JP2007090522A - Winder of lithographic printing form original plate, and winding method of lithographic printing form the original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain the winder of a lithographic printing form original plate, in which working winding qualities are improved, and at the same time, stable quality is ensured without marring the planeness of the plate, and to provide its winding method. <P>SOLUTION: A laying-on roll 28 is provided so as to come into contact with a rolled web 52 at a winding part 62, when the web is wound into a small-sized roll mode 60 by means of a product wind-up roll 26. This laying-on roll 28 is at all times pressed against the rolled web 52 at the winding part 62. Since the rolled web 52 is wound at all times under a state being pressed against in the direction of the product wind-up roll 26 at the winding part 62, its winding is performed under a state such that the occurrence of neither the so-called "winding slippage" nor "winding ruck" takes place. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a lithographic printing plate precursor winding apparatus and a lithographic printing plate precursor winding method, for example, a high-sensitivity dampening capable of forming an image by heat mode recording with a laser beam and capable of printing without fountain solution. The present invention relates to a winding device and a winding method for winding a water-free lithographic printing plate precursor (hereinafter referred to as a waterless lithographic printing plate precursor).

  In conventional printing methods that require dampening water, it is difficult to control the delicate balance between dampening water and ink, which causes emulsification of ink and ink mixing with dampening water, resulting in poor ink density and soiling. And has a major problem such as causing waste paper. In contrast, waterless lithographic printing plates have a number of advantages because they do not require fountain solution.

  On the other hand, recent printing systems such as prepress systems, image setters, and laser printers have made rapid progress in digitizing printed images, and printing plates can be obtained by new plate making methods such as computer-to-plate and computer-to-cylinder. Methods have been proposed, and new types of printing materials for these printing systems are desired and are being developed.

  Examples of waterless lithographic printing plates that can be formed by laser writing include ink repellent on a layer containing a laser light absorber such as carbon black and a binder or a layer that converts light into heat (hereinafter referred to as a photothermal conversion layer). A printing original plate provided with a heat-resistant silicone rubber layer is prepared, and this is irradiated with a laser to remove the silicone rubber layer in the irradiated area to form an ink-adhering area (image area). Examples include ink repellent areas (non-image areas) that enable waterless printing (see, for example, Patent Document 1).

Such a waterless lithographic printing plate is inexpensive to manufacture and forms an image by utilizing the ablation of the photothermal conversion layer of the laser irradiation part. It has the merit that the rubber layer is pushed up, and the removal of the silicone rubber layer in the laser irradiation portion in the subsequent development (hereinafter referred to as developability) can be performed efficiently.
JP 2002-131894 A

  However, in such a waterless lithographic printing plate precursor, since the silicone layer is difficult to slip with respect to the support, once the winding deviation occurs in the winding process in a roll form, the correction is not effective and a winding failure occurs. Cheap. Further, the air entrained at the time of winding cannot be removed from the roll, so that the flatness of the plate is impaired, and performance problems are likely to occur.

  For example, when the plate is pressure-deformed by the entrained air, the focus unevenness at the time of laser exposure occurs, the ablation level of the image area slightly decreases, and the silicone layer that should be removed in the subsequent processing is Since it is not completely removed, a portion having a lower ink density than the normal portion is likely to occur on the printing paper. Alternatively, the adhesive portion between the photothermal conversion layer and the silicone layer deteriorates due to the influence of the outside air humidity at the storage location during the storage time in the roll form. As a result, there has been a problem that, during image processing after laser exposure, a portion of the silicone layer that should originally become a non-image portion is peeled off and stains are likely to occur on the printing paper surface.

  Such a problem may occur not only in the waterless lithographic printing plate precursor but also in other lithographic printing plate precursors.

  Accordingly, an object of the present invention is to solve the problems in the method for producing a lithographic printing plate precursor, and to improve the work winding property and to ensure stable quality without impairing the flatness of the plate. It is to provide a plate original winding device and a winding method.

  In particular, it is to provide a winding device and a winding method that can be preferably applied to the production of a waterless lithographic printing plate precursor that forms an image using the ablation described above.

  As a result of intensive studies, the inventors apply a lithographic printing plate precursor winding apparatus and a lithographic printing plate precursor winding method having the following configuration when winding into a roll in the manufacturing process of a lithographic printing plate precursor. Thus, the inventors have found that the above object can be achieved and have reached the present invention.

  That is, the lithographic printing plate precursor winding apparatus of the present invention is a winding device for winding a lithographic printing plate precursor comprising at least a photothermal conversion layer and a silicone rubber layer sequentially laminated on a support with the silicone rubber layer inside. And a lion roll that contacts the lithographic printing plate precursor at a portion where the lithographic printing plate precursor is wound around the winding shaft and partially presses the lithographic printing plate precursor during winding. And

  Further, the lithographic printing plate precursor winding method of the present invention comprises a lithographic printing plate precursor obtained by sequentially laminating at least a photothermal conversion layer and a silicone rubber layer on a support. While winding up, the lithographic printing plate precursor is brought into contact with the lithographic printing plate precursor at the portion where the lithographic printing plate precursor is wound up at the winding shaft, and the lithographic printing plate precursor in the middle of winding is partially pressed It is characterized by winding.

  In the lithographic printing plate precursor winding apparatus and the lithographic printing plate precursor winding method of the present invention, when winding the lithographic printing plate precursor on the winding shaft, a lion roll is brought into contact with a portion where the lithographic printing plate precursor is wound, Winding while partially pressing with a lion roll. Thereby, generation | occurrence | production of winding deviation at the time of winding can be prevented. Further, the air entrained at the time of winding is pushed out by a lion roll when the lithographic printing plate precursor is sequentially wound, so that the flatness of the lithographic printing plate precursor can be secured.

  Thus, in the planographic printing plate precursor winding apparatus and the planographic printing plate precursor winding method of the present invention, in the winding apparatus and winding method of the planographic printing plate precursor, the workability of winding is improved and the plane of the plate is improved. Stable quality can be guaranteed without impairing the performance.

  In particular, it can be preferably applied to the production of a waterless lithographic printing plate precursor for performing image formation using ablation.

  Also, it is supplied into the printing press plate cylinder in roll form, mounted on the plate cylinder so that the printing surface of the planographic printing plate precursor is on the front side, and spooled so that the new surface is located in the printing area on the plate cylinder And a waterless lithographic printing plate precursor for producing a waterless lithographic printing plate precursor having excellent processability and stability over time in a method of printing after image-wise laser scanning on the plate cylinder and removing the silicone rubber layer of the laser-irradiated portion. And can be preferably applied to a manufacturing method.

  Since the present invention has the above-described configuration, it is possible to provide a lithographic printing plate precursor winding apparatus and a winding method that improve the work-up property and guarantee stable quality without impairing the flatness of the plate.

  The planographic printing plate precursor winding apparatus and winding method of the present invention, and the planographic printing plate precursor manufacturing apparatus and method to which these are applied will be described below.

In the following, in particular, on the support, at least a light-to-heat conversion layer that converts laser light into heat and enables the upper layer to be peeled off by the heat, and a silicone rubber layer having an ink-repellent surface on the support in this order. A waterless lithographic plate that has excellent stability over time while suppressing entrained air during roll-form processing and winding of the waterless lithographic printing plate precursor laminated to First, a lithographic printing plate precursor manufacturing apparatus and manufacturing method according to the present invention will be described with reference to FIG.

  In FIG. 1, in the production process of a waterless lithographic printing plate precursor, after the silicone rubber layer is applied and dried, the surface of the silicone rubber layer is protected on the surface of the silicone rubber layer without contacting the roller of the coating machine. An outline of a processing machine (die cutter / slitter / winder) 12 used when cutting a raw roll wound in a roll shape while laminating a cover film is formed into a product form is shown.

  The processing machine 12 has an unwinding shaft 14 to which a raw roll 54 is mounted. The original fabric (waterless lithographic printing plate precursor laminated with a cover film) 52 unwound from the original fabric roll 54 by the rotation of the unwinding shaft 14 is along the flow direction (right to left in the drawing, arrow F direction). It is sandwiched between the plurality of feed rolls 16 and conveyed. In the middle of the conveyance, first, the die cutter 18 including the tip shape cutting die set 20 and the press hydraulic cylinder 22 is punched and cut according to the tip shape of the product roll.

  Next, the cover film 56 on the upper side of the original fabric 52 which is conveyed while being in close contact with the feed roll 16 and cut in accordance with the shape of the front end of the product is taken up by the cover film take-up roll 24. The lower waterless lithographic printing plate precursor 58 is further conveyed by the feed roll 16 and taken up into the small roll form 60 by the product take-up roll 26. When a predetermined length is taken up by the product take-up roll 26, the web cut die set 30 cuts it into a fixed length.

  Here, in this embodiment, when the product take-up roll 26 takes up the small roll form 60, the lion roll 28 is provided so that the take-up portion 62 contacts the planographic printing plate precursor 58. The lion roll 28 is always pressed against the planographic printing plate precursor 58 at the winding unit 62. Thus, since the lithographic printing plate precursor 58 is wound up while being always pressed in the direction toward the product take-up roll 26 in the take-up portion 62, the so-called winding deviation and wrinkle are not taken up and taken up. .

  Further, even if air is likely to be entrained between the lithographic printing plate precursor 58 that has already been wound in the winding unit 62 and the lithographic printing plate precursor 58 that has not yet been wound up, It is pushed out so as to be squeezed by the rayon roll 28 and consequently is not accompanied.

  As described above, in the present invention, when the product take-up roll 26 takes up the small roll form 60, the take-up portion 62 is wound while being pressed by the lion roll 28. 52, that is, the flatness of the plate can be maintained.

As the material of the lion roll 28 of the present invention, in order to obtain the effect, it is preferable to use a material having a hardness of 30 degrees or more and 100 degrees or less, and more preferably a material of 40 degrees or more and 90 degrees or less. In order to prevent dust from adhering, it is preferable to use a material having a volume resistivity of 10 ² Ω · cm to 10 ¹² Ω · cm, preferably 10 ⁴ Ω · cm to 10 ⁸ Ω · cm. Further preferred.

  The cutting to the final product roll width may be performed at the time of processing the raw roll, and the raw roll attached to the processing machine 12 may already have the final product roll width. Moreover, you may cut by providing the slitter which slits to a final product width between a raw fabric roll and a front-end | tip shape cutting die set.

  Further, the lithographic printing plate precursor processed by the processing machine 12 is not limited to the one provided with a silicone rubber layer described later, and is not limited to the waterless lithographic printing plate precursor. In short, when the product take-up roll 26 is wound into the small roll form 60, the occurrence of winding slip and air entrainment due to friction between the support and the surface in contact with the support (layer opposite to the support). It can be widely applied when there are concerns.

  Next, the waterless lithographic printing plate precursor produced by the method of the present invention will be described.

  The structure of the waterless planographic printing plate precursor is formed by sequentially laminating at least a photothermal conversion layer and a silicone rubber layer on a support. Here, “sequential lamination” means that these layers are laminated in the above order, and does not negate the existence of other layers such as an undercoat layer, an overcoat layer, and an intermediate layer. Absent. Further, a back layer may be provided on the support opposite to the surface on which the photothermal conversion layer and the silicone rubber layer are sequentially laminated, and further, the surface is protected after the silicone rubber layer is applied or dust is adhered. It is preferable to laminate a cover film from the viewpoint of prevention.

[Support]
The support used in the present invention must be flexible enough to be set in a normal printing press, and must be able to withstand the load applied during printing. Therefore, typical supports include coated paper, metal plates such as aluminum and aluminum-containing alloys, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyvinylidene chloride. , Polyvinyl alcohol, fluororesin, polycarbonate, polyacetate, polyamide, polyimide and other plastic films, rubber, and composites of these (for example, composite plates with the top and bottom of paper sandwiched between aluminum) can be used. It is not limited to. The plastic film may be unstretched, uniaxially stretched, or biaxially stretched, and is preferably a biaxially stretched polyethylene terephthalate film. As this polyethylene terephthalate film, as disclosed in JP-A-9-314794, a film containing a cavity can be used. The thickness of the support used in the present invention is 25 μm to 3 mm, preferably 75 μm to 500 μm, but the optimum thickness varies depending on the printing conditions. In general, the thickness is most preferably from 100 μm to 300 μm.

  In order to improve surface adhesion and antistatic properties, the support may be subjected to various surface treatments such as corona discharge treatment, matting easy adhesion treatment, and antistatic treatment. Further, a conventional lithographic original plate substrate may be bonded to the surface of the support opposite to the surface on which the photothermal conversion layer and the silicone rubber layer are laminated with an adhesive or the like. Typical examples of the substrate include a metal plate such as aluminum, an aluminum-containing alloy (for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel). And a plastic film such as polyethylene terephthalate and polyethylene naphthalate, and a composite sheet in which a plastic film such as paper or polyethylene or polypropylene is laminated.

(Photothermal conversion layer)
The photothermal conversion layer used in the waterless lithographic printing plate precursor according to the present invention is a layer having a function of converting laser light used for writing into heat (photothermal conversion). Among the known photothermal conversion layers formed by dissolving or dispersing in other components and coating, photothermal conversion is such that a part of the photothermal conversion layer of the irradiated portion by the practically usable laser remains after plate making. Any layer can be used. The residual amount of the photothermal conversion layer after plate making is preferably 0.01 g / m ² or more, more preferably 0.1 g / m ² or more, and further preferably 0.2 g / m ² or more. If the photothermal conversion layer after plate making does not remain, and the undercoat layer described later provided if necessary is exposed, the inking property is deteriorated. Further, in the present invention, when the thickness of the silicone rubber layer is 2.0 g / m ² or more from the viewpoint of improving ink resilience, the weight loss amount of the photothermal conversion layer after plate making for improving the developability of the laser irradiation part. Is preferably 0.5 g / m ² or more. More preferably, it is 0.6 g / m ² or more.

  As the photothermal conversion agent used in the present invention, a known substance having a function of converting laser light used for writing into heat (photothermal conversion) can be used. When the laser light source is an infrared laser, infrared absorption is possible. It is conventionally known that various organic and inorganic materials that absorb light having a wavelength used for a writing laser, such as pigments, infrared absorbing dyes, infrared absorbing metals, and infrared absorbing metal oxides, can be used. These photothermal conversion agents are used in the form of mixed films with other components such as binders and additives.

  Examples of such photothermal conversion agents include various carbon blacks such as acidic carbon black, basic carbon black, and neutral carbon black, various carbon blacks that have been surface-modified or surface-coated for improving dispersibility, nigrosines, Black pigments such as aniline black and cyanine black, phthalocyanine, naphthalocyanine green pigment, carbon graphite, aluminum, iron powder, diamine metal complex, dithiol metal complex, phenolthiol metal complex, mercaptophenol metal complex, aryl Aluminum metal salts, crystal water-containing inorganic compounds, copper sulfate, chromium sulfide, silicate compounds, metal oxides such as titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, tungsten oxide, indium tin oxide, etc. this Hydroxides of metals, sulfates, further bismuth, tin, tellurium, iron, adding an additive such as metal powder of aluminum preferred.

  In addition, as an organic dye, "infrared sensitizing dye" (Matsuoka, Plenum Press, New York, NY (1990)), US Pat. No. 4,833,124, EP-321923, US-4772583, US-4942141 Publication, US-494876 publication, US-4948777 publication, US-4948778 publication, US-4950639 publication, US-4912083 publication, US-4952552 publication, US-5023229 publication, etc. Although various compounds are mentioned, it is not limited to this.

  Among these, carbon black is particularly preferable from the viewpoints of photothermal conversion, economic efficiency, and handleability. Carbon black is classified into furnace black, lamp black, channel black, roll black, disk black, thermal black, acetylene black, etc., depending on its manufacturing method. Furnace black is a different type of particle size and other aspects. Since it is commercially available and is commercially inexpensive, it is preferably used. In carbon black, the degree of aggregation of primary particles affects the sensitivity of the plate material. When the degree of aggregation of the primary particles of carbon black is high (having a high structure structure), when compared with the same addition amount, the blackness of the plate material does not increase, resulting in a decrease in the absorption rate of the laser beam. Sensitivity will decrease. Moreover, the viscosity of the photothermal conversion layer coating solution becomes high or thixotropic due to the particle aggregation, making it difficult to handle the coating solution, and the coating film is not uniform. On the other hand, when the oil absorption is low, the dispersibility of the carbon black is lowered and the plate material sensitivity is likely to be lowered. The degree of aggregation of the primary particles of the carbon black can be compared by the value of the oil absorption amount. The higher the oil absorption amount, the higher the aggregation degree, and the lower the oil absorption amount, the lower the aggregation degree. That is, it is preferable to use carbon black having an oil absorption of 20 to 300 ml / 100 g, more preferably 50 to 200 ml / 100 g.

Carbon blacks having various particle sizes are commercially available, and the particle size of the primary particles also affects the plate material sensitivity. When the average particle diameter of the primary particles is too small, the photothermal conversion layer itself becomes transparent and cannot absorb the laser light efficiently, so that the plate material sensitivity is lowered. On the other hand, if the particle size is too large, the particles are not dispersed at a high density, the blackness of the photothermal conversion layer does not increase, and the laser beam cannot be absorbed efficiently, and the plate material sensitivity also decreases. That is, it is preferable to use carbon black having an average particle diameter of primary particles in the range of 10 to 50 nm, and more preferably 15 to 45 nm. Further, by using conductive carbon black, it is possible to improve plate material sensitivity. Electrical conductivity of this time is preferably in the range of 0.01~100Ω ^-1 cm ^-1, more preferably 0.1~10Ω ^-1 cm ^-1. Specifically, "CONDUCTEX" 40-220, "CONDUCTEX" 975BEADS, "CONDUCTEX" 900BEADS, "CONDUCTEX" SC, "BATTERY BLACK" (made by Colombian Carbon Japan Co., Ltd.), # 3000 (Mitsubishi Chemical Corporation) DENKA BLACK "(manufactured by Denki Kagaku Kogyo Co., Ltd.)," VULCAN XC-72R "(manufactured by Cabot Corporation), and the like are more preferably used. The addition amount of the photothermal conversion agent of the photothermal conversion layer used for this invention is 1 to 70 weight% with respect to the total photothermal conversion layer composition, Preferably, it is 5 to 50 weight%. When the addition amount is 1% by weight or more, the sensitivity of the plate material is not lowered, and when it is 70% by weight or less, the film strength of the photothermal conversion layer does not decrease and the adhesion with the adjacent layer does not decrease.

  When the photothermal conversion layer is a single film, metals such as aluminum, titanium, tellurium, chromium, tin, indium, bismuth, zinc, lead, alloys thereof, metal oxides, metal carbides, metal nitrides, metal borons A film containing at least one of chemical compounds, metal fluorides, and organic dyes can be formed on the support by vapor deposition or sputtering.

  When the photothermal conversion layer is a mixed film, the photothermal conversion agent can be dissolved or dispersed in a binder and formed together with other components by a coating method. Known binders that dissolve or disperse the photothermal conversion agent are used as the binder. Examples thereof include cellulose derivatives such as cellulose, nitrocellulose, and ethylcellulose, homopolymers and copolymers of acrylate esters, polymethyl, and the like. Homopolymers and copolymers of methacrylic esters such as methacrylate and polybutyl methacrylate, homopolymers and copolymers of styrene monomers such as acrylic ester-methacrylic ester copolymers, polystyrene, α-methylstyrene, Various synthetic rubbers such as polyisoprene and styrene-butadiene copolymer, homopolymers of vinyl esters such as polyvinyl acetate, vinyl ester-containing copolymers such as vinyl acetate-vinyl chloride copolymer, polyurea, polyurethane , Polyester & polycar Various condensate polymers such as Nate, “J. Imaging Sci., P59-64, 30 (2), (1986) (Frechet et al.)”, “Polymers in Electronics (Symposium Series, P11, 242, T. Davidson, Ed. ACS Washington, DC (1984) (Ito, Willson)) and “Microelectronic Engineering, P3-10, 13 (1991) (E. Reichmanis, L. F. Thompson)”. Examples include binders used.

  Among these, a polyurethane resin is preferable from the viewpoint of adhesion with a silicone rubber layer described below and an undercoat layer described below if necessary. The polyurethane resin used for the photothermal conversion layer can be obtained by a polyaddition reaction of a diisocyanate compound and a diol compound. Examples of the diisocyanate compound include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4 ′. -Aromatic diisocyanate compounds such as diphenylmethane diisocyanate, 4,4 '-(2,2-diphenylpropane) diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate; Aliphatic diisocyanate compounds such as methylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4′-methylenebis (cyclohexane Silisocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and the like; 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate And a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of

  Examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,2-dipropylene glycol, 1,2-tripropylene glycol, 1,2-tetrapropylene glycol. 1,3-dipropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,3-dibutylene glycol, neopentyl glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2, 2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol S, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, 2,2′-dimethylolpropanoic acid, bis (2-hydroxyethyl) -2,4-tolylene dicarbamate 2,4-tolylene-bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylene dicarbamate, bis (2-hydroxyethyl) isophthalate, and the like. Furthermore, the polyether obtained by the condensation reaction of these diol compounds, and the polyester diol obtained by the condensation reaction of dicarboxylic acid compounds, such as adipic acid and terephthalic acid, and the said diol compound can also be mentioned. These polyurethane resins may use a chain linking agent such as a diamine compound, hydrazine, or a hydrazine derivative at the time of synthesis.

  When forming the photothermal conversion layer as a mixed film, improve the mechanical strength of the photothermal conversion layer, improve the laser recording sensitivity, improve the dispersibility of the photothermal conversion agent in the photothermal conversion layer, Various additives can be added to the light-to-heat conversion layer according to various purposes such as improving adhesion to a layer adjacent to the light-to-heat conversion layer such as an undercoat layer, an intermediate layer, and a silicone rubber layer, which will be described later.

  For example, in order to improve the mechanical strength of the photothermal conversion layer, various crosslinking agents that cure the photothermal conversion layer may be added. Examples of the crosslinking agent include a combination of a polyfunctional isocyanate compound or a polyfunctional epoxy compound and a hydroxyl group-containing compound, a carboxylic acid compound, a thiol compound, an amine compound, a urea compound, and the like. It is not limited. The addition amount of the crosslinking agent used in the present invention is 1 to 50% by weight, preferably 2 to 20% by weight, based on the total photothermal conversion layer composition. When the added amount is 1% by weight or more, a crosslinking effect appears. When the added amount is 50% by weight or less, the film strength of the photothermal conversion layer does not become too strong, and the shock absorber effect when an external pressure is applied to the silicone rubber layer Will not disappear and scratch resistance will not be reduced.

  In order to improve the laser recording sensitivity, a known compound that decomposes by heating to generate gas can be added. In this case, the laser recording sensitivity can be improved by rapid volume expansion of the light-to-heat conversion layer. Examples of these additives include dinityropentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosoterephthalate. Amides, p-toluenesulfonyl hydrazide, 4,4-oxybis (benzenesulfonyl hydrazide), diamidobenzene and the like can be used. In order to improve laser recording sensitivity, various iodonium salts, sulfonium salts, phosphonium tosylate, oxime sulfonate, dicarbodiimide sulfonate, triazine, etc. Known compounds of generators can be used as additives. By using these together with the chemical amplification binder, it is possible to greatly reduce the decomposition temperature of the chemical amplification binder which is a constituent material of the photothermal conversion layer, and as a result, it is possible to improve the laser recording sensitivity. When a pigment such as carbon black is used as the photothermal conversion agent, various pigment dispersants can be used as additives in order to improve the degree of dispersion of the pigment.

  The addition amount of the pigment dispersant used in the present invention is 1 to 70% by weight, preferably 5 to 50% by weight, based on the photothermal conversion agent. If the added amount is 1% by weight or more, the effect of improving the pigment dispersibility is obtained, and the sensitivity of the plate material is not lowered. In order to improve adhesion to adjacent layers, known adhesion improvers such as silane coupling agents and titanate coupling agents, vinyl group-containing acrylate resins, hydroxyl group-containing acrylate resins, acrylamide resins, ethylene-acetic acid You may add the binder with favorable adhesiveness with respect to an adjacent layer, such as a vinyl copolymer, a vinyl chloride-vinyl acetate copolymer, a cellulose derivative, and gelatin. The addition amount of the adhesion improver or adhesion improvement binder used in the present invention is 5 to 70% by weight, preferably 10 to 50% by weight, based on the total photothermal conversion layer composition. If the addition amount is 5% by weight or more, there is an effect of improving the adhesion with the adjacent layer, and if it is 70% by weight or less, the plate material sensitivity does not decrease.

  In order to improve the coating property, a surfactant such as a fluorine-based surfactant or a nonionic surfactant can be used as an additive. The addition amount of the surfactant used in the present invention is 0.01 to 10% by weight, preferably 0.05 to 1% by weight, based on the total photothermal conversion layer composition. When the addition amount is 0.01% by weight or more, it is easy to form a uniform photothermal conversion layer with good coatability, and when it is 10% by weight or less, the adhesion with an adjacent layer does not decrease. In addition, various additives can be used as necessary.

The film thickness of the photothermal conversion layer used in the present invention is 0.05 to 10 g / m ² , preferably 0.1 to 5 g / m ² . If the film thickness of the photothermal conversion layer is too thin, a sufficient optical density cannot be obtained, the laser recording sensitivity is lowered, uniform film formation becomes difficult, and the image quality deteriorates. On the other hand, if the film thickness is too thick, it is not preferable from the viewpoints of lowering the laser recording sensitivity and manufacturing cost. The light-to-heat conversion layer used in the present invention is a generally well-known coating method, for example, dip coating, on a support or a surface of an undercoat layer to be described later formed as necessary. It can be formed by applying and drying by a method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method or the like.

(Silicone rubber layer)
The ink-repellent silicone rubber layer used in the present invention is formed by reacting a silicone rubber film on the photothermal conversion layer. Specifically, it is preferable to form by condensing condensation type silicone with a crosslinking agent or addition polymerization of addition type silicone with a catalyst. When using condensation type silicone, (b) 3 to 70 parts by weight of condensation type crosslinking agent and (c) 0.01 to 40 parts by weight of catalyst are added to 100 parts by weight of diorganopolysiloxane. It is preferred to use a different composition. The component (a) diorganopolysiloxane is a polymer having a repeating unit represented by the following general formula. R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms, a vinyl group, and an aryl group, and may have other appropriate substituents. In general, it is preferable that 60% or more of R ¹ and R ² is a methyl group, a vinyl halide group, a halogenated phenyl group, or the like.

  Such a diorganopolysiloxane is preferably one having hydroxyl groups at both ends. The component (a) has a number average molecular weight of 3,000 to 600,000, more preferably 5,000 to 100,000. The crosslinking agent of component (b) may be any as long as it is a condensation type, but is preferably one represented by the following general formula.

Here, R ¹ has the same meaning as R ¹ described above, and X represents a halogen atom such as Cl, Br, or I, a hydrogen atom, a hydroxyl group, or an organic substituent as shown below.

In the formula, R ³ represents an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms.

  As the component (c), there are known catalysts such as tin, zinc, lead, calcium, manganese and the like, for example, dibutyl laurate, lead octylate, lead naphthenate, or chloroplatinic acid. Can be mentioned. When using addition type silicone, (d) 0.1 to 25 parts by weight of organohydrogenpolysiloxane with respect to 100 parts by weight of diorganopolysiloxane having addition reactive functional groups, and (f) It is preferable to use a composition to which 0.00001 to 1 part by weight of an addition catalyst is added. The above-mentioned diorganopolysiloxane having an addition-reactive functional group (d) is an organopolysiloxane having at least two alkenyl groups (more preferably vinyl groups) directly bonded to silicon atoms in one molecule. The group may be either at the molecular weight end or in the middle, and may have a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group as an organic group other than the alkenyl group. Further, the component (d) optionally has a trace amount of hydroxyl groups. The component (d) has a number average molecular weight of 3,000 to 600,000, more preferably 5,000 to 150,000.

  Component (e) includes polydimethylsiloxane having hydrogen groups at both ends, α, ω-dimethylpolysiloxane, methylsiloxane / dimethylsiloxane copolymer of both ends methyl groups, cyclic polymethylsiloxane, trimethylsilyl groups at both ends. Examples thereof include polymethylsiloxane and a dimethylsiloxane / methylsiloxane copolymer having trimethylsilyl groups at both terminals. The component (f) is arbitrarily selected from known polymerization catalysts, but platinum-based compounds are particularly desirable, and examples thereof include platinum alone, platinum chloride, chloroplatinic acid, and olefin coordinated platinum.

  In order to control the curing rate of the silicone rubber layer in these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohols, acetone, methyl ethyl ketone, methanol, ethanol, It is also possible to add a crosslinking inhibitor such as propylene glycol monomethyl ether. The (D) silicone rubber layer used in the present invention can be formed by applying and drying the above-described silicone-containing composition on the (C) photothermal conversion layer using a solvent. At this time, since the silicone rubber layer composition undergoes a condensation reaction or addition reaction when the solvent is dried after the application of the coating solution for forming the silicone rubber layer, a film is formed by lowering the drying temperature. There is a risk of poor curing. For this reason, 80 degreeC or more is preferable and, as for the drying temperature after application | coating of a silicone rubber layer, 100 degreeC or more is more preferable.

If necessary, the silicone rubber layer may be a fine powder of an inorganic material such as silica, calcium carbonate, titanium oxide, an adhesion aid such as a silane coupling agent, a titanate coupling agent or an aluminum coupling agent, or photopolymerization. An initiator may be added. The thickness of the silicone rubber layer used in the present invention is preferably 0.5 to 5.0 g / m ² , more preferably 1.0 to 3.0 g / m ² , and even more preferably ² as a dry film thickness. 0.0 to 2.5 g / m ² . When the film thickness is 0.5 g / m ² or more, ink repellency is not lowered and problems such as easy scratching are eliminated, and when it is 5.0 g / m ² or less, developability is not deteriorated. . Further, various silicone rubber layers may be further coated on the silicone rubber layer for the purpose of improving printing durability, scratch resistance, image reproducibility, stain resistance and the like to form a surface layer.

[Other layers]
The waterless planographic printing plate precursor applied to the present invention can be provided with other layers depending on the purpose as long as the effects of the present invention are not impaired, in addition to the above-described layer configuration. Below, another layer is demonstrated.

(Undercoat layer)
The waterless lithographic printing plate precursor used in the present invention preferably comprises an undercoat layer containing a water-soluble or water-dispersible polymer and formed by aqueous coating between the support and the photothermal conversion layer. This undercoat layer is useful as an adhesive layer between the support and the light-to-heat conversion layer, and also serves as a cushion layer for relieving pressure on the silicone rubber layer during printing. Since this undercoat layer is formed by water-based coating, the composition contains a water-soluble polymer as a binder, a water-dispersible polymer that can be used in a water-dispersed state such as an emulsion, or both. In order to form a uniform layer by aqueous coating, other components of the binder, for example, various additives, water-soluble materials or materials capable of being dispersed in water such as emulsions may be used. is necessary. An aqueous solution or an aqueous dispersion containing these materials is prepared as a coating solution for forming an undercoat layer, and this is applied and dried to form the undercoat layer used in the present invention.

  Hereinafter, the constituent components of the undercoat layer will be sequentially described.

<Binder>
Examples of binders used in the undercoat layer include proteins such as gelatin and casein, cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, and triacetyl cellulose, saccharides such as dextran, agar, sodium alginate, and starch derivatives. And synthetic polymers such as polyvinyl alcohol, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polystyrene, polyacrylamide, poly-N-vinylpyrrolidone, polyester, polyurethane, polyvinyl chloride, polyacrylic acid, etc. it can. Further, from the viewpoints of adhesion between the support and the undercoat layer, blocking property during production, and the like, the undercoat layer preferably has a crosslinked structure. Examples of the method of forming a crosslinked structure include a method of forming a crosslinked structure by reaction with a crosslinking agent using a binder having a crosslinkable group capable of reacting with a crosslinking agent, but is not limited thereto. Absent. When forming a crosslinked structure by the said method, it is preferable that the binder used has any of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group as a crosslinkable group.

<Crosslinking agent>
In the case where a crosslinked structure is formed by the above method, examples of the crosslinking agent to be added include, for example, “The Theory of Photographic Process” 3rd edition (1966) by C.E.K.Meers and T.H.James. US 3,316,095, US 3,232,764, US 3,288,775, US 2,732,303, US 3,635,718, US 3,232,763, US 2, No. 732,316, US 2,586,168, US 3,103,437, US 3,017,280, US 2,983,611, US 2,725,294, US 2,725, No. 295, US 3,100,704, US 3,091,537, US 3,32 , 313 JP can include US3,543,292 and JP US3,125,449 and JP UK994,869 JP, and those described in, UK1,167,207 JP. Typical examples include melamine compounds, aldehyde compounds and derivatives thereof, active vinyl compounds, active halogen compounds, epoxy compounds, and the like.

  As the melamine compound, a compound containing two or more (preferably three or more) methylol groups and / or alkoxymethyl groups in the melamine molecule, and a melamine resin or melamine urea resin which is a condensation polymer thereof. Can be mentioned. Examples of the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and the like. (Sumitex Resin) M-3, MW, MK, MC (manufactured by Sumitomo Chemical Co., Ltd.) and the like, but are not limited thereto. Examples of the condensation polymer include hexamethylol melamine resin, trimethylol melamine resin, and trimethylol trimethoxymethyl melamine resin. Commercially available products include MA-1, and MA-204 (manufactured by Sumitomo Bakelite Co., Ltd.), becamine (BECKAMINE) MA-S, becamine APM, and becamine J-101 (manufactured by Dainippon Ink & Chemicals, Inc.), Examples include, but are not limited to, Euroid 344 (manufactured by Mitsui Toatsu Chemical Co., Ltd.), Oka Resin M31, and Oka Resin PWP-8 (manufactured by Oka Shinko Co., Ltd.).

  As a melamine compound used for this invention, it is preferable that the functional group equivalent shown by the value which divided the molecular weight by the number of functional groups in 1 molecule is 50-300. Here, the functional group represents a methylol group or an alkoxymethyl group. By setting this value to 300 or less, the curing density becomes moderate and high strength can be obtained. By setting the functional group equivalent to 50 or more, the curing density is not high and the stability with time of the coating solution is not impaired, and the quality is improved. The addition amount of the melamine compound used for this invention is 0.1 to 100 weight% with respect to the said binder, Preferably it is 10 to 90 weight%.

  Representative examples of aldehyde-based compounds and derivatives thereof include mucochloric acid, mucobromic acid, mucofenoxycyclolic acid, mucophenoxybromic acid, formaldehyde, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1,4-dioxane, Examples include 2,3-dihydroxy-5-methyl-1,4-dioxane succinaldehyde, 2,5-dimethoxytetrahydrofuran, and glutaraldehyde. Typical examples of the active vinyl compound include divinylsulfone-N, N′-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2-propanol, methylenebismaleimide, and 5-acetyl. Examples include -1,3-diacryloyl hexahydro-s-triazine, 1,3,5-triacryloyl hexahydro-s-triazine, and 1,3,5-trivinylsulfonylhexahydro-s-triazine.

  Representative examples of the active halogen compounds include 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6- (4-sulfoanilino) -s-triazine sodium salt, 2 , 4-dichloro-6- (2-sulfoethylamino) -s-triazine, N, N′-bis (2-chloroethylcarbamyl) piperazine, and the like. Typical examples of the epoxy compound include bis (2,3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, , 3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-acetoxy-β-oxypropyl) isocyanurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers , Diglycerol polyglycidyl ether, 1,3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol polyglycerol ethers, and trimethylolpropane polyglycidyl ether.

  In addition, ethyleneimine compounds such as 2,4,6-triethylene-s-triazine, 1,6-hexamethylene-N, N′-bisethyleneurea, and bis-β-ethyleneiminoethylthioether; 1 , 2-di (methanesulfoneoxy) ethane, 1,4-di (methanesulfoneoxy) butane, and 1,5- (methanesulfoneoxy) pentane; methanesulfonate-based compounds; dicyclohexylcarbodiimide, and 1-dicyclohexyl Carbodiimide compounds such as -3- (3-trimethylaminopropyl) carbodiimide hydrochloride; isoxazole compounds such as 2,5-dimethylisoxazole; inorganic compounds such as chromium alum and chromium acetate; N-carboethoxy-2 -Isopropoxy-1,2-dihydroquino And dehydrated condensed peptide reagents such as N- (1-morpholinocarboxy) -4-methylpyridinium chloride; N, N′-adipoyldioxydisuccinimide, and N, N′-terephthaloyldioxydi Active ester compounds such as succinimide; isocyanates such as toluene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate; and epichlorohydrin compounds such as polyamide-polyamine-epichlorohydrin reactant, It is not limited to these.

<Metal oxide particles>
It is desirable to add metal oxide particles to the undercoat layer used in the present invention from the viewpoints of improving the adhesion between the support and the undercoat layer, imparting antistatic properties, and suppressing blocking during production. Examples of the material of the metal oxide particles include ZnO, SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ , V ₂ O ₅ and composite oxides thereof and / or metal oxides thereof. In addition, metal oxides further containing different atoms can be given. These may be used alone or in combination. As the metal oxide, ZnO, SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ and MgO are preferable, ZnO, SnO ₂ and In ₂ O ₃ are more preferable, and SnO ₂ is particularly preferable. As an example containing a small amount of hetero atoms, Al or In with respect to ZnO, Sb, Nb or halogen elements with respect to SnO ₂ , and hetero atoms such as Sn with respect to In ₂ O ₃ of 30 mol% or less, preferably 10 What doped the quantity below mol% can be mentioned. When the doping amount of different atoms is 30 mol% or less, the adhesion between the support and the undercoat layer is improved.

  The metal oxide particles may be contained in the range of 10 to 1000% by weight with respect to the binder of the undercoat layer. Preferably it is the range of 100 to 800 weight%. If it is 10% by weight or more, sufficient adhesion between the support and the undercoat layer can be obtained, and if it is 1000% by weight or less, the metal oxide particles can be prevented from falling off from the undercoat layer. The average particle diameter of the metal oxide particles is in the range of 0.001 to 0.5 μm, and preferably in the range of 0.003 to 0.2 μm. If the average particle size is 0.001 μm or more, sufficient adhesion between the support and the undercoat layer can be obtained, and if the average particle size is 0.5 μm or less, the metal oxide particles can be removed from the undercoat layer in the production process. Can be prevented. The average particle diameter here is a value including not only the primary particle diameter of the metal oxide particles but also the particle diameter of the higher order structure.

<Additive (additive for undercoat layer)>
In the undercoat layer used in the present invention, various additives can be used in addition to the binder, the optionally added crosslinking agent, and the metal oxide particles. These additives can be used for various purposes such as improved adhesion to adjacent layers such as a photothermal conversion layer and a support, inhibition of blocking during production, improved dispersibility of metal oxide particles in the undercoat layer, and improved coatability. For example, blend binders, adhesion assistants, matting agents, surfactants, dyes and the like can be mentioned. As the blend binder, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, polyurethane, polyamide, styrene-butadiene rubber, carboxy-modified styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxy-modified acrylonitrile-butadiene rubber, polyisoprene, acrylate rubber, polyethylene Polymers such as chlorinated polyethylene, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, nitrocellulose, halogenated polyhydroxystyrene, and chlorinated rubber can be used. The addition ratio is arbitrary, and the undercoat layer may be formed only with the blend binder as long as the film layer can be formed.

  Examples of the adhesion assistant include a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. Examples of the matting agent include inorganic particles and organic particles having an average particle diameter of 0.5 to 20 μm, more preferably an average particle diameter of 1.0 to 15 μm. In particular, crosslinked particles of polymethyl methacrylate, polystyrene, polyolefin, and copolymers thereof are preferable. Generally, the film thickness of the undercoat layer is a dry film thickness, preferably in the range of 0.01 to 10 μm, and more preferably in the range of 0.1 to 5 μm. If it is 0.01 μm or more, it is easy to apply the coating agent uniformly, so that uneven coating does not occur on the product, and if it is 10 μm or less, it is advantageous from an economical point of view.

[Middle layer]
In the present invention, an intermediate layer formed by aqueous coating can be provided between the undercoat layer and the photothermal conversion layer. The intermediate layer is provided mainly for assisting the function of preventing the metal oxide particles of the undercoat layer from falling off during production, and for improving slipping and scratch resistance during production.

<Binder>
As the binder for the intermediate layer, the same binder as the undercoat layer can be used. Furthermore, waxes, resins and rubber-like materials (for example, polyethylene, polypropylene) composed of homo- or copolymers of 1-olefin unsaturated hydrocarbons such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene. , Poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and propylene / 1-butene copolymer) Rubbery copolymers of at least species and conjugated or non-conjugated dienes (eg, ethylene / propylene / ethylidene norbornene copolymers, ethylene / propylene / 1,5-hexadiene copolymers, and isobutene / isoprene copolymers), Copolymers of 1-olefins with conjugated or non-conjugated dienes (eg ethylene / butadiene copolymers and ethylene Ethylidene norbornene copolymer), 1-olefins, especially copolymers of ethylene and vinyl acetate, and complete or partially saponified products thereof, 1-olefins alone or in copolymers, the above conjugated or nonconjugated dienes or vinyl acetate, etc. Examples include grafted graft polymers and complete or partially saponified products thereof. The intermediate layer binder used in the present invention must be water-soluble or used in a water-dispersed state such as an emulsion, and in particular, polymers of acrylic resin, vinyl resin, polyurethane resin, and polyester resin. Latex and water-soluble polyolefin resin are preferred.

<Additives (intermediate layer additives)>
Similarly to the undercoat layer, various additives such as a matting agent and a surfactant can be used for the intermediate layer used in the present invention. The film thickness of the intermediate layer used in the present invention is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.01 to 0.2 μm. When the thickness is 0.01 μm or more, the coating agent is easily applied uniformly, and uneven coating is hardly generated on the product, and when the thickness is 1 μm or less, it is advantageous from an economical viewpoint.

[Back layer]
The waterless planographic printing plate precursor of the present invention can be provided with at least one back layer on the side of the support opposite to the surface on which the photothermal conversion layer and the silicone rubber layer are provided.

  The back layer is not particularly limited, but a layer in which conductive metal oxide particles are dispersed in a cured product of an acrylic resin and a melamine compound is preferable.

  Further, the back layer of the present invention may have a layer structure of two or more layers as necessary. When the back layer has a layer structure of two or more layers, in a broad sense, all the layers of the two or more layers are collectively referred to as a back layer, and in a narrow sense, the lower layer is a back layer and a layer above it. It may also be referred to as an overcoat layer or may be referred to as a back first layer, a back second layer, etc. from the lower layer.

  The back layer may contain a matting agent. Further, the back layer may contain a lubricant such as a wax or a surfactant.

(Matting agent)
The matting agent is preferably an oxide such as silicon oxide, aluminum oxide or magnesium oxide having an average particle size of 0.5 μm to 20 μm, more preferably an average particle size of 1.0 μm to 15 μm, or polymethyl Examples thereof include polymers and copolymers such as methacrylate and polystyrene. In particular, crosslinked particles of these polymers or copolymers are preferred.

  By containing a predetermined amount of these matting agents in at least one layer on the back layer side (back layer and / or overcoat layer), the Beck smoothness (second) on the surface on the back layer side is 50 to 500 seconds, Preferably, it can be 60 to 450 seconds, more preferably 200 to 400 seconds. Here, the Beck smoothness (second) of the surface on the back layer side is JIS-P8119-1998 and J.P. TAPPI paper pulp test method no. 5 means the value measured by the method described in 5. By making the Beck smoothness (seconds) on the surface on the back layer side 50 seconds or more, the unevenness on the surface on the back side is not too large and the matting agent is difficult to fall off the layer, and the transportability of the original plate decreases with time. do not do. On the other hand, if the Beck smoothness (seconds) on the surface on the back layer side is 500 seconds or less, the smoothness on the back layer side is not too high and the transportability of the original plate does not deteriorate, and various adverse effects due to poor transport occur. Absent.

(Metal oxide particles)
The back layer may contain conductive metal oxide particles. Examples of the material of the conductive metal oxide particles include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO and MoO ₃ and their composite oxides, and / or the metal oxide. Mention may be made of metal oxides containing different atoms.

As the metal oxide, SnO ₂ , ZnO, Al ₂ O ₃ , TiO ₂ , In ₂ O ₃ and MgO are preferable, SnO ₂ , ZnO, In ₂ O ₃ and TiO ₂ are more preferable, and SnO ₂ is particularly preferable. Examples of containing a small amount of different atoms include Zn or Al, In, TiO ₂ Nb or Ta, In ₂ O ₃ Sn, and SnO ₃ Sb, Nb or halogen elements. An element doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of the element can be used. When the amount of the different element added is 0.01 mol% or more, sufficient conductivity can be imparted to the oxide or composite oxide, and the blackening degree of the particles is increased by setting it to 30 mol% or less. The back layer is not black and is suitable for a sensitive material. Therefore, in the present invention, the material of the conductive metal oxide particles is preferably one containing a small amount of a different element with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.

  The conductive metal oxide particles are preferably contained in the back layer in a range of 10 to 1000% by weight, more preferably 100 to 800% by weight, based on the binder (total of acrylic resin and melamine compound, etc.). The range of is preferable. When it is 10% by weight or more, sufficient antistatic properties can be obtained, and when it is 1000% by weight or less, the conductive metal oxide particles can be prevented from falling off the photosensitive material.

  The particle diameter of the conductive metal oxide particles is preferably as small as possible in order to reduce light scattering as much as possible, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter, and Mie's theory Can be obtained using

  The average particle diameter of the metal oxide particles in the back layer of the fountain solution-less lithographic printing plate precursor according to the present invention is preferably 0.001 to 0.5 μm, more preferably 0.003 to 0.2 μm. It is a range. Here, the average particle size is a value including not only the primary particle size of the conductive metal oxide particles but also the particle size of the higher order structure.

  When the fine particles of the metal oxide are added to the coating solution for forming the back layer, they may be added and dispersed as they are, but they are dispersed in a solvent such as water (including a dispersant and a binder as necessary). It is preferable to add a dispersion.

In the present invention, when the metal oxide particles of the present invention described above are contained in the back layer, the surface electrical resistance value at 10 ° C. and 15% RH on the back layer side of the original is 1 × 10 7 to 1 × 10 12 Ω, preferably 1 × 10 ⁹ to 1 × 10 ¹¹ Ω can be adjusted, and the surface electrical resistance value under high temperature and high humidity can also be adjusted to a predetermined value. When the surface electrical resistance value at 10 ° C. and 15% RH on the back layer side of the original plate is set to 1 × 10 ⁷ Ω or more, a large amount of conductive metal oxide particles are not required, so that the particles are difficult to drop off. Such a secondary failure that the particles become the core of the repellency of the coating film is not caused. In addition, if it is 1 × 10 ¹² Ω or less, it has a desired antistatic performance even under high temperature and high humidity, and prevents coating defects during the production of a lithographic plate precursor that does not require dampening water under high temperature and high humidity. It is possible to prevent the laser beam from defocusing at the time of recording writing due to adhesion of dust or the like to the original plate, and to improve the sharpness (reproducibility) of image recording.

  Although it does not specifically limit as a binder used for the back layer of the waterless planographic printing plate precursor used for the platemaking method of this invention, The hardened | cured material of an acrylic resin and a melamine compound is desirable. In the present invention, from the viewpoints of maintaining a good working environment and preventing air pollution, it is preferable to use either a water-soluble polymer or a melamine compound, or an aqueous dispersion such as an emulsion. Moreover, it is preferable that a polymer has any group of a methylol group, a hydroxyl group, a carboxyl group, and a glycidyl group so that a crosslinking reaction with a melamine compound is possible. Among these, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is particularly preferable. The content of the hydroxyl group or carboxyl group in the polymer is preferably 0.0001 to 10 equivalent / 1 kg, and particularly preferably 0.01 to 1 equivalent / 1 kg.

  Acrylic resins include acrylic acid esters such as acrylic acid and alkyl acrylate, acrylamide, acrylonitrile, methacrylic acid esters such as methacrylic acid and alkyl methacrylate, and homopolymers of any monomer of methacrylamide and methacrylonitrile. Or the copolymer obtained by superposition | polymerization of 2 or more types of these monomers can be mentioned. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers preferable. For example, mention may be made of homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers. it can.

  The acrylic resin is mainly composed of a monomer having any one of a methylol group, a hydroxyl group, a carboxyl group and a glycidyl group so that a crosslinking reaction with the melamine compound is possible with the composition as a main component. The resulting polymer.

  The melamine compound used in the present invention includes a compound containing two or more (preferably three or more) methylol groups or alkoxymethyl groups in the melamine molecule, and a melamine resin or melamine urea that is a condensation polymer thereof. Examples thereof include resins.

  Examples of the initial condensate of melamine and formalin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and the like. Specific examples of commercially available products include, for example, SMITEX RESIN ( Sumitex Resin) M-3, MW, MK, and MC (manufactured by Sumitomo Chemical Co., Ltd.) and the like, but are not limited thereto.

  Examples of the condensation polymer include hexamethylol melamine resin, trimethylol melamine resin, trimethylol trimethoxymethyl melamine resin, and the like. Commercially available products include MA-1 and MA-204 (Sumitomo Bakelite Co., Ltd.), Bekkamin MA-S, Bekkamin APM and Bekkamin J-101 (Dainippon Ink Chemical Co., Ltd.), Euroid 344 ( Examples include, but are not limited to, Mitsui Toatsu Chemical Co., Ltd.), Oka Resin M31, and Oka Resin PWP-8 (Oshika Promotion Co., Ltd.).

  As said melamine compound, it is preferable that the functional group equivalent shown by the value which divided the molecular weight by the number of functional groups in 1 molecule is 50-300. Here, the functional group represents a methylol group or an alkoxymethyl group. When this value is 300 or less, the curing density becomes moderate and high strength is obtained. When the functional group equivalent is 50 or more, the curing density is appropriate, transparency is not impaired, and the quality is improved. The amount of the aqueous melamine compound added is 0.1 to 100% by weight, preferably 10 to 90% by weight, based on the polymer.

  These melamine compounds may be used alone or in combination of two or more. Further, it can be used in combination with other compounds, for example, “The Theory of the Photographic Process” 3rd edition (1966) by C.E.K.Meers and T.H.James, US Pat. No. 3,316,095, 3232764, 3288775, 2732303, 3635718, 3323767, 2323276, 2732316, 2586168, 3103437, 3017280, 2998611, 2725294, 2725295, 3100704 , Nos. 3091537, 3321313, 3543292 and 3125449, and British Patent Nos. 994869 and 1167207.

Representative examples include mucochloric acid, mucobromic acid, mucofenoxycyclic acid, mucophenoxypromic acid, formaldehyde, glyoxal, monomethylglioxal, 2,3-dihydroxy-1,4 dioxane, 2,3-dihydroxy-5. -Aldehyde compounds such as methyl-1,4-dioxanesuccinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde and derivatives thereof;
Divinylsulfone-N, N′-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2-propanol, methylenebismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-s-triazine Active vinyl compounds such as 1,3,5-triacryloyl-hesahydro-s-triazine and 1,3,5-trivinylsulfonyl-hexahydro-s-triazine;
2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6- (4-sulfoanilino) -s-triazine sodium salt, 2,4-dichloro-6- (2-sulfoethylamino) ) Active halogen compounds such as -s-triazine and N, N'-bis (2-chloroethylcarbamyl) piperazine;
Bis (2,3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1 , 3-diglycidyl-5- (γ-acetoxy-β-oxypropyl) isocyanurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether, 1, Epoxy compounds such as 3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol polyglycerol ethers and trimethylolpropane polyglycidyl ethers;
Ethyleneimine compounds such as 2,4,6-triethylene-s-triazine, 1,6-hexamethylene-N, N′-bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-di ( Methanesulfonic acid ester compounds such as methanesulfonoxy) ethane, 1,4-di (methanesulfoneoxy) butane and 1,5-di (methanesulfoneoxy) pentane; dicyclohexylcarbodiimide and 1-dicyclohexyl-3- (3- Carbodiimide compounds such as trimethylaminopropyl) carbodiimide hydrochloride; isoxazole compounds such as 2,5-dimethylisoxazole; inorganic compounds such as chromium alum and chromium acetate;
Dehydrated condensed peptide reagents such as N-carboethoxy-2-isopropoxy-1,2-dihydroquinoline and N- (1-morpholinocarboxy) -4-methylpyridinium chloride; N, N′-adipoyldioxydi Active ester compounds such as succinimide and N, N′-terephthaloyldioxydisuccinimide: Isocyanates such as toluene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate; and polyamide-polyamine-epichlorohydrin reactant An epichlorohydrin-based compound such as, but not limited to, can be mentioned.

  Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

  Examples of the slip agent include phosphate esters of higher alcohols having 8 to 22 carbon atoms or amino salts thereof; palmitic acid, stearic acid, behenic acid and esters thereof; and silicone compounds.

  The back layer is a dispersion obtained by dispersing the above components as they are or in a solvent such as water (including a dispersant and a binder as necessary) into an aqueous dispersion or aqueous solution containing a binder and appropriate additives. It is obtained by adding and mixing (dispersing if necessary) to prepare a coating solution for forming a back layer and coating and drying it.

  The back layer is a coating method generally known on the surface of the support (the side where the photothermal conversion layer and the silicone rubber layer are not provided), such as dip coating, air knife coating, It can be applied by a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method or the like.

The thickness of the back layer is not particularly limited, but is preferably in the range of 0.01 to 1 μm, and more preferably in the range of 0.1 to 0.5 μm. When it is 0.01 μm or more, it is easy to apply the coating agent uniformly, and uneven application is unlikely to occur on the product, and when it is 1 μm or less, the antistatic performance and scratch resistance are not deteriorated.
(Laminate film)
In the present invention, as described above, it is preferable to laminate the cover film from the viewpoint of protecting the surface after applying the silicone layer or preventing dust adhesion. Examples of the cover film (laminate film) include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, and cellophane.

  Specifically, biaxially stretched polypropylene, biaxially stretched nylon, and biaxially stretched polyethylene terephthalate are preferable, biaxially stretched nylon and biaxially stretched polyethylene terephthalate are more preferable, and biaxially stretched polyethylene terephthalate is particularly preferable.

From the viewpoint of preventing the cover film from being cut, it is preferable that the tensile strength in the longitudinal direction (MD) is 100 MPa or more, and biaxially stretched polyethylene terephthalate is suitable. Furthermore, it is preferable that the thickness of the cover film is 20 μm or less in order to improve economy and productivity by reducing the winding diameter. Further, in order to prevent dust adhesion, at least one surface of the cover film may be subjected to antistatic treatment.
[Plate making method]
Next, a method for making a lithographic printing plate from the waterless lithographic printing plate precursor will be described. In the same way as the general plate making method, the plate making is performed by removing the silicone rubber layer with reduced exposure and the exposure step for reducing the adhesion with the adjacent layer of the silicone rubber layer in the exposed portion by imagewise exposure, And a developing step for forming a receptive region.

(I) Exposure step As described above, the plate making method of the lithographic printing plate from the waterless lithographic printing plate precursor according to the present invention, it is important that a part of the photothermal conversion layer of the laser irradiation part remains after the plate making, Therefore, in the laser used for exposing the waterless lithographic original plate, the adhesive force is sufficiently lowered to peel and remove the silicone rubber layer, and the photothermal conversion layer of the laser irradiation portion remains after the plate making. It must give such an exposure amount. The remaining amount of the photothermal conversion layer can be easily controlled by adjusting the laser output or adjusting the main scanning speed (writing speed) of the laser according to the composition and film thickness of the photothermal conversion layer. can do. As long as the above conditions are satisfied, there is no particular limitation on the type of laser, and a gas laser such as an Ar laser or a carbon dioxide gas laser, a solid laser such as a YAG laser, a semiconductor laser, or the like can be used. A laser with a normal output of 50 mW class or higher is required. From practical aspects such as maintainability and cost, a semiconductor laser and a semiconductor-excited solid laser (YAG laser or the like) are preferably used. The recording wavelength of these lasers is in the infrared wavelength region, and an oscillation wavelength of 800 nm to 1100 nm is often used. In addition, exposure can be performed using an imaging apparatus described in JP-A-6-186750 or a full color printing system “Quickmaster DI46-4” (trade name) manufactured by Heidelberg. Even in this case, it is important to control the remaining amount of the photothermal conversion layer by adjusting the laser irradiation output and the scanning speed according to the thickness of the photothermal conversion layer.

(II) Development step The developer used in making the waterless lithographic printing plate precursor according to the present invention is known as a developer for a waterless lithographic printing plate precursor, such as hydrocarbons, polar solvents, water. However, from the viewpoint of safety, it is preferable to use water or an aqueous solution of an organic solvent containing water as a main component. In consideration of safety and flammability, the concentration of the organic solvent is 40. Less than wt% is desirable. Examples of hydrocarbons that can be used include aliphatic hydrocarbons (specifically, for example, hexane, heptane, gasoline, kerosene, commercially available solvents “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd.), etc.) , Aromatic hydrocarbons (for example, toluene, xylene, etc.), halogenated hydrocarbons (tricrene, etc.), and the like. Examples of polar solvents include alcohols (specifically, for example, methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene Glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), esters (eg, ethyl acetate, lactic acid) Methyl, butyl lactate, propylene glycol monomethyl ether acetate, diethyl Glycol acetate, diethyl phthalate), other, triethyl phosphate, tricresyl phosphate and the like. Moreover, water itself, such as tap water, pure water, distilled water, can also be used. These may be used alone or in combination of two or more, for example, water is added to hydrocarbons, water is added to polar solvents, or hydrocarbons and polar solvents are used in combination. Further, among the hydrocarbons and polar solvents having a low affinity for water, a surfactant or the like may be added to improve the solubility in water. Further, an alkali agent (for example, sodium carbonate, diethanolamine, sodium hydroxide, etc.) can be added together with the surfactant.

  The development can be performed by a known method such as rubbing the plate surface with a developing pad containing the developer as described above, or pouring the developer onto the plate surface and rubbing with a developing brush in water. The developer temperature can be any temperature, but is preferably 10 ° C to 50 ° C. As a result, the silicone rubber layer which is the ink repellent layer in the image portion is removed, and that portion becomes the ink receiving portion. The development processing as described above, or the subsequent washing and drying processing can be performed by an automatic processor. A preferred example of such an automatic processor is described in JP-A-2-220061. Further, by using the above-described full color printing system “Quickmaster DI46-4” manufactured by Heidelberg, exposure and on-press development can be continuously performed under suitable conditions.

  The waterless planographic printing plate precursor of the present invention can also be developed by peeling off the adhesive layer after the adhesive layer is bonded to the surface of the silicone rubber layer. Any known adhesive layer that can adhere to the surface of the silicone rubber layer can be used. A material in which these adhesive layers are provided on a flexible support is commercially available, for example, under the trade name “Scotch Tape # 851A” manufactured by Sumitomo 3M Limited.

  When waterless planographic plates that have been treated and made in this way are stacked and stored, it is preferable to insert and sandwich a slip sheet to protect the printing plate. The waterless lithographic printing plate obtained by the plate making method is mounted on a printing machine, and a large number of excellent printed matter excellent in ink depositing property in the image area can be obtained.

The invention is explained in more detail by means of examples. However, the present invention is not limited to the following examples.
[Example 1]
(Formation of undercoat layer)
On the polyester film “E-5101” (manufactured by Toyobo Co., Ltd.) whose corona discharge treatment was applied to the surface having a thickness of 188 μm, the following coating solution was applied by the wire bar coating method, dried at 180 ° C. for 30 seconds and dried. An undercoat layer having a thickness of 0.2 μm was formed.
(Undercoat layer coating solution)
-Takelac W-6061 (Polyurethane latex manufactured by Mitsui Takeda Chemical Co., Ltd., solid content 30% by weight) 7.9 parts by weight-Denacol EX-521 (epoxy compound manufactured by Nagase ChemteX Corporation, active ingredient concentration: 100) % By weight) 0.48 parts by weight Nipol UFN1008 (polystyrene matting agent manufactured by Nippon Zeon Co., Ltd.)
0.04 parts by weight Emulex 710 (polyoxyethylene alkyl ether manufactured by Nippon Emulsion Co., Ltd., 100% by weight) 0.07 parts by weight 92 parts by weight of distilled water (Formation of photothermal conversion layer)
The following mixture is stirred with a glass bead for 30 minutes in a paint shaker to disperse the carbon black, and the glass beads are filtered off. Then, a surfactant KF333 (Dainippon Ink Chemical Co., Ltd.) is added in an amount of 0.006 wt. Part addition and stirring were carried out to prepare a photothermal conversion layer coating solution.

This coating solution was applied onto the undercoat layer so as to have a dry film thickness of 1.0 μm, and dried by heating at 80 ° C. for 2 minutes to form a photothermal conversion layer.
(Photothermal conversion layer coating solution)
Diphenylmethane diisocyanate: 5 mol, polypropylene glycol:
1 mol, 2,2′-dimethylolpropanoic acid: 4 mol of reaction product
3.0 parts by weight-MA-230 (carbon black, manufactured by Mitsubishi Chemical Corporation) 2.0 parts by weight-Solsperse S24000R (manufactured by ICI) 0.15 parts by weight-Solsperse S17000 (manufactured by ICI) 0.15 weight Part ・ Methyl ethyl ketone 29 parts by weight ・ Propylene glycol monomethyl ether 15 parts by weight (formation of silicone rubber layer)
The following coating solution was applied onto the photothermal exchange layer and dried by heating at 100 ° C. for 1 minute to form an addition type silicone rubber layer having a dry film thickness of 1.5 g / m ² .
(Coating liquid for silicone rubber layer)
・ Α, ω-Divinylpolydimethylsiloxane (average polymerization degree 1300)
9.0 parts by weight • (CH ₃ ) ₃ SiO (SiH (CH ₃ ) O) ₈ —Si (CH ₃ ) ₃ 0.2 parts by weight • Olefin coordination platinum catalyst 0.1 parts by weight • Control agent [HC≡C -C (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ ] 0.2 parts by weight • Isopar E (manufactured by Exxon Chemical Co., Ltd.) 120.0 parts by weight After applying and drying this silicone rubber layer, the silicone rubber layer Before the surface comes into contact with the coater roller, a 15 μm thick antistatic treated biaxially stretched PET film is laminated and wound up, and the waterless lithographic printing plate precursor used in Example 1 having good adhesion between each layer The raw roll was obtained.

  After slitting this to a width of 340 mm, using a winding machine 12 shown in FIG. When processed into a waterless lithographic printing plate precursor 58, a processed product free from winding deviation was obtained. Moreover, when this processed product was opened and entrainment of entrained air (hereinafter referred to as air pool) was confirmed, it was confirmed that there was no air pool and the flatness of the plate was not impaired.

Furthermore, this processed product was aged for one week in an environment of 45 ° C. Wet (75% RH), and then printed after plate-making with the Heidelberg full-color printing system “Quickmaster DI46-4”. was gotten.
[Comparative Example 1]
Except for winding without using the lion roll 28, the same processing as in Example 1 was performed. Moreover, when this processed product was opened and air accumulation was confirmed, a large amount of air was entrained, the plate had many irregularities, and the flatness was remarkably poor. When this plate was made and printed with the same environmental conditions and printing machine as in Example 1, compared with the portion where there was no air accumulation, the portion where the air accumulation was present was thin, and the non-image area was A part of the unexposed silicone layer to be removed was peeled off by the plate making process, and stains were generated on the printed matter.
[Comparative Example 2]
Except for installing the lion roll 28 at a position 64 (see FIG. 1) opposite to the winding portion 62 and performing winding processing, the processing is performed in the same manner as in Example 1 and winding deviation occurs, so that uniform processing cannot be performed. Things were generated. Moreover, when this processed product was opened and air accumulation was confirmed, a large amount of air was entrained, the plate had many irregularities, and the flatness was remarkably poor. When this plate was made and printed with the same environmental conditions and printing machine as in Example 1, compared with the portion where there was no air accumulation, the portion where the air accumulation was present was thin, and the non-image area was A part of the unexposed silicone layer to be removed was peeled off by the plate making process, and stains were generated on the printed matter.

It is the schematic which shows the lithographic printing plate precursor processing apparatus provided with the lithographic printing plate precursor winding apparatus of one Embodiment of this invention.

Explanation of symbols

12 Processing machine (lithographic printing plate precursor processing equipment)
14 Unwinding shaft 16 Feed roll 18 Die cutter 20 Tip shape cutting die set 22 Press pressure cylinder 24 Cover film take-up roll 26 Product take-up roll 28 Rayon roll 52 Original fabric 54 Original fabric roll 56 Cover film 58 Planographic printing plate precursor 60 Small roll form 62 Winding part

Claims (2)

A take-up shaft for winding a lithographic printing plate precursor, which is obtained by sequentially laminating at least a photothermal conversion layer and a silicone rubber layer on a support, with the silicone rubber layer inside;
A lion roll that contacts the lithographic printing plate precursor at a portion where the lithographic printing plate precursor is wound on the winding shaft, and partially presses the lithographic printing plate precursor during winding;
A lithographic printing plate precursor winding device comprising: A lithographic printing plate precursor obtained by sequentially laminating at least a light-to-heat conversion layer and a silicone rubber layer on a support is wound on a winding shaft with the silicone rubber layer inside, and
The lithographic printing plate precursor is brought into contact with the lithographic printing plate precursor at the portion where the lithographic printing plate precursor is wound at the time of winding with the winding shaft, and the lithographic printing plate precursor in the middle of winding is partially wound while being wound. A lithographic printing plate precursor winding method characterized by

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