JP2005254696A - Laser engravable cylindrical printing original plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cylindrical printing original plate which has less liquid dreg amount occurring when a relief image is formed by directly engraving with laser, can be optically hardened in the atmosphere in the forming process of the laser engravable cylindrical printing original plate, has a high plate thickness precision, has less tucks on the surface and a smaller surface frictional resistance value, and in addition, has a high wear-resistance and is suitable for gravure printing, anilox roll and rotary screen printing. <P>SOLUTION: This laser engravable cylindrical printing original plate comprises a cylindrical supporting body and a photo-sensitive resin hardened substance layer (A) which is formed on the cylindrical support. The photo-sensitive resin hardened substance layer (A) contains at least one kind selected from an organic silicon compound or an organic fluorine compound in the layer internal section or the surface, and is a laser engravable layer. Also, in the cylindrical printing original plate for intaglio printing, the Shore D hardness ranges 30° to 100°. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention provides relief image creation for gravure printing plates by laser engraving, conductors for electronic components, semiconductors, insulators, pattern formation, antireflection films for optical components, color filters, and patterns of functional materials such as (near) infrared cut filters Gravure printing capable of laser engraving suitable for forming coating films and patterns for alignment films, underlayers, light-emitting layers, electron-transporting layers, and encapsulating layers in the production of display elements such as liquid crystal displays and organic electroluminescence displays The present invention relates to a cylindrical printing original plate that can be used as an original plate, anilox roll, and a rotary screen printing plate.

  Conventionally, gravure printing is used for printing high-quality photographs and the like. In general, a gravure printing plate (gravure cylinder) uses a hard copper plate for the plate cylinder, engraves a concave portion on the surface of the copper plate using a diamond blade, etc., and further hards such as chromium on the plate surface. A metal is plated. The depth of the recess can be freely controlled. Recently, a method of engraving using a laser beam to form a recess and a method of patterning a photoresist using a photoengraving technique and further etching a metal may be used. By storing the ink in the concave portions formed in this manner and transferring the ink to the printing material, it is possible to form a high-quality printed material in which gradation is expressed by the film thickness of the ink. A gravure cylinder using a metal plate cylinder requires a considerable amount of time for production and is very expensive. In addition, since the cylinder itself has a considerable weight, an apparatus such as a dedicated crane is required to move the cylinder. For these reasons, there has been a demand for a gravure cylinder that can be easily manufactured, is inexpensive, and is lightweight.

  In Patent Document 1 (Japanese Patent Laid-Open No. 58-185296) and Patent Document 2 (Japanese Patent Laid-Open No. 61-64767), there is a method of engraving a surface of a printing original plate formed using an epoxy resin by irradiating it with laser light. Has been described. Patent Document 3 (Japanese Patent Laid-Open No. Sho 56-166094) describes a method of engraving a printing original plate surface formed from a mixture of a urethane polymer and an acetal polymer using a laser. Patent Document 4 (Japanese Patent Application Laid-Open No. 47-5121) describes a polymer-like printing plate, in which a recess is formed using laser engraving. However, none of the patent literatures are obtained by laser engraving a printing original plate obtained by photocuring a photosensitive resin composition.

In Patent Document 5 (Japanese Patent Laid-Open No. 50-60301) and Patent Document 6 (Japanese Patent Laid-Open No. 9-171259), a photosensitive resin is used for gravure printing formed through exposure and development processes. Although a method for forming a cylindrical printing plate is described, there is no description regarding laser engraving in which a concave portion is directly formed by laser light irradiation.
Patent Document 7 (U.S. Pat. No. 5,259,311) describes a method of forming a printing plate by laser engraving a photosensitive resin cured product. However, a photosensitive resin cured product molded on a cylindrical support is disclosed. There is no description of laser engraving.
In addition, cylindrical materials such as metals, ceramics, and rubber are also used in anilox rolls that are incorporated in a printing press and used to transfer ink to a printing plate, and are processed using laser light. There has been a demand for these materials that can be manufactured inexpensively and easily.

In this way, a doctor blade contact type cylinder that can easily and quickly form a cured photosensitive resin layer on a cylindrical support, and engraves the formed cured cured resin layer with a laser to form a recess. Nothing was known about the original printing plate.
JP 58-185296 A JP-A 61-64767 Japanese Patent Laid-Open No. 56-166094 JP 47-5121 A Japanese Patent Laid-Open No. 50-60301 JP-A-9-171259 US Pat. No. 5,259,311

  The amount of liquid residue generated when forming a relief image by direct laser engraving is small, and can be photocured in the atmosphere in the formation process of the laser engraving printing original plate, with high plate thickness accuracy, surface tack and surface Providing a cylindrical printing master with low frictional resistance and high wear resistance suitable for gravure printing, anilox roll, and rotary screen printing.

  The present inventors have intensively studied and are a cylindrical printing original plate for producing a cylindrical printing substrate of a type having a concave pattern on the surface and contacting a doctor blade, and the cylindrical printing original plate has a cylindrical support Body and a photosensitive resin cured product layer (A) formed thereon, and the photosensitive resin cured product layer (A) is capable of laser engraving containing an organic silicon compound or an organic fluorine compound inside or on the surface It was found that the above problems can be solved by producing a cylindrical printing original plate that is a simple layer and has a Shore D hardness of 30 degrees or more, and has completed the present invention.

The present invention is as follows.
1. It consists of a cylindrical support and a photosensitive resin cured product layer (A) formed thereon, and the photosensitive resin cured product layer (A) contains at least one selected from organic silicon compounds or organic fluorine compounds inside the layer. Alternatively, a cylindrical printing original plate for intaglio printing, which is a layer capable of laser engraving contained on the surface and has a Shore D hardness of 30 to 100 degrees.

2. The organosilicon compound includes a silicone compound represented by the following average composition formula (1): The cylindrical printing original plate described in 1.
_{R p Q r X s SiO (} 4-p-r-s) / 2 (1)
(In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkylene group having 5 to 20 carbon atoms, a cycloalkylene group, or 1 carbon atom. ˜20 alkoxy group substituted with hydroxyl group or amino group, C 1-20 alkyl group substituted with aryl group, C 7-30 alkyl group substituted with aryl group, methacryl group, acrylic group, vinyl group, cinnamoyl group, Alkyl group substituted with acetylene group, thiol group, epoxy group, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, spiroorthoester group, cyclic iminoether group, bicycloorthoester group, cyclosiloxane ring group, Or an aryl group having 6 to 20 carbon atoms and an alkoxycarbonyl having 2 to 30 carbon atoms substituted with a halogen atom Represents a monovalent group, a sulfo group or a monovalent group, consisting of one or more selected from polyoxyalkylene hydrocarbon group containing a salt thereof containing a carboxyl group or a salt thereof.

Q and X are a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 20 carbon atoms. Or an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 7 to 30 carbon atoms substituted with an aryl group, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, or an alkoxycarbonyl having 2 to 30 carbon atoms A monovalent group containing a group, a carboxyl group or a salt thereof, a monovalent group containing a sulfo group or a salt thereof, a hydrocarbon group consisting of one or more selected from a polyoxyalkylene group,
0 <p <4,
0 ≦ r <4,
0 ≦ s <4,
And (p + r + s) <4. )

3. The organosilicon compound has at least one organic group selected from the group consisting of an aryl group, a linear or branched alkyl group substituted with at least one aryl group, an alkoxycarbonyl group, an alkoxy group, and a polyoxyalkylene group. And a compound having a hydrogen atom (α-position hydrogen) bonded to a carbon atom to which the organic group is directly bonded. The cylindrical printing original plate described in 1.
4). 1. The silicone compound has at least one organic group selected from the group consisting of a methylstyryl group, a phenyl group, a styryl group, and a carbinol group, The cylindrical printing original plate described in 1.
5). The cured photosensitive resin layer (A) is a compound having at least one type of bond selected from the group consisting of carbonate bond, urethane bond, ester bond, amide bond and imide bond in the molecular main chain, and aromatic in the molecule. A compound having a group or / and an alicyclic group; To 4. A cylindrical printing original plate according to any one of the above.

6). 1. The cured photosensitive resin layer (A) is a layer obtained by photocuring a liquid photosensitive resin composition (a) at 20 ° C. To 5. A cylindrical printing original plate according to any one of the above.
7). The weight of the cured photosensitive resin constituting the cured photosensitive resin layer (A) was measured by thermogravimetric analysis in which the temperature was raised from room temperature under conditions of a nitrogen flow rate of 100 ml / min and a heating rate of 10 ° C./min. The temperature at which the weight is reduced to 50% is 150 ° C. or higher and 450 ° C. or lower, and the difference between the temperature at which the weight is reduced to 90% and the temperature at which the weight is reduced to 50% is 120 ° C. or lower. To 6. A cylindrical printing original plate according to any one of the above.
8). The cured photosensitive resin layer (A) further contains an inorganic porous material, the specific surface area of the inorganic porous material is 10 m ² / g to 1500 m ² / g, the average pore diameter is 1 nm to 1000 nm, The pore volume is 0.1 ml / g or more and 10 ml / g or less, and the oil absorption is 10 ml / 100 g or more and 2000 ml / 100 g or less. To 7. The doctor blade contact type cylindrical printing according to any one of the above.

9. 7. The number average particle diameter of the inorganic porous material is 0.1 μm or more and 100 μm or less, and at least 70% of the particles are spherical particles having a sphericity of 0.5 to 1. The cylindrical printing original plate described in 1.
10. The surface of the cured photosensitive resin layer (A) capable of laser engraving has an indicator liquid with an energy of 30 mN / m (trademark “mixture No. 30.0 for wetting tension test” manufactured by Wako Pure Chemical Industries, Ltd.) on the surface. When the maximum diameter of a portion where a droplet (20 μl) is dropped and the droplet spreads after 30 seconds is measured, the droplet has a wetting property in which the diameter of the droplet is 4 mm or more and 20 mm or less 1 . To 9. A cylindrical printing original plate according to any one of the above.
11. The photosensitive resin cured product layer (A) capable of laser engraving is sensitive to a near infrared laser having an oscillation wavelength in the range of 700 nm to 3 μm, and has a pulse output with a pulse width of 1 ns to 10 ns and a peak power of 5 kW to 20 kW. A concave portion having a depth of 1 μm or more is formed when laser light is irradiated with laser light having an energy amount of 0.2 mJ per pulse. To 10. The doctor blade contact type cylindrical printing original plate according to any one of the above.

12 1. A circumference adjustment layer for adjusting the circumference of the cylindrical printing original plate is provided between the cylindrical support and the cured photosensitive resin layer (A). To 11. A cylindrical printing original plate according to any one of the above.
13. The circumference adjusting layer is composed of a photosensitive resin cured product layer (B), 12. The cylindrical printing original plate described in 1.
14 The laser-engravable photosensitive resin cured product layer (A) contains a photopolymerization initiator or a decomposition product of the photopolymerization initiator, and the photopolymerization initiator is a hydrogen abstraction type photopolymerization initiator and a decay type light. 1. A polymerization initiator is included. To 13. A cylindrical printing original plate according to any one of the above.
15. The hydrogen abstraction type photopolymerization initiator is composed of at least one compound selected from benzophenones, xanthenes and anthraquinones, and the decay type photopolymerization initiator is a benzoin alkyl ether, 2,2-dialkoxy-2 -Consisting of at least one compound selected from phenylacetophenones, acyloxime esters, azo compounds, organic sulfur compounds, and diketones, The cylindrical printing original plate described in 1.

16. 13. The photopolymerization initiator contains a compound having both a site functioning as a hydrogen abstraction type photopolymerization agent and a site functioning as a decay type photopolymerization initiator in the same molecule. The cylindrical printing original plate described in 1.
17. A sheet having a thickness of 2.8 mm made of a cured photosensitive resin having the same composition as the cured photosensitive resin layer (A) is prepared separately. Using the sheet, the load is 4.9 N and the rotational speed of the rotating disk is every minute. When the taper wear test is performed under the condition of 60 ± 2 times and the test number is 1000 times continuously, the wear amount per unit area of the surface of the cured photosensitive resin layer is 2.5 mg / cm ² or less. Features 1. To 16. A cylindrical printing original plate according to any one of the above.

18. 1. To 17. A method for producing a cylindrical printing original plate according to any one of the above, wherein a step of applying a photosensitive resin composition on a cylindrical support to form a photosensitive resin composition layer, a photosensitive resin formed in a cylindrical shape The photosensitive resin composition layer is irradiated with light in the atmosphere and cured by crosslinking to form a laser-engraved photosensitive resin cured product layer (A), and the irradiated light has a wavelength of 200 nm to 450 nm. The illuminance on the surface of the photosensitive resin composition layer included is a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.) and a filter (trademark “UV-35-APR filter” manufactured by Oak Manufacturing Co., Ltd.). when measured using, it is 20 mW / cm ² or more, the UV meter and a filter (ORC Manufacturing Co., Ltd., trademark "UV-25 filter") when measured using a is 5 mW / cm ² or more Wherein the bets method for producing a cylindrical printing original plate.
19. In the method for producing a doctor blade or squeegee contact type cylindrical printing substrate having a concave pattern, To 17. A doctor blade or a squeegee contact type cylindrical printing having a concave pattern, comprising the step of irradiating the cylindrical printing original plate according to claim 2 with a laser beam and forming a concave pattern by removing the laser irradiation portion. A method for forming a substrate.
20. 19. A doctor blade contact type cylindrical printing substrate, characterized in that the cylindrical printing substrate described in 1 is used as a gravure printing plate or an anilox roll.

  The amount of liquid residue generated when forming a relief image by direct laser engraving is small, and can be photocured in the atmosphere in the formation process of the laser engraving printing original plate, with high plate thickness accuracy, surface tack and surface A cylindrical printing original plate suitable for gravure printing and anilox roll having a low frictional resistance and high wear resistance can be provided.

Hereinafter, preferred embodiments of the present invention will be described in more detail.
The present invention relates to a cylindrical printing original plate suitable for producing a cylindrical printing substrate having a concave pattern on the surface and in contact with a doctor blade, the cylindrical printing original plate comprising a cylindrical support and an upper surface thereof. The cured photosensitive resin layer (A) is formed on the photosensitive resin cured layer (A), and the cured photosensitive resin layer (A) is a layer capable of laser engraving containing an organosilicon compound or an organofluorine compound inside or on the surface. In addition, the present invention relates to a cylindrical printing original plate having a Shore D hardness of 30 degrees or more.

  The cylindrical printing original plate of the present invention is used for the production of a cylindrical cylinder for gravure printing, a doctor blade such as an anilox roll for ink transfer used on a printing press, a rotary screen printing plate, or a squeegee contact type cylindrical printing substrate. It is suitable. Here, the doctor blade is the thickness used to scrub off excess ink on the printing plate in gravure printing, as described in “Extended Printing Encyclopedia” (edited by the Japan Printing Society, published in 1987). There is a thin steel plate of 0.12 to 0.15 mm. However, the doctor blade in the present invention is not particularly required to be made of metal as long as it has a function of scraping off excess ink on the plate surface, and ceramic or resin-made ones can also be used. A squeegee is a rubber tool that transfers ink from a plate used in screen printing to a printing medium, and the ink rubs the surface of the screen printing plate on which ink is placed with the squeegee so that the ink opens the opening of the printing plate. Pass through and transfer to the substrate. Since the cylindrical printing original plate of the present invention is used in contact with a doctor blade or a squeegee, the cured photosensitive resin layer (A) is preferably relatively hard, and the Shore D hardness is 30 degrees to 100 degrees, More preferably, they are 40 degree | times or more and 100 degrees or less, More preferably, they are 50 degree | times or more and 100 degrees or less. If the Shore D hardness is 30 degrees or more and 100 degrees or less, the ink can be removed without deforming the cylindrical printing substrate when the ink attached to the cylindrical printing substrate surface is scraped off with a doctor blade. . In addition, pattern deformation can be suppressed when the printing plate surface is rubbed with a squeegee. In order to obtain the cured photosensitive resin layer (A) in this hardness range, two or more in the molecule of the resin (a) and the organic compound (b), which are components constituting the photosensitive resin composition, Preferably, the compound containing 3 or more polymerizable unsaturated groups is contained in an amount of 10 wt% or more, more preferably 20 wt% or more of the total amount of the resin (a) and / or the organic compound (b). Further, a compound having a rigid skeleton such as an aromatic hydrocarbon group or / and an alicyclic hydrocarbon group in the molecule of the resin (a) or / and the organic compound (b) is converted into the resin (a) or / And 10 wt% or more of the total amount of the organic compound (b), more preferably 20 wt% or more. Furthermore, it is desirable that the monomer unit having a rigid part is contained in an amount of 1% or more, more preferably 5% or more, and still more preferably 10% or more of all monomer units constituting the resin (a).

Further, since the cylindrical printing substrate contacts with the doctor blade or the squeegee while rotating, a material with good wear resistance is preferable. As an index indicating the performance, the wear amount per unit area in the taper wear test can be used. The preferable wear amount on the surface of the cylindrical printing original plate is 2.5 mg / cm ² or less, more preferably 1.5 mg / cm ^2. cm ² or less, more preferably 0.5 mg / cm ² or less. When the wear amount is 2.5 mg / cm ² or less, durability can be secured when the surface of the cylindrical printing substrate comes into contact with the doctor blade or squeegee, and it can be used for a long time.

  In the present invention, the cured photosensitive resin layer (A) preferably contains an organosilicon compound or an organofluorine compound inside or on the surface. As a method of containing an organic silicon compound or an organic fluorine compound in the layer, an organic silicon compound or an organic fluorine compound is contained in the photosensitive resin composition (a) for forming the cured photosensitive resin layer (A). A method can be mentioned. Moreover, as a method for containing an organosilicon compound or an organofluorine compound on the surface of the layer, a method of applying and spraying a treatment liquid containing an organosilicon compound or an organofluorine compound, a cured photosensitive resin layer (A) in the treatment liquid And the like. The organosilicon compound or the organofluorine compound has an effect of greatly improving the abrasion resistance of the photosensitive resin cured product layer (A), an effect of reducing the surface friction resistance value, and an effect of controlling ink wettability.

As the organosilicon compound used in the present invention, a compound having at least one Si—O bond in the molecule is preferable. Further, it may be a compound having or not having a polymerizable unsaturated group in the molecule. A silicone compound having a siloxane structure having a Si—O—Si bond or a polysiloxane structure is particularly preferred from the viewpoints of weather resistance, structural stability, and storage stability.
Preferred silicone compounds in the present invention include, for example, one or more silicone compounds containing at least one structure of silicone bonds represented by the general formulas (2), (3), (4), and (5). Can do.

(In the formula, each R ₁ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or substituted carbon group having 1 carbon atom. An alkyl group having 20 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 7 to 30 carbon atoms substituted with an aryl group, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, 2 carbon atoms 1 to 2 or more hydrocarbon groups selected from 1 to 30 alkoxycarbonyl groups, monovalent groups including carboxyl groups or salts thereof, monovalent groups including sulfo groups or salts thereof, and polyoxyalkylene groups. .)
The silicone compound is represented by the following average composition formula (1).
_{R p Q r X s SiO (} 4-p-r-s) / 2 (1)
(Wherein R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group substituted with 7 carbon atoms. ~ 30 alkyl group, vinyl group, acetylene group, acrylic group, methacryl group, cinnamoyl group, thiol group, azide group, epoxy group that undergoes ring-opening addition reaction, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, Spiro ortho ester group, bicyclo ortho ester group, alkyl group substituted by cyclic imino ether group, aryl group having 6 to 20 carbon atoms substituted by halogen atom, alkoxycarbonyl group having 2 to 30 carbon atoms, carboxyl group Or a monovalent group containing a salt thereof, a monovalent group containing a sulfo group or a salt thereof, or a polyoxyalkylene group. It represents one or a hydrocarbon group of two or more was.

Q and X are hydrogen, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon substituted with an aryl group. An alkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted by a halogen atom, an alkoxycarbonyl group having 2 to 30 carbon atoms, a monovalent group including a carboxyl group or a salt thereof, a sulfo group, or A monovalent group containing the salt, a hydrocarbon group composed of one or more selected from a polyoxyalkylene group,
0 <p <4,
0 ≦ r <4,
0 ≦ s <4,
And (p + r + s) <4. )

  Although the molecular structure is not particularly limited, a compound having a polyalkylsiloxane such as polydimethylsiloxane or polydiethylsiloxane in the main chain can be cited as a preferred compound. A compound having a polysiloxane structure in a part of the molecule may also be used. Furthermore, a compound in which a specific organic group is introduced into the polysiloxane structure can be used. Specifically, a compound having an organic group introduced into the side chain of polysiloxane, a compound having an organic group introduced into both ends of polysiloxane, a compound having an organic group introduced into one end of polysiloxane, a side chain of polysiloxane, A compound having an organic group introduced at both ends can be used. Specific examples of the organic group introduced into the polysiloxane structure include an amino group, a carboxyl group, a carbinol group, an aryl group, an alkyl group, an alkoxycarbonyl group, an alkoxy group, a straight chain substituted with at least one aryl group, or Examples include branched alkyl groups and polyoxyalkylene groups. Here, preferred examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a phenanthryl group. Further, a linear or branched alkyl group substituted with an aryl group, such as a methyl styryl group or a styryl group, is preferable. Furthermore, an organic group in which the hydrogen atom bonded to the aromatic carbon of the aryl group is substituted with another functional group can also be used. Moreover, what substituted some or all of the hydrogen atoms couple | bonded with these organic groups with halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom, can also be used.

  The organosilicon compound used in the present invention has at least one organic group selected from the group consisting of a phenyl group, a methylstyryl group, a styryl group, an alkoxycarbonyl group, an alkoxy group, and a polyoxyalkylene group. A compound having a hydrogen atom bonded to a directly bonded carbon atom, that is, a compound having a hydrogen atom bonded to the α-position carbon of the linear compound (hereinafter abbreviated as α-position hydrogen) is particularly preferred. These compounds are added as additives to the photosensitive resin composition, but the amount of components extracted from the cured product obtained by photocrosslinking and curing using these compounds to the ink side used in the printing process. There is very little. In addition, the effect of suppressing the ink residue on the plate surface and the sustainability of curing that lowers the frictional resistance of the plate surface are extremely high. The reason is not clear, but when a cured product obtained by photopolymerizing a photosensitive resin composition to which these compounds are added is immersed in a solvent, there is a phenomenon that the weight change before and after immersion is small. It is done. This means that there are few components that elute in the ink used during printing. When the printing process is repeated, changes in mechanical properties and printing characteristics of the plate can be reduced, which is extremely important for practical use. It is. This phenomenon is presumed to be because the compound having hydrogen at the α-position contributes to the reaction from the course of the photopolymerization reaction and is incorporated into the cured product by a chemical bond.

  As the organosilicon compound, commercially available products that are usually available, for example, various organic group-substituted silicone oils manufactured by Shin-Etsu Chemical Co., Ltd., Asahi Kasei Wacker Silicone Co., GE Toshiba Silicone Co., Toray Dow Corning Silicone Co., Ltd. may be used. it can. For example, trade name “KF-410” (methylstyryl-modified silicone oil), trade name “X-22-160AS” (carbinol-modified silicone oil), trade name “X-22-715” (manufactured by Shin-Etsu Chemical Co., Ltd.) Examples of useful compounds include ester-modified silicone oil), “KF-412” (alkyl-modified silicone oil), and the like. Moreover, it does not specifically limit as reactive silicone oil which has a polymerizable unsaturated group in a molecule | numerator, For example, the Shin-Etsu Chemical Co., Ltd. make, brand name "X-22-164A", "X-22-164B" "," X-22-164C "," X-22-2404 "," X-22-174DX "(compound having a methacrylic group)," X-22-3667 "," X-22-4741 "," X-22-173DX "(compound having an epoxy group)," X-22-167B "," KF-2001 "," KF-2004 "(compound having a mercapto group), and the like.

  A preferable range of the addition amount of the organosilicon compound is 0.1 wt% or more and 10 wt% or less, more preferably 0.3 wt% or more and 5 wt% or less, and further preferably 0.5 wt% or more and 3 wt% or less with respect to the entire photosensitive resin composition. It is as follows. When the addition amount is 0.1 wt% or more, the tackiness and surface friction resistance value of the photocured product surface of the photosensitive resin composition can be suppressed to a low level, and further, there is an effect of suppressing ink entanglement during printing. Moreover, if the addition amount is 10 wt% or less, the phenomenon of repelling ink during printing is not observed, and a good printed matter can be obtained. In addition, when the photosensitive resin composition is applied in a cylindrical shape and then photocured, and when cutting and shaping to obtain a smooth surface by removing subtle irregularities on the surface, the tool blade used is extremely low in life. As a result, cutting performance can be greatly improved. Furthermore, if the addition amount is 10 wt% or less, a pattern is formed on the plate surface without reducing the engraving speed when laser engraving printing original plate which is a photocured product of the photosensitive resin composition is laser engraved. Can do.

  The number average molecular weight of the organosilicon compound is in the range of 100 to 100,000, preferably 300 to 10,000, and more preferably 500 to 5000. If the number average molecular weight is 100 or more, the extraction amount from the inside of the photocured photosensitive resin composition to the solvent used for ink or plate washing can be kept low. Moreover, if a number average molecular weight is 100,000 or less, the mixability with the other component which comprises the photosensitive resin composition is favorable. Particularly preferred are compounds that are liquid at 20 ° C.

  A method for measuring the number average molecular weight (Mn) of the organosilicon compound will be described. It is dissolved in a solvent in which the organosilicon compound is dissolved, analyzed by gel permeation chromatography (GPC method), and converted to standard polystyrene with a known molecular weight to calculate the number average molecular weight (Mn). This method is used for compounds having a wide molecular weight distribution. As a measure for the molecular weight distribution, the ratio of the number average molecular weight (Mn) and the weight average molecular weight (Mw) calculated simultaneously with Mn, that is, the polydispersity (Mw / Mn) is used. When the polydispersity is 1.1 or more, the number average molecular weight determined by the GPC method is adopted on the assumption that the molecular weight distribution is wide. In addition, those having a polydispersity of less than 1.1 have a very narrow molecular weight distribution, so that molecular structure analysis is possible, and the molecular weight calculated using nuclear magnetic resonance spectroscopy (NMR method) or mass spectrometry is the number average. The molecular weight.

  The refractive index of the organosilicon compound used in the present invention is 1.400 or more and 1.590 or less, more preferably 1.430 or more and 1.490 or less, as measured using an Abbe refractometer at 25 ° C. It is preferable. Within this range, mixing with other components constituting the photosensitive resin composition can be performed without extremely clouding, ensuring photocurability, and further improving the mechanical properties of the photocured product. Can be secured. Unlike photosensitive resin plates, which are exposed and developed using photolithography to form a fine pattern, there is no need to form a fine pattern in the process of making a laser engraving printing original plate. In the process. In general, in photosensitive resins, a uniform composition with little light scattering due to turbidity is said to be preferable for the formation of fine patterns, whereas laser engraving printing plates only require curing properties at a constant plate thickness. It can be cured even in a composition in which some turbidity is present and light scattering. Therefore, when forming a laser engraving printing original plate using a photosensitive resin composition as a raw material, there is a great feature that the degree of freedom in selecting a compound that can be used is extremely high. When the refractive index of the organosilicon compound used in the present invention is significantly different from the refractive index of components other than the organosilicon compound in the photosensitive resin composition, it may become extremely cloudy. Therefore, it is desirable that the difference between the refractive index of the organosilicon compound in the photosensitive resin composition and the refractive index of other components is ± 0.1 or less, more preferably ± 0.05 or less.

  The organic fluorine compound used in the present invention may be a compound having a polymerizable unsaturated group in the molecule or not. Polytetrafluoroethylene, perfluoroethylene propene copolymer, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polytetrafluoroethylene-perfluorodiode are effective for reducing the surface friction resistance. Examples thereof include a method of containing organic fine particles containing materials such as xol copolymer, polyvinylidene fluoride, polyvinyl fluoride, and polychlorotrifluoroethylene. The preferable range of the average particle diameter of the organic fine particles is 0.05 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 0.5 μm or more and 5 μm or less. Moreover, the method of processing the surface of the photosensitive resin cured material layer (A) using the silane coupling agent which has a fluorine atom in a molecule | numerator, a titanium coupling agent, etc. can be mentioned.

  The cylindrical printing original plate of the present invention can form a concave pattern on the surface using laser engraving. Laser engraving is a method of forming a concave pattern by irradiating the surface of a substrate with laser light and removing the resin in the portion irradiated with the laser light. In laser engraving, near-infrared lasers and infrared lasers are preferred because they produce large outputs. Since these lasers decompose and remove the resin by heat, it is preferable that the cured photosensitive resin layer has a high thermal decomposability. Thermogravimetric analysis is preferred as an evaluation of thermal decomposability. When the cured photosensitive resin is measured by raising the temperature from room temperature under conditions of a nitrogen flow rate of 100 ml / min and a heating rate of 10 ° C./min, the temperature at which the weight decreases to 50% is preferably 150 ° C. It is more than 450 degreeC, More preferably, it is 200 degreeC or more and 420 degrees C or less, More preferably, it is 200 degreeC or more and 400 degrees C or less. If the temperature at which the weight is reduced to 50% is 150 ° C. or more and 450 ° C. or less, it can be used without deformation even under a temperature condition of about 100 ° C., and if it is 450 ° C. or less, the concave pattern can be easily formed using a laser. Can be formed. The difference between the temperature at which the weight is reduced to 90% and the temperature at which the weight is reduced to 50% is 120 ° C. or less, more preferably 90 ° C. or less, and still more preferably 70 ° C. or less. If the difference between the temperature at which the weight is reduced to 90% and the temperature at which the weight is reduced to 50% is 120 ° C. or less, the thermal decomposition rate is high, and there is little molten residue at the edge of the pattern that can be formed, and the formation of a good shape pattern Can do.

  The cured photosensitive resin layer (A) is composed of a compound having at least one bond selected from the group consisting of a carbonate bond, a urethane bond, an ester bond, an amide bond, and an imide bond in the molecular main chain, and an aromatic group in the molecule. It is preferable to contain a compound having a group or / and an alicyclic group. As a bond existing in the molecular main chain, a carbonate bond and a urethane bond are particularly preferable, and a compound having these bonds is a compound that is easily thermally decomposed. In addition, a compound having an amide bond or an imide bond, or a compound having an aromatic group and / or an alicyclic group in the molecule has an effect of increasing the Shore D hardness of the photosensitive resin cured product layer. Here, the aromatic group is an atomic group excluding one hydrogen atom of the skeleton of an aromatic compound such as a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. It is. The alicyclic group refers to a remaining atomic group obtained by removing one hydrogen atom of a compound that does not belong to an aromatic compound among carbocyclic compounds having a structure in which carbon atoms are bonded in a ring shape. Examples thereof include a cyclohexyl group, a bicyclooctyl group, a cyclopentadienyl group, and a cyclooctyl group.

As the photosensitive resin composition (a) for forming the cured photosensitive resin layer (A), those having the resin (a) as a polymer component and the organic compound (b) as a monomer component are preferable.
The resin (a) is preferably a polymer compound having a number average molecular weight of 1,000 or more and 300,000 or less, and among them, a polymer compound having a polymerizable unsaturated group in the molecule is particularly preferable. A more preferable range of the number average molecular weight of the resin (a) is 2000 or more and 100,000 or less, and a more preferable range is 2000 or more and 50,000 or less. If the number average molecular weight of the resin (a) is 1000 or more, the printing original plate produced by crosslinking later maintains strength, and the relief image produced from this original plate is strong, and when used as a printing plate, it can be used repeatedly. I can bear it. Moreover, if the number average molecular weight of the resin (a) is 300,000 or less, a cylindrical printing original plate capable of laser engraving is produced without excessively increasing the viscosity at the time of molding the photosensitive resin composition. Can do. The number average molecular weight referred to here is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

  The definition of “polymerizable unsaturated group” in the present invention is a polymerizable unsaturated group involved in a radical or addition polymerization reaction. Preferable examples of the polymerizable unsaturated group involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acrylic group, and a methacryl group. Preferred examples of the polymerizable unsaturated group involved in the addition polymerization reaction include cinnamoyl group, thiol group, azide group, epoxy group that undergoes ring-opening addition reaction, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, spiro An ortho ester group, a bicyclo ortho ester group, a cyclic imino ether group and the like can be mentioned. Particularly preferred are polymers having an average of 0.7 or more polymerizable unsaturated groups per molecule. When the average is 0.7 or more per molecule, the printing original plate obtained from the resin composition of the present invention is excellent in mechanical strength, and the relief shape is difficult to collapse during laser engraving. Furthermore, its durability is good, and it can withstand repeated use, which is preferable. Considering the mechanical strength of the printing original plate, the polymerizable unsaturated group of the resin (a) is preferably 0.7 or more per molecule, and more preferably more than 1. In the resin (a), the position of the polymerizable unsaturated group is preferably directly bonded to the end of the polymer main chain, the end of the polymer side chain, the polymer main chain, or the side chain. The average number of polymerizable unsaturated groups contained in one molecule of the resin (a) can be determined by a molecular structure analysis method using a nuclear magnetic resonance spectrum method (NMR method).

  As a method for producing the resin (a) having a polymerizable unsaturated group, for example, a resin in which a polymerizable unsaturated group is directly introduced into the molecular end may be used. Alternatively, a hydroxyl group or an amino group may be used. Of the above components having a molecular weight of about several thousand having a plurality of reactive groups such as epoxy groups, carboxyl groups, acid anhydride groups, ketone groups, hydrazine residues, isocyanate groups, isothiocyanate groups, cyclic carbonate groups, and alkoxycarbonyl groups. After reacting with a binder having a plurality of groups capable of binding to the reactive group (for example, polyisocyanate in the case of a hydroxyl group or an amino group), the molecular weight is adjusted and converted to a terminal binding group. A method such as a method of introducing a polymerizable unsaturated group at a terminal by reacting with an organic compound having a polymerizable unsaturated group and a group that reacts with a bonding group is preferred.

  As the resin (a) to be used, a resin that is easily liquefied or a resin that is easily decomposed is preferable. Examples of resins that are easily decomposed include styrene, α-methylstyrene, α-methoxystyrene, acrylic esters, methacrylic esters, ester compounds, ether compounds, nitro compounds, carbonates as monomer units that are easily decomposed in the molecular chain. Preferably, compounds, carbamoyl compounds, hemiacetal ester compounds, oxyethylene compounds, aliphatic cyclic compounds, and the like are included. Especially polyethers such as polyethylene glycol, polypropylene glycol, polytetraethylene glycol, aliphatic polycarbonates, aliphatic carbamates, polymethyl methacrylate, polystyrene, nitrocellulose, polyoxyethylene, polynorbornene, polycyclohexadiene hydrogenated product Alternatively, a polymer having a molecular structure such as a dendrimer having many branched structures is a representative example of those that are easily decomposed. A polymer containing a large number of oxygen atoms in the molecular chain is preferred from the viewpoint of degradability. Among these, a compound having a carbonate group, a carbamate group, and a methacryl group in the polymer main chain is preferable because of its high thermal decomposability. For example, polyesters and polyurethanes synthesized from (poly) carbonate diol and (poly) carbonate dicarboxylic acid as raw materials, polyamides synthesized from (poly) carbonate diamine as raw materials, and the like can be cited as examples of polymers having good thermal decomposability. . These polymer main chains and side chains may contain a polymerizable unsaturated group. In particular, when a reactive functional group such as a hydroxyl group, an amino group, or a carboxyl group is present at the terminal, it is easy to introduce a polymerizable unsaturated group at the terminal of the main chain.

  Examples of the resin (a) include compounds having a polymerizable unsaturated group in the molecular main chain or side chain, such as polydienes such as polybutadiene and polyisoprene. In addition, a polymer compound in which a polymerizable unsaturated group is introduced into the molecule by a chemical reaction such as a substitution reaction, elimination reaction, condensation reaction, addition reaction, etc., starting from a polymer compound having no polymerizable unsaturation You can also Examples of polymer compounds having no polymerizable unsaturated groups include polyolefins such as polyethylene and polypropylene, polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal, poly In addition to CC chain polymers such as acrylic acid, poly (meth) acrylic esters, poly (meth) acrylamide, and polyvinyl ether, polyethers such as polyphenylene ether, polythioethers such as polyphenylene thioether, and polyesters such as polyethylene terephthalate , Polycarbonate, polyacetal, polyurethane, polyamide, polyurea, polyimide, polydialkylsiloxane and other polymer compounds, or the main chain of these polymer compounds It may be mentioned a polymer compound having a hetero atom, a random copolymer synthesized from a plurality of types of monomer components, a block copolymer. Furthermore, it is possible to use a mixture of a plurality of polymer compounds having a polymerizable unsaturated group introduced in the molecule.

  When the resin (a) is a liquid resin at 20 ° C., the photosensitive resin composition is also liquid at 20 ° C. The photosensitive resin composition of the present invention capable of obtaining good thickness accuracy and dimensional accuracy when the relief image forming original plate obtained from this is formed into a cylindrical shape, preferably has a viscosity at 20 ° C. of 10 Pa · s or more. 50 kPa · s or less. More preferably, it is 50 Pa · s or more and 10 kPa · s or less, and further preferably 100 Pa · s or more and 5 kPa · s or less. If the viscosity is 10 Pa · s or more, the mechanical strength of the produced printing original plate is sufficient, and the shape can be easily maintained and processed even when it is formed into a cylindrical printing original plate. If the viscosity is 50 kPa · s or less, it is easily deformed even at room temperature and easy to process. It is easy to form into a cylindrical printing original plate and the process is simple. In particular, in order to obtain a cylindrical printing original plate with high plate thickness accuracy, when the liquid photosensitive resin layer is formed on the cylindrical support, the photosensitive resin composition does not cause a phenomenon such as liquid dripping due to gravity. Thus, it is desirable that the photosensitive resin composition has a relatively high viscosity with a viscosity of 100 Pa · s or more, more preferably 200 Pa · s or more, and even more preferably 500 Pa · s or more. Moreover, when the photosensitive resin composition used by this invention is a liquid especially in 20 degreeC, it is preferable to have thixotropic property. By having thixotropy, a predetermined thickness can be maintained without causing dripping due to gravity, particularly when the photosensitive resin composition layer is formed on a cylindrical support.

The organic compound (b) is preferably a compound having a polymerizable unsaturated group having a number average molecular weight of less than 1,000. The number average molecular weight is preferably 1000 or less because of easy dilution with the resin (a). The definition of a polymerizable unsaturated group is a polymerizable unsaturated group that participates in a radical or addition polymerization reaction as described in the section of the resin (a).
Specific examples of the organic compound (b) include radical reactive compounds such as olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, acrylonitrile and the like. Saturated nitriles, (meth) acrylamide and derivatives thereof, aryl compounds such as aryl alcohol and aryl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof, vinyl acetates, N-vinylpyrrolidone, N-vinyl carbazole and the like can be mentioned, and (meth) acrylic acid and derivatives thereof are preferable examples from the viewpoints of abundant types, price, decomposability upon laser light irradiation, and the like. Examples of the derivative of the compound include alicyclic such as cycloalkyl-, bicycloalkyl-, cycloalkene-, bicycloalkene-, aromatic such as benzyl-, phenyl-, phenoxy-, fluorene-, alkyl-, halogen Alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl-, glycidyl-, alkylene glycol-, polyoxyalkylene glycol-, (alkyl / allyloxy) polyalkylene glycol- and trimethylolpropane Examples thereof include esters of polyhydric alcohols such as polydimethylsiloxane and compounds having a polysiloxane structure such as polydiethylsiloxane. Moreover, you may be a heteroaromatic compound containing elements, such as nitrogen and sulfur.

  In addition, as a compound having an epoxy group that undergoes a ring-opening addition reaction, a compound obtained by reacting a polyol such as various diols or triols with epichlorohydrin, an epoxy compound obtained by reacting a peracid with an ethylene bond in the molecule, etc. Can be mentioned. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, bisphenol A Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol di of compounds with addition of lenoxide or propylene oxide Examples thereof include epoxy compounds such as glycidyl ether and epoxy-modified silicone oil (trade name “HF-105” manufactured by Shin-Etsu Chemical Co., Ltd.).

In addition, a compound having an oxetane group, a cyclic ester group, a dioxirane group, a spiroorthocarbonate group, a spiroorthoester group, a bicycloorthoester group, a cyclic iminoether group or the like in the molecule is used as a compound that undergoes a ring-opening addition polymerization reaction. You can also.
In this invention, the organic compound (b) which has these polymerizable unsaturated groups can select the 1 type (s) or 2 or more types according to the objective. For example, when used as a printing plate, it has at least one long-chain aliphatic, alicyclic or aromatic derivative as an organic compound used to suppress swelling with respect to an organic solvent such as alcohol or ester which is a solvent for printing ink. Is preferred.

In order to increase the mechanical strength of the printing original plate obtained from the resin composition, the organic compound (b) preferably has at least one alicyclic or aromatic derivative. In this case, the organic compound (b) The total amount is preferably 20 wt% or more, more preferably 50 wt% or more. The aromatic derivative may be an aromatic compound having an element such as nitrogen or sulfur.
Hydrogen atom in which resin (a) or organic compound (b) is directly bonded to a sulfur atom such as thiol, a compound having a hydrogen atom that is in the α position with respect to an oxygen atom or nitrogen atom present in the molecular chain It is preferable to contain at least 20 wt% or more of the compound having a weight of the total amount of the photosensitive resin composition. More preferably, it is 40 wt% or more. Examples of the atomic group derived from the oxygen atom include alcohols, ethers, esters, and carbonates, and examples of the atomic group derived from the nitrogen atom include urethane, urea, and amide.

  The photosensitive resin composition (a) is crosslinked by irradiation with light or an electron beam to develop physical properties as a printing plate, and a photopolymerization initiator can be added at that time. The photopolymerization initiator can be selected from commonly used ones. For example, radical polymerization, cationic polymerization, and anion polymerization illustrated in “Polymer Data Handbook-Fundamentals” edited by the Society of Polymer Sciences, published in 1986 by Fufukan. An agent can be used. In addition, crosslinking by photopolymerization using a photopolymerization initiator is useful as a method for producing a printing original plate with high productivity while maintaining the storage stability of the resin composition. A well-known thing can be used. As photopolymerization initiators that induce radical polymerization reactions, hydrogen abstraction type photopolymerization initiators and decay type photopolymerization initiators are widely used as particularly effective photopolymerization initiators.

  Although it does not specifically limit as a hydrogen abstraction type photoinitiator, It is preferable to use an aromatic ketone. Aromatic ketone is efficiently converted into an excited triplet state by photoexcitation, and a chemical reaction mechanism has been proposed in which this excited triplet state generates a radical by extracting hydrogen from the surrounding medium. The generated radical is considered to be involved in the photocrosslinking reaction. Any compound can be used as the hydrogen abstraction type photopolymerization initiator used in the present invention as long as it is a compound that extracts radicals from the surrounding medium through an excited triplet state to generate radicals. Examples of aromatic ketones include benzophenones, Michler ketones, xanthenes, thioxanthones, and anthraquinones, and it is preferable to use at least one compound selected from these groups. Benzophenones refer to benzophenone or derivatives thereof, specifically 3,3 ', 4,4'-benzophenone tetracarboxylic anhydride, 3,3', 4,4'-tetramethoxybenzophenone, and the like. Michler ketones refer to Michler ketone and its derivatives. Xanthenes refer to derivatives substituted with xanthene and an alkyl group, phenyl group, or halogen group. Thioxanthones refer to thioxanthone and derivatives substituted with an alkyl group, a phenyl group, and a halogen group, and examples thereof include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone. Anthraquinones are anthraquinone and derivatives substituted with alkyl groups, phenyl groups, halogen groups, and the like. The addition amount of the hydrogen abstraction type photopolymerization initiator is desirably 0.1 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% or less of the total amount of the photosensitive resin composition. When the addition amount is within this range, when the liquid photosensitive resin composition is photocured in the air, the curability of the surface of the cured product can be sufficiently secured, and the weatherability can be secured.

  The decay type photopolymerization initiator refers to a compound in which an active radical is generated by generating a cleavage reaction in the molecule after light absorption, and is not particularly limited. Specific examples include benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, azo compounds, organic sulfur compounds, diketones, and the like. It is preferable to use at least one compound selected from the group consisting of: Examples of benzoin alkyl ethers include benzoin isopropyl ether, benzoin isobutyl ether, and compounds described in “Photosensitive polymer” (Kodansha, 1977, page 228). Examples of 2,2-dialkoxy-2-phenylacetophenones include 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-phenylacetophenone. Examples of acetophenones include acetophenone, trichloroacetophenone, 1-hydroxycyclohexylphenylacetophenone, 2,2-diethoxyacetophenone, and the like. Examples of acyl oxime esters include 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime. Examples of the azo compound include azobisisobutyronitrile, diazonium compound, and tetrazene compound. Examples of the organic sulfur compound include aromatic thiol, mono- and disulfide, thiuram sulfide, dithiocarbamate, S-acyl dithiocarbamate, thiosulfonate, sulfoxide, sulfinate, and dithiocarbonate. Examples of diketones include benzyl and methylbenzoyl formate. The addition amount of the collapsible photopolymerization initiator is desirably 0.1 wt% or more and 10 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less of the total amount of the photosensitive resin composition. If the addition amount is within this range, when the photosensitive resin composition is photocured in the air, the curability inside the cured product can be sufficiently secured.

In particular, when the liquid photosensitive resin composition is photocured in the air, it is preferable to use a combination of a hydrogen abstraction type photopolymerization initiator and a decay type photopolymerization initiator.
A compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule can also be used as the photopolymerization initiator. There may be mentioned α-aminoacetophenones. Examples thereof include 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one and compounds represented by the following general formula (6).

(In the formula, each R ₂ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X represents an alkylene group having 1 to 10 carbon atoms.)
The amount of the compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule is 0.1 wt% or more and 10 wt% of the total amount of the photosensitive resin composition. In the following, it is desirable that the content be 0.3 wt% or more and 3 wt% or less. When the addition amount is within this range, the mechanical properties of the cured product can be sufficiently ensured even when the photosensitive resin composition is photocured in the atmosphere.

A photopolymerization initiator that induces an addition polymerization reaction by absorbing light and generating an acid can also be used. For example, photocationic polymerization initiators such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, or polymerization initiators that absorb light and generate bases. The addition amount of these photopolymerization initiators is preferably in the range of 0.1 wt% to 10 wt% of the total amount of the photosensitive resin composition.
It is preferable to add an inorganic porous material to the photosensitive resin composition (a). The inorganic porous material is an inorganic particle having fine pores or fine voids in the particle, and is an additive for absorbing and removing viscous liquid debris generated in large quantities in laser engraving. Also, it has an anti-tacking effect on the plate surface. The inorganic porous material of the present invention is added for the purpose of removing viscous liquid waste, and the number average particle size, specific surface area, average pore size, pore volume, and loss on ignition greatly affect its performance. To do.

The inorganic porous body preferably has a number average particle size of 0.1 to 100 μm. When one smaller than the number average particle diameter is used, dust tends to fly when the original plate obtained from the resin composition of the present invention is engraved with a laser, and mixed with the resin (a) and the organic compound (b). Viscosity is likely to increase when performing.
On the other hand, when a larger particle than the above-mentioned number average particle size is used, the relief image tends to be defective when laser engraving. A more preferable range of the average particle diameter is 0.5 to 20 μm, and a further preferable range is 3 to 10 μm. The average particle size of the porous inorganic absorbent of the present invention is a value measured using a laser scattering type particle size distribution measuring device.

The range of the specific surface area of the inorganic porous body is preferably 10 m ² / g or more and 1500 m ² / g or less. A more preferable range is 100 m ² / g or more and 800 m ² / g or less. When the specific surface area is 10 m ² / g or more, removal of the liquid residue during laser engraving is sufficient, and when the specific surface area is 1500 m ² / g or less, an increase in the viscosity of the photosensitive resin composition is suppressed, and thixotropic properties are obtained. Can be suppressed. The specific surface area of this invention is calculated | required based on a BET type | formula from the adsorption isotherm of nitrogen in -196 degreeC.

  The average pore diameter of the inorganic porous material has a great influence on the amount of liquid residue absorbed during laser engraving. A preferable range of the average pore diameter is 1 nm to 1000 nm, more preferably 2 nm to 200 nm, and still more preferably 2 nm to 50 nm. If the average pore diameter is 1 nm or more, the absorbability of liquid debris generated during laser engraving can be ensured, and if it is 1000 nm or less, the specific surface area of the particles is large and the amount of liquid debris absorbed can be sufficiently ensured. When the average pore diameter is less than 1 nm, the reason why the amount of absorbed liquid debris is small is not clear, but because liquid debris is viscous, it is estimated that it is difficult to enter the micropores and the amount of absorption is small. doing.

The average pore diameter referred to in the present invention is a value measured using a nitrogen adsorption method. Those having an average pore diameter of 2 to 50 nm are particularly called mesopores, and the ability of porous particles having mesopores to absorb liquid waste is extremely high. The pore size distribution of the present invention is determined from the nitrogen adsorption isotherm at -196 ° C.
The pore volume of the inorganic porous material is preferably from 0.1 ml / g to 10 ml / g, more preferably from 0.2 ml / g to 5 ml / g. When the pore volume is 0.1 m / g or more, the amount of viscous liquid residue absorbed is sufficient, and when it is 10 ml / g or less, the mechanical strength of the particles can be ensured. In the present invention, a nitrogen adsorption method is used to measure the pore volume. The pore volume of the present invention is determined from an adsorption isotherm of nitrogen at −196 ° C.

There is an oil absorption amount as an index for evaluating the liquid residue adsorption amount. This is defined by the amount of oil absorbed by 100 g of the inorganic porous body. The preferred range of oil absorption of the inorganic porous material used in the present invention is 10 ml / 100 g or more and 2000 ml / 100 g or less, 50 ml / 100 g or more and 1000 ml / 100 g or less. If the oil absorption is 10 ml / 100 g or more, removal of the liquid residue generated during laser engraving is sufficient, and if it is 2000 ml / 100 g or less, the mechanical strength of the inorganic porous body can be sufficiently secured. The oil absorption was measured according to JIS-K5101.
The inorganic porous material used in the present invention preferably retains its porosity without being deformed or melted by irradiation with laser light in the infrared wavelength region. The loss on ignition when treated at 950 ° C. for 2 hours is preferably 15 wt% or less, more preferably 10 wt% or less.

  The particle shape of the inorganic porous material is not particularly limited, and spherical, flat, needle-shaped, amorphous, or particles having protrusions on the surface can be used. In particular, spherical particles are preferable from the viewpoint of wear resistance. It is also possible to use particles having hollow inside particles, spherical granules having a uniform pore diameter such as silica sponge, and the like. Although not particularly limited, for example, porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, porous glass and the like can be mentioned. Moreover, since the pore diameter cannot be defined for a layer having a gap of several to 100 nm such as a layered clay compound, in the present invention, the gap between the layers is defined as the pore diameter.

Furthermore, organic pigments such as pigments and dyes that absorb light of the wavelength of the laser beam can be incorporated into these pores or voids.
Sphericality is defined as an index that defines spherical particles. The sphericity used in the present invention is the ratio (D ₁ / D) of the maximum value D ₁ of the circle that completely enters the projection figure when the particle is projected to the minimum value D ₂ of the circle that completely enters the projection figure. ₂ ). In the case of a true sphere, the sphericity is 1.0. The sphericity of preferred spherical particles used in the present invention is preferably 0.5 or more and 1.0 or less, more preferably 0.7 or more and 1.0 or less. If it is 0.5 or more, the wear resistance as a printing plate is good. The sphericity of 1.0 is an upper limit value of sphericity. As spherical particles, it is desirable that 70% or more, more preferably 90% or more of the particles have a sphericity of 0.5 or more. As a method of measuring the sphericity, a method of measuring based on a photograph taken using a scanning electron microscope can be used. At that time, it is preferable to take a picture at a magnification at which at least 100 particles enter the monitor screen. The D ₁ and D ₂ are measured based on a photograph, but it is preferable to process the photograph using a digitizing device such as a scanner and then process the data using image analysis software.

Moreover, the surface of the inorganic porous body can be coated with a silane coupling agent, a titanium coupling agent, or other organic compounds, and subjected to a surface modification treatment to make particles more hydrophilic or hydrophobic.
In the present invention, one or two or more of these inorganic porous materials can be selected, and by adding the inorganic porous material, generation of liquid debris during laser engraving, prevention of tacking of the relief printing plate, etc. Improvements are made effectively.
The ratio of the resin (a), the organic compound (b), and the inorganic porous body) in the photosensitive resin composition (a) is usually 5 for the organic compound (b) with respect to 100 parts by weight of the resin (a). -200 weight part is preferable and the range of 20-100 weight part is more preferable. The inorganic porous body is preferably 1 to 100 parts by weight, and more preferably 2 to 50 parts by weight. A more preferable range is 2 to 20 parts by weight.

When the ratio of the organic compound (b) is smaller than the above range, it may be difficult to balance the hardness and tensile strength / elongation of the obtained printing plate and the like. Shrinkage tends to increase.
When the amount of the inorganic porous material is smaller than the above range, depending on the types of the resin (a) and the organic compound (b), the effect of suppressing the generation of engraving liquid debris when laser engraving is sufficient. In some cases, the printing plate is not exhibited, and when it is larger than the above range, the printing plate tends to be brittle. Further, the transparency may be impaired, and particularly when used as a flexographic plate, the hardness may become too high. When a photosensitive resin composition is cured using light, particularly ultraviolet rays, to prepare a laser engraving printing original plate, light transmittance affects the curing reaction. Therefore, it is effective to use a material having a refractive index close to that of the photosensitive resin composition.

As a method of mixing the inorganic porous material in the photosensitive resin composition (a), a method of directly adding the inorganic porous material in a state where the thermoplastic resin is heated and fluidized, or photopolymerization with the thermoplastic resin. Any method may be used in which the inorganic porous material is added to the first kneaded organic organic compound (b).
In addition, a polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the resin composition depending on the application and purpose.

  The laser-engravable cylindrical printing original plate of the present invention is formed by photocrosslinking and curing a photosensitive resin composition. Therefore, a three-dimensional crosslinked structure is formed by the reaction between the polymerizable unsaturated groups of the organic compound (b) or the polymerizable unsaturated group of the resin (a) and the polymerizable unsaturated group of the organic compound (b). Insolubilizes in commonly used ester, ketone, aromatic, ether, alcohol and halogen solvents. This reaction occurs between the organic compounds (b), between the resins (a), or between the resin (a) and the organic compound (b), and the polymerizable unsaturated group is consumed. In addition, when the photopolymerization initiator is used for crosslinking and curing, the photopolymerization initiator is decomposed by light. Therefore, the cross-linked cured product is extracted with a solvent, and mass-separated by GC-MS (gas chromatography). Analysis method), LC-MS method (method for mass spectrometry of those separated by liquid chromatography), GPC-MS method (method for separation and mass spectrometry by gel permeation chromatography), LC-NMR method (liquid chromatography) By analyzing using the method of analyzing the product separated in (1) by nuclear magnetic resonance spectrum, unreacted photopolymerization initiator and decomposition products can be identified. Furthermore, by using the GPC-MS method, LC-MS method, and GPC-NMR method, the unreacted polymer, the unreacted organic compound (b), and the polymerizable unsaturated group in the solvent extract are reacted. The resulting relatively low molecular weight product can also be identified from analysis of the solvent extract. For the high molecular weight component insoluble in the solvent in which the three-dimensional cross-linked structure is formed, by using the pyrolysis GC-MS method, the site formed by the reaction of the polymerizable unsaturated group is formed as a component constituting the high molecular weight body. It is possible to verify whether it exists. For example, it can be estimated from the mass spectrometry spectrum pattern that there is a site where a polymerizable unsaturated group such as a methacrylate group, an acrylate group, or a vinyl group has reacted. The pyrolysis GC-MS method is a method in which a sample is thermally decomposed and a generated gas component is separated by gas chromatography and then mass spectrometry is performed. The decomposition product derived from the photopolymerization initiator and the unreacted photopolymerization initiator are detected together with the unreacted polymerizable unsaturated group or the site obtained by the reaction of the polymerizable unsaturated group in the crosslinked cured product. Then, it can be concluded that the photosensitive resin composition was obtained by photocrosslinking and curing.

Identification of the organosilicon compound present in the photosensitive resin composition or in the photocrosslinked cured product can be made by making full use of the various analytical methods described above.
Further, the amount of the inorganic porous fine particles present in the photosensitive resin cured product can be obtained by heating the crosslinked cured product in the air to burn off the organic component and measuring the weight of the residue. it can. In addition, the presence of inorganic porous fine particles in the residue is due to morphological observation with a field emission type high resolution scanning electron microscope, particle size distribution with a laser scattering type particle size distribution measuring device, and nitrogen adsorption method. It can be identified from the measurement of pore volume, pore diameter distribution and specific surface area.

  As a method for molding the photosensitive resin resin composition of the present invention into a cylindrical shape, an existing resin molding method can be used. For example, a casting method, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, or adjusting the thickness by calendering with a roll can be exemplified. In that case, it is also possible to perform the molding while heating within a range that does not deteriorate the performance of the resin. Moreover, you may perform a rolling process, a grinding process, etc. as needed. A cylinder of a printing press can also be used as the cylindrical support. In view of ease of handling, it is preferable to use a cylindrical support made of fiber reinforced plastic (FRP), plastic or metal. The cylindrical support can be hollow with a constant thickness for weight reduction. The role of the cylindrical support is to ensure the dimensional stability of the printing original plate. Therefore, it is necessary to select one having high dimensional stability. When evaluated using the linear thermal expansion coefficient, the upper limit value of a preferable material is 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less. Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used. For example, a sheet or the like in which layers of polyethylene terephthalate having a thickness of 50 μm are laminated on both surfaces of a 4.5 μm thick wholly aromatic polyamide film may be used. In addition, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as a back film. When a porous sheet is used as the back film, the photosensitive resin cured product layer is integrated with the back film by photocuring after impregnating the photosensitive resin composition into the pores, so that high adhesion is obtained. be able to. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, natural materials such as cotton and hemp Examples thereof include semi-synthetic fibers such as fibers, rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.

  Examples of a method for reducing the linear thermal expansion coefficient of the cylindrical support include a method of adding a filler, a method of impregnating or coating a resin on a mesh cloth such as wholly aromatic polyamide, or a glass cloth. it can. As the filler, generally used organic fine particles, inorganic fine particles such as metal oxide or metal, organic / inorganic composite fine particles, and the like can be used. In addition, porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular compound intercalates can be used. In particular, metal oxide fine particles such as alumina, silica, titanium oxide, and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, natural product-based organic fine particles such as highly crystalline cellulose, and the like are useful.

  By performing physical and chemical treatment on the surface of the cylindrical support used in the present invention, the adhesiveness with the photosensitive resin composition layer or the adhesive layer can be improved. Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidant treatment method, a coupling agent treatment method, and the like.

A method of forming a printing original plate by crosslinking the molded photosensitive resin composition layer by light irradiation is simple. Further, it can be crosslinked by light irradiation while molding. Examples of the light source used for curing include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The light applied to the photosensitive resin composition layer preferably has a wavelength of 200 nm to 450 nm. In particular, many hydrogen abstraction type photopolymerization initiators have strong light absorption in the wavelength region of 200 nm to 300 nm. Therefore, when the light has a wavelength of 200 nm to 300 nm, the surface of the photosensitive resin cured product layer has sufficient curability. Can be secured. Although the light source used for curing may be one type, the curability of the resin may be improved by curing using two or more types of light sources having different wavelengths, so two or more types of light sources may be used. There is no problem. Moreover, the thing with the high illumination intensity of the light in the photosensitive resin composition layer surface is preferable. The illuminance on the surface of the photosensitive resin composition layer was measured using a UV meter (Oak Manufacturing Co., Ltd., trademark “UV-M02”) and a filter (Oak Manufacturing Co., Ltd., trademark “UV-35-APR filter”). If it is 20 mW / cm ² or more, the UV meter and a filter (ORC Manufacturing Co., Ltd., trademark "UV-25 filter") when measured using a is preferably 5 mW / cm ² or more. By using such a light source with illuminance, not only can it be photocured in a short time, but there is also an effect that the amount of unreacted polymerizable unsaturated groups can be reduced.

  The thickness of the original plate used for laser engraving may be arbitrarily set according to the purpose of use. When used as a gravure printing plate or an anilox roll, the depth of the concave pattern formed by irradiating a laser beam is generally in the range of 5 μm to 50 μm. A deeper concave pattern may be formed partially. In some cases, a plurality of materials having different compositions may be laminated. For example, a layer that can be engraved using a laser having an oscillation wavelength in the near infrared region such as a YAG laser, a fiber laser, or a semiconductor laser is formed on the outermost surface, and an infrared laser such as a carbon dioxide laser or the like is formed under the layer. It is also possible to form a layer capable of laser engraving using a visible / ultraviolet laser. By forming such a laminated structure, a relatively high-power carbon dioxide laser is used to deeply engrave a relatively rough pattern, and a very fine pattern near the surface is used using a near-infrared laser such as a YAG laser or fiber laser. Can be engraved. Since an extremely fine pattern may be engraved relatively shallowly, the thickness of the layer sensitive to the near infrared laser is preferably in the range of 5 μm to 0.5 mm. Thus, by laminating a layer sensitive to the near infrared laser and a layer sensitive to the infrared laser, the depth of the pattern engraved using the near infrared laser can be accurately controlled. This is because a layer that is sensitive to an infrared laser utilizes a phenomenon that is difficult to engrave with a near infrared laser. The difference in the fineness of the engraving pattern is caused by the difference in the oscillation wavelength inherent to the laser device, that is, the difference in the diameter of the laser beam that can be narrowed. When laser engraving is performed in this way, engraving can be performed using separate laser engraving equipment equipped with infrared laser and near infrared laser, and laser engraving equipment equipped with both infrared laser and near infrared laser can be used. It is also possible to use.

  The wettability of the surface of the laser engraving printing original plate of the present invention is an extremely important factor in ink acceptance and transfer. In the surface wettability evaluation carried out at a temperature of 25 ° C., 20 μl of an indicator liquid having a surface energy of 30 mN / m was dropped on the surface of the laser engraving printing original plate, and after 30 seconds, the droplet spread. When the maximum diameter is measured, the diameter of the droplet is preferably 4 mm or more and 20 mm or less. A more preferable range is 5 mm or more and 15 mm or less. In many cases, the indicator liquid spreads concentrically, but depending on the state of the original surface, the concentric circle may not necessarily spread. In that case, the minimum value of the diameter of the circle in which the expanded portion completely enters is defined as the maximum diameter of the expanded portion of the indicator droplet. If the maximum diameter of the portion where the droplets are wide is in the range of 4 mm or more and 20 mm or less, the printed matter does not become non-uniform by repelling the ink, and the ink remaining on the plate surface is suppressed.

  In the present invention, a peripheral length adjusting layer for adjusting the peripheral length of the printing plate can be formed below the photosensitive resin cured product layer (A) capable of laser engraving. The resin used as the circumference adjustment layer may be any of a thermoplastic resin, a thermosetting resin, and a photosensitive resin. From the viewpoint of easy formation of the circumference adjusting layer, the photosensitive resin cured product layer (B) obtained by photocuring the photosensitive resin composition is particularly preferable. The photosensitive resin composition used for forming the circumference adjusting layer is preferably a liquid photosensitive resin composition at 20 ° C. from the viewpoint of moldability. In particular, a composition that can be cured in the air is desirable in order to simplify the structure of the apparatus. The photosensitive resin composition for forming the photosensitive resin cured product layer (B) has the same composition as the photosensitive resin composition (A) for forming the photosensitive resin cured product layer (A). May be different. It is preferable that the Shore D hardness of the photosensitive resin cured product layer (B) is also not less than 30 degrees and not more than 100 degrees so as not to be deformed when the surface of the cylindrical printing substrate comes into contact with the doctor blade. A more preferable range of Shore D hardness is 40 degrees or more and 100 degrees or less.

Furthermore, since the weight increases when the circumferential length adjusting layer becomes thick, bubbles can be included in the circumferential length adjusting layer to reduce the weight.
Further, by forming a modified layer on the surface of the laser engraving printing plate of the present invention, the tack of the printing plate surface can be reduced and the ink wettability can be improved. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles.
A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one of these functional groups exists in the molecule, and is immobilized on the surface of the base material by reacting with the surface hydroxyl group of the base material. Further, the compound constituting the silane coupling agent of the present invention is selected from acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule. Those having at least one functional group or those having a long-chain alkyl group can be used.

Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (octylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyl Dimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate Over DOO, isopropyl tri (dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) may include compounds such as titanates.
When the coupling agent molecule immobilized on the surface has a polymerizable reactive group in particular, it is possible to obtain a stronger coating by irradiating light, heat, or an electron beam and crosslinking after immobilization on the surface. .

In the present invention, the above-described coupling agent is diluted with water-alcohol or acetic acid water-alcohol mixed solution as necessary. The concentration of the coupling agent in the treatment liquid is preferably 0.05 to 10.0% by weight.
The coupling agent treatment method in the present invention will be described. The treatment liquid containing the coupling agent is applied to the printing original plate or the surface of the printing plate after laser engraving. The method for applying the coupling agent treatment liquid is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, or a brush coating method can be applied. Further, the coating treatment temperature and the coating treatment time are not particularly limited, but are preferably 5 to 60 ° C., and the treatment time is preferably 0.1 to 60 seconds. Furthermore, it is preferable to dry the treatment liquid layer on the surface of the resin plate under heating, and the heating temperature is preferably 50 to 150 ° C.
Before treating the printing plate surface with a coupling agent, a method of irradiating light in a vacuum ultraviolet region with a wavelength of 200 nm or less such as a xenon excimer lamp, or by exposing it to a high energy atmosphere such as plasma, a hydroxyl group on the printing plate surface. And the coupling agent can be immobilized at a high density.

  In addition, when the layer containing inorganic porous particles is exposed on the printing plate surface, it is treated in a high-energy atmosphere such as plasma, and the organic layer on the surface is slightly etched away to remove minute particles on the printing plate surface. Unevenness can be formed. By this treatment, the effect of improving the ink wettability can be expected by reducing the tack of the printing plate surface and making the inorganic porous particles exposed on the surface easy to absorb the ink.

  In laser engraving, a relief image is created on an original by operating a laser device using a computer as an image to be formed as digital data. Any laser may be used for the laser engraving as long as the original plate includes a wavelength having absorption, but in order to perform engraving at a high speed, a laser with a high output is desirable. Infrared or infrared emitting solid lasers such as YAG lasers and semiconductor lasers are preferred. In addition, the second harmonic of a YAG laser having an oscillation wavelength in the visible light region, a copper vapor laser, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, and a YAG laser wavelength-converted to the third or fourth harmonic are It can be ablated by cutting the bonds of organic molecules and is suitable for fine processing. The laser may be continuous irradiation or pulse irradiation. In general, resin has absorption in the vicinity of 10 μm of carbon dioxide laser, so it is not essential to add a component that helps the absorption of laser light, but YAG laser has a wavelength in the vicinity of 1.06 μm. There is not much that has. In that case, it is preferable to add a dye or a pigment, which is a component that assists in the absorption thereof.

  Examples of such dyes include poly (substituted) phthalocyanine compounds and metal-containing phthalocyanine compounds; cyanine compounds; squarylium dyes; chalcogenopyrylarylidene dyes; chloronium dyes; Indolizine dyes; bis (aminoaryl) polymethine dyes; merocyanine dyes; and quinoid dyes. Examples of pigments include carbon black, graphite, copper chromite, chromium oxide, cobalt chrome aluminate, dark inorganic pigments such as copper oxide and iron oxide, and metal powders such as iron, aluminum, copper and zinc, and these metals And those doped with Si, Mg, P, Co, Ni, Y or the like. These dyes and pigments may be used alone, in combination of a plurality, or in any form such as a multilayer structure. However, in the case of a system in which the photosensitive resin composition is cured using light, the amount of the organic / inorganic compound that absorbs a large amount of light at the wavelength of light used for curing should be within a range that does not hinder the photocurability. The addition ratio with respect to the total amount of the photosensitive resin composition is preferably 5 wt% or less, more preferably 2 wt% or less.

Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out in the presence of carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed with an appropriate method such as water containing a solvent or a surfactant, or a water-based cleaning agent is irradiated by a high-pressure spray or the like. Alternatively, it may be removed using a method of irradiating high-pressure steam.
In the present invention, when the laser engraving printing original plate is irradiated with laser light to form a concave pattern, the laser engraving printing original plate surface can be heated to assist laser engraving. Examples of the heating method of the laser engraving printing original plate include a method of heating a sheet or cylindrical surface plate of a laser engraving machine using a heater, and a method of directly heating the surface of the laser engraving printing original plate using an infrared heater. Can do. The laser engraving property can be improved by this heating step. The degree of heating is desirably in the range of 50 ° C. to 200 ° C., more preferably in the range of 80 ° C. to 200 ° C., and still more preferably in the range of 100 ° C. to 200 ° C.

  In the present invention, after engraving to form a concave pattern by irradiating a laser beam, following the step of removing powdery or viscous liquid residue remaining on the plate surface, the surface of the printing plate on which the pattern is formed has a wavelength of 200 nm to 450 nm. Post-exposure can be performed by irradiating light. This is an effective method for removing tack on the surface. The post-exposure may be performed in any environment such as air, inert gas atmosphere, and water. This is particularly effective when the photosensitive resin composition used contains a hydrogen abstraction type photopolymerization initiator. Furthermore, before the post-exposure step, the printing plate surface may be exposed to a treatment liquid containing a hydrogen abstraction type photopolymerization initiator. Moreover, you may expose in the state which immersed the printing plate in the process liquid containing a hydrogen abstraction type photoinitiator.

  The cylindrical printing substrate of the present invention can also have a hard coat layer formed on the surface before forming the concave pattern by laser engraving or after forming the concave pattern. The hard coat layer can be formed using a generally available hard coat material, but as a method of forming a particularly thin and uniform hard coat layer, a photocurable material is formed by a spray method, Thereafter, a method of photocuring by irradiating ultraviolet rays or the like is preferable. Moreover, as a preferable material that can be used, a material using a ring-opening addition polymerization reaction such as an epoxy resin or an oxetane resin containing nanoparticles can be used.

  Furthermore, the surface on which the concave pattern is formed can be thinly coated with a metal having high hardness such as chromium or titanium. As a coating method, a metal is chemically or electrochemically applied by a thin film formation technique such as a vacuum deposition method, an ion plating method, a sputtering method, an electroless plating method, a combination of an electroless plating method and an electrolytic plating method, or the like. The method of making it precipitate can be mentioned. In the electroless plating method, it is necessary that metal fine particles such as palladium serving as a catalyst exist on the surface. Therefore, it is preferable to perform a pretreatment by thinly applying a resin containing palladium fine particles. In order to expose the palladium fine particles on the surface, it is also effective to partially remove the resin on the surface by plasma treatment, a method of irradiating light in the vacuum ultraviolet region, or the like.

  The printing original plate of the present invention is a relief image for a printing plate, a stamp / stamp, a design roll for embossing, a relief image for patterning an insulator, a resistor, and a conductor paste used for creating an electronic component, and a reflection of an optical component. Pattern formation of functional materials such as prevention films, color filters, (near) infrared absorption filters, alignment films, underlayers, light-emitting layers, electron transport layers, sealing in the manufacture of display elements such as liquid crystal displays or organic electroluminescence displays It can be applied and used for various applications such as coating film / pattern formation of agent layers, relief images for mold materials of ceramic products, relief images for displays such as advertisements and display boards, and prototypes / mother molds of various molded products.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by these.
(1) Laser engraving Laser engraving was performed using a carbon dioxide laser engraving machine (trademark: ZED-mini-1000, UK, manufactured by ZED, USA, coherent, equipped with an output 250 W carbon dioxide laser). The engraving was performed by creating a pattern including halftone dots (250 lines per inch, area ratio 50%) and 500 μm wide white lines. The engraving depth was 20 μm.
(2) Shape of halftone dot portion The shape of the halftone dot portion having an area ratio of about 10% at 80 lpi (Lines per inch) among the engraved portions was observed with an electron microscope at a magnification of 200 to 500 times. In the case where the halftone dot is conical or pseudo-conical (a divergent shape obtained by cutting the vicinity of the apex of the cone with a plane parallel to the bottom of the cone), the printing plate is good.

(3) Pore volume, average pore diameter, and specific surface area of porous body and nonporous body Take 2 g of porous body or nonporous body into a sample tube, and conditions of 150 ° C. and 1.3 Pa or less with a pretreatment device And dried under reduced pressure for 12 hours. The pore volume, average pore diameter, and specific surface area of the dried porous body or non-porous body were measured by adsorbing nitrogen gas in a liquid nitrogen temperature atmosphere using Autosoap 3MP (trademark) manufactured by Cantachrome, USA. Measured. Specifically, the specific surface area was calculated based on the BET equation. The pore volume and average pore diameter were calculated based on a pore distribution analysis method called BJH (Brrett-Joyner-Halenda) method, assuming a cylindrical model from the adsorption isotherm at the time of nitrogen desorption.

(4) Loss on ignition of porous body and nonporous body Record the weight of the porous body or nonporous body for measurement. Next, the measurement sample was placed in a high-temperature electric furnace (FG31 type; manufactured by Yamato Kagaku Co., Ltd., Japan) and treated for 2 hours in an air atmosphere at 950 ° C. The change in weight after treatment was defined as loss on ignition.
(5) Average particle diameter of porous body and nonporous body The particle diameter distribution of the porous body and nonporous body was measured by a laser diffraction particle size distribution measuring device (SALD-2000J type; manufactured by Shimadzu Corporation, Japan). ). According to the specification of the apparatus, it is described in the catalog that a particle size range from 0.03 μm to 500 μm can be measured. Methyl alcohol was used as a dispersion medium, and ultrasonic waves were applied for about 2 minutes to disperse the particles to prepare a measurement solution.

(6) Viscosity The viscosity of the photosensitive resin composition was measured at 20 ° C. using a B-type viscometer (B8H type; manufactured by Tokyo Keiki Co., Ltd., Japan).
(7) Taper abrasion test The taper abrasion test was carried out in accordance with JIS-K6264 by separately producing a printing original plate having a thickness of 2.8 mm. The load applied to the test piece was 4.9 N, the rotational speed of the rotating disk was 60 ± 2 times per minute, the number of tests was 1000 times continuously, and the amount of wear after the test was measured. The area of the test part was 31.45 cm ² . In an excellent printing plate, the wear amount is 80 mg or less (2.5 mg / cm ² or less). If the wear amount is small, the printing plate can be used for a long period of time, and a high-quality printed matter can be provided. it can.

(8) Surface Friction Resistance Measurement A printing original plate having a thickness of 2.8 mm was separately prepared, and a surface friction resistance value μ was measured using a friction measuring machine (TR type: manufactured by Toyo Seiki Seisakusho, Japan). The weight placed on the sample surface was 63.5 mm square and the weight W was 200 g, and the pulling speed of the weight was 150 mm / min. Also, liner paper (not including recycled paper and made of pure pulp, 220 μm thick paper used for corrugated board, trade name “White Liner”, manufactured by Oji Paper Co., Ltd., Japan) is used on the surface of the weight. , Use the one that is pasted so that the smooth surface is exposed on the surface, the liner paper exists between the printing original plate and the weight, and the printing original plate surface and the smooth surface of the liner paper are in contact, The surface friction resistance value μ was measured by moving horizontally. The surface friction resistance value μ is a ratio of the measured load Fd to the weight of the weight, that is, a dynamic friction coefficient expressed by μ = Fd / W, and is a dimensionless number. A region where the measured value is stabilized after starting to move the weight, that is, an average value of the measured load from 5 mm to 30 mm is defined as Fd. A printing plate having a small surface frictional resistance value μ is preferable. In an excellent printing plate, the surface friction resistance value μ is 2.5 or less, and when the surface friction resistance value μ is small, there is little adhesion of paper dust to the printing plate surface during printing, and a high-quality printed matter can be obtained. Can do. When the surface friction resistance value μ is larger than 4, a phenomenon that paper dust adheres to the printing plate surface when printing on paper such as corrugated cardboard is observed. Frequently, the ink is not transferred to the top and causes defects.

(9) Measurement of number average molecular weight The number average molecular weights of the resin (a) and the organosilicon compound (c) were determined by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC device (HLC-8020 manufactured by Tosoh Corporation, Japan) and a polystyrene-filled column (trademark: TSKgel GMHXL; manufactured by Tosoh Corporation, Japan), the measurement was performed with tetrahydrofuran (THF). The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a THF solution having a resin concentration of 1 wt% was prepared, and the injection amount was 10 μl. As the detector, for the resin (a), an ultraviolet absorption detector was used, and 254 nm light was used as monitor light. The organosilicon compound (c) was detected using a parallax refractometer. Since the resin (a) and the organosilicon compound (c) used in the examples or comparative examples of the present invention had a polydispersity (Mw / Mn) determined by the GPC method of greater than 1.1. The number average molecular weight Mn obtained by the GPC method was employed.

(10) Measurement of the number of polymerizable unsaturated groups The average number of polymerizable unsaturated groups present in the molecule of the synthesized resin (a) was obtained by removing unreacted low-molecular components using liquid chromatography. Thereafter, molecular structure analysis was performed using a nuclear magnetic resonance spectrum method (NMR method).
(11) Printing evaluation Printing evaluation was carried out using a printing plate in which a pattern was formed by laser engraving on a printing original plate separately formed into a sheet. For printing, a desktop proofing machine (trademark “Flexiproof 100” manufactured by RK Print Coat Instruments, UK) is used. The printing plate is pasted onto the plate cylinder using double-sided tape, and cyan water-based ink is applied. Used to print on a coated paper sheet-fed. In a state where an excessive pressure is applied between the anilox roll and the plate cylinder (from a state where ink is uniformly transferred to the plate, a pressure of 0.08 mm is applied), and the plate cylinder and the impression cylinder Was set to 0.15 mm, and when 10 sheets were printed, the remaining ink remaining on the plate surface was visually observed.

(12) Wetting test of printing original plate The wettability test on the surface of laser engraving printing original plate was performed using an indicator having a surface energy of 30 mN / m (made by Wako Pure Chemical Industries, Ltd., trademark “mixture No. 30.0 for wet tension test”) at 20 μm. One drop of liter is dropped on the surface of the laser engraving printing original plate, and after 30 seconds, the maximum diameter of the portion where the droplet spreads is measured, and this value is used as an indicator of the wettability test. It means that it is easy to get wet with this indicator, so that this value is large. A suitable laser engraving master has a value of 4 mm or more and 20 mm or less.
(13) Measurement of Shore D Hardness The Shore D hardness of the cured photosensitive resin layer was measured using a trademark “GS-720G Type D” manufactured by Teclock Corporation. The Shore D hardness of the cured photosensitive resin layer formed on the cylindrical support was measured while still in a cylindrical shape. The weight of the weight used for the measurement was 8 kg.

(Production Example 1)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDL L4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate After adding 30.83 g and reacting at 80 ° C. for about 3 hours, 14.83 g of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours, and the terminal was a methacrylic group (intramolecular polymerization). A resin (A) having a number average molecular weight of about 10,000 having an average of about 2 unsaturated unsaturated groups per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 2)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDL L4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate After adding 30.83 g and reacting at 80 ° C. for about 3 hours, adding 7.42 g of 2-methacryloyloxyisocyanate and further reacting for about 3 hours, the terminal is a methacrylic group (intramolecular polymerization). A resin (I) having a number average molecular weight of about 10,000 having an average of about 1 unsaturated unsaturated group per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 3)
To a 1 L separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 500 g of polytetramethylene glycol (number average molecular weight 1830, OH number 61.3) manufactured by Asahi Kasei Co., Ltd. and 52.40 g of tolylene diisocyanate were added and heated to 60 ° C. After reacting for about 3 hours under temperature, 6.2 g of 2-hydroxypropyl methacrylate and 7.9 g of polypropylene glycol monomethacrylate (Mn400) were added and reacted for another 2 hours, and then 20 g of ethanol was added for another 2 hours. Reacted. A resin (c) having a number average molecular weight of about 20000 having a terminal methacrylic group (an average of 0.5 polymerizable unsaturated groups per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Examples 1-4)
As the liquid resin (a) at 20 ° C., the resins (a) to (c) prepared in Production Examples 1 to 3 were used, and as shown in Table 1, the organic compound (b), the organic silicon compound (c), and the inorganic A resin composition was prepared by adding a porous material, a photopolymerization initiator, and other additives.
As the organic silicon compound (c) used, Shin-Etsu Chemical Co., Ltd., methylstyryl-modified silicone oil (trademark “KF-410”, refractive index: 1.480, number average molecular weight: 7890 and 700 has two peaks. Since it was 4.3: 1, it was distributed in an area ratio, and the number average molecular weight was 6530. Liquid at 20 ° C.), carbinol-modified silicone oil (trademark “KF-160AS”, refractive index: 1.420, number average molecular weight: 750, liquid at 20 ° C.). These compounds are silicone compounds having no polymerizable unsaturated group in the molecule.

In addition, as an inorganic porous material, a trade name “Pyrospher C-1504” (hereinafter abbreviated as C-1504, number average particle diameter 4.5 μm, specific surface area), which is a porous fine powder silica manufactured by Fuji Silysia Chemical Co., Ltd. 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g). The porosity of the porous fine powder silica used was 780 when calculated with a density of 2 g / cm ³ . When the sphericity of Pyrospher C-1504, which was added porous spherical silica, was observed using a scanning electron microscope, almost all of the particles were 0.9 or more.

On the cylindrical support made of glass fiber reinforced plastic having an inner diameter of 213.384 mm, a width of 300 mm, and a thickness of 2.00 mm mounted on an air cylinder, the adjusted photosensitive resin composition was applied using a doctor blade, While rotating the air cylinder at a speed of 0.2 revolutions per second, the light emitted from the opening (opening size: 40 mm × 310 mm) of the metal halide lamp (trade name “M056-L21” manufactured by Eye Graphics) The photosensitive resin composition was irradiated in the atmosphere to form a cured photosensitive resin layer. The amount of energy irradiated was 4000 mJ / cm ² (a value obtained by integrating the illuminance measured with the UV-35-APR filter over time). The lamp illuminance on the irradiated surface was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.). The lamp illuminance measured using the trademark “UV-35-APR filter” (manufactured by Oak Manufacturing Co., Ltd.) is 100 mW / cm ² , and the lamp measured using the trademark “UV-25 filter” (manufactured by Oak Manufacturing Co., Ltd.) The illuminance was 14 mW / cm ² . After adjusting the film thickness of the obtained photosensitive resin cured product layer, cutting with a super hard tool so that the circumference of the cylindrical printing substrate becomes 700 mm, roughing with a grinder, and then a fine grindstone on the surface A cylindrical printing substrate was produced by precision polishing using a film with a mark.

As for the photoinitiator used, benzophenone (BP) was a hydrogen abstraction type photoinitiator (d), and 2,2-dimethoxy-2-phenylacetophenone (DMPAP) was a decay type photoinitiator.
The photosensitive resin compositions of Examples 1 to 4 were all liquid at 20 ° C. The viscosity measured using a B-type viscometer was 100 Pa · s or more and 5 kPa · s or less in any system at 20 ° C.
These were engraved with a pattern using a carbon dioxide laser engraving machine manufactured by ZED. As a result of observing the obtained concave pattern with a scanning electron microscope, it was a good pattern with no residue remaining in the engraving portion.

In Examples 1 to 4, both the surface friction resistance value and the wear amount were low. The surface friction resistance values were all less than 1. The amount of wear was 0.5 mg / cm ² or less for all systems. Furthermore, as a result of the wettability test, in Examples 1 to 4, the spread of the indicator was in the range of 4 mm to 20 mm. Separately, a sheet-like sample having a thickness of 1.7 mm was formed, and the ink remaining on the plate surface was evaluated. As a result, no ink residue was observed at the halftone dots.
In addition, the gravure ink is filled in the concave portion on the surface of the cylindrical printing substrate obtained in Examples 1 to 4, and after removing the ink adhered to the surface other than the concave portion using a plastic squeegee, the coated paper is formed into a cylindrical shape. The ink was transferred by pressing against the surface of the printing substrate to obtain a printed pattern on the coated paper. Furthermore, after mounting the cylindrical printing base material obtained in Examples 1 to 4 on an air cylinder and applying gravure ink to the surface, the cylindrical printing base material was rotated for 2 minutes under the condition that the rotational speed was 100 times per minute. A plastic squeegee was brought into contact with the surface while rotating. As a result, no large scratch was found on the surface of the cylindrical printing substrate.

In addition, a sheet-like printing substrate having a thickness of 2.8 mm was separately prepared, and a taper abrasion test was performed. As a result, in the sheet-like printing substrate formed by photocuring the photosensitive resin compositions of Examples 1 to 3, the wear amount was 0.5 mg / cm ² or less in all cases.
The Shore D hardness of the cylindrical printing original plate obtained in Examples 1 to 4 showed a large value exceeding 30 degrees.
Among the polymerizable unsaturated group-containing organic compounds used in the examples of the present invention, the aromatic derivative is phenoxyethyl methacrylate (PEMA).

(Example 5)
A cylindrical support was formed by attaching a double-sided adhesive tape on a fiber reinforced plastic sleeve having an inner diameter of 213 mm and a thickness of 2 mm, and a PET film coated with the adhesive on the sleeve so that the adhesive would come out on the surface. On this cylindrical support, the photosensitive resin composition prepared by removing benzophenone as a photopolymerization initiator from the photosensitive resin composition of Example 1 was heated to 50 ° C., and thickened using a doctor blade. It applied to about 2 mm. Thereafter, in the air, the light of the metal halide lamp was irradiated with 4000 mJ / cm ² (a value obtained by integrating the illuminance measured with a UV-35-APR filter over time) to cure the photosensitive resin composition layer.

To 100 parts by weight of the photosensitive resin composition of Example 1, 1 part by weight of copper oxide ultrafine particles (trade name “Nano Tek CuO”, manufactured by CI Kasei Co., Ltd.) having light absorption in the near-infrared wavelength region is added, and planetary type A black photosensitive resin composition was prepared by stirring and defoaming using a vacuum stirring deaerator (trade name “Mazerustar DD-300” manufactured by Kurashiki Boseki Co., Ltd.). The black photosensitive resin composition heated to 50 ° C. is applied onto the cured cylindrical photosensitive resin layer to a thickness of 0.1 mm using a doctor blade, and the light of the metal halide lamp is 4000 mJ in the atmosphere. / Cm ² (value obtained by time-integrating the illuminance measured with a UV-35-APR filter) was irradiated to cure the black photosensitive resin composition layer. Next, the silicon nitride cutting tool was cut to a thickness of 0.08 mm, and the surface was polished using a film-like polishing cloth.

  Using a carbon dioxide laser engraving machine (trademark “ZED-mini-1000”, manufactured by ZED, UK), a cylindrical laser engraving printing original plate formed in this way is 0.5 mm deep and 2 cm square. A convex pattern was formed. Further, while rotating the sleeve at a speed of 6 cm per minute, a pulse oscillation fiber laser with a wavelength of 1550 nm (manufactured by Mitsubishi Cable Industries, Ltd., the peak output is 10 kW, the pulse width is 2 ns, the repetition frequency is 5000 per second. Irradiating light having a condensed diameter of about 11 μmφ to form a line pattern. The formed line pattern had a width of 10 μm and a depth of 15 to 20 μm. When the formed line pattern was observed using a scanning electron microscope, the edge shape was satisfactory.

(Example 6)
1.5 parts by weight of a silicone compound (trade name “KF-410” manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of a commercially available liquid photosensitive resin composition (trade name “APR-G-42” manufactured by Asahi Kasei Chemicals Co., Ltd.) 5 parts by weight of porous fine-powdered silica (trade name “Pyrospher C” manufactured by Fuji Silysia Chemical Co., Ltd.)-1504) and 1 part by weight of benzophenone as a photopolymerization initiator (Kurashiki) Mixing and defoaming was performed using a trademark “Mazerustar DD-300” manufactured by Spinning Co., Ltd. to obtain a liquid photosensitive resin composition.
A cylindrical printing substrate was produced in the same manner as in Example 1 using the obtained photosensitive resin composition.

The obtained cylindrical printing substrate was engraved with a pattern using a carbon dioxide laser engraving machine manufactured by ZED. As a result of observing the obtained concave pattern with a scanning electron microscope, it was a good pattern with no residue remaining in the engraving portion.
Also, the surface friction resistance value and the wear amount were low. The surface frictional resistance value was less than 1. The amount of wear was 0.5 mg / cm ² or less. Furthermore, as a result of the wettability test, the spread of the indicator was in the range of 4 mm to 20 mm. Separately, a sheet-like sample having a thickness of 1.7 mm was formed, and the ink remaining on the plate surface was evaluated. As a result, no ink residue was observed at the halftone dots.

In addition, the gravure ink is filled in the concave portion of the surface of the obtained cylindrical printing substrate, and after removing the ink attached to the surface other than the concave portion using a plastic squeegee, the coated paper is applied to the surface of the cylindrical printing substrate. The ink was transferred by pressing to obtain a printed pattern on the coated paper. Furthermore, after the obtained cylindrical printing substrate is mounted on an air cylinder and gravure ink is applied to the surface, the cylindrical printing substrate is made of plastic while rotating the cylindrical printing substrate at a rotation speed of 100 times for 2 minutes. A squeegee was brought into contact with the surface. As a result, no large scratch was found on the surface of the cylindrical printing substrate.
The Shore D hardness of the obtained cylindrical printing original plate was 62 degrees.

(Comparative Example 1)
KF-410 which is a silicone compound is not included, and amorphous porous silica (trade name “Silicia 470” manufactured by Fuji Silysia Chemical Co., Ltd. (number average particle diameter of 14.1 μm, in place of Cyrossphere C-1504) is used as an inorganic porous body. A cylindrical printing substrate and a sheet-like printing substrate having a thickness of 2.8 mm were obtained in the same manner as in Example 1 except that the specific surface area was 300 m ² / g and the average pore diameter was 17 nm.
As a result of performing a taper abrasion test on the sheet-like printing substrate, the abrasion amount was larger than 2.5 mg / cm ² . Further, in the same manner as in Example 1, gravure ink was applied to the surface of the cylindrical printing substrate, and a test was conducted in which a plastic squeegee was brought into contact. As a result, linear scratches were visually observed on the surface.

  The present invention provides relief image creation for gravure printing plates by laser engraving, conductors for electronic components, semiconductors, insulators, pattern formation, antireflection films for optical components, color filters, and patterns of functional materials such as (near) infrared cut filters Gravure printing capable of laser engraving suitable for forming coating films and patterns for alignment films, underlayers, light-emitting layers, electron-transporting layers, and encapsulating layers in the production of display elements such as liquid crystal displays and organic electroluminescence displays It is most suitable as a cylindrical printing substrate that can be used for an original plate, anilox roll, and a rotary screen printing original plate.

Claims (20)

  It consists of a cylindrical support and a photosensitive resin cured product layer (A) formed thereon, and the photosensitive resin cured product layer (A) contains at least one selected from organic silicon compounds or organic fluorine compounds inside the layer. Alternatively, a cylindrical printing original plate for intaglio printing, which is a layer capable of laser engraving contained on the surface and has a Shore D hardness of 30 to 100 degrees. The cylindrical printing original plate according to claim 1, wherein the organosilicon compound contains a silicone compound represented by the following average composition formula (1).
_{R p Q r X s SiO (} 4-p-r-s) / 2 (1)
(In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkylene group having 5 to 20 carbon atoms, a cycloalkylene group, or 1 carbon atom. ˜20 alkoxy group substituted with hydroxyl group or amino group, C 1-20 alkyl group substituted with aryl group, C 7-30 alkyl group substituted with aryl group, methacryl group, acrylic group, vinyl group, cinnamoyl group, Alkyl group substituted with acetylene group, thiol group, epoxy group, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, spiroorthoester group, cyclic iminoether group, bicycloorthoester group, cyclosiloxane ring group, Or an aryl group having 6 to 20 carbon atoms and an alkoxycarbonyl having 2 to 30 carbon atoms substituted with a halogen atom Represents a monovalent group, a sulfo group or a monovalent group, consisting of one or more selected from polyoxyalkylene hydrocarbon group containing a salt thereof containing a carboxyl group or a salt thereof.
Q and X are a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or alkyl group having 1 to 20 carbon atoms. Or an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 7 to 30 carbon atoms substituted with an aryl group, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, or an alkoxycarbonyl having 2 to 30 carbon atoms A monovalent group containing a group, a carboxyl group or a salt thereof, a monovalent group containing a sulfo group or a salt thereof, a hydrocarbon group consisting of one or more selected from a polyoxyalkylene group,
0 <p <4,
0 ≦ r <4,
0 ≦ s <4,
And (p + r + s) <4. )   The organosilicon compound has at least one organic group selected from the group consisting of an aryl group, a linear or branched alkyl group substituted with at least one aryl group, an alkoxycarbonyl group, an alkoxy group, and a polyoxyalkylene group. The cylindrical printing original plate according to claim 1, comprising a compound having a hydrogen atom (α-position hydrogen) bonded to a carbon atom to which the organic group is directly bonded.   The cylindrical printing original plate according to claim 2, wherein the silicone compound has at least one organic group selected from the group consisting of a methylstyryl group, a phenyl group, a styryl group, and a carbinol group.   The cured photosensitive resin layer (A) is a compound having at least one type of bond selected from the group consisting of carbonate bond, urethane bond, ester bond, amide bond and imide bond in the molecular main chain, and aromatic in the molecule. The cylindrical printing original plate according to any one of claims 1 to 4, comprising a compound having a group or / and an alicyclic group.   The photosensitive resin cured product layer (A) is a layer obtained by photocuring a liquid photosensitive resin composition (a) at 20 ° C, according to any one of claims 1 to 5. The cylindrical printing original plate as described.   The weight of the cured photosensitive resin constituting the cured photosensitive resin layer (A) was measured by thermogravimetric analysis in which the temperature was raised from room temperature under conditions of a nitrogen flow rate of 100 ml / min and a heating rate of 10 ° C./min. The temperature at which the temperature decreases to 50% is 150 ° C. or more and 450 ° C. or less, and the difference between the temperature at which the weight decreases to 90% and the temperature at which the weight decreases to 50% is 120 ° C. or less. The cylindrical printing original plate according to any one of 1 to 6. The cured photosensitive resin layer (A) further contains an inorganic porous material, the specific surface area of the inorganic porous material is 10 m ² / g to 1500 m ² / g, the average pore diameter is 1 nm to 1000 nm, 8. The cylindrical printing original plate according to claim 1, wherein the pore volume is 0.1 ml / g or more and 10 ml / g or less, and the oil absorption is 10 ml / 100 g or more and 2000 ml / 100 g or less.   The number average particle size of the inorganic porous body is 0.1 μm or more and 100 μm or less, and at least 70% of the particles are spherical particles having a sphericity of 0.5 to 1. The cylindrical printing original plate according to 8.   The surface of the cured photosensitive resin layer (A) capable of laser engraving has an indicator liquid with an energy of 30 mN / m (trademark “mixture No. 30.0 for wetting tension test” manufactured by Wako Pure Chemical Industries, Ltd.) on the surface. Droplet (20 μL) is dropped, and when the maximum diameter of the portion where the droplet spreads after 30 seconds is measured, the droplet has a wetting property that the diameter of the droplet is 4 mm or more and 20 mm or less. The cylindrical printing original plate according to any one of claims 1 to 9.   The photosensitive resin cured product layer (A) capable of laser engraving is sensitive to a near infrared laser having an oscillation wavelength in the range of 700 nm to 3 μm, and has a pulse output with a pulse width of 1 ns to 10 ns and a peak power of 5 kW to 20 kW. 11. The concave portion having a depth of 1 μm or more is formed when laser light is irradiated with laser light having an energy amount of 0.2 mJ per pulse. The cylindrical printing original plate described in 1.   It has a circumference adjustment layer which adjusts the circumference of a cylindrical printing original plate between a cylindrical support and a photosensitive resin hardened material layer (A). The cylindrical printing original plate as described.   The cylindrical printing original plate according to claim 12, wherein the circumference adjusting layer is composed of a photosensitive resin cured product layer (B).   The laser-engravable photosensitive resin cured product layer (A) contains a photopolymerization initiator or a decomposition product of the photopolymerization initiator, and the photopolymerization initiator is a hydrogen abstraction type photopolymerization initiator and a decay type light. The cylindrical printing original plate according to claim 1, comprising a polymerization initiator.   The hydrogen abstraction type photopolymerization initiator is composed of at least one compound selected from benzophenones, xanthenes and anthraquinones, and the decay type photopolymerization initiator is a benzoin alkyl ether, 2,2-dialkoxy-2 The cylindrical printing original plate according to claim 14, comprising at least one compound selected from phenylacetophenones, acyloxime esters, azo compounds, organic sulfur compounds, and diketones.   The photopolymerization initiator contains a compound having both a site functioning as a hydrogen abstraction type photopolymerization agent and a site functioning as a decay type photopolymerization initiator in the same molecule. Cylindrical printing original plate. A sheet having a thickness of 2.8 mm made of a cured photosensitive resin having the same composition as that of the cured photosensitive resin layer (A) is separately prepared. Using the sheet, the load is 4.9 N and the rotational speed of the rotating disk is every minute. When the taper abrasion test is performed under the condition that 60 ± 2 times and the number of tests is 1000 times continuously, the abrasion amount per unit area of the surface of the cured photosensitive resin layer is 2.5 mg / cm ² or less. The cylindrical printing original plate according to any one of claims 1 to 16, characterized in that it is characterized in that: A method for producing a cylindrical printing original plate according to any one of claims 1 to 17, wherein a step of applying a photosensitive resin composition on a cylindrical support to form a photosensitive resin composition layer, cylindrical The photosensitive resin composition layer formed in the above is irradiated with light in the atmosphere to be crosslinked and cured to form a laser-engravable photosensitive resin cured product layer (A), and the irradiated light has a wavelength of 200 nm or more. Light having a wavelength of 450 nm or less is contained, and the illuminance on the surface of the photosensitive resin composition layer is UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.) and a filter (trade name “UV-35 manufactured by Oak Manufacturing Co., Ltd.”). in the case where measurements are performed using the APR filter "), it is 20mW / cm ² or more, the UV meter and filter (Oak Seisakusho Co., Ltd., in the case where measurements are performed using the trademark" UV-25 filter "), 5mW / characterized in that m ² or more, a manufacturing method of a cylindrical printing original plate.   In the manufacturing method of the doctor blade or squeegee contact type cylindrical printing base material which has a concave pattern, a concave pattern is obtained by irradiating the cylindrical printing original plate of Claim 1-17 with a laser beam, and removing this laser irradiation part. A method for forming a doctor blade having a concave pattern or a squeegee contact type cylindrical printing substrate, comprising the step of:   A doctor blade or a squeegee contact type cylindrical printing substrate, wherein the cylindrical printing substrate according to claim 19 is used as a gravure printing plate, an anilox roll, or a rotary screen printing plate.