JP2000258899A - Lithographic printing plate material and method for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lithographic printing plate material having improved printing resistance, dimensional stability and sensitivity by forming an image forming layer which does not substantially require a developing process on a polyethylene naphthalate film or a plastic film containing a fiber. SOLUTION: This lithographic printing plate material 4 consists of a polyethylene naphthalate film or a plastic film 2 containing a fiber, and an image forming layer 3 which does not substantially require a developing process formed on the film. The image forming layer 3 is a hydrophilic image forming layer containing a hydrophilic resin and oleophilic thermoplastic resin particles having the melting point of 90-130 deg.C or the glass transition temp. (Tg) of 50-80 deg.C. The hydrophilic image forming layer is formed by the self film-forming property of the hydrophilic resin. The opposite surface of the supporting body to the image forming layer 3 is fixed through an adhesive layer 5 to the cylinder surface of a printing machine, and printing is carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate material used for producing a lithographic printing plate and a printing method.
More specifically, a lithographic printing plate material having a flexible support capable of forming an ink receptive and ink repellent lithographic surface substantially without treatment with a developer by imagewise radiation or heating and using the same It relates to a printing method (plate printing method).

[0002]

2. Description of the Related Art A lithographic printing plate material capable of obtaining a lithographic printing plate by a simple developing process of developing with a dampening solution on a printing press after image exposure using a flexible support, and a lithographic printing plate manufacturing technique using the same It has been known.

[0003] Japanese Patent Application Laid-Open No. 7-175212 discloses a method in which a support is provided with a layer of a photosensitive composition whose tackiness and / or adhesiveness is changed by actinic light, and the image is formed substantially without using a liquid. A technology for improving the dimensional stability, resolution, and ease of processing of an image to be peeled and developed or transferred under heating and / or pressure by using polyethylene naphthalate as a support of an image forming material for forming an image. It has been disclosed.
However, this technique is a technique relating to peeling development or image transfer under heat and / or pressure, and is not a technique that does not substantially require development processing.

Japanese Patent Application Laid-Open No. 8-314157 discloses an image forming element having a photosensitive layer containing thermoplastic polymer particles which are fused by heat and a photosensitive diazo compound on a hydrophilic support. There is disclosed a method for preparing a lithographic printing plate in which a photosensitive layer in a non-exposed area is removed with fresh water and then heat-treated. However, there is a problem that a lithographic printing plate made with the imaging element lacks printing durability and dimensional stability.

Japanese Patent Application Laid-Open No. 8-62846 discloses a flexible support having a surface that becomes ink-receptive and ink-repellent during an image exposure and, optionally, during a development step, wherein the support is made of polyethylene naphthalenedicarboxy. Lithographic printing plate materials are disclosed as polyesters containing a rate. However, the embodiment is a silver salt DTR, which is not an image recording material that does not substantially require development processing.

[0006] Japanese Patent Application Laid-Open No. Hei 9-12387 discloses thermoplastic polymer particles dispersed on a hydrophilic support and dispersed by a thermal energy, and a compound capable of converting light into heat. A method is disclosed in which an image forming element having an image recording layer to be image-exposed is exposed to light and developed on a printing press with a fountain solution or ink to form a lithographic printing plate. However, there are problems with printing durability and dimensional stability.

JP-A-9-127683 discloses a lithographic printing plate in which a self-water-dispersible thermoplastic resin particle layer which can be made lipophilic by heat is formed on the surface of a hydrophilic substrate, and a lithographic printing plate having a lithographic printing plate. A method is disclosed in which energy is applied to make the particles lipophilic to form a heat-sealed image, and the heat-sealed image is filled with ink using immersion water, transferred to a recording medium, and printed. However, there are problems with printing durability and dimensional stability.

[0008] Japanese Patent No. 2801777 discloses a lithographic printing plate material provided with an ink repellent layer containing specific crystalline metal oxide particles and a conductive layer on an ink receptive substrate. However, there is room for improvement in the sensitivity, which is an important performance of the lithographic printing plate material, and the printing durability of the obtained printing plate.

On the other hand, Japanese Patent Application Laid-Open No. Hei 8-216546 discloses a method of preparing a lithographic printing plate in which a sheet-like support is processed on the back surface of the lithographic printing plate with an adhesive, and the plate is prevented from being stretched by printing. Says the effect. However, although the adhesive layer is in contact with the plate, it is not in direct contact with the printing press cylinder surface because of the support. In the processing procedure, first, a sheet-like support is attached to the back surface of the plate via an adhesive, and then attached to a printing machine. Therefore, the above effects are not sufficiently exhibited.

Japanese Patent Application Laid-Open No. 10-83072 discloses an element containing a lithographic surface or a latent lithographic surface which becomes a lithographic surface upon development on a flexible support, wherein the element is laminated on a dimensional stability base. Discloses a technique for improving the ease of exposure in an image setter and the like. But,
The embodiment is a silver salt DTR, not an image recording material technology that does not substantially require development processing.

Japanese Patent Application Laid-Open No. Hei 10-193828 discloses a lithographic printing plate having a plastic film as a support through a sheet having an average surface roughness of 2 or more for the purpose of preventing image displacement. There is disclosed a printing method which is performed while being fixed to a printer. The pressure-sensitive adhesive layer of the present application is not disclosed, and a noticeable problem does not occur while the plate material size is small, but image displacement becomes a problem when the plate material size is large.

[0012]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems of the prior art, and an object of the present invention is to substantially solve the following problems and to substantially require development processing. An object of the present invention is to provide a lithographic printing plate material that does not have a printing method or a printing method (plate hanging method) using the same.

[0013] A lithographic printing plate material from which a lithographic printing plate having improved printing durability is obtained is provided.

Provided are a lithographic printing plate material capable of obtaining a lithographic printing plate having improved dimensional stability and thereby improved image defects and image deviation, and a printing method using the lithographic printing plate material.

Provided are a lithographic printing plate material capable of obtaining a lithographic printing plate having improved printing durability and dimensional stability, and a printing method using the lithographic printing plate material.

A lithographic printing plate material with improved sensitivity is provided.

[0017]

The constitution of the present invention for achieving the above object of the present invention is as follows (1) to (11). Further, according to the following (1) to (8), the above-mentioned problem and the above objects are achieved, and according to the following (9) to (11), the above-mentioned problems are achieved.

(1) A lithographic printing plate material characterized in that a polyethylene naphthalate film or a plastic film containing fibers is provided with an image forming layer substantially requiring no development treatment.

(2) The image forming layer has a melting point of at least 90 ° C.
30 ° C or less or glass transition temperature (Tg) of 50 ° C or more and 8
A hydrophilic image forming layer containing lipophilic thermoplastic resin particles of 0 ° C. or lower and a hydrophilic resin, wherein the hydrophilic image forming layer is a layer formed by self-forming a hydrophilic resin. The lithographic printing plate material according to the above (1).

(3) The lithographic printing plate material as described in (1) or (2) above is subjected to image exposure, and then mounted on a printing press cylinder for printing without development processing. Printing method.

(4) A lithographic printing plate material having an image forming layer on one side of a plastic support is prepared by fixing the support side opposite to the image forming layer to the cylinder surface of a printing press via an adhesive layer. A printing method, wherein printing is performed.

(5) The printing method according to the above (4), wherein the adhesive layer is in direct contact with the back surface of the lithographic printing plate material support and the cylinder of the printing press.

(6) The printing method according to the above (4), wherein the adhesive layer is provided in advance on the surface of the cylinder of the printing press.

(7) The printing method according to the above (4), wherein the sheet having the adhesive layer on the surface and the lithographic printing plate are mounted in this order on the surface of the cylinder of the printing press.

(8) The printing method according to any one of (4) to (7), wherein the adhesive layer is a silicone rubber layer.

(9) A lithographic printing plate material comprising a support having a light-to-heat conversion layer containing a ferromagnetic metal powder and an ink repellent layer.

(10) A lithographic printing plate material having a light-heat conversion layer and an ink repellent layer on a support, wherein the ink repellent layer contains thermoplastic resin particles. .

(11) After performing image exposure on the lithographic printing plate material as described in (9) or (10) above, printing is performed by supplying printing ink to the plate surface without any development processing. Characteristic printing method.

As described above, JP-A-8-62846 discloses a lithographic printing plate using a polyethylene naphthalate film support.
No. 072 discloses a lithographic printing plate using a plastic film support containing fibers. These all have the effect of dimensional stability when the plate is set on the printing cylinder, and all the embodiments are silver salt DTR type, and the image forming material which does not substantially require development processing is only a liquid development method. Is not disclosed.

Japanese Patent Application Laid-Open No. 7-175212 discloses an image-forming material in which the tackiness and / or the adhesiveness changes upon exposure to a polyethylene naphthalate support and which is not substantially subjected to liquid development. This has an effect of dimensional stability when development processing by peeling development and transfer is performed under heat and pressure. In this technique, liquid development is not performed, but peeling development, development processing by transfer, and heating and pressure processing are performed, which is different from an image forming material that does not substantially require development processing.

As described above, by using a plastic film containing polyethylene naphthalate or fiber as a support of a lithographic printing plate material on which an image is formed by performing liquid development, peeling development or thermal transfer, dimensional stability at the time of setting a printing cylinder is achieved. It is publicly known that there is an effect on the properties, and there is also known an image forming material which does not require a developing treatment. However, there is no description of a combination of both. The features of the inventions according to claims 1 to 8 reside in the above-described combination, which provides a new effect that the effect of preventing dimensional stability, image defects and image shift is unexpectedly large, and that the printing durability is good. It was discovered.

According to a ninth aspect of the present invention, the ferromagnetic metal powder easily causes ablation from the light-to-heat conversion layer, thereby contributing to improvement in sensitivity and printing durability. By incorporating thermoplastic resin particles into the ink, sensitivity and printing durability could be improved.

Hereinafter, the present invention will be described in detail.

The polyethylene naphthalate film used as a support in the lithographic printing plate material of the invention according to claims 1 to 3 is obtained by biaxially stretching a polyethylene naphthalate polymer produced by condensation polymerization of naphthalenedicarboxylic acid and ethylene glycol. This film is manufactured by Teijin Limited under the trade name “Theonex Film”.
Monthly (Vol. 41 No. 6) p. 31 to 36 can be referred to.

The plastic film containing fibers used as a support in the lithographic printing plate material of the invention according to claims 1 to 3 is a film produced from a composite material containing fibers and a resin matrix. The fibers are preferably selected from carbon fibers, borate fibers, silicon carbide fibers, and mixtures thereof, but using other fibers such as natural fibers such as glass fibers, aramid fibers, polyamide fibers and hemp. Is also good. Suitably, the fibers have an average diameter of 3-20 μm. The flexural E-modulus of the fiber is preferably greater than 200 GPa.

The majority of the fibers suitably have a length that extends in the direction of loading from one end of the film to the other, but mixtures of long and short fibers can also be used. In fact, the maximum length of the fibers may be somewhat longer than the length of the film in which the fibers are applied obliquely.

The fibers can make up from 30 to 70% by volume of the composite material, but higher filling rates are possible with fibers of mixed diameter.

The resin is preferably a thermosetting or thermoplastic polymer and a mixture thereof, for example, an epoxy resin, a furan resin, a silicone resin, a polyester resin, a phenol resin, a vinyl ester resin, a polyamide (PA) resin, a polypropylene. (PP) resin, polyethylene resin (PE), polyethylene terephthalate resin (PET)
P), polybutylene terephthalate resin (PBT), and polyphenyl oxide resin (PPO).

The thickness of the polyethylene naphthalate film and the plastic film containing fibers is preferably 20 to 400 μm, more preferably 25 to 300 μm.
m, most preferably in the range of 50 to 250 μm.

In the invention according to the first aspect, the image forming layer which does not substantially require a developing process is a process in which a radiation or heat is applied to the image forming layer in an imagewise manner, and then the image forming layer is developed. A liquid, for example, an image forming layer that becomes a printing plate without requiring development with an aqueous alkali solution. 2. The image forming layer according to claim 1, wherein the image forming layer does not substantially require a developing treatment, for example, a hydrophilic image forming layer containing a lipophilic thermoplastic resin and a hydrophilic resin. A layer formed by a self-forming film of a hydrophilic resin, and a hydrophilic image forming layer containing a cross-linking agent exhibiting lipophilicity by a thermal reaction and a hydrophilic resin, wherein the hydrophilic image forming layer Can be used as a layer formed by self-forming a hydrophilic resin. In the present specification, “by self-forming a hydrophilic resin” means “lipophilic thermoplastic resin (particles) that coexists”
Means that the hydrophilic resin forms a film without contributing to film formation.

As the lipophilic thermoplastic resin, known resins can be used, and waxes, acrylic resins,
Examples include ionomer resins, vinyl acetate resins, vinyl chloride resins, synthetic rubbers, polyurethane resins, polyester resins, fluorine resins, and silicone resins.

In a preferred embodiment of the image forming layer according to the first aspect of the present invention which does not substantially require development processing, the image forming layer has a melting point of 90 ° C. or more and 130 ° C. or less or a glass transition temperature (Tg) of 50 ° C. A hydrophilic image forming layer containing lipophilic thermoplastic resin particles having a temperature in the range of 80 ° C. as described above, wherein the hydrophilic image forming layer is formed by self-forming a hydrophilic resin. In order to bring out the performance as a lithographic printing plate, the melting point of the thermoplastic resin particles must be 90.
℃ 130 ° C or lower or glass transition temperature (Tg) 50
It is preferable that it is 80 to 80 degreeC. Further, the hydrophilic component (H) having a surface energy γ of the thermoplastic resin particles is preferably 5 dyn / cm ² or less. When the melting point is lower than 90 ° C. or the glass transition temperature is lower than 50 ° C., the contamination of the non-image area due to fogging during storage tends to deteriorate, and the melting point is higher than 130 ° C. If the glass transition temperature is lower than 80 ° C., it may be difficult to obtain sensitivity during exposure. In this regard, waxes, acrylic resins, and synthetic rubbers are particularly preferred as the resin forming the lipophilic thermoplastic resin particles.

As waxes, natural waxes such as carnauba wax, beeswax, whale wax, wood wax, jojoba oil, lanolin, ozokerite, paraffin wax, montan waxes, candeline wax, ceresin wax, microcrystalline wax and rice wax. ,
Examples include polyethylene wax, Fischer-Tropsch wax, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, higher fatty acids, and the like.

Examples of the acrylic resin include copolymers containing acrylate and methacrylate as essential components, such as methyl methacrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and styrene. And copolymers of at least one of the above.

Examples of synthetic rubbers include polybutadiene, polyisoprene, polychloroprene, styrene-butadiene copolymer, acrylate-butadiene copolymer, methacrylate-butadiene copolymer, isobutylene-isoprene copolymer, Acrylonitrile
Butadiene copolymer, acrylonitrile-isoprene copolymer and styrene-isoprene copolymer are exemplified.

Examples of the crosslinking agent which exhibits lipophilicity by a thermal reaction include those which exhibit lipophilicity by self-crosslinking or by crosslinking with a hydrophilic resin forming a hydrophilic image forming layer. Specifically, for example, melamine-formaldehyde resins, urea-formaldehyde resins, amino resins such as methylolated melamine, U.S. Pat. No. 3,325,28
No. 7, 3,288,775, 3,549,377
And dichlorotriazine compounds described in Belgian Patent No. 6,602,226 and the like; US Pat.
No. 392,024, an aziridine compound described in U.S. Pat. No. 3,549,378, an ethyleneimine compound, a resin having a carboxyl group or a copolymer of maleic anhydride, formaldehyde, glyoxal, U.S. Pat. Nos. 291,624 and 3,232,764,
French Patent 1,543,694, British Patent 1,27
No. 0,578, and a blocked isocyanate having a protecting group that dissociates the isocyanate group by heat, such as alcohols, phenols, and amines. The above protective group preferably has a dissociation temperature of 90 to 180 degrees.

Of these, those which react with the hydrophilic groups (eg, -OH, -NH ₂ groups, etc.) of the hydrophilic resin and substantially eliminate the hydrophilic groups are preferable in view of the image SN and the image strength. In particular, a blocked isocyanate is preferable because it is excellent in the inking property of the image area and the stain property of the non-image area.

A known reaction accelerator can be added to these crosslinking agents in order to adjust the sensitivity of image drawing. Such things include, for example,
Ammonium chloride, ammonium acetate, ammonium sulfate, ammonium nitrate, ammonium phosphate, diammonium phosphate, ammonium thiocyanate, ammonium sulfamate and other ammonium salt compounds, dimethylaniline hydrochloride, pyridine hydrochloride, picoline monochloroacetic acid, catalyst AC (Manufactured by Monsanto), Catanit A (manufactured by Nitto Kagaku), Sumilizer ACX-P
(Manufactured by Sumitomo Chemical Co., Ltd.) and inorganic salt compounds such as stannic chloride, ferric chloride, magnesium chloride, zinc chloride and zinc sulfate.

The preferred content of the above-mentioned "lipophilic thermoplastic resin" or "crosslinking agent which exhibits lipophilicity by a thermal reaction" is 5% by weight or more and 80% by weight or less, and this content is less than 5% by weight. In this case, the ink adhesion of the image area tends to decrease, and if it exceeds 80% by weight, the background may be stained in the non-image area.

As the hydrophilic resin, a resin capable of forming a self-film by heat treatment is preferable in view of production suitability and prevention of fogging of a non-image portion. Further, it is preferable that the film has water resistance after film formation, and the hydrophilic component (H) having a surface energy γ of 30 dyn / cm ² or more has printing durability and does not cause stain on a non-image portion.

The “layer formed by self-forming” refers to a sample obtained by applying a coating solution for an image forming layer to a support, heat-treating the coating solution at a temperature of 100 ° C. or lower for 3 minutes, and drying. If the weight reduction rate after immersion for 2 hours in water has a water resistance of 5% or less, it is regarded as a layer formed by self-forming.

The compound having such properties is, for example, an aqueous dispersion of a polyester resin modified with a copolymer containing at least one selected from unsaturated carboxylic acid amides and derivatives thereof, and the polyester resin component A water dispersion of a so-called modified polyester resin, which contains at least one hydrophilic component selected from polyalkylene glycol groups, polyalkylene glycol carboxyl groups, carboxylate, sulfonate and sulfate salts. .

The aqueous dispersion of the modified polyester resin is as follows:
It is obtained by adding a radical polymerization initiator to an aqueous dispersion of a polyester resin, adding a polymerizable monomer component for modifying the polyester, and performing heat polymerization.

As the above-mentioned polyester resin, HO-
Polyesters obtained by polycondensing a polyalkylene glycol represented by (CH ₂ ) n-OH with an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid, and a hydroxycarboxylic acid such as p-hydroxybenzoic acid are preferred. Aroma having substituents such as alkali metal sulfonates such as sodium sulfoisophthalic acid, ammonium sulfoisophthalic acid, 4-methylammonium sulfoisophthalic acid, potassium sulfoisophthalic acid, sodium sulfoterephthalic acid, potassium sulfophthalic acid, and sodium sulfosuccinic acid Polycondensation of a part or several of aromatic dicarboxylic acids having an aromatic dicarboxylic acid or a sulfate salt as a substituent is preferable from the viewpoint of enhancing hydrophilicity.

Polymerizable monomers used for modifying the polyester include vinyl compounds such as vinyl propionate, vinyl stearate, and vinyl chloride; methyl (meth) acrylate, ethyl (meth) acrylate, butyl methacrylate, and the like. Unsaturated carboxylic esters such as 2-ethylhexyl acrylate, methyl maleate, octyl maleate, butyl fumarate, octyl fumarate, glycidyl (meth) acrylate, hydroxyethyl methacrylate, hydroxypropyl (meth) acrylate , Unsaturated carboxylic acids such as acrylonitrile, acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and hydrocarbons such as ethylene, propylene, hexene, and styrene. In the present invention, (meth) acrylamide, methylol Acrylic De, butoxy methylol acrylamide, N, N-dimethyl (meth) unsaturated carboxylic acid amides such as acrylamide, it is preferred from the viewpoint of enhancing the hydrophilicity used in an amount of 20 to 100% by weight of the total polymerizable monomers.

Further, in the image forming layer according to the first to third aspects of the present invention, the weight loss after immersion for 2 hours in an etchant used for printing is preferably 5% or less. The content of the polymer composed of the polymerizable monomer with respect to the polyester is preferably 1 to 150% by weight. The method of measuring the weight loss rate is calculated as follows. Weight reduction rate = (weight of image forming layer reduced 2 hours after immersion in etchant used for printing) / (weight of image forming layer) × 100 If this value is 5 or less, the image forming layer dissolves during printing. The printing durability is good, but when it exceeds 5, the hydrophilic image forming layer is dissolved at the time of printing, the image fixed on the image forming layer is eluted, and the printing durability tends to deteriorate. It is in.

As the radical polymerization initiator used for polymerizing the polymerizable monomer and modifying the polyester, a known organic peroxide is mainly used.

The image forming layer is required that the image forming layer radiated or heated imagewise changes its physical property from hydrophilic to hydrophobic. For this reason, for example, when image exposure is performed as an image forming unit, it is preferable that a compound that causes light-to-heat conversion (hereinafter referred to as a light-to-heat conversion substance) is contained in the image forming layer or another layer. By designing in this way, it is possible to perform high-precision writing using light of a high-output laser or the like in addition to writing by heating a thermal head or the like.

When using such a light-to-heat conversion material,
Although it depends on the light source, a substance that absorbs light and efficiently converts it to heat is preferable. For example, when using a semiconductor laser as a light source, a substance having an absorption band in the near infrared is preferable,
Examples of near-infrared light absorbers include organic compounds such as carbon black, cyanine-based, polymethine-based, azurenium-based, squarylium-based, thiopyrylium-based, naphthoquinone-based, and anthraquinone-based dyes, phthalocyanine-based, azo-based, and thioamide-based organic metals. Complexes and the like are preferably used, and specifically, JP-A-63-139191 and JP-A-64-139191.
No. 33547, JP-A-1-160683 and 1-28
No. 0750, No. 1-293342, No. 2-2074
No. 3-26593, No. 3-30991, No. 3-
No. 34891, No. 3-36093, No. 3-36094
Nos. 3-36095, 3-42281, 3-
97589, 3-103476 and the like. These can be used alone or in combination of two or more.

As the light-to-heat conversion layer formed by containing a light-to-heat conversion substance in another layer other than the image forming layer, a vapor-deposited layer (film) can also be used. Gold and silver described in JP-A-52-20842,
Examples include a deposited layer of metal black such as aluminum, chromium, nickel, antimony, tellurium, bismuth, and selenium, and a layer containing colloidal silver.

The image forming layer according to the first to third aspects of the present invention comprises:
The invention is not limited to the above, and a known image forming layer which does not substantially require a development process can be applied. For example, as described in JP-A-9-12387, an image-forming layer which can be combined under the influence of heat and contains hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and can convert light into heat An image-forming element containing a compound contained in said image-forming layer or an adjacent layer thereof;
And a self-water-dispersible thermoplastic resin particle layer which can be made lipophilic by heat.

Next, the invention according to claims 4 to 8 will be described.

The invention according to claims 4 to 8 relates to a lithographic printing plate material having an image forming layer on one surface of a support, and a lithographic printing plate material of a printing machine in which the support surface opposite to the image forming layer is provided with an adhesive layer. It is characterized by being fixed on the cylinder surface and printing. As a preferred embodiment, an embodiment in which the adhesive layer is in direct contact with the back surface of the lithographic printing plate material support and the cylinder of the printing press, for example, an embodiment in which the adhesive layer is provided in advance on the surface of the cylinder of the printing press, an adhesive layer And a lithographic printing plate material on the surface of the cylinder of the printing press in this order, and the above-mentioned embodiment in which the adhesive layer is a silicone rubber layer.

These embodiments will be described with reference to the drawings. FIG. 1 shows that a pressure-sensitive adhesive layer 5 is applied on the peripheral surface of a cylinder (plate cylinder) 1 in advance, and a lithographic printing plate material 4 composed of a support 2 and an image forming layer 3 is adhered to the peripheral surface of the cylinder 1. FIG. 4 is a schematic cross-sectional view showing a state in which the semiconductor device is fixed via a conductive layer 5. FIG. 2 shows a state in which a sheet 6 provided with an adhesive layer 5 on both sides is attached to the cylinder 1 and a lithographic printing plate material 4 is placed on the adhesive layer 5.
It is a schematic sectional drawing which shows the state which attaches. In both figures,
The blanket cylinder, impression cylinder, inking roller, dampening device and the like are omitted, and the size of each element is exaggerated for understanding.

In the invention according to claims 4 to 8, the pressure-sensitive adhesive layer is in direct contact with the back surface of the lithographic printing plate material support and the cylinder of the printing press, and the pressure-sensitive adhesive layer is formed on the surface of the cylinder of the printing press in advance. It is preferable to provide them. Further, as shown in FIG. 2, it is preferable that the sheet having the adhesive layer on the surface and the lithographic printing plate material are attached to the cylinder surface of the printing press in this order.

Examples of the sheet on which the adhesive layer is provided include metals such as aluminum and iron, plastic films such as polyester films and acetate films, and paper. As a sheet having an adhesive layer on the surface, an adhesive layer is provided on the surface side of a rigid sheet such as an aluminum plate, and the sheet is fixed to the cylinder by a normal clamping mechanism incorporated in the cylinder, and the sheet is The lithographic printing plate material may be attached to the adhesive layer by adhesion.

The pressure-sensitive adhesive layer in the invention according to claims 4 to 8 is a layer containing rubber and utilizing this as a slip-preventing effect. Natural rubber can be used as the rubber, but is preferably synthetic rubber.

Examples of the synthetic rubber include styrene / butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, urethane rubber, polysulfide rubber, ethylene tetrapropylene / propylene rubber, acrylic rubber, epichlorohydrin rubber, ethylene vinyl acetate rubber, 1,2-polybutadiene rubber, thermoplastic elastomer (eg, styrene, olefin, urethane, polyester, polyamide, fluorine), ethylene, propylene copolymer, ethylene / propylene / diene copolymer, nitrile / butadiene Rubber, butyl rubber, fluorine rubber, chlorosulfonated polyethylene, propylene oxide rubber, ethylene / acryl rubber, norbornene rubber, silicone rubber and the like can be mentioned, with silicone rubber being particularly preferred. This may be used in combination.

The adhesive layer contains (a) rosin, polyterpene, phenol resin, xylene resin, epoxy resin,
Sticking resin such as petroleum carbonized resin, (b) plasticizer such as phthalate ester, phosphate ester, chlorinated paraffin,
(C) Oil and fats such as animal fats and mineral oils may be added to adjust the adhesiveness to the sheet. In addition, anti-aging agents,
Stabilizers, fillers, coloring agents and the like may be added.

As the silicone rubber suitable as the rubber contained in the adhesive layer, a silicone rubber containing a linear organic polysiloxane having a molecular weight of several thousand to several hundred thousand and having the following repeating units as a main component is preferable.

[0071]

Embedded image

Here, n is an integer of 2 or more, and R is 1 carbon atom.
10 to 10 alkyl groups, halogenated alkyl groups, alkyl groups, vinyl groups, and aryl groups, and preferably 60% or more of R is a methyl group.

The silicone rubber useful in the present invention is
It is obtained by a condensation reaction of such a silicone base polymer with the following silicone crosslinking agent.

[0074] (1) R-Si- (OR ') (2) R-Si- (OAc) (3) R-Si- (ON = CR' 2) 2 where R is as defined R previously described R 'is an alkyl group such as a methyl group or an ethyl group, and Ac is an acetyl group.

These silicone rubbers are also available as commercial products, for example, “YS-308” manufactured by Toshiba Silicone Co., Ltd.
5 "and the like.

Another useful silicone rubber is
Reaction of the base polymer as described above with an H-type silicone oil having the following repeating unit, or addition reaction with a silicone base polymer in which about 3% of R is a vinyl group, or the H-type silicone It can also be obtained by a reaction between oils.

[0077]

Embedded image

(Wherein, R has the same meaning as R above, and m
Is an integer of 2 or more, and n is 0 or an integer of 1 or more. In order to obtain a silicone rubber by such a crosslinking reaction, in addition to the above components, an organic carboxylate of a metal such as tin, zinc, cobalt, lead, calcium, and manganese, for example, dibutyltin laurate, tin (II) ) A catalyst such as octoate, cobalt naphthenate, or chloroplatinic acid is added.

In order to improve the strength of the silicone rubber, a filler may be mixed.
Silicone rubber premixed with filler is commercially available as silicone rubber stock or silicone rubber dispersion, and if coated,
When it is preferable to obtain an adhesive layer of a silicone rubber film, RTV or LTV silicone rubber disversion is preferably used. Thus, as an example, “Syl Off 23” manufactured by Toray Silicone Co., Ltd.,
There are silicone rubber disversions for paper coating such as "SRX-257" and "SH 237".

The silicone rubber layer preferably contains a silane coupling agent in order to further improve the adhesion to the support.

Examples of the silane coupling agent include the following.

(A) H ₂ NCH ₂ CH ₂ NHCCH ₂ CH
₂ CH ₂ Si (OCH ₃ ) ₃

[0083]

Embedded image

(C) HS (CH ₂ ) ₃ Si (OCH ₃ )
₃ (d) CH ₂ ＣＨCHSi (OCOCH ₃ ) ₃ (e) CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (O
CH ₃ ) ₃ (f) CH ₂ ＣＨCHSi (OCH ₂ CH ₃ ) ₃ (g) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OC
H ₃ ) ₂ (CH ₃ ) (h) Chlorosilane The thickness of the adhesive layer is preferably in the range of 0.1 to 300 μm.

As the support for the photosensitive lithographic printing plate material in the inventions according to claims 4 to 8, a conventionally known plastic support can be used without any particular limitation. Materials, layer configurations and sizes can be appropriately selected and used. Examples of the support include a vinyl chloride resin sheet, an ABS resin sheet, a polyethylene terephthalate (PET) film, a polybutylene terephthalate film, a polyethylene naphthalate (PEN) film, a polyarylate film, a polycarbonate film, and a polyether ether ketone film. , Polysulfone film, polyethersulfone film, polyetherimide film,
A single layer such as a polyimide film or a plastic film or sheet obtained by laminating them in two or more layers and the like, the surface of which is subjected to a hydrophilic treatment is exemplified. As the above-mentioned method for hydrophilizing a plastic film, sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, providing a water-soluble resin layer coating layer, and the like are preferably used.

As the image forming layer of the invention according to claims 4 to 8, the image forming layer according to claims 1 to 3 can be preferably mentioned.

The ninth aspect of the present invention will be described.

The ferromagnetic metal powders contained in the light-to-heat conversion layer include Fe, Co, Fe-Al, Fe-Al-
Ni-based, Fe-Al-Zn-based, Fe-Al-Co-based, F
e-Al-Ca system, Fe-Ni system, Fe-Ni-Al
System, Fe-Ni-Co system, Fe-Ni-Zn system, Fe-
Ni-Mn system, Fe-Ni-Si system, Fe-Ni-Si
-Al-Mn system, Fe-Ni-Si-Al-Zn system, F
e-Ni-Si-Al-Co system, Fe-Al-Si system,
Fe-Al-Zn system, Fe-Co-Ni-P system, Fe-
Co-Al-Ca system, Ni-Co system, Fe, Ni, Co
Ferromagnetic metal powders such as metal magnetic powders mainly composed of, for example, Fe-based metal powders are preferable.
o-containing γ-Fe ₂ O ₃ , Co-coated γ-Fe ₂ O ₃ , Co-containing Fe ₃ O ₄ , Co-coated Fe ₃ O ₄ , Co-containing magnetic FeOx
(4/3 <x <3/2) Cobalt-containing iron oxide-based magnetic powder such as powder. Also, from the viewpoint of corrosion resistance and dispersibility, among the Fe-based metal powders, Fe-Al-based and Fe-
Al-Ca system, Fe-Al-Ni system, Fe-Al-Zn
System, Fe-Al-Co system, Fe-Ni-Si-Al-C
Fe-Al-based ferromagnetic powders such as o-based and Fe-Co-Al-Ca-based are preferable, and among them, the content ratio of Fe atoms to Al atoms contained in the ferromagnetic powder is expressed by the atomic ratio. F
e: Al = 100: 1 to 100: 20, and Fe atoms and Al existing in a surface area of 100 ° or less at an analysis depth of ferromagnetic powder by ESCA (X-ray photoelectron spectroscopy).
Fe: Al = 30: 70 when the content ratio with the atom is the atomic ratio.
~ 70: 30, or Fe atom, Ni atom, Al atom, Si atom, and Co atom, Ca atom
At least one of the atoms is contained in the ferromagnetic powder;
The atomic content is 90 atomic% or more and the Ni atomic content is 1
-10 atomic%, the content of Al atoms is 0.1-5 atomic%,
Si atom content of 0.1-5 atomic%, Co atom or C
The content of the a-atom (the total amount when both are contained) is 0.
1-13 atomic% and a ferromagnetic powder ESCA (X
Atoms, Ni atoms, Al atoms, and Si existing in a surface area of 100 ° or less at an analysis depth by X-ray photoelectron spectroscopy.
The content ratio of the atoms to the Co atoms and / or Ca atoms is expressed as Fe: Ni: Al: Si: (Co and / or C
a) = 100: (4 or less) :( 10-60) :( 10-60)
70): Those having a structure of (20 to 80) are preferable.

The shape of the ferromagnetic metal powder has a major axis diameter of 0.30 μm or less, preferably 0.20 μm or less. According to such a ferromagnetic metal powder, the surface property of the colorant layer is improved.

Examples of the hexagonal plate-like powder include hexagonal ferrites such as barium ferrite and strontium ferrite.
i, Co, Zn, In, Mn, Ge, Hb, etc.).
E trans on MAG, p18, 16 (198
Those described in 2) can be mentioned. Among these, as an example of the barium ferrite magnetic powder, an average particle size in which at least a part of Fe is replaced by Co and Zn (diagonal height of the plate surface of hexagonal ferrite) is 400.
And a plate ratio (a value obtained by dividing a diagonal length of a plate surface of hexagonal ferrite by a plate thickness) of 2.0 to 10.0 °.
It is. In addition, barium ferrite magnetic powder further contains F
A part of e may be replaced with a transition metal such as Ti, In, Mn, Cu, Ge, and Sn.

A method for producing a cubic magnetic powder includes, for example, melting an oxide and a carbonate of each atom necessary for forming a target barium ferrite together with a glass-forming substance such as boric acid; The obtained melt is quenched to form a glass, then the glass is heat-treated at a predetermined temperature to precipitate the desired barium ferrite crystal powder, and finally the glass component is removed by a heat treatment. In addition to the chemical conversion method, there are a coprecipitation-calcination method, a hydrothermal synthesis method, a flux method, an alkoxide method, a plasma jet method and the like.

The content of the ferromagnetic metal powder contained in the light-to-heat conversion layer is about 50 to 99% by weight, preferably 60 to 95% by weight of the light-to-heat conversion layer.

The light-to-heat conversion layer preferably contains a binder resin. The binder resin can be used without any particular limitation as long as it can sufficiently hold a colorant capable of absorbing the wavelength light of the exposure light source and a metal atom-containing powder.

Representative examples of such binder resins include vinyl chloride resins such as polyurethane, polyester, and vinyl chloride copolymers. These resins include -SO ₃ M, -OSO ₃ M,- COOM and -PO (OM
₁ ) ₂ [where M is a hydrogen atom or an alkali metal, M ₁
Represents a hydrogen atom, an alkali metal or an alkyl group. ] It is preferable to include a repeating unit having at least one type of polar group selected from the above], and by using a resin into which such a polar group is introduced, the dispersibility of the ferromagnetic foot-resistant powder can be improved. In addition, the content ratio of this polar group in each resin is about 0.1 to 8.0 mol%, preferably 0.2 to 8.0 mol%.
~ 6.0 mol%.

The binder resin may be used alone or in combination of two or more kinds. When two or more kinds are used in combination, for example, the weight ratio of the polyurethane and / or polyester to the vinyl chloride resin is 90: 10 to 10:90
, Preferably 70:30 to 30:70.

As the polar group-containing vinyl chloride, for example,
Vinyl chloride - a resin having a vinyl alcohol copolymer _{hydroxyl, Cl-CH 2 CH 2 SO} 3 M, Cl-CH 2 CH
_{2 OSO 3 M, Cl-CH} 2 CO 2 M, Cl-CH 2 P (=
O) It can be synthesized by an addition reaction with a compound having a polar group such as (OM ₁ ) ₂ and a chlorine atom. One example is shown below.

-CH ₂ C (OH) H- + Cl-CH ₂
CH ₂ SO ₃ Na → —CH ₂ C (OCH ₂ CH ₂ SO ₃ N
a) H-Polar group-containing vinyl chloride resin is prepared by charging a predetermined amount of a reactive monomer having an unsaturated bond into which a repeating unit containing a polar group is introduced into a reaction vessel such as an autoclave, and adding benzoyl peroxide and azobisisobutyrate. General radical polymerization initiator such as lonitrile, redox polymerization initiator,
Specific examples of the reactive monomer for introducing sulfonic acid or a salt thereof, which can be obtained by polymerization using a cationic polymerization initiator or the like, include vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, p- Examples include unsaturated hydrocarbon sulfonic acids such as styrene sulfonic acid and salts thereof. When a carboxylic acid or a salt thereof is introduced, for example, (meth) acrylic acid or maleic acid is used, and when a phosphoric acid or a salt thereof is introduced, (meth) acryl-2-phosphate may be used.

Further, in order to improve the thermal stability of the binder resin, it is preferable to introduce an epoxy group into the vinyl chloride copolymer. In this case, the content of the repeating unit having an epoxy group in the copolymer is about 1 to 30 mol%, preferably 1 to 20 mol%, and glycidyl acrylate or the like is used as a monomer for introducing an epoxy group. be able to.

The polyester having a polar group can be synthesized by a dehydration condensation reaction between a polyol and a polybasic acid partially having a polar group. Examples of the polybasic acid having a polar group include 5-sulfoisophthalic acid, -Sulfoisophthalic acid, 4-sulfoisophthalic acid, 3-sulfophthalic acid, 5
-Dialkyl sulfoisophthalate, dialkyl 2-sulfoisophthalate, dialkyl 4-sulfoisophthalate,
Examples thereof include dialkyl 3-sulfophthalates and alkali metal salts thereof. Examples of the polyol include trimethylolpropane, hexanetriol, glycerin, trimethylolethane, neopentyl glycol, pentaerythritol, ethylene glycol, propylene glycol, and 1,3-butane. Examples thereof include diol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanedimethanol.

The polyurethane having a polar group can be synthesized by reacting a polyol with a polyisocyanate. Specifically, the polyurethane is obtained by reacting a polyol with a polybasic acid partially having a polar group as a polyol. It is synthesized by using the obtained polyester polyol as a raw material. Examples of the polyisocyanate include diphenylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, and lysine isocyanate methyl ester. As the other synthetic methods of the polyurethane having a polar _{group, Cl-CH 2 CH 2 SO} 3 M with polyurethane and polar group and a chlorine atom with a hydroxyl group, Cl-CH ₂ CH
_{2 OSO 3 M, Cl-CH} 2 CO 2 M, Cl-CH 2 P (=
An addition reaction with a compound such as O) (OM ₁ ) ₂ is also effective.

Other binder resins include vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer, polyolefin resins such as butadiene-acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, and celluloses such as nitrocellulose. Resin, styrene resin such as styrene-butadiene copolymer, acrylic resin such as polymethyl methacrylate, polyamide,
A phenol resin, an epoxy resin, a phenoxy resin, or the like may be used in combination, but when these are used in combination, the content is preferably 20% by weight or less of the total binder resin.

The content of the binder resin in the light-to-heat conversion layer is about 1 to 50% by weight, preferably 5 to 40% by weight in the components for forming the image forming layer.

The light-to-heat conversion layer may contain additives such as a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler and a curing agent as long as the effects of the present invention are not impaired. Good.

Examples of the lubricant include fatty acids, fatty acid esters, fatty acid amides, (modified) silicone oils, (modified) silicone resins, fluororesins, and carbon fluorides. Can be mentioned. Examples of the dispersant include fatty acids having 12 to 18 carbon atoms, such as lauric acid and stearic acid, and amides, alkali metal salts, and alkaline earth metal salts thereof; polyalkylene oxide alkyl phosphates, lecithin, trialkyl polyolefinoxy A quaternary ammonium salt; an azo compound having a carboxyl group and a sulfone group; etc. Examples of the antistatic agent include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and a polymer charging agent. Inhibitors, conductive fine particles, etc., and "11290 Chemical Products", Chemical Daily, p.
And the compounds described in 875-876 and the like.

As fillers, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgC
O ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ , M
gO, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeO
OH, SiC, CeO ₂ , BN, SiN, MoC, B
Inorganic fillers such as C, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, silica stone, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluororesin particles, guanamine resin particles, acrylic resin particles, silicon resin particles And organic fillers such as melamine resin particles.

Examples of the filler include inorganic fine particles and organic resin particles, and these may also serve as a releasing agent. Examples of the inorganic particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, and alumina.
Resin particles such as guanamine resin particles, acrylic resin particles, and silicon resin particles can be used. These inorganic / organic resin particles differ depending on the specific gravity, but are preferably added in an amount of 0.1 to 70% by weight.

The curing agent can be used without any particular limitation as long as it can cure the image forming layer.
Examples of such a curing agent include, for example, polyisocyanate used when synthesizing polyurethane in the binder resin described above.

By adding such a curing agent to cure the light-to-heat conversion layer, it is possible not only to improve the durability of the formed image but also to eliminate the background stain on the portion where ablation has occurred. The amount of these additives is about 0 to 20% by weight, preferably 0 to 15% by weight.

The light-to-heat conversion layer has a thickness of 0.05 to 5.0 μm.
m, preferably in the range of 0.1 to 3.0 μm.
Further, the light-to-heat conversion layer may be formed as a single layer or may be formed as multiple layers having different compositions. It is preferable to contain a coloring agent in a larger amount. Further, a colorant capable of absorbing light having a wavelength other than the wavelength of the exposure light source may be added to the layer farther from the support.

The light-to-heat conversion layer is formed, for example, by kneading a magnetic powder, a binder resin and, if necessary, a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler, a curing agent, and the like, and a solvent. Then, a high-concentration magnetic paint is prepared, and then the high-concentration magnetic paint is diluted to form a magnetic paint for application, applied on a support and dried to form a magnetic paint.

Examples of the solvent include alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve), aromatics (toluene, xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), and esters. Use of solvents (such as ethyl acetate and butyl acetate), ethers (such as tetrahydrofuran and dioxane), halogen solvents (such as chloroform and dichlorobenzene), and amide solvents (such as dimethylformamide and N-methylpyrrolidone). Can be. The kneading and dispersing of the light-heat conversion layer components include a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder,
Sqegvari Attritor, High Speed Impeller Disperser, High Speed Stone Mill, High Speed Impact Mill, Disper,
A high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader, or the like can be used.

The formation of the light-to-heat conversion layer on the support is carried out, for example, by coating and drying with an extrusion-type extrusion coater. If necessary, a calendering treatment may be performed to make the orientation of the magnetic powder uniform or to make the surface properties of the light-to-heat conversion layer uniform. In particular, in order to obtain a high-resolution image, it is preferable to orient the magnetic powder because the cohesive force in the layer can be easily controlled.

The ink repellent layer of the invention according to the ninth aspect is not particularly limited as long as it has an ink repellent property such as a silicone rubber layer or a fluororesin layer used in this technical field. It is particularly preferable to use a condensation-crosslinking type silicone rubber layer.

The silicone rubber has a molecular weight of several thousand to 1,000 having a repeating unit represented by the following general formula [1].
It is preferable to use hundreds of thousands of linear organic polycycloxane having a hydroxyl group at the terminal of the main chain as a main component.

[0115]

Embedded image

Here, n is an integer of 2 or more, and R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group or a silanol group. Those in which the above is a methyl group are preferred. The silanol group may be in the main chain or at the terminal of the main chain, but is preferably at the terminal.

The silane coupling agent (or silicone cross-linking agent) which is a reagent for forming a silicone rubber by a condensation reaction with a silicone base polymer (linear organic polysiloxane having a hydroxyl group at a terminal) is R _n SiX _{4 -n} In the formula, n is an integer of 1 to 3, R represents alkyl, aryl, alkenyl or a monovalent group in which these are combined, and these groups are halogen, amine, hydroxy,
It may have a functional group such as alkoxy, aryloxy and thiol. R also

[0118]

Embedded image

And the like. Here, R ² and R ³ each represent the same as R described above, R ² and R ³ may be the same or different, and Ac represents an acetyl group.

Examples of the silane coupling agent include:
HN [(CH ₂ ) ₂ Si (OCH ₃ ) ₃ ] ₂ , vinyltriethoxysilane, Cl (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH
₃ Si (OCOCH ₃ ) ₃ , HS (CH ₂ ) ₃ Si (OC
H ₃ ) ₃ and vinyltris (methylethylketoxime) silane.

Useful silicone rubbers are those obtained by the condensation reaction of such silicone base polymers with the silicone crosslinkers mentioned above.

The above silicone rubber is also available as a commercial product, for example, YE-3085 manufactured by Toshiba Silicone Co., Ltd. Another useful silicone rubber is a reaction of the base polymer as described above with a silicone oil having a repeating unit represented by the following general formula [2],
Alternatively, it can be obtained by an addition reaction with a silicone base polymer in which about 3% of R is a vinyl group, or a reaction between the silicone oils.

[0123]

Embedded image

(Wherein, R has the same meaning as R which is a substituent of the polymer represented by the general formula [1], m is an integer of 2 or more, and n is 0 or an integer of 1 or more.) In order to obtain a silicone rubber by such a crosslinking reaction, the crosslinking reaction is performed using a catalyst. Examples of the catalyst include organic carboxylic acids of metals such as tin, zinc, cobalt, lead, calcium, and manganese, such as dibutyltin laurate, tin (II) octoate, and cobalt naphthenate.
Alternatively, chloroauric acid or the like is used.

In order to improve the strength of the silicone rubber and obtain a silicone rubber which can withstand the frictional force generated during the printing operation, a filler may be mixed. Silicone rubber premixed with a filler is commercially available as silicone rubber stock or silicone rubber dispersion. When it is preferable to obtain a silicone rubber film by coating, RTV is used.
Alternatively, a dispersion of LTV silicone rubber is preferably used. Such examples include Syl Off 23, SRX-257, and SH
237 and the like are available for paper coating silicone rubber dispersions.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve the adhesiveness. Examples of preferable silane coupling agents include the following. .

(A) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ S
i (OCH ₃ ) ₃ (b) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₂ Si (OCH ₃ )
₂ (CH ₃ ) (c) A small amount of a photosensitizer can be further contained in the H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ silicone rubber layer.

The light-to-heat conversion layer of the invention according to claim 10 is a layer that absorbs light irradiated in an image form and rises in temperature. It is preferable to add a pigment or a dye to this layer in order to effectively use the energy of high illuminance light such as laser light or flash light. Any pigment or dye used for this purpose can be used as long as it converts a pattern of high illuminance light into a heat pattern. The light-heat conversion layer can also serve as a layer other than the ink repellent layer, for example, a primer layer.

When flash light is used for exposure, a pigment having a wide absorption range is preferred. In particular, carbon black, carbon graphite, phthalocyanine pigments, iron powder, graphite powder, iron oxide powder, lead oxide, pigments having absorption in the visible and near infrared regions such as blackened silver are preferred, and carbon black is particularly preferably used. .

When a laser is used for exposure, a dye or pigment having a laser emission wavelength can be used. When using a laser that does not have a light-emitting region in the visible region, such as an infrared semiconductor laser, it is not necessary to use a dye or pigment that has absorption in the visible region. Can be used. Needless to say, dyes and pigments which are preferable when the flash light is used are also suitably used.

The light-to-heat conversion layer is formed by dissolving or dispersing the above dyes and pigments in a suitable binder to prepare a coating solution, and coating the primer layer or the support with a coating means such as a wire bar. You.

The thickness of the light-to-heat conversion layer is preferably from 0.1 to 5 μm, more preferably from 0.5 to 3 μm.

The ink repellent layer according to the tenth aspect is the ink repellent layer according to the ninth aspect, wherein the ink repellent layer contains thermoplastic resin particles. The thermoplastic resin particles are preferably at least 90 ° C., more preferably at least 100 ° C.
It has a glass transition temperature of ° C. Also, the thermoplastic resin particles are preferably above 50 ° C., or more preferably 70 ° C.
Has a solidification temperature above ℃. Solidification may result from softening or melting of the thermoplastic particles under the influence of heat. There is no particular upper limit on the solidification temperature of the thermoplastic resin particles, but this temperature must be sufficiently lower than the decomposition point of the resin particles. Suitably the coagulation temperature is at least 10 ° C below the temperature at which decomposition of the thermoplastic resin particles occurs. When the resin particles are subjected to temperatures above the coagulation temperature, they coagulate to form a hydrophobic agglomerate in the hydrophilic layer, so that in these portions the hydrophilic layer is placed in ordinary water or aqueous liquid. Becomes insoluble.

Specific examples of thermoplastic resin particles include, for example,
Polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole and the like, or a copolymer and / or a mixture thereof. Polymethyl methacrylate is most preferably used. The weight average molecular weight of the polymer is 5000 to 1
It may be in the range of 000000 g / mol. The thermoplastic resin particles have a particle size of 0.01-50 μm, more preferably 0.05 μm.
It may have a particle size between ２2 μm.

As the support of the lithographic printing plate material of the invention according to claims 9 to 11, a support known as a support of a photosensitive lithographic printing plate can be used without particular limitation. Various materials, layer configurations, and sizes can be appropriately selected and used according to the requirements. For example, paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by bonding them to paper)
Paper, vinyl chloride resin sheet, ABS resin sheet, polyethylene terephthalate (PET) film, polybutylene terephthalate film, polyethylene naphthalate (PEN) film, polyarylate film, polycarbonate film, polyether ether ketone film, polysulfone Film, polyethersulfone film, polyetherimide film,
A single layer such as a polyimide film or various plastic films or sheets obtained by laminating them in two or more layers, a film or sheet formed of various metals, a film or sheet formed of various ceramics, further aluminum, stainless steel, A metal plate of chromium, nickel, etc., for example, a plastic film such as polyester film, polyethylene film, polypropylene film, paper, synthetic paper, resin-coated paper laminated or vapor-deposited with the above-mentioned metal thin film, for example, polyester film, vinyl chloride film And those obtained by subjecting a surface of a nylon film or the like to a hydrophilic treatment. As the above-mentioned method for hydrophilizing a plastic film, sulfuric acid treatment, oxygen plasma etching treatment, corona discharge treatment, providing a water-soluble resin layer coating layer, and the like are preferably used.

The lithographic printing plate material of the invention according to the ninth or tenth aspect can perform printing by supplying printing ink to the plate surface without performing any development processing after image exposure.

[0137]

Example 1 An image forming layer coating solution having the following composition was applied to a 0.24 mm thick polyethylene naphthalate film (Teonex, manufactured by Teijin Limited) using a wire bar to give a dry film thickness of 2. The solution was coated so as to be 0 g / m ² and dried at 50 ° C. for 3 minutes to form an image recording layer to obtain a lithographic printing plate material.

Coating solution for image forming layer 45.0 parts by weight of the following modified polyester aqueous dispersion Wax aqueous dispersion (Chemipearl W700; manufactured by Mitsui Petrochemical, solid content 40%, melting point 115 ° C.) 11.2 parts by weight Aqueous dispersion of carbon black (SD9020; manufactured by Dainippon Ink, solid content 30%) 3.3 parts by weight Pure water 40.5 parts by weight Synthesis of modified polyester The following and were charged into a four-necked flask and stirred. While the following and were mixed little by little, nitrogen gas was blown into this system to perform deoxygenation. Then 65-85 ° C
After the reaction was performed for 5 hours, the mixture was stirred until the liquid temperature reached room temperature, and ion-exchanged water was added so that the solid content became 10% to obtain an aqueous dispersion of a modified polyester.

Aqueous dispersion of polyester resin obtained by dehydration condensation of terephthalic acid (45), isophthalic acid (45), 5-sodium sulfoisophthalic acid (10), ethylene glycol (40), neopentylene glycol (60) Product (mole% in parenthesis, solid content 25%) 520.0 parts by weight Surfactant 2.0 parts by weight Methyl methacrylate 20.0 parts by weight Acrylamide 50.0 parts by weight Benzoyl peroxide 2.0 parts by weight Ion 406.0 parts by weight of exchange water After fixing the lithographic printing plate material to the cylinder of the printing press, the semiconductor laser light source (semiconductor laser output: 100 W, emission wavelength: 830 nm, 2.2 m / sec, spot size: 10 μm) on the printing press was applied. After performing image exposure, ink supply and fountain solution supply were performed, and normal printing was performed. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the printing durability, image shift, image defects, and dimensional stability of this printing plate.

Example 2 A hydrophilic layer coating solution having the following composition was coated on a polyethylene terephthalate film having a thickness of 0.24 mm and containing 20% glass fiber using a wire bar to a dry film thickness of 2.0 g / m ^2. And dried at 80 ° C. for 3 minutes to apply a hydrophilic layer to obtain a hydrophilic lithographic printing plate support.

Coating solution for hydrophilic layer Colloidal silica (Snowtex OL; 20% aqueous dispersion; manufactured by Nissan Chemical Industries, Ltd.) 25 parts by weight Porous silica (Syloid 435; manufactured by Grace Japan) 4 parts by weight Polyvinyl alcohol (KL05; Japan) 1 part by weight Pure water 70 parts by weight Next, a dry film thickness of 1.0 g /
m ² and dried at 40 ° C. for 3 minutes to form an image forming layer to obtain a lithographic printing plate material.

Image forming layer coating solution SD9020 (carbon black aqueous dispersion; 30% aqueous dispersion; manufactured by Dainippon Ink and Chemicals, Inc.) 0.90 parts by weight Wax resin aqueous dispersion (microcrystalline wax A206; manufactured by Gifu Shellac) 3.84 parts by weight Pure water 19.33 parts by weight Printing and evaluation were performed in the same manner as in Example 1 using this lithographic printing plate material. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the printing durability, image shift, image defects, and dimensional stability of this printing plate.

Example 3 A hydrophilic layer coating solution having the following composition was applied on a polyethylene terephthalate film having a thickness of 0.24 mm and containing 40% kenaf fiber using a wire bar to a dry film thickness of 2.0 g /
m ² , and dried at 80 ° C. for 3 minutes to apply a hydrophilic layer to obtain a hydrophilic lithographic printing plate support.

Coating liquid for hydrophilic layer Colloidal silica (Snowtex OL; 20% aqueous dispersion; manufactured by Nissan Chemical Industries, Ltd.) 25 parts by weight Porous silica (Syloid 435; manufactured by Grace Japan) 4 parts by weight Polyvinyl alcohol (KL05; Japan) 1 part by weight of pure water 70 parts by weight of pure water Next, a coating solution of an image forming layer having the following composition was applied to the above-mentioned hydrophilic support using a wire bar to give a dry film thickness of 1.
The solution was coated to 0 g / m ² and dried at 40 ° C. for 3 minutes to form an image forming layer to obtain a lithographic printing plate material.

Image forming layer coating solution SD9020 (carbon black aqueous dispersion; 30% aqueous dispersion; manufactured by Dainippon Ink and Chemicals, Inc.) 0.90 parts by weight KL05 (80% saponified polyvinyl alcohol; manufactured by Nippon Synthetic Chemical) % Aqueous solution 5.94 parts by weight Iodosol GD87B (styrene acrylic resin emulsion; 50% aqueous dispersion, Tg = 60 ° C; manufactured by NSC Japan) 3.84 parts by weight Pure water 19.33 parts by weight This planographic printing plate Printing and evaluation were performed in the same manner as in Example 1 using the materials. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the printing durability, image shift, image defects, and dimensional stability of this printing plate.

Example 4 A lithographic printing plate material was produced in the same manner as in Example 1 except that a polyethylene terephthalate film was used instead of the polyethylene naphthalate film in Example 1.
The following adhesive layer coating solution is applied to the back surface of the lithographic printing plate material using a wire bar so that the dry film thickness becomes 2.0 g / m ² , and dried at 100 ° C. for 3 minutes to apply an adhesive layer. And
A lithographic printing plate material was obtained.

Coating solution for adhesive layer Silicone rubber 10 parts by weight Toluene 90 parts by weight Printing and evaluation were performed in the same manner as in Example 1 using this lithographic printing plate material. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the printing durability, image shift, image defects, and dimensional stability of this printing plate.

Example 5 A lithographic printing plate material was produced in the same manner as in Example 1 except that a polyethylene terephthalate film was used instead of the polyethylene naphthalate film in Example 1.
On the other hand, an ink repellent tape made of silicone rubber (IRT-L manufactured by Toray Industries, Inc.) was attached to a cylinder (plate cylinder) of a printing press.

The surface of the support of the lithographic printing plate material was attached so as to be in contact with the surface of the adhesive layer adhered to the cylinder (plate cylinder) of the printing press. Printing and evaluation were performed in the same manner as in Example 1. Good prints were obtained from the tenth printing. Table 1 shows the evaluation results of the printing durability, image shift, image defects, and dimensional stability of this printing plate.

Example 6 A lithographic printing plate material was produced in the same manner as in Example 1 except that a polyethylene terephthalate film was used instead of the polyethylene naphthalate film in Example 1.
On the other hand, a sheet having an adhesive layer prepared as described below was attached to a cylinder (plate cylinder) of a printing machine such that the support surface was in contact with the surface of the cylinder.

Sheet Having Adhesive Layer An ink-repellent tape made of silicone rubber (IR made by Toray Industries, Inc.) was placed on a 0.1 mm thick aluminum plate having an adhesive layer.
TL) by lamination.

The support surface of the lithographic printing plate material was attached so as to be in contact with the adhesive layer surface attached to the plate cylinder of a printing press.
Printing and evaluation were performed in the same manner as in Example 1. Start printing 10
Good prints were obtained from the first sheet. Table 1 shows the evaluation results of the printing durability, image shift, image defects, and dimensional stability of this printing plate.

Comparative Example 1, Comparative Example 2 A polyethylene naphthalate film having a thickness of 0.24 mm (Teonex, manufactured by Teijin Limited, Comparative Example 1) or 20%
A lithographic printing plate material was prepared according to the examples described in JP-A-8-62846 except that a glass fiber-containing polyethylene terephthalate film (Comparative Example 2) was used, and printing and evaluation were performed in the same manner as in Example 1. Was. Table 1 shows the evaluation results of printing durability, image shift, image defects, and dimensional stability.

Comparative Example 3 A lithographic printing plate material was prepared in the same manner as in Example 5, and the adhesive layer surface of the sheet having the adhesive layer prepared in Example 6 was adhered to the back of the support. Using this planographic printing plate material, printing and evaluation were performed in the same manner as in Example 1. Press life,
Table 1 shows the evaluation results of image shift, image defect, and dimensional stability.

Comparative Example 4 A lithographic printing plate material was produced in the same manner as in Example 5. On the other hand, the sheet material A of Invention 1 of JP-A-10-193828 was attached between a cylinder (plate cylinder) of a printing press and a lithographic printing plate, and printing and evaluation were performed in the same manner as in Example 1. Table 1 shows the evaluation results of printing durability, image shift, image defects, and dimensional stability.

[0156]

[Table 1]

(Note) Meanings of symbols in columns of image shift, image defect, and dimensional stability ○: No problem in practical use ×: There is trouble in practical use Which remarks column corresponds to which claim (Table 2 below also shows the same).

Example 7 A coating solution of a photothermal conversion layer having the following composition kneaded and dispersed using a kneader on a polyethylene terephthalate film having a thickness of 0.175 mm and having been subjected to corona discharge treatment was extruded to give a dry film thickness of 1 0.2 g / m ² , a magnetic field orientation treatment was performed while the coating film was not dried, and after drying, the surface was calendered to produce a light-to-heat conversion layer.

Coating solution for photothermal conversion layer Fe-Al based ferromagnetic metal powder [Fe: Al atomic ratio = 100: 4 (whole), Fe: Al atomic ratio = 50: 50 (surface), average major axis diameter 0 .14 μm] 10.0 parts by weight Potassium sulfonate group-containing vinyl chloride resin (MR-110; manufactured by Zeon Corporation) 10 parts by weight Sodium sulfonate group-containing polyurethane resin (UR-8700; manufactured by Toyobo Co., Ltd.) 10 parts by weight α -Alumina (average particle diameter 0.15 μm) 8 parts by weight Stearic acid 1 part by weight butyl stearate 1 part by weight Polyisocyanate compound (Coronate L; manufactured by Nippon Polyurethane Industry Co., Ltd.) 5 parts by weight Cyclohexanone 100 parts by weight Methyl ethyl ketone 100 parts by weight α, ω-dihydroxypolydimethylsiloxane 100 parts by weight 1,3,5-tris (3-trimethoxy (Rylpropyl) isocyanurate 3.5 parts by weight Dibutyl Sn dilaurate 0.8 parts by weight Isopar E (isoparaffin-based solvent manufactured by Esso Chemical Co.) 800 parts by weight Toluene 100 parts by weight After fixing the lithographic printing plate material to a cylinder of a printing press, After performing image exposure using a semiconductor laser light source (semiconductor laser output: 100 W, emission wavelength: 830 nm, 2.2 m / sec, spot size: 10 μm) on a printing machine, ink was supplied, and normal printing was performed. Good prints were obtained from the tenth printing. Table 2 shows the evaluation results of the sensitivity and the printing durability of this printing plate.

Example 8 A coating solution of a photothermal conversion layer having the following composition was applied on an aluminum plate having a thickness of 0.24 mm using a wire bar so that the dry film thickness became 1.2 g / m ² . After drying at 80 ° C. for 3 minutes, a light-to-heat conversion layer was applied.

Coating solution for light-to-heat conversion layer SD9020 (water dispersion of carbon black; 30% water dispersion; manufactured by Dainippon Ink and Chemicals, Inc.) 0.90 parts by weight Iodozol GD87B (styrene acrylic resin emulsion; 50% water dispersion) 3.84 parts by weight Pure water 19.33 parts by weight The following silicone rubber layer coating solution was applied on the photothermal conversion layer prepared above using a wire bar to give a dry film thickness of 2.84 parts by weight. 0g /
m ² and dried at 100 ° C. for 2 minutes to apply a silicone rubber layer to obtain a lithographic printing plate material.

Silicone rubber layer coating liquid α, ω-dihydroxypolydimethylsiloxane 100 parts by weight 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate 3.5 parts by weight DibutylSn dilaurate 0.8 parts by weight Polyethylene 100% by weight of Isopar E 20% dispersion of wax (Sunwax 131P, manufactured by Sanyo Kasei) 700 parts by weight of Isopar E (isoparaffinic solvent manufactured by Esso Chemical Co.) 100 parts by weight of toluene Using this lithographic printing plate material, After performing image exposure with an exposing machine (Trendsetter 3244; semiconductor laser output 10 W, 240 channel machine) manufactured by Toshiba Corporation, it was attached to a cylinder of a printing machine, and printing and evaluation were performed in the same manner as in Example 7. Good prints were obtained from the tenth printing. Table 2 shows the evaluation results of the sensitivity and the printing durability of this printing plate.

Comparative Example 5 An experiment similar to that of Example 7 was performed except that iron oxide powder (Fe ₃ O ₄ ) was used instead of the Fe—Al-based ferromagnetic metal powder of the coating solution for the light-to-heat conversion layer in Example 7. The results are shown in Table 2.

Comparative Example 6 A wax dispersion having the following composition was applied on the photothermal conversion layer of Example 8 so that the dry film thickness was 0.3 μm. The coating liquid of the silicone rubber layer used in Example 7 was applied on the wax layer so that the dry film thickness became 2.0 g / m ² ,
It dried at 2 degreeC for 2 minutes, and applied the silicone rubber layer, and obtained the lithographic printing plate. Using this planographic printing plate material, the same procedure as in Example 8 was carried out, and the results shown in Table 2 were obtained.

[0165]

[Table 2]

[0166]

According to the first to eighth aspects of the present invention, the following is improved, and according to the ninth to eleventh aspects, the following is improved, and a lithographic printing plate substantially requiring no development processing is provided. A material or a printing method (plate-mounting method) using the material is provided.

A lithographic printing plate material from which a lithographic printing plate having improved printing durability is obtained is provided.

Provided are a lithographic printing plate material capable of obtaining a lithographic printing plate having improved dimensional stability and thereby improved image defects and image shifts, and a printing method using the lithographic printing plate material.

Provided are a lithographic printing plate material capable of obtaining a lithographic printing plate having improved printing durability and dimensional stability, and a printing method using the lithographic printing plate material.

A lithographic printing plate material having improved sensitivity is provided.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one example of the invention according to claims 4 to 8;

FIG. 2 is a schematic sectional view showing another example of the invention according to claims 4 to 8;

[Description of Signs] 1 cylinder 2 support 3 image forming layer 4 lithographic printing plate material 5 adhesive layer 6 sheet

Claims (11)

[Claims] 1. A lithographic printing plate material comprising a polyethylene naphthalate film or a plastic film containing fibers provided with an image forming layer which does not substantially require development processing. 2. An image forming layer having a melting point of 90 ° C. or more and 130 ° C.
℃ or below or glass transition temperature (Tg) 50 ℃ or more and 80 ℃
A hydrophilic image forming layer containing the following lipophilic thermoplastic resin particles and a hydrophilic resin, wherein the hydrophilic image forming layer is a layer formed by self-forming a hydrophilic resin. The lithographic printing plate material as described. 3. A printing method, comprising: after performing image exposure on the lithographic printing plate material according to claim 1 or 2, mounting the lithographic printing plate material on a printing press cylinder without performing development processing. 4. Printing a lithographic printing plate material having an image forming layer on one side of a plastic support with the support side opposite to the image forming layer fixed to the cylinder surface of a printing press via an adhesive layer. Is performed. 5. The printing method according to claim 4, wherein the adhesive layer is in direct contact with the back surface of the lithographic printing plate material support and the cylinder of the printing press. 6. The printing method according to claim 4, wherein the adhesive layer is provided on the surface of the cylinder of the printing press in advance. 7. The printing method according to claim 4, wherein the sheet having the adhesive layer on the surface and the lithographic printing plate material are attached in this order to the surface of the cylinder of the printing press. 8. The printing method according to claim 4, wherein said adhesive layer is a silicone rubber layer. 9. A lithographic printing plate material comprising a support having a light-to-heat conversion layer containing a ferromagnetic metal powder and an ink repellent layer. 10. A lithographic printing plate material having a light-to-heat conversion layer and an ink repellent layer on a support, wherein the ink repellent layer contains thermoplastic resin particles. 11. A printing method, characterized in that printing is performed by supplying printing ink to the plate surface without subjecting the planographic printing plate material according to claim 9 or 10 to image exposure and then performing any development processing. .