JP2018097302A - Printing plate material and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing plate material capable of achieving a printing process with high resolution and excellent use efficiency of ink, and a method for manufacturing the plate material.SOLUTION: A printing plate material 1 includes: a printing surface comprising a protrusion pattern part 3 of a photoresist layer (layer 3-1) subjected to a fluorine-based coating treatment (layer 3-2), and a recess pattern part 2 made of a crosslinked silicone rubber, in which a height difference between the protrusion pattern part and the recess pattern part is 0.5 μm or more. The protrusion pattern part shows a retreat contact angle of 40° or more with respect to a solvent; and a difference between contact angles of the protrusion pattern part and the recess pattern part with respect to an ink solvent that is at least one solvent in the group consisting of hexane, heptane, octane, decane, undecane, dodecane, tridecane, tetradecane, trimethyl pentane, and the like is 20° or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a printing plate and a method for producing the same.

  In the printing method for organic devices, a high resolution printing process is required. As the printing method, a micro contact printing (μCP) method capable of patterning a large area on the order of sub μm is known (Non-Patent Document 1).

  Patent Document 1 discloses a direct-drawing waterless lithographic printing plate precursor obtained by laminating at least an ink receiving layer and a silicone rubber layer in this order on a support, and the water contact with the ink receiving layer. A direct-drawing waterless lithographic printing plate precursor having an angle of 85 ° or less and developing with water or an aqueous solution obtained by adding a surfactant to water is described.

JP 2001-322227 A

Applied Physics, Vol. 77, No. 2, pp. 173-177 (2008)

  However, the technique disclosed in Patent Document 1 is not a sufficient printing process in terms of high resolution and ink use efficiency. Therefore, the problem to be solved by the present invention is to provide a printing plate material capable of realizing a printing process with high resolution and excellent use efficiency of ink, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a printing surface comprising a specific resin having a specific contact angle difference between the convex pattern portion and the concave pattern portion. It has been found that the above problems can be solved by using a printing plate having a difference, and the present invention has been completed.

  That is, the printing plate material according to an embodiment of the present invention includes, as a printing surface, a convex pattern portion made of a photoresist subjected to a fluorine-based coating treatment and a concave pattern portion made of a crosslinked silicone rubber. And In the printing plate material according to one embodiment of the present invention, the receding contact angle of the convex pattern portion with respect to the solvent is preferably 40 ° or more.

  The printing plate material manufacturing method according to one embodiment of the present invention includes a first film forming step of forming a rubber layer made of a crosslinked silicone rubber on a base material, and a resist layer made of a photoresist on the rubber layer. A second film forming step, an exposure step of pattern exposing the resist layer, a developing step of removing the uncured photoresist from the resist layer to form a concavo-convex structure, and a fluorine coating treatment of the resist layer And a resist surface treatment step. In addition, a rubber surface treatment step for treating the rubber layer with a fluorine-based gas plasma may be included between the first film formation step and the second film formation step.

  ADVANTAGE OF THE INVENTION According to this invention, the printing plate material which can implement | achieve the printing process which is excellent in the use efficiency of the high resolution and ink, and its manufacturing method can be provided.

It is a cross-sectional schematic diagram of the printing plate material of this embodiment. It is a schematic diagram of the receding contact angle measurement method by the sliding-down method. It is a schematic diagram of the transfer rate measurement method in this embodiment.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

  The printing plate material of the present embodiment is a printing plate material that includes, as a printing surface, a convex pattern portion made of a photoresist subjected to a fluorine-based coating treatment and a concave pattern portion made of a crosslinked silicone rubber.

  The printing plate material of this embodiment has a cross-sectional structure schematically shown in FIG. In the present embodiment, the printing surface of the printing plate 1 has a convex pattern portion 3 and a concave pattern portion 2, and the printing pattern is determined by the concave pattern portion 2. In printing using the printing plate material 1 of the present embodiment, ink is added to the concave pattern portion 2, and then printing is performed by transferring the ink of the concave pattern portion 2 to the print target. The printing plate material 1 of the present embodiment is a plate material used in intaglio printing.

  Further, as shown in FIG. 1, the convex pattern portion 3 of the printing plate material in the present embodiment is obtained by applying a fluorine-based coating process to the photoresist layer 3-1, and the photoresist layer 3- 1 is laminated with a fluorine-based coating layer 3-2. Thereby, the convex pattern portion 3 has liquid repellency (hereinafter also simply referred to as “liquid repellency”) with respect to ink. On the other hand, since the surface of the concave pattern portion 2 is the crosslinked silicone rubber 2 ′, the concave pattern portion 2 has lyophilicity with respect to ink (hereinafter, also simply referred to as “lyophilic”). And as a printing surface, the convex pattern part 3 is liquid-repellent, and the concave pattern part 2 has lyophilicity, and the difference in liquid repellency is produced between the convex pattern part 3 and the concave pattern part 2, and Since the ink transfer property is excellent, a printing process with high resolution and excellent ink use efficiency can be realized.

  In the present embodiment, a photoresist having a hydroxyl group in its molecular structure is used as the photoresist used for the photoresist layer 3-1. For example, a novolac type phenol resin or a polyhydroxystyrene derivative can be used. Hydroxy groups can react with silane coupling agents to form covalent bonds. By the reaction of the silane coupling agent, the fluorine coating treatment agent or the pretreatment agent of the fluorine coating treatment agent can be brought into close contact with the photoresist layer 3-1.

  Further, as described above, the photoresist layer 3-1 is subjected to a fluorine coating treatment. The fluorine-based coating treatment agent includes an organic compound having a carbon-fluorine bond (C—F), for example, a low molecular compound or polymer having a fluoroalkyl group, a perfluoroalkyl group, and the like, and spin coating, dip coating, spraying, and the like. What can be applied can be used. By the fluorine-based coating treatment, the surface free energy of the convex pattern portion 3 is reduced, and a high contact angle with respect to the solvent is exhibited. As will be described later, the contact angle between the convex pattern portion 3 and the concave pattern portion 2 is reduced. A difference can be made.

  In the present embodiment, a crosslinked silicone rubber 2 ′ is used as the material for the concave pattern portion 2. The crosslinked silicone rubber 2 ′ has a crosslinked structure, whereby the concave pattern portion 2 has a network structure. Since the concave pattern portion 2 has a network structure made of the crosslinked silicone rubber 2 ′, the concave pattern portion 2 has a porous structure, and the solvent is absorbed in the pores, and the concave pattern portion 2 has a property of swelling.

  The crosslinked silicone rubber 2 'is a rubber having a siloxane bond (Si-O-Si) as a main skeleton, and is a rubber obtained by crosslinking silicone rubber in an uncured state before crosslinking. For example, addition polymerization type cross-linked silicone rubber can be obtained in a state where a polymer having a hydroxyl group at the end, a polymer having a vinyl group at the end and a polymerization initiator (the combination of these is divided into two or three liquids) ) To cause a crosslinking reaction.

  As the silicone rubber before crosslinking, only silicone may be polymerized, or modified silicone rubber obtained by polymerizing silicone and an organic monomer may be used. For example, rubber obtained by modifying ethylene propylene rubber with silicone may be used.

  Examples of the crosslinked silicone rubber 2 'include a crosslinked organopolysiloxane and a crosslinked organohydrogenpolysiloxane, and a crosslinked polydimethylsiloxane is preferred.

  The concave pattern portion 2 made of the crosslinked silicone rubber 2 'may be subjected to a lyophilic treatment such that hydrophilic functional groups other than hydroxy groups are provided on the surface of the concave pattern portion.

  In the present embodiment, the height difference between the convex pattern portion 3 and the concave pattern portion 2 (that is, the thickness of the convex pattern portion 3) is 0.5 μm or more. When the height difference between the convex pattern portion 3 and the concave pattern portion 2 is 0.5 μm or more, the ink enters the concave pattern portion 2 and high-resolution printing can be performed.

  From the viewpoint of the ink transfer rate, the side end of the convex pattern portion 3 adjacent to the concave pattern portion 2 is preferably formed with a forward taper of 50 ° or less, and more preferably 25 ° or less. The height difference between the convex pattern portion 3 and the concave pattern portion 2 is preferably 100 μm or less, and more preferably 10 μm or less. In this embodiment, the height difference between the convex pattern portion 3 and the concave pattern portion 2 can be measured by the method described in the examples described below.

  In the present embodiment, the receding contact angle of the convex pattern portion 3 with respect to the solvent is preferably high, and is preferably 40 ° or more. The receding contact angle is measured by, for example, the sliding method shown in FIG. In the sliding method, a droplet 5 (corresponding to a solvent used for ink in the present embodiment) is applied to the surface of a sample 6 (corresponding to a convex pattern portion or a concave pattern portion of a printing plate material in the present embodiment). In this method, the sample 6 on which the droplet 5 is placed is tilted and then the angle 8 of the sample when the droplet 5 starts to move is measured. An angle 8 with respect to the horizontal plane of the sample 6 when the droplet 5 starts to move is called a sliding angle, and it can be said that the larger this is, the stronger the droplet 5 adheres to the surface of the sample 6. Further, the angle (7 in FIG. 2) formed by the rear portion of the droplet 5 and the surface of the sample 6 when the droplet 5 starts to move is referred to as a receding contact angle. In the printing plate material, it is desirable that the ink slides from the convex pattern portion to the concave pattern portion. Therefore, in order to make it difficult for the ink to remain in the convex pattern portion, it is desirable that the receding contact angle is large. The contact angle is an important parameter.

  In general, an angle formed between the droplet 5 and the surface of the sample 6 when the droplet 5 is deposited on the surface of the sample 6 in a horizontal state is called a contact angle (or static contact angle). Also in this embodiment, the angle formed by the surface of the sample 6 in the horizontal state and the droplet 5 is referred to as a contact angle. The difference between the contact angle of the convex pattern portion with respect to the solvent and the contact angle of the concave pattern portion with respect to the solvent is preferably as large as possible, but is preferably 20 ° or more, more preferably 30 ° or more, and 40 ° or more. More preferably, it is more preferably 50 ° or more.

The difference between the contact angle of the convex pattern portion with respect to the solvent and the contact angle of the concave pattern portion with respect to the solvent is (contact angle with respect to the solvent of the convex pattern portion) − (contact angle with respect to the solvent of the concave pattern portion).
As required.

  The contact angle of the concave pattern portion and the convex pattern portion is determined as a value with respect to the solvent. Examples of the solvent include hexane, heptane, octane, decane, undecane, dodecane, tridecane, tetradecane, trimethylpentane, cyclohexane, cycloheptane, and cyclooctane. , Benzene, toluene, xylene, trimethylbenzene, dodecylbenzene, hexanol, heptanol, octanol, decanol, cyclohexanol, dimethicone and terpineol are preferably used. That is, the difference between the contact angle of the convex pattern portion with respect to the solvent and the contact angle of the concave pattern portion with respect to the solvent may be 20 ° or more in at least one of the aforementioned solvents and in the same solvent.

  Here, the solvent is preferably a solvent contained in the ink, and may be a mixed solvent of the above-described solvents. The difference in the contact angle with respect to the solvent between the convex pattern portion and the concave pattern portion is 20 ° or more, thereby causing a difference in liquid repellency between the convex pattern portion and the concave pattern portion, so that the ink enters the concave pattern portion. It becomes easy and is suitable.

  In the present embodiment, the concave pattern portion 2 has a low contact angle, and the convex pattern portion 3 has a high contact angle, so that liquid repellency is generated between the concave pattern portion 2 and the convex pattern portion 3 due to a difference in contact angle. When the ink pattern is inked into the printing plate material, the ink spreads in the concave pattern portion 2 and repels ink in the convex pattern portion 3, so that the ink is transferred from the convex pattern portion 3 to the concave pattern portion 2. Thus, the ink easily enters the concave pattern portion 2. As a result, inking can be performed only in the concave pattern portion 2, and a high-resolution printing process can be realized.

  The convex pattern portion 3 has a high contact angle, preferably 60 ° or more, and the concave pattern portion 2 has a low contact angle, and preferably 10 ° to 40 ° from the viewpoint of ink transferability. Note that the greater the difference in the contact angle, the smaller the difference in height between the convex pattern portion 3 and the concave pattern portion 2, and the better the ink penetration into the pattern, even if the pattern line width is small.

  In the present embodiment, the contact angle is measured by measuring the contact angles of the convex pattern portion 3 and the concave pattern portion 2 with respect to the same solvent, and calculating the difference between the convex pattern portion 3 and the concave pattern portion 2. The difference in contact angle can be measured. Specifically, by using a contact angle meter, the difference in contact angle with respect to the solvent between the convex pattern portion 3 and the concave pattern portion 2 can be measured.

  The shape of the printing surface in the printing plate material is not particularly limited, and examples thereof include a flat surface and a cylindrical surface. From the viewpoint of printing efficiency, a substantially cylindrical surface is preferable. In the present embodiment, the “substantially cylindrical” means that a printing plate material is attached to a part of the cylinder and has a cylindrical shape as a shape. That is, it means a plate having a printing plate material that is a part of a cylindrical plate that is approximately one round of the cylindrical plate that is attached to the cylinder for approximately one round.

  The printing method of the present embodiment includes a step of applying an ink containing a solvent to the printing plate material of the present embodiment. The ink containing a solvent when printing using the printing plate material of the present embodiment is an ink containing an organic solvent.

  Examples of the organic solvent used for the ink include hexane, heptane, octane, decane, undecane, dodecane, tridecane, tetradecane, trimethylpentane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene, trimethylbenzene, dodecylbenzene, hexanol, One or more selected from heptanol, octanol, decanol, cyclohexanol, dimethicone, and terpineol are preferably used, and a nonpolar organic solvent is preferably used. Specifically, tetradecane is preferably used.

  In the printing method of the present embodiment, printing is performed using a printing plate material in which the difference between the contact angle of the convex pattern portion 3 with respect to the organic solvent and the contact angle of the concave pattern portion 2 with respect to the organic solvent is 20 ° or more. It is preferable to do.

  A method for producing a printing plate material including a convex pattern portion made of a photoresist subjected to a fluorine-based coating treatment and a concave pattern portion made of a crosslinked silicone rubber as a printing surface in the present embodiment is as follows.

The method for producing the printing plate material is as follows:
1. A first film forming step of forming a rubber layer made of a crosslinked silicone rubber on a substrate;
2. A second film forming step of forming a resist layer made of a photoresist on the rubber layer;
3. An exposure step of pattern exposing the resist layer;
4). A development step of removing the uncured photoresist to form a concavo-convex structure; and
5. A resist surface treatment step of treating the resist layer with a fluorine coating;
including.

  Further, the printing plate material manufacturing method of the present embodiment is a rubber in which the rubber layer is treated with a fluorine-based gas plasma between the first film forming step 1 and the second film forming step 2 described above. You may have a surface treatment process. Moreover, you may perform the primer process by a silane coupling agent before the fluorine-type coating process performed by said 5.

  A layer of crosslinked silicone rubber can be obtained by laminating and molding a crosslinked silicone rubber on the base material of the printing plate material. The method of forming the crosslinked silicone rubber on the substrate is not particularly limited as long as it can be a flat layer, but can be performed by spin coating, injection molding, or the like.

  Next, a photoresist is laminated on the entire surface of the crosslinked silicone rubber layer by spin coating or the like. In the case of a positive resist, after the photoresist is laminated, the printed pattern is obtained by prebaking (semi-curing), exposing and developing the removed portion that becomes the concave pattern portion, and removing and washing the photoresist in the exposed portion. Can be formed. In the case of a negative resist, after laminating a photoresist, the non-removed portion that becomes the convex pattern portion is exposed to be cured and developed to remove and wash the non-exposed portion that becomes the concave pattern portion. A printing pattern can be formed.

  Further, when the rubber surface treatment step (fluorine gas plasma treatment of the rubber layer) is performed, the type of fluorine gas used for the fluorine gas plasma treatment is not limited to a specific one, but for example, CF4 Fluorinated hydrocarbon gases such as C 2 F 6 and C 3 F 8 can be used.

  A specific method for manufacturing a printing plate material according to this embodiment includes, for example, the following procedure.

1. A cross-linked silicone rubber is formed by spin coating on a metal plate such as an aluminum plate or a plastic plate such as a PET plate, which is a base material for a printing plate.
2. As a pretreatment for laminating a photoresist, a fluorine-based gas plasma treatment is performed on the crosslinked silicone rubber layer on the substrate. By subjecting the crosslinked silicone rubber layer to a fluorine-based gas plasma treatment, a photoresist can be uniformly laminated on the crosslinked silicone rubber layer as the concave pattern portion. The fluorine-based gas plasma treatment can be performed by appropriately controlling the fluorine-based gas flow rate, high-frequency output, and treatment time. For example, it can be performed under the conditions of a fluorine-based gas flow rate of 100 ml / min, a high-frequency output of 200 W, and a processing time of 1 min.
3. A photoresist is formed on the crosslinked silicone rubber layer by spin coating.
4). For example, the photoresist is pre-baked under the conditions of a pre-baking temperature range of 100 ° C. to 120 ° C. and a baking time of 2 minutes to 30 minutes.
5. The printed pattern portion is irradiated with UV light using UV light in a wavelength band including 365 nm.
6). By developing and rinsing, the photoresist in the exposed area is removed to form a concavo-convex pattern structure. As the developer, for example, a tetramethylammonium hydroxide (TMAH) aqueous solution or the like can be used, and the development time can be suitably performed, for example, in the range of 0.1 min to 2 min. As the rinsing liquid, pure water or the like can be used, and the rinsing time can be suitably performed, for example, at 0.5 min or more and 1 min or less.
7). For example, the photoresist is post-baked under the conditions of 150 ° C. and baking time of 20 minutes.
8). After post-baking, a fluorine-based coating treatment is performed. By performing the fluorine-based coating treatment, the convex pattern portion made of photoresist becomes liquid repellent, and the difference in contact angle between the convex pattern portion and the concave pattern portion is 20 ° or more, so that the convex pattern portion and the concave pattern portion A difference in liquid repellency can be created. The fluorine-based coating treatment can be performed by a silane coupling reaction between the hydroxy group of the convex pattern portion photoresist and the fluorine-based coating agent or primer agent. Primer treatment with a silane coupling agent may be performed before the fluorine-based coating treatment.

  Hereinafter, although an example and a comparative example are given and the present invention is explained, this embodiment is not limited to the following examples. Evaluation methods for printing plate materials in Examples and Comparative Examples are as follows.

[Example]
<Manufacture of printing plate>
The printing plate material according to the example was manufactured by performing the following steps.
1. Polydimethylsiloxane (X-32-3279A / B manufactured by Shin-Etsu Chemical Co., Ltd., a cross-linking reaction by liquid mixing with an aluminum plate having a thickness of 0.3 mm as the base material of the printing plate material is converted to cross-linked polydimethylsiloxane. In the section of Examples, the crosslinked polydimethylsiloxane is described as “PDMS”.) Was formed by a spin coat method using a spin coater (MS-A150 manufactured by Mikasa).
2. PDMS using MPC-5000S manufactured by Yamato Scientific Co. respect after film, CF ₄ gas flow rate of 100 mL / min and treated high frequency output 200 W, 1 minute, was CF ₄ plasma treatment.
3. A photoresist (OFPR-800LB, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was formed on PDMS after CF ₄ plasma by spin coating using a spin coater (MS-A150 manufactured by Mikasa). The film thickness of the photoresist was adjusted by changing the rotation speed of the spin coater.
4). The photoresist was pre-baked at 110 ° C. for 15 minutes using an oven (Espec Corp. clean oven PVHC-212).
5. The printed pattern part was irradiated with UV light (ME1000-RD1E manufactured by Hitachi High-Tech Co., Ltd., UV having a wavelength of 365 nm of 500 mJ / cm ² ).
6). 2. Using a 38% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer, developing by immersing and shaking for 10 seconds, and then immersing and shaking for 30 seconds using pure water as a rinse solution A rinsing process was performed to remove the resist in the exposed portion, thereby forming a concavo-convex structure.
7). The photoresist was post-baked at 150 ° C. for 20 minutes using an oven (Espec Corp. clean oven PVHC-212).
8). A primer agent (DS-PC-3B manufactured by Harves) was applied to the plate by a spin coating method using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.), and saturated water vapor on a hot plate at 80 ° C. for 30 minutes. Heated.
9. A fluorine-based coating agent (DS-5210-TH made by Harves) was applied to the plate by a spin coat method using a spin coater (MS-A150 made by Mikasa) and heated at 120 ° C. for 20 minutes on a hot plate. did. Subsequently, it was spin-washed twice using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.) with a rinse agent (Haves DS-TH), and then spin-washed once with 2-propanol to obtain a printing plate material.
Here, the contact angle of the convex pattern portion with respect to tetradecane increased from 20 ° to 60 ° by the fluorine-based coating treatment.

  Ink penetration was evaluated using the obtained printing plate material. When the printing plate material of Example is used, even when the line width of the concave pattern portion is 20 μm, the ink enters only the concave pattern portion, and no ink drop mark (circular shape) is observed in the convex pattern portion. It was.

[Comparative example]
<Manufacture of printing plate>
Moreover, in order to compare with the printing plate material which concerns on the Example described above, the printing plate material which concerns on a comparative example was manufactured by performing the following each process. The main difference between the printing plate material according to the embodiment described above and the printing plate material according to the comparative example is that the convex printing portion is subjected to a fluorine-based coating treatment in the printing plate material according to the comparative example. There is no point.

1. The PDMS described in the above example was formed on an aluminum plate having a thickness of 0.3 mm as a base material for printing plate material.
2. Oxygen plasma treatment was performed on the PDMS after film formation by using MPC-5000S manufactured by Yamato Scientific Co., Ltd., using an oxygen gas flow rate of 100 mL / min and a high-frequency output of 200 W for 4 minutes.
3. A photoresist (OFPR-800LB manufactured by Tokyo Ohka Kogyo Co., Ltd.) was formed on PDMS after oxygen plasma by spin coating using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.). The film thickness of the photoresist was adjusted by changing the rotation speed of the spin coater.
4). The photoresist was pre-baked at 110 ° C. for 15 minutes using an oven (Espec Corp. clean oven PVHC-212).
5. The printed pattern part was irradiated with UV light (ME1000-RD1E manufactured by Hitachi High-Tech Co., Ltd., UV having a wavelength of 365 nm of 500 mJ / cm ² ).
6). 2. Using a 38% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer, developing by immersing and shaking for 10 seconds, and then immersing and shaking for 30 seconds using pure water as a rinse solution A rinsing process was performed to remove the resist in the exposed portion, thereby forming a concavo-convex structure.
7). The photoresist was post-baked at 150 ° C. for 20 minutes using an oven (clean spec PVHC-212 manufactured by Espec Corp.) to obtain a printing plate material.

<Printing method using printing plate>
Printing was performed by performing the following steps.
1. The printing plate materials produced in the examples and comparative examples were inked using L-Ag1TeH manufactured by ULVAC as an ink and using an ink jet of 1 pL per droplet (droplet diameter of about 13 μm).
2. After inking, the ink was dried on the plate for several minutes. Here, the ink penetration was evaluated.
3. A PEN film (Q65HA manufactured by Teijin Ltd.) was pressed against the plate using a roller. The pressing linear pressure was 98 N / m, and the pressing time was 3 seconds.
4. The ink was transferred by releasing the film from the plate.

  Using the printing plate material according to the example and the printing plate material according to the comparative example created by the method described above, the height difference between the convex pattern portion and the concave pattern portion, the contact angle, the transfer rate, etc. Measurements were made. The measuring method is as follows.

<Measurement of height difference between convex pattern part and concave pattern part>
As a non-contact type surface shape measuring apparatus, a step measurement was performed using a confocal laser microscope (OPTELICS H1200 manufactured by Lasertec).

<Measurement of contact angle>
Using a contact angle meter (DM-701, manufactured by Kyowa Interface Science), a contact angle measurement with respect to tetradecane, which is an ink solvent described later, was performed.

<Measurement of transfer rate>
As Figure 3, from the cross-sectional area of the plate pattern portion before and after the transfer was calculated transfer rate T ₁ based on the following equation.
T1 (%) = S1 / S0 × 100

Here, as shown in FIG. 3, S ₀ means the cross-sectional area of the concave pattern portion of the printing plate material before transfer, and S ₁ is the concave pattern portion of the printing plate material after transfer. Means the cross-sectional area of the portion where no ink remains. If all the ink is transferred to the film without ink remaining on the printing plate material, it becomes 100%.

<Measurement of ink penetration>
The following steps were performed to evaluate ink penetration.
1. Using an inkjet printer (DMP3000 manufactured by FUJIFILM Global Graphic Systems Co., Ltd.), 1 pL of ink (L-Ag1TeH manufactured by ULVAC, Inc., the ink solvent was tetradecane) was applied to the periphery of the concave pattern portion of the printing plate as 1 pL.
2. The plate after droplet ejection was observed with a camera.
3. When an ink droplet trace (circular) is observed in the convex pattern portion, X is assumed to be insufficient, and ink enters only the concave pattern portion, and ink droplet trace (circular shape) enters the convex pattern portion. ) Is not observed at all.

  The measurement results are shown in Table 1, Table 2, and Table 3 below. Table 1 shows the sliding angle, contact angle (static contact angle), and receding contact angle, measured using the printing plate material according to the example. Table 2 shows the sliding angle, contact angle, and receding contact angle measured using the printing plate according to the comparative example. Table 3 shows the height difference between the convex pattern portion and the concave pattern portion and the transfer rate measured for each of the printing plate materials according to the example and the comparative example. The column “contact angle difference” in Tables 1 and 2 represents the difference between the contact angle of the convex pattern portion with respect to the solvent and the contact angle of the concave pattern portion with respect to the solvent.

  As shown in Table 1, in the printing plate material according to the example, the receding contact angle with respect to tetradecane of the convex pattern portion is 40 ° or more, and the contact angle with respect to tetradecane between the convex pattern portion and the concave pattern portion. It was found that there was a difference of 20 ° or more.

  As shown in Table 3, it was found that the printing plate material according to the example had a height difference of 0.5 μm or more between the convex pattern portion and the concave pattern portion. In addition, since the printing plate material according to the comparative example does not perform the repellent control, the ink remains on the printing plate material after transfer, whereas the printing plate material according to the example It was found that there was almost no ink remaining after the transfer, and it had favorable properties as a printing plate material.

1: Printing plate material
2: Concave pattern
2 ′: Cross-linked silicone rubber 3: Convex pattern portion 3-1: Photoresist layer 3-2: Fluorine-based coating layer

Claims (12)

On the printed surface, a convex pattern portion made of a photoresist subjected to a fluorine-based coating treatment, and a concave pattern portion made of a crosslinked silicone rubber,
A printing plate material.   The printing plate material according to claim 1, wherein a receding contact angle of the convex pattern portion with respect to the solvent of the printing ink is 40 ° or more.   The solvent is hexane, heptane, octane, decane, undecane, dodecane, tridecane, tetradecane, trimethylpentane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene, trimethylbenzene, dodecylbenzene, hexanol, heptanol, octanol, decanol, The printing plate material according to claim 2, which is at least one selected from the group consisting of cyclohexanol, dimethicone, and terpineol.   The printing plate material according to claim 2 or 3, wherein a difference between a contact angle of the convex pattern portion with respect to the solvent and a contact angle of the concave pattern portion with respect to the solvent is 20 ° or more.   The printing plate material according to claim 2 or 3, wherein a difference between a contact angle of the convex pattern portion with respect to the solvent and a contact angle of the concave pattern portion with respect to the solvent is 30 ° or more.   The printing plate material according to any one of claims 1 to 5, wherein the crosslinked silicone rubber is a crosslinked polydimethylsiloxane.   The printing plate material according to any one of claims 1 to 6, wherein the photoresist contains a hydroxy group in a molecular structure.   A printing method comprising a step of applying an ink containing a solvent to the printing plate material according to any one of claims 1 to 7.   The difference between the contact angle of the convex pattern portion with respect to the solvent and the contact angle of the concave pattern portion with respect to the solvent is 20 ° or more, and the solvent is hexane, heptane, octane, decane, undecane, dodecane, tridecane, tetradecane. , Trimethylpentane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene, trimethylbenzene, dodecylbenzene, hexanol, heptanol, octanol, decanol, cyclohexanol, dimethicone, and terpineol The printing method according to claim 8, wherein the printing method is a solvent contained in the ink. A first film forming step of forming a rubber layer made of a crosslinked silicone rubber on a substrate;
A second film forming step of forming a resist layer made of a photoresist on the rubber layer;
An exposure step of pattern exposing the resist layer;
A development step of removing uncured photoresist from the resist layer to form a concavo-convex structure; and a resist surface treatment step of subjecting the resist layer to a fluorine coating treatment;
A method for producing a printing plate material. A rubber surface treatment step of performing fluorine gas plasma treatment on the rubber layer between the first film formation step and the second film formation step;
The manufacturing method of the printing plate material of Claim 10. Before the resist surface treatment step, a primer treatment step with a silane coupling agent of the resist layer is performed.
The manufacturing method of the printing plate material of Claim 10 or 11.

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