JP2003190876A - Method for producing pattern sheet and method for forming fine pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing pattern sheet using a sheet-like material having a hydrophilic-water repellent pattern which does not deteriorate the performance of a coating solution and to provide a method for forming a fine pattern using the pattern sheet which is produced by the method for producing the pattern sheet, and the method for forming the fine pattern using the pattern sheet produced by the method for producing the pattern sheet wherein the pattern sheet is produced by applying the coating solution on the part having hydrophilicity of the sheet-like material formed with the hydrophilic- water repellent pattern on the surface thereof and solidifying the coating solution. <P>SOLUTION: The part of rugged structure 21 which confirms the lotus effect repelling liquid by forming a microscopic rugged structure on the surface of the sheet-like material 2 is arranged across a flatter part than the rugged structure 21 and, subsequently, the coating solution is applied on the flatter part of the surface of the sheet-like material 2 and is solidified. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern for producing a pattern sheet by applying a coating solution to a hydrophilic portion of a sheet-like material having a hydrophilic-water repellent pattern formed on the surface and solidifying the coating solution. The present invention relates to a sheet manufacturing method and a fine pattern forming method using a pattern sheet manufactured by such a pattern sheet manufacturing method.

[0002]

2. Description of the Related Art Conventionally, as a material for an electronic display such as a color filter or an organic EL, a micron of a single color or a plurality of colors, for example, R (red), G (green) and B (blue), on a sheet. A pattern sheet on which an orderly fine stripe-shaped or matrix-shaped pattern is formed is used.

As a method for producing this pattern sheet, first, a sheet-like article having a hydrophilic-water-repellent pattern having a hydrophilic portion and a water-repellent portion is prepared on the surface, and then this sheet-like article is prepared. There is known a method for producing a pattern sheet having a patterned coating layer by applying a coating liquid to the hydrophilic portion of the above and solidifying the coating liquid. Various methods have been proposed for obtaining a hydrophilic-water repellent pattern on the surface of a sheet-like material (Japanese Patent Laid-Open No. 2000-8).
7016, JP-A-2000-228240,
JP 2000-223270 A, JP 2001-2
57073, JP-A-7-244370, etc.). For example, in Japanese Patent Laid-Open No. 2000-87016,
It has been proposed to use a sheet-like material containing a photocatalyst that becomes hydrophilic by light irradiation. In this publication, it is described that the water repellency of the unexposed portion is unexpectedly increased by forming the surface of the sheet-shaped material into a finely textured structure.

[0004]

However, this publication does not clarify the mechanism by which the fine concavo-convex structure enhances the water repellency, and as a preferable roughness of the fine concavo-convex structure for enhancing the water repellency, the center line is used. While it is described that the average roughness is 0.1 to 50 μm, in the description of Comparative Example 1, the center line average roughness is 0.26.
It is described that the water repellency is not sufficiently improved when it is μm, and it cannot be said that the explanation about the improvement of the water repellency by the fine concavo-convex structure lacks logicality. Further, the photocatalyst contained in the surface of the sheet-like material may affect the coating liquid, and the performance of the coating liquid may be degraded.

As a material for electronic displays,
The coating layer formed on the pattern sheet is transferred onto the surface of the support on which the electrodes are formed without using the pattern sheet thus manufactured, and the support on which the coating layer is transferred is used as a material for an electronic display. Sometimes used as.

In view of the above circumstances, the present invention provides a method for producing a pattern sheet using a sheet material having a hydrophilic-water repellent pattern which does not deteriorate the performance of a coating solution, and a method for producing such a pattern sheet. An object of the present invention is to provide a fine pattern forming method using a pattern sheet manufactured by.

[0007]

A method for manufacturing a patterned sheet according to the present invention which achieves the above-mentioned object is to provide a surface of a sheet-like material with a concavo-convex structure portion which effectively repels liquid by a fine concavo-convex structure. It is characterized in that a smoother portion than the concavo-convex structure is arranged so as to sandwich it, and then a coating liquid is applied to the smooth portion of the surface of the sheet-like material to be solidified.

According to the method for producing a pattern sheet of the present invention, a hydrophilic-water-repellent pattern is obtained by the above-mentioned smooth portion and the concavo-convex structure which makes the Lotus effect effective, so that the performance of the coating solution is not deteriorated. .

Further, in the method for producing a patterned sheet of the present invention, the height of the uneven structure portion on the surface of the sheet material is 10 nm or more and 3 μm or less, or the height of the uneven structure portion on the surface of the sheet material. The pitch is preferably 10 nm or more and 3 μm or less.

By doing so, the Lotus effect can be surely made effective.

Further, in the method for producing a patterned sheet according to the present invention, it is more preferable that both the height and pitch of the concave-convex structure portion on the surface of the sheet material are 10 nm or more and 3 μm or less.

By thus defining both the height and the pitch of the concave-convex structure portion, the Lotus effect can be more reliably achieved.

In the method for producing a patterned sheet of the present invention, it is preferable that the uneven structure on the surface of the sheet-like material is formed by an embossing method.

By adopting the embossing method, a sheet-like material having a hydrophilic-water repellent pattern can be easily obtained.

Further, in the method for producing a patterned sheet of the present invention, it is more preferable that the embossing method is performed at a temperature of 100 ° C. or higher.

By doing so, a sheet-like material having a hydrophilic-water repellent pattern can be obtained more efficiently.

Here, in the method for producing a patterned sheet of the present invention, the coating liquid may be an organic electroluminescent material, or the sheet-like material may be polyethylene terephthalate, polyether sulfone, and polyimide. It may be one selected from the group consisting of

In the fine pattern forming method of the present invention for achieving the above object, the pattern sheet produced by the method for producing a pattern sheet of the present invention is placed on a support on which electrodes are formed, and the above coating solution is applied. It is characterized in that it is transferred to the support side.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a case of forming an organic thin film layer will be described as an embodiment of the present invention. The organic thin film layer formed in this embodiment is sandwiched between a pair of counter electrodes and used as a light emitting element. That is, by applying an electric field between a pair of opposing electrodes sandwiching the organic thin film layer, while injecting electrons from the cathode into the organic thin film layer,
Holes are injected from the anode. The injected electrons and holes are recombined in the organic thin film layer, energy is emitted as light when the energy level returns from the conduction band to the valence band, and the organic thin film layer emits light.

In the following description, a patterned organic thin film layer is once formed on the surface of a sheet-shaped temporary support, and the organic thin film layer is transferred to the surface of the support to form the organic thin film layer on the surface of the support. A method of forming will be described.

FIG. 1 is a simplified view showing a state of a temporary support treatment line during the formation of the organic thin film layer on the temporary support.

The temporary support treatment line 1 shown in FIG. 1 is for carrying out a method for forming an organic thin film layer on the surface of a temporary support, which is one embodiment of the method for producing a patterned sheet of the present invention. It is a line, while transporting the temporary support,
This is a line for sequentially performing embossing, coating, and drying on a temporary support. In such a temporary support processing line 1, a delivery roll 10 is provided at the upstream end, and a heating roll 20, a rotating roll 30, a coating device 40, and a drying device 50 are also provided along the transport path. Furthermore, in this temporary support processing line 1, a rotating roll 30
An embossing roll 60 is provided at a position facing the.

The temporary support 2 shown in FIG. 1 is a long sheet-like material made of polyethylene terephthalate (PET) and having a thickness of 100 μm. The surface of this sheet-like material is smooth, and the height and pitch of the uneven structure when viewed microscopically are both less than 10 nm, and the hydrophilicity of 60 degrees in terms of contact angle with water is obtained. Have. Such a temporary support 2
Is set on the delivery roll 10 in a state of being wound into a roll, and is transported through the transport path of the temporary support processing line 1 (see the arrow in the figure). The temporary support is not limited to that of the present embodiment, and may be a flexible sheet-like material that is chemically and thermally stable and has a hydrophilic surface. Specifically, polyether sulfone (PES),
Polyimide, polyester [eg polyethylene terephthalate, polyethylene naphthalate (PEN)]],
A thin sheet of polyarylate, polycarbonate, or the like, or a laminate of these is preferable. Moreover, the thickness of the temporary support may be 1 μm to 300 μm, and particularly 3 μm when an organic thin film layer having a fine pattern is formed.
It is preferably m to 20 μm.

The temporary support 2 delivered from the delivery roll 10 is heated to about 120 ° C. by the heating roll 20 and then embossed. If the heating temperature of the temporary support by the heating roll 20 is 100 ° C. or higher, embossing can be efficiently performed.

The embossing is performed between the rotating roll 30 and the embossing roll 60. This emboss roll 6
An uneven pattern is formed on the peripheral surface of 0.

Here, once separated from FIG. 1, the peripheral surface of the embossing roll will be described in detail with reference to FIG.

FIG. 2 is a view showing a part of the peripheral surface of the embossing roll shown in FIG.

A plan view showing a part of the peripheral surface 61 of the embossing roll 60 is shown on the left side of FIG. 2, and a right side of FIG. 2 is surrounded by a one-dot chain line in the plan view on the left side. A partially enlarged view of the range is shown.

The peripheral surface 61 of the embossing roll 60 shown in FIG. 2 is provided with a plurality of rectangular regions 511 in a matrix. Each of these rectangular regions 511 has a vertical length of 100 μm and a horizontal length of 50 μm, as shown in a partially enlarged view on the right side. The vertical and horizontal intervals between the rectangular regions 511 adjacent to each other are 10 μm. The height and pitch of the peripheral surface 61 of the embossing roll 60 excluding these rectangular areas 511 are 30
An uneven pattern of 0 nm is formed. On the contrary, each of these rectangular areas 511 is a smooth area,
Both the height and pitch of the uneven structure when viewed microscopically are less than 10 nm.

The temporary support is embossed by being embossed by the peripheral surface 61 of the embossing roll 60 as shown in FIG. 2 while being wound around the rotating roll 30. On the surface of the temporary support that has been embossed,
Both height and pitch are 300 nm with a rectangular smooth surface sandwiched between them.
The uneven pattern of is patterned. The concavo-convex pattern formed on the surface of the temporary support has a concavo-convex structure that makes the Lotus effect of repelling liquid effective, and the portion of the surface of the temporary support on which the concavo-convex pattern is formed is made water repellent. The water repellent portion of the surface of the temporary support has a water repellency of 104 degrees in terms of the contact angle with water. On the other hand, of the surface of the temporary support, the rectangular smooth surface portion is 6 in terms of contact angle with water.
It remains hydrophilic at 0 degrees.

By the embossing as described above,
On the surface of the temporary support, the water-repellent portions are arranged with the rectangular hydrophilic portions sandwiched therebetween. As described above, in the temporary support treatment line of this embodiment, a hydrophilic-water-repellent pattern can be formed on the surface of the temporary support simply by passing the temporary support between the rotating roll 30 and the embossing roll 60. . Also, while the temporary support is being transported,
Such embossing can be continuously performed, and the processing efficiency is good.

In the process of casting a molten polyethylene terephthalate (PET) on the peripheral surface of a rotating cooling drum and cooling on the peripheral surface, a sheet-shaped temporary support is manufactured. The peripheral surface of the temporary support may be formed on the peripheral surface of the cooling drum in the same manner as the peripheral surface 61 of the embossing roll 60 shown in FIG. Does not require embossing.

Here, referring to FIG. 1 again, the process after the embossing in the temporary support processing line 1 will be described.

The temporary support 2 having the hydrophilic-water repellent pattern formed thereon is conveyed to the coating device 40 and subjected to coating treatment. The coating liquid 3 applied by this coating treatment contains at least one luminescent compound. The content of the luminescent compound is not particularly limited, but is, for example, 0.1 to 70% by mass.
And is preferably 1 to 20 mass%. When the content of the light emitting compound is less than 0.1% by mass or exceeds 70% by mass, the light emitting effect may not be sufficiently exhibited. Further, the light emitting compound is not particularly limited, and may be a fluorescent light emitting compound or a phosphorescent light emitting compound, or a fluorescent light emitting compound and a phosphorescent light emitting compound may be used at the same time. .

In the present embodiment, a phosphorescent compound is used from the viewpoint of luminous brightness and luminous efficiency. Specifically, an orthometalated complex which is a compound capable of emitting light from triplet excitons is used. The ortho-metallated complex referred to here is “Organometallic Chemistry: Fundamentals and Applications” by Akio Yamamoto, pp. 150 and 232, Sokabosha (198)
2 years), H. Yersin "Photochemi
story and Photophysics of
Coordination Compounds ",
71-77 and 135-146, Springe
It is a general term for a group of compounds described in r-Verlag (1987) and the like. The ligand forming the orthometallated complex is not particularly limited, but it may be a 2-phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2- (2-thienyl) pyridine derivative, a 2- (1-naphthyl) pyridine derivative or It is preferably a 2-phenylquinoline derivative. These derivatives may have a substituent. Further, it may have other ligands in addition to the ligands essential for forming the orthometalated complex. As the central metal forming the ortho-metallated complex, any transition metal can be used, and rhodium, platinum, gold, iridium, ruthenium, palladium and the like can be preferably used. The organic compound layer containing such an orthometalated complex is excellent in light emission brightness and light emission efficiency. Specific examples of orthometalated complexes are described in Japanese Patent Application No. 2000-254171, paragraphs 0152 to 0180. In addition, the ortho-metallated complex used in the present embodiment is described in Inorg. Chem. , 30, 168
5, 1991, Inorg. Chem. , 27,
3464, 1988, Inorg. Chem. ，
33, 545, 1994, Inorg. Chi
m. Acta, 181, 245, 1991,
J. Organomet. Chem. , 335
293, 1987, J. Am. Chem. S
oc. , 107, 1431, 1985 and the like, can be used for the synthesis.

A porphyrin complex may be used instead of the orthometalated complex. The porphyrin complex is also a phosphorescent compound like the orthometalated complex. Among the porphyrin complexes, the porphyrin platinum complex is preferable. The phosphorescent compounds may be used alone or in combination of two or more.

Further, when a fluorescent light emitting compound is used as the light emitting compound, a benzoxazole derivative, a benzimidazole derivative, a benzothiazole derivative, a styrylbenzene derivative, a polyphenyl derivative, a diphenylbutadiene derivative, a tetraphenylbutadiene derivative, naphthalimide. Derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, pyraridine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, styrylamine derivatives, aromatics Dimethylidene compound, metal complex (metal complex of 8-quinolinol derivative, rare earth complex, etc.), polymer light-emitting compound (polythiophene derivative, polyphenylene compound) Vinylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives and the like), or the like can be used. These may be used alone or in combination of two or more.

Furthermore, if necessary, the coating liquid 3
A host compound, a hole transport material, an electron transport material, an electrically inactive polymer binder and the like may be contained.

The host compound is a compound that causes energy transfer from its excited state to the light emitting compound, and as a result causes the light emitting compound to emit light. Specific examples thereof include a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivative, and a styrylanthracene derivative. , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidene compound, porphyrin compound, anthraquinodimethane derivative, anthrone derivative, diphenylquinone derivative, thiopyran dioxide Heterocyclic tetra derivatives such as derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, and naphthaleneperylene Rubonic acid anhydride, phthalocyanine derivative, metal complex of 8-quinolinol derivative, metal phthalocyanine, metal complex having benzoxazole or benzothiazole as a ligand, polysilane compound, poly (N-vinylcarbazole) derivative, aniline copolymer Conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives and the like. The host compounds may be used alone or in combination of two or more.

The hole transport material is not particularly limited as long as it has any of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking the electrons injected from the cathode, and it is not particularly limited. It may be a molecular material or a polymeric material. Specific examples thereof include a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino-substituted chalcone derivative, and a styrylanthracene derivative. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, poly (N
-Vinylcarbazole) derivative, aniline copolymer, thiophene oligomer, conductive polymer such as polythiophene, polythiophene derivative, polyphenylene derivative, polyphenylenevinylene derivative, polyfluorene derivative and the like. These may be used alone or in combination of two or more.

The electron transport material is not particularly limited as long as it has any of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking the holes injected from the anode. Triazole derivative, oxazole derivative, oxadiazole derivative, fluorenone derivative, anthraquinodimethane derivative, anthrone derivative, diphenylquinone derivative, thiopyran dioxide derivative, carbodiimide derivative, fluorenylidenemethane derivative, distyrylpyrazine derivative, naphthaleneperylene, etc. Heterocyclic tetracarboxylic acid anhydride, phthalocyanine derivative, metal complex of 8-quinolinol derivative, metallophthalocyanine, metal complex having benzoxazole, benzothiazole, etc. as a ligand, aniline copolymer, thiophene oligomer, Conductive polymer, polythiophene derivatives such as thiophene, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives and the like can be used.

As the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin,
Polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal and the like can be used. When a coating solution contains a polymer binder,
The coating liquid can be easily applied to a large area.

Coating device 4 for coating such coating liquid 3
Reference numeral 0 is a coating device adopting a roll coating method, which includes a roll coater 401. This roll coater 40
No. 1 is arranged such that its surface is in contact with the surface of the transported temporary support, and is rotated during the coating process. In the coating process, by rotating the roll coater 401, the coating liquid 3 is supplied to the surface of the roll coater and the coating liquid is coated on the surface of the temporary support. In addition, a coating device employing a spin coating method, a screen printing method, a gravure coating method (for example, a micro gravure coating method), a dip coating method, a casting method, a die coating method, a bar coating method, an extrusion coating method, an inkjet coating method, or the like. May be used.

When the coating treatment as described above is performed, the applied coating liquid is repelled in the water-repellent portion of the transported temporary support, and the coating liquid 3 is applied only to the hydrophilic portion. Remains. As described above, in the present embodiment, since the other coating liquid is not coated on the surface of the temporary support before the coating treatment is performed, there is no fear that the performance of the coating liquid is deteriorated.

A coating solution containing a blue light-emitting compound, a coating solution containing a green light-emitting compound, and a coating solution containing a red light-emitting compound were prepared, and these coating solutions were applied. It is also possible to form an organic thin film layer in which light emitting pixels of three primary colors of blue, green and red are patterned on the surface of the temporary support by sequentially applying it in a predetermined pattern through a mask for use. The material of the coating mask is not limited, but a durable and inexpensive material such as metal, glass, ceramic, and heat resistant resin is preferable. Further, these materials can be used in combination. From the viewpoint of mechanical strength and pattern accuracy of the light emitting pixel of the organic thin film layer,
The thickness of the mask is preferably 2 to 100 μm,
5-60 micrometers is more preferable.

Finally, the temporary support 2 coated with the coating liquid
Is transported to the drying device 50 and dried. In this drying process, the coating liquid applied in the previous coating process is dried and solidified. The solidified coating solution becomes an organic thin film layer. Therefore, the organic thin film layer is formed along the hydrophilic pattern on the temporary support that has been subjected to the drying treatment.

Subsequently, the organic thin film layer formed on the surface of the temporary support thus manufactured is transferred to the surface of the support on which the electrodes are formed to form an organic thin film layer on the surface of the support. The method for doing so will be described.

FIG. 3 is a diagram showing a rough flow from the formation of the organic thin film layer on the temporary support to the formation of the organic thin film layer on the support using the temporary support and the support.

FIGS. 3A to 3C show the flow of forming the organic thin film layer on the above-mentioned temporary support, and FIG. 3A schematically shows the state of embossing. It is a figure which shows, and (b) is a figure which shows the temporary support body after the embossing process typically. As described above, the embossing shown in (a) utilizes the Lotus effect by embossing the peripheral surface 61 of the embossing roll 60 as shown in FIG. 2 on the hydrophilic surface of the temporary support. The water repellent pattern is formed. By performing such embossing, as shown in (b), an uneven pattern 21 having a height and a pitch of 300 nm is imprinted on the surface of the temporary support 2 to form a hydrophilic-water repellent pattern. . (C) is a figure which shows typically the temporary support body in which the organic thin film layer was formed. The organic thin film layer 3 is formed only on a portion of the surface of the temporary support 2 on which the uneven pattern 21 is not molded.
0 is formed.

FIGS. 3D and 3E show the flow of forming the organic thin film layer on the surface of the support. The formation of the organic thin film layer on the surface of the support is roughly divided. Transfer processing and peeling processing are performed. (D) is a figure which shows the mode of the transfer process, (e) is a figure which shows the mode of the peeling process.

First, the support 4 is a substrate 41 on which a transparent electrode 42 is formed. Therefore, the support 4
Is the surface of the transparent electrode 42.

The substrate 41 is made of glass.
However, not limited to glass, inorganic materials such as zirconia-stabilized yttrium (YSZ), polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polystyrene, polycarbonate, polyether sulfone, polyarylate,
It may be made of a polymer material such as allyl diglycol carbonate, polyimide, polycycloolefin, norbornene resin, poly (chlorotrifluoroethylene), Teflon (registered trademark), polytetrafluoroethylene-polyethylene copolymer, or the like. . Among them, polymer materials are preferable for forming a flexible organic thin film layer on the support 4, and are excellent in heat resistance, dimensional stability, solvent resistance, electric insulation and processability, and have low air permeability and low moisture absorption. More preferred are polymeric materials containing a fluorine atom such as polyester, polycarbonate, polyether sulfone, poly (chlorotrifluoroethylene), Teflon, and polytetrafluoroethylene-polyethylene copolymer, which are organic. The substrate 41 may be formed of these single materials or two or more kinds of materials.

The substrate 41 has a plate-like single layer structure but may have a laminated structure, and the shape and size of the substrate 41 can be appropriately selected according to the use and purpose of the organic thin film layer. . Further, the substrate 41 is colorless and transparent in that it does not scatter or attenuate the light emitted from the organic thin film layer, but it may be colored and transparent.

The transparent electrode 42 formed on the substrate 41 has a function as an anode for supplying holes to the organic thin film layer, but can also function as a cathode. Hereinafter, the case where the transparent electrode 42 is used as an anode will be described.

The transparent electrode 42 of this embodiment is made of indium tin oxide (ITO). The shape, structure, size, etc. of the transparent electrode 42 are not particularly limited and can be appropriately selected according to the use and purpose of the organic thin film layer. The material for forming the transparent electrode 42 is not limited to indium tin oxide (ITO), and various metals, alloys, metal oxides, electrically conductive compounds, mixtures thereof, and the like can be used. It is preferable that the material has a function of 4 eV or more. Specifically, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), semiconductive metal oxides (tin oxide, zinc oxide, indium oxide, zinc indium oxide (IZ)
O) etc.), metals (gold, silver, chromium, nickel, etc.), mixtures or laminates of these metals and conductive metal oxides, inorganic conductive substances (copper iodide, copper sulfide, etc.), organic conductive materials (Polyaniline, polythiophene, polypyrrole, etc.) and laminates of these with ITO.

The transparent electrode 42 is formed on the substrate by the vacuum evaporation method. The method for forming the transparent electrode 42 may be appropriately selected in consideration of the suitability for the transparent electrode material, and may be a printing method, a wet method such as a coating method, a sputtering method including a vacuum deposition method, an ion plating method. And the like, and chemical methods such as CVD and plasma CVD. When ITO is used as the transparent electrode material as in this embodiment, a direct current or high frequency sputtering method, an ion plating method or the like can be used in addition to the vacuum deposition method. When an organic conductive material is used as the material of the transparent electrode 42, the wet film forming method is suitable.

The thickness of the transparent electrode 42 thus formed is 10 μm, and depending on the material, the thickness is from 10 nm to 10 nm.
It may be appropriately selected within a range of 50 μm, and may be 50 nm to 20 nm.
It is preferable to select appropriately in the range of μm. The resistance value of the transparent electrode 42 is preferably 10 ³ Ω / □ or less, more preferably 10 ² Ω / □ or less. Further, the transparent electrode 42 may be colorless and transparent or colored and transparent. Further, in order to take out the light emission of the organic thin film layer from the transparent electrode side, the transmittance thereof is preferably 60% or more, more preferably 70% or more. The transmittance can be measured according to a known method using a spectrophotometer. “New development of transparent conductive film”
Electrodes described in detail in (Supervised by Yutaka Sawada, published by CMC, 1999) and the like can also be applied as the transparent electrode of the present embodiment. In particular, when forming a transparent electrode on a plastic substrate having low heat resistance, it is preferable to use ITO or IZO as a transparent electrode material and form the film at a low temperature of 150 ° C. or lower.

In the transfer process shown in (d), the organic thin film layer 30 formed on the surface of the temporary support 2 is treated with such a support 4.
In the state of facing the surface of the transparent electrode 42, it is sandwiched between the temporary support 2 and the support 3 and brought into close contact with the surface of the transparent electrode 42. At this time, the organic thin film layer 30 is heated and softened using a thermal head. As the thermal head, for example, a thermal head for thermal transfer printing can be used. Further, the heating of the organic thin film layer 30 is not limited to using the thermal head, and a heating method using a laminator, an infrared heater, a laser, or the like can be used. The temperature for heating the organic thin film layer 30 (transfer temperature) is not particularly limited and can be changed depending on the material of the organic thin film layer. However, the heat resistant temperature of most organic coating layers is 200 ° C. or less. Therefore, it is preferable that the transfer temperature is 200 ° C. or lower.
By such a transfer process, the organic thin film layer 30 formed on the surface of the temporary support 2 adheres to the surface of the transparent electrode 42.

In the peeling process shown in (e), the temporary support 2 is peeled off from the organic thin film layer 30 adhered to the surface of the transparent electrode 42 by the transfer process, and the organic thin film layer 3 is formed on the surface of the transparent electrode 42.
This is a process of leaving only 0. By completing this peeling process, the organic thin film layer 42 is formed on the surface of the support 4. The organic thin film layer thus formed has a thickness of 10 to 10.
The thickness is preferably 200 nm, more preferably 20 to 80 nm. If the thickness exceeds 200 nm, the driving voltage may increase, and if it is less than 10 nm, the organic thin film layer may short-circuit.

The method of forming the organic thin film layer described above can be widely applied to the formation of multicolor fine patterns for electronic displays.

[0061]

EXAMPLES Examples to which the fine pattern forming method of the present invention is applied will be described below.

(Example 1) 60 in terms of contact angle with water
A polyethylene terephthalate (PET) film having a degree of hydrophilicity and a thickness of 100 μm was embossed by using the peripheral surface of the embossing roll shown in FIG. 2 while being heated to 120 ° C. By this embossing, an uneven pattern having a height and a pitch of 300 nm was imprinted on the surface of the PET film. Then, the organic EL light-emitting material is applied to the surface of the PET film on which such a concavo-convex pattern is formed by a roll coater at 10 m /
It was applied at a speed of min. As a result, 30 cc / m ² of organic EL light-emitting material was applied only to the portion of the PET film surface where the uneven pattern was not imprinted. After that, the PET film is dried at 100 ° C.
A fine pattern of the organic EL light emitting layer was formed on the surface of the TE film.

Subsequently, a PET film was introduced on a glass substrate on which a transparent electrode made of indium tin oxide (ITO) was formed so that the organic EL light emitting layer faced the transparent electrode, and between two rotating rubber rolls. Using a laminator (first laminator VA-400III manufactured by Taisei Laminator Co., Ltd.) of a type to be laminated at
kg / cm ² , temperature 160 ° C., delivery speed 5.0 cm / m
The glass substrate and the PTE film were thermocompression bonded under the condition of in, the organic EL light emitting layer formed on the PET film surface was transferred to the transparent electrode surface, and the organic EL light emitting layer was formed on the glass substrate.

In each of Examples 2 to 4 described below, embossing rolls having an uneven pattern having a height and a pitch different from the uneven pattern of the embossing roll used in Example 1 were used for embossing. Organic EL was formed on the glass substrate under the same conditions as in Example 1 except that the processing was performed.
A light emitting layer was formed.

(Embodiment 2) In the embossing processing in this Embodiment 2, an embossing roll having an uneven pattern with a height of 3 μm and a pitch of 4 μm formed on the peripheral surface was used. As a result, the height of the PET film was 3 μm and the pitch was 4
A μm relief pattern was imprinted.

(Embodiment 3) In the embossing processing in this Embodiment 3, an embossing roll having a concavo-convex pattern with a height of 4 μm and a pitch of 3 μm formed on the peripheral surface was used. As a result, the height of the PET film was 4 μm and the pitch was 3 μm.
A μm relief pattern was imprinted.

(Embodiment 4) In the embossing processing in this Embodiment 4, an embossing roll having a concavo-convex pattern of 3 μm in height and pitch on the peripheral surface was used. As a result, the height and pitch of the PET film are 3
A μm relief pattern was imprinted.

Further, similarly to the second to fourth embodiments, the organic EL light emitting layer is formed on the glass substrate by making only the pitch and height of the uneven pattern on the peripheral surface of the embossing roll different from the first embodiment. When I tried to do so, two cases were formed that could not be formed well, so I will introduce them as comparative examples.

(Comparative Example 1) In the embossing process in Comparative Example 1, an embossing roll having a concavo-convex pattern having a height and a pitch of 5 μm formed on the peripheral surface was used. As a result, on the surface of the PET film, both height and pitch are 5
A μm relief pattern was imprinted.

(Comparative Example 2) In the embossing process in Comparative Example 2, an embossing roll having an uneven pattern having a height and a pitch of 8 nm formed on the peripheral surface was used. As a result, the height and pitch of the PET film are 8
A nm asperity pattern was imprinted.

Table 1 shows each of the examples and the comparative examples.
The state of formation of the organic EL light emitting layer on the glass substrate and the water repellency determination result are shown in horizontal rows.

[0072]

[Table 1]

In Table 1, the degree of formation means that the size of the smooth rectangular area formed on the peripheral surface of the embossing roll is 1.
The ratio (formation rate) of the size of one fine rectangular pattern of the organic EL light emitting layer formed on the glass substrate with respect to the size of this rectangular region is shown as 00%. However, in the organic EL light emitting layer formed in Comparative Example 1, there were many rectangular patterns in which non-formed portions were scattered, so that the formation rate was not calculated and “there is a non-formed portion”. Further, since the organic EL light emitting layer formed in Comparative Example 2 was formed on almost the entire surface of the glass substrate and no pattern was formed, the pattern was not formed without determining the formation rate. The water repellency judgment result is P
It is the result of judging the water repellency of the TE film surface. That is, from the forming condition in each example and each comparative example,
The high formation rate of the organic EL light emitting layer on the glass substrate means that the formation rate on the PTE film is also high, and the high formation rate on the PTE film means that
The water repellency of the PTE film surface was judged as showing that the water repellency of the PTE film surface was reliably performed. Here, the formation rate of 98% or more is ⊚, and the formation rate of 80% or more is ∘. For each comparative example, it is determined that the portion of the uneven pattern does not sufficiently exhibit the Lotus effect and is not water repellent. did.

Comparing the forming conditions in Example 1, Example 2, and Comparative Example 1, the pitch of the concavo-convex structure of the concavo-convex pattern formed on the surface of the PET film was 3 μm.
It was found that the water repellency was improved when the thickness was m or less, and when the forming conditions in Example 1, Example 3, and Comparative Example 1 were compared, it was found that the water repellency was improved even when the height was 3 μm or less. . Further, from these two improvements in water repellency, it is understood that the water repellency is improved even if the pitch and height of the concavo-convex structure formed on the surface of the PET film are specified separately. It turns out to be preferable. That is, it is preferable that both the pitch and the height of the concavo-convex structure formed on the surface of the PET film are 3 μm or less. Further, it can be seen from the formation condition in Comparative Example 2 that the pitch and height of the concavo-convex structure molded on the surface of the PET film are close to a smooth surface and the Lotus effect is not exhibited if the pitch is too small. It is preferable that both the pitch and the height of the concavo-convex structure formed on the surface of the PET film are 10 nm or more. Furthermore, as a result of further study by the present inventors regarding the pitch and height of the concavo-convex structure to be molded on the surface of the PET film, both the pitch and height are
More preferably 100 nm or more and 1 μm or less,
It was concluded that the most preferable range is 200 nm or more and 400 nm or less.

Further, the present inventors have found that the glass substrate and PTE
As a result of further studies on the temperature (transfer temperature) for thermocompression bonding of the film, if the transfer temperature exceeds the heat-resistant temperature of the organic EL light-emitting material, the organic EL light-emitting material may be invalidated. It was found that the transfer efficiency was inferior even if it was too low. Therefore, the present inventors have found that the transfer temperature is
It is preferably 60 ° C or higher and 200 ° C or lower, and 80 ° C
It was concluded that the temperature is more preferably 180 ° C. or lower, and most preferably 100 ° C. or higher and 150 ° C. or lower.

[0076]

As described above, according to the present invention, a pattern sheet using a sheet-like material having a hydrophilic / water-repellent pattern on the surface of the sheet-like material which does not deteriorate the performance of the coating liquid. And a fine pattern forming method using the pattern sheet manufactured by such a method for manufacturing a pattern sheet.

[Brief description of drawings]

FIG. 1 is a diagram showing a simplified state of a temporary support treatment line during the formation of an organic thin film layer on a temporary support.

FIG. 2 is a diagram showing a part of a peripheral surface of the embossing roll shown in FIG.

FIG. 3 is a diagram showing a rough flow from the formation of the organic thin film layer on the temporary support to the formation of the organic thin film layer on the support using the temporary support and the support.

[Explanation of symbols]

1 Temporary support processing line 20 heating rolls 30 rotating rolls 40 coating device 50 dryer 60 embossing roll 601 circumference 2 Temporary support 21 uneven pattern 3 coating liquid 30 organic thin film layer 4 Supporting body 41 substrate 42 transparent electrode

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shotaro Ogawa             200, Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo             Within Film Co., Ltd. (72) Inventor Yoshihito Hosawa             200, Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 4D075 AC21 AC43 AC72 AC96 AE02                       BB06Y BB26Z BB93Y CA36                       CB08 CB26 CB33 CB37 DA04                       DA06 DB13 DB14 DB36 DB37                       DB39 DB48 DB53 DB55 DC24                       EA07 EB07 EB08 EB12 EB14                       EB15 EB19 EB22 EB33 EB35                       EB36 EB38 EB39 EB43 EB44                       EC07 EC60

Claims (11)

[Claims] 1. A sheet-shaped product is provided with a surface having an uneven structure for activating the Lotus effect of repelling a liquid by a fine uneven structure sandwiching a portion smoother than the uneven structure, and then the sheet-shaped product. A method for producing a pattern sheet, which comprises applying a coating solution to a smooth surface portion and solidifying the coating solution. 2. The method for producing a patterned sheet according to claim 1, wherein the height of the uneven structure portion on the surface of the sheet-like material is 10 nm or more and 3 μm or less. 3. The method for producing a patterned sheet according to claim 1, wherein the pitch of the portion of the uneven structure on the surface of the sheet is 10 nm or more and 3 μm or less. 4. The method for producing a patterned sheet according to claim 1, wherein both the height and pitch of the portion of the uneven structure on the surface of the sheet-like material are 10 nm or more and 3 μm or less. 5. The method for producing a patterned sheet according to claim 1, wherein the uneven structure on the surface of the sheet-like material is formed by an embossing method. 6. The method for producing a pattern sheet according to claim 5, wherein the embossing method is performed at a temperature of 100 ° C. or higher. 7. The method for producing a pattern sheet according to claim 1, wherein the coating liquid is an organic electroluminescent material. 8. The method for producing a patterned sheet according to claim 1, wherein the sheet-like material is polyethylene terephthalate. 9. The method for producing a patterned sheet according to claim 1, wherein the sheet-shaped material is polyether sulfone. 10. The method for producing a patterned sheet according to claim 1, wherein the sheet-shaped material is polyimide. 11. A pattern sheet manufactured by the method for manufacturing a pattern sheet according to claim 1 is placed on a support on which electrodes are formed, and the coating liquid is applied to the support side. A fine pattern forming method characterized by transferring.