fine particle polymers having different particle sizes, so that light irradiation can be performed. The inventors have found that it reduces the volume shrinkage that occurs when the particulate polymer undergoes heat fusion due to heat generation, enables uniform film formation, and improves the discrimination between the image area and the non-image area. Was completed. That is, the present invention is as follows.

1. An original plate for lithographic printing, comprising a three-dimensionally crosslinked hydrophilic resin layer on a support, wherein the hydrophilic resin layer contains at least two kinds of fine particle polymers having different particle sizes.

2. 2. The lithographic printing plate according to claim 1, wherein at least one of the fine particle polymers having different particle sizes is a fine particle polymer having a thermoreactive functional group.

3. 3. The lithographic printing plate according to claim 1, wherein the hydrophilic resin layer or a layer adjacent to the hydrophilic resin layer contains a photothermal conversion agent composed of metal fine particles.

The hydrophilic resin layer having a hydrophilic surface of the lithographic printing plate of the present invention preferably contains a light-to-heat conversion agent. The light-to-heat conversion agent can be dispersed in a binder resin and has a light-to-heat conversion function. Metal fine particles are preferred. The metal fine particles have a light-to-heat conversion property, that is, a property of absorbing light energy and converting it into heat energy.

Further, the hydrophilic resin layer contains, together with the photothermal conversion agent, a fine particle polymer that makes the vicinity thereof hydrophobic by the action of heat, which will be described in detail later. Is supplied with heat from the light-to-heat conversion agent to make the vicinity hydrophobic, whereby the inking property of the image portion is improved, the printing quality is further improved, and at the same time the discrimination is further improved. The fine-particle polymer is an organic polymer dispersion described in detail below, may be a single-structured polymer particle, or may be a particle dispersion of a composite composition containing other components, and is particularly preferable. As an embodiment, a dispersion of microcapsule particles may be used. In addition, the second
The inclusion of a heat-reactive functional group in the microcapsule particles in connection with the item is also one of the excellent aspects of the present invention.

In such image recording means, when drawing with high illuminance light such as laser light, the fine particle polymer undergoes thermal melting within a short time to form a uniform phase. Cannot follow the volumetric shrinkage of the particles, resulting in a state in which the particles come off in a particle form, which causes a problem that the film property is deteriorated.
This problem is solved by using at least two types of fine particle polymers having different particle sizes. That is, in the method of the present invention, the porosity in the hydrophilic resin layer can be greatly reduced by allowing the small-sized fine particle polymer to exist in the voids of the large-sized fine particle polymer, and the volume at the time of heat fusion can be reduced. The amount of shrinkage can be reduced, and as a result, formation of a good and uniform fused film without any omission can be realized. In the following description, the `` particle size '' of the fine particle polymer refers to the particle size corresponding to the mode (mode) of the particle size distribution, and the `` particle size differs '' of two or more types of fine particle polymer , Standard deviation width (± 1σ) centered on the mode of the size distribution curve
Means that the mode value of the other particle does not fall within.

As described above, in the light-irradiated portion of the hydrophilic resin layer, the heat-sealed material of the fine particle polymer forms an imagewise hydrophobic region, and the printing quality with excellent discrimination and the excellent printing durability are improved. Realize. In addition, the plate making process using the lithographic printing original plate of the present invention is a simple one that does not require a developing treatment.

This will be further described with reference to the schematic diagram of FIG. FIG. 1 is a schematic diagram showing a process of producing a printing plate using the lithographic printing plate of the present invention. An original printing plate 1 of the present invention shown on the left side of FIG. 1 has a support 2 and a lower layer 3 containing a photothermal conversion agent provided on the support 2, and a polarity conversion accompanying the photothermal conversion applied on the lower layer 3. Metal particles 5 and hydrophilic fine particle polymers 6 and 7 (the sizes of 6 and 7 are different from each other)
And an image recording layer 4 containing The metal fine particles 5 as the photothermal conversion agent in the image recording layer 4 are, for example, metal silver fine particles. In the printing plate 11 shown on the right side of FIG. 1, the fine particle polymer 6 becomes a heat-sealable layer 15 by the irradiation of the laser beam 8 shown by the arrow above the original plate 1 on the left side, and the surface of the irradiated area of the image recording layer becomes hydrophobic. It shows that the active region is formed. Since the drawing of laser light is usually performed in a short time with high illuminance, the thermal effect is strong, and polymer particles, which cannot be said to be a photothermal conversion agent in a general concept, generate heat and melt, and the vicinity thereof becomes hydrophobic. In some cases, the present invention includes such cases as long as the polymer satisfies the above-mentioned conditions.

[0021]

Embodiments of the present invention will be described below in detail. In the present specification, the hydrophilic resin layer containing the photothermal conversion agent and the fine particle polymer may be referred to as “upper layer” or “image recording layer”.

[Image Recording Layer] (Photothermal Conversion Agent) As the photothermal conversion substance to be contained in the image recording layer, metal and metal oxide particles, pigment particles, and dyes are preferable. As the metal and metal oxide particles, A
1, Si, Ti, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Y, Zr, Mo, Ag, Au, Pt, P
Those selected from d, Rh, In, Sn, and W, which can be formed into particles and dispersed in the heat insulating layer resin can be used.
In particular, metal fine particles of iron, silver, platinum, gold, and palladium are preferable. In addition, TiOx (x = 1.0-2.
0), SiOx (x = 0.6 to 2.0), AlOx (x
= 1.0-2.0) and metal azide compounds such as copper, silver and tin azides. Each of the above-mentioned metal oxides, nitrides and sulfides which can be contained in these image forming layers can be obtained by a known production method. Many are commercially available under the names of titanium black, iron black, molybdenum red, emerald green, cadmium red, cobalt blue, dark blue, ultramarine and the like.

In addition to the above-mentioned metal compound and metal particles, non-metal single particles such as carbon black, graphite (graphite) and bone charcoal (bone black) and various organic and inorganic pigments can also be used as photothermal conversion fine particles as image-forming layers. Can be contained. Further, a light-heat converting dye which is not in the form of particles can also be added to the resin layer.

The preferred dye contained in the image recording layer as a photothermal conversion agent exists in the form of solid fine particles, dyed with other components in the image recording layer, or molecularly dispersed in the binder. An IR (infrared) absorber, specifically, a dye selected from a polymethine dye, a cyanine dye, a squarylium dye, a pyrylium dye, a diimmonium dye, a phthalocyanine compound, a triarylmethane dye, and a metal dithiolene. Of these, polymethine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, diimmonium dyes, and phthalocyanine compounds are more preferable. Among them, polymethine dyes, cyanine dyes, and phthalocyanine compounds are most preferable from the viewpoint of synthesis suitability. The above-mentioned dye may be a water-soluble dye having a water-soluble group in the molecule. Preferred water-soluble groups of the dye include a sulfonic acid group, a carboxyl group and a phosphonic acid group. Specific examples of the dye (infrared absorbing agent) used as a photothermal converting agent contained in the image recording layer are shown below, but are not limited thereto.

[0025]

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[0026]

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[0027]

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The content of the photothermal conversion agent contained in the image forming layer is 2 to 50% by mass of the solid constituents. If the amount is less than 2% by mass, the calorific value is insufficient, and the sensitivity is reduced.
Above, the film strength decreases.

(Fine Particle Polymer) As the fine particle polymer, any particles may be used as long as they are mainly composed of an organic substance whose vicinity is made hydrophobic by various known heats. Among them, the surface hydrophilic fine particle polymers shown in the following items (1) and (2) are preferable from the viewpoint of the effect of hydrophobicity and dispersibility in the image recording layer, but the present invention is not limited to these examples. Not something. (1) A particle dispersion having a composite structure in which a core contains a hydrophobic substance and has a surface layer having a hydrophilic surface, and the particle shape is broken and included by the action of heat by light irradiation and photothermal conversion. A fine particle polymer that is made hydrophobic by a hydrophobic substance. (2) A fine particle polymer which is a heat-crosslinkable particle dispersion having a surface hydrophilicity and which exhibits hydrophobicity when a crosslinking reaction is initiated by the action of heat. These will be further described below.

(1) A composite particle dispersion in which a core contains a hydrophobic substance and has a surface layer having a hydrophilic surface. The preferred form of the particles of the particle dispersion having the above-mentioned composite structure is a so-called hetero-aggregated surface layer in which a resin that softens or melts at a temperature caused by heat mode image exposure is included, and a hydrophilic sol particle layer is aggregated and adhered to the surface. Composite particles (hereinafter also referred to as “hetero-aggregated surface layer particles”), composite particles of surface hetero phase (hereinafter referred to as surface hetero phase particles) in which the surface is treated with a sol-gel conversion substance to form a hydrophilic gel surface layer by sol-gel conversion. ), Core-shell type composite particles (hereinafter also referred to as core-shell type particles) in which a hydrophobic fine particle of a polymer obtained by dispersion polymerization is formed as a core and a polymer layer of a hydrophilic polymer is formed around the core. Emulsion particles (hereinafter also referred to as hydrophobic organic substance-containing particles) in which a hydrophobic organic compound is emulsified and dispersed in a hydrophilic medium; Microcapsule particles (hereinafter simply referred to as microcapsules particles) protected with sexual wall materials. (2) Surface hydrophilic, heat-crosslinkable particle dispersion. The latter (2) particle dispersion exhibiting hydrophobicity by the initiation of thermal crosslinking includes a mixed dispersion of a polymerizable monomer, a crosslinking compound and a thermal polymerization initiator.

<Hetero-agglomerated surface layer particles> The hetero-aggregated surface layer particles of the above (1) are obtained by heat-softening or heat-melting obtained by emulsifying and dispersing a monomer, protecting the monomer with a surfactant micelle, and polymerizing. Emulsified polymer dispersion particles of a conductive resin are included,
The resin particles are softened or melted by the effect of heat due to light irradiation and photothermal conversion, breaking the hydrophilic surface layer and rendering the vicinity existing as particles hydrophobic. The hydrophilic surface layer is a protective layer formed by adding a very hydrophilic sol-like fine particle dispersion such as silica fine particles and alumina fine particles and adsorbing the dispersion around the emulsion polymerization dispersion particles of the resin. The sol-like fine particle dispersion is the same as the sol-like fine particles described below as a component to be added to the medium of the hydrophilic image recording layer.

<Surface Heterophase Particles> As described above, the heterosurface phase particles described in the above (1) are obtained by emulsifying the emulsion-polymerized dispersion particles of a heat-softening or hot-melting resin as core particles and treating the surface thereof. These are particles having a hydrophilic surface, which have been treated with a sol-gel converting substance described in the section of the medium of the hydrophilic image recording layer to form a gel phase on the particle surface.

<Core-shell type particles> The above-mentioned core-shell type composite particles are prepared by preparing a particle dispersion of a resin which softens or melts by the action of heat by emulsion polymerization of its monomer, and uses this as a core particle (seed). It is a core-shell type hetero-phase structured particle in which a hydrophilic monomer is added to the dispersion and the surface of the core particle is polymerized with the hydrophilic monomer to form a surface hydrophilic layer. The monomer constituting the core particles is selected from hydrophobic and resin-based ones in the group of A to L shown as the monomer component for the polymer compound described in the following section. Similarly, monomers that form a hydrophilic shell phase are:
It can be selected from the group of hydrophilic monomers A to L.

<Hydrophobic Organic Inclusion Particles> The hydrophobic organic inclusion particles are in the form of particles having a hydrophilic surface in which the encapsulated hydrophobic substance is emulsified and dispersed. The emulsified particles cannot maintain the particle shape due to the action of heat due to heat mode light irradiation, and the vicinity of the polymer particles is made hydrophobic by leaching, diffusing, dissolving, etc. into the medium. Among hydrophobic organic low molecular weight compounds and organic high molecular weight compounds, there are compounds suitable for this purpose.

Organic low molecular weight compound When the fine particle polymer contains an organic low molecular weight compound, a preferable organic low molecular weight compound has a melting point of 300 at normal pressure.
The solubility or water absorption of a solid or liquid organic compound or water having a boiling point of 100 ° C. or lower at 100 ° C. or lower is 2/100 g.
g or less, and it is also a preferable embodiment to use both of them. Since organic low molecular weight compounds have relatively high diffusion permeability, when mobility is given by heat, they are diffused in the vicinity of the presence of particles to make them hydrophobic directly or indirectly. Also included are compounds that are solid at room temperature and melt by heat to form a hydrophobic region. If the mobility is too large, the hydrophobic region is too wide, and the local concentration of heat energy is reduced, thereby reducing the effect of hydrophobicity. Therefore, a compound satisfying the above conditions of the boiling point and the melting point is preferable. Here, the term "low molecular weight compound" is used to mean a compound having a boiling point or a melting point, and such a compound usually has a molecular weight of 2000 or less, and often 1000 or less.

The conditions of the above-mentioned solubility or water absorption are as follows:
These conditions are empirically found as an index that the organic polymer compound is hydrophobic. Under this condition, hydrophobicity in the vicinity of the particles can be expressed by a change in the state of the organic polymer in the vicinity where the particles were present due to the action of heat.

Suitable low molecular weight organic compounds suitable for the purpose of hydrophobization are, in addition to the melting point and boiling point aspects related to the mobility of the above compounds, sufficiently hydrophobic in the vicinity of the particulate polymer by itself. It is necessary to have a very low solubility in water or a high degree of organicity. The conditions were embodied and shown as described above. As described above, the organic low molecular weight compound has a solubility in 100 g of water at 25 ° C. of 2%.
g or less, or the ratio of organic / inorganic in the organic conceptual diagram is at least 0.7 or more.

The organic conceptual diagram is a practical and simple practical scale for indicating the degree of organicity and inorganicity of a compound. The first edition of this year is published on pages 1-31. The reason why the organic compounds in the above range on the organic conceptual diagram have an action of promoting hydrophobicity is unknown, but the compounds in this range are compounds having relatively large organicity, and the vicinity of the composite particles is hydrophobic. To 1 in the organic conceptual diagram
The upper limit is not particularly limited to 00 or more, but is usually 100 to 1200, preferably 100 to 800, and the organic / inorganic ratio is 0.7 to infinity (that is, the inorganic property is 0), preferably Is an organic compound falling within the range of 0.9 to 10.

The organic low molecular weight compounds having a boiling point in this temperature range are, for example, aliphatic and aromatic hydrocarbons, aliphatic and aromatic carboxylic acids, aliphatic and aromatic alcohols, aliphatic and aromatic esters, Aliphatic and aromatic ethers,
It is found in organic amines, organic silicon compounds, and various solvents and plasticizers which are not so effective but can be added to printing inks.

Preferred aliphatic hydrocarbons are those having 8 to 3 carbon atoms.
0, more preferably an aliphatic hydrocarbon having 8 to 20 carbon atoms, and a preferred aromatic hydrocarbon has 6 to 40 carbon atoms.
And more preferably an aromatic hydrocarbon having 6 to 20 carbon atoms. Preferred aliphatic alcohols have 2 to 30 carbon atoms.
Are more preferably aliphatic alcohols having 2 to 18 carbon atoms, and preferred aromatic alcohols are those having 6 to 30 carbon atoms.
And more preferably an aromatic alcohol having 6 to 18 carbon atoms. Preferred aliphatic carboxylic acids have 2 to 24 carbon atoms.
Aliphatic carboxylic acid, more preferably having 2 to 2 carbon atoms
Preferred are aliphatic monocarboxylic acids having 20 and aliphatic polycarboxylic acids having 4 to 12 carbon atoms, and preferred aromatic carboxylic acids are those having 6 to 30 carbon atoms, and more preferably having 6 to 30 carbon atoms.
18 aromatic carboxylic acids. Preferred aliphatic esters have 2 to 30 carbon atoms, more preferably 2 to 1 carbon atoms.
And preferred aromatic esters are those having 8 to 30 carbon atoms, more preferably 8 to 18 carbon atoms.
Is an aromatic carboxylate. Preferred aliphatic ethers are those having 8 to 36 carbon atoms, more preferably 8 carbon atoms.
To 18 aromatic ethers, and preferred aromatic ethers are those having 7 to 30 carbon atoms, more preferably 7 to 1 carbon atoms.
8 aromatic ethers. In addition, carbon number 7-30
And more preferably an aliphatic or aromatic amide having 7 to 18 carbon atoms.

Specific examples include 2,2,4-trimethylpentane (isooctane), n-nonane, n-decane,
Aliphatic hydrocarbons such as n-hexadecane, octadecane, eicosane, methylheptane, 2,2-dimethylhexane and 2-methyloctane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene, naphthalene, anthracene and styrene; dodecyl Monohydric alcohols such as alcohol, octyl alcohol, n-octadecyl alcohol, 2-octanol and lauryl alcohol; polyhydric alcohols such as propylene glycol, triethylene glycol, tetraethylene glycol, glycerin, hexylene glycol, dipropylene glycol; benzyl alcohol , 4-hydroxytoluene, phenethyl alcohol, 1-naphthol, 2-naphthol, catechol, aromatic alcohols such as phenol; acetic acid, propionic acid, butyric acid, Prong acid, acrylic acid, crotonic acid, capric acid, stearic acid, aliphatic monocarboxylic acids such as oleic acid; oxalic acid, succinic acid, adipic acid, maleic acid, polyvalent aliphatic carboxylic acids such as glutaric acid;
Aromatic carboxylic acids such as benzoic acid, 2-methylbenzoic acid and 4-methylbenzoic acid; ethyl acetate, isobutyl acetate,
Aliphatic esters such as n-butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl acrylate, dimethyl oxalate, dimethyl succinate and methyl crotonate; and methyl benzoate and methyl 2-methylbenzoate Aromatic carboxylic esters; organic amines such as imidazole, triethanolamine, diethanolamine, cyclohexylamine, hexamethylenetetramine, triethylenetetramine, aniline, octylamine, aniline, and phenethylamine; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and benzophenone , Methoxybenzene, ethoxybenzene,
Examples include ethers such as methoxytoluene, lauryl methyl ether, and stearyl methyl ether, and amides such as stearyl amide, benzoyl amide, and acetamide. In addition, organic solvents such as ethylene glycol monoethyl ether, cyclohexanone, butyl cellosolve, and cellosolve acetate having a boiling point within the above preferred range can also be used.

Also, oils and fats such as linseed oil, soybean oil, poppy oil, safflower oil, etc., which are components of the printing ink, tributyl phosphate, tricresyl phosphate, dibutyl phthalate,
Plasticizers such as butyl laurate, dioctyl phthalate, and paraffin wax are also included.

Esters of long-chain fatty acids and long-chain monohydric alcohols, ie, waxes, are also hydrophobic, have suitably low melting points, and are melted by heat generated by light irradiation in the vicinity of light-to-heat converting fine particles. It is a preferred low molecular weight organic compound that renders the region hydrophobic. Wax is 50-20
It is preferable to melt at 0 ° C., and examples thereof include carnauba wax, caster wax,
Microcrystalline wax, paraffin wax,
Any of so-called shell wax, palm wax, beeswax and the like can be used. In addition to waxes, low molecular weight polyethylene; solid acids such as oleic acid, stearic acid, and palmitic acid; and fine particle dispersions of metal salts of long chain fatty acids such as silver behenate, calcium stearate, and magnesium palmitate can also be used. it can.

Organic Polymer Compound A preferable organic polymer compound satisfying the above-mentioned conditions of solubility or water absorption is a hydrophobic polymer compound which is soluble in coexisting low molecular organic compounds or is itself a hydrophobic polymer.
Polyvinyl chloride, polyvinyl acetate, polyvinyl phenol, polyvinyl halogenated phenol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyamide, polyurethane, polyurea, polyimide, polycarbonate, epoxy resin, phenol, volak, or resole phenols and aldehydes or ketones , Polyvinylidene chloride, polystyrene, acrylic copolymer resin and the like.

One of the preferable compounds is a phenol novolak resin or a resole resin which is a slightly poor organic low molecular weight compound condensate, and is preferably phenol, cresol (m-cresol, p-cresol, m / p mixed cresol). ), Phenol / cresol (m-cresol,
p-cresol, m / p mixed cresol), phenol-modified xylene, tert-butylphenol, octylphenol, resorcinol, pyrogallol, catechol, chlorophenol (m-Cl or p-Cl), bromophenol (m-Br, p-Br) ), Novolak resins and resole resins obtained by condensing salicylic acid, phloroglucinol and the like with formaldehyde, and condensed resins of the above phenolic compounds and acetone.

As other suitable high molecular compounds, there can be mentioned copolymers having a molecular weight of usually from 10,000 to 200,000, having the following structural units as monomers (A) to (L). (A) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, for example, N- (4
-Hydroxyphenyl) acrylamide or N- (4
-Hydroxyphenyl) methacrylamide, o-, m-
And p-hydroxystyrene, o-, m- and p-
Hydroxyphenyl acrylate or methacrylate and the like. (B) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (C) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, (Substituted) acrylates such as 4-hydroxybutyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate. (D) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, (Substituted) methacrylates such as 4-hydroxybutyl methacrylate, glycidyl methacrylate and N-dimethylaminoethyl methacrylate.

(E) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
Acrylamides such as -phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide Or methacrylamides.

(F) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as octyl vinyl ether and phenyl vinyl ether. (G) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate. (H) Styrenes such as styrene, methylstyrene and chloromethylstyrene. (I) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone. (J) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(K) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (L) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide , Acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N-
(O-aminosulfonylphenyl) methacrylamide,
N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacryl Methacrylamides such as amides, o-aminosulfonylphenyl acrylate, m-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate; unsaturated sulfonamides such as methacrylic esters such as p-aminosulfonylphenyl methacrylate and 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

These organic high molecular compounds have a weight average molecular weight of 500 to 500,000 and a number average molecular weight of 200 to 500.
It is preferably 60,000.

The fine particle polymer may be composed of only an organic low molecular weight compound or a high molecular weight organic compound, but may contain both an organic low molecular weight compound and a high molecular weight organic compound, and furthermore, have an affinity for both. It may contain a third component for the purpose of enhancing the properties.

In order to make the surface of the fine particle polymer hydrophilic, for example, a surfactant which is hydrophilic and has an adsorptivity to the fine particle polymer is added to form a hydrophilic group interfacial adsorption layer on the particle surface. A method of dispersing, in which case, a method of providing a protective and colloidal hydrophilic and surface-adsorbing polymer film such as gelatin, polyvinyl alcohol, and polyvinylpyrrolidone, and further interposing a surfactant to make the particle surface more hydrophilic. Dispersion method to stabilize,
A method of performing a surface treatment with a substance having a hydrophilic group that reacts with the constituent material of the particles, or the like can be used. The surfactant used for making the fine particle polymer hydrophilic can also be selected from the compounds described later as the surfactant used for the image forming layer and the heat insulating layer.

The total amount of the hydrophobic constituents (core substances) in the above-mentioned fine particles of the hydrophilic polymer is preferably 10 to 95% by weight based on the total amount of the fine particles of the polymer. 80% by weight is preferred. In the case where a low-molecular organic compound and a high-molecular organic compound are used together, the ratio is arbitrary. On the other hand, the components forming the hydrophilic surface layer are different from surfactants, protective colloids, hydrophilic polymer resins, hydrophilic sols, sol-gel conversion components, etc. depending on the form of, but are also distributed in the medium of the image recording layer. In some cases, the amount constituting the surface layer of the fine particle polymer is 5 to 8 with respect to the total amount of the fine particle polymer.
0% by weight, preferably 10 to 50% by weight.

<Microcapsule Particles> Next, as the term of the composite particle dispersion having a hydrophobic substance in the core and having a surface layer having a hydrophilic surface, the heat of the capsules is determined using the constituent materials of the microcapsules described above. The following describes a fine particle polymer whose vicinity is made hydrophobic by breaking. The microcapsules used in the present invention can be prepared by various known methods, and the core substance (the substance contained in the capsule) is the above-mentioned organic low-molecular compound and high-molecular organic compound, and an organic solvent that mixes them. Can be used. That is, it can be prepared by mixing the core substance with an organic solvent or directly emulsifying and dispersing it in an aqueous medium to form a wall film composed of a polymer substance around oily droplets. Specific examples of the polymer substance serving as the wall film of the microcapsule include, for example, polyurethane resin, polyurea resin,
Examples include polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, gelatin, and polyvinyl alcohol. Of these, a particularly preferred wall film is polyurethane resin or polyurethane.
This is a microcapsule having a wall film made of a polyurea resin.

Microcapsules having a wall film made of a polyurethane resin or a polyurethane / polyurea resin are:
A wall material such as a polyvalent isocyanate is used for encapsulation. Specific examples are shown below. For example, as an isocyanate compound, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4- Tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 3,3'-diphenylmethane-4,4'-diisocyanate, xylene-1,
4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-
Diisocyanates such as diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, toluene-2, Triisocyanates such as 4,6-triisocyanate, tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, hexamethylene diisocyanate, etc. Diol as a reactive component to diisocyanate (Butanediol, glycol, diethylene glycol, triethylene glycol), polypropylene glycol, polyols (eg, trimethylolpropane), diamines (eg,
Ethylenediamine or propylenediamine), ureas (eg, urea, ethyleneurea), bisurethane, and the like. Furthermore, adducts of 2,4-tolylene diisocyanate with tremethylolpropane, adducts of xylylene diisocyanate with trimethylolpropane, adducts of tolylene diisocyanate with hexanetriol, which are low molecular weight adducts of both components, etc. But is not limited to the above compounds. Also, two or more kinds can be used in combination as needed. Of these, particularly preferred are those having three or more isocyanate groups in the molecule.

As the capsule wall material, the above-mentioned gelatin, polyurea, polyurethane, polyimide, polyester, polycarbonate, melamine and the like can be used. preferable. In order to impart thermal responsiveness to the capsule wall, the capsule wall may have a glass transition point of room temperature or more and 200 ° C. or less, and particularly preferably in the range of 70 ° C. to 150 ° C.

The glass transition temperature of the capsule wall can be controlled by selecting a polymer type of the capsule wall or adding an appropriate plasticizer. Examples of such an auxiliary include a phenol compound, an alcohol compound, an amide compound, a sulfonamide compound, and the like. Is also good.

For a general method of microencapsulation and materials to be used, see US Pat. No. 3,726,804,
No. 3,796,696, and can be applied to the present invention.

(2) A fine particle polymer containing a polymerizable monomer / crosslinkable compound and forming a hydrophobic polymer / crosslinking structure in the vicinity of particles upon thermal destruction. The fine particle polymer described in the above item (2) has a heat-reactive functional group that does not react at room temperature and initiates a polymerization or cross-linking reaction by the action of heat, and is a polymerizable monomer that makes the vicinity of the fine particle polymer hydrophobic. And a dispersion containing a crosslinkable compound. Examples of such a system include a polymerizable monomer that undergoes a polymerization reaction, particularly a crosslinking reaction, at a high temperature, and a system containing a thermally crosslinkable polymer or oligomer having a crosslinking group and a thermal polymerization initiator. In order to make the surface of the dispersion hydrophilic, the dispersion can be dispersed using the surface hydrophilizing means described above in the section of the hydrophobic fine particle polymer.

As the above-mentioned heat-reactive functional group, an ethylenically unsaturated group (for example, acryloyl group,
A methacryloyl group, a vinyl group, an allyl group, etc.), an isocyanate group for performing an addition reaction or a block thereof and a functional group having an active hydrogen atom as a reaction partner thereof (for example, an amino group, a hydroxyl group, a carboxyl group, etc.), Epoxy group and addition partner amino group, carboxyl group or hydroxyl group for addition reaction, carboxyl group and hydroxyl group or amino group for condensation reaction, acid anhydride and amino group or hydroxyl group for ring opening addition reaction, etc. Can be mentioned. However, a functional group that performs any reaction may be used as long as a chemical bond is formed.

In the present invention, as the fine particle polymer having a thermoreactive functional group used for the hydrophilic resin layer, acryloyl group, methacryloyl group, vinyl group, allyl group,
Examples thereof include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an acid anhydride and those having a group protecting them. The 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 polymerization.

When introduced during polymerization, it is preferable to carry out emulsion polymerization or suspension polymerization of monomers having these functional groups. Specific examples of the monomer having such a functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate,
Block isocyanate with isocyanate ethyl methacrylate or its alcohol, block isocyanate with 2-isocyanate ethyl acrylate or its alcohol, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, Examples include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, bifunctional acrylate, bifunctional methacrylate, and the like. Examples of the monomer having no heat-reactive functional group copolymerizable with these monomers include, for example, styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, and vinyl acetate. The monomer is not limited to these as long as it has no monomer. As the polymer reaction used when the heat-reactive functional group is introduced after the polymerization, for example, WO96-34316
The polymer reaction described in Japanese Patent Application Laid-Open No. H10-260, can be mentioned.

Among the above-mentioned fine particle polymers having a thermoreactive functional group, those in which the fine particle polymers are united by heat are preferable, and those whose surface is hydrophilic and which is dispersed in water are particularly preferable. The contact angle (water droplets in the air) of a film produced by applying only the fine particle polymer and drying at a temperature lower than the coagulation temperature is lower than the contact angle of the film produced by drying at a temperature higher than the coagulation temperature ( (Water droplets in the air). In order to make the surface of the fine particle polymer hydrophilic as described above, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol, or a hydrophilic low-molecular compound may be adsorbed on the surface of the fine particle polymer. However, the present invention is not limited to this.

The solidification temperature of these fine particles of a polymer having a thermoreactive functional group is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher in view of the stability over time. The average particle size of the fine particle polymer is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm, and most preferably 0.1 to 1.0 μm. If the average particle size is too large, the resolution will be poor, and if it is too small, the stability over time will be poor.

The addition amount of the fine particle polymer having a reactive functional group is preferably 50% by weight or more, more preferably 60% by weight or more based on the solid content of the image recording layer.

The microcapsules used in the present invention can contain a compound having a thermoreactive functional group. The compound having a heat-reactive functional group is selected from polymerizable unsaturated groups, hydroxyl groups, carboxyl groups or carboxylate groups or acid anhydrides, amino groups, epoxy groups, and isocyanate groups or blocks thereof. And compounds having at least one functional group.

Compounds having a polymerizable unsaturated group include:
At least one ethylenically unsaturated bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group;
And preferably two or more compounds. Such a compound group is widely known in the industrial field, and in the present invention, these can be used without particular limitation. These are, in chemical form, monomers, prepolymers, ie, dimers, trimers and oligomers, or mixtures thereof, or copolymers thereof.

Examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids and fatty acids. Esters with aliphatic polyhydric alcohols and amides of unsaturated carboxylic acids with aliphatic polyhydric amines. Also,
An addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxide; A dehydration-condensation reaction product with a functional carboxylic acid is also preferably used. Further, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol,
Addition reactants with amines and thiols, and also substituted reactants with unsaturated carboxylic esters or amides having a leaving group such as a halogen group or tosyloxy group, and monofunctional or polyfunctional alcohols, amines and thiols. It is suitable. Another preferred example is a compound in which the above unsaturated carboxylic acid is replaced with unsaturated phosphonic acid or chloromethylstyrene.

Specific examples of the polymerizable compound which is an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate,
3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyloxypropyl) ether, trimethylolethane Triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate,
Examples thereof include sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, and polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloyloxy-2 Hydroxypropoxy) phenyl]
Examples thereof include dimethylmethane and bis- [p- (methacryloyloxyethoxy) phenyl] dimethylmethane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
Examples thereof include 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like can be mentioned. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Maleic esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate,
Sorbitol tetramalate and the like can be mentioned.

Examples of other esters include, for example, JP-B-46-27926, JP-B-51-47334,
Aliphatic alcohol esters described in JP-A-57-196231, JP-A-59-5240 and JP-A-59-196231
Examples thereof include those having an aromatic skeleton described in JP-A-5241 and JP-A-2-226149 and those containing an amino group described in JP-A-1-165613.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples thereof include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide. Examples of other preferred amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

A urethane-based addition-polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable.
JP-A-8-41708 discloses a polyisocyanate compound having two or more isocyanate groups in one molecule and an unsaturated monomer having a hydroxyl group represented by the following formula (I) added to one molecule. Urethane compounds containing at least two polymerizable unsaturated groups are exemplified. General formula (I) CH2 = C (R1) COOCH2CH (R2) OH (where R1 and R2 represent H or CH3)

Also, urethane acrylates described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and JP-B-58-4.
9860, JP-B-56-17654, JP-B-62-
Urethane compounds having an ethylene oxide skeleton described in 39417 and JP-B-62-39418 are also preferable.

Further, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277563, JP-A-63-260909, and JP-A-1-105238 are preferable. It can be mentioned as.

Other preferred examples include polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting a resin with (meth) acrylic acid. In addition, JP-B-46-43946,
Specific unsaturated compounds described in JP-B-1-40337 and JP-A-1-40336 and vinylphosphonic acid-based compounds described in JP-A-2-25493 can also be mentioned as preferable ones. In some cases, compounds containing a perfluoroalkyl group described in JP-A-61-22048 are also preferably used. Furthermore, The Journal of the Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (198
Those introduced as photocurable monomers and oligomers in (4 years) can also be suitably used.

Suitable epoxy compounds include glycerin polyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene diglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, bisphenols and polyphenols or hydrogenated products thereof. And polyglycidyl ether.

Suitable isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate, cyclohexane phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, or alcohols such as alcohols. Alternatively, a compound blocked with an amine can be mentioned.

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

Suitable compounds having a hydroxyl group include compounds having a terminal methylol group, polyhydric alcohols such as pentaerythritol, bisphenol and other polyphenols. Preferred compounds having a carboxyl group include aromatic polycarboxylic acids such as pyromellitic acid, trimellitic acid and phthalic acid, and aliphatic polycarboxylic acids such as adipic acid. Suitable acid anhydrides include pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like.

Suitable copolymers of the ethylenically unsaturated compound include allyl methacrylate copolymers. For example, an allyl methacrylate / methacrylic acid copolymer, an allyl methacrylate / ethyl methacrylate copolymer, an allyl methacrylate / butyl methacrylate copolymer, and the like can be given.

In the image recording layer of the present invention, since a fine particle polymer or a microcapsule having a thermoreactive group is used, a compound for initiating or promoting these reactions may be added as necessary. Examples of the compound that initiates or promotes the reaction include compounds that generate radicals or cations by heat, and include, for example, lophine dimers, trihalomethyl compounds, peroxides, azo compounds, diazonium salts, and diphenyliodonium salts. Onium salts, acylphosphines, imidosulfonates and the like.
These compounds can be added in the range of 1 to 20% by weight of the solid content of the hydrophilic resin layer. Preferably 3 to 10
% By weight. Within this range, a favorable reaction initiation or acceleration effect can be obtained without impairing the on-press developability.

The size of the fine polymer particles contained in the image forming layer varies in the optimum size range depending on the form, but is preferably about 10 μm or less and 0.01 μm or more on a volume average, more preferably 5 to 0.02 μm. It is particularly preferable to adjust the thickness to a range of 3 to 0.05 μm. As a combination of two kinds of fine particle polymer particles having different sizes, the size of the small particles is preferably 50% or less and 1% or more of the size of the large particles, more preferably 40% to 3%, particularly preferably 30%. It is preferably in the range of ５5%. The weight ratio of the small particles to the large particles is preferably in the range of 1: 100 to 10: 1, more preferably 5:95 to 5: 1, particularly preferably 10:90 to 2: 1. Is preferred. Further, at least two or more kinds of fine polymer particles having different sizes may be the same or different.

(Structure of Image Recording Layer) The metal fine particles and the fine particle polymer having a hydrophilic surface as the photothermal conversion agent contained in the image recording layer have been described above. Next, the structure of an image recording layer, that is, a hydrophilic resin layer containing the same will be described. The configuration of the image recording layer of the present invention is a layer configuration in which a fine particle polymer is dispersed in a binder resin, and preferably, a metal particle having photothermal conversion, and a fine particle polymer having a surface hydrophilic are dispersed in a hydrophilic binder resin. It is a layer configuration. By adding a hydrophilic binder resin, the film strength of the image recording layer itself can be improved, and the resin can be cross-linked and cured to give a printing plate that does not require development processing. Especially hydrophilic binder resin,
It is preferably a hydrophilic polymer binder resin or a hydrophilic sol-gel conversion binder resin. Among them, the gel structure of polysiloxane as a binder resin having high hydrophilicity and withstanding the destruction of the image recording layer due to a thermal reaction Sol-gel conversion type binder resins having the property of forming Hereinafter, the hydrophilic binder resin of the image recording layer will be described.

<Sol-Gel Conversion Binder Resin> In the present invention, a particularly preferred binder for the image recording layer is a sol-gel conversion binder resin described below. The sol-gel conversion system preferably applicable to the present invention is a system in which a bonding group derived from a polyvalent element forms a network structure via an oxygen atom, and the polyvalent metal also has an unbonded hydroxyl group or an alkoxy group. It is a polymer having a resin-like structure in which these are mixed, and is in a sol state at a stage where there are many alkoxy groups and hydroxyl groups, and a network-like resin structure is formed as the ether bonding proceeds. Be strong.

Further, in addition to the property that the degree of hydrophilicity of the resin structure changes, the function of modifying the surface of the solid fine particles by binding a part of the hydroxyl groups to the solid fine particles and changing the degree of hydrophilicity is also provided. I have. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that performs sol-gel conversion is aluminum, silicon, titanium, zirconium, or the like,
Although any of these can be used in the present invention, the sol-gel conversion system based on a siloxane bond which is most preferably used will be described below. Sol-gel conversion using aluminum, titanium and zirconium,
The present invention can be implemented by substituting silicon described below with each element.

That is, a system containing a silane compound having at least one silanol group and capable of sol-gel conversion is particularly preferably used.

Hereinafter, a system utilizing the sol-gel conversion will be further described. The inorganic hydrophilic binder resin formed by the sol-gel conversion is preferably a resin having a siloxane bond and a silanol group, and the image recording layer of the lithographic printing plate precursor according to the present invention is preferably a silane having at least one silanol group. A coating solution, which is a sol system containing a compound,
During the lapse of time after the application, the hydrolytic condensation of the silanol groups proceeds to form the structure of the siloxane skeleton, which is formed by the progress of gelation. In addition, the layer formed by the sol-gel conversion may be added with an organic hydrophilic polymer or a cross-linking agent described below for the purpose of improving physical properties such as film strength and flexibility, and improving coatability. It is possible.

The siloxane resin forming a gel structure is represented by the following general formula (I), and the silane compound having at least one silanol group is represented by the following general formula (II). Further, the substance system contained in the image recording layer does not necessarily have to be a silane compound of the general formula (II) alone, and may generally be composed of an oligomer obtained by partially hydrolyzing the silane compound. And its oligomer may be a mixed composition.

[0092]

Embedded image

The siloxane resin represented by the general formula (I) is
It is formed by sol-gel conversion from a dispersion containing at least one silane compound represented by the following general formula (II), and at least one of R ^{01 to} R ^{03 in} the general formula (I) represents a hydroxyl group; Others represent organic residues selected from the symbols R ⁰ and Y in the following general formula (II).

Formula (II) (R ⁰ ) _n Si (Y) _{4-n In} Formula (II), R ⁰ represents a hydroxyl group, a hydrocarbon group or a heterocyclic group. Y is a hydrogen atom, a halogen atom, -O
R ¹ , —OCOR ² , or —N (R ³ ) (R ⁴ ) (R ¹ and R ² each represent a hydrocarbon group; R ³ and R ⁴ may be the same or different; Represents an atom or a hydrocarbon group). n represents 0, 1, 2 or 3.

In general formula (II), the hydrocarbon group or heterocyclic group represented by R ⁰ is, for example, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group, An ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and the like; , A bromine atom), a hydroxy group, a thiol group, a carboxy group, a sulfo group, a cyano group, an epoxy group, an —OR ′ group (R ′ is a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, Octyl, decyl, propenyl, butenyl, hexenyl, octenyl, 2-hydroxyethyl, 3-chloropropyl, 2-cyanoethyl, N, N-dimethyla Minoethyl group, 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.),

A —OCOR ″ group (R ″ has the same meaning as the above R ′), a —COOR ″ group, a —COR ″ group,
N (R ′ ″) (R ″ ″) (R ″ ″ represents the same content as a hydrogen atom or R ′ and may be the same or different), —NHCONHR ″ group, —NHCOOR '' Group,-
Si (R ") ₃ group, -CONHR"'group, -NHCO
R ″ group, and the like. These substituents may be substituted plurally in the alkyl group), a linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (for example,
Vinyl group, propenyl group, butenyl group, pentenyl group,
The group substituted by these groups, such as hexenyl group, octenyl group, decenyl group, dodecenyl group, and the like, include those having the same contents as the group substituted by the alkyl group.) Aralkyl groups which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc .; the group substituted by these groups is the above-mentioned alkyl group Groups having the same contents as the group, and may be substituted plurally),

An optionally substituted alicyclic group having 5 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, 2
-Cyclohexylethyl group, 2-cyclopentylethyl group, norbornyl group, adamantyl group and the like, the group substituted with these groups include those having the same contents as the substituents of the alkyl group, and those substituted with a plurality of And a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (e.g., a phenyl group or a naphthyl group, examples of the substituent include those having the same contents as the group substituted with the alkyl group.
Two or more may be substituted), or a nitrogen atom, an oxygen atom,
A condensable heterocyclic group containing at least one atom selected from sulfur atoms (for example, the heterocyclic ring includes a pyran ring, a furan ring, a thiophene ring, a morpholine ring, a pyrrole ring, a thiazole ring, an oxazole ring , A pyridine ring, a piperidine ring, a pyrrolidone ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a tetrahydrofuran ring, etc., which may contain a substituent. The contents of which may be mentioned, and a plurality may be substituted).

In the general formula (II), -OR ¹ group of Y, -OC
As a substituent of the OR ² group or the —N (R ³ ) (R ⁴ ) group,
For example, the following substituents are represented. —OR ¹ group includes R ¹
Is an aliphatic group having 1 to 10 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, pentyl group, octyl group, nonyl group, decyl group, propenyl group) , Butenyl, heptenyl, hexenyl, octenyl, decenyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2- (methoxyethyloxo) ethyl, 2- (N, N -Diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxapropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chlorocyclohexyl group, methoxycyclohexyl group, benzyl group, Phenethyl group, dimethoxybenzyl group, methylbenzyl group, bromobenzyl It represents a group and the like).

In the —OCOR ² group, R ² is an aliphatic group having the same contents as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group is an aryl group in the aforementioned R). And the same as those exemplified for the group). In the —N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same or different from each other.
10 optionally substituted aliphatic groups (for example, -O
R ¹ has the same contents as R ¹ ). More preferably, the total number of carbon atoms of R ³ and R ⁴ is up to 16. Specific examples of the silane compound represented by the general formula (II) include the following, but are not limited thereto.

Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propylsilane, tetra-t-butoxysilane, tetra-n-butoxysilane, methyltrichlorosilane, methyl Tribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane , Ethyltri-t-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyl Triisopropoxysilane, n-
Propyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltrit -Butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-
Decyltriisopropoxysilane, n-decyltri-t-
Butoxysilane, n-octadecyltrichlorosilane,
n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n
Octadecyltri-t-butoxysilane,

Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldibromosilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane , Triethoxyhydrosilane, tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxy Drosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrisilane Methoxysilane, trifluoropropyltriethoxysilane,

Trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldi Ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-
Methacryloxypropyltri-t-butoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane , Γ-
Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-
Butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

In addition to the silane compound represented by the general formula (II) used for forming the inorganic hydrophilic binder resin of the hydrophilic layer of the present invention, the resin is used in the sol-gel conversion of Ti, Zn, Sn, Zr, Al and the like. Can be used in combination with a metal compound capable of forming a film. As the metal compound used, for example,
Ti (OR ″) ₄ (R ″ is methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.), TiC
l ₄ , Zn (OR ″) ₂ , Zn (CH ₃ COCHCOC
H ₃ ) ₂ , Sn (OR ″) ₄ , Sn (CH ₃ COCHCOC)
H ₃ ) ₄ , Sn (OCOR ″) ₄ , SnCl ₄ , Zr (O
R '') ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , Al (O
R '') ₃ , Al (CH ₃ COCHCOCH ₃ ) _{3 and the} like.

Further, in order to accelerate the hydrolysis and polycondensation reaction of the silane compound represented by the general formula (II), and the metal compound used in combination, it is preferable to use an acidic catalyst or a basic catalyst in combination. As the catalyst, an acid or basic compound used as it is or in a state of being dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst, respectively) is used. The concentration at that time is not particularly limited, but when the concentration is high, hydrolysis,
The polycondensation rate tends to increase. However, when a highly concentrated basic catalyst is used, a precipitate may be formed in the sol solution. Therefore, the concentration of the basic catalyst is preferably 1 N (concentration conversion in an aqueous solution) or less.

The type of the acidic catalyst or the basic catalyst is not particularly limited, but when it is necessary to use a catalyst having a high concentration, a catalyst composed of an element that hardly remains in the catalyst crystal grains after sintering is used. Good. Specifically, examples of the acidic catalyst include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid,
Examples of basic catalysts include carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids in which R of the structural formula represented by RCOOH is substituted with another element or a substituent, sulfonic acids such as benzenesulfonic acid, and the like. Examples include ammoniacal bases and amines such as ethylamine and aniline.

As described above, the image recording layer formed by the sol-gel method is particularly preferable for the lithographic printing plate precursor according to the invention. Further details of the above sol-gel method,
Saio Sakuhana, "Science of Sol-Gel Method", Agne Shofusha Co., Ltd. (published) (1988), Hirashima Tsuyoshi, "Functional Thin Film Fabrication Technology by Latest Sol-Gel Method," Integrated Technology Center (published) (19)
1992) and the like.

<Hydrophilic polymer compound> As the binder resin contained in the image recording layer of the lithographic printing plate precursor according to the present invention, in addition to the above-mentioned sol-gel conversion binder resin, a suitable image recording layer An organic polymer compound having a hydroxyl group that imparts strength and surface hydrophilicity can be used. Specifically, polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone, and vinyl acetate-crotonic acid. Polymer, styrene-maleic acid copolymer, alginic acid and its alkali metal salt, alkaline earth metal salt or ammonium salt, polyacrylic acid, polyacrylate, poly (ethylene oxide), water-soluble urethane resin, water-soluble polyester Water-soluble resins such as resin, polyhydroxyethyl acrylate, polyethylene glycol diacrylate-based polymer, and N-vinyl carboxylic acid amide polymer.

Examples of the waterproofing agent for crosslinking and curing the above-mentioned organic polymer compound having a hydroxyl group include aldehydes such as glyoxal, melamine formaldehyde resin and urea formaldehyde resin, N-methylol urea and N-methylol urea.
-Methylol melamine, methylol compounds such as methylolated polyamide resin, divinyl sulfone and bis (β-
Active vinyl compounds such as hydroxyethylsulfonic acid), epichlorohydrin, polyethylene glycol diglycidyl ether, adducts of polyamide / polyamine / epichlorohydrin, epoxy compounds such as polyamide epichlorohydrin resin, monochloroacetate and thioglycolate Ester compounds, polycarboxylic acids such as polyacrylic acid and methyl vinyl ether / maleic acid copolymer, inorganic cross-linking agents such as boric acid, titanyl sulfate, Cu, Al, Sn, V, and Cr salts, modified polyamide polyimide resin, etc. Is mentioned.
In addition, ammonium chloride, silane coupling agent,
A crosslinking catalyst such as a titanate coupling agent can be used in combination.

(Other Additives to Image Recording Layer) In the image recording layer, the above-mentioned photothermal conversion agent, fine particle polymer,
In addition to the hydrophilic binder resin, improvement of sensitivity, control of the degree of hydrophilicity, improvement of physical strength of the recording layer, improvement of dispersibility of the constituents of the layer, improvement of coating properties, printing suitability Various compounds can be added for the purpose of improving the quality and the convenience of plate making. These additives include, by way of example, the following:

<Hydrophilic sol-like particles> Examples of the inorganic fine particles to be added to the image recording layer include hydrophobic sols such as silica, alumina, magnesium oxide, magnesium carbonate, and calcium alginate. Can also be used for strengthening the film or enhancing the interfacial adhesion by surface roughening. When inorganic fine particles are added to the image recording layer, the content thereof is 1.0 to 70% by mass, preferably 5.0 to 50% by mass of the solid constituent components. At less than 1%, the expected effect is not obtained, and 70% by mass
Above, there is a possibility that the amount of the originally required light-to-heat conversion agent may be restricted. The hydrophilic sol-like particles are not particularly limited, but are preferably silica sol, alumina sol, magnesium oxide, magnesium carbonate, and calcium alginate, which promote hydrophilicity even if they are not light-to-heat converting or strengthen sol-gel films. And so on.
More preferably, it is a silica sol, an alumina sol, a calcium alginate sol or a mixture thereof.

The silica sol has many hydroxyl groups on the surface, and the inside of the sol forms a siloxane bond (—Si—O—Si). Ultrafine silica particles having a particle diameter of 1 to 100 nm,
It is dispersed in water or a polar solvent, and is also called colloidal silica. Specifically, Toshiro Kaga and Ei Hayashi supervised “Applied Technology of High Purity Silica” Volume 3,
Co., Ltd. (1991).

Alumina sol is an alumina hydrate (boehmite) having a colloidal size of 5 to 200 nm.
And an anion (for example, a halogen ion such as a fluorine ion or a chloride ion, or a carboxylate anion such as an acetate ion) in water is dispersed as a stabilizer.

The hydrophilic sol particles have an average particle diameter of 10
The average particle size is preferably from 10 to 40 nm, more preferably from 10 to 40 nm. All of these hydrophilic sol-like particles can be easily obtained as commercial products.

When the particle size of the hydrophilic sol-like particles (also simply referred to as silica particles) is within the above range, both the metal fine particles and the fine particle polymer as the photothermal conversion agent are stably dispersed in the binder resin. When the plate is made by exposing it with laser light or the like to maintain sufficient film strength of the image recording layer, and printed as a printing plate, it is extremely hydrophilic without causing adhesion of printing ink to non-image areas. The effect that becomes. The metal fine particles and silica particles used in the present invention have a weight ratio of 100/0 to 30/70 (metal fine particles or carbon black / silica particles), preferably 100/0 to 40/60. It is a weight ratio. The total amount of the metal fine particles, the fine particle polymer and the hydrophilic sol particles is 2 to 95% by weight, preferably 5 to 85% by weight of the solid component of the image recording layer.
It is.

<Surfactant> In the image recording layer of the lithographic printing plate precursor according to the present invention, in addition to nonionic and anionic surfactants, JP-A-2-195356 may be used in order to enhance stability under printing conditions. Patent application title: Cationic surfactant, fluorinated surfactant, and JP-A-5
An amphoteric surfactant described in JP-A-9-121044 and JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene nonylphenyl. Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, and aliphatic groups having 5 to 24 carbon atoms are ether-bonded to hydroxyl groups at the terminals of polyoxyethylene / polyoxypropylene block copolymers. Complex polyoxyalkylene alkyl ethers, also complex polyoxyalkylene alkyl aryl ethers having alkyl-substituted aryl groups ether-bonded, sorby Emissions monolaurate, sorbitan monostearate, sorbitan tristearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan trioleate,
Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan triolate and the like. Can be

Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N , N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like.

Specific examples of anionic surfactants include alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, alkylnaphthalenesulfonic acids, alkylnaphthalenesulfonic acids or condensation type of naphthalenesulfonic acid and formaldehyde, and those having 9 carbon atoms. To 26-26 aliphatic sulfonic acids, alkylbenzene sulfonic acids, polyoxyethylene-containing sulfuric acid such as lauryl polyoxyethylene sulfate, cetyl polyoxyethylene sulfonic acid, oleyl polyoxyethylene phosphonic acid, and polyoxyethylene-containing phosphoric acid.

Specific examples of the cationic activator include laurylamine acetate, lauryltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride and the like.

In the image recording layer, if necessary, a fluorine-based surfactant may be used within the range of the above-mentioned surfactant. Specifically, a surfactant having a perfluoroalkyl group is preferable, and a carboxylic acid, a sulfonic acid, an anionic surfactant having any of a sulfate ester and a phosphate ester, or an aliphatic amine,
Cationic surfactants such as quaternary ammonium salts, or betaine-type amphoteric surfactants, or nonionic surfactants such as aliphatic esters of polyoxy compounds, polyalkylene oxide condensate, and polyethyleneimine condensate Agents and the like. The proportion of the surfactant in the total solids of the image forming layer is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

[Heat insulation layer] Next, the heat insulation layer will be described. The heat insulating layer provided as a lower layer of the image recording layer,
This layer has a low thermal conductivity and a function of suppressing heat diffusion to the support. Furthermore, the heat insulation layer may contain a photothermal conversion agent, which generates heat by light irradiation and is effective for improving the heat fusion sensitivity. Such a heat insulating layer is made of an organic or inorganic resin. Organic or inorganic resin
It can be selected widely from hydrophilic or hydrophobic ones. For example, as a resin having hydrophobicity, polyethylene, polypropylene, polyester, polyamide, acrylic resin, vinyl chloride resin, pinylidene chloride resin, polyvinyl butyral resin, nitrocellulose, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polystyrene, vinyl chloride resin -Vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-resin vinyl-maleic acid copolymer, vinyl chloride-acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer And the like.

In the present invention, as the hydrophobic resin, a resin composed of an aqueous emulsion can be used. The aqueous emulsion is a hydrophobic polymer suspension aqueous solution in which particles comprising fine polymer particles and, if necessary, a protective agent for stabilizing the dispersion of the particles are dispersed in water. Specific examples of the aqueous emulsion to be used include vinyl polymer latex (polyacrylate, vinyl acetate, ethylene-vinyl acetate, etc.) and conjugated cyan polymer latex (methyl methacrylate).
Butadiene-based, styrene-butadiene-based, aggreonitrile-butadiene-based, chloroprene-based, etc.) and polyurethane resins.

Examples of the hydrophilic resin include polyvinyl alcohol (PVA), modified PVA such as carboxy-modified PVA, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, and alginic acid. Ammonium,
Polyacrylic acid, polyacrylate, polyethylene oxide, water-soluble urethane resin, water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol diacrylate polymer, N-vinyl carboxylic acid amide polymer, casein, gelatin, polyvinyl pyrrolidone, acetic acid And water-soluble resins such as a vinyl-crotonic acid copolymer and a styrene-maleic acid copolymer.

Further, the above hydrophilic resin is cross-linked,
It is preferable to use after curing, and as a crosslinking agent (also referred to as a water-resistant agent), aldehydes such as glyoxal, melamine formaldehyde resin, urea formaldehyde resin, N-methylol urea and N-methylol melamine,
Methylol compounds such as methylolated polyamide resins,
Active vinyl compounds such as divinyl sulfone and bis (β-hydroxyethyl sulfonic acid), epoxy compounds such as epichlorohydrin and polyethylene glycol glycidyl ether, adducts of polyamide / polyamine / epichlorohydrin, polyamide epichlorohydrin resin, and monochloroacetic acid Ester compounds such as esters and thioglycolic acid esters, polycarboxylic acids such as polyacrylic acid and methyl vinyl ether / maleic acid copolymer, boric acid, titanyl sulfate, Cu, A1, Sn, V,
An inorganic crosslinking agent such as a Cr salt, a modified polyamide-polyimide resin, and the like can be given. In addition, ammonium chloride,
A crosslinking catalyst such as a silane coupling agent and a titanate coupling agent can be used in combination.

Further, as the inorganic polymer, an inorganic matrix formed by sol-gel conversion is preferable. A system capable of sol-gel conversion that can be preferably applied to the present invention includes:
The bonding group bonded to the polyvalent element forms a network structure via the oxygen atom, and at the same time, the polyvalent metal has an unbonded hydroxyl group or an alkoxy group, and has a resin-like structure in which these are mixed. It is a molecular body and is in a sol state at a stage where there are many alkoxy groups and hydroxyl groups, and the network-like resin structure becomes strong as the ester bonding proceeds. Further, in addition to the property of changing the degree of hydrophilicity of the resin structure, it also has a function of modifying the surface of the solid fine particles by binding a part of hydroxyl groups to the solid fine particles, thereby changing the degree of hydrophilicity. The polyvalent bonding element of the compound having a hydroxyl group or an alkoxy group that undergoes sol-gel conversion is aluminum, silicon, titanium, zirconium, or the like, and any of them can be used in the present invention. From the viewpoint of the adhesiveness to the image recording layer, a hydrophilic resin is particularly preferable among these resins.

As the light-to-heat converting substance contained in the heat insulating layer, the same substance as the light-to-heat converting agent contained in the above-mentioned image forming layer can be used.

The content of the photothermal conversion agent contained in the heat insulating layer is from 2 to 95% by mass of the solid components. 2% by mass
Below, the calorific value is insufficient and the sensitivity is reduced, and above 95% by mass, the film strength is reduced.

In the heat-insulating layer, in addition to the above-mentioned resin and light-to-heat converting agent, the physical strength of the heat-insulating layer, the dispersibility of the components constituting the layer, the applicability, and the hydrophilicity of the hydrophilic layer are improved. Various objective compounds can be added for reasons such as an improvement in the adhesiveness with the compound. These additives include, by way of example, the following:

<Inorganic Fine Particles> As the inorganic fine particles to be added to the heat insulating layer, the same inorganic fine particles as those added to the above-described image recording layer can be added, and the same effects can be obtained. The content when the inorganic fine particles are added to the heat insulating layer is also in the same range as when it is added to the image recording layer.

<Surfactant> Those described as those which can be added to the image recording layer can also be used for the heat insulating layer. The addition amount is also the same as the range described for the image recording layer.

[Water-soluble protective layer] The water-soluble protective layer is provided because the surface of the lithographic printing plate precursor of the present invention is hydrophilic.
When originals are transported or stored in product form,
Or, in handling before use, prevent hydrophobicity due to the influence of the environmental atmosphere, temperature and humidity, or mechanical scratches or dirt, etc. Therefore, it functions as a surface protective layer of a hydrophilic lithographic printing plate.

FIG. 2 is a schematic diagram showing a cross-sectional configuration of an original plate having a water-soluble layer of the lithographic printing original plate of the present invention and a plate making process using the original plate. In FIG. 2, the numbers indicating the respective constituent members represent the same contents as the numbers used in FIG.
FIG. 1 on the left side of FIG. 2 shows the configuration of the printing original plate, in which a protective layer 16 is provided on a hydrophilic resin layer (image recording layer) 4, but it has been subjected to imagewise light irradiation. In the central process diagram 11 showing the state of the original plate later, in the light irradiation region of the image recording layer, a hydrophobic region 15 in which the metal fine particles 5 and the fine particle polymer 6 are heat-fused occurs, but the protective layer 16 is not changed. Not shown. FIG. 21 on the right side showing the printing stage shows a state in which the protective layer has been lost by the dampening solution. The water-soluble protective layer is dissolved in dampening water at the initial stage of printing and is washed away. Therefore, it is not necessary to take extra trouble to remove the protective layer, and it does not hinder printing. Hereinafter, components contained in the protective layer of the water-soluble layer will be described.

<Water-soluble polymer> The water-soluble polymer contained in the water-soluble layer functions as a binder resin for the water-soluble layer. Examples of the water-soluble polymer include a polymer having sufficient groups such as a hydroxyl group, a carboxyl group, and a basic nitrogen-containing group. Specifically, polyvinyl alcohol (PV
A), modified PVA such as carboxy-modified PVA, gum arabic, polyacrylamide and copolymers thereof, acrylic acid copolymer, vinyl methyl ether / maleic anhydride copolymer, vinyl acetate / maleic anhydride copolymer, styrene / Maleic anhydride copolymer, roasted dextrin, oxygen-decomposed dextrin, enzyme-decomposed etherified dextrin,
Starch and its derivatives, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, cellulose derivatives such as hydroxyethylcellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-
Crotonic acid copolymer, styrene-maleic acid copolymer,
Alginic acid and its alkali metal salts, alkaline earth metal salts or ammonium salts, polyacrylic acid, poly (ethylene oxide), water-soluble urethane resin, water-soluble polyester resin, polyhydroxyethyl acrylate, polyethylene glycol, polypropylene glycol, N-vinyl Carboxamide polymers and the like. Among them, it is preferable to use modified PVA such as polyvinyl alcohol (PVA) and carboxy-modified PVA, gum arabic, polyacrylamide, polyacrylic acid, acrylic acid copolymer, polyvinylpyrrolidone, alginic acid and alkali metal salts thereof.

The content of the water-soluble resin in the coating solution is 3
To 25% by mass is suitable, and a preferable range is 10 to 25% by mass.
% By mass. In the present invention, two or more of the above water-soluble resins may be used in combination.

<Other Components Contained in Protective Layer of Water-Soluble Layer> Various surfactants may be added to the coating solution. Surfactants that can be used include anionic or nonionic surfactants. Examples of the anionic surfactant include aliphatic alcohol sulfates, tartaric acid, malic acid, lactic acid, repric acid, and organic sulfonic acid, and nitric acid, sulfuric acid, and phosphoric acid are useful as mineral acids. At least one of a mineral acid, an organic acid or an inorganic salt;
Species or two or more species may be used in combination. As the surfactant used, those similar to the surfactant used in the above-mentioned image recording layer can be used. The surfactant is preferably used in an amount of 0.01 to 1 per total solid content of the water-soluble layer.
% By mass, and more preferably 0.05 to 0.5% by mass.
It is.

In addition to the above components, if necessary, lower polyhydric alcohols such as glycerin, ethylene glycol and triethylene glycol can be used as wetting agents. The amount of the wetting agent used is suitably from 0.1 to 5.0% by mass in the surface protective layer, and the preferred range is from 0.5 to 3.0%.
The amount is 0% by mass. In addition to the above, a preservative or the like can be added to the coating solution for the surface protective layer of the lithographic printing plate of the present invention. For example, benzoic acid and its derivatives, phenol, formalin, sodium dehydroacetate and the like can be used in 0.1%.
It can be added in the range of 005 to 2.0% by mass. An antifoaming agent can be added to the coating solution. Preferred antifoaming agents include organosilicone compounds, the amount of which is 0.000.
The range of 1 to 0.1% by mass is preferred.

Further, a light-to-heat conversion agent may be added to the water-soluble protective layer. In this case, the sensitivity of heat fusion of the fine particle polymer of the image recording layer by light irradiation is further increased, and thus a preferable result is obtained. As the light-to-heat converting agent, those described above as the light-to-heat converting agent that may be added to the image recording layer can be used in the above-mentioned range of the amount to be added.

[Coating] The above-mentioned image recording layer, heat insulating layer and protective layer are prepared by mixing the respective constituent components and applying a prepared coating solution to a support by using any of the conventionally known coating methods. Coating and drying to form a coating layer. As a method of coating, various known methods can be used, and examples thereof include bar coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. .

In the image recording layer of the lithographic printing plate precursor according to the present invention, a surfactant for improving coating properties, for example, the various surfactants described above can be added. A preferable addition amount as a coating aid is 0.01 to 1% by mass, more preferably 0.1 to 1% by mass, based on the total solid content of the image recording layer.
05 to 0.5% by mass. The coating amount (solid content) of the image recording layer obtained after coating and drying varies depending on the application,
Speaking of general lithographic printing plate precursors, 0.1 to 3
Preferably ^{0g / m 2, 0.3~10g / m} 2 is more preferable.

The coating amount (solid content) of the heat-insulating layer also varies depending on the constitution, but in the case of a general lithographic printing plate precursor,
0.1-10 g / m < ² > is preferable, and 0.3-5 g / m < ² > is more preferable. Protective layer coating amount (solid content) also varies depending on the configuration, As for the original plate for general lithographic printing plate is preferably ^{0.1~5g / m 2, 0.2~3g / m} 2
Is more preferred. The coating is usually performed on a heat insulating layer, an image recording layer,
It is performed in the order of the protective layer.

[Organic sulfur compound treatment] The image recording layer of the lithographic printing plate precursor on which the image recording layer was formed in the above coating step was treated with a carboxyl group, a hydroxyl group, a sulfuric acid group, a sulfonic acid group,
When treated with an organic sulfur compound having both a hydrophilic group such as a sulfine group, a phosphate group, a nitrate group, and a halide group and a metal-adsorbing group that adsorbs to silver halide shown in the description of R ^{1 in} each of the following general formulas, When the photothermal conversion substance containing the sulfur compound in the image recording layer is a metal fine particle, it is adsorbed on the surface thereof, and the hydrophilicity of the image recording layer is improved. Since the metal fine particles in the image-irradiated area form a heat-sealing layer, the effect of the organic sulfur compound is lost, and the metal fine particles are hydrophobic as in the case where the treatment with the organic sulfur compound is not performed. As a result, preferred sulfur compounds having a larger difference between the hydrophilicity of the non-irradiated area and the hydrophobicity of the irradiated area and higher discrimination are represented by the following general formulas (A) to (D).

RSM General Formula (A) RSR General Formula (B) RSSR General Formula (C)

[0143]

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In the above general formulas (A), (B) and (C), M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group.
Represents XnR ¹ . Where X is OH, CO ₂ M, N
A water-soluble group selected from H ₂ , SO ₃ M, SO ₄ M, SO ₂ M, and an amino group, wherein M is as defined above. n is
It is an integer of 1 to 4. R ¹ is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, having 1 to 12, preferably 1 to 8 carbon atoms, which is substituted by a water-soluble group represented by X;
Represents an alkylamino group and a heterocyclic group.

When R ¹ is a heterocyclic group, preferred heterocyclic groups are imidazole, oxazole, thiazole, pyrazole, isothiazole, indazole, triazole, tetrazole, thiadiazole, imidazoline and oxazoline groups. , Thiazoline group,
Examples thereof include azole groups such as a pyrazoline group, an isothiazoline group, an indazoline group, and a thiazolidine group, a pyrazyl group, a piperazyl group, a piperidyl group, a pyridazine group, a pyrrolo group, a pyridyl group, a morpholino group, and a thiazino group. The R ¹ group may have an R ′ group as a substituent, and the R ′ group has the same meaning as the R ¹ group. Also, two R ¹ groups may combine to form a ring. Multiple Rs in the same molecule
^{When one} or R ′ groups are included, the R ¹ groups, the R ′ groups, or the R ¹ and R ′ groups may be the same or different.
Two Rs in the same molecule in the general formulas (B) and (C) may be the same or different from each other as long as the definition of the above R is followed.

In the general formula (D), R ² and R ³ groups are
It is bonded to a thiocarbonyl group and has the same meaning as R. In each of the general formulas, two or more R
If they have groups R ² and R ³ , they can be the same or different. Specific examples of the compounds represented by the general formulas (A) to (D) are shown below.

[0147]

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[0148]

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[0149]

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The treatment with the organic sulfur compound is carried out by immersing the printing plate in a solution containing the organic sulfur compound. The concentration of the organic sulfur compounds of a solution containing an organic sulfur compound may be selected any concentration less than the solubility of the compound, usually 10 ^-5 ~10 ¹ mo1 / L, preferably 10 ^-4 to 10 ⁰ MO1 / L, more preferably 10 ^-3 to 1
Using an aqueous solution of 0 ^-1 mol / L for about 30 seconds to 10 minutes,
The immersion treatment is preferably performed for about 30 seconds to 3 minutes. At this time, the temperature may be room temperature, but may be warm water, and it is preferable to add appropriate stirring to the solution. Water is usually used as a solvent for the solution of the organic sulfur compound, but an aqueous solvent in which an organic solvent miscible with water such as methanol, ethanol, or acetone may be used.

[Support] Next, the support on which the image recording layer is provided will be described. A dimensionally stable plate is used for the support. Examples of the support that can be used in the present invention include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, nickel, stainless steel, etc.), plastic Films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited.

Preferred supports are polyester film, aluminum, or SUS which is not easily corroded on a printing plate.
It is a steel plate, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include:
Silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element.
As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the support used in the present invention is approximately 0.05 mm to
About 0.6 mm, preferably 0.1 mm to 0.4 mm,
Particularly preferably, it is 0.15 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing rolling oil on the surface is performed. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. The chemical method is disclosed in
The method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Japanese Patent No. 31187 is suitable. As an electrochemical surface roughening method, there is a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Also, an electrolytic surface roughening method using a mixed acid as disclosed in JP-A-54-63902 can be used. Among such surface roughening methods, in particular,
A surface roughening method which combines mechanical surface roughening and electrochemical surface roughening as described in JP-A-5-137933 is preferable because the adhesive force of the oil-sensitive image to the support is strong. The surface roughening by the above method is preferably performed in a range such that the center line surface roughness (Ra) of the surface of the aluminum plate is 0.3 to 1.0 μm. The roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide or sodium hydroxide as necessary, and further neutralized, and then, if necessary, anodized to enhance abrasion resistance. Processing is performed.

As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes forming a porous oxide film can be used. Generally, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. Can be The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte. Anodizing treatment conditions vary depending on the electrolyte to be used, and thus cannot be specified unconditionally.
~ 80 wt% solution, liquid temperature 5 ~ 70 ° C, current density 5 ~ 6
0 A / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. The amount of oxide film formed is
1.0 to 5.0 g / m ² , particularly 1.5 to 4.0 g / m ²
It is preferred that The amount of anodized film is 1.0 g / m ²
If the amount is smaller, the printing durability becomes insufficient or the surface is easily scratched.

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

When the heat insulating layer is a resin having hydrophobicity, it is desirable to make the surface of the support hydrophobic. The surface of the support is hydrophobized by applying an undercoating liquid containing, for example, a silane coupling agent or, in some cases, a titanium coupling agent. The silane coupling agent is mainly represented by the general formula (RO) ₃ SiR ′ (R, R ′ is an alkyl group or a substituted alkyl group), and the RO group is hydrolyzed into an OH group to form an OH group and an ether bond with the support surface. Combine
The R 'groups provide a hydrophobic surface for receiving the ink.

Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and γ-glycoxide. There may be mentioned, for example, propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptotrimethoxysilane, γ-ureidopropyltriethoxysilane, N- (β-aminoethyl)-(β-aminopropyl) dimethoxysilane. In order to ensure the adhesion to the image recording layer, the plastic support is subjected to a charging treatment by a known method before coating.

[Plate making method] Next, a plate making method for the lithographic printing plate precursor will be described. The lithographic printing plate precursor may be a solid laser or semiconductor laser that emits infrared light having a wavelength of 760 to 1200 nm, a high-intensity flash light such as a xenon discharge lamp, or a photothermal conversion type exposure such as an infrared lamp exposure.

The writing of an image may be performed by either a surface exposure method or a scanning method. In the former case, an infrared irradiation method,
This is a method of irradiating a short time light of high illuminance of a xenon discharge lamp onto an original plate to generate heat by light-heat conversion. When using a surface exposure light source such as an infrared lamp is preferred exposure amount varies by this illumination, usually, the surface exposure intensity before modulation by printing image is 0.1~10J / cm ²
, And more preferably 0.1 to 1 J / cm ² . When the support is transparent, exposure can be performed through the support from the back side of the support. The exposure time is preferably selected such that the above-mentioned exposure intensity is obtained by irradiation of 0.01 to 1 msec, preferably 0.01 to 0.1 msec.
When the irradiation time is long, it is necessary to increase the exposure intensity due to the competition between the heat energy generation rate and the generated heat energy diffusion rate.

In the latter case, a method is used in which a laser light source containing a large amount of infrared components is used to modulate the laser beam with an image and scan the original plate. Examples of the laser light source include a semiconductor laser, a helium neon laser, a helium cadmium laser, and a YAG laser. Irradiation can be performed with a laser having a laser output of 0.1 to 300 W. When a pulse laser is used, it is preferable to irradiate a laser having a peak output of 1000 W, preferably 2000 W. In this case, the exposure amount is preferably in the range of 0.1 to 10 J / cm ^{2 in} the surface exposure intensity before being modulated with the print image,
More preferably, it is in the range of 0.3 to 1 J / cm ² . When the support is transparent, exposure can be performed through the support from the back side of the support. Further, the image recording is not necessarily performed by laser light, and may be performed by, for example, a high-illuminance xenon discharge lamp, a carbon arc, or a high-pressure mercury lamp. Further, image recording may be performed by applying thermal printing using a thermal head of a thermal printer.

The printing original plate that has been subjected to image exposure can be mounted on a printing machine to perform printing. Alternatively, it is also possible to form a lithographic printing plate on a printing press by mounting an original printing plate on the printing press and performing image-wise scanning exposure using a laser. That is, in the plate making method using the lithographic printing plate precursor of the present invention, a lithographic printing plate can be made without any particular development processing.

[0162]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not construed as being limited by the examples.

Synthesis Examples 1 to 7

<Preparation of Fine Particle Polymer A> Styrene 10
0 g, 200 g of water and 10 g of a surfactant XL-102F (manufactured by Lion Corporation) (4.7% aqueous solution) were placed in a three-necked flask, and the temperature was raised to 80 ° C. while injecting nitrogen. Thereafter, after stirring for about 30 minutes, 1 g of K ₂ S ₂ O ₈ was added, and 80 ° C.
For 6 hours to prepare polystyrene fine particles A having a particle diameter of about 0.1 μm and a dispersion coefficient of 15%.

<Preparation of Fine Particle Polymer B> Styrene 60
g, Saponified Poval (Kuraray Co., Ltd.) 5% aqueous solution 1
0 g and 200 g of water were placed in a three-neck flask and heated to 80 ° C. while injecting nitrogen. Thereafter, AIBN is set to 0.
3 g, suspension polymerization was carried out at 80 ° C. for 6 hours, and polystyrene fine particles B having a particle diameter of about 1.2 μm and a dispersion coefficient of 15% were added.
It was created.

<Preparation of Fine Particle Polymer C> Styrene 70
g, trimethoxysilylpropyl methacrylate 30
g, 200 g of water, and 10 g of a surfactant XL-102F (manufactured by Lion Corporation) (4.7% aqueous solution) were placed in a three-necked flask, and heated to 80 ° C. while injecting nitrogen. Thereafter, after stirring for about 30 minutes, 1 g of K ₂ S ₂ O ₈ was added, and emulsion polymerization was carried out at 80 ° C. for 6 hours to obtain resin particles having a particle size of about 0.1 μm. 30 g of Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) was added to this resin particle dispersion, and silica sol fine particles were heteroaggregated on the surface of the resin particles. The core was a resin, and the shell was dispersed with a silica layer particle size of 0.15 μm. A composite particle having a hetero-aggregated hydrophilic surface layer having a coefficient of 12% was prepared.

<Preparation of fine particle polymer D> Ethyl acetate 1
9.0 parts (hereinafter, all parts by mass), 5.9 parts of isopropyl biphenyl, 5 parts of glycerol laurate, and 2.5 parts of tricresyl phosphate were mixed by heating. As a capsule wall material (also a fine particle polymer at the same time),
Xylylenediisocyanate / trimethylolpropane adduct (75% ethyl acetate solution Takenate D110)
7.6 parts of N (trade name of Takeda Pharmaceutical Co., Ltd.) was further added to this solution and stirred uniformly. Separately, 64 parts of a 6% by mass gelatin (MGP-9066: trade name of Nippi Gelatin Industries) aqueous solution to which 2.0 parts of a 10% by mass aqueous sodium dodecyl sulfonate solution was added was prepared, and emulsified and dispersed by a homogenizer.

After 20 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 40 ° C. with stirring, and an encapsulation reaction was carried out for 3 hours. Thereafter, the temperature of the solution was lowered to 35 ° C., and the ion-exchange resin Amberlite IRA68 (manufactured by Organo) was used.
5 parts, Amberlite IRC50 (Organo) 13
And stirred for an additional hour. Thereafter, the ion exchange resin was filtered to obtain a desired capsule dispersion liquid. The average particle size of the capsule was 0.64 μm, and the dispersion coefficient was 10%.

<Preparation of Fine Particle Polymer E> Glycidyl methacrylate 2.0 g, methyl methacrylate 13.0
g, polyoxyethylene phenol aqueous solution (concentration 9.8)
(× 10 ⁻³ mol / l) 200 ml and add 250 ml
While stirring at rpm, the inside of the system is replaced with nitrogen gas.
After the temperature of the solution was raised to 25 ° C., an aqueous cerium (IV) ammonium salt solution (concentration: 0.984 × 10 ⁻³ mol / l) was used.
Add 10 ml. At this time, an aqueous ammonium nitrate solution (concentration: 58.8 × 10 ⁻³ mol / l) was added, and the pH was adjusted.
Adjust to 1.3-1.4. It was then stirred for 8 hours. The liquid thus obtained has a solid content of 9.5%.
And the average particle size was 0.4 μm. In addition, Snowtex C (Nissan Chemical Co., Ltd.)
30g was added, and silica sol fine particles were hetero-aggregated on the surface of the resin particles to prepare particles having a hetero-aggregated hydrophilic surface layer having a core of resin, a silica layer of 0.5 μm in diameter of a silica layer and a dispersion coefficient of 10%. did.

<Production of Fine Particle Polymer F> 7.5 g of allyl methacrylate and 7.5 g of styrene were polymerized in the same manner. The solid content of the liquid thus obtained was 9.
5%, and the average particle size was 0.4 μm. further,
30 g of Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) was added to the resin particle dispersion, and silica sol fine particles were heteroaggregated on the surface of the resin particles. The core was a resin, the shell was a silica layer having a particle diameter of 0.45 μm, and the dispersion coefficient was Prepared particles having a 10% hetero-aggregated hydrophilic surface layer.

<Preparation of Fine Particle Polymer G> As an oil phase component, 40 g of xylene diisocyanate, 10 g of trimethylolpropane diacrylate, a copolymer of allyl methacrylate and butyl methacrylate (molar ratio 7/3) 1
0 g and 0.1 g of Pionin A41C (manufactured by Takemoto Yushi) were dissolved in 60 g of ethyl acetate. PVA2 as an aqueous phase component
120 g of a 4% aqueous solution 05 (produced by Kuraray) was prepared. The oil phase component and the aqueous phase component were separated using a homogenizer for 100 hours.
Emulsified at 00 rpm. Thereafter, 40 g of water was added, and the mixture was stirred at room temperature for 30 minutes and further at 40 ° C. for 3 hours. The solid content concentration of the microcapsule solution thus obtained is 20%
And the average particle size was 0.5 μm. In addition, Snowtex C (Nissan Chemical Co., Ltd.)
Of silica sol on the surface of the resin particles to form particles having a hetero-aggregated hydrophilic surface layer having a core of resin, a shell of 0.6 μm in diameter of a silica layer, and a dispersion coefficient of 12%. did.

Example 1 <Preparation of Aluminum Support> 0.01% by weight of copper, 0.03% by weight of titanium, 0.3% by weight of iron, and 0.1% by weight of silicon were added to 99.5% by weight of aluminum. A 0.24 mm-thick rolled sheet of JIS 105 aluminum material containing 20% by mass of a 20% by mass aqueous suspension of 400 mesh bamiston (manufactured by Kyoritsu Ceramics) and a rotating nylon brush (6.1)
0-nylon) and the surface is grained,
Washed well with water. Next, after immersing in a 10% by mass aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching,
It was washed with running water. Further, it was neutralized with a 20% by mass aqueous solution of nitric acid and washed with water. The obtained aluminum plate was placed in a 1.0% by mass aqueous nitric acid solution (containing 0.5% by mass of aluminum nitrate) in an anode voltage of 12.7 volts, and the ratio of the amount of electricity at the cathode to the amount of electricity at the anode was 0.9. The electrolytic surface roughening treatment was performed using a current having a rectangular wave alternating waveform under the condition of an anode charge of 160 clones / dm ² . The surface roughness of the obtained substrate was 0.1.
It was 6 μm (Ra indication). Following this processing, 40
It was immersed in a 1% by mass aqueous solution of sodium hydroxide at 30 ° C. for 30 seconds, etched, and washed with water. Next, at 55 ° C, 3
It was immersed in a 0% by mass aqueous sulfuric acid solution for 1 minute. In addition, 3
Anodizing treatment was performed in a 20% by mass aqueous sulfuric acid solution (containing 0.8% by mass of aluminum) at 5 ° C. using a direct current so that the mass of the anodic oxide film became 2.5 g / dm ² .
This was washed with water and dried to prepare a support.

<Preparation of Heat Insulating Layer> A coating solution having the following composition was prepared, and 1.0 g of the coating solution was coated on the anodized aluminum support.
/ M ² thick heat insulating layer was prepared. Butyral resin BM-S (manufactured by Sekisui Chemical Co., Ltd.) 10% MEK solution 59 g Carbon black dispersion (solid content 21%) 13.5 g MEK (methyl ethyl ketone) 62.7 g

<Coating of Image Recording Layer> A water-based coating solution having the following composition was prepared, and coated on the aluminum support by a bar coater so that the dry film mass became 3.0 g / m ^2. Then, it was dried in an oven at 100 ° C. for 10 minutes. The silver colloidal dispersion is a so-called CareyLea
Silver sol of Sausanne M. H. , Fr
anz G .; , Collin G .; B. , J. et al. Coll
oid Interface Science, vo
l. 93, 545 (1983) having an average particle diameter of 20 nm.

(Composition of Image Recording Layer Coating Solution) PVA117 (manufactured by Kuraray Co., Ltd.) 5% aqueous solution 70 g Colloidal silica dispersion 20% aqueous solution 60 g Silver colloid aqueous solution (6% by mass) 86 g Sol gel preparation liquid 28 g Fine polymer A fine particles (20 % By weight aqueous dispersion) 50 g Fine polymer B particles (20% by weight aqueous dispersion) 50 g water 20 g The sol-gel preparation used here has the following composition. (Sol-gel preparation solution: room temperature, aging for 2 hours) Tetraethoxysilane 15.0 g Ethanol 30.0 g 0.1 mol / L nitric acid 4.5 g The contact angle of water droplet on the surface of the obtained printing original plate was measured.
The surface showed extended wetting and was very hydrophilic.

<Image formation> Trendsetter 3244V manufactured by Creo Corporation equipped with a water-cooled 40 W infrared semiconductor laser
FS, output 10.5W, outer drum rotation speed 100r
pm, plate energy 250 mJ / cm ² , resolution 24
Exposure was performed under the condition of 00 dpi, and an image area thermally fused to the exposed portion surface was formed. The contact angle of the water droplet on the surface of the irradiation area of this printing plate was 108 degrees, which changed to a highly hydrophobic surface. Thereafter, plate-making was performed without development processing.

<Printing> RYOBI-3200M
A CD was used, a 1% by volume aqueous solution of EU-3 (manufactured by Fuji Photo Film Co., Ltd.) was used as a dampening solution, and the ink was GEOS.
(N) Ink was used. First, a 30-roll roll-up (run-in operation) was performed with a dampening solution, and then printing was started by supplying ink, and a high-quality printed matter was obtained without stain on 20,000 sheets.

Examples 2 to 8 and Comparative Examples 1 to 5 <Coating and Printing Evaluation of Image Recording Layer> Example 1 was repeated except that the fine particle polymers A and B described in Example 1 were used in combination as shown in Table 1. A lithographic printing plate was prepared in the same manner as described above.
Next, imagewise irradiation by laser exposure and printing evaluation were performed. The results are shown in Table 1.

As described above, a lithographic printing plate provided with a three-dimensionally crosslinked hydrophilic resin layer containing at least two kinds of fine particle polymers having different particle sizes has a high contact angle and sufficient printing durability. Indicated.

[0180]

[Table 1]

Example 9 The procedure of Example 1 was repeated, except that the dye (1) having the following structural formula was added instead of using silver colloid as the photothermal conversion agent.
A lithographic printing plate was produced in the same manner as in Example 1. Next, imagewise irradiation by laser exposure and printing evaluation were performed. The results were the same as in Example 1, and high-quality printed matter was obtained without print stains on 20,000 sheets.

[0182]

Embedded image Dye (1)

Example 10 An aqueous coating solution having the following composition was prepared, and a dry film thickness of 1.0 g / m ² was applied to the hydrophilic image recording layer of the printing plate precursor described in Example 1 with a bar coater. Was coated with an overcoat layer and dried in an oven at 100 ° C. for 5 minutes.

(Composition of Overcoat Layer Coating Solution) Polyacrylic acid (average molecular weight: 20,000) 10% solution 350 g Dye (1) having the above structural formula, (1% by mass aqueous solution) 2.5 g

For image recording, a trend setter 3244 manufactured by Creo Corporation equipped with a water-cooled 40 W infrared semiconductor laser was used.
VFS was used. The irradiation conditions were as follows: output 8.5 W, outer drum rotation speed 100 rpm, plate surface energy 200 m
Exposure was performed under the conditions of J / cm ² and a resolution of 2400 dpi, and an image area that was thermally fused was formed on the exposed surface. In this printing plate, an image was formed with a smaller exposure energy as compared with Example 1, but as in Example 1,
High-quality printed matter was obtained without printing stains on 20,000 sheets.

Example 11 A printing plate was prepared and printed in the same manner as in Example 1 except that the original plate for a printing plate described in Example 1 was used and the following thermal transfer recording was used as an image recording means. Was. For thermal transfer recording, energized at a recording speed of 400 msec / m using a thermal printer in which 150 x 150 micron thermal heads provided with a sialon abrasion protection layer on a Ta-SiO heating resistor were arranged at 250 micron intervals. Recorded. The temperature rise rate of this thermal head reaches 450 ° C. in 20 msec. As in the case of Example 1, the printed matter was free of print stains up to 20,000 sheets, and a high quality printed matter was obtained.

According to the present invention, a three-dimensionally crosslinked hydrophilic resin layer is provided on a support, and the hydrophilic resin layer contains at least two kinds of fine particle polymers having different particle sizes. The lithographic printing plate does not require development processing, the light quantity latitude is wide and the plate can be made easily, and it can be directly mounted on the printing machine to make the plate. Less print stains on the print surface.
In particular, by using a scanning type image exposure method using laser light, plate making can be easily performed based on high sensitivity and a sufficiently wide light amount latitude, and excellent discrimination between the image part and the non-image part is achieved. Excellent.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a typical lithographic printing original plate of the present invention and a plate making process using the same.

FIG. 2 is a schematic view showing a cross-sectional configuration of an original plate having a water-soluble layer of a lithographic printing original plate of the present invention and a plate making process using the original plate.

[Explanation of symbols]

 1. Lithographic printing plate 2. support 3. Heat insulation layer (lower layer) 4. 4. hydrophilic resin layer (image recording layer) Metal silver fine particles 6. 6. Fine particle polymer (small size) 7. Fine particle polymer (large size) Laser light 11. Print version 15. Hydrophobic region by thermal fusion Water-soluble protective layer

Continued on the front page F-term (reference) 2H025 AA12 AB03 AC08 AD01 BC13 BC83 BH03 BJ03 CB51 CC11 CC17 DA36 DA40 FA10 2H096 AA06 BA06 CA20 EA04 EA23 2H114 AA04 AA22 AA23 AA24 BA01 BA10 DA04 DA41 DA43 DA51 DA06 DA75 DA60 DA60 DA06 DA60

Claims (3)

[Claims] A lithographic plate having a three-dimensionally crosslinked hydrophilic resin layer on a support, wherein the hydrophilic resin layer contains at least two kinds of fine particle polymers having different particle sizes. Original plate for printing. 2. The lithographic printing original plate according to claim 1, wherein at least one of the fine particle polymers having different particle sizes is a fine particle polymer having a thermoreactive functional group. 3. The lithographic printing original plate according to claim 1, wherein the hydrophilic resin layer or a layer adjacent to the resin layer contains a photothermal conversion agent composed of metal fine particles.