JP2007181947A - Supporting body for photosensitive lithographic printing plate, its manufacturing method and photosensitive lithographic printing plate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive lithographic printing plate material with good resistance to a processing liquid on a printing machine, excellent printing wear, and excellent stain resistance during printing, a supporting body providing it and a method for manufacturing the printing plate. <P>SOLUTION: In a method for manufacturing the supporting body for the photosensitive lithographic printing plate formed by applying a roughened processing on an aluminum plate or an aluminum alloy plate, then applying an anodizing processing, and furthermore, applying an after-treatment, the supporting body for the photosensitive lithographic printing plate, its manufacturing method and the photosensitive lithographic printing plate material are characterized in that the after-treatment is a treatment with a polyvinyl phosphonic acid water solution or the treatment with the polyvinyl phosphonic acid water solution after treatment with sodium silicate, and thereafter, the after-treated aluminum plate or aluminum alloy plate is washed with a water solution with a pH of 4-9 and a liquid temperature of 70-90°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive lithographic printing plate material, an aluminum plate support used therefor, and a method for producing the same.

  In recent years, CTP recording digital image data directly on a photosensitive printing plate with a laser light source has been developed and is being put to practical use in the technology for producing printing plates for offset printing.

  Among these, in the field of printing that requires a relatively high printing durability, it is known to use a printing plate material having an aluminum plate as a support and an image recording layer thereon.

  As the aluminum plate, a surface subjected to roughening treatment and anodizing treatment is generally used. However, there are problems such as damage to small spots or stains when performing a large amount of printing. there were.

  For the purpose of improving these problems, as a printing plate material using an aluminum plate support, a projection having a specific average height made of boehmite is generated on the surface of the aluminum grain support, and polymerizable thereon. A printing plate material provided with an assembled photosensitive layer is known (for example, see Patent Document 1).

  Further, a printing plate material using an aluminum support that has been subjected to a specific roughening treatment, anodized, and then hydrophilized with polyvinylphosphonic acid (see, for example, Patent Document 2), an aluminum support and a photosensitive material. A printing plate material (see, for example, Patent Document 3) in which an intermediate layer containing polyvinylphosphonic acid is provided between layers is known.

However, even with the above printing plate material, when a large amount of printing is performed, the small dots may be damaged or stains may occur during printing, and the printing durability and stain resistance are not sufficient.
JP 2000-255177 A JP 2002-103834 A JP 2003-57831 A

  An object of the present invention is to provide a photosensitive lithographic printing plate material excellent in printing durability and anti-staining properties during printing, a support for providing the same, and a plate making method thereof.

  The above object of the present invention can be achieved by the following configuration.

  1. In the method for producing a photosensitive lithographic printing plate support, which is obtained by subjecting an aluminum plate or an aluminum alloy plate to a surface roughening treatment, followed by an anodizing treatment, and further performing a post-treatment. Treatment with an aqueous acid solution or treatment with an aqueous polyvinylphosphonic acid solution after sodium silicate treatment, and then the post-treated aluminum plate or aluminum alloy plate has a pH of 4 to 9 and a liquid temperature of 70 to 90 ° C. A method for producing a support for a photosensitive lithographic printing plate, comprising washing with an aqueous solution.

  2. 2. A photosensitive lithographic printing plate support produced by the method for producing a photosensitive lithographic printing plate support according to 1 above.

  3. 3. A photosensitive lithographic printing plate material comprising an image forming layer on the photosensitive lithographic printing plate support described in 2 above.

  4). 4. The photosensitive lithographic printing plate material as described in 3 above, wherein the image forming layer is a heat-sensitive image forming layer.

  5. 5. The photosensitive lithographic printing plate material as described in 3 or 4 above, wherein the image forming layer is a photopolymerization type image forming layer.

  According to the present invention, there is provided a photosensitive lithographic printing plate material having good treatment liquid resistance on a printing press, excellent printing durability, and excellent antifouling property during printing, a support for providing the same, and a plate making method thereof. I was able to.

  The present invention will be described in more detail.

(Aluminum plate support and surface treatment)
The aluminum plate support according to the present invention is a pure aluminum plate or an aluminum alloy plate.

  Various aluminum alloys can be used, for example, alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, etc. An aluminum plate produced by the method can be used. In addition, a recycled aluminum plate obtained by rolling recycled aluminum ingots such as scrap materials and recycled materials that are becoming popular in recent years can also be used.

  The aluminum plate support according to the present invention is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface prior to roughening (graining treatment). As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, it is immersed in an acid such as phosphoric acid, nitric acid or sulfuric acid, or a mixed acid thereof and subjected to a desmut treatment. It is preferable.

  Next, a roughening process is performed. Examples of the roughening method include a mechanical method and a method of etching by electrolysis. In the present invention, AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid is preferable, but prior to that, mechanical surface roughening treatment and electrolytic surface roughening treatment mainly composed of nitric acid may be performed.

The mechanical roughening method is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. The roughening by honing polishing is performed by, for example, uniformly dispersing volcanic ash particles having a particle size of 10 to 100 μm in water, injecting pressure from a nozzle, and causing the surface to collide obliquely with the support surface. Can do. Further, for example, abrasive particles having a particle size of 10 to 100 μm are applied to the support surface so as to be present at a density of 2.5 × 10 ³ to 10 × 10 ³ particles / cm ² at intervals of 100 to 200 μm. Roughening can also be performed by laminating the sheets and applying a pressure to transfer the rough surface pattern of the sheet.

After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The dissolution amount of aluminum in the support surface, 0.5 to 5 g / m ² is preferred. After the immersion treatment with an alkaline aqueous solution, it is preferable to neutralize by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid or a mixed acid thereof.

The electrolytic surface-roughening treatment mainly composed of nitric acid can be generally performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts. Current density may be in the range of 10 to 200 A / dm ^2, preferably selected from the range of 20 to 100 A / dm ^2. The quantity of electricity, may be in the range of 5000 C / dm ^2, preferably selected from the range of 100~2000c / dm ^2. The temperature at which the electrochemical roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, acetic acid phosphate, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.

After the electrolytic surface-roughening treatment mainly composed of nitric acid, it is preferably immersed in an acid or alkali aqueous solution in order to remove the aluminum hydroxide compound and the like on the surface. Examples of the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of aluminum hydroxide compound and aluminum dissolved on the surface is preferably 0.5 to 5 g / m ² . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid or sulfuric acid or a mixed acid thereof.

In the AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid, the hydrochloric acid concentration is 5 to 20 g / l, preferably 6 to 15 g / l. The current density is 15 to 120 A / dm ² , preferably 20 to 90 A / dm ² . The quantity of electricity was 400~2000C / dm ^2, preferably 500~1200C / dm ^2. The frequency is preferably in the range of 40 to 150 Hz. The temperature of the electrolytic solution can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. If necessary, nitrate, chloride, amines, acetic acid, oxalic acid, aluminum ions and the like can be added to the electrolytic solution.

After the electrolytic surface roughening treatment is performed in the electrolytic solution mainly containing hydrochloric acid, it is preferably immersed in an acid or alkali aqueous solution in order to remove the aluminum hydroxide compound and the like on the surface. Examples of the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of the aluminum hydroxide compound and aluminum dissolved on the surface is preferably 0.5 to ² g / m ² . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid or sulfuric acid or a mixed acid thereof.

  The arithmetic average roughness (Ra) of the surface on the photosensitive layer side of the obtained aluminum support is preferably 0.4 to 0.6 μm, and is controlled by a combination of hydrochloric acid concentration, current density, and electric quantity in the roughening treatment. I can do it.

Following the roughening treatment, an anodizing treatment is performed to form an anodized film. The anodizing method according to the present invention is preferably carried out using sulfuric acid or an electrolytic solution mainly composed of sulfuric acid as the electrolytic solution. The concentration of sulfuric acid is preferably 5 to 50% by mass, particularly preferably 10 to 35% by mass. The temperature is preferably 10 to 50 ° C. The treatment voltage is preferably 18V or more, and more preferably 20V or more. Current density is preferably 1~30A / dm ^2. Quantity of electricity is preferably from 200~400C / dm ^2.

The formed anodic oxidation coating amount is preferably ² to 4 g / m ² , and preferably 2.5 to 3.5 g / m ² . The anodized coating amount is obtained by, for example, immersing an aluminum plate in a chromic phosphate solution (85% phosphoric acid solution: 35 ml, prepared by dissolving 20 g of chromium (IV) oxide in 1 L of water) to dissolve the oxide film, It is obtained from mass change measurement before and after dissolution of the coating on the plate. Micropores are generated in the anodized film, and the density of the micropores is preferably 400 to 700 / μm ^{2, and} more preferably 400 to 600 / μm ² .

  The anodized support may be sealed as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, ammonium acetate treatment and the like.

  The treatment with the aqueous solution containing polyvinylphosphonic acid according to the present invention is to bring the anodized surface of the aluminum plate support into contact with the aqueous solution containing polyvinylphosphonic acid.

  The polyvinyl phosphonic acid according to the present invention is a vinyl polymer having a phosphonic group, preferably having a number average molecular weight of 5,000 to 40,000, particularly preferably 10,000 to 25,000.

  As content of the said polyvinylphosphonic acid, it is preferable to exist in 0.05-0.6 mass% with respect to aqueous solution. Furthermore, it is still more preferable to use in 0.1-0.4 mass%.

  Examples of the treatment with an aqueous solution containing polyvinylphosphonic acid include, but are not limited to, a coating method, a spray method, a dip method, and the like. As this process, a dip type is suitable for making the equipment inexpensive.

  In the case of a dip type, it is preferable to treat with a 0.1 to 0.4 mass% aqueous solution of polyvinylphosphonic acid. The treatment temperature is preferably 50 to 90 ° C., and the treatment time is preferably 10 to 50 seconds.

  After bringing polyvinylphosphonic acid into contact with the anodized film, the surface is washed with water, and then washed with an aqueous solution having a pH of 4 to 9 and a liquid temperature of 70 to 90 ° C. These washings leave polyvinylphosphonic acid reacting with the anodized surface, remove the polyvinylphosphonic acid adhering to the surface, and remove the adhering polyvinylphosphonic acid, It seems that a support having excellent adhesion to the support can be obtained. After these treatments, drying is performed at 150 to 230 ° C.

  Drying at 150 to 230 ° C. means that the temperature of the support surface is within this range. The surface temperature can be measured with a commercially available non-contact surface thermometer. The drying time is preferably 2 seconds to 60 seconds, particularly preferably 5 seconds to 40 seconds.

  The heating method for drying may be drying using hot air, or using a quartz heater or a far infrared heater.

(Image forming layer)
The image forming layer according to the present invention is a layer capable of forming an image by image exposure, and any of a negative type and a positive type image forming layer conventionally used as a photosensitive layer of a lithographic printing plate can be used.

  The present invention is effective particularly when the image forming layer according to the present invention is a heat-sensitive image forming layer or a polymerization type image forming layer.

  As the heat-sensitive image forming layer, a layer that causes a change capable of forming an image by using heat generated by laser exposure is preferably used.

  Examples of the heat-sensitive image forming layer using heat generated by laser exposure include a positive heat-sensitive image forming layer containing a substance decomposable by acid, a heat-sensitive image forming layer containing a polymerization component, and a heat-sensitive image containing a thermoplastic substance. A negative thermal image forming layer such as a forming layer is preferably used.

  As a positive type image forming layer containing a substance decomposable by acid, for example, a photo acid generator that generates acid by laser exposure described in JP-A-9-171254 and a photo acid generator that generates acid by the laser exposure described above, And an image-forming layer comprising an acid-decomposable compound and an infrared absorber that increase solubility in water.

Examples of the photoacid generator include various known compounds and mixtures. For example, diazonium, phosphonium, sulfonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , organic halogen compounds, orthoquinone-diazide sulfonyl chloride, and organometallic / An organic halogen compound is also an actinic ray-sensitive component that forms or separates an acid upon irradiation with actinic rays, and can be used as a photoacid generator. In principle, all organic halogen compounds known as free radical-forming photoinitiators are compounds that form hydrohalic acid and can be used as photoacid generators. Examples of the above-mentioned compounds forming hydrohalic acid include U.S. Pat. Nos. 3,515,552, 3,536,489 and 3,779,778, and West German Patent 2,243,621. In addition, compounds that generate an acid by photolysis described in West German Patent 2,610,842 can also be used. Further, o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-50-36209 can be used.

  As the photoacid generator, an organic halogen compound is preferable from the viewpoints of sensitivity in image formation by infrared exposure and storage stability of the image forming material. As the organic halogen compound, triazines having a halogen-substituted alkyl group and oxadiazoles having a halogen-substituted alkyl group are preferable, and s-triazines having a halogen-substituted alkyl group are particularly preferable.

  The content of the photoacid generator can vary widely depending on its chemical properties and the composition or physical properties of the image forming layer, but it is about 0.1 to about 20 with respect to the total mass of the solid content of the image forming layer. The range of mass% is appropriate, and preferably in the range of 0.2 to 10 mass%.

  Specific examples of the acid-decomposing compound are described in JP-A Nos. 48-89003, 51-120714, 53-133429, 55-12995, 55-126236, and 56-17345. Compounds having a C—O—C bond, compounds having a Si—O—C bond described in JP-A-60-37549, JP-A-60-121446, JP-A-60-3625, Other acid-decomposing compounds described in No. 60-10247. Further, compounds having a Si—N bond described in JP-A-62-222246, carbonates described in JP-A-62-251743, ortho described in JP-A-63-107127 Carbonate ester, orthotitanate ester described in JP-A-62-280841, orthosilicate ester described in JP-A-62-280842, acetal described in JP-A-63-10153, and Ketal, compounds having a C—S bond described in JP-A-62-244038, and the like. Among these, JP-A-53-133429, JP-A-56-17345, and JP-A-60-112446 are mentioned. No. 60-37549 and JP-A 63-107127 and 63-10153. Compounds having a bond, a compound having Si-O-C bonds, orthocarbonates, acetals, ketals and silyl ethers are preferable.

  The content of the acid-decomposing compound is preferably from 5 to 70% by mass, particularly preferably from 10 to 50% by mass, based on the total solid content of the composition forming the image forming layer. The acid decomposition compound may be used alone or in combination of two or more.

  The heat-sensitive image forming layer is preferably a mode including a photothermal conversion material that converts exposure light into heat. As the photothermal conversion material, the following photoconversion dyes and other photothermal conversion materials are used.

[Photothermal conversion dye]
The following can be used as the photothermal conversion dye.

  General infrared absorbing dyes such as cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes, anthraquinone dyes, organic compounds such as phthalocyanine dyes and naphthalocyanine dyes , Azo-based, thioamide-based, dithiol-based, and indoaniline-based organometallic complexes. Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, Kaihei 3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-36094, JP-A-3-36095, JP-A-3-42281, JP-A-3-42281 Examples thereof include compounds described in JP-A-3-97589, JP-A-3-103476, and the like. These can be used alone or in combination of two or more.

  JP-A-11-240270, JP-A-11-265062, JP-A-2000-309174, JP-A-2002-49147, JP-A-2001-162965, JP-A-2002-144750, JP-A-2001-219667. The compounds described in (1) can also be preferably used.

[Other photothermal conversion materials]
In addition to the photothermal conversion dye, other photothermal conversion materials can be used in combination.

  Examples of the photothermal conversion material preferably used include carbon, graphite, metal, metal oxide and the like.

As carbon, furnace black or acetylene black is particularly preferable. The particle size (d ₅₀ ) is preferably 100 nm or less, and more preferably 50 nm or less.

  As the graphite, fine particles having a particle size of 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less can be used.

  As the metal, any metal can be used as long as the particle diameter is 0.5 μm or less, preferably 100 nm or less, more preferably 50 nm or less. The shape may be any shape such as a spherical shape, a piece shape, or a needle shape. Colloidal metal fine particles (Ag, Au, etc.) are particularly preferable.

  As the metal oxide, a material that is black in the visible light region, or a material that has conductivity or is a semiconductor can be used.

Examples of the former include black iron oxide (Fe ₃ O ₄ ) and black composite metal oxides containing two or more metals.

Examples of the latter include SnO ₂ doped with Sb (ATO), In ₂ O ₃ doped with Sn (ITO), TiO ₂ , TiO ₂ with reduced TiO ₂ (titanium oxynitride, generally titanium black), etc. Is mentioned.

Further, it can also be used those obtained by coating the core material _{(BaSO 4, TiO 2, 9Al} 2 O 3 · 2B 2 O, K 2 O · nTiO 2 , etc.) in these metal oxides.

  These particle sizes are 0.5 μm or less, preferably 100 nm or less, and more preferably 50 nm or less.

  Of these photothermal conversion materials, a black composite metal oxide containing two or more metals is more preferable.

  Specifically, it is a composite metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These are disclosed by methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529, JP-A-10-231441, and the like. Can be manufactured.

  The composite metal oxide used in the present invention is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide. In the case of a Cu—Cr—Mn system, it is preferable to perform the treatment disclosed in JP-A-8-27393 in order to reduce the elution of hexavalent chromium. These composite metal oxides are colored with respect to the amount added, that is, they have good photothermal conversion efficiency.

  These composite metal oxides preferably have an average primary particle size of 1 μm or less, and more preferably have an average primary particle size in the range of 0.01 to 0.5 μm. When the average primary particle diameter is 1 μm or less, the photothermal conversion ability with respect to the addition amount becomes better, and when the average primary particle diameter is within the range of 0.01 to 0.5 μm, the photothermal conversion ability with respect to the addition amount is obtained. Better.

  However, the photothermal conversion ability with respect to the addition amount is greatly affected by the degree of dispersion of the particles, and the better the dispersion, the better.

  Therefore, it is preferable to disperse these composite metal oxide particles by a known method separately before adding them to the layer coating solution to prepare a dispersion (paste). An average primary particle size of less than 0.01 is not preferable because dispersion becomes difficult. A dispersing agent can be appropriately used for the dispersion. The addition amount of the dispersant is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the composite metal oxide particles.

  This image forming layer may appropriately contain a binder as necessary.

  A positive image forming layer containing an o-naphthoquinonediazide compound can also be preferably used.

  The light-to-heat conversion material may be contained in the image forming layer, or a layer adjacent to the image forming layer may be provided and contained in this adjacent layer.

  Examples of the heat-sensitive image forming layer containing the above polymerization component include (a) a photothermal conversion material having absorption in the wavelength range of 700 nm to 1300 nm, (b) a polymerization initiator, and (c) a polymerizable unsaturated group-containing compound. Examples thereof include a heat-sensitive image forming layer.

(Photothermal conversion material having absorption in the wavelength range of 700 nm to 1300 nm)
As the photothermal conversion material having absorption in the wavelength range of 700 nm to 1300 nm, the above-described infrared absorbers and the like can be used. Preferably, cyanine dyes, squarylium dyes, oxonol dyes, pyrylium dyes, thiopyrylium dyes, polymethine dyes, Oil-soluble phthalocyanine dyes, triarylamine dyes, thiazolium dyes, oxazolium dyes, polyaniline dyes, polypyrrole dyes, and polythiophene dyes are used.

  In addition, pigments such as carbon black, titanium black, iron oxide powder and colloidal silver can also be preferably used. From the viewpoints of absorption coefficient, photothermal conversion efficiency, price, etc., cyanine dyes are particularly preferable as the dyes, and carbon black is particularly preferable as the pigments.

The addition amount of the photothermal conversion material having absorption in the wavelength range from 700 nm to 1300 nm in the image forming layer varies depending on the extinction coefficient of the photothermal conversion material, but the reflection density of the lithographic printing plate material at the exposure wavelength is 0.3 to It is preferable to add an amount in the range of 3.0. More preferably, the addition amount is such that the concentration is in the range of 0.5 to 2.0. For example, in the case of the cyanine dyes mentioned in the above preferred specific examples, an amount of about 10 to 100 mg / m ² is added to the image forming layer in order to obtain the concentration.

  These photothermal conversion materials may be contained in the image forming layer in the same manner as described above, or an adjacent layer adjacent to the image forming layer may be provided and contained in this adjacent layer.

(Polymerization initiator)
The polymerization initiator is a compound capable of initiating polymerization of a compound having a polymerizable unsaturated group by laser exposure. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.

  That is, the following can be used as the polymerization initiator.

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, JP-A-61-9621 and JP-A-60-60104 Triazine derivatives described in Japanese Patent Publication No. JP-A-59-1504 and JP-A-61-243807; JP-B Nos. 43-23684, 44-6413, 44-6413 No. 47-1604 and U.S. Pat. No. 3,567,453; diazonium compounds; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 O-quinonediazides described in JP-B-36-22062, JP-A-37-13109, JP-A-38-18015 and JP-A-45-9610; JP-B-55-39162, JP-A-59-14023 No. and “Macromolecules”, Vol. 10, p. 1307 (1977) Various onium compounds; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109,851, 126,712 and “Journal of Imaging Science (J. Imag) Sci.)], 30, 174 (1986); (oxo) sulfonium organoboron complexes described in JP-A-5-213861 and 5-255347; JP-A-59-152396 And titanocenes described in JP-A-61-151197; “Coordination Chemistry Review” Vol. 84, pages 85-277 (1988) and transitions such as ruthenium described in JP-A-2-182701 Including metal 2,4,5-triarylimidazole dimer of JP-A 3-209477 JP; carbon tetrabromide, organic halogen compounds in JP 59-107344 JP such as a transition metal complex.

  Further, examples of the polymerization initiator include compounds capable of generating radicals described in JP-A-2002-537419, JP-A-2001-175006, JP-A-2002-278057, JP-A-2003-5363. In addition, an onium salt having two or more cation moieties in one molecule, an N-nitrosamine compound described in JP-A-2001-133966, described in JP-A-2003-76010, Japanese Patent Application Laid-Open No. 2001-343742 A compound that generates a radical by heat, Japanese Patent Application Laid-Open No. 2002-6482 a compound that generates an acid or radical by heat, Japanese Patent Application Laid-Open No. 2002-116539, Japanese Patent Application Laid-Open No. 2002-148790 A compound that generates an acid or a radical by the heat of heat, JP-A-2002-207293 Japanese Patent Application Laid-Open No. 2002-328465, photo- or thermal polymerization initiator having a polymerizable unsaturated group, Japanese Patent Application Laid-Open No. 2002-268217, an onium salt having a divalent or higher anion as a counter ion, and Japanese Patent Application Laid-Open No. 2002-328465 A compound such as a compound or a compound that generates a radical by heat described in JP-A-2002-341519 can also be used.

  Of these, onium salt compounds and polyhalogen compounds are preferred.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal etal, Polymer, 21, 423 (1980); ammonium salts described in US Pat. Nos. 4,069,055, 4,069,056, 4,027,992, and the like; D. C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wenetal, Teh, Proc. Conf. Rad. CuringASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, etc .; V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), Chem. &Amp;; Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat. Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-296514 and the like; J. et al. V. Crivello et al., Polymer J .; 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Wattal, J. et al. PolymerSci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al., Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al., Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 3,902,114, 233,567, 297,443, 297,442, US Pat. No. 4,933,377 No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, Yasukuni Patent No. 2, Sulfonium salts described in Nos. 904, 626, 3,604, 580, 3,604, 581, etc .; V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. , 17, 1047 (1979), etc .; C.I. S. Wenetal, Teh, Proc. Conf. Rad. CuringASIA, p478 Tokyo, Oct (1988), and the like.

  Of the onium salts mentioned above, iodonium salts and sulfonium salts are particularly preferably used.

  Preferred examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenylsulfonium hexafluorophosphate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, Tri (4-phenoxyphenyl) sulfonium hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetonylphenyldiphenylsulfonium tetrafluoroborate, 4-thiomethoxyphenyldiphenylsulfonium hexafluorophosphate, di ( Methoxysulfonylphenyl) methylsulfonium Xafluoroantimonate, di (nitrophenyl) phenylsulfonium hexafluoroantimonate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, 4-acetamidophenyldiphenylsulfonium tetrafluoroborate, dimethylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenyl Sulfonium tetrafluoroborate, p- (phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, 10-methylphenoxathinium hexafluorophosphate, 5-methylthiantrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthio Xanthenium hexafluorophosphate, triphenylsulfonium tetra Scan can be given (pentafluorophenyl) borate.

  Preferred examples of the iodonium salt include diphenyliodonium iodide, diphenyliodonium hexafluoroantimonate, 4-chlorophenyliodonium tetrafluoroborate, di (4-chlorophenyl) iodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium trioxide. Fluoroacetate, 4-trifluoromethylphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroazenate, ditolyliodonium hexafluorophosphate, di (4-methoxyphenyl) iodonium hexafluoroantimonate, di (4-methoxyphenyl) iodonium chloride , (4-Methylphenyl) phenyliodonium teto Fluoroborate, di (2,4-dimethylphenyl) iodonium hexafluoroantimonate, di (4-tert-butylphenyl) iodonium hexafluoroantimonate, 2,2′-diphenyliodonium hexafluorophosphate, tricumyldiphenyliodonium tetrakis (Pentafluorophenyl) borate and the like can be mentioned.

  The polyhalogen compound is a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group, and particularly preferably a halogen compound represented by the following general formula (1) and a compound in which the above group is substituted with an oxadiazole ring. Used. Among these, a halogen compound represented by the following general formula (2) is particularly preferably used.

Formula (1) R ¹ —CY ₂ — (C═O) —R ²
In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group. R ² represents a monovalent substituent. R ¹ and R ² may be bonded to form a ring. Y represents a halogen atom.

Formula (2) CY ₃ — (C═O) —X—R ³
In the formula, R ³ represents a monovalent substituent. X represents —O— or —NR ⁴ —. R ⁴ represents a hydrogen atom or an alkyl group. R ³ and R ⁴ may be bonded to form a ring. Y represents a halogen atom. Among these, those having a polyhalogenacetylamide group are particularly preferably used.

  A compound in which a polyhalogenmethyl group is substituted with an oxadiazole ring is also preferably used.

  The amount of the polymerization initiator added to the photosensitive layer is not particularly limited, but is preferably in the range of 0.1 to 20% by mass in the constituent components of the photosensitive layer. Furthermore, Preferably it is 0.8-15 mass%.

(Polymerizable unsaturated group-containing compound)
A polymerizable unsaturated group-containing compound is a compound having a polymerizable unsaturated group in the molecule, and is an addition polymerization in a molecule generally used for general radical polymerizable monomers and UV curable resins. Polyfunctional monomers having a plurality of possible ethylenic double bonds and polyfunctional oligomers can be used.

  These polymerizable ethylenic double bond-containing compounds are not particularly limited, but preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxy. Monofunctional acrylic acid esters such as ethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, ε-caprolactone adduct of 1,3-dioxane alcohol, 1,3-dioxolane acrylate, or Methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc. in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate. Tel, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate neo Diacrylate of pentyl glycol, diacrylate of neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl- 5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylo Difunctional acrylic acid esters such as ε-caprolactone adduct of diacrylate, diglycidyl ether diacrylate of 1,6-hexanediol, or methacrylic acid, itacon in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acids, crotonic acid, maleic esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, ε-cap of dipentaerythritol hexaacrylate Lactone adducts, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate and other polyfunctional acrylic acid esters, or these acrylates Examples thereof include methacrylic acid, itaconic acid, crotonic acid, and maleic acid ester instead of methacrylate, itaconate, crotonate, and maleate.

  Prepolymers can also be used as described above. A prepolymer may use together 1 type, or 2 or more types, and may mix and use the above-mentioned monomer and / or oligomer.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  This image forming layer includes phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylate benzoate, It can contain addition-polymerizable oligomers and prepolymers having monomers such as alkylene glycol type acrylic acid-modified, urethane-modified acrylate and the like and structural units formed from the monomers.

  Furthermore, examples of the compound that can be used in combination include a phosphoric ester compound containing at least one (meth) acryloyl group. The compound is a compound in which at least a part of the hydroxyl group of phosphoric acid is esterified.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- No. 67189, JP-A-1-244891, and the like. Further, "11290 Chemical Products", Chemical Industry Daily, compounds described on pages 286 to 294, "UV / EB curing" The compounds described in "Handbook (raw material)", Kobunshi Shuppankai, pages 11 to 65, and the like can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  An addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule can also be preferably used. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, polymerizable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, in the present invention, a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule is also preferably used. . In particular, a compound having a tertiary amino group and an amide bond is preferably used.

  Examples of the polyhydric alcohol having a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert. -Butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ', N'-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N', N'- Tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol N, N-di (n-propyl) amino-2,3-propanediol, N, N-di (iso-propyl) amino-2,3-propanediol, 3- (N-methyl-N-benzylamino) ) -1,2-propanediol and the like, but not limited thereto.

  Diisocyanate compounds include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. In Not a constant.

  Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3- Examples include dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.

  These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

Specific examples of these reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. .
M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanate-1-methylethyl) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanate) Reaction of methyl) benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product M-6 of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol): Reaction product M-7 of triethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) benzene (3 mol), 2-hydroxyethyl methacrylate (3 mol): ethylenediaminetetraethanol (1 mol), reaction product of 1,3-bis (1-isocyanato-1-methylethyl) benzene (4 mol), 2-hydroxyethyl methacrylate (4 mol). An acrylate or an alkyl acrylate described in JP-A-2-127404 can be used.

  5-80 mass% is preferable with respect to an image forming layer layer, and, as for the addition amount of the unsaturated group containing compound which can superpose | polymerize, it is more preferable that it is 15-60 mass%.

  The heat-sensitive image forming layer containing the above polymerization component preferably contains an alkali-soluble polymer compound.

  The alkali-soluble polymer compound is a polymer compound having an acid value, and specifically, copolymers having various structures as described below can be preferably used.

  As the copolymer, acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, other natural resins, etc. are used. I can do it. Two or more of these may be used in combination.

  Among these, a polymer having a carboxy group and a hydroxyl group is preferably used, and a polymer having a carboxy group is particularly preferably used.

  Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferably used. Furthermore, the copolymer composition is preferably a copolymer of (a) a carboxyl group-containing monomer, (b) a methacrylic acid alkyl ester, or an acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable.

  Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

  Furthermore, what used the monomer as described in following (1)-(14) as another copolymerization monomer can also be used.

  1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.

  2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.

  3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p -Aminosulfonylphenyl) acrylamide and the like.

  4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.

  5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.

  6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N- Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.

  7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.

  8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.

  9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.

  10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.

  12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.

  13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.

  14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

  Furthermore, other monomers that can be copolymerized with these monomers may be copolymerized.

  Also, an unsaturated bond-containing vinyl copolymer obtained by addition reaction of a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Are also preferably used.

  Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  Among these alkali-soluble polymer compounds, compounds having an acid value of 30 to 200 are preferable, and those having a mass average molecular weight of 15,000 to 500,000 are more preferable.

  Among these, those having a polymerizable unsaturated group are preferred, and those having a polymerizable unsaturated group-containing unit of 5 to 50% with respect to the repeating units of the whole polymer compound are particularly preferred.

  As the alkali-soluble polymer compound having a polymerizable unsaturated group, a known method can be used without limitation.

  Examples thereof include a method of reacting a glycidyl group with a carboxyl group, a method of reacting an isocyanate group with a hydroxyl group, and the like.

  Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl are used as the copolymer having a monomer unit having a carboxyl group. Aliphatic epoxy group-containing unsaturated compounds such as glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, or 3,4-epoxycyclohexylmethyl (meth) acrylate It is a reaction product obtained by reacting an alicyclic epoxy group or unsaturated group-containing compound such as the above with the carboxyl group. In the present invention, it is preferable that the mole percentage in which the carboxyl group, the epoxy group, and the unsaturated group-containing compound are reacted as a unit ratio, and the unit reacted in terms of sensitivity and printing durability is 5 to 50 mole%. Especially preferably, it is 10-30 mol%.

  The reaction of the copolymer having a monomer unit having a carboxyl group with the epoxy group and unsaturated group-containing compound can be carried out, for example, at a temperature of about 80 to 120 ° C. for about 1 to 50 hours. As a synthesis method of the reaction product, it can be synthesized by a generally known polymerization method. R. Sorenson, T.W. W. It can be synthesized according to the literature described in Campbell, the methods described in JP-A Nos. 10-315598 and 11-271963, and the like.

  The amount of the alkali-soluble polymer compound added is preferably 10 to 90% by mass and more preferably 15 to 70% by mass with respect to the image forming layer. Most preferably, it is 20-50 mass%.

  Moreover, the copolymer which has at least 1 sort (s) of the monomer of the following (1)-(17) as a copolymer as a copolymer which has a monomer unit which has the said carboxyl group is mentioned.

(1) a monomer having an aromatic hydroxyl group,
(2) a monomer having an aliphatic hydroxyl group,
(3) a monomer having an aminosulfonyl group,
(4) a monomer having a sulfonamide group,
(5) α, β-unsaturated carboxylic acids,
(6) substituted or unsubstituted alkyl acrylate,
(7) substituted or unsubstituted alkyl methacrylate,
(8) Acrylamide or methacrylamides,
(9) a monomer containing an alkyl fluoride group,
(10) vinyl ethers,
(11) vinyl esters,
(12) Styrenes,
(13) vinyl ketones,
(14) olefins,
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc.
(16) a monomer having a cyano group,
(17) A monomer having an amino group.

  Specific examples of the compound include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide. Acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic ester such as 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester; for example, ethylene glycol diacrylate, triethylene glycol Coal diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol adipate di Acrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexanediol Difunctional acrylates such as diacrylate of diglycidyl ether, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate; Acrylates, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε- of dipentaerythritol hexaacrylate Caprolactone adduct, pyrogallol triacrylate, propionic acid Polyfunctional acrylic acid ester acid such as pentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, and their EO-modified products, or these acrylates as methacrylate, itaconate, crotonate And methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of maleate.

(Polymer binder)
The heat-sensitive image forming layer can further contain a polymer binder.

  Examples of the polymer binder include acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins. Can be used. Two or more of these may be used in combination.

(Polymerization inhibitor)
The thermal image forming layer may contain a polymerization inhibitor as necessary.

  Examples of the polymerization inhibitor include hindered amine compounds having a piperidine skeleton having a base constant (pKb) of 7 to 14.

  The addition amount of the polymerization inhibitor is preferably about 0.001 to 10% by mass, particularly preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass with respect to the polymerizable unsaturated group-containing compound. Is preferred.

  In addition to the polymerization inhibitor described above, other polymerization inhibitors may be added to the thermal image forming layer. Other polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.

  Moreover, a colorant can also be used for the said heat-sensitive image forming layer, and a conventionally well-known thing can be used conveniently as a colorant including a commercially available thing. Examples include those described in the revised new edition “Pigment Handbook”, edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.

  Examples of the pigment include black pigment, yellow pigment, red pigment, brown pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, and metal powder pigment. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.

  Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. Moreover, as an addition amount of a pigment, 0.1-10 mass% is preferable with respect to solid content of the said composition, More preferably, it is 0.2-5 mass%.

  It is preferable to provide a protective layer on the thermal image forming layer. The protective layer (oxygen barrier layer) is preferably highly soluble in a developer solution (generally an alkaline aqueous solution) described later, and specifically includes a layer mainly composed of polyvinyl alcohol and polyvinyl pyrrolidone. it can. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesiveness with an adjacent image forming layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

The polymerization type image forming layer according to the present invention is a polymerization initiator, an image forming layer containing a polymerizable unsaturated group-containing compound, and a polymerization initiator used for a heat sensitive image forming layer containing the above polymerization component, The thing similar to the polymerizable unsaturated group containing compound can be used.
.

  As the photopolymerization initiator used in the polymerization type image forming layer, titanocene compounds, monoalkyltriarylborate compounds, iron arene complex compounds, trihaloalkyl compounds and the like are preferably used.

  Examples of titanocene compounds include compounds described in JP-A-63-41483 and JP-A-2-291. More preferred specific examples include bis (cyclopentadienyl) -Ti-di-chloride, bis (Cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,6 -Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis- , 3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis -2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRUGACURE 784: Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2, 4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titanium and the like It is below.

  Examples of the monoalkyl triaryl borate compound include compounds described in JP-A-62-150242 and JP-A-62-143044, and more preferable specific examples include tetra-n-butylammonium n-butyl-tri. Naphthalen-1-yl-borate, tetra-n-butylammonium n-butyl-triphenyl-borate, tetra-n-butylammonium n-butyl-tri- (4-tert-butylphenyl) -borate, tetra-n-butylammonium Examples include n-hexyl root- (3-chloro-4-methylphenyl) -borate and tetra-n-butylammonium n-hexyl root- (3-fluorophenyl) -borate.

  Examples of the iron arene complex compound include compounds described in JP-A-59-219307. More preferred specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η-cumene. -(Η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η- And xylene- (η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate, and the like.

  As the trihaloalkyl compound, the above-mentioned trihaloalkyl compound can be used.

  In addition, any photopolymerization initiator can be used in the same manner as described above.

  Examples of the polymerization initiator include coumarin derivatives B-1 to B-22 in JP-A-8-129258, coumarin derivatives D-1 to D-32 in JP-A 2003-211901, and JP-A 2002-363206. No. 1 to 21 Coumarin Derivatives, JP-A No. 2002-363207 No. 1 to 40 Coumarin Derivatives, JP-A No. 2002-363208 No. 1 to 34 Coumarin Derivatives, JP-A No. 2002-363209 No. 1 56 coumarin derivatives and the like can also be preferably used.

  The polymerization type image forming layer can contain the above-mentioned polymer binder as a polymer binder.

(Various additives)
In addition to the components described above, the polymerization type image forming layer used in the present invention includes unnecessary polymerization of an ethylenically unsaturated double bond monomer that can be polymerized during the production or storage of a photosensitive lithographic printing plate material. In order to prevent this, a hindered phenol compound, a hindered amine compound and other polymerization inhibitors may be added.

  Examples of hindered phenol compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphene Acrylate, etc., preferably 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate having a (meth) acrylate group, 2- [ And 1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate.

  Examples of hindered amine compounds include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-tert-butyl-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3 And 8-triazaspiro [4.5] decane-2,4-dione.

  Other polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol) Hindered amines such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, 2,2,6,6-tetramethylpiperidine derivatives, and the like. .

  The addition amount of the polymerization inhibitor is preferably about 0.01% to about 5% with respect to the mass of the total solid content of the composition. Also, if necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to prevent polymerization inhibition by oxygen, or unevenly distributed on the surface of the photopolymerizable photosensitive layer during the drying process after coating. You may let them. The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

  In addition to the components described above, a colorant can also be used in the polymerization type image forming layer used in the present invention in the same manner as described above.

(Application)
Examples of the solvent used when preparing the coating solution for the image forming layer of the present invention include alcohols: sec-butanol, isobutanol, n-hexanol, benzyl alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, etc .; ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc .; ketones, aldehydes: diacetone alcohol, cyclohexanone, methylcyclohexanone, etc .; esters: ethyl lactate , Butyl lactate, diethyl oxalate, methyl benzoate and the like.

  The prepared coating composition (image forming layer coating solution) can be coated on a support by a conventionally known method and dried to produce a photopolymerizable photosensitive lithographic printing plate material. Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method. Can be mentioned.

  The drying temperature of the photosensitive layer is preferably in the range of 60 to 160 ° C, more preferably in the range of 80 to 140 ° C, and particularly preferably in the range of 90 to 120 ° C.

(Protective layer)
It is preferable to provide a protective layer on the upper side of the image forming layer according to the present invention. The protective layer (oxygen barrier layer) is preferably highly soluble in a developer (generally an alkaline aqueous solution).

  The material constituting the protective layer is preferably polyvinyl alcohol, polysaccharide, polyvinyl pyrrolidone, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate , Sodium alginate, polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, water-soluble polyamide and the like. These compounds can be used alone or in combination of two or more as a protective layer coating composition. A particularly preferred compound is polyvinyl alcohol.

  In order to prepare the protective layer coating composition, the above-mentioned material can be dissolved in a suitable solvent to form a coating solution, which is coated on the photopolymerizable photosensitive layer according to the present invention and dried. Thus, a protective layer can be formed. The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm. The protective layer can further contain a surfactant, a matting agent and the like as required.

  As the method for coating the protective layer, the known coating methods mentioned above for coating the photosensitive layer can be suitably used. The drying temperature of the protective layer is preferably lower than the drying temperature of the photosensitive layer, preferably the difference from the photosensitive layer drying temperature is 10 ° C. or more, more preferably 20 ° C. or more, and the upper limit is about 50 ° C. at most. .

  Moreover, it is preferable that the drying temperature of a protective layer is lower than the glass transition temperature (Tg) of the binder which a photosensitive layer contains. The difference between the drying temperature of the protective layer and the glass transition temperature (Tg) of the binder contained in the photosensitive layer is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and the upper limit is about 60 ° C. at most.

(Platemaking-Printing)
The photosensitive lithographic printing plate material of the present invention is subjected to image formation by image exposure, subjected to development treatment as necessary, and subjected to printing.

  Examples of light sources for image exposure include lasers, light emitting diodes, xenon lamps, xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, high pressure mercury lamps, and electrodeless light sources.

  In the case of batch exposure, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be superimposed on the photopolymerizable photosensitive layer and exposed.

  When using an array-type light source such as a light-emitting diode array, or when controlling exposure of a light source such as a halogen lamp, metal halide lamp, or tungsten lamp with an optical shutter material such as liquid crystal or PLZT, digital Exposure is possible and preferable. In this case, direct writing can be performed without using a mask material.

  Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.

  Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.

  In the case where development processing is required, a method of developing the photosensitive lithographic printing plate material using an automatic processor is an embodiment.

  Printing can be performed using a general lithographic printing machine.

  In recent years, the printing industry has been screaming for environmental protection, and in printing inks, inks that do not use petroleum-based volatile organic compounds (VOC) have been developed and are becoming popular. This is particularly noticeable when the printing inks are used. Examples of environmentally friendly printing inks include soybean oil ink “Naturalis 100” manufactured by Dainippon Ink & Chemicals, Inc., VOC zero ink “TK Hi-Echo NV” manufactured by Toyo Ink, and process ink “Soyselbo” manufactured by Tokyo Ink. It is done.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the examples, “parts” represents “parts by mass” unless otherwise specified.

Preparation of photosensitive lithographic printing plate support 0.24 mm thick, JIS 1050 aluminum plate was degreased in 5% aqueous sodium hydroxide solution at 50 ° C. for 10 seconds, washed with water, 25% in 10% aqueous nitric acid solution, 25 After neutralizing by dipping at 10 ° C. for 10 seconds, it was washed with water.

This aluminum plate was subjected to electrolytic surface roughening in an aqueous solution of hydrochloric acid: 10 g / L, acetic acid 10 g / L, dissolved aluminum: 5 g / L at a temperature of 30 ° C. and a current density of 60 A / dm ² for 20 seconds, and then 10 After treatment in a 50% aqueous phosphoric acid solution at 50 ° C. for 10 seconds, it was washed with water.

Next, anodization was performed in a 20% sulfuric acid aqueous solution at 30 ° C., a current density of 10 A / dm ² for 25 seconds to obtain an anodic oxide film mass of 3.0 g / m ² , followed by washing with water. Subsequently, it was immersed in a 0.2% by mass aqueous solution of polyvinylphosphonic acid (number average molecular weight: 21000) at 60 ° C. for 30 seconds and washed with water. Thereafter, as a final treatment, it was immersed in water having a pH of 4 to 9 at 70 to 90 ° C. for 10 seconds. (The pH and temperature of the water in the final treatment conditions are shown in Table 1.) Thereafter, it was dried at 150 ° C. for 15 seconds by hot air drying, and then used as a support for a photosensitive lithographic printing plate.

Example 1
In the production of the photosensitive lithographic printing plate support described above, the coating for the image forming layer B having the following composition was carried out on the photosensitive lithographic printing plate support that was changed to the pH and temperature of water in the final processing conditions shown in Table 1. The liquid was applied with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. 1-4 and 21-25 were obtained.

Coating liquid for image forming layer B (positive photosensitive layer resin composition for infrared laser)
Novolac resin (below) 8.0 parts Ketal compound (below) 2.0 parts 1,3-bis (trichloromethyl) -5-methyl-s-triazine 0.1 part Infrared absorbing dye (below) 0.1 part Cyan Group-containing resin (below) 1.0 part 2-butanone 54.0 parts propylene glycol monomethyl ether 36.0 parts Novolac resin: formaldehyde condensate of m-cresol, p-cresol, phenol (60/35/5) mixture ( Mw = 4000)
Cyano group-containing resin: 30:20:50 copolymer of methacrylonitrile, 4-hydroxyphenylmaleimide and methyl methacrylate Mw = 20,000

(Exposure development method)
The obtained photosensitive lithographic printing plate material was scanned and exposed in an image form with an infrared laser, and immersed in a Kodak polychrome PS plate developer PD-1 (diluted stock solution 6 times) at 30 ° C. for 20 seconds. Then, development was performed by eluting the exposed area. At that time, the amount of energy required for the exposed part to completely elute was 125 mJ / cm ² . At this time, the unexposed area corresponding to the image area was not dissolved by the development process, and a clear image was obtained.

Example 2
In the production of the photosensitive lithographic printing plate support described above, the coating for the image forming layer C having the following composition was applied to the photosensitive lithographic printing plate support having the final processing conditions shown in Table 1 changed to the pH and temperature of water. The solution was applied with a wire bar to 1.5 g / m ² when dried and dried at 95 ° C. for 1.5 minutes. Thereafter, a protective layer coating solution having the following composition was further applied onto the image forming layer with an applicator so as to have a dry weight of 2.0 g / m ² , and dried at 75 ° C. for 1.5 minutes. Sample No. of photosensitive lithographic printing plate material having a protective layer 5-9 and 27 were obtained.

Image forming layer C coating solution (photopolymerization type image forming layer coating solution-1)
Polymer binder B-1 (below) 40.0 parts Sensitizing dye (below) 3.0 parts Photopolymerization initiator (below) 4.0 parts Addition-polymerizable ethylenically unsaturated double bond-containing monomer (Below) 40.0 parts NK ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
15.0 parts hindered amine compound (LS-770: manufactured by Sankyo Co., Ltd.) 2.5 parts trihaloalkyl compound (below) 5.0 parts phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd.) 6.0 parts fluorine-based surfactant ( F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 parts methyl ethyl ketone 80 parts cyclohexanone 820 parts (synthesis of polymer binder B-1)
In a three-necked flask under a nitrogen stream, methyl methacrylate (125 parts: 1.25 mol), ethyl methacrylate (12 parts: 0.10 mol), methacrylic acid (63 parts: 0.73 mol), cyclohexanone (240 parts), Isopropyl alcohol (160 parts) and α, α′-azobisisobutyronitrile (5 parts) were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a polymer. Thereafter, 4 parts of triethylbenzylammonium chloride and glycidyl methacrylate (52 parts: 0.73 mol) were added to the polymer and reacted at a temperature of 25 ° C. for 3 hours to obtain a polymer binder B-1. The mass average molecular weight was about 55,000 (GPC: polystyrene conversion).

(Protective layer coating solution)
Polyvinyl alcohol (GL-05: Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: Toray Industries, Inc.) 10 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 parts Water 900 Part (exposure development method)
About the photopolymerization type photosensitive lithographic printing plate material thus produced, 2400 dpi (1 inch is 2.54 cm) using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with an FD-YAG laser light source. Image exposure was performed at a resolution of (representing the number of dots per hit).

  Next, before development, a heating device part, a pre-washing part for removing the protective layer, a developing part filled with the following developer composition, a washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image line part ( Developed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with GW-3: Kodak polychrome diluted twice), a lithographic printing plate material was obtained. At this time, the heating unit was set so that the plate surface temperature was 115 ° C. and the plate staying time was 15 seconds. The plate was inserted into the heating unit of the self-machine after the end of exposure within 60 seconds.

Developer composition (aqueous solution containing the following additives)
Potassium silicate aqueous solution (SiO ₂ : 26%, K ₂ O: 13.5%) 40.0 g / L
Potassium hydroxide 4.0g / L
Ethylenediaminetetraacetic acid 0.5g / L
Polyoxyethylene (13) naphthyl ether sulfonate 20.0 g / L
1 L with water. The pH was 12.3.

Example 3
The photopolymerizable photosensitive layer coating solution-1 used for the image forming layer C of Example 2 was subjected to the following photopolymerization on a surface-treated support with the pH and temperature of water in the final processing conditions shown in Table 1 changed. Sample No. of photosensitive lithographic printing plate material having a protective layer on the photosensitive layer in the same manner as in Example 2 except that the photosensitive photosensitive layer coating solution-2 was used. 9-12 and 28 were obtained.

Coating solution for image forming layer D (photopolymerizable photosensitive layer coating solution-2)
Polymer binder B-1 (above) 40.0 parts Sensitizing dye A (described below) 1.5 parts Sensitizing dye B (described below) 1.5 parts Photopolymerization initiator (above) 4.0 Part Addition-polymerizable ethylenically unsaturated double bond-containing monomer (above) 40.0 parts NK ester 4G (polyethylene glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
15.0 parts hindered amine compound (LS-770: manufactured by Sankyo Co., Ltd.) 2.5 parts trihaloalkyl compound (previously described) 5.0 parts phthalocyanine pigment (MHI 454: manufactured by Gokoku Dye Co., Ltd.) 6.0 parts fluorinated surfactant ( F178K: manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 parts methyl ethyl ketone 80 parts cyclohexanone 820 parts

(Exposure development method)
About the photosensitive lithographic printing plate material obtained as described above, except that exposure was performed using a plate setter (Tiger Cat: modified product manufactured by ECRM) equipped with a light source equipped with a laser of 408 nm and 30 mWW output, The same operation as in Example 2 was performed.

Example 4
In the preparation of the above-described photosensitive lithographic printing plate support, a negative thermal photopolymerization photosensitive layer having the following composition was formed on the photosensitive lithographic printing plate support that was changed to the pH and temperature of water in the final processing conditions shown in Table 1. The coating solution was applied with a wire bar so as to be 1.5 g / m ² when dried, and dried at 95 ° C. for 1.5 minutes. 13-16 and 29 were obtained.

Coating solution for image forming layer E (negative type thermal photopolymerization photosensitive layer coating solution)
(Negative type thermal photopolymerization photosensitive layer coating solution)
Addition-polymerizable ethylenic double bond-containing monomer-1 20.0 parts Addition-polymerizable ethylenic double bond-containing monomer-2 20.0 parts Addition-polymerizable ethylenic double bond-containing monomer Form-3 10.0 parts Trihaloalkyl compound (above) 5.0 parts Cyanine dye-1 2.5 parts Acrylic copolymer 1 40.0 parts N-phenylglycine benzyl ester 4.0 parts Phthalocyanine pigment (MHI454: 6.0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 5 parts Fluorosurfactant (F-178K; manufactured by Dainippon Ink & Co.) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 parts (Binder synthesis)
(Synthesis of acrylic copolymer 1)
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 250 parts of isopropyl alcohol, 250 parts of propylene glycol monomethyl ether acetate, and α, α'-azobisisobutyronitrile. Three parts were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The mass average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

Addition-polymerizable ethylenic double bond-containing monomer-1: n-butyl-diethanolamine (1 mol), tetramethylxylene diisocyanate (2 mol) and 1-methacryloyloxy-3-acryloyloxy-2-propanol Polymerizable ethylenic double bond-containing monomer-2: reaction product of hexane-1,6-diisocyanate (1 mol) and 2-hydroxypropylene-1,3-dimethacrylate (2 mol) Ethylenic double bond-containing monomer-3: tetraethylene glycol dimethacrylate

(Exposure development method)
The obtained photosensitive lithographic printing plate material was exposed at 2400 dpi (dpi represents the number of dots per 2.54 cm) using a plate setter (Trend Setter 3244: manufactured by Creo) equipped with a light source of 830 nm. Went.

  Development unit filled with a developer having the following composition, washing unit for removing developer adhering to the plate surface, gum solution for protecting the image area (GW-3: two-fold diluted by Kodak Polychrome) processing unit Development processing was carried out with a CTP automatic developing machine (Raptor Thermal: Glunz & Jensen) equipped with a lithographic printing plate.

(Developer composition)
A Potassium silicate 8.0% by mass
New Coal B-13SN: Nippon Emulsifier Co., Ltd. 3.0% by mass
Caustic potash pH = 12.3 [Amount of evaluation]
The lithographic printing plates (Sample Nos. 1 to 16 and 21 to 29) prepared in Examples 1 to 4 were evaluated by the following method, and the results are shown in Table 1.

Printing smudges A lithographic printing plate that has been printed is coated with a printing machine (DAIYA1F-1: manufactured by Mitsubishi Heavy Industries), printing ink (process ink: TOKA HiEcho, soybean oil ink: Naturalis 100: Dainippon Ink and Chemicals, Inc.) Printing) and dampening water (H liquid SG-51 concentration 1.5%: manufactured by Tokyo Ink Co., Ltd.). After printing 10,000 sheets, the blanket was wiped and printing was continued, and the number of printed sheets until the printed material was soiled was confirmed. The symbols in Table 1 are as follows.
A: More than 40,000 sheets O: More than 30,000 sheets and less than 40,000 sheets Δ: More than 20,000 sheets and less than 30,000 sheets x: Less than 20,000 sheets.

Printing durability A lithographic printing plate which has been subjected to printing is printed on a high-quality paper, printing ink (process ink: high echo red: manufactured by TOKA) and dampening water (liquid H SG-51) using a printing machine (DAIYA1F-1: manufactured by Mitsubishi Heavy Industries). Printing was performed using a density of 1.5%: manufactured by Tokyo Ink Co., Ltd. A small dot of 5% was observed with 175 LPI, and the point at which the dot disappeared by about 10% was regarded as the end point of printing durability.

  The photosensitive lithographic printing plate material using the support for photosensitive lithographic printing plate produced by the production method of the present invention from Table 1 has good processing solution resistance on a printing press, excellent printing durability, and printing. It can be seen that a lithographic printing plate having excellent antifouling property can be provided.

Claims (5)

In the method for producing a photosensitive lithographic printing plate support, which is obtained by subjecting an aluminum plate or an aluminum alloy plate to a surface roughening treatment, followed by an anodizing treatment, and further performing a post-treatment. Treatment with an aqueous acid solution or treatment with an aqueous polyvinylphosphonic acid solution after sodium silicate treatment, and then the post-treated aluminum plate or aluminum alloy plate has a pH of 4 to 9 and a liquid temperature of 70 to 90 ° C. A method for producing a support for a photosensitive lithographic printing plate, comprising washing with an aqueous solution. A photosensitive lithographic printing plate support produced by the method for producing a photosensitive lithographic printing plate support according to claim 1. A photosensitive lithographic printing plate material comprising an image forming layer on the photosensitive lithographic printing plate support according to claim 2. 4. The photosensitive lithographic printing plate material according to claim 3, wherein the image forming layer is a heat-sensitive image forming layer. The photosensitive lithographic printing plate material according to claim 3 or 4, wherein the image forming layer is a photopolymerization type image forming layer.