JP2007258217A - Printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing method for stably printing a high precision pattern with excellent reproducibility on a flexible substrate. <P>SOLUTION: The printing method includes an ink-peelable substrate preparing step of forming a peelable layer on a base material to prepare the ink-peelable substrate, an ink liquid film forming step of forming an ink liquid film on the peelable layer, an image pattern and non-image pattern forming step of forming an image pattern and a non-image pattern on the peelable layer by bringing a mold into contact with the ink liquid film, and an image pattern transfer step of transferring the image pattern onto the flexible substrate to be printed by bringing the image pattern into contact with the substrate. The base material is glass, a semiconductor wafer or metal. The mold is glass, a semiconductor wafer or metal. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a method for finely printing on a flexible substrate, and more particularly to a nanoimprint method using a mold.

In recent years, nanoimprinting has attracted attention as a fine printing method.
The nanoimprint method is a method of forming a pattern of indentation on a transfer material by pressing a mold (mold) on which a pattern has been formed in advance onto a substrate, and then applying the transfer material on which the pattern of indentation has been formed to the substrate to be printed. And forming a pattern on the substrate to be printed.

However, it is difficult to reflect the shape of the convex portion formed in the mold on the shape of the concave portion of the transfer material.

As a method for overcoming this problem, an offset liquid embossing method has been proposed. (See Non-Patent Document 1)

Appl. Phys. Lett. 84, 3507 (2004).

However, since the mold and the ink releasable substrate used in the offset liquid embossing method are soft materials mainly composed of polydimethylsiloxane, they are liable to swell and alignment defects due to stress deformation are likely to occur.
In addition, since the indentation pattern cannot be strongly pressed when the transfer material is formed, the transfer material and the mold pattern are limited.

An object of the present invention is to provide a printing method for stably printing a high-definition pattern having excellent reproducibility on a flexible substrate.

The invention according to claim 1 is an ink releasable substrate preparation step for forming an ink releasable substrate by forming a release layer on a substrate;
An ink liquid film forming step of forming an ink liquid film on the release layer;
An image pattern and a non-image pattern forming step for forming an image pattern and a non-image pattern on the release layer by contacting a mold with the ink liquid film;
A printing method comprising an image pattern transfer step of transferring an image pattern onto a flexible printing substrate by contacting the image pattern with the flexible printing substrate,
The printing method is characterized in that the substrate is made of glass, a semiconductor wafer, or a metal, and the mold is made of glass, a semiconductor wafer, or a metal.

The invention according to claim 2 is the printing method according to claim 1, wherein the release layer has a silicone resin.

According to a third aspect of the present invention, the ink-peelable substrate is obtained by chemically bonding at least one of an alkyl group, a siloxane group, and a fluorine atom to the substrate surface via a silane coupling agent. The printing method according to claim 1, wherein:

The printing method of the present invention can stably print a high-definition pattern having excellent reproducibility on a flexible substrate.

The printing method of the present invention will be described with reference to FIG.

First, the release layer 2 is formed on the substrate 1. (See Fig. 1 (a))

As a material of the substrate 1, glass, a semiconductor wafer, and a metal can be used.

As a material for the release layer 2, a silicone resin or a silane coupling agent can be used.

The thickness of the silicone resin layer is 500 μm or less, preferably 100 μm or less, more preferably 10 μm or less.
When this silicone resin layer is thick, the flatness of the release layer 2 is impaired, and uneven printing pressure is likely to occur.

As a method for forming the silicone resin on the substrate 1, a method in which a solution in which a silicone resin is dissolved in a solvent such as alcohol is applied on the substrate 1 using a spin coating method and then dried can be used. .

By using a silane coupling agent as the material of the release layer 2, it is possible to form a release layer having a molecular thickness.

As the silane coupling agent, trimethoxysilanes and triethoxysilanes that can react with a glass plate can be used.
One part of this silane coupling agent can be selected from those having a reactive group with an organic compound such as a vinyl group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an alkyl group or a part thereof. Those having a fluorine atom substituted thereon and those having a substituent bonded to form a surface with a small surface energy by bonding with siloxane can be used.
In the case of using the former reactive group-containing silane coupling agent, after treating the surface of the glass plate with the silane coupling agent, coating with other monomer components so as to have a predetermined surface free energy, Can be combined.
Examples of the silane coupling agent having a reactive group include vinyl methoxy silane, vinyl ethoxy silane, p-styryl trimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 2- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane. , 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, etc., and styrene, ethylene glycol diglycidyl ether, trimethylpropane triglycidyl ether, lauryl acrylate, dipentaerythritol hexa Acrylate or the like can be used.
As the silane coupling agent having no reactive group, methyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, dodecyltrimethoxysilane and the like can be used.
However, it is not limited to an alkyl group.

As a method for forming the silane coupling agent on the substrate 1, for example, a solution in which the silane coupling agent is diluted with water, acetic acid water, a water-alcohol mixed solution, or an alcohol solution is prepared, and the solution is spin-coated. It is possible to use a method in which coating is performed on the substrate 1 using a method, a roll coating method, an applicator method, or the like, followed by drying.

Next, an ink liquid film 3 is formed on the release layer 2. (See Fig. 1 (b))

Examples of the method for forming the ink liquid film 3 include spin coating, die coating, cap coating, roll coating, applicator method, spray coating method, and dispenser method. Among these, the spin coat method, die coat method, cap coat method, roll coat method, and applicator method can form a uniform ink liquid film for inks having a wide range of viscosities.

Next, the mold 10 is brought into contact with the ink liquid film 3 and then released to reflect the shape of the convex portion formed on the mold 10 in the ink liquid film (the image pattern 31 and the non-image). A mixed pattern of patterns 32) was formed. (See FIG. 1 (c), FIG. 1 (d), FIG. 1 (e))

Finally, the flexible printed substrate 4 was brought into contact with the mixed pattern 30 and then released to form an image pattern 31 on the flexible printed substrate 4. (See FIG. 1 (f), FIG. 1 (g), FIG. 1 (h))

As a material of the flexible substrate 4 to be printed, any material other than a flexible material such as glass can be applied. For example, polyethylene terephthalate, polyethylene naphthalate, poly A film or sheet of ether sulfone, cycloolefin polymer, polyimide, nylon, aramid, polycarbonate, polymethyl methacrylate, polyvinyl chloride, triacetyl cellulose, or the like can be used.
What is necessary is just to select according to the drying conditions of the ink applied to printing, and polyethylene naphthalate, polyether sulfone, a cycloolefin polymer, a polyimide, etc. are suitable as a heat resistant thing.
Moreover, the base material which consists of the material which added the inorganic filler to resin and improved heat resistance may be sufficient.
The film and sheet may be a stretched film or an unstretched film, and the flexible substrate has a gas barrier layer, a smoothing layer, or a sliding layer laminated on the printing surface or other surface as necessary. Also good.

In order to ensure the close contact between the flexible printed substrate 4 and the image pattern 31, an adhesive layer may be provided on the flexible printed substrate 4.

Here, an example of the printing apparatus of the present invention will be described with reference to FIG.

The printing apparatus includes a movable stage 5, an ink peelable substrate 9, a coating die 6, a dryer 21, a mold 10, a mold fixing tool 7 for fixing the mold, a back roll 20, and a cleanup roll 8. It is installed. (Fig. 2 (a))

The movable stage 5 can be driven by a ball screw or a linear motor. The movable stage 5 can reciprocate while maintaining at least the horizontal direction, and the ink-peelable substrate 9 is fixed to the movable stage.

A predetermined ink can be supplied to the coating die 6 from a separately prepared ink supply pump.
The distance between the die head of the coating die 6 and the ink peelable substrate 9 is set before the start of printing.

A mechanism for adjusting the distance between the ink-peelable substrate 9 and the die head by moving the die head up and down in accordance with the conveyance of the movable stage 5 may be provided.

When the ink-peelable substrate 9 reaches under the coating die by the transport of the movable stage 5, ink discharge is started from the coating unit die head to form the ink liquid film 3 on the ink-peelable substrate 9. (Fig. 2 (b))

The ink-peelable substrate 9 is conveyed in the direction of the mold fixing tool 7, but a dryer 21 such as an oven, a hot air blower, a vacuum dryer, or an ultraviolet irradiator may be provided on the way.

A mold 10 is fixed to the mold fixing device 7.
The mold fixing tool 7 may be provided with a mechanism for moving up and down in accordance with the transport state of the movable stage.

After the movable stage 5 is conveyed directly below the mold 10, the mold 10 is lowered and the mold 10 is pressed against the ink liquid film 3, whereby the shape of the mold 10 is transferred to the ink liquid film 3.

The flexible printed substrate 4 can be brought into contact with the mixed pattern 30 (mixed pattern of the image pattern 31 and the non-image pattern 32) by the back roll 20.
By rotating the back roll 20, the ink liquid film 3 formed on the ink peelable substrate 9 can be transferred onto the flexible substrate 4 to obtain the image pattern 31.

The cleanup roll 8 is in contact with the ink peelable substrate 9 via an adhesive base 40 made of an adhesive tape or the like, and the non-image pattern 32 on the ink peelable substrate 9 is rotated by the rotation of the cleanup roll 8. Can be transferred to the adhesive substrate 40 to clean up the non-image pattern 32 from the ink-peelable substrate 9.

First, a solution in which n-hexyltrimethoxysilane was dissolved in isopropyl alcohol was applied on a glass plate having a thickness of 700 μm using a spin coating method, and then dried at 120 ° C. to form a release layer. .

Next, a mixture of the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm mesh filter to prepare a red pigment dispersion. .
・ C. I. Pigment Red 254 (Irga Four Red B-CFJ manufactured by Ciba Specialty Chemicals) 18 parts by weight C.I. I. Pigment Red 177 (Chromotar Red A2BJ, manufactured by Ciba Specialty Chemicals) 2 parts by weight / Acrylic varnish (solid content 20%) 108 parts by weight

Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm mesh filter to obtain a red ink for a color filter.
-100 parts by weight of the above-mentioned red pigment dispersion-20 parts by weight of methylated methylol melamine: MW-30 (manufactured by Sanyo Kasei Co., Ltd.)-Leveling agent: 1 part by weight of Megafac F-483SF (manufactured by Dainippon Ink & Chemicals, Inc.) 85 parts by weight of propylene glycol monomethyl ether, 45 parts by weight of propylene glycol monomethyl ether acetate

Next, after applying the adjusted red ink for color filter on the release layer, preliminary drying was performed at 60 ° C. to form an ink liquid film.

Next, an image pattern was formed on the release layer by bringing a silicon wafer mold into contact with the ink liquid film and then releasing the mold.

Finally, PEN (polyethylene naphthalate) (manufactured by Teijin DuPont) was brought into contact with the image pattern, and then released to form an image pattern on the PEN.

First, a solution in which dodecyltrimethoxysilane was dissolved in isopropyl alcohol was applied on a glass plate having a thickness of 700 μm using a spin coating method, and then dried at 120 ° C. to form a release layer.

Next, after applying a conductive ink composed of a silver particle aqueous dispersion (average particle size 20 nm) (volume average particle size (Dv)) on the release layer, the ink liquid film is preliminarily dried at 60 ° C. Formed.

Next, an image pattern was formed on the release layer by bringing a glass mold into contact with the ink liquid film and then releasing the mold.

Next, an acrylic aqueous emulsion material was applied onto polyethylene terephthalate (PET) (manufactured by Toray Industries, Inc.) with a bar coater, and then dried at 60 ° C. to form an ink adhesion layer on polyethylene terephthalate (PET).

Finally, the ink adhesion layer was brought into contact with the image pattern formed on the release layer, and then released to form an image pattern on the PET substrate.

Since the printing method of the present invention can stably perform high-definition printing on a flexible substrate such as a plastic film, a color filter member such as a black matrix, a white matrix, a color pattern, or a spacer, a gate electrode, and a source It can be used for the production of polymer organic EL members such as electrodes, drain electrodes, gate insulating films, transistor members such as organic semiconductor materials, and light emitting layers.

It is sectional drawing for demonstrating one example of the printing method of this invention. It is a schematic diagram for demonstrating one example of the printing apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base body 2 ... Release layer 3 ... Ink liquid film 4 ... Flexible substrate 5 ... Movable stage 6 ... Coating die 7 ... Mold fixing device 8 for fixing the mold ... Clean roll 9 ... Ink peelable substrate 10 ... Mold 20 ... Back roll 21 ... Dryer 30 ... ..Mixed pattern 30 (mixed pattern of image pattern 31 and non-image pattern 32)
31 ... Image pattern 32 ... Non-image pattern 40 ... Adhesive substrate

Claims (5)

An ink releasable substrate production process for producing an ink releasable substrate by forming a release layer on the substrate;
An ink liquid film forming step of forming an ink liquid film on the release layer;
An image pattern and a non-image pattern forming step for forming an image pattern and a non-image pattern on the release layer by contacting a mold with the ink liquid film;
A printing method comprising an image pattern transfer step of transferring an image pattern onto a flexible printing substrate by contacting the image pattern with the flexible printing substrate,
The printing method, wherein the substrate is made of glass, a semiconductor wafer, or a metal, and the mold is made of glass, a semiconductor wafer, or a metal. The printing method according to claim 1, wherein the release layer includes a silicone resin. 2. The ink-peelable substrate is obtained by chemically bonding at least one of an alkyl group, a siloxane group, and a fluorine atom to the substrate surface via a silane coupling agent. Printing method. Cleaning up the non-image pattern remaining on the ink peelable substrate after the image pattern forming step, and again, a printing method using the ink peelable substrate,
By feeding the adhesive substrate from the feeder and running the fed adhesive substrate, pressing it with a back roll to contact the non-image pattern and transferring the non-image pattern onto the adhesive substrate The printing method according to claim 1, wherein the non-image pattern is cleaned from the ink-peelable substrate. Means for applying ink to the ink releasable substrate;
Means for semi-drying the ink;
A mold used to form an image pattern and a non-image pattern on the ink-peelable substrate;
A fixing device for fixing the mold;
Means for transferring the image pattern and the non-image pattern to a flexible substrate to be printed;
A printing apparatus having means for cleaning up the non-image pattern from the ink-peelable substrate,
The means for applying ink to the ink peelable substrate includes: a movable stage; the ink peelable substrate that can be fixed to the movable stage; and a coating die for applying the ink to the ink peelable substrate. Have
A means for transferring the image pattern to the flexible printing substrate supplies a back roll for pressing the flexible printing substrate against the image pattern, and the flexible printing substrate. And a holder for winding up the flexible substrate to be printed on which the image pattern is formed,
Means for cleaning up the non-image pattern from the ink-peelable substrate includes an adhesive substrate, a cleanup roll for pressing the adhesive substrate against the non-image pattern, and the adhesive substrate. A printing apparatus comprising a feeder for feeding and a holder for winding up an adhesive substrate to which a non-image pattern is attached.