JP2010051928A - Surface reforming method and apparatus, multilayer coating method and apparatus, and coated material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface reforming method and apparatus, and a multilayer coating method and apparatus which can obtain a rugged shape onto a surface, and to provide a coated material. <P>SOLUTION: The surface reforming apparatus comprises: a coating part 18 which coats a support body 16 with a polymer solution prepared by dissolving a thermoplastic resin into a first solvent; a drying part 20 which dries a coated film dried up to the dry point by supplying a hot air containing vapor of a second solvent having a molar volume smaller than that of the first solvent to the coated film; and a coating part 22 which coats the dried coated film with the coating liquid to form an overcoat layer. The drying part 20 performs drying treatment under conditions satisfying the relation: 1.0≤C×R(273.15+T)/(M×P<SB>T</SB>)≤1.8, wherein T presents film temperature [°C] at the dry point, C presents solvent vapor amount [g/m<SP>3</SP>], P<SB>T</SB>presents saturated water vapor amount [Pa] at the film surface temperature T, R denotes gas constant, and M presents molecular weight of the second solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a surface modification method and apparatus, a multi-layer coating method and apparatus, and a coated material, and in particular, manufactures magnetic recording materials such as lithographic printing plates, various optical films, silver salt films, photographic paper, and video tape base films. The present invention relates to a surface modification method and apparatus, a multilayer coating method and apparatus, and a coated product, which are performed in the process of performing the above.

  Magnetic recording materials such as lithographic printing plates, various optical films, silver salt films, photographic papers, and video tape base films are used for photosensitive layers while running strips such as support webs, base films, and baryta paper in a fixed direction. It is manufactured by applying a coating solution such as a forming solution, a heat-sensitive layer forming solution, a photosensitive emulsion, or a magnetic layer forming solution to form a coating film, drying it, and then cutting it into predetermined dimensions as necessary. The As a drying method in this production process, a method using dry hot air is generally used. In addition, a drying method using hot air containing solvent vapor is also proposed. Furthermore, Patent Document 1 by the present applicant proposes a method for effectively drying and removing the high boiling point solvent (first solvent) by drying in an atmosphere of low boiling point solvent vapor (second solvent). Has been. According to this method, the second solvent vapor is absorbed in the film, thereby increasing the free volume in the film and diffusing the residual solvent (first solvent or other remaining solvent) in the film. Because the speed increases, residual solvent can be removed quickly and at relatively low temperatures. And since the absorbed second solvent vapor has a molecular volume smaller than that of the residual solvent, it can be easily removed by drying in dry air, and the drying time can be shortened as a whole.

  By the way, in general, a planographic printing plate, various optical films, and the like may be advantageously subjected to a surface treatment for forming irregularities on the surface to roughen the surface. For example, a lithographic printing plate is collected after being cut into a product size, but if the coefficient of friction of the coating film surface is low, it will cause bundle deviation after accumulation and cause scratches, so it is advantageous to roughen the surface. . In addition, when layering organic layers sequentially, if the wettability of the lower organic film is poor, the upper organic film may be difficult to stick and may cause repellency, so roughen the lower organic film. It will be advantageous.

  Known surface treatment methods for roughening include EB, UV, IB irradiation, plasma treatment, and the like (see Patent Document 2). However, when the surface to be processed is a photosensitive layer such as an organic film, there is a concern that these processing methods may cause covering. Therefore, there is a need for a new coating surface modification method that does not use light, electron beam, or plasma.

  Other surface modification methods include mechanical surface roughening methods such as ball grains, wire grains, and brush grains, and electrochemical surface roughening methods. In the case of a mechanical roughening method, there are problems that uniform surface treatment and continuous treatment are difficult, and that skill is required. In particular, in the case of a lithographic printing plate, it is difficult to obtain sufficient performance. In addition, in the case of the electrochemical surface roughening method, there are a problem that processing unevenness is likely to occur and a problem that complicated control is required.

Thus, it is very difficult to roughen a lithographic printing plate and various optical films, and there is a problem that a desired surface shape cannot be obtained. Conventionally, in order to roughen the surface coating film, a surface treatment step must be performed separately from the coating step and the drying step, which increases the number of steps.
International Publication Number 2007/136005 Japanese Patent No. 3041032

  The present invention has been made in view of such circumstances, and an object thereof is to provide a surface modification method and apparatus capable of obtaining desired surface properties. Furthermore, it aims at providing the multilayer coating method and apparatus using the same, and a coating material.

In order to achieve the above object, the invention according to claim 1 is a coating step of forming a coating film by applying a polymer solution in which a thermoplastic resin is dissolved in a first solvent, and a drying point of the coating film. A drying step in which a solvent vapor-containing hot air of a second solvent having a molecular volume smaller than that of the first solvent is supplied to the coating film, and the coating film is dried. Film temperature [° C.], C: solvent vapor amount [g / m ³ ], P _T : saturated water vapor amount [Pa] at film surface temperature T, R: gas constant, M: molecular weight of second solvent. Provided is a surface modification method characterized by satisfying an equation represented by 0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8.

When the inventor of the present invention supplies the solvent vapor-containing hot air of the second solvent, which is normally supplied so as not to condense, under a specific narrow condition under the condition of dew condensation, a fine substantially hemispherical shape is formed on the coating film surface after drying. The following knowledge was obtained that a recess (hereinafter also referred to as a pore) was formed. Further, the inventors of the present invention say that the drying condition is the following formula: 1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8 (hereinafter referred to as Formula 1). Obtained knowledge. The present invention has been made based on such knowledge, and since the drying process is performed under the above-described drying conditions, a coating film having pores on the surface can be formed. Thereby, the physical properties of the coating film can be controlled. For example, the static friction coefficient of the coating film surface is controlled to more than 1 to 1.7 times or the contact angle of the coating film surface is decreased by 1 to 20 °. Can be controlled as well.

  In addition, since the present invention only changes the drying conditions in the drying step, there is no possibility that the properties of the coating film will change unlike the surface treatment method using light, electron beam, or plasma.

  In the present invention, “drying point” means a state in which the coating liquid does not adhere to the cloth even when the cloth touches the coating film, in other words, a state in which the gloss of the coating film surface has finished changing. To do.

  The invention according to claim 2 is characterized in that, in the invention according to claim 1, the surface physical properties of the coating film are controlled by adjusting the temperature of the solvent vapor-containing hot air of the second solvent.

  The inventors of the present invention have found that when the above-described pores are formed, the pore diameter of the pores can be controlled by adjusting the temperature of the steam-containing hot air. The present invention has been made on the basis of such knowledge. Since the temperature of the hot air containing the solvent vapor of the second solvent is adjusted, the pore diameter can be controlled, and as a result, the coating The surface physical properties of the film can be controlled.

  A third aspect of the invention is characterized in that, in the first aspect of the invention, the surface physical properties of the coating film are controlled by adjusting a solvent vapor amount of the second solvent.

  The inventors of the present invention have found that when the above-described pores are formed, the number of pores can be controlled by adjusting the solvent vapor amount of the second solvent. The present invention has been made on the basis of such knowledge, and since the amount of the solvent vapor of the second solvent is adjusted, the number of pores can be controlled, and as a result, the surface of the coating film Physical properties can be controlled.

  According to a fourth aspect of the present invention, in the second or third aspect of the invention, the surface property is a coefficient of static friction.

  The invention according to claim 5 is the invention according to claim 2 or 3, wherein the surface property is a contact angle.

  The invention according to claim 6 is the invention according to any one of claims 1 to 5, wherein the coating film is an image forming layer of a lithographic printing plate, and the static friction coefficient of the surface of the image forming layer is obtained by the drying step. It is characterized by controlling.

  Invention of Claim 7 is invention of any one of Claims 1-5, The said coating film is an overcoat layer formed on the image forming layer of a lithographic printing plate, The said drying process WHEREIN: The coefficient of static friction of the overcoat layer is controlled.

In order to achieve the above object, the invention described in claim 8 is provided with a coating device for applying a polymer solution in which a thermoplastic resin is dissolved in a first solvent, and provided at a subsequent stage of the coating device, and dried to a drying point. A drying device that supplies the coating film with hot air containing a solvent vapor containing a second solvent having a molecular volume smaller than that of the first solvent, and the drying device includes: T: film temperature at the drying point [° C.] , C: solvent vapor amount [g / m ³ ], P _T : saturated water vapor amount [Pa] at the film surface temperature T, R: gas constant, M: molecular weight of the second solvent, 1.0 ≦ C × R ( There is provided a surface modifying apparatus characterized by performing a drying treatment under a drying condition represented by 273.15 + T) / (M × P _T ) ≦ 1.8.

  The invention of claim 8 is an apparatus claim corresponding to the method claim of claim 1, and can form a coating film having irregularities on the surface, and can increase the static friction coefficient of the coating film.

In order to achieve the above object, the invention according to claim 9 is a lower layer coating step in which a polymer solution in which a thermoplastic resin is dissolved in a first solvent is applied to a support to form a lower layer, and the lower layer is a drying point. After drying to a lower layer, a solvent vapor-containing hot air of a second solvent having a molecular volume smaller than that of the first solvent is supplied to the lower layer and dried, and a coating solution is applied on the dried lower layer An upper layer coating step for forming an upper layer, wherein the lower layer drying step includes: T: film temperature [° C.] at the drying point, C: solvent vapor amount [g / m ³ ], P _T : film surface temperature T Saturated water vapor amount [Pa], R: gas constant, M: molecular weight of the second solvent, 1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8 A multilayer coating method characterized by satisfying the above is provided.

  According to this invention, an unevenness | corrugation is formed in the surface of a lower layer by performing the drying process of a lower layer drying process on the drying conditions of Formula (1). Therefore, the wettability of the lower layer with respect to the upper coating solution is improved, and for example, the contact angle of the film surface with respect to a solvent having good wettability (that is, a solvent having a contact angle of less than 90 ° with the film surface) can be lowered by 1 to 20 °. it can. Thereby, the repellency of the upper layer coating liquid can be prevented, and the coating accuracy of the upper layer can be improved.

  The “lower layer” and “upper layer” in the present invention mean relative positional relationships, and the coating film on the support side is referred to as the lower layer and the surface side is referred to as the upper layer. Therefore, even when three or more layers are applied, the effect of the present invention can be obtained when two adjacent layers satisfy the above conditions.

  The invention of claim 10 is the invention of claim 9, wherein the lower layer is an image forming layer of a lithographic printing plate, and the upper layer is an overcoat layer applied on the image forming layer, and the lower layer The contact angle of the lower layer with respect to the upper layer coating solution is reduced by a drying step.

In order to achieve the above-mentioned object, the invention according to claim 11 applies a polymer solution in which a thermoplastic resin is dissolved in a first solvent to a support, and forms a lower layer, and a lower layer coating device for the lower layer coating device. A lower layer drying apparatus that is provided in a subsequent stage and supplies the vapor to the lower layer dried to the drying point by supplying hot air containing a solvent vapor of a second solvent having a molecular volume smaller than that of the first solvent, and provided in the subsequent stage of the lower layer drying step. And an upper layer coating apparatus that coats the dried lower layer to form an upper layer, wherein the lower layer drying apparatus includes: T: film temperature at the drying point [° C.], C: amount of solvent vapor [ g / m ³ ], P _T : saturated water vapor amount [Pa] at the film surface temperature T, R: gas constant, M: molecular weight of the second solvent, 1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8, which satisfies the formula A multilayer coating apparatus is provided.

  The invention of claim 11 is an apparatus claim corresponding to the method claim of claim 9, can form a coating film having irregularities on the surface of the lower layer, can prevent repellency of the upper coating liquid, The coating accuracy can be improved.

  In order to achieve the above object, the invention described in claim 12 is a coated product in which a coating film containing a thermoplastic resin is formed on the surface, and the surface has a large number of pores composed of substantially concave depressions. In addition, the peripheral edge portion of the pore forms a smooth curved surface by gradually denting toward the center of the pore, and the diameter of the pore is 0.2 μm or more and 4.0 μm or less. A coated product is provided.

  According to the present invention, the peripheral edge of the pore is a smoothly curved surface, and the peripheral edge portion of the pore can be prevented from being scraped by abrasion. That is, when forming pores by a conventional method, (A) a method of forming bubbles by grinding and (B) a method of pressing a convex portion with a needle or the like to form a concave portion can be considered. In the case of A), the peripheral edge of the hole does not become a smooth curved surface, and in the case of (B), the peripheral edge rises, so that there is a risk of scraping due to friction. However, according to the present invention, since the peripheral edge of the pore forms a smooth curved surface, it can be prevented from being scraped by abrasion. The pore diameter is preferably 0.2 μm or more and 2.0 μm or less, and more preferably 0.2 μm or more and 0.5 μm or less.

  Moreover, it is preferable that the parts other than the fine pores on the surface of the coated product of the present invention are smooth. Smoothness is a state in which a coating film is formed on a flat support and visually observed with an SEM of 20,000 times and looks smooth with no irregularities. The coating obtained under normal drying conditions instead of the drying conditions according to claim 1 It is in the same state as the surface of the film.

  The invention described in claim 13 is the invention according to claim 12, wherein the coated material is a lithographic printing plate. Since the lithographic printing plate has a gently wavy surface and is not a completely flat surface, pores can be created only by the method of the present invention.

  According to the present invention, the solvent vapor-containing hot air is blown onto the coating film under a predetermined condition so as to be dried, so that irregularities can be formed on the surface of the coating film.

  Hereinafter, preferred embodiments of a surface modification method and apparatus, a multilayer coating method and apparatus, and a coated material according to the present invention will be described with reference to the accompanying drawings. The following embodiment is an example in which the present invention is applied to an apparatus for producing a lithographic printing plate, but the present invention is not limited to this technical field, and is used for surface modification and multilayer coating in various technical fields. Applicable.

(First embodiment)
In the first embodiment, the present invention is applied as an apparatus for modifying the surface of a lithographic printing plate (that is, forming irregularities). FIG. 1 is a diagram illustrating a basic configuration of a planographic printing plate manufacturing apparatus 10 according to the present embodiment, and an arrow A in FIG. 1 indicates a conveyance direction of the support 16.

  As shown in FIG. 1, the planographic printing plate precursor manufacturing apparatus 10 mainly includes a delivery device 12, a surface treatment unit 14, a coating unit 18, a drying unit 20, and a winding device 26. A support 16 wound in a roll shape is attached to the delivery device 12, and this support 16 is delivered from the delivery device 12. The fed support 16 is sent to the surface treatment unit 14, the coating unit 18, and the drying unit 20 in order while being guided by the guide roller 27, subjected to various treatments, and then taken up by the take-up device 26. . The configuration of FIG. 1 is an example of a planographic printing plate manufacturing apparatus, and is not limited to this. For example, an application unit for applying the undercoat coating solution may be provided in the front stage of the application unit 18.

  Next, each process part will be described.

  The surface treatment unit 14 is an apparatus that performs various pretreatments necessary for the support 16 before coating. As pretreatment, the adhesion between the support 16 and the image forming layer is improved, and degreasing treatment or surface roughening treatment (graining treatment or the like) for imparting water retention to the non-image area is performed. Anodic oxidation treatment that forms an oxide film on the surface to improve wear resistance, chemical resistance, water retention, silicate treatment that improves coating strength, hydrophilicity, and adhesion to the image forming layer is there. Instead of the surface treatment unit 14, the surface modification device of the present invention (that is, having the same configuration as the coating unit 18 and the drying unit 20) is provided to form a coating film having unevenness (for example, an undercoat layer). May be.

  The coating unit 18 is a device that coats the surface of the support 16 with the image forming layer coating solution. As the coating method, for example, a slide bead coating method, a curtain coating method, a bar coating method, a spin coating method, a spray coating method, a dip coating method, an air knife coating method, a blade coating method, a roll coating method, etc. are used. A bead coating method, a curtain coating method, a bar coating method, or the like is preferably used. In FIG. 1, it is illustrated as bar coating.

  The drying unit 20 is a device that dries the coating film (image forming layer coating solution) formed on the support 16. The coating film contains a hardly volatile high boiling point solvent as the first solvent, and it is important for the quality of the lithographic printing plate precursor to effectively evaporate and dry the first solvent in the drying unit 20. .

  The drying unit 20 includes a hot air drying unit 28, a steam drying unit 29, and a cooling unit 30. The hot air drying unit 28, the steam drying unit 29, and the cooling unit 30 each have a box shape, and the support 16 is configured to pass through the inside thereof. First, the hot air is blown by the hot air drying unit 28 to dry the support 16 to the drying point. And in the steam drying part 29, after the steam containing hot air containing a 2nd solvent is sprayed on the support body 16, the cool air is sprayed by the cooling part 30, and it cools. As a result, a dried image forming layer coating film is formed on the support 16.

  By the way, the hot air drying part 28 of the drying part 20 is provided with the box 40 formed along the conveyance direction of the support body 16, as shown in FIG. The box 40 includes slit-like openings 40A and 40B at both ends, and the support 16 enters and exits the box 40 through the openings 40A and 40B.

  In the box 40, a chamber 42 is provided above the support 16, and hot dry air (hot air) is supplied to the chamber 42. A large number of nozzles 44 are provided on the lower surface of the chamber 42, and hot air is blown from the nozzles 44 to the upper surface (that is, the image forming layer) of the support 16.

  An exhaust part 46 is provided in the lower part of the box 40, and exhausting from the exhaust part 46 forms a downflow of hot air in the box 40.

  In this hot air drying section 28, the drying point (the state where the coating liquid does not adhere to the cloth when touched with the cloth, the surface glossiness does not change, or the solid content concentration is 60% or more, preferably 70% to 80%. ) Drying is carried out. The dried support 16 is guided by the guide roller 27 and turned upside down, and then sent to the steam drying unit 29.

  FIG. 3 shows a steam supply / exhaust mechanism for supplying and exhausting solvent vapor to the vapor drying section 29. 4 shows the internal configuration of the steam drying unit 29, and FIG. 5 is a cross-sectional view taken along line 5-5 of FIG.

  The vapor drying unit 29 shown in these drawings is an apparatus for evaporating and drying the first solvent in the coating film applied to the support 16. As a 1st solvent to dry, a solvent with a mainly high boiling point is preferable, and a 150 degreeC or more is more preferable. Examples of the first solvent include γ-butyl lactone (204 ° C), acetamide (222 ° C), 1,3-dimethyl-2-imidazolidinone (225.5 ° C), N, N-dimethylformamide (153 ° C). , Tetramethyluric acid (175 ° C-177 ° C), nitrobenzene (211.3 ° C), formamide (210.5 ° C), N-methylpyrrolidone (202 ° C), N, N-dimethylacetamide (166 ° C), dimethyl sulfoxide (189 ° C) , Etc. The numbers in parentheses are boiling points.

  As shown in FIG. 4, the steam drying unit 29 includes a hollow box 50, and slit-shaped openings 50 </ b> A and 50 </ b> B are formed on opposite sides of the box 50. The support 16 enters the box 50 through the opening 50A and is conveyed to the outside of the box 50 through the opening 50B. As a material of the box 50, for example, SUS (304, 306, 316, etc.) or iron (SECC, etc.) is preferable, and a heat insulating material such as glass wool, rock wool, ALK24 may be provided inside thereof.

  Inside the box 50, a steam-containing hot air supply unit 52 is provided below the support 16. The supply unit 52 is formed in a hollow box shape, and the solvent vapor-containing hot air of the second solvent is supplied into the inside thereof by the vapor supply / exhaust mechanism shown in FIG.

  The steam supply / exhaust mechanism includes a tank 62, a blower 64, and heat exchangers 66, 68 and 70, and the second solvent is stored in the tank 62. As the second solvent, one having a molecular volume equal to or lower than the molecular volume of the first solvent described above is used. This second solvent usually has a lower boiling point than that of the first solvent, and preferably a liquid at room temperature (about 20 ° C.). As an example of the second solvent, water, methanol, acetone, methyl ethyl ketone, or the like can be used. In addition, an organic solvent may be used as the second solvent. In that case, it is desirable that the use concentration be a concentration that does not fall within the explosion range, and that an explosion-proof measure is taken.

  The second solvent stored in the tank 62 is heated by the heat exchanger 66 to become steam, the temperature of the second solvent is adjusted by the heat exchanger 68, the air sent from the blower 64 and heated by the heat exchanger 70. And supplied to the supply unit 52.

  As shown in FIG. 4, a rectifying plate 56 is provided inside the supply unit 52, and the steam-containing hot air of the second solvent is uniformly supplied by the rectifying plate 56. A nozzle 54 is provided above the supply unit 52, and hot air containing solvent vapor of the second solvent is blown from the nozzle 54 toward the lower surface of the support 16 (that is, the image forming layer). The nozzle 54 is configured to uniformly blow the solvent vapor-containing hot air of the second solvent in the width direction of the support 16. For example, the nozzle 54 has a slit in the width direction, and contains the solvent vapor of the second solvent from the slit. Hot air is blown out. A plurality of nozzles 54 are provided in the transport direction of the support 16, and the solvent vapor-containing hot air of the second solvent is blown in a predetermined range in the transport direction of the support 16. Further, as shown in FIG. 5, the width W of the supply unit 52 is formed to be larger than the width of the support 16, and the solvent vapor-containing hot air of the second solvent is blown over the entire width of the support 16. . The width W of the supply unit 52 may be set larger than the length L of the zone in which the solvent vapor atmosphere of the second solvent is formed (specifically, an interval between wind shielding plates 60A and 60B described later) L. Preferably, the ratio W / L is preferably 1 or more, and more preferably 2 or more. This is because the larger the W / L, the smaller the device can be made by reducing L, but the residual distribution of the first solvent is likely to occur in the width direction, and in particular when the W / L is 1 or more, the residual distribution. However, this can be prevented in this embodiment.

  The solvent vapor-containing hot air of the second solvent is blown out from the nozzle 54 of the supply unit 52 configured as described above, whereby a solvent vapor atmosphere of the second solvent is formed in the box 50. Thereby, the 1st solvent in the film | membrane of the support body 16 is dried.

  As shown in FIG. 4, exhaust units 58 </ b> A and 58 </ b> B are provided on the upstream side and the downstream side of the supply unit 52 with respect to the conveyance direction of the support 16. The exhaust parts 58 </ b> A and 58 </ b> B are provided on the lower side of the support 16 like the supply part 52, and suck air downward from the vicinity of the lower surface of the support 16. As shown in FIG. 5, the exhaust parts 58 </ b> A and 58 </ b> B are formed with a width wider than that of the support 16, and preferably with the same width W as the supply part 52. Further, the exhaust units 58A and 58B are connected to the distillation column 72 as shown in FIG. 3, and the exhaust air from the exhaust units 58A and 58B is sent to the distillation column 72. In the exhaust air sent to the distillation column 72, the second solvent and the solvent are separated, and the separated second solvent is returned to the tank 62, while the solvent is recovered. The air volume exhausted from the exhaust units 58A and 58B is set to be larger than the air volume of the solvent vapor-containing hot air of the second solvent blown out from the supply unit 52. Thereby, the solvent vapor-containing hot air of the second solvent blown out from the supply unit 52 can be prevented from flowing out of the box 50.

  As shown in FIG. 4, a wind shield plate 60 </ b> A is provided between the exhaust unit 58 </ b> A and the supply unit 52, and a wind shield plate 60 </ b> B is provided between the exhaust unit 58 </ b> B and the supply unit 52. The wind shielding plates 60 </ b> A and 60 </ b> B are provided vertically below the support body 16, and are arranged with a predetermined gap amount S on the lower surface of the support body 16. The supply unit 52 and the exhaust units 58A and 58B communicate with each other only through this gap, and the solvent vapor-containing hot air of the second solvent blown out from the supply unit 52 is exhausted from the exhaust units 58A and 58B through the gap. 4 shows an example in which the wind shielding plates 60A and 60B are integrally provided in the box 50. However, the present invention is not limited to this, and the wind shielding plates 60A and 60B are attached to and detached from the box 50 as separate members. You may attach freely. In that case, the wind shielding plates 60A and 60B may be attached to the box 50 so as to be slidable in the vertical direction, and the height position (that is, the gap amount S) may be adjusted.

  Thus, by providing exhaust parts 58A and 58B on both sides of the supply part 52 with respect to the conveying direction of the support 16, and further providing wind shielding plates 60A and 60B between the supply part 52 and the exhaust parts 58A and 58B. Since the solvent vapor-containing hot air of the second solvent blown out from the supply unit 52 flows to the exhaust units 58A and 58B through the gap between the wind shielding plates 60A and 60B and the support body 16, the lower surface of the support body 16 The solvent vapor-containing hot air of the second solvent comes into contact almost evenly. As a result, the first solvent in the film of the support 16 can be uniformly dried in the width direction, and even in the range of “W / L ≧ 1” where uniform drying has been difficult conventionally, The occurrence of residual distribution of one solvent can be prevented.

By the way, in the steam drying part 29, a drying process is performed on the following drying conditions. That is, in the steam drying section 29, T: film temperature [° C.] at the drying point, C: water vapor amount [g / m ³ ], P _T : saturated water vapor amount [Pa] at the film surface temperature T, R: gas constant, M: When the molecular weight of the second solvent is 18 (because it is water in the present embodiment),
1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8 (Formula 1)
The drying process is performed under the following drying conditions. In this drying condition, “C × R (273.15 + T) / (M × P _T )” means a ratio of vapor pressure to saturated vapor pressure (hereinafter referred to as relative vapor pressure ratio). In the present embodiment, since the second solvent is water, (Expression 1) means that the relative humidity is 100% or more and 180% or less.

  When the drying process is performed under such a drying condition, the solvent vapor-containing hot air of the second solvent is blown onto the surface of the coating film, whereby the second solvent is condensed on the surface of the coating film in the form of fine droplets. Due to the condensation heat generated by this dew condensation, the coating film where the micro droplets are generated is partially heated and softened, and further, the second solvent droplet pushes away the softened coating film. When passing through the solvent vapor-containing hot air zone, minute droplets of the second solvent are instantly evaporated by the heat of the coating film. Through such a process, innumerable hemispherical pores 82 are formed on the surface of the dried coating film 80 as shown in FIG. The pores 82 are formed in a substantially hemispherical shape having a pore diameter of 0.2 μm or more and 4.0 μm or less, and are randomly arranged. Although omitted in FIG. 6, the peripheral portion of the pore 82 is gradually recessed to form a gentle curved surface. (The same applies to FIGS. 8 and 9.)

  On the other hand, when the film is dried under a drying condition having a relative vapor pressure ratio of less than 1, no condensation occurs, so that no pores are formed in the coating film. On the contrary, when the value of the relative vapor pressure ratio exceeds 1.8, the second solvent is condensed on the surface of the coating film to form a water film, so that no pores are formed in the coating film.

  As described above, in the present embodiment, since the drying process is performed under the drying condition of the formula (1), the pores 82, that is, the irregularities can be formed on the surface of the coating film. Therefore, irregularities are formed on the surface of the lithographic printing plate after production, and the coefficient of friction of the surface is increased, so that it is possible to prevent bundle deviation when the lithographic printing plates are accumulated.

  Moreover, since this Embodiment only sets the conditions of the steam drying part 29 to Formula (1), it is not necessary to perform a new surface treatment separately. That is, according to the present embodiment, the surface treatment of the coating film can be performed simultaneously with the drying treatment.

  Furthermore, even if this embodiment forms irregularities on the surface of the coating film, the properties of the coating film do not change. That is, there is no possibility that the physical properties of the coating film change as in the case of using light, electron beam, or plasma as the surface treatment method. Therefore, according to this Embodiment, an unevenness | corrugation can be formed, without changing the physical property of a coating film.

In the above-described embodiment, the surface property (that is, the uneven shape) can be adjusted by changing the drying conditions. For example, as the relative vapor pressure ratio is reduced to approach 1.0, the diameter of the hemispherical pores 82 is reduced, and the number of pores 82 is reduced. Conversely, as the relative vapor pressure ratio is increased to approach 1.8, the diameter of the hemispherical pores 82 increases and the number of pores 82 also increases. Therefore, according to the present embodiment, since the uneven shape of the coating film surface can be changed by changing the drying conditions, the surface roughness and wettability can be easily adjusted.
(Second Embodiment)
In the second embodiment, the present invention is applied as an apparatus that modifies the surface of the lower layer (that is, forms irregularities on the surface of the lower layer) when applying multiple layers. FIG. 7 is a diagram showing a basic configuration of a planographic printing plate manufacturing apparatus according to the second embodiment, and an arrow A in FIG. 7 indicates the conveyance direction of the support 16. The second embodiment shown in FIG. 7 is different from the first embodiment shown in FIG. 1 in that an application unit 22 and a drying unit 24 are provided. That is, the application unit 22 and the drying unit 24 are provided between the drying unit 20 and the winding device 26.

  The application unit 22 is a device that forms a water-soluble overcoat layer on the image forming layer in order to block oxygen from the image forming layer and prevent contamination of the surface of the image forming layer with a lipophilic substance. The water-soluble overcoat layer can be easily removed at the time of printing, and contains a resin selected from water-soluble organic polymer compounds. As a method for applying the water-soluble overcoat layer, the same method as that for the application part 18 described above can be used.

  The drying unit 24 is a device that dries the overcoat layer applied by the application unit 22, and the drying method may be any method such as a drying method using hot air. The support 16 to which the overcoat layer is applied is dried by the drying unit 24 and is finally wound by the winding device 26.

  According to the second embodiment configured as described above, the image forming layer coating solution is applied as a lower layer by the applying unit 18, and the lower layer is dried by the drying unit 20. At that time, similarly to the first embodiment described above, the drying process is performed under the drying condition of the formula (1). Therefore, as shown in FIG. 8, substantially hemispherical pores 82 are formed in the dried coating film (lower layer) 80. This state is a state in which the contact angle of the film surface with respect to the solvent having good wettability (that is, the solvent having a contact angle of less than 90 ° with the film surface) is reduced by 1 to 20 °.

  In the support 16 on which the lower layer (the coating film 80 of the image forming layer) is formed, the coating liquid of the overcoat layer is applied as an upper layer on the lower layer in the coating unit 22. At that time, since pores 82 are formed on the surface of the lower layer (coating film 80) and wettability is improved, it is possible to prevent repelling of the coating liquid for the overcoat layer. Thereby, the coating accuracy of the upper layer can be improved. The applied upper layer coating 84 is dried by the drying unit 24.

  As described above, in the second embodiment, since the lower layer is dried under the drying condition of the formula (1), the wettability of the lower layer can be improved and the repellency of the upper layer coating liquid can be prevented. Can do.

(Third embodiment)
The third embodiment is configured in the same manner as the second embodiment shown in FIG. That is, the manufacturing apparatus of the third embodiment mainly includes a delivery device 12, a surface treatment unit 14, a coating unit 18, a drying unit 20, a coating unit 22, a drying unit 24, and a winding device 26.

  However, in the drying unit 24 of the third embodiment, the drying process is performed under the drying conditions in the formula (1). In addition, in the drying part 20 of 3rd Embodiment, a drying process is performed on arbitrary drying conditions. That is, the drying process may be performed under a condition where the relative vapor pressure ratio is 1 or less and no condensation occurs, or the drying process may be performed under a pore forming condition where the relative vapor pressure ratio is 1 to 1.8.

  In the third embodiment described above, the drying unit 24 performs the drying process under the drying condition of the formula (1). Therefore, as shown in FIG. 9, the coating film (overcoat layer) 84 after the drying is described above. Similar to the coating film 80 of the first embodiment (see FIG. 6), substantially hemispherical pores 82 are formed. Therefore, irregularities are formed on the surface of the lithographic printing plate after production, and the coefficient of friction of the surface is increased, so that it is possible to prevent bundle deviation when the lithographic printing plates are accumulated.

  Next, various materials used in this embodiment will be described.

[Support]
In the present invention, the material of the support is not particularly limited, and may be metal, resin, paper, cloth or the like. Moreover, the shape of a support body is not limited to strip | belt shape, Other than strip | belt shape may be sufficient.

  The aluminum plate used for the lithographic printing plate precursor according to the present embodiment is a metal mainly composed of dimensionally stable aluminum, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic film or paper on which aluminum or an aluminum alloy is laminated or vapor-deposited can also be used. Furthermore, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film can also be used.

  The composition of the aluminum plate used in the present embodiment is not particularly limited, but it is preferable to use a pure aluminum plate. Since completely pure aluminum is difficult to manufacture in terms of scouring techniques, it may be used that contains slightly different elements. For example, known materials described in Aluminum Handbook 4th Edition (Light Metal Association (1990)), specifically, for example, JIS A1050, JIS A1100, JIS A3003, JIS A3004, JIS A3005, international registered alloy 3103A, etc. These aluminum alloy plates can be used as appropriate. In addition, the aluminum content is 99.4 to 95% by mass, and includes an aluminum alloy, scrap aluminum material, or three or more selected from the group consisting of Fe, Si, Cu, Mg, Mn, Zn, Cr and Ti An aluminum plate using a secondary metal can also be used.

  Further, the aluminum content of the aluminum alloy plate is not particularly limited, but the aluminum content may be 95 to 99.4% by mass, and this aluminum plate is made of Fe, Si, Cu, Mg, Mn, Zn It is preferable to contain three or more different elements selected from the group consisting of Cr, Ti in the following ranges. This is because aluminum crystal grains become finer. Fe: 0.20 to 1.0 mass%, Si: 0.10 to 1.0 mass%, Cu: 0.03 to 1.0 mass%, Mg: 0.1 to 1.5 mass%, Mn: 0.1-1.5 mass%, Zn: 0.03-0.5 mass%, Cr: 0.005-0.1 mass%, Ti: 0.01-0.5 mass%. The aluminum plate may contain elements such as Bi and Ni and inevitable impurities.

  The production method of the aluminum plate may be either a continuous casting method or a DC casting method, and an aluminum plate that omits DC casting method intermediate annealing or soaking treatment may also be used. In the final rolling, it is possible to use an aluminum plate provided with irregularities by lamination rolling or transfer. The aluminum plate used in the present embodiment may be an aluminum support that is a continuous strip-shaped sheet material or plate material, and is a sheet that has been cut to a size corresponding to a planographic printing plate precursor that is shipped as a product. A leaf-like sheet may be used.

  The thickness of the aluminum plate used in the present embodiment is usually about 0.05 mm to 1 mm, and preferably 0.1 mm to 0.5 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's desire.

  In the method for producing a lithographic printing plate support in the present embodiment, the aluminum plate is subjected to at least a surface treatment including a roughening treatment, an anodizing treatment, and a specific sealing treatment to support the lithographic printing plate. A body is obtained, but this surface treatment may further include various treatments. In the various steps of this embodiment, since the alloy component of the aluminum plate used in the treatment liquid used in the step is eluted, the treatment solution may contain the alloy component of the aluminum plate. It is preferable to add the alloy components before the treatment and use the treatment liquid in a steady state.

  As the surface treatment, an alkali etching treatment or a desmut treatment is preferably performed before the electrolytic surface roughening treatment, and an alkali etching treatment and a desmut treatment are also preferably performed in this order. Moreover, it is preferable to perform an alkali etching process or a desmut process after an electrolytic roughening process, and it is also preferable to perform an alkali etching process and a desmut process in this order. Further, the alkali etching treatment after the electrolytic surface roughening treatment can be omitted. Moreover, it is also preferable to perform a mechanical surface roughening process before these processes. Moreover, you may perform an electrolytic surface roughening process twice or more. Thereafter, it is also preferable to perform anodizing treatment, sealing treatment, hydrophilization treatment, and the like.

[Second solvent]
As the second solvent used in the present embodiment, a solvent having a molecular volume smaller than that of the first solvent is preferable, and such a solvent is generally a low boiling point solvent having a boiling point of 30 ° C. or higher and 130 ° C. The following are preferred. Examples of such a low boiling point solvent include the following, but the present invention is not limited thereto. The boiling point is described in parentheses.

  Methanol (64.5 ° C-64.65 ° C), ethanol (78.32 ° C), n-propanol (97.15 ° C), isopropanol (82.3 ° C), n-butanol (117.7 ° C), iso Alcohols such as butanol (107.9 ° C), ethers such as ethyl ether (34.6 ° C), isopropyl ether (68.27 ° C), acetone (56.2 ° C), methyl ethyl ketone (79.59 ° C), Ketones such as methyl-n-propyl ketone (103.3 ° C.), methyl isobutyl ketone (115.9 ° C.), diethyl ketone (102.2 ° C.), methyl acetate (57.8 ° C.), ethyl acetate (77. 1 ° C), esters such as acetic acid-n-propyl (101.6 ° C), acetic acid-n-butyl (1265 ° C), n-hexane (68742 ° C), cyclohexane ( Hydrocarbons such as 0.738 ° C.), water and the like.

[First solvent]
The first solvent used in the present embodiment is preferably a high boiling point solvent having a boiling point of 150 ° C. or higher. Examples of such a high boiling point solvent include the following, but the present invention is not limited thereto. The boiling point is described in parentheses.

  γ-butyllactone (204 ° C.), acetamide (222 ° C.), 1,3-dimethyl-2-imidazolidinone (225.5 ° C.), N, N-dimethylformamide (153 ° C.), tetramethyluric acid (175 ° C.) 177 ° C.), nitrobenzene (211.3 ° C.), formamide (210.5 ° C.), N-methylpyrrolidone (202 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like.

[Image forming layer]
In the present invention, a lithographic printing plate precursor can be obtained by providing an image forming layer on the treatment layer formed as described above.

  In the present invention, the image forming layer provided here may be any known one, but is preferably one that can be recorded in a heat mode or a photon mode, and from the viewpoint of the effect, a heat mode exposure such as an infrared laser. It is preferable that the image forming layer be capable of forming an image.

  Further, the image forming layer may have a single layer structure or a laminated structure composed of a plurality of layers.

  Hereinafter, various lithographic printing plate precursors having different types of image forming layers will be described.

<Infrared laser recording type lithographic printing plate precursor>
A lithographic printing plate precursor capable of forming an image with an infrared laser suitable for the present invention will be described. These contain a negative or positive image forming layer using a material whose solubility in an alkaline aqueous solution is changed by infrared laser exposure, and a hydrophobizing precursor capable of forming an ink receiving region. A known image recording method such as an image forming layer in which a digitized region is formed is arbitrarily selected.

  First, a positive or negative image forming layer will be described. Such an image forming layer is developed with an alkaline aqueous solution after imagewise exposure with an infrared laser, the alkali developability is reduced by irradiation with actinic rays, and the negative (exposed) portion becomes an image portion region. On the contrary, the developability is improved, and the irradiation (exposure) portion is divided into two types, that is, a non-image portion region.

  Examples of the positive type image forming layer include an interaction release system (thermal positive) image forming layer, a known acid catalyst decomposition system, and an o-quinonediazide compound-containing system. These are soluble in water or alkaline water by the action of the polymer compound that formed the layer being released by the acid or heat energy generated by light irradiation or heating, and are removed by development and non-development. An image part is formed.

  Examples of the negative type image forming layer include known acid-catalyzed cross-linking (including cationic polymerization) image forming layers and polymerization-curing image forming layers. In these compounds, an acid generated by light irradiation or heating serves as a catalyst, and a compound that forms an image forming layer undergoes a crosslinking reaction to be cured to form an image portion, or is polymerizable by radicals generated by light irradiation or heating. The polymerization reaction of the compound proceeds and cures to form an image portion.

  The specific intermediate layer in the invention exhibits an excellent effect when any of the image forming layers described above is formed, but is preferably used for a positive type image forming layer.

Hereinafter, each image forming layer will be described in detail.
1. Positive type image forming layer As a preferred embodiment of the present invention, an alkali-soluble resin and a sulfonium compound or an ammonium compound are contained, and 50% by mass or more of the alkali-soluble resin is a novolak resin, and recording is performed by an infrared laser. A lithographic printing original plate having a positive image forming layer provided with a possible image forming layer may be mentioned. In addition, it is a more preferable aspect that the positive type image forming layer contains an infrared absorber (A) described later in order to increase sensitivity. The positive image forming layer may be a single layer or may have a laminated structure composed of a plurality of image forming layers.

(Novolac type phenolic resin)
First, the novolac type phenol resin will be described. The novolak resin refers to a resin obtained by polycondensation of at least one phenol with at least one of aldehydes or ketones under an acidic catalyst.

  Here, examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, and p-ethylphenol. , Propylphenol, n-butylphenol, tert-butylphenol, 1-naphthol, 2-naphthol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, phloroglucinol, 4,4′-biphenyldiol, 2,2-bis (4′-hydroxyphenyl) propane and the like. Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, furfural and the like, and examples of ketones include Acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  Preferably, phenols selected from phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, and aldehydes selected from formaldehyde, acetaldehyde, propionaldehyde Or a polycondensate with ketones is preferable, and the mixing ratio of m-cresol: p-cresol: 2,5-xylenol: 3,5-xylenol: resorcinol in a molar ratio of 40 to 100: 0 to 50: 0. -20: 0 to 20: 0 to 20 mixed phenols, or (mixed) phenols whose mixing ratio of phenol: m-cresol: p-cresol is 0-100: 0 to 70: 0-60 in molar ratio And a polycondensate of formaldehyde are preferred.

  As these novolak resins, a polystyrene-reduced weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography is preferably 500 to 20,000, more preferably 1,000 to 15, 000, particularly preferably 3,000 to 12,000. It is preferable for the weight average molecular weight to fall within this range because it is excellent in sufficient film-forming properties and alkali developability in the exposed area.

  When using the said novolak resin as binder resin of an image forming layer, only 1 type may be used and 2 or more types may be used together. Further, all of the binder resins may be the above-mentioned novolak resins, and other resins may be used in combination. Even when other resins are used in combination, the novolak resin is preferably the main binder, and the proportion of the novolak resin in the binder resin (alkali-soluble resin) constituting the image forming layer is 50% by mass or more. Preferably, the range is 65 to 99.9% by mass.

  As the binder resin that can be used in combination, a commonly used water-insoluble and alkali-soluble alkali-soluble resin having an acidic group in at least one of the main chain and the side chain in the polymer can be used. Phenol resins other than novolak resins, for example, resole resins, polyvinyl phenol resins, acrylic resins having phenolic hydroxyl groups, and the like are also preferably used. Specific examples of the resin that can be used in combination include polymers described in JP-A Nos. 11-44956 and 2003-167343.

(Photothermal conversion agent)
The image forming layer in the invention preferably contains a photothermal conversion agent. The photothermal conversion agent used here can be used without any limitation on the absorption wavelength range as long as it absorbs light energy irradiation and generates heat, but is compatible with readily available high-power lasers. From the above viewpoint, an infrared-absorbing dye or pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm is preferable.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, oxonol dyes And dyes such as diimonium dyes, aminium dyes, and croconium dyes.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A 59-73996, JP-A 60-52940, JP-A 60-63744, etc., naphthoquinone dyes, JP-A 58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. .

  Another example of a preferable dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formulas (I) and (II).

  Particularly preferred among these dyes are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Further, the compound described on pages 26-38 of JP-A-2005-99685 is preferred because of its excellent photothermal conversion efficiency. In particular, the cyanine dye represented by formula (a) in JP-A-2005-99685 is preferred. When used in the photosensitive composition of the invention, it is most preferable because it gives high interaction with the alkali-soluble resin and is excellent in stability and economy.

(Degradable dissolution inhibitor)
A decomposable dissolution inhibitor can be further added to the positive image forming layer in the invention. In particular, use in combination with substances (degradable dissolution inhibitors) that are thermally decomposable, such as onium salts, o-quinonediazide compounds, sulfonic acid alkyl esters, and that substantially reduce the solubility of alkali-soluble resins when not decomposed. However, this is preferable from the viewpoint of improving the dissolution inhibition of the image area in the developer. As the decomposable dissolution inhibitor, onium salts such as sulfonium salts, ammonium salts, diazonium salts, iodonium salts, and o-quinonediazide compounds are preferable, and sulfonium salts, ammonium salts, and diazonium salts are more preferable.

  Suitable onium salts for use in the present invention include, for example, U.S. Pat. Nos. 4,069,055, 4,069,056, JP-A-3-140140, JP-A-2006-293162, Ammonium salts described in the specification of JP-A-2004-117546, V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Watt et al, J.A. Polymer Sci. , 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, J.A. Polymer Sci. , Polymer Chem. Ed. 17, 2877 (1979), European Patents 370,693, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 3,902,114 No. 5,041,358, No. 4,491,628, No. 4,760,013, No. 4,734,444, No. 2,833,827, German Patent No. 2,904 Examples thereof include sulfonium salts described in JP-A Nos. 626, 3,604,580, 3,604,581, JP-A 2006-293162, and JP-A 2006-258879.

  S. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), JP-A-5-158230, JP-A-5-158230, general formula (I), JP-A-11-143064, general formula ( 1), and diazonium salts represented by the general formula (1) described in JP-A-11-143064.

  Other preferable onium salts include D.I. C. Necker et al, Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Pat. Nos. 5,041,358, 4,491,628, JP-A-2-150848 and JP-A-2-296514. Iodonium salts, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988).

  The counter ion of the onium salt includes tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfone Examples include acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and paratoluenesulfonic acid. Of these, particularly preferred are alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.

  These onium salts may be used alone or in a plurality of compounds. In addition, when the image forming layer has a laminated structure, it may be added to only a single layer or a plurality of layers, or a compound of a plurality of types may be added separately in layers. Good.

  Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide helps the solubility of the sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder due to thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described in pages 339 to 352 of “Light-sensitive systems” by John Coley (John Wiley & Sons. Inc.) can be used, and in particular, o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. The sulfonic acid esters or sulfonic acid amides are preferred. Further, benzoquinone (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403 Esters of benzoquinone- (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide- described in US Pat. Nos. 3,046,120 and 3,188,210 Esters of 5-sulfonic acid chloride and phenol-formaldehyde resin are also preferably used.

  Further, esters of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride with phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Similarly, the esters are also preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, Japanese Patent Publication Nos. 41-11222, 45-9610, 49-17482, U.S. Pat. Nos. 2,797,213, 3,454,400, and 3,544 No. 323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602, No. 1,251,345, No. No. 1,267,005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890 and the like. .

  The amount of the onium salt and / or the o-quinonediazide compound that is a degradable dissolution inhibitor is preferably 0.1 to 10% by mass with respect to the total solid content of the image forming layer according to the present invention. More preferably, it is 0.1-5 mass%, Most preferably, it is the range of 0.2-2 mass%. These compounds can be used alone, but may be used as a mixture of several kinds.

  The amount of additives other than the o-quinonediazide compound is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and particularly preferably 0.1 to 1.5% by mass. The additive and binder used in the present invention are preferably contained in the same layer.

  Further, a dissolution inhibitor having no decomposability may be used in combination, and preferred dissolution inhibitors include sulfonate esters, phosphate esters, and aromatic carboxylic acids described in detail in JP-A-10-268512. Esters, aromatic disulfones, carboxylic anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, etc., as well as lactone skeletons described in detail in JP-A-11-190903, N, N- Examples thereof include an acid color-forming dye having a diarylamide skeleton and a diarylmethylimino skeleton, which also serves as a colorant, and nonionic surfactants described in detail in JP-A No. 2000-105454.

(Other additives)
In the image forming layer according to the present invention, Japanese Patent Application Laid-Open No. 2000-187318 discloses further enhancement of image discrimination (hydrophobic / hydrophilic discrimination) and surface scratch resistance. As described, a polymer having a polymerization component of a (meth) acrylate monomer having 2 or 3 perfluoroalkyl groups having 3 to 20 carbon atoms in the molecule can be used in combination. The addition amount of such a compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the image forming layer according to the present invention.

  In the image forming layer according to the present invention, a compound that lowers the static friction coefficient of the surface can be added for the purpose of imparting resistance to scratches. Specific examples include esters of long-chain alkyl carboxylic acids as used in US Pat. No. 6,117,913. The addition amount of such a compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total solid content of the image forming layer.

  Further, the image forming layer according to the present invention may contain a compound having a low molecular weight acidic group, if necessary. Examples of acidic groups include sulfonic acid groups, carboxylic acid groups, and phosphoric acid groups. Of these, compounds having a sulfonic acid group are preferred. Specific examples include aromatic sulfonic acids such as p-toluenesulfonic acid and naphthalenesulfonic acid, and aliphatic sulfonic acids.

  In addition, for the purpose of further improving sensitivity, cyclic acid anhydrides, phenols, and organic acids can be used in combination. Examples of cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ4-tetrahydrophthalic anhydride described in US Pat. No. 4,115,128, Tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ′, 4 “-Trihydroxytriphenylmethane, 4,4 ′, 3”, 4 ”-tetrahydroxy-3,5,3 ′, 5′-tetramethyltriphenylmethane and the like. There are sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters, carboxylic acids, and the like, which are described in Japanese Laid-Open Patent Publication No. 60-88942 and Japanese Patent Application Laid-Open No. 2-96755. , P-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate Phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1, Examples include 2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like.

  When the above cyclic acid anhydride, phenols and organic acids are added to the image forming layer, the proportion in the image forming layer is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass. Especially preferably, it is 0.1-10 mass%.

  Further, when preparing a coating solution for an image forming layer according to the present invention, it is described in Japanese Patent Application Laid-Open Nos. 62-251740 and 3-208514 in order to broaden the stability of processing with respect to development conditions. Nonionic surfactants, amphoteric surfactants as described in JP-A-59-121044, JP-A-4-13149, siloxane compounds as described in EP950517, A fluorine-containing monomer copolymer as described in JP-A-11-288093 can be added.

  Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of the double-sided activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

  The siloxane compound is preferably a block copolymer of dimethylsiloxane and polyalkylene oxide. Specific examples include DBE-224, DBE-621, DBE-712, DBP-732, DBP-534, manufactured by Chisso Corporation. And polyalkylene oxide-modified silicones such as Tego Glide 100 manufactured by Tego, Germany.

  The proportion of the nonionic surfactant and amphoteric surfactant in the image forming layer is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

  In the image forming layer of the lithographic printing plate precursor according to the invention, a printing-out agent for obtaining a visible image immediately after heating by exposure, or a dye or pigment as an image colorant can be added.

  Typical examples of the printing-out agent include a combination of a compound that releases an acid by heating by exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, 36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440, and trihalomethyl compounds and salt-forming organic dyes Can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear printout images.

  As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Manufactured by Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI522015), and the like. The dyes described in JP-A-62-293247 are particularly preferred. These dyes can be added in a proportion of 0.01 to 10% by mass, preferably 0.1 to 3% by mass, based on the total solid content of the image forming layer. Furthermore, a plasticizer is added to the image forming layer coating solution according to the present invention, if necessary, in order to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.

  In addition to these, epoxy compounds, vinyl ethers, phenol compounds having a hydroxymethyl group, phenol compounds having an alkoxymethyl group, and JP-A No. 11-160860 described in JP-A-8-276558. A crosslinkable compound having an alkali dissolution inhibiting action described in the publication can be appropriately added depending on the purpose.

  The image forming layer in the image recording material of the present invention obtained as described above is excellent in film formability and film strength, and the exposed area exhibits high alkali solubility upon infrared exposure.

2. Negative type image forming layer 2-1. Polymerized and cured layer As one of the negative type image forming layers, a polymerized and cured layer is exemplified. This polymerization hardened layer contains (A) an infrared absorber, (B) a radical generator (radical polymerization initiator), and a radical polymerizable compound that is cured by causing a polymerization reaction with the generated radical (C), Preferably (D) a binder polymer is contained. The infrared rays absorbed by the infrared absorbent are converted into heat, and the heat generated at this time decomposes a radical polymerization initiator such as an onium salt to generate radicals. The radically polymerizable compound is selected from compounds having at least one ethylenically unsaturated double bond and having at least one terminal ethylenically unsaturated bond, preferably two or more, and polymerizes in a chain manner by the generated radicals. A reaction takes place and cures.

2-2. Acid cross-linked layer Another embodiment of the image forming layer is an acid cross-linked layer. The acid cross-linking layer contains (E) a compound that generates an acid by light or heat (hereinafter referred to as an acid generator) and (F) a compound that cross-links by the generated acid (hereinafter referred to as a cross-linking agent). And (G) an alkali-soluble polymer capable of reacting with a crosslinking agent in the presence of an acid to form a layer containing them. In this acid cross-linking layer, the acid generated by decomposition of the acid generator by light irradiation or heating promotes the action of the cross-linking agent, and a strong cross-linking structure between the cross-linking agents or between the cross-linking agent and the binder polymer. As a result, the alkali solubility is lowered and the developer becomes insoluble. At this time, in order to efficiently use the energy of the infrared laser, (A) an infrared absorber is blended in the image forming layer.

((A) Infrared absorber])
The image forming layer capable of forming an image with an infrared laser contains an infrared absorber. As an infrared absorber, any material that absorbs light energy radiation used for recording and generates heat can be used without any limitation in the absorption wavelength range. From the viewpoint, an infrared-absorbing dye or pigment having an absorption maximum at a wavelength of 800 nm to 1200 nm is preferable.

  As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, etc. Is mentioned.

  Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.

  Also, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 The pentamethine thiopyrylium salts described above and the pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used. . Another example of a preferable dye is a near-infrared absorbing dye described in US Pat. No. 4,756,993 as formulas (I) and (II).

  Other preferred examples of the infrared absorbing dye of the present invention include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 as exemplified below.

  Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and one particularly preferred example is a cyanine dye represented by the following general formula (A).

In the general formula (A), ^{X 1} represents a hydrogen atom, a halogen _atom, -NPh ^2, X 2 -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom, or a sulfur atom, and L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or 1 to 1 carbon atom including a hetero atom. 12 hydrocarbon groups are shown. In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. Xa ^- the Za described later ^- it has the same definition as, Ra is a hydrogen atom, Al
It represents a substituent selected from a kill group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom.

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the image forming layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring. Alternatively, it is particularly preferable that a 6-membered ring is formed.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za ⁻ represents a counter anion. However, Za ⁻ is not necessary when the cyanine dye represented by formula (A) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the image forming layer coating solution. Hexafluorophosphate ions and aryl sulfonate ions.

  Specific examples of the cyanine dye represented by formula (A) that can be suitably used in the present invention include those described in paragraph numbers [0017] to [0019] of JP-A No. 2001-133969. Can do.

  Further, other particularly preferable examples include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 described above.

  Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Yokoshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, preferably in the range of 0.05 μm to 1 μm, from the viewpoint of the stability of the dispersion in the image forming layer coating solution and the uniformity of the image forming layer. More preferably, the thickness is preferably in the range of 0.1 μm to 1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

  The content of the infrared absorber in the image forming layer is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.5 to 10% by mass relative to the total solid mass of the image forming layer. 10 mass% is most preferable. Within this range, high-sensitivity recording is possible, and high-quality image formation is possible without the occurrence of contamination in non-image areas.

((B) Compound generating radical)
The radical generator refers to a compound that initiates and accelerates polymerization of a compound having a polymerizable unsaturated group by generating radicals by energy of light, heat, or both. As a radical generator applicable to the present invention, a known thermal polymerization initiator or a compound having a bond with a small bond dissociation energy can be selected and used. For example, an onium salt, an s having a trihalomethyl group can be used. -Organic halogen compounds such as triazine compounds and oxazole compounds, peroxides, azo polymerization initiators, arylazide compounds, benzophenones, acetophenones, carbonyl compounds such as thioxanthones, metallocene compounds, hexaarylbiimidazole compounds, organic boron Examples thereof include salt compounds and dizulphone compounds.

  In the present invention, particularly preferable radical generators include onium salts, and among them, onium salts represented by the following general formulas (B-1) to (B-3) are preferably used.

In formula (B-1), Ar ¹¹ and Ar ¹² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. Z ^11- represents an inorganic anion or an organic anion.

In the formula (B-2), Ar ²¹ represents an aryl group having 20 or less carbon atoms which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. Z ^21- represents a counter ion having the same ^meaning as Z ^11- .

In formula (B-3), R ³¹ , R ³² and R ³³ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. Z ^31- represents a counter ion having the same ^meaning as Z ^11- .

In the general formulas (B-1) to (B-3), Z ¹¹⁻ , Z ²¹⁻ , and Z ³¹⁻ represent an inorganic anion or an organic anion. As the inorganic anion, a halogen ion (F ⁻ , Cl ^{-, Br -, I -)} , perchlorate ion (ClO ₄ ^-), perborate ion (BrO ₄ ^-), tetrafluoroborate ion _{^{(BF 4 -), SbF 6}} -, PF 6 - , and the like As organic anions, organic borate anions, sulfonate ions, phosphonate ions, carboxylate ions, R ⁴⁰ —SO ₃ H ⁻ , R ⁴⁰ —SO ₂ ^— , R ⁴⁰ —SO ₂ S ⁻ , R ⁴⁰ —SO _{2 are used.} N ^{- -Y-R 40} ion ^{(wherein, R 40} is an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, Y is a single bond, -CO -, - SO -, and represented) and the like a..

  In the present invention, specific examples of onium salts that can be suitably used include those described in paragraph numbers [0030] to [0033] of JP-A No. 2001-133696.

  The onium salt used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. By making the absorption wavelength in the ultraviolet region in this way, the lithographic printing plate precursor can be handled under white light.

  These onium salts may be used alone or in combination of two or more.

  These onium salts may be added in a proportion of 0.1 to 50% by mass, preferably 0.5 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total solid content of the image forming layer coating solution. it can. When the addition amount is in the above range, highly sensitive recording is achieved, and the occurrence of smudges in the non-image area during printing is suppressed.

  These onium salts are not necessarily added to the image forming layer, and may be added to another layer provided adjacent to the image forming layer.

((C) radical polymerizable compound)
The radically polymerizable compound used in the image forming layer in this embodiment is a radically polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably two. It is selected from the compounds having the above. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, unsaturated carboxylic acid esters having nucleophilic substituents such as hydroxyl groups, amino groups, mercapto groups, amides and monofunctional or polyfunctional isocyanates, addition reaction products of epoxies, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, halogen A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

  Specific examples of acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, which are radical polymerizable compounds that are esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, It describes in paragraph number [0037]-[0042] of Unexamined-Japanese-Patent No. 2001-133696, and these are applicable also to this invention.

  Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.

  Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula (VI) to a polyisocyanate compound having two or more isocyanate groups. Etc.

Formula (VI)
^{_{CH 2 = C (R 41)}} COOCH 2 CH (R 42) OH
^{(Wherein, R 41} and ^{R 42} represent H or CH _3.)
Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable.

  Furthermore, radical polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 may be used.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Examples thereof include polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. In addition, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, and JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 can also be exemplified. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  For these radically polymerizable compounds, the details of how to use them, such as what structure to use, whether they are used alone or in combination, and how much they are added, can be selected according to the performance design of the final recording material. Can be set. For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and compounds having different functional numbers and different polymerizable groups (for example, acrylate ester compounds, methacrylate esters). It is also effective to adjust both photosensitivity and strength by using a combination of a compound, a styrene compound, and the like. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in sensitivity and film strength, but may not be preferable in terms of development speed and precipitation in a developer. Further, the selection and use method of the radical polymerization compound is also an important factor for the compatibility and dispersibility with other components (for example, binder polymer, initiator, colorant, etc.) in the image forming layer. The compatibility may be improved by using a low-purity compound or using a combination of two or more compounds. In addition, a specific structure may be selected for the purpose of improving the adhesion of the support, overcoat layer and the like. As for the compounding ratio of the radically polymerizable compound in the image forming layer, a larger amount is advantageous in terms of sensitivity. However, when the amount is too large, undesirable phase separation may occur or the manufacturing process due to the adhesiveness of the image forming layer may occur. Problems (for example, transfer of image forming layer components, manufacturing defects due to adhesion) and precipitation from the developer may occur.

  From these viewpoints, the preferred blending ratio of the radical polymerizable compound is often 5 to 80% by mass, preferably 20 to 75% by mass, based on the total components of the composition. These may be used alone or in combination of two or more. In addition, the usage of the radical polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

((D) Binder polymer)
In such an image forming layer, it is preferable to further use a binder polymer from the viewpoint of improving the film properties of the image forming layer, and it is preferable to use a linear organic polymer as the binder. Any such “linear organic polymer” may be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent for forming an image forming layer, but also according to the use as water, weak alkaline water or an organic solvent developer.

  For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP 54-92723, JP 59-53836, JP 59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer. Examples thereof include a polymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  Among these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxyl group in the side chain is particularly preferable because of excellent balance of film strength, sensitivity, and developability.

  In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane-based binder polymers containing acid groups described in No. 271741, JP-A-11-352691 and the like are very excellent in strength, and are advantageous in terms of printing durability and suitability for low exposure.

  In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  The weight average molecular weight of the polymer used in the present invention is preferably 5000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1000 or more, more preferably 2000 to 2000. The range is 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

  These polymers may be random polymers, block polymers, graft polymers or the like, but are preferably random polymers.

  The binder polymer used in the present invention may be used alone or in combination. These polymers are added to the image forming layer in a proportion of 20 to 95% by mass, preferably 30 to 90% by mass, based on the total solid content of the image forming layer coating solution. When the addition amount is less than 20% by mass, the strength of the image portion is insufficient when an image is formed. If the amount added exceeds 95% by mass, no image is formed. Moreover, it is preferable that the compound which has an ethylenically unsaturated double bond which can be radically polymerized, and a linear organic polymer shall be 1 / 9-7 / 3 by mass ratio.

  Next, the components of the acid cross-linking layer will be described. The infrared absorber used here can be the same as that used in the polymerization curable image forming layer.

  The content is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.5 to 10% by mass with respect to the total solid mass of the image forming layer.

  In the range of the content, highly sensitive recording can be achieved, and the occurrence of stains in the obtained non-image portion for lithographic printing can be suppressed.

((E) acid generator)
In the present embodiment, an acid generator that generates an acid by being decomposed by heat refers to a compound that generates an acid when irradiated with light in a wavelength region of 200 to 500 nm or heated to 100 ° C. or higher.

  Examples of the acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or a known acid generator used for a microresist And the like, and known compounds and mixtures thereof that can generate an acid upon thermal decomposition.

  Of the acid generators described above, compounds represented by the following general formulas (E-1) to (E-5) are preferred.

In the general formulas (E-1) to (E-5), R ¹ , R ² , R ^4, and R ⁵ may be the same or different and may have a substituent and have 20 or less carbon atoms. Represents a hydrocarbon group. R ³ represents a halogen atom, an optionally substituted hydrocarbon group having 10 or less carbon atoms or an alkoxy group having 10 or less carbon atoms. Ar ¹ and Ar ² may be the same or different and each represents an aryl group having 20 or less carbon atoms which may have a substituent. R ⁶ represents a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent. n represents an integer of 0 to 4.

In the above formula, R ¹ , R ² , R ⁴ and R ⁵ are preferably hydrocarbon groups having 1 to 14 carbon atoms.

  The preferable aspect of the acid generator represented by the general formulas (E-1) to (E-5) is described in paragraphs [0197] to [0222] of JP-A No. 2001-142230. It is described in detail as a compound of (V). These compounds can be synthesized, for example, by the method described in JP-A-2-100054 and JP-A-2-100055.

  Examples of the acid generator (E) include onium salts having a halide, sulfonic acid, or the like as a counter ion. Among them, iodonium represented by the following general formulas (E-6) to (E-8): Preferred examples include salts having any structural formula of salts, sulfonium salts and diazonium salts.

In the general formulas (E-6) to (E-8), X ⁻ represents a halide ion, ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ or R ⁷ SO ₃ ⁻ , , R ⁷ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Ar ³ and Ar ⁴ each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. R ⁸ , R ⁹ and R ¹⁰ represent a hydrocarbon group having 18 or less carbon atoms which may have a substituent.

  Such onium salts are described as compounds of general formulas (I) to (III) in paragraph numbers [0010] to [0035] of JP-A-10-39509.

  The addition amount of the acid generator is preferably 0.01 to 50% by mass, more preferably 0.1 to 25% by mass, and most preferably 0.5 to 20% by mass with respect to the total solid mass of the image forming layer. .

  When the addition amount is less than 0.01% by mass, an image may not be obtained. When the addition amount exceeds 50% by mass, the non-image area is smeared during printing when used as a lithographic printing original plate. Sometimes.

  The above acid generators may be used alone or in combination of two or more.

((F) Crosslinking agent)
Next, the crosslinking agent will be described. The following are mentioned as a crosslinking agent.

(I) Aromatic compound substituted with hydroxymethyl group or alkoxymethyl group (ii) Compound having N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group (iii) Epoxy compound ) To (iii) will be described in detail.

  Examples of the aromatic compound substituted with the hydroxymethyl group or alkoxymethyl group (i) include an aromatic compound or a heterocyclic compound polysubstituted with a hydroxymethyl group, an acetoxymethyl group or an alkoxymethyl group. . However, resinous compounds obtained by condensation polymerization of phenols and aldehydes known as resol resins under basic conditions are also included.

  Of the aromatic compounds or heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, among them, a compound having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group is preferable.

  Moreover, in the aromatic compound or heterocyclic compound poly-substituted with an alkoxymethyl group, a compound having an alkoxymethyl group having 18 or less carbon atoms is preferable, and is represented by the following general formulas (F-1) to (F-4). More preferred is a compound.

In the general formulas (F-1) to (F-4), L ^{1 to} L ⁸ are each independently a hydroxymethyl group substituted with an alkoxy group having 18 or less carbon atoms such as methoxymethyl or ethoxymethyl, or Represents an alkoxymethyl group.

  These crosslinking agents are preferable in that they have high crosslinking efficiency and can improve printing durability.

  (Ii) As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “EP-A”) No. 0,133,216, West Germany Monomer and oligomer-melamine-formaldehyde condensates and urea-formaldehyde condensates described in Japanese Patent Nos. 3,634,671 and 3,711,264, EP-A 0,212,482 And alkoxy-substituted compounds described in the book.

  Among these, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups are preferable, and N-alkoxymethyl derivatives are most preferable.

  (Iii) Examples of the epoxy compound include monomers, dimers, oligomers, and polymeric epoxy compounds having one or more epoxy groups. For example, a reaction product of bisphenol A and epichlorohydrin, a low molecular weight phenol-formaldehyde resin, and Examples include reaction products with epichlorohydrin.

  In addition, there can be mentioned epoxy resins described and used in US Pat. No. 4,026,705 and British Patent 1,539,192.

  The amount of addition when the compounds (i) to (iii) are used as the crosslinking agent is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, based on the total solid content of the image forming layer. 20-70 mass% is the most preferable.

  When the addition amount is less than 5% by mass, the durability of the image forming layer of the resulting image recording material may be reduced, and when it exceeds 80% by mass, stability during storage may be reduced. .

  In the present invention, (iv) a phenol derivative represented by the following general formula (F-5) can also be suitably used as the crosslinking agent.

In the general formula (F-5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent, and R ¹ , R ² and R ³ are a hydrogen atom or a carbon atom having 12 or less carbon atoms. Represents a hydrogen group. m represents an integer of 2 to 4, and n represents an integer of 1 to 3.

  From the viewpoint of availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. As the substituent, a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, or the like is preferable.

Among the above, Ar ¹ is a benzene ring, naphthalene ring, halogen atom, hydrocarbon group having 6 or less carbon atoms, or 6 or less carbon atoms, which has no substituent, in that sensitivity can be increased. And a benzene ring or a naphthalene ring having, as a substituent, an alkoxy group of 6 or less, an alkylthio group having 6 or less carbon atoms, an alkylcarbamoyl group having 12 or less carbon atoms, or a nitro group.

As the hydrocarbon group represented by R ¹ or R ² , a methyl group is preferable because synthesis is easy. The hydrocarbon group represented by R ³ is preferably a hydrocarbon group having 7 or less carbon atoms such as a methyl group and a benzyl group because of its high sensitivity. Furthermore, m is preferably 2 or 3 and n is preferably 1 or 2 for ease of synthesis.

((G) Alkali water soluble polymer compound)
Examples of the alkaline water-soluble polymer compound that can be used in the crosslinked layer applicable to the present invention include novolak resins and polymers having a hydroxyaryl group in the side chain. Examples of the novolak resin include resins obtained by condensing phenols and aldehydes under acidic conditions.
Among them, for example, novolak resin obtained from phenol and formaldehyde, novolak resin obtained from m-cresol and formaldehyde, novolak resin obtained from p-cresol and formaldehyde, novolak resin obtained from o-cresol and formaldehyde, octylphenol and formaldehyde Novolak resin obtained, novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (m-, p-, o- or m- / p-, m- / o-, o- / p- A high molecular weight polymer having a high ortho bond rate obtained by reacting under no pressure using a catalyst and using a novolac resin obtained from formaldehyde and phenol and paraformaldehyde in a sealed state under high pressure without using a catalyst. Rack resin and the like are preferable.

  The novolak resin may be selected from those having a weight average molecular weight of 800 to 300,000 and a number average molecular weight of 400 to 60,000 depending on the purpose.

  A polymer having a hydroxyaryl group in the side chain is also preferred, and examples of the hydroxyaryl group in the polymer include an aryl group having one or more OH groups bonded thereto.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group, and among them, a phenyl group or a naphthyl group is preferable from the viewpoint of availability and physical properties.

  Examples of the polymer having a hydroxyaryl group in the side chain that can be used in the present embodiment include any one of the structural units represented by the following general formulas (G-1) to (G-4). The polymer containing can be mentioned. However, the present invention is not limited to these.

In General Formulas (G-1) to (G-4), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, or an aryloxy group having 10 or less carbon atoms. R ¹² and R ¹³ may be bonded and condensed to form a benzene ring or a cyclohexane ring. R ¹⁴ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁵ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ¹⁶ represents a single bond or a divalent hydrocarbon group having 10 or less carbon atoms. X ¹ represents a single bond, an ether bond, a thioether bond, an ester bond or an amide bond. p represents an integer of 1 to 4. q and r each independently represents an integer of 0 to 3.

  These alkali-soluble polymers are described in detail in paragraph numbers [0130] to [0163] of JP-A No. 2001-142230.

  The alkaline water-soluble polymer compound that can be used in this embodiment may be used alone or in combination of two or more.

  The addition amount of the alkaline water-soluble polymer compound is preferably 5 to 95% by mass, more preferably 10 to 95% by mass, and most preferably 20 to 90% by mass with respect to the total solid content of the image forming layer.

  When the addition amount of the alkali water-soluble resin is less than 5% by mass, the durability of the image forming layer may be deteriorated, and when it exceeds 95% by mass, image formation may not be performed.

  Further, as a known recording material applicable to the image forming layer according to the present invention, a negative type image recording material containing a phenol derivative described in JP-A-8-276558, or described in JP-A-7-306528 is disclosed. Negative recording material containing a diazonium compound, negative type using an acid-catalyzed crosslinking reaction using a polymer having a heterocyclic group having an unsaturated bond in the ring described in JP-A-10-203037 Examples thereof include image forming materials, and the image forming layer described in these materials can be applied to the acid crosslinking layer as the negative image forming layer in the present invention.

(Other ingredients)
In addition to these, various compounds other than these may be added to such a negative type image forming layer. For example, a dye having a large absorption in the visible light region can be used as an image colorant. In addition, pigments such as phthalocyanine pigments, azo pigments, carbon black, and titanium oxide can also be suitably used.

  Further, in the present invention, when the image forming layer is a polymerization hardened layer, in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond capable of radical polymerization during preparation or storage of a coating solution. It is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal 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-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen and unevenly distributed on the surface of the image forming layer in the drying process after coating. Good. The amount of the higher fatty acid derivative added is preferably about 0.1% by mass to about 10% by mass of the total composition.

  Further, in the image forming layer coating solution of the present invention, nonionic surface activity as described in JP-A Nos. 62-251740 and 3-208514 is used in order to broaden the processing stability against development conditions. An amphoteric surfactant as described in JP-A-59-121044 and JP-A-4-13149 can be added.

  Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like.

  Specific examples of amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N, N- Examples include betaine type (for example, trade name Amorgen K, manufactured by Dai-ichi Kogyo Co., Ltd.).

  The proportion of the nonionic surfactant and amphoteric surfactant in the image forming layer coating solution is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

  Furthermore, a plasticizer is added to the image forming layer coating solution in the present invention, if necessary, in order to impart flexibility of the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate and the like are used.

3. Hydrophobized precursor-containing image forming layer As a further image forming layer that can be applied to the lithographic printing plate support of the present invention, a compound capable of forming a hydrophobic region by heating or irradiation with radiation (hereinafter, appropriately hydrophobized precursor) Heat-sensitive image-forming layer containing the body). Such an image-forming layer is fused to each other by heating, such as (a) a fine particle polymer having a heat-reactive functional group, or (b) a microcapsule containing a compound having a heat-reactive functional group. For example, if it is a microcapsule, it contains a compound that forms an image area region, that is, a hydrophobic region (parent ink region) by causing a chemical reaction of the inclusion by heat, and these are preferably Since it is dispersed in a hydrophilic binder, after image formation (exposure), a lithographic printing plate precursor is mounted on a printing machine cylinder, and a dampening solution and / or ink is supplied to perform special development processing. It is characterized in that it can be developed on the machine without performing it.

  Such an image forming layer contains (a) a fine particle polymer having a thermoreactive functional group, or (b) a microcapsule encapsulating a compound having a thermoreactive functional group.

  Examples of the heat-reactive functional group common to the above (a) and (b) include, for example, an ethylenically unsaturated group (for example, acryloyl group, methacryloyl group, vinyl group, allyl group) that undergoes a polymerization reaction, and an addition reaction. Isocyanate group or block thereof, functional group having an active hydrogen atom that is a reaction partner (for example, amino group, hydroxyl group, carboxyl group), epoxy group that similarly performs an addition reaction, amino group that is a reaction partner, carboxyl group Or a hydroxyl group, the carboxyl group and hydroxyl group or amino group which perform a condensation reaction, the acid anhydride and amino group or hydroxyl group which perform a ring-opening addition reaction are mentioned. The thermoreactive functional group used in the present invention is not limited to these, and may be any functional group that performs any reaction as long as a chemical bond is formed.

((A) Fine particle polymer having a thermally reactive functional group)
(A) Thermally reactive functional groups suitable for the fine particle polymer include, for example, acryloyl group, methacryloyl group, vinyl group, allyl group, epoxy group, amino group, hydroxyl group, carboxyl group, isocyanate group, and acid anhydride group. And groups protecting them. The introduction of the thermally reactive functional group into the polymer fine particles may be performed at the time of polymerizing the polymer, or may be performed by utilizing a polymer reaction after the polymerization.

  When a thermoreactive functional group is introduced during the polymerization of the polymer, it is preferable to perform emulsion polymerization or suspension polymerization using a monomer having a thermoreactive functional group.

  Specific examples of the monomer having a heat-reactive functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate, and its blocked alcohol, 2-isocyanate ethyl acrylate. Block isocyanates with alcohol, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, difunctional acrylate, difunctional methacrylate Can be mentioned. The monomer having a heat-reactive functional group used in the present invention is not limited to these.

  Examples of the monomer having no thermally reactive functional group that can be copolymerized with these monomers include styrene, alkyl acrylate, alkyl methacrylate, acrylonitrile, and vinyl acetate. The monomer having no heat-reactive functional group used in the present invention is not limited to these.

  Examples of the polymer reaction used when the thermally reactive functional group is introduced after polymerization of the polymer include the polymer reaction described in International Publication No. 96/34316.

  Among the above-mentioned (a) fine-particle polymers having a heat-reactive functional group, those in which the fine-particle polymers are easily fused and coalesced by heat are preferable from the viewpoint of image formability, and from the viewpoint of on-press developability. Particularly preferred are those having a hydrophilic surface and being dispersed in water. In addition, the film contact angle (water droplets in the film) when it is prepared by applying only the fine particle polymer and drying at a temperature lower than the solidification temperature is the contact of the film when it is prepared by drying at a temperature higher than the solidification temperature. It is preferable to be lower than the corner (water droplet in the air).

  In order to make the hydrophilicity of the surface of the fine particle polymer in such a preferable state, a hydrophilic polymer or oligomer such as polyvinyl alcohol or polyethylene glycol, or a hydrophilic low molecular weight compound may be adsorbed on the surface of the fine particle polymer. The surface hydrophilization method is not limited to these, and various known surface hydrophilization methods can be applied.

  (A) The thermal fusing temperature of the fine particle polymer having a heat-reactive functional group is preferably 70 ° C. or higher, but more preferably 80 ° C. or higher in view of the temporal stability. However, if the heat fusion temperature is too high, it is not preferable from the viewpoint of sensitivity, so the range of 80 to 250 ° C is preferable, and the range of 100 to 150 ° C is more preferable.

  (A) The average particle diameter of the fine particle polymer is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm, and more preferably 0.1 to 1.0 μm. preferable. Within this range, good resolution and stability over time can be obtained.

  (A) The addition amount of the fine particle polymer is preferably 50 to 98% by mass, more preferably 60 to 95% by mass, based on the solid content of the image forming layer.

((B) Microcapsule enclosing a compound having a thermally reactive functional group)
(B) Thermally reactive functional groups suitable for microcapsules include, for example, polymerizable unsaturated groups, hydroxyl groups, carboxyl groups in addition to the functional groups previously mentioned as common to (a) and (b). , Carboxylate groups, acid anhydride groups, amino groups, epoxy groups, isocyanate groups, isocyanate block bodies, and the like.

  The compound having a polymerizable unsaturated group is preferably a compound having at least one, preferably two or more ethylenically unsaturated bonds such as acryloyl group, methacryloyl group, vinyl group and allyl group. Such a compound group is widely known in the said industrial field | area, and in this invention, these can be used without being specifically limited. These are monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof in chemical form.

  Specific examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid), esters thereof, and unsaturated carboxylic acid amides. Of these, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols and amides of unsaturated carboxylic acids and aliphatic polyvalent amines are preferred.

  Further, an addition reaction product of unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanate or epoxide, and monofunctional Alternatively, a dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used.

  In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and a halogen group or a tosyloxy group Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent with monofunctional or polyfunctional alcohols, amines or thiols.

  Another preferred example is a compound in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid or chloromethylstyrene.

  Specific examples of these compounds include the paragraphs [0014] to [0035] of JP-A No. 2001-27742 previously proposed by the applicant of the present invention, and detailed production of microcapsules containing these compounds. The method is described in [0036] to [0039], and these descriptions can also be applied to the present invention.

  (B) The microcapsule wall preferably used for the microcapsule has a three-dimensional cross-linking and has a property of swelling with a solvent. From such a viewpoint, the wall material of the microcapsule is preferably polyurea, polyurethane, polyester, polycarbonate, polyamide, or a mixture thereof, and polyurea and polyurethane are particularly preferable. Further, a compound having a thermally reactive functional group may be introduced into the microcapsule wall.

  (B) The average particle size of the microcapsules is preferably 0.01 to 20 μm, more preferably 0.05 to 2.0 μm, and particularly preferably 0.10 to 1.0 μm. Within the above range, good resolution and stability over time can be obtained.

  (B) In an image forming mechanism using a microcapsule having a heat-reactive functional group, a microcapsule material, a compound encapsulated in the microcapsule material, and other image forming layers in which the microcapsule is dispersed Any component that reacts to form an image area, that is, a hydrophobic area (parent ink area) may be used. For example, a type in which microcapsules are fused together by heat, a microcapsule inclusion Of these, compounds that ooze out from the capsule surface or outside the microcapsule during application, or a compound that enters the microcapsule wall from the outside causes a chemical reaction by heat, or those microcapsule materials or encapsulated compounds A type that reacts with a hydrophilic resin to which is added, or a low molecular compound to which it is added. The capsule wall material or its inclusions, by using those to have a functional group such as thermally react with each other in different functional groups each, such as the type of reacting microcapsules each other and the like.

  Therefore, although it is preferable for image formation that the microcapsules are fused together by heat, it is not essential.

  (B) The addition amount of the microcapsules to the image forming layer is preferably 10 to 60% by mass, and more preferably 15 to 40% by mass in terms of solid content. Within the above range, good on-press developability as well as good sensitivity and printing durability can be obtained.

  (B) When microcapsules are added to the image forming layer, a solvent that dissolves the inclusions and swells the wall material can be added to the microcapsule dispersion medium. By such a solvent, diffusion of the encapsulated compound having a heat-reactive functional group to the outside of the microcapsule is promoted.

  Such a solvent depends on the microcapsule dispersion medium, the material of the microcapsule wall, the wall thickness, and the inclusions, but can be easily selected from many commercially available solvents. For example, in the case of water-dispersible microcapsules composed of crosslinked polyurea and polyurethane walls, alcohols, ethers, acetals, esters, ketones, polyhydric alcohols, amides, amines, fatty acids and the like are preferable.

  A solvent that does not dissolve in the microcapsule dispersion but dissolves when the solvent is mixed can also be used. The amount of addition is determined by the combination of materials. When the amount is less than the appropriate value, image formation is insufficient, and when the amount is large, the stability of the dispersion deteriorates. Usually, it is preferably 5 to 95% by mass of the coating solution, more preferably 10 to 90% by mass, and particularly preferably 15 to 85% by mass.

(Other ingredients)
In the heat-sensitive image forming layer in this embodiment, in addition to (a) a fine particle polymer having a heat-reactive functional group having the image-forming property, or (b) a microcapsule encapsulating a compound having a heat-reactive functional group, Various additives can be used in combination depending on the purpose.

(Reaction initiator, reaction accelerator)
In the heat-sensitive image forming layer, a compound that initiates or accelerates these reactions may be added as necessary. Examples of the compound that initiates or accelerates the reaction include compounds that generate radicals or cations by heat. Specific examples include lophine dimers, trihalomethyl compounds, peroxides, azo compounds, diazonium salts, diphenyliodonium salts, onium salts, acyl phosphines, and imide sulfonates.

  These compounds are preferably added in the range of 1 to 20% by mass of the solid content of the image forming layer, and more preferably in the range of 3 to 10% by mass. When it is within the above range, good onset reaction reaction effect or reaction promoting effect can be obtained without impairing on-press developability.

(Hydrophilic resin)
A hydrophilic resin may be added to such a heat-sensitive image forming layer in the present invention. Addition of the hydrophilic resin not only improves the on-press developability, but also improves the film strength of the thermal image forming layer itself.

  As the hydrophilic resin, those having a hydrophilic group such as hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl, aminopropyl, carboxymethyl and the like are preferable.

  Specific examples of hydrophilic resins include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and its sodium salt, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acids and Salts thereof, polymethacrylic acids and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, hydroxybutyl Methacrylate homopolymers and copolymers, hydroxybutyl acrylate homopolymers and copolymers, polyethylene Glycols, hydroxypropylene polymers, polyvinyl alcohols, and hydrolyzed polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, acrylamide homopolymers and copolymers having a degree of hydrolysis of at least 60% by weight, preferably at least 80% by weight Methacrylamide homopolymers and polymers, N-methylolacrylamide homopolymers and copolymers, and the like.

  The addition amount of the hydrophilic resin to the heat-sensitive image forming layer is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the solid content of the image forming layer. Within this range, good on-press developability and film strength can be obtained.

  In order to form an image of such a heat-responsive image forming layer (heat-sensitive image forming layer) by scanning exposure of infrared laser light or the like, (A) an infrared absorber is contained in the image forming layer. A preferable addition amount is preferably 1 to 30% by mass and more preferably 5 to 25% by mass in the total solid content of the image forming layer coating solution. When the content is in the above range, an image forming layer excellent in both sensitivity and image formability is obtained.

  The image forming layer containing the hydrophobizing precursor is coated on the hydrophilic surface of the support by dissolving or dispersing the necessary components in a solvent to prepare a coating solution. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

(Other lithographic printing plate precursors)
The present invention can be preferably used for lithographic printing plate precursors other than infrared laser exposure. Hereinafter, examples of the planographic printing plate precursor and the image forming layer other than the infrared laser exposure will be described in detail.

  Preferable examples of the positive type image forming layer include conventionally known positive type image forming layers [(a) to (b)] shown below.

  (A) Conventionally used conventional positive image forming layer comprising naphthoquinonediazide and novolak resin.

  (B) A chemically amplified positive image-forming layer comprising a combination of an alkali-soluble compound protected with an acid-decomposable group and an acid generator.

  The above (a) and (b) are well known in the art, but are more preferably used in combination with the following positive type image forming layers ((c) to (f)). It is.

  (C) A laser-sensitive positive image-forming layer comprising a sulfonate polymer and an infrared absorber, which can produce a lithographic printing plate that does not require development processing as described in JP-A-10-282672.

  (D) Laser sensitivity comprising a carboxylic acid ester polymer and an acid generator or an infrared absorber capable of producing a lithographic printing plate which does not require development processing as described in EP 652483 and JP-A-6-502260. Positive image forming layer.

  (E) a laser-sensitive positive type comprising an alkali-soluble compound described in JP-A-11-095421 and a substance that is thermally decomposable and substantially reduces the solubility of the alkali-soluble compound in a state where it does not decompose. Image forming layer.

  (F) An alkali development elution positive image forming layer comprising an infrared absorber, a novolak resin, and a dissolution inhibitor, which can produce an alkali development elution type positive lithographic printing plate.

  On the lithographic printing plate support of the present invention, an image forming layer is formed by dissolving a coating liquid component of the desired layer such as the image recording coating liquid in a solvent and coating it, and a lithographic printing plate precursor is produced. can do. In the lithographic printing plate precursor, in addition to the image forming layer, a protective layer, a resin intermediate layer, an undercoat layer, a backcoat layer, and the like can be formed in the same manner depending on the purpose.

  Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, etc., and water-soluble images When the formation layer is used, water or an aqueous solvent such as alcohols can be used, but the present invention is not limited to this, and it may be appropriately selected according to the physical properties of the image formation layer. These solvents are used alone or in combination.

  The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.

  The coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but generally 0.5 to 5.0 g / m 2 is preferable for the photosensitive printing plate. As the coating amount decreases, the apparent sensitivity increases, but the film properties of the photosensitive film deteriorate.

  Various methods can be used as the coating method, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

  The lithographic printing plate precursor of the present invention is excellent in adhesion between the support and the image forming layer, and the hydrophilic support surface is exposed promptly by development, so that the printing smearing property of the non-image area is improved, A large number of high-quality prints can be obtained even under severe printing conditions.

  The lithographic printing plate precursor according to the invention can be obtained by applying a known plate making method according to the image forming layer.

Thereafter, the obtained lithographic printing plate is put on a printing machine and used for printing a large number of sheets.
[Formation of overcoat layer]
In the overcoat layer coating / drying section, an oxygen-blocking overcoat layer coating material is coated on the photosensitive layer with a coating coater. As the coating coater and the drying device, those similar to those having an undercoat layer and a photosensitive layer can be used, but the drying device is preferably a hot air drying method.

  In the present invention, an overcoat layer paint is applied on the photosensitive layer with a coating coater to form an overcoat layer, and then dried with hot air so that the crystallinity of the overcoat layer is 0.2 to 0.5. At least one drying condition is adjusted among the drying air temperature, wind speed, dew point, and drying time in the apparatus. By controlling the crystallinity of the water-soluble polymer in the overcoat layer, it is possible to improve the sensitivity that affects the quality of the photosensitive lithographic printing plate, the stability of the printing durability, the remaining film failure, the setter transportability, and the like. In this case, if the degree of crystallinity is less than 0.2, setter transportability, minute film dropout failure, and minute residual film failure cannot be improved, and if it exceeds 0.5, sensitivity, stability of printing durability and residual This is because development failure failures such as film and residual color cannot be improved.

  The water-soluble polymer contained in the overcoat layer contains polyvinyl alcohol and its partial esters, ethers, and acetals, or a substantial amount of unsubstituted vinyl alcohol units that make them necessary water-soluble. Examples thereof include copolymers thereof. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100 mol% and a polymerization degree in the range of 300 to 2400. Specifically, Kuraray Co., Ltd. PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA- 203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, L-8, etc. are mentioned. Examples of the copolymer include 88-100 mol% hydrolyzed polyvinyl acetate chloroacetate or propionate, polyvinyl formal, polyvinyl acetal, and copolymers thereof. Other useful polymers include polyvinyl pyrrolidone, gelatin and gum arabic, and these may be used alone or in combination. These water-soluble polymers are contained in a proportion of 30 to 99% by mass, preferably 50 to 99% by mass, based on the total solid content of the overcoat layer.

The overcoat layer may further contain a known additive such as a surfactant for improving the coating property and a water-soluble plasticizer for improving the physical properties of the film. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. Further, a water-soluble (meth) acrylic polymer may be added. The coating amount is suitably in the range of about 0.1 g / m ² to about 15 g / m ² in terms of the mass after drying. More preferably, it is 1.0 g / m ² to about 5.0 g / m ² . The dry coating mass of the overcoat layer is usually 0.5 to 10 g / m ² , preferably 1.0 to 5.0 g / m ² .

[Back coat layer]
The lithographic printing plate precursor obtained as described above has a coating layer made of an organic polymer compound on the back surface (the surface on which the image forming layer is not provided) so that the image forming layer is not damaged even if it is stacked. (Hereinafter also referred to as “back coat layer”) may be provided as necessary. As a main component of the back coat layer, at least one resin selected from the group consisting of a saturated copolymerized polyester resin, a phenoxy resin, a polyvinyl acetal resin, and a vinylidene chloride copolymer resin having a glass transition point of 20 ° C. or higher is used. Is preferred.
The saturated copolyester resin is composed of a dicarboxylic acid unit and a diol unit. Examples of the dicarboxylic acid unit include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, tetrabromophthalic acid, and tetrachlorophthalic acid; adipic acid, azelaic acid, succinic acid, oxalic acid, suberic acid, and sebacic acid , Saturated aliphatic dicarboxylic acids such as malonic acid and 1,4-cyclohexanedicarboxylic acid.
The backcoat layer further comprises a dye or pigment for coloring, a silane coupling agent for improving the adhesion to the support, a diazo resin comprising a diazonium salt, an organic phosphonic acid, an organic phosphoric acid, a cationic polymer, Wax, higher fatty acids, higher fatty acid amides, silicone compounds composed of dimethylsiloxane, modified dimethylsiloxane, polyethylene powder and the like that are usually used as slipping agents can be appropriately contained.

  The thickness of the backcoat layer may basically be a level that does not damage the image forming layer even if no interleaf is present, and is preferably 0.01 μm to 8 μm. When the thickness is less than 0.01 μm, it is difficult to prevent the image forming layer from being scratched when the planographic printing plate precursors are handled in layers. On the other hand, when the thickness exceeds 8 μm, the backcoat layer swells due to chemicals used around the lithographic printing plate during printing, the thickness varies, and the printing pressure may change to deteriorate the printing characteristics.

Various methods can be used for providing the backcoat layer on the back surface of the lithographic printing plate precursor. For example, a method in which the above components for the back coat layer are dissolved in a suitable solvent and applied as a solution, or an emulsion dispersion is applied and dried; A method of bonding to a printing plate precursor; a method of forming a molten film with a melt extruder and bonding to a lithographic printing plate precursor. The most preferable method for securing a suitable thickness is a method in which the components for the backcoat layer are dissolved in an appropriate solvent, applied as a solution, and dried.
In the production of a lithographic printing plate precursor, either the back coat layer on the back surface or the image forming layer on the front surface may be provided on the support first, or both may be provided simultaneously.

  The lithographic printing plate precursor thus obtained is cut into an appropriate size, if necessary, exposed and developed to produce a lithographic printing plate. In the case of a lithographic printing plate precursor provided with a visible light exposure type plate making layer (photosensitive plate making layer), it is exposed by irradiating normal visible light with a transparent film on which a printed image is formed, and then developed. It is possible to make a plate by performing. In the case of a lithographic printing plate precursor provided with a laser exposure type plate making layer, exposure can be performed by directly writing a printed image by irradiating various types of laser light, and then developing can be carried out.

  As mentioned above, although the manufacturing method of the lithographic printing plate precursor has been described as an example of the present invention, the application of the present invention is not limited to the lithographic printing plate. For example, as an application to photosensitive materials other than printing plates, it can be applied to the production of DDCP films represented by JP-A-2002-347358, or to the production of color filter materials for liquid crystals represented by JP-A-2003-248321. Applicable. Furthermore, when forming a film having a gas barrier property by applying a water-soluble polymer material onto a thermoplastic resin substrate represented by JP-A-2003-170522, it is applied as a pretreatment by applying a solvent and drying. In some cases, when a base paper is coated with a thermoplastic resin composition, an ink receiving layer is applied by water-based coating, and a solvent is applied and dried to apply as a pretreatment.

The coating process was performed using PMMA (methacrylic resin) / DMSO (dimethyl sulfoxide) / MEK (methyl ethyl ketone) at a solid content of 5 wt% and a coating amount of 20 cc. At that time, DMSO and MEK were mixed at a weight ratio of 1: 2. The coating method was bar coating, and the line speed was 60 m / min. As the support, Al having a width of 1300 mm and a thickness of 0.24 t was used. Furthermore, the drying conditions were dry hot air (85 ° C., 100 ° C., 10 g / m ³ , 20000 m ³ / h zone length 30 m). Moreover, the conditions of the solvent vapor-containing hot air were 120 ° C., the solvent vapor amount was as follows, the zone length was 1 m, and the second solvent was water and IPA.

(Test 1)
After coating on the aluminum web by the coating apparatus of FIG. 1, it was dried for 30 seconds through a hot air drying zone using dry air. As a result, the coating film reached the drying point, and immediately after that, it was conveyed to a drying box in a solvent vapor atmosphere and dried for 1 second. The prepared sample was cut out, and the coefficient of static friction and the contact angle with respect to ethanol were measured. In addition, when using IPA vapor | steam, the drying box was enclosed with the casing which can be purged with nitrogen, and the test was implemented. The coefficient of static friction was measured using a slant type measuring instrument with a load of 500 g, and the contact angle was measured using a contact angle meter and ethanol as a solvent.

The results when water is used as the second solvent are shown in Table 1. At this time, the state of the membrane at the drying point: residual DMSO amount 110 mg / m ² , and the membrane surface is smooth (no porosity). Table 2 shows the results when IPA was used as the second solvent. At this time, the membrane state at the drying point: residual DMSO amount 120 mg / m ² , and the membrane surface is smooth (no porosity).

  The amount of residual DMSO was measured as follows. That is, three coating film samples having a diameter of 10 mm were cut out and sealed in a vial bottle. This vial was placed in a head spacer (Tekmar 7000HT, GL Science) connected to a gas chromatography (GC390B, GL Science). The vial bottle was heated with the head spacer at 180 ° C. for 5 minutes. The operating conditions of the gas chromatography were performed using a packed column (Silicone DC-550, GL Sciences) at an oven temperature of 180 ° C. and an FID temperature of 180 ° C. Residual solvent vapor volatilized in the vial was automatically introduced into the gas chromatography from the head spacer, and the concentration of the solvent remaining in the coating film was calculated from the obtained peak area and DMSO calibration curve.

  In Tables 1 and 2, the amount of solvent vapor in the box is measured with a thermo-hygrometer (Higroflex, manufactured by Lotronic) when the solvent is water, and when the solvent is an organic solvent (IPA). Then, 10 μl of solvent vapor-containing hot air was collected using a syringe at the temperature of each condition and measured by gas chromatography (GC390B, GL Sciences Inc.). The IPA vapor amount of the solvent vapor-containing hot air was calculated from the obtained peak area and IPA calibration curve.

  As can be seen from Tables 1 and 2, in both cases of water and IPA, the surface modification of the film occurred only when the formula (1) was satisfied, and the static friction coefficient increased and the contact angle with respect to ethanol decreased.

(Test 2)
The same test was carried out by changing the temperature of the solvent vapor within the range of the above relational expression, and the obtained sample surface SEM observation, static friction coefficient measurement, contact angle measurement, and number of pores were measured. The results when water is used as the second solvent are shown in Table 3. The static friction coefficient was measured according to JIS using a static friction coefficient measuring instrument (Tribogear, Shinto Kagaku Co.). At that time, the load was 200 g, and the sliding angle was 30 °. The contact angle was measured using a contact angle meter (Drop Master 700, Kyowa Interface Science Co., Ltd.). At that time, ethanol was used as a droplet dropped on the film. Further, the number of pores was obtained by photographing the film surface with a confocal laser microscope at a magnification of 10,000 to 50,000 times according to the pore diameter, counting the number of pores present in the image, and converting them to 10/10 μm ² . As the definition of the pore, when the cross-sectional image of the film taken with the confocal laser microscope (FIG. 10) is viewed, the angle formed by the straight line between the tangent at the side of the pore and the vertical direction is 60 °. A space between the two is defined as a width L, and a case where the aspect ratio D / L between the width L and the depth D is 1/4 or more and 2 or less is regarded as a pore.

  As can be seen from Table 3, the pore size can be controlled by the solvent vapor temperature, and the number of pores can be controlled by the solvent vapor amount.

(Test 3)
The coating solution was further applied and dried on the coating film obtained in Test 2, and the number of repels was counted. The test conditions are as follows.
-Sample used: Coating film obtained in Example 3 of Test 2-Coating solution used: PVA / ethanol, solid content 4 wt%, coating wet amount 15 cc
・ Coating method: Bar coating ・ Line speed: 60 m / min
Drying conditions: Dry hot air 140 ° C., 10 g / m ³ , 20000 m ³ / h Zone length 30 m

  As can be seen from Table 4, the repellency of the upper layer coating solution could be greatly suppressed by drying the lower layer with solvent vapor.

The figure which shows the basic composition of the manufacturing line of the lithographic printing plate precursor of this embodiment Diagram showing the configuration of the drying device Diagram showing the steam supply / exhaust mechanism to the steam drying section The figure which shows the internal structure of the steam-drying part of 1st Embodiment. Sectional view along line 5-5 in FIG. Cross section of planographic printing plate after drying The figure which shows the structure of the manufacturing line of the lithographic printing plate precursor of 2nd Embodiment Sectional drawing of the lithographic printing plate obtained in the second embodiment Sectional drawing of the lithographic printing plate obtained in the third embodiment Diagram showing the definition of pores

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Planographic printing plate precursor manufacturing apparatus, 16 ... Support, 18 ... Coating section, 20 ... Drying section, 28 ... Hot air drying section, 29 ... Steam drying section, 30 ... Cooling section, 50 ... Box, 52 ... Supply section 54 ... Nozzle, 58A, 58B ... Exhaust section, 60A, 60B ... Wind shielding plate, 62 ... Tank, 64 ... Blower, 66, 68, 70 ... Heat exchanger, 72 ... Distillation tower

Claims (13)

An application step of forming a coating film by applying a polymer solution in which a thermoplastic resin is dissolved in a first solvent;
A drying step of drying the coating film to a drying point, supplying a solvent vapor-containing hot air of a second solvent having a molecular volume smaller than that of the first solvent to the coating film, and drying the coating film;
In the drying step, T: film temperature at the drying point [° C.], C: solvent vapor amount [g / m ³ ], P _T : saturated water vapor amount [Pa] at the film surface temperature T, R: gas constant, M: As the molecular weight of the second solvent,
1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8,
The surface modification method characterized by satisfy | filling the formula shown by these.   2. The surface modification method according to claim 1, wherein the surface physical properties of the coating film are controlled by adjusting the temperature of the hot air containing the solvent vapor of the second solvent.   2. The surface modification method according to claim 1, wherein the surface physical properties of the coating film are controlled by adjusting a solvent vapor amount of the second solvent.   4. The surface modification method according to claim 2, wherein the surface physical property of the coating film is a static friction coefficient of the coating film surface.   The surface modification method according to claim 2, wherein the surface physical property of the coating film is a contact angle of the coating film surface. The coating film is an image forming layer of a lithographic printing plate,
The surface modification method according to claim 1, wherein a static friction coefficient of the surface of the image forming layer is controlled by the drying step. The coating film is an overcoat layer formed on the image forming layer of the lithographic printing plate,
The surface modification method according to claim 1, wherein a static friction coefficient of the overcoat layer is controlled by the drying step. A coating apparatus for coating a polymer solution obtained by dissolving a thermoplastic resin in a first solvent;
A drying apparatus that is provided at a subsequent stage of the coating apparatus and that supplies the coating film that has been dried to a drying point by supplying a solvent vapor-containing hot air of a second solvent having a molecular volume smaller than that of the first solvent to dry the coating film;
The drying apparatus includes: T: film temperature at the drying point [° C.], C: solvent vapor amount [g / m ³ ], P _T : saturated water vapor amount at the film surface temperature T [Pa], R: gas constant, M: As the molecular weight of the second solvent,
1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8,
A surface modification apparatus characterized by performing a drying treatment under the drying conditions indicated by A lower layer coating step of applying a polymer solution in which a thermoplastic resin is dissolved in a first solvent to a support and forming a lower layer;
After drying the lower layer to a drying point, a lower layer drying step of supplying a solvent vapor-containing hot air of a second solvent having a molecular volume smaller than that of the first solvent to the lower layer and drying the lower layer;
An upper layer coating step of applying an application liquid on the dried lower layer and forming an upper layer;
In the lower layer drying step, T: film temperature at the drying point [° C.], C: solvent vapor amount [g / m ³ ], P _T : saturated water vapor amount at the film surface temperature T [Pa], R: gas constant, M : As the molecular weight of the second solvent,
1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8,
The multilayer coating method characterized by satisfy | filling the formula shown by these. The lower layer is an image forming layer of a lithographic printing plate, and the upper layer is an overcoat layer applied on the image forming layer,
The multi-layer coating method according to claim 9, wherein a contact angle of the lower layer with respect to the upper layer coating liquid is controlled by the lower layer drying step. A polymer solution in which a thermoplastic resin is dissolved in a first solvent is applied to a support, and a lower layer coating device for forming a lower layer, and a first layer on the lower layer provided after the lower layer coating device and dried to a drying point. A lower layer drying apparatus for supplying and drying solvent vapor-containing hot air of a second solvent having a molecular volume smaller than that of the solvent;
An upper layer coating device that is provided in a subsequent stage of the lower layer drying step, coats a coating solution on the dried lower layer, and forms an upper layer;
In the lower layer drying apparatus, T: film temperature [° C.] at the drying point, C: solvent vapor amount [g / m ³ ], P _T : saturated water vapor amount [Pa] at the film surface temperature T, R: gas constant, M : As the molecular weight of the second solvent,
1.0 ≦ C × R (273.15 + T) / (M × P _T ) ≦ 1.8,
A multi-layer coating apparatus characterized by satisfying the formula shown in FIG. A coating having a thermoplastic resin formed on the surface, and a coating having a large number of pores consisting of substantially concave depressions on the surface,
The peripheral edge of the pore forms a smooth curved surface by gradually denting toward the center of the pore,
The diameter of the said pore is 0.2 micrometer or more and 4.0 micrometers or less, The coating material characterized by the above-mentioned.   The coated material according to claim 12, wherein the coated material is a lithographic printing plate.

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