WO1997028007A1

WO1997028007A1 - Lithographic plate material for laser direct makeup, and printing method using same

Info

Publication number: WO1997028007A1
Application number: PCT/JP1997/000268
Authority: WO
Inventors: Katsuji Konishi; Seiji Arimatsu; Hiroyuki Hiraoka; Yasuyuki Takimoto
Original assignee: Nippon Paint Co., Ltd.
Priority date: 1996-02-05
Filing date: 1997-02-04
Publication date: 1997-08-07

Abstract

A lithographic plate material for laser direct makeup, comprising a recording layer irradiated with pulsed laser, which includes a matrix of a thermoplastic polymer having an absorption band in the ultraviolet region, and particulates dispersed in the matrix, wherein the recording layer has an excellent print recovery property. A lithographic plate material for laser direct makeup is provided which has an excellent water retentivity in a portion of a recording layer surface irradiated by laser and by which scumming is hard to generate on a printed matter.

Description

Specification

Lithographic printing plate material for laser direct plate making and printing method using the same

The present invention relates to a lithographic printing plate material for laser direct plate making, and more particularly to a material used for offset printing.

Conventional technology

With the expansion and diversification of the offset printing market, new printing systems are being developed. For several years, the printing streak information recorded in the computer can be directly reproduced on the printing plate, the wastewater is not discharged in the development process, the natural environment can be protected, and the conventional production process plan has been significantly improved. A new computer-to-plate system that can use existing printing machines and ancillary equipment without any change and requires a small capital investment is proposed and its realization is desired. The printing plate material suitable for the computer `` toe-plate system '' has a photosensitive layer that has a light-sensitive property that enables image formation with low energy, can be developed without using water or chemical agents, and is equal to or better than the PS plate Printability, for example, hydrophilicity of the printing plate, water retention, print recovery (the property that printing can be performed as usual even after normal printing work after ink adheres to the entire surface of the plate), printing durability It is necessary to have

However, printing plates currently under development are multi-layered, require special materials, special manufacturing methods, and special plate-making equipment. For example, in a discharge-discharge type printing plate material, an image forming member consisting of an aluminum metal film and a silicone layer is provided on a polyester film, and the aluminum metal layer is broken by a multi-stylus discharge head modulated by image signals. It is used as a printing plate by forming an ink repellent layer. Without using such special materials and plate making equipment, using general-purpose polymer materials, pigments and existing laser irradiation equipment, We believe that if a printing plate suitable for the computer-toe-plate system can be obtained, it will contribute to technological innovation in the printing industry.

Among the present inventors, Hiroyuki Hiraoka is described in the journal 'OB' Photopolymer Science 'and Technology 1, Vol. 4, No. 3 (1991), pp. 463-468, and in Vol. 7, No. 2 ( 1994), pp. 299-308, reported that thermoplastic polymer films become hydrophilic upon irradiation with laser light. The present inventors applied this finding to a lithographic printing plate and invented a lithographic printing plate material for laser direct plate making (Japanese Patent Application No. 7-117125).

Summary of the Invention

The present invention is to further enhance the performance of the lithographic printing plate according to the above invention, and the object thereof is to have excellent water retention at a laser beam irradiated portion on the surface of a recording layer, hardly cause background stain on printed matter, and An object of the present invention is to provide a planographic printing plate material for laser direct plate making that has excellent recoverability.

The present invention provides a pulsed laser having a matrix made of a thermoplastic polymer having an ultraviolet absorption band (or a matrix containing a thermoplastic polymer and an additive) and particles dispersed therein. Another object of the present invention is to provide a lithographic printing plate material for laser direct plate making characterized by having a recording layer, and the above object is achieved.

Detailed description of the invention

The thermoplastic polymer used in the present invention is a general-purpose thermoplastic polymer known to those skilled in the art. A thermoplastic polymer having a high glass transition temperature (hereinafter abbreviated as Tg) and a high ultraviolet absorbance is preferred. Particularly preferred thermoplastic polymers are those having a Tg of at least 160 ° C. and an absorbance at the lasing wavelength of the laser of at least 1 × lf ^ cnr ¹ , especially at least 5 × 10 ² .

When the Tg of the polymer falls below 160 ° C, the parent surface of the recording layer Insufficient water solubility and soiling easily occur. The absorbance at the oscillation wavelength of the laser of the polymer is decreased absorption efficiency of the irradiation energy below ¹ χ ΐΟ ^ πΓ 1, the hydrophilicity is insufficient laser irradiated surface of the recording layer, tends to occur scumming.

Specific examples of the thermoplastic polymer of the present invention include polyimide resin, polyphenylquinosaline (PPQ), polysulfone, tetrafluoroethylene and 2,2-bis (trifluoromethyl) -4,5-difluoro- Examples thereof include a copolymer with 1,3-dioxolen and a soluble polyimide resin.

The particulate matter dispersed in the polymer refers to a component that forms a closed interface and exists in a matrix made of a thermoplastic polymer. “Particles” includes solids and liquids.

Particles which have good affinity and adhesion to the thermoplastic polymer and improve the water retention thereof are preferred as particulate matter. Particles that have been surface-treated to improve dispersibility may be used. Generally, inorganic particles, metal particles, organic particles and the like are used as the above-mentioned granular material. These may be used in combination as appropriate.

As the inorganic particles, for example, zinc oxide, titanium dioxide, white carbon (eg, maleic anhydride, hydrated calcium silicate and hydrated aluminum silicate), clay, tanolek, kaolin and the like can be used. As the metal particles, for example, aluminum, copper, nickel, etc. can be used. The inorganic or metal particles have an average particle size of less than 10 jum, preferably from 0.001 to 8111, more preferably from 0.01 to 5 zm. When the average particle size of the inorganic particles or the metal particles is less than 0.001 ID, the water retention of the laser-irradiated portion becomes insufficient, and the soil is easily generated. If it exceeds 10π, the resolution of the printed matter will be poor, the adhesion to the support will be poor, and particles near the surface will be easily removed.

The inorganic or metal particles are preferably 2 to 50% by volume, based on the total composition, preferably Is contained in the recording layer in an amount of 5 to 40% by volume, more preferably 10 to 30% by volume. When the content of the particles is less than 2% by volume, the water retention of the laser-irradiated portion on the surface of the recording layer becomes insufficient, and background fouling easily occurs. If it exceeds 50% by weight, the strength of the recording layer is reduced and the printing durability is reduced, and the adhesion between the support and the recording layer is reduced.

Organic particles other than inorganic particles or metal particles can be used as the granular material. The organic particles are not particularly limited as long as they enhance water retention, but resin particles can be used as the organic particles in a granular form. The following precautions need to be taken during use. When a solvent is used to disperse the resin particles, it is necessary to select a resin particle that does not dissolve in the solvent or a solvent that does not dissolve the resin particles. When dispersing the resin particles by heat with the thermoplastic polymer, it is necessary to select a material that does not melt, deform, or decompose due to the heat at the time of dispersing the resin particles.

Crosslinked resin particles can be preferably used to reduce these cautions. The organic particles have an average particle size of 0.01 to: 10 / m, preferably 0.05 to 5 // 01, more preferably 0.1 to 2; / m. If the average particle size of the organic particles is less than 0.01 zm, the water retention of the laser-irradiated portion becomes insufficient, and soiling tends to occur. If it exceeds 10 / Z ID, the resolution of the printed matter will be poor, the adhesion to the support will be poor, and particles near the surface will be easily removed. The organic particles are contained in the recording layer in an amount of 3 to 50% by volume, preferably 5 to 40% by volume, more preferably 10 to 30% by volume based on the total composition. If the content of the particles is less than 3% by volume, the water retention at the laser-irradiated portion of the recording layer surface will be insufficient, and background fouling will easily occur. It decreases the strength of the recording layer to exceed 50 wt% printing durability decreased, also, adhesion between the support and the recording layer you decrease ₀ Examples of the organic particles include polystyrene particles (particle diameter: 4 to 10 im), silicon particles (particle diameter: 2 to 4 zni), and the like. Examples of the crosslinked resin particles include a microgel (particle diameter: 0.01 to 1 m) composed of two or more ethylenically unsaturated monomers, and a crosslinked resin particle composed of styrene and divinylbenzene (particle diameter: 4 to 10). / zm), crosslinked resin particles (particle diameter: 4 to 10πι) composed of methyl methacrylate and diethylene glycol dimethacrylate, such as acrylic resin microgel, crosslinked polystyrene, crosslinked methyl methacrylate, and the like. These are prepared by general methods such as emulsion polymerization, soap-free emulsion polymerization, seed emulsion polymerization, dispersion polymerization, and suspension polymerization.

It is also possible to prepare inorganic particles from a solution. For example, a metal lower alkoxide is added to a solvent such as ethanol, and in the presence of water and an acid or alkali, inorganic particles containing the metal can be obtained. The resulting inorganic particle solution can be added to a solvent-soluble thermoplastic polymer solution to form an inorganic particle dispersion. Alternatively, it is also possible to add the metal lower alkoxide to the thermoplastic polymer solution first, and then add water and an acid or aluminum salt to obtain inorganic particles containing the metal.

When inorganic particles are prepared by adding a metal lower alkoxide to a thermoplastic polymer precursor solution, a polymer-inorganic composite is obtained when the polymer precursor is converted into a thermoplastic polymer by heat. As the metal lower alkoxide, tetraethoxyquin silane, tetraethoxyquin titanium and the like can be used. The recording layer is formed using any layer forming method known to those skilled in the art. For example, coating of a thermoplastic polymer solution containing granules or melt molding of a thermoplastic polymer containing granules can be mentioned.

When forming a recording layer using a thermoplastic polymer solution containing particulate matter, first, a thermoplastic polymer (or a thermoplastic polymer and an additive) is used. Put the granules and the glass beads in a container dissolved in a solvent, and shake using a paint shredder to disperse the granules. Next, the glass beads are removed with a stainless sieve to obtain a dispersion of the thermoplastic polymer containing the particulate matter. This dispersion is applied to a support and dried. Instead of the thermoplastic polymer, a solution containing the precursor and the particulate matter may be applied on a support, dried and, at the same time, the precursor is thermally cured to form a recording layer as a thermoplastic polymer. The coating thickness is generally between 0.1 and 10 ^ m, preferably between 0.5 and 5 ηι.

As the support, those well known to those skilled in the art can be used. For example, various plastic sheets having good dimensional stability, laminates thereof, metal plates, and composites thereof may be mentioned.

The support may be provided in advance with a layer of an adhesion promoter to improve the adhesion to the recording layer. Examples of the adhesion promoter include commercially available silane coupling agents and urethane adhesives. For example, silane coupling agents such as a- (aminoethyl) aminopropyltrimethoxysilane and avarininopropyltrimethoxysilane are suitable for bonding polyimides to metal supports.

The recording layer may be formed by adding a granular material to a solution of a commercially available thermoplastic polymer or a precursor thereof as exemplified below.

For example, a dimethylformamide solution of an aromatic polyimide resin with an aromatic ring marketed by Ciba Geigy Corporation under the trade name of “Matrimid 5218”: a product of “LARC-TPI” from Mitsui Toatsu Chemicals, Inc. Polyamic acid having an aromatic ring commercially available under the name (eg, 3.3 ', 4,4'-benzophenonetetracarboxylic anhydride and 3,3'-diaminobenzophenone) Dimethylacetamide solution) and commercially available from DuPont under the trade name “Teflon AF”. And tetrafluoroethylene and 2,2'-bis (trifluoromethyl) -4,5-difluoro-1,3-dioxylene copolymer.

In the case where the recording layer is formed by melt-molding a thermoplastic polymer containing particulate matter, a compression molding method is preferable. The injection molding method and the extrusion molding method are not suitable when the Tg is relatively high as in the present invention.

According to the compression molding method, a thermoplastic polymer (or a thermoplastic polymer and an additive) and a granular material are mixed in a powder or molten state, and the mixture is filled into a mold having a gap corresponding to a desired thickness of a recording layer. Heat to give fluidity. After pressing with a press while heating, the mold is opened and the recording layer is taken out. A suitable heating temperature is around Tg of the thermoplastic polymer.

When the recording layer is used alone as a printing plate material without using a support, the recording layer should have a thickness of 50 ζπι or more, preferably 80 to 500 // πι, more preferably 100 to 300 // πι. Molding. When the thickness of the recording layer is less than 50 m, the mechanical strength is insufficient for use as a printing plate.

Using the printing plate material of the present invention obtained as described above, offset printing can be performed by a so-called laser direct plate making method. The laser direct plate making method is to irradiate the surface of a recording layer (for example, a high Tg high absorbance thermoplastic polymer film with an absorption band in the ultraviolet) with a pulsed laser beam to increase the hydrophilicity of the irradiated area. This is a plate making method that enhances the thermoplastic polymer film to give the ink a selective adhesion.

In order to perform offset printing using the plate material of the present invention, for example, first, the surface of the recording layer of the plate material of the present invention is irradiated with a pulsed laser beam according to an image. As a result, the irradiated portion on the surface of the recording layer becomes hydrophilic. Then, a lithographic printing ink may be applied to the surface of the clerk for printing.

The energy of the laser light necessary to increase the hydrophilicity of the irradiated part of the recording Energy density 10~200mJ / cni ^2, preferably 40: a lOOmJ / cm ^2. When the energy density of the laser beam is lower than 10 mJ / cm ² , the recording layer surface is not provided with the selective adhesion of the ink. Irradiation at an energy density exceeding 200 fflJ / cm ² has little effect on improving printability.

Specifically, image formation on the surface of the recording layer can be performed by scanning and exposing the surface of the recording layer with laser light in response to print image information.

In order to impart hydrophilicity to the irradiated portion of the recording layer surface, it is necessary that the energy density of the irradiated surface reaches a certain threshold or more. Therefore, it is necessary to irradiate a pulsed laser beam with a large peak output by a short powerful pulse discharge.

As a pulsed laser, a multimode Nd: YAG laser, an excimer laser, a titanium-sapphire-laser, a nitrogen gas laser, a copper gas laser, a gallium arsenide semiconductor laser, and the like can be used. From the viewpoint of ease of maintenance and operation costs, solid-state lasers are preferred over gas lasers. Pulse oscillation lasers can be used up to wavelengths in the ultraviolet, visible, and even infrared light regions.

Another method of irradiating the surface of the recording layer according to an image is a method in which a mask processed according to the image is superimposed on the surface of the recording layer, and a laser beam is irradiated from above. As the mask, a photo negative for printing, a metal mask, or the like is used.

When plate making is performed using a laser light source having a pulse oscillation wavelength in the visible light region, an additive having a spectral sensitivity can be added to the oscillation region to increase the photosensitivity to the recording layer. The following can be used as additives.

Photopolymerization initiator: Photopolymerization initiator for aromatic ketones such as benzophenone and thioxanthene, and acetophene such as benzoin ether and acetophenone Non-photopolymerization initiators, photopolymerization initiators for diketones such as benzyl, organic peroxides: benzoyl peroxide,

Azo compound: azobis disoptyronitrile,

Halide: 2,4,6-tripromophenol,

Aromatic diazonium salt,

Aromatic eodonium salt,

Aromatic sulfonium salt,

Light power thione polymerization initiator,

Dyes that absorb visible light: carbonium dyes, onium dyes, anthraquinone dyes, cyanine / merocyanine dyes,

Xanthene dyes such as fluorescein, eosin, rose bengal, rhodamine 6G,

Thiazine dyes such as thionine and methylene blue,

Azine dyes such as riboflavin and noremiflavin,

Coumarin-based dyes such as coumarin,

Acridine dyes such as acridine orange,

Azo-based dyes such as Disperse Orange 3 and Disperse Yellow 9, and metal complexes of tetrabenzoborfurin.

In the relatively short wavelength region, the number of additives that can be used is large. However, as the absorption wavelength approaches the longer wavelength region, the solubility in organic solvents decreases, and the number of additives that can be used decreases. In the long wavelength region of 600 nm or more, a metal complex of mesophenyltetrabenzoborphyrin is preferable. An example of such a case is disclosed in Kunihiro Takamura et al., Journal “OB PHOTOPOLYMER“ Science ”AND” Technology, Vol. 1, Νο. 2 (1988), pp. 205-211. Additives that feel infrared pulsed laser light can also be used. As an additive Ordinary IR absorbers can be used. For example, there are carbon black pigment, titanium carbonate, silicon, green pigment, tungsten oxide, manganese oxide, and the like.

As the pulse oscillation laser of the present invention, a laser from ultraviolet to infrared can be used. The wavelength is preferably from visible to ultraviolet with a wavelength of 700 nm or less. When using an infrared laser, there is a problem in handling and safety because the laser beam cannot be seen. In addition, a lot of energy is required, and energy loss is also large.

The amount of the additives is generally from 0.:! To 5% by weight, preferably from 0.5 to 2% by weight. If the content is more than 5% by weight, the amount of light required for image formation is insufficient, and the hydrophilicity of the irradiated portion becomes insufficient.

In addition, the contrast between the irradiated part and the non-irradiated part can be improved by discoloring by laser irradiation by adding a dye. This is useful for plate calibration.

Action

Irradiation of the surface of the recording layer with laser light to enhance the hydrophilicity of the irradiated portion is a result of many causes. Although the reason is not clear, in the printing plate material of the present invention, due to the presence of the particulate matter on the surface of the recording layer, surface roughening due to laser light irradiation effectively occurs, and the water retention and hydrophilicity of the irradiated portion are improved. This is presumed to be one of the factors.

For example, (1) Hiroyuki Hiraoka et al., Journal of Photopolymer Science and Technology, Vol. 4, No. 3 (1991) pp. 463-468, (2) ) Hiroyuki Hiraoka et al., Journal 'Ob' Photochemistry. And Photobiology, A: Chemistry, 65 (1992) pp. 293-302, (3) Akira Yabe, Applied Physics Letter, 60 Vol. 21, No. 21, May 25, (1992) pp. 2697-2699, and (4) Akira Yabe et al., Applied Surface Science, Vol. 69 (1993), pp. 1-6. .

The hydrophilicity can be represented by a change in the contact angle between the plate surface and water. When a 40 mJ / cm ² laser beam is applied, the contact angle changes from 80 degrees to 0 degrees. It is said that when performing offset printing, the contact angle of the printing plate with water should be 20 degrees or less. The products of the present invention all satisfy this value. Generally, the hydrophilicity after laser irradiation increases in the order of polyester, polysulfone, polyimide and PPQ. The hydrophilicity of PPQ is equivalent to polyimide. Polycarbonate, polystyrene, polymethacrylate and the like show little hydrophilicity.

The hydrophilicity of these polymers decreases as the Tg decreases. It is considered that a high Tg makes it easier to maintain the porous structure and surface roughness of the surface site generated by irradiation.

In addition, the Tg of the thermoplastic polymer must be at least 160 ° C in order to exhibit hydrophilicity and maintain it for a long time. The hydrophilicity of the irradiated part can last for at least several months, but it must be maintained semipermanently for practical use as a printing plate. For this purpose, the conventional method for desensitizing offset printing plates containing phosphoric acid as a main component can be applied as it is.

Example

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” are based on weight, and the volume% of the granular material is added in parentheses after the weight%, and the average particle size and the true specific gravity of the granular material are based on the data described in the force tag. The scanning exposure method of the plate material was performed by moving the plate material with a moving table at a speed of 1 cm / sec. All pulse frequencies were fixed at 10 Hz.

Example 1

After adjusting soluble polyimide (trade name: Matriniid 5218, specific gravity 1.2, manufactured by Ciba Geigy Corporation) to 8% NV with DMF (dimethylformamide), silica particles (trade name: Carplex BS304F, average) Particle size 5 zm, specific gravity 2, Shionogi Pharmaceutical Co., Ltd.) was added to make up 40% (28.6%) of the total solids, glass beads were added, and this solution was applied to a paint shaker for 2 hours. The sily particles were dispersed. After filtering the glass beads, the filtrate was applied to an aluminum plate using a bar coater # 16, and dried at 130 at 4 minutes. The plate was heat treated at 300 ° C. for l hr. This plate was scan-exposed with an energy density of 50 ffiJ / cm ² and a pulse width of 15 nsec using a Nd: YAG laser (4th synchronous mode, 266 nm, Spectra, Quantix Ray GCR-4 manufactured by Physics). . Tap water / acid etchant (trade name: EU-3, manufactured by Fuji Photo Film Co., Ltd.) / IPA (isopropyl alcohol) = 1650/16. 7 / 185.3 as dampening water Printing was carried out using an offset printing machine (trade name: Hamadastar 700CDX, manufactured by Hamada Printing Machine Co., Ltd.) using an ink (trade name: New Campion F Gloss 59 indigo, manufactured by Dainippon Ink). Table 2 shows the print quality and evaluation.

Examples 2 to 15

Plate production, exposure, and printing were performed in the same manner as in Example 1 except that the granular material, the amount of the granular material added, the laser, and the energy density were changed as shown in Table 1 below. Table 2 shows the print quality and evaluation.

", ²⁾ , ³⁾ : silica particles (specific gravity: 2.2), manufactured by Nippon Aerosil 4 ⁾ · Titanium oxide particles (specific gravity: 3.7), manufactured by Nippon Aerosil

5) Clay particles (specific gravity: 2.6), manufactured by Shiraishi Calcium Co.

6) Aluminum oxide particles (specific gravity: 3.2), manufactured by Nippon Aerosil

7)

⁸⁾ : Silica particles (specific gravity: 2), manufactured by Shionogi

⁹⁾ : Zinc oxide particles (specific gravity: 5.6), manufactured by Sakai Chemical Co.

¹⁰ · Questec

1) Lambda Physic

12) Lambda Physic

A printing plate material was prepared in the same manner as in Example 12, and was subjected to etching treatment with an etchant (trade name: PP Clean B, manufactured by Kenken Kagaku Kenkyusho) before printing, followed by printing in the same manner as in Example 1. . Table 2 shows the print quality and evaluation.

Example 17

Soluble polyimide (trade name: Matrimid 5218, specific gravity 1.2, manufactured by Ciba-Geigy Corporation) is adjusted to 8% NV with DMF (dimethylformamide), and then aluminum pigment (trade name: Alpaste 5680NS) ) [Aluminum content 70%], average particle size 8.2 / πι, specific gravity of aluminum 2.7, manufactured by Toyo Aluminum Co., Ltd. And a glass bead was added thereto, and this solution was dispersed in a paint shaker for 2 hours to disperse the aluminum pigment. After filtration of the glass beads, it was applied to an aluminum plate surface-treated with a silane coupling agent (trade name: SZ6020, manufactured by Toray 'Dow Corning' Silicone Co., Ltd.) using a bar coater # 16 and dried at 130 ° C for 4 minutes. . To treat the aluminum plate with a silane coupling agent, a 1% methanol solution was applied to the aluminum plate with a bar coater # 8, dried at 60 ° C, and further dried at 100 ° C for 10 minutes. The obtained plate was scanned and exposed at an energy density of 100 mJ / cm ² and a pulse width of 15 nsec using a Nd: YAG laser (second synchronous mode 533 nm). Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation. The adhesion to the aluminum indicator was also good.

Example 18

Soluble polyimide (brand name: liatrimid 5218, specific gravity 1.2, manufactured by Ciba Geigy) was adjusted with DMF (dimethylformamide) to 8% NV, and then copper particles (average particle size 1 ιη, 8.9) to 20% (3.3%) of the total solids, add glass beads, and apply this liquid to a paint shaker for 2 hr. Was dispersed. After filtering the glass beads, the silane coupling agent (trade name: s

It was applied to an aluminum plate surface-treated with Z6020 (Toray Dow Corning Silicone Co., Ltd.) using a bar coater # 16 and dried at 130 ° C for 4 minutes. To treat the aluminum plate with a silane coupling agent, a 1% methanol solution was applied to the aluminum plate with a bar coater # 8, dried at 60 ° C, and further dried at 100 ° C for 10 minutes. The obtained plate was subjected to scanning exposure with an energy density of 200 mJm ² and a pulse width of 15 nsec using a Nd: YAG laser (second synchronous mode 533 nm). Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation. The adhesion to the aluminum support was also good.

Example 19

After adjusting soluble polyimide (trade name: Matrinid 5218, specific gravity 1.2, manufactured by Ciba-Geigy Co., Ltd.) to 8% NV with DMF (dimethylformamide), nickel (average particle diameter 1 / m, specific gravity) 8.85) was added to 20% (3.3%) of the total solids, glass beads were added, and this liquid was dispersed in a paint shaker for 2 hours to disperse nickel particles. After filtering the glass beads, apply it to an aluminum plate surface-treated with a silane coupling agent (trade name: SZ6020, manufactured by Toray Industries, Inc., Silicone Co., Ltd.) using a bar coater # 16, and then 4 minutes at 130 ° C. Dried. To treat the aluminum plate with a silane coupling agent, a 1% methanol solution was applied to the aluminum plate with a bar coater # 8, dried at 60 ° C, and further dried at 100 ° C for 10 minutes.

The obtained plate was scanned and exposed using an Nd: YAG laser (second synchronous mode 533 nm) at an energy density of 200 mJ / cro ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation. The adhesion to the aluminum support was also good.

Example 20

Soluble polyimide (trade name: Matrimid 5218, specific gravity 1.2, Ciba-Geigy) Manufactured by DMF (dimethylformamide) to make the NV 8%, and then cross-linked acryl resin microgel (trade name: AZP-1430, average particle size 0.48 xm, specific gravity 1.1, Nippon Paint) Was added to make up to 40% (42.1%) of the total solids, glass beads were added, and this liquid was applied to a paint shaker for 2 hours to disperse the crosslinked resin particles. After filtering the glass beads, apply with a bar coater # 16 to an aluminum plate surface-treated with a silane coupling agent (trade name: S Z6020. Toray, Dow Corning, Silicone Co., Ltd.) and dry at 130 ° C for 4 minutes. did. Treatment of the aluminum plate with the silane coupling agent was performed by applying a 1% methanol solution to the aluminum plate with a bar coater # 8 plate, drying at 60 ° C, and then drying at 100 ° C for 10 minutes. . The obtained plate was scanned and exposed using an Nd: YAG laser (fourth synchronous mode, 266 nm) with an energy density of 10 OmJ / cm ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation.

Example 21

Soluble polyimide (trade name: Matrimid 5218, specific gravity 1.2, manufactured by Ciba-Geigy Corporation) is adjusted to 8% NV with DMF (dimethylformamide), and then crosslinked polymethyl methacrylate resin particles (trade name: Techpolymer MBX-4, average particle size 4 / zm, specific gravity 1.2, manufactured by Sekisui Plastics Co., Ltd.) to 20% (20%) of the total solids, add glass beads, and paint this liquid. The crosslinked resin particles were dispersed in the shaker over 2 hours. After filtering the glass beads, apply it with a bar coater # 16 to an aluminum plate surface-treated with a silane coupling agent (trade name: SZ6083, manufactured by Toray 'Dauco One' Silicone) and dried at 130 ° C for 4 minutes did. The treatment of the aluminum plate with the silane coupling agent is performed by applying a 1% methanol solution to the aluminum plate with a bar coater # 8 plate, drying at 60 ° C, and further drying at 100 ° C for 10 minutes. went. Using a Nd: YAG laser (fourth synchronous mode, 266 nm), the obtained plate was scanned and exposed at an energy density of 100 mJ / cm ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation. Example 22

Polyamic acid (trade name: LARC-TPI, NV = 28.6%, solid specific gravity 1.4, manufactured by Mitsui Toatsu Chemicals, Inc.) and silica particles (trade name: Carplex BS304F, average particle size m, specific gravity 2, Shionogi) (Manufactured by Pharmaceutical Co., Ltd.) to 30% (23.1%) of the total solid content, and then adjusted to 10% NV with DMAC (dimethylacetamide). A glass bead was added, and this solution was applied to a paint shaker for 2 hours to disperse the particles of the sili-can. After filtering the glass beads, the filtrate was applied to an aluminum plate with a bar coater # 16 and dried at 130 ° C for 4 minutes. This plate was subjected to heat treatment at 100 ° C. for 1 hr, at 150 ° C. for 1 hr, at 200 ° C. for 1 hr, and at 300 ° C. for 2 hr to complete the polyimide treatment. This plate was scanned and exposed using an Nd: YAG laser (fourth synchronous mode, 266 nm) at an energy density of 50 niJ / cin ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation.

Example 23

Poriamikku acid (trade name:. LARC-TPI, NV = 28 6%, solids specific gravity 1.4, Mitsui East pressure chemical Co.) 30% of the total solids in the tetraethoxysilane as calculated on Si0 ₂ (23. 1%), adjusted to 10% NV with DMAC (dimethylacetamide), and stirred at room temperature for 8 hr. To the solution were added ion-exchanged water corresponding to 1.3 times the number of moles of tetraethoxysilane and HC1 0.01 times the number of moles of tetraethoxysilane, and the mixture was stirred at room temperature for 6 hr. The solution was applied to an aluminum plate with a bar coater # 16 and dried at 130 ° C for 4 minutes. The plate was then heat treated for lhr at 100 ° C, lhr at 150 ° C, lhr at 200 ° C, and 2hr at 300 ° C to form a polyimide to form a polyimide / silica composite. This plate was scanned and exposed with an energy density of 100 nJ / cm ² and a pulse width of 15 nsec using a Nd: YAG laser (4th synchronous mode: 266 mn). Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation.

Example 24

Polyamide Kkusan (trade name:. LARC-TPI, NV = 28 6%, solids specific gravity 1.4, Mitsui East pressure chemical Co.) 40% of the total solids in tetraethoxy titanium as calculated on Ti0 ₂ ( 25.1%), adjusted to NV10% with DMAC (dimethyl acetate amide), and stirred at room temperature for 8 hr. Ion-exchanged water equivalent to 1.3 times the number of moles of tetraethoxytitanium and HC1 0.01% relative to the number of moles of tetraethoxytitanium were added to the solution, and the mixture was stirred at room temperature for 6 hr. The solution was applied to an aluminum plate with a bar coater # 10 and dried at 130 ° C for 4 minutes. 100 of this board. Heat treatment was continued for 1 hr at C, 1 hr at 150 ° C, 1 hr at 200 ° C, and 2 hr at 300 ° C to form a polyimide / titanium oxide composite. This plate was scanned and exposed using an Nd: YAG laser (fourth synchronous mode 266ηιη) at an energy density of 100 mJ / cm ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation.

Example 25

Thermoplastic polyimide (trade name: Aurum, specific gravity 1.33, manufactured by Mitsui Toatsu Chemicals, Inc.) and silica particles (trade name: Curve Lettuce BS304N, average particle size 9.3〃m, specific gravity 2, manufactured by Shionogi Pharmaceutical Co., Ltd.) ) Was added at 55% (44.9%) of the total solids and kneaded in a kneader at 300 ° C for about 30 minutes. Take out the kneaded material, insert it into a mold heated to 140 to 170 ° C, close the female mold and the female mold, and press with a press while maintaining the temperature at 310 to 360 ° C to obtain a thickness. Formed into 100 / z iD film. The molding conditions are: 1) molding temperature: 310-360 ° C, 2) molding pressure: 210-350 kg / cm ² , 3) gap setting: lOO / zm (with spacer thickness), 4) molding time: 10 minutes And

The obtained film was subjected to scanning exposure with an energy density of 100 mJ / cm ² and a pulse width of 15 nsec using a Nd: YAG laser (fourth synchronous mode, 266 nm). The light offset etch solution (Ricofax etch solution) was diluted with water to make a dampening solution, and printing was performed. The ink used was process ink (CAPS-G, manufactured by Dainippon Ink and Chemicals, Inc.), and high-quality paper (35 kg in gold) was used. The print quality and evaluation are shown in Table 2.

Example 26

Polyethersulfone (trade name: polyether sulfone (PES), specific gravity 1.37, manufactured by Mitsui Toatsu Chemicals, Inc.) and silica particles (trade name: AER0SIL 130, primary average particle diameter 16 nm, specific gravity 2.2, Japan AEROSIL Co., Ltd.) was added to make up 40% (29.4%) of the total solids, and the recording layer film was formed in the same manner as in Example 19 except that the following molding conditions were used. did. The molding conditions were 1) molding temperature: 177 ° C, 2) molding pressure: 210 to 350 kg / cm ² , 3) gap setting: lOO ^ m (though spacer thickness), and 4) molding time: 10 minutes. . Using the same Nd: YAG laser (the fourth synchronous mode, 266 nm) used in Example 1, the obtained film was scanned and exposed at an energy density of 100 mJ / cm ² and a pulse width of 15 nsec.

Printing was performed according to the method described in Example 25. The print quality and evaluation are not shown in Table 2.

Example 27

Polyphenylquinosaline (specific gravity 1.6) with silica particles (trade name: Carplex BS304F, average particle size 5 m, specific gravity 2, Shionogi Pharmaceutical Co., Ltd.) to 30% (25.5%) of the total solids And a recording layer film was formed in the same manner as in Example 19, except that the following conditions were applied. The molding conditions were: 1) molding temperature: 177 ° C, 2) molding pressure: 210-350 kg / cm ² , 3) gap setting: 100 m (but spacer thickness), 4) molding time: 10 minutes . Using the same Nd: YAG laser (the fourth synchronous mode, 266 nm) used in Example 1, the obtained film was scanned and exposed at an energy density of 100 mJ / cm ² and a pulse width of 15 nsec. Printing was performed according to the method described in Example 25. Table 2 shows the print quality and evaluation.

Example 28

Organic solvent soluble ethylene tetrafluoride and 2,2-bis (trifluoromethyl) -4,5-difluoro-1,3-dioxolene copolymer (specific gravity 1.6) are converted to 8% NV with fluorocarbon. After adjusting to 20% (15.4%) of silica particles (trade name: AEROSIL R972, primary average particle size 16 nm, specific gravity 2.2, manufactured by Nippon Aerosil Co., Ltd.) and adding glass beads The leverage solution was applied to a paint shaker for 2 hr to disperse silica particles. After filtering the glass beads, the filtrate was applied to an aluminum plate with a bar coater # 10 and dried at 80 ° C for 4 minutes. After doping this plate with 25% tri-C ₉ F ₁₈ -substituted triazine, heating at 200 ° C for lhr and then irradiating with far ultraviolet light, the ultraviolet absorption coefficient improves (absorbance 0.14, wavelength 240nm) )did. The obtained plate was subjected to scanning exposure using the same Nd: YAG laser (the fourth synchronization mode of 266 nm) as used in Example 1 at an energy density of lOOraJ / cm ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation.

Example 29

After adjusting the soluble polyimide (trade name: Matrimid 5218, specific gravity 1.2, manufactured by Ciba Geigy Co., Ltd.) to 8% NV with DMF (dimethylformamide), the silica particles (trade name: Carplex BS304F, Average particle size 5 // m, specific gravity 2, Shionogi Pharmaceutical Co., Ltd.) is added to 30% (20.5%) of the total solids, glass beads are added, and this liquid is added to paint shaker for 2 hr. To disperse the silica particles. After filtering the glass beads, apply it to an aluminum plate surface-treated with a silane coupling agent (trade name: SZ6020, Toray * Dawko Isingu, Silicone Co., Ltd.) at # 16 with Barco # 1 and 4 minutes at 130 ° C Dried. To treat an aluminum plate with a silane coupling agent, apply a 1% methanol solution to the aluminum plate with a bar coater # 8 plate And dried at 60 ° C for 10 minutes at 100 ° C. Using a Nd: YAG laser (fourth synchronous mode, 266nra), the obtained plate was subjected to scanning exposure at an energy density of 50 mJ / cm ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the printing quality and evaluation. The adhesion to the aluminum support was also good.

Example 30

After adjusting soluble polyimide (trade name: Matrimid 5218, specific gravity 1.2, manufactured by Ciba Geigy Co., Ltd.) to 8% NV with DMF (dimethylformamide), the silica particles (trade name: Carpretas BS304F) , Average particle size 5 // m, specific gravity 2, Shionogi Pharmaceutical Co., Ltd.) was added to soluble polyimide at 30% (20.5%), glass beads were added, and this solution was applied to a paint shaker for 2 hours. The sily particles were dispersed. After filtering the glass beads, the filtrate was applied to an aluminum plate provided with a two-component curing type urethane adhesive layer thereon using a bar coater # 10, and dried at 130 ° C for 4 minutes. The adhesive layer is a polyester-based adhesive (trade name: Hybon 7031, manufactured by Hitachi Chemical Co., Ltd.) / Curing agent (trade name: Takenate D-101, manufactured by Takeda Pharmaceutical Co., Ltd.) / Dibutyltin dilaurate / ethyl acetate = 40 parts / 2 parts / 0.4 parts / 57.6 parts of the solution was applied to an aluminum plate with a bar coater # 8 and dried at 90 ° C. for 5 minutes. Using a Nd: YAG laser (4th synchronous mode 266ηπι), the obtained plate was scanned and exposed at an energy density of 50 mJ / ciD ² and a pulse width of 15 nsec. Printing was performed in the same manner as in Example 1. Table 2 shows the print quality and evaluation. The adhesion to the aluminum support was also good.

Example 31

Soluble polyimide (trade name: Matrimid 5218, specific gravity 1.2, manufactured by Ciba Geigy Co., Ltd.) and 1% of rhodamine 6G as an additive to soluble polyimide were added to NV8 with DMF (dimethylformamide). %, And then adjust the particle size (product name: Carplex BS304F, average particle size 5ζ πι, specific gravity 2, Shionogi (Manufactured by Pharmaceutical Co., Ltd.) was added to make up 20% (12.9%) of the total solids, glass beads were added, and the solution was dispersed on a paint shaker for 2 hours to disperse the particles of silicic acid. After filtering the glass beads, apply it to an aluminum plate surface-treated with a silane coupling agent (trade name: SZ6083, Toray Duco One Silicone Co., Ltd.) at # 10 with Barco # 10, and 4 minutes at 130 ° C Dried. The treatment of the aluminum plate with the silane coupling agent was performed by applying a 1% methanol solution to the aluminum plate with a bar coater # 8 plate, drying at 60 ° C, and further drying at 100 ° C for 10 minutes. The obtained plate was scanned and exposed at an energy density of 100 mJ / cm ² and a pulse width of 15 nsec using a Nd: YAG laser (second synchronous mode 533ηπι). In the exposed area, the dye faded and a latent image appeared. This plate was printed in the same manner as in Example 1. Table 2 shows the printing quality and evaluation. The adhesion to the aluminum support was also good.

Example 32

1% of soluble polyimide (trade name: ilatrimid 5218, specific gravity 1.2, manufactured by Ciba Geigy) and Benzov Xnon as an additive are added to soluble polyimide and DMF (dimethylformamide) NV 8% After that, the silica particles (trade name: Carplex BS304F, average particle size 5 ^ m, specific gravity 2, Shionogi Pharmaceutical Co., Ltd.) were adjusted to 20% (12.9%) of the total solids. The glass beads were added, and the solution was dispersed in a paint shaker for 2 hours to disperse the particles. After filtering the glass beads, apply it to an aluminum plate surface-treated with a silane coupling agent (trade name: SZ6083, Toray's Dawco One Silicone Co., Ltd.) at # 10 with Barco # 10, and 4 minutes at 130 ° C Dried. Treatment of the aluminum plate with the silane coupling agent was performed by applying a 1% methanol solution to the aluminum plate using a Verco # 8 plate, drying at 60 ° C, and further drying at 100 ° C for 10 minutes. The obtained plate was scanned and exposed using an Nd: YAG laser (second synchronous mode: 358 nm) at an energy density of 50 mJ / cm ² and a pulse width of 15 nsec. This plate is the same as in Example 1 Printing. Table 2 shows the print quality and evaluation. The adhesion to the aluminum support was also good.

Comparative Example 1

A plate was prepared, exposed, and printed in the same manner as in Example 1 except that the particles of the sily force were removed. As shown in Table 2, the print quality is lower than in Example 1 in recoverability.

Comparative Example 2

A plate was prepared, exposed, and printed in the same manner as in Example 22 except that the particles of the sily force were removed. As shown in Table 2, the print quality is lower than that of Example 22.

Comparative Example 3

Film forming, exposure, and printing were performed in the same manner as in Example 25 except that the particles of the sily force were removed. As shown in Table 2, the print quality is inferior to Example 25 in recoverability.

Comparative Example 4

Film forming, exposure, and printing were performed in the same manner as in Example 26 except that the particles of the sily force were removed. As shown in Table 2, the print quality is lower than that of Example 26 in recoverability.

Comparative Example 5

Film forming, exposure, and printing were performed in the same manner as in Example 27 except that the silicide particles were omitted. As shown in Table 2, the print quality is lower in recoverability than in Example 27.

Comparative Example 6

A plate was prepared, exposed, and printed in the same manner as in Example 28 except that the particles of the sily force were removed. Table 2 shows the print quality compared to Example 28 as shown in the print quality. You can see that the reversion is inferior,

Table 2

tat

Example Recoverability Background dirt Printing durability

1 〇 ϋ 5

2 〇〇 6

3 Δ 〇 4

4 〇〇 5 “

5 〇〇 5

6 〇〇 4

1 Δ ~

o 〇 4

8 Δ 〇 3

9 Δ 〇 3

10 〇〇 3

11 Li 〇 5

12 Δ 〇 2

13 〇〇 5

14 〇〇 6

15 〇〇 5

16 Δ ~ 〇〇 4

17 Δ 〇 3

18 Δ 〇 2

19 Δ 〇 2

20 △ 〜〇〇 3

21 Δ 〇 2

22 〇〇 5

23 Ο 〇 3

24 △ 〜〇〇 4

25 Δ 〇 1

26 Δ 〇 1

27 Δ 〇 1

28 Δ 〇 2

29 〇〇 8

30 〇〇 7

01

ύ 丄 ri o o

32 〇〇 8

Compare 1 X 〇 0.3

Comparison 2 Δ 〇 0.5

Compare 3 X 〇 0.2

Compare 4 X 〇 0.2

Compare 5 X 〇 0.2

Compare 6 X 〇 0.3

PS version ^d 〇〇 5 ~ 10 ^e

a) After printing the plate completely with ink, we checked whether it could be printed.

〇… Recovery; Δ · Recovery; X… No recovery

b) The presence or absence of background stain during printing was visually evaluated. 〇… No background stain: X… Background stain

C) Indicates the number of copies that can be printed.

d) Fuji Photo Film PS version "Product name; Positive type PS-PLATE FPSJ" e) Reprinted from Fuji Photo Film catalog

The invention's effect

The present invention provides a coating film in which inorganic fine particles, metal fine particles or organic fine particles are dispersed in a general-purpose thermoplastic polymer (or a thermoplastic polymer and an additive) having a high glass transition temperature (hereinafter abbreviated as Tg) and a high ultraviolet absorbance. Alternatively, write laser directly on the film. As a result, a lithographic printing plate material for laser direct plate making that has excellent water retention in the laser light-irradiated portion of the recording layer surface and is less likely to cause soiling on printed matter is provided, reducing printing costs, making the plate making environment cleaner, and improving materials. It brings effects such as eliminating supply anxiety.

Claims

The scope of the claims

1. In a lithographic printing plate material for laser direct plate making having a recording layer obtained by irradiating a pulsed laser, the recording layer is dispersed in a matrix made of a thermoplastic polymer having an ultraviolet absorption band. A lithographic printing plate material for laser direct plate making characterized by having a granular material.

2. The lithographic printing plate material according to claim 1, wherein the matrix further contains an additive.

3. The lithographic printing plate material according to claim 1, wherein the pulsed laser is a multimode Nd: YAG laser, excimer laser, titanium-sapphire-laser, nitrogen gas laser, nitrogen gas laser, or gallium arsenide semiconductor laser.

4. The lithographic printing plate material according to claim 1, wherein the thermoplastic polymer has a glass transition temperature of 160 ° C. or more, and an absorbance at a laser oscillation wavelength of ¹ × 10 ² cnr ¹ or more.

5. The lithographic printing plate material according to claim 1, wherein the thermoplastic polymer is at least one selected from the group consisting of a condensation type polyimide resin, polyphenylquinosaline and polysulfone.

6. The particulate matter is an inorganic particle selected from the group consisting of zinc oxide, titanium dioxide, white carbon, and clay, or a metal particle selected from the group consisting of aluminum, copper, and nickel. The lithographic printing plate material described.

7. The lithographic printing plate material according to claim 1, wherein the granular material has an average particle size of 10 πι or less.

8. The lithographic printing plate material according to claim 1, wherein the particulate matter is contained in the recording layer in an amount of 2 to 50% by volume based on the total composition.

9. The flat printing plate material according to claim 1, wherein the particulate matter is an organic particle made of a crosslinked resin.

10. The lithographic printing plate material according to claim 1, wherein the granular material has an average particle size of 0.01 to:

11. The lithographic printing plate material according to claim 1, wherein the particulate matter is contained in the recording layer in an amount of 3 to 50% by volume based on the total composition.

12. a) providing a lithographic printing plate according to claim 1;

b) irradiating the surface of the recording layer of the lithographic printing plate material with an image of a pulsed laser beam according to an image, thereby hydrophilizing an irradiated portion:

c) applying a lithographic printing ink to the surface of the recording layer and printing.