JP2004074608A - Resin printing plate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin printing plate which transfers a desired pattern shape and prints a highly fine-defined image with high resolving power, and a method for manufacturing the resin printing plate. <P>SOLUTION: The resin printing plate for intaglio or relief printing has at least an ink transfer part and the width of a recessed part or a projecting part of 0.1 to 500 μm and its interval of 0.1 to 500 μm. The method for manufacturing the resin printing plate of a recessed or projecting type comprises the process to coat a recessed part on the surface of the resin printing plate with a resist, the process to coat the projecting part or recessed part of the resin printing plate with a primary coat, the process to remove the resist and the process to coat the surface of the primary coat with a non-transfer layer having a contact angle of not less than 90° with ink. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin plate for forming a fine pattern used for an electronic or optical element and a manufacturing process thereof, and a method of manufacturing the plate.
[0002]
[Prior art]
Aiming at application of organic thin films to devices, research has been conducted on techniques for forming fine patterns of organic thin films. Alternatively, a technique of patterning an organic thin film with high precision and using it as a resist for lithography has been studied.
As a technique for forming a fine pattern of an organic thin film, a method called “microcontact printing method (hereinafter, referred to as μCP method)” is known (for example, described in US Patent 6060121). The μCP method is a method of forming an organic thin film pattern by attaching ink to a resin plate having a desired concavo-convex pattern, contacting the resin plate with a substrate, transferring the ink onto the substrate, and forming an organic thin film pattern. In U.S. Pat. No. 6,060,121, a self-assembled film (hereinafter referred to as SAMs) can be formed as an organic thin film on a variety of substrates (metals, semiconductors, oxides, etc.) with good reproducibility. I use.
[0003]
In the μCP method, ink is placed on a resin plate, and the ink is attached to the entire surface of the uneven pattern. However, in this method, when the resin plate and the substrate are brought into contact with each other, the resin plate is deformed, ink attached to a portion other than a desired pattern is transferred to the substrate, a desired pattern shape cannot be transferred, resolution is reduced, and the like. There was a problem.
[0004]
[Problems to be solved by the invention]
The present invention has been made to solve these problems, and it is an object of the present invention to provide a resin plate capable of transferring a desired pattern shape, performing high-resolution, high-definition printing, and a method for manufacturing the same.
[0005]
[Means for Solving the Problems]
The invention according to claim 1 is a relief printing plate having at least an ink transfer portion, and the width and the interval of the projections are 0.1 to 500 μm and 0.1 to 500 μm, respectively. A convex resin plate, wherein the concave portion is coated with a non-transfer layer having a contact angle with ink of 90 degrees or more.
[0006]
The invention according to claim 2 is a resin plate for intaglio printing having at least an ink transfer portion, wherein the width and interval of the concave portions are 0.1 to 500 μm and 0.1 to 500 μm, respectively. The concave resin plate is characterized in that a non-transfer layer having a contact angle with ink of 90 ° or more is coated on the portion.
[0007]
The invention according to claim 3 is the resin plate according to claim 1 or 2, wherein the non-transfer layer is a monomolecular layer.
[0008]
The invention according to claim 4 is the resin plate according to claim 3, wherein the monomolecular layer is made of any one of a thiol compound, a disulfide compound, and an organic silane compound.
[0009]
The invention according to claim 5 is the resin plate according to any one of claims 1 to 4, wherein a base layer is provided below the non-transfer layer.
[0010]
The invention according to claim 6 is a resin plate for letterpress printing, which has at least an ink transfer portion, and the width and interval of the protrusions are 0.1 to 500 μm and 0.1 to 500 μm, respectively. A step of coating the convex portion with a resist, a step of coating the concave portion of the resin plate with a base layer, a step of removing the resist, and a step of coating the base layer with a non-transfer layer having a contact angle with ink of 90 ° or more. A method of manufacturing a convex resin plate.
[0011]
The invention according to claim 7 is a resin plate for intaglio printing having at least an ink transfer portion, wherein the width and interval of the concave portions are 0.1 to 500 μm and 0.1 to 500 μm, respectively. Applying a resist to the resin plate, covering the convex portion of the resin plate with a base layer, removing the resist, and coating the base layer with a non-transfer layer having a contact angle with ink of 90 ° or more. And a method of manufacturing a concave resin plate.
[0012]
The invention according to claim 8 is the manufacturing method according to claim 6 or 7, wherein the non-transfer layer is a monolayer.
[0013]
The invention according to claim 9 is the manufacturing method according to claim 8, wherein the monomolecular layer is made of any one of a thiol compound, a disulfide compound, and an organic silane compound.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is a letterpress printing or intaglio printing resin plate having an ink transfer portion, wherein a non-transfer layer having a contact angle with ink of 90 degrees or more is provided in a non-transfer portion of the ink. And
Hereinafter, an example of the resin plate of the present invention and a method for producing the same will be described with reference to the drawings.
[0015]
Known resins can be used as the resin used for the resin plate of the present invention. In addition, it is preferable that the resin plate is selected such that the contact angle with the ink is less than 90 degrees in order to make the ink adhere to the resin plate 1. For example, a thermosetting resin such as a silicon resin, a phenol resin, an unsaturated polyester, or the like, a photocurable resin, or an electron beam curable resin can be used. Among them, polydimethylsiloxane (hereinafter referred to as PDMS) and the like can be preferably used.
[0016]
The non-transfer layer of the present invention may be of any material and constitution as long as the material has a contact angle with ink of 90 degrees or more. In particular, a monolayer is preferable, and SAMs (self-assembled films) that can form a dense film with few defects are preferable. The use of SAMs enables higher resolution and higher definition patterning.
[0017]
For such a non-transfer layer, a thiol compound, a disulfide compound, an organic silane compound, or the like can be used.
[0018]
As the thiol compound, decanethiol, dodecanethiol, tetradecanethiol, hexadecanethiol, octadecanethiol, oleylthiol, dithiohexadecanoic acid, dithiotetradecanoic acid, dithiooctadecanoic acid, dithiododecanoic acid, dithiodecanoic acid, mercaptohexadecanoic acid, dithiohexadecanoic acid methyl ester Known compounds such as methyl dithiotetradecanoate, methyl dithiooctadecanoate, methyl dithiododecanoate, and methyl dithiodecanoate can be used.
[0019]
As disulfide compounds, didecyl sulfide, didodecyl sulfide, ditetradecyl sulfide, dihexadecyl sulfide, dioctadecyl sulfide, dioleyl sulfide, didecyl disulfide, didodecyl disulfide, ditetradecyl disulfide, dihexadecyl disulfide, Known compounds such as dioctadecidisulphide and dioleyldisulfide can be used.
[0020]
Examples of the organic silane compound include aminopropyltriethoxysilane, mercaptopropyltriethoxysilane, dodecyltrichlorosilane, hexadecyltrichlorosilane, heptadecafluorotetrahydrodecylotrichlorosilane, heptadecafluorotetrahydrodecylotriethoxysilane, heptadecafluorotetraoctyltrisilane. Known such as chlorosilane, trifluoropropyltrimethoxysilane, octadecyltrichlorosilane, [2- (perfluorooctyl) ethyl] trichlorosilane, [3- (1H, 1H, 2H, 2H perfluorododecyloxy) propyl] triethoxysilane Can be used.
[0021]
In the present invention, one or more underlayers may be provided below the non-transfer layer. The base layer is selected depending on the material used for the non-transfer layer, and a metal film such as gold chemically bonded to the non-transfer layer or a metal oxide film such as a SiO ₂ film can be suitably used. This is because the adhesion is large.
[0022]
[Method of manufacturing resin plate]
Hereinafter, a convex resin plate for letterpress printing will be described as an example. Here, an example in which the base layer 5 is provided will be described, but the base layer 5 may not be provided.
First, a master having an uneven pattern formed by lithography using UV or EB is manufactured. The matrix is made of a metal, a semiconductor, an oxide or a nitride. Alternatively, a concavo-convex pattern may be formed on a substrate made of a metal, a semiconductor, an oxide, or a nitride by a resist by lithography using UV or EB.
[0023]
Next, a resin is applied on a matrix having an uneven pattern on the surface. After the resin is cured, the resin is peeled off from the matrix to transfer the concavo-convex pattern on the matrix to the resin to obtain a resin plate 1 (FIG. 2A).
[0024]
Next, a resist layer 4 is formed on the resin plate 1, and the resist 4 is patterned by lithography using UV or EB. Here, patterning is performed so that the convex portion (the portion where the ink is to be attached) of the resin plate is covered with the resist 4 (FIG. 2B).
[0025]
Next, the underlayer 5 is formed by vacuum evaporation or sputtering (FIG. 2C). After that, the resist pattern 4 is peeled off, and the underlayer 5 is formed only in the concave portion (the portion where the ink is not to be adhered) of the resin plate 1 (FIG. 2D).
[0026]
Next, the resin plate 1 is immersed in the non-transfer layer solution to form the non-transfer layer 2 on the base layer 5. For the non-transfer layer 2, a molecule is selected so that the contact angle with the ink becomes 90 degrees or more (FIG. 2E).
[0027]
[Pattern forming method]
First, the ink 3 is adhered to the resin plate 1 having a concave / convex pattern on the surface. At this time, except where the ink 3 is to be attached, the ink 3 does not adhere because the contact angle of the ink 3 is 90 degrees or more, and the ink 3 adheres only to a predetermined position (FIG. 3A). ).
Next, the resin plate 1 to which the ink 3 has adhered is brought into contact with the substrate 6 (FIG. 3B), and the ink 3 is transferred to the substrate 6 (FIG. 3C). Since the ink 3 adheres only to a predetermined position, a desired pattern can be transferred to the substrate with high accuracy.
[0028]
Further, as the ink 3 used in the present invention, various known materials can be used depending on the purpose. Further, in the present invention, since an ink pattern can be formed without using light, it is particularly effective for forming a pattern of an organic material which is deteriorated by light.
[0029]
Here, the convex resin plate for letterpress printing has been described as an example, but the concave resin plate for letterpress printing can be formed by forming the resist layer in the concave portion, the base layer in the convex portion, and the non-transfer layer on the base layer. Can be used as
[0030]
Further, as the pattern to be transferred becomes finer, the influence of the protrusion of the ink from the transfer pattern becomes greater. In particular, in the case of using a resin plate having fine irregularities such as microcontact printing, the accuracy of the transfer pattern is reduced due to distortion of the plate at the time of transfer. Therefore, providing a non-transfer layer is more effective.
[0031]
Specifically, it is particularly effective when transferring a pattern having a line width of about 50 μm or less.
In addition, the convex resin plate for relief printing at this time, the height of the convex portion is preferably in the range of 0.1 to 500 μm, the width of the convex portion, the interval is 0.1 to 500 μm, respectively. It is preferable that the thickness is in the range of 0.1 to 500 μm, and more effective when it is in the range of 0.1 to 100 μm and 0.1 to 100 μm, respectively. Further, in the case of a concave resin plate for intaglio printing, the depth of the concave portion is preferably in the range of 0.1 to 500 μm, and the width and interval of the concave portion are 0.1 to 500 μm and 0.1 to 500 μm, respectively. It is preferable that the thickness be in the range of 500 μm, and more effective when it is in the range of 0.1 to 100 μm and 0.1 to 100 μm, respectively.
[0032]
【Example】
Hereinafter, the present invention will be described more specifically based on examples. Here, a convex resin for letterpress printing will be described as an example, but the present invention is not limited to this.
[0033]
<Example 1>
[Method of manufacturing resin plate]
First, a resist layer was formed on a Si substrate, and the resist was patterned by lithography using UV to produce a matrix having an uneven pattern of the resist. The concavo-convex pattern width was 10 μm / 10 μm. The height of the irregularities was 1 μm.
Next, a polydimethylsiloxane (hereinafter, referred to as PDMS) resin (Sylgrad 184 manufactured by DowCornig) was applied onto a matrix having a concavo-convex pattern on the surface. The PDMS resin was heated at 70 ° C. for 12 hours to cure the PDMS resin. The cured PDMS resin was peeled off from the matrix to obtain a convex resin plate in which the height of the convex portions was 1 μm, the width and the interval of the convex portions were 10 μm and 10 μm, respectively.
Next, a resist layer was formed, and the resist was patterned by lithography using UV. Here, patterning was performed so that the convex portions of the resin plate were covered with a resist.
Next, a 100-nm-thick gold film was formed as an underlayer by EB evaporation. Thereafter, the resist pattern was peeled off using a peeling liquid to obtain a resin plate having a base layer in the concave portion.
Next, the resin plate was immersed in an octadecanethiol (HS (CH ₂ ) ₁₅ CH ₃ ) ethanol solution (10 mM) for 5 hours. After washing with ethanol, it was dried to form a non-transfer layer on the underlayer.
[0034]
[Pattern forming method]
First, an ethanol solution (10 mM) of mercaptohexadecanoic acid (HS (CH ₂ ) ₁₁ COOH) is placed as an ink 3 on a resin plate. At this time, the contact angle between Ink 3 and the non-transfer layer on the PDMS resin plate was 90 degrees. Therefore, the ink 3 did not adhere to the non-transfer layer, but adhered only to other positions (projections).
Next, the resin plate to which the ink 3 was adhered was brought into contact with the gold substrate for 1 minute to transfer the ink 3 to the gold substrate. Note that a gold substrate was used in which chromium and gold were sequentially formed to a thickness of 50 nm and 100 nm on a glass substrate by an EB evaporation method. After the transfer, the gold substrate was washed with ethanol and then dried.
When the ink 3 on the gold substrate was observed by AFM, an ink pattern having a pattern line width and a space width of 10 μm and 10 μm, respectively, was observed.
[0035]
<Example 2>
[Method of manufacturing resin plate]
First, a resist layer was formed on a Si substrate, and the resist was patterned by lithography using EB, thereby producing a matrix having an uneven pattern of the resist. The concavo-convex pattern width was 1 μm / 1 μm. The height of the unevenness was 0.5 μm.
Next, a polydimethylsiloxane (hereinafter, referred to as PDMS) resin (Sylgrad 184 manufactured by DowCornig) was applied onto a matrix having a concavo-convex pattern on the surface. The PDMS resin was heated at 70 ° C. for 12 hours to cure the PDMS resin. The cured PDMS resin was peeled from the matrix to obtain a convex resin plate in which the height of the convex portions was 0.5 μm, and the width and the interval of the convex portions were 1 μm and 1 μm, respectively.
Next, a resist layer was formed, and the resist was patterned by lithography using EB. Here, patterning was performed so that the convex portions of the resin plate were covered with a resist.
Next, an SiO ₂ film having a thickness of 100 nm was formed as a base layer by a sputtering method. Thereafter, the resist pattern was stripped using a stripper.
Next, the resin plate was immersed in a toluene solution of octadecyltrimethoxysilane (CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ ) for 30 minutes. Thereafter, drying was performed at 70 ° C. for 30 minutes to form a non-transfer layer on the SiO ₂ film.
[0036]
[Pattern forming method]
First, an HS (CH ₂ ) ₁₅ CH ₃ ethanol solution (10 mM) is placed as an ink 3 on a resin plate. At this time, the contact angle between the ink 3 and the non-transfer layer on the resin plate was 90 degrees. Therefore, the ink 3 does not adhere to the non-transfer layer portion, but adheres only to other positions (projections).
Next, the resin plate to which the ink 3 was adhered was brought into contact with the gold substrate for 1 minute to transfer the ink 3 to the gold substrate. Note that a gold substrate was used in which chromium and gold were sequentially formed to a thickness of 50 nm and 100 nm on a glass substrate by an EB evaporation method. After the transfer, the gold substrate was washed with ethanol.
When the ink 3 on the gold substrate was observed by AFM, an ink pattern having a pattern line width and a space width of 1 μm and 1 μm, respectively, was observed.
[0037]
<Comparative example>
[Method of manufacturing resin plate]
A PDMS resin plate was prepared in the same manner as in Example 1 except that the underlayer and the non-transfer layer were not formed, and the height of the convex portions was 1 μm, and the width and interval of the convex portions were 10 μm and 10 μm, respectively. A resin plate was obtained.
[0038]
[Pattern forming method]
As in the first embodiment, first, an ethanol solution of mercaptohexadecanoic acid (HS (CH ₂ ) ₁₁ COOH) (10 mM) is placed on the resin plate as the ink 3. At this time, the contact angle between Ink 3 and the PDMS resin plate was 60 degrees.
Next, the resin plate to which the ink 3 was adhered was brought into contact with the gold substrate for 1 minute to transfer the ink 3 to the gold substrate. Note that a gold substrate was used in which chromium and gold were sequentially formed to a thickness of 50 nm and 100 nm on a glass substrate by an EB evaporation method. After the transfer, the gold substrate was washed with ethanol and then dried.
When the ink 3 on the gold substrate was observed by AFM, an ink pattern having a pattern line width and a space width of 12 μm and 8 μm, respectively, was observed. In the comparative example, the line width of the ink pattern was increased as compared with the uneven pattern of the resin plate, and a desired ink pattern could not be formed.
[0039]
【The invention's effect】
With the configuration of the present invention, it is possible to prevent erroneous transfer due to distortion of the uneven shape when transferring using a resin plate having irregularities such as a concave or convex resin plate. In other words, it is possible to prevent the ink from adhering to places other than the desired pattern, form the shape of the formed pattern with good reproducibility, and obtain a resin plate that can be used for high-resolution, high-definition printing. .
[0040]
[Brief description of the drawings]
FIG. 1 is an explanatory diagram showing a cross-sectional structure of an example of a resin plate of the present invention.
FIG. 2 is an explanatory view showing one example of a method for producing a resin plate of the present invention.
FIG. 3 is an explanatory view showing an example of the pattern forming method of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Resin plate 2 Non-transfer layer 3 Ink 4 Resist 5 Underlayer 6 Substrate

Claims (9)

A relief printing plate having at least an ink transfer portion and a width and a spacing of the protrusions of 0.1 to 500 μm and 0.1 to 500 μm, respectively. A convex resin plate, wherein the non-transfer layer has an angle of 90 ° or more. A resin plate for intaglio printing having at least an ink transfer portion and a width and an interval of the concave portions of 0.1 to 500 μm and 0.1 to 500 μm, respectively, and a contact angle between the convex portion of the resin plate and the ink. Characterized by being coated with a non-transfer layer having an angle of 90 ° or more. The resin plate according to claim 1, wherein the non-transfer layer is a monomolecular layer. The resin plate according to claim 3, wherein the monomolecular layer is made of any one of a thiol compound, a disulfide compound, and an organic silane compound. The resin plate according to any one of claims 1 to 4, wherein a base layer is provided below the non-transfer layer. In a resin plate for letterpress printing having at least an ink transfer portion and the width and interval of the protrusions being 0.1 to 500 μm and 0.1 to 500 μm, respectively, the protrusions on the resin plate are coated with a resist. A step of coating a concave layer of the resin plate with a base layer, a step of removing the resist, and a step of coating a non-transfer layer having a contact angle with ink of 90 ° or more on the base layer. A method for producing a convex resin plate, which is a feature. At least having an ink transfer portion, the width of the concave portion, the resin plate for intaglio printing having an interval of 0.1 to 500 μm and 0.1 to 500 μm, respectively, a step of coating a resist on the concave portion on the resin plate, A step of coating the convex portion of the resin plate with a base layer, a step of removing the resist, and a step of coating the base layer with a non-transfer layer having a contact angle with ink of 90 ° or more. A method for producing a concave resin plate. The method according to claim 6, wherein the non-transfer layer is a monomolecular layer. The method according to claim 8, wherein the monomolecular layer is made of any one of a thiol compound, a disulfide compound, and an organic silane compound.

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