JP2001166120A - Transfer body and method utilizing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer body including at least peelable layer 20, a transparent electrically conductive layer 30 and an adhesive layer 60 on the substrate 10. SOLUTION: The substrate 10 of glass or the like has such a heat resistance that it withstands heat treatment to each layer on the substrate 10 and also has a higher rigidity than a member (plastic film) to which each layer on the substrate 10 is transferred. A polyimide resin layer as the peelable layer 20 is formed in such a way that it has a tensile strength which is >=100 g/cm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

2. Description of the Related Art Conventionally, a transparent conductive layer, which is releasably laminated on a temporary support, is transferred onto a transparent substrate made of plastic via an adhesive, and the transparent substrate and the transparent conductive layer are transferred. Methods for producing laminates comprising are known.
Such a transparent conductive layer usually comprises an ITO (indium-tin-oxide) film.

For example, Japanese Patent Application Laid-Open No. 60-231396 discloses a transfer type laminate in which an ITO layer is provided on a temporary support so as to be peelable. This publication discloses a transfer-type laminate formed by evaporating an ITO layer on a support made of a Teflon (registered trademark) film and then performing a heat treatment in an oven at 300 ° C. to reduce the resistance of the ITO layer. Is described in which an ITO layer is transferred onto a polymethyl methacrylate substrate through an adhesive. It also describes that an aromatic polyimide can be used as a support. Further, JP-A-59-204
No. 542 discloses that I.P.
A method is disclosed in which after the TO layer is deposited, the ITO layer is transferred to a film via a low-temperature curable epoxy resin adhesive.

JP-A-58-177345 discloses that an ITO layer is sputtered on a release surface of a polyester film having a silicone release surface, and the ITO layer and a polyvinyl butyral sheet are thermocompressed. A method for transferring an ITO layer to the surface of a polyvinyl butyral sheet is disclosed. Japanese Patent Application Laid-Open No. S59-151705 discloses that a layer of an ITO vapor-deposited film is formed on a temporary support such as a Teflon film or a polyimide film.
A method of transferring a layer to the surface of a plastic transparent substrate via a thermosetting or photocurable adhesive is disclosed. Further, Japanese Patent Application Laid-Open No. 7-80980 discloses a transparent conductive transfer sheet in which an ITO layer and an adhesive layer are sequentially laminated on a substrate made of a film having a low surface energy. As a specific example, oriented polypropylene is disclosed.

On the other hand, Japanese Patent Application Laid-Open No. 2-174011 discloses that a resin film is laminated on a temporary support (release sheet), an ITO layer is laminated on the resin film, A transfer sheet is formed by laminating a heat-bondable adhesive layer onto the glass substrate, and the transfer sheet is pressed against a glass substrate while being heated, and the laminate including the ITO layer and the resin film is transferred via the adhesive layer. A method is disclosed. This application publication discloses that a synthetic resin film of polyethylene, polypropylene, polyester, or the like can be used as a support, and that a release treatment is performed on the support as necessary. At this time, the release layer functions as a protective film for the ITO layer, and the material is preferably selected from the group consisting of cellulose resin, acrylic resin, and nylon resin. It is disclosed that the thickness is 1.5 μm or less, preferably 1 μm or less.

Japanese Patent Application Laid-Open No. H11-24081 discloses an adhesive layer comprising a polyimide resin layer on a temporary carrier, and an ITO layer laminated and formed by vapor deposition, sputtering, paste coating or the like. Discloses a method of transferring the polyimide resin layer from a polyimide resin layer to a transparent base material through a substrate, and using a heat-resistant film such as Kapton or polyetherimide as a support. At this time, a polyimide resin layer is also transferred from the temporary support to the transparent substrate, and the polyimide resin layer has a thickness of 100 nm suitable for being used as an alignment film.

[0006]

In the conventional method as described above, the IT method is performed on a heat-resistant plastic film.
Since an O layer is formed and transferred again onto a plastic film or a glass substrate via an adhesive, a change in the dimensions of the film (expansion and contraction) that occurs when the ITO layer is formed on the plastic film ) Is not taken into account. Further, as the pattern accuracy of the ITO layer becomes finer, this effect is not taken into account despite the influence becoming larger. For example, in the former series of transfer laminates and transfer methods, an ITO layer is directly laminated on a temporary support, and a resin layer transferred together with the ITO layer is provided between the support and the ITO layer. Not provided. In such a configuration, the ITO layer formed on the support cannot be etched and patterned. Because, ITO
This is because the adhesion between the layer and the underlying layer is not good, so that the etching solution penetrates into this interface when the ITO layer is etched, and the patterned ITO layer is peeled off. Also,
In the latter method, since an ITO layer is formed on a plastic film as a support, if the pattern of the ITO layer is formed in this state, the plastic film expands and contracts due to thermal expansion and humidity during the formation of the pattern. A highly accurate ITO layer cannot be formed.

Further, since a plastic film is used as the temporary support, there is another problem that the long dimension accuracy is not obtained due to the distortion of the film. In particular, when a Kerr filter is formed on the ITO layer, it is necessary to align the color pixels constituting the ITO layer and the color filters, or to align the color pixels, but the pattern accuracy (position accuracy) of the ITO layer is required. If it is not good, it becomes a fatal disadvantage that color pixels cannot be accurately provided on the ITO layer. For example, the thermal expansion coefficient of a typical heat-resistant polymer of the polyimide (Kapton) is, 4 × a 10 -5 ^/ ° C. approximately. This means that when the temperature changes by 1 ° C, 12 cm for a length of 30 cm.
It means extending μm. However, in actual production, it is difficult to control the temperature within a range of 1 ° C. Also, considering that the space width between the lines of the ITO for the liquid crystal is usually 10 to 20 μm, when a color filter or ITO is manufactured on a film, the color filter layer is formed due to a variation in the heat treatment temperature during the manufacturing. Color pixel overlaps with a different color pixel,
A phenomenon that TO crosses over different color pixels may occur. In addition, as an example of the change due to humidity, when a film made of polyethersulfone resin is used, for example, the film is simply dipped in water for washing.
The length of cm has increased by 150 μm. When this film was treated at 100 ° C. for drying and returned to room temperature, it shrunk by 300 μm as compared to before the washing.
This film was stored at a constant temperature and humidity, but it took three days for the dimensions to stabilize. Such a dimensional change makes it difficult not only to align the ITO and the color filter layer during manufacturing, but also to align the ITO with the driver circuit.

It is an object of the present invention to provide a transfer body which can solve these problems, a method of reproducing the transfer body, and a method of forming a transparent conductive layer using the transfer body.

[0009]

According to a first aspect of the present invention, there is provided a transfer body in which at least a release layer, a transparent conductive layer and an adhesive layer are sequentially laminated on a rigid support having excellent heat resistance. Has a tensile strength of 100 g / cm or more. Here, the heat resistance of the support is required only to withstand the heat treatment of each layer on the support, and the rigidity is greater than that of the partner to which each layer on the support is transferred. In the second invention, when reproducing the color filter layer formed on the transfer body, a plasma etching method or RIE (reactive ion etching) mainly using oxygen is used.
The color filter layer is etched and removed by a method, and thereafter, at least a Kerr filter layer and an adhesive layer are sequentially formed. A third aspect of the present invention is to form at least a release layer, a transparent conductive layer, and an adhesive layer in this order on a rigid support having excellent heat resistance, and form the transparent conductive layer on a film made of a plastic material via the adhesive layer. Glued on one side,
Next, a method for forming a transparent conductive layer, which is separated from the interface between the support and the release layer, and transfers and forms the transparent conductive layer on a film made of the plastic material, wherein the tensile strength of the release layer is 100 g / cm or more. It is characterized by the following. According to a fourth aspect of the present invention, at least a release layer, a transparent conductive layer, and an adhesive layer are sequentially formed on a rigid support having excellent heat resistance, and the transparent conductive layer is provided on one side of a film made of a plastic material via the adhesive layer. A method of forming a color filter using a method of forming a transparent conductive layer by transferring and forming the transparent conductive layer on a film made of the plastic material by peeling off from the interface between the support and the release layer. The film made of plastic is temporarily fixed to an end of the film made of the plastic material on a roll having a diameter of 50 mm or more, preferably 100 mm or more, and then the roll is substantially rotated to thereby support the transfer body. The transparent conductive layer is transferred to a film made of a plastic material by peeling from an interface between a body and the peeling layer.

The support of the transfer member used in the present invention includes:
Use a material having heat resistance, a coefficient of thermal expansion of 1.5 × 10 ^-5 / ° C or less, and a rigidity which does not undergo dimensional change due to humidity. The most suitable as such a support is a soda lime glass (coefficient of thermal expansion: 9 to 10 < ^10-6 / C). Further, when the pattern of the transparent conductive layer and the color pixels is fine-pitched, and the alignment accuracy between the transparent conductive layer and the color filter including the color pixels of Y, M, C, R, G, and B becomes severe, etc. Low expansion glass (4-5 times)
10 ⁻⁶ / ° C.).

As the release layer used in the present invention, a resin material having high heat resistance such as a polyimide resin is used. The release layer has a thickness of several g / 90 ° between the release layer and the support.
It requires an adhesion of about cm to 100 g / cm. At this time, considering that the transfer body is transferred and peeled of the film, the smaller the adhesion, the better.However, in order to withstand manufacturing processes such as washing and etching accompanying the pattern forming process of the transparent conductive layer, a certain degree or more is required. Adhesion is required. The strength of the release layer was 100 g / cm (1 c in width) in tensile strength.
(per m) or more, preferably 150 g / cm or more (the reason will be described later). In order to increase the tensile strength of the release layer, it is possible to increase the thickness of the release layer. It is. As the function required for the release layer, the temperature at the time of forming the transparent conductive layer and the resistance to the chemical used for patterning the transparent conductive layer are also required. Moreover, it goes without saying that the release layer must have good adhesion to the transparent conductive layer. As described above, polyimide is most suitable as a material suitable for the release layer. When this is formed into a film having a thickness of 1.3 μm or more, preferably 2 μm or more on a support, necessary tensile strength can be obtained.

As the transparent conductive layer used in the present invention, ITO (indium-tin-oxide), indium oxide, tin oxide, or the like can be used, and ITO shows the best physical characteristics at present. ITO is deposited by film forming means such as vacuum evaporation, sputtering, ion plating, etc.
When the film is formed under a temperature condition of 50 ° C. or more, a low-resistance film is obtained. It is difficult to lower the resistance, but the sol-gel method
It is also possible to form O. The transparent conductive layer thus formed is patterned to form a transparent electrode. Patterning can be performed by a well-known photolithography process.
At this time, if the adhesion between the release layer and the support is 90 g / cm or less in the peel test, the release layer is peeled off in the patterning step of the transparent conductive layer. Further, at this time, since a support having a small expansion coefficient is used, patterning with excellent dimensional accuracy is possible.

[0013] Further, between the release layer and the transparent conductive layer, SiO 2
By providing a barrier layer made of an inorganic compound such as x, SiN, Al ₂ O ₃ , TiO _2, etc., it is possible to impart protection of the transparent conductive layer and gas barrier properties after transferring the transfer body to a film. The barrier layer made of this inorganic material,
The film can be formed to a thickness of 0.1 μm or less by using a vacuum film forming means such as a sputtering method or an ion plating method. Thereafter, an intermediate layer and a color filter layer are formed as necessary. As the intermediate layer, an acrylic or alkyd resin or an inorganic material such as SiOx can be used. Note that the barrier layer Si
A layer of an inorganic material such as Ox can also serve as the intermediate layer. Such an intermediate layer, in conjunction with the release layer, sandwiches the transparent conductive film to be transferred in a sandwich shape, relieves stress during transfer, particularly stress due to curing shrinkage of the adhesive, and cracks the transparent conductive film. Is prevented from occurring. In addition, when there is a color filter layer, the intermediate layer has a role of protecting the color filter layer against peeling of the peeling layer.

The color filter layer can be formed by a general method using photolithography. At this time, since the support is formed as described above, no problem occurs in alignment. In addition, since the step of forming the color filter layer includes a wet process similarly to the step of forming the ITO, it is desirable to use a support that does not change its dimensions due to humidity or moisture. The transparent conductive layer and the color filter layer thus formed on the support are transferred onto a film made of a plastic material. As a plastic material, polyethersulfone, polycarbonate, etc.
A thickness of 300 μm, preferably 100 μm to 200 μm is good. An adhesive layer is bonded between a support having a transparent conductive layer such as ITO and a film made of a plastic material via an adhesive layer, and the adhesive layer is cured. As the adhesive layer, an adhesive layer that cures at room temperature is preferable for maintaining dimensional accuracy, and a photocurable adhesive layer is particularly preferable.

The adhesive layer used in the present invention must be capable of obtaining strong adhesion to the uppermost layer such as a color filter layer formed on the support. Also, there are some problems when the film made of a plastic material and the support are peeled off from the interface of the release layer. The problem is
First, at least the release layer, the transparent conductive layer and the adhesive layer are transferred from a rigid support onto a film made of a highly flexible plastic material. That is, when a film made of a plastic material is peeled off from a rigid support, the film must be peeled so as to be bent. At this time, although the transparent conductive layer can follow a certain degree of bending, it is essentially Since it is an inorganic substance, it is hard and brittle, and cracks may occur depending on the force applied in the bending direction. Therefore, it is necessary to control the force applied in the bending direction when the film made of a plastic material and the support are peeled off from the interface of the release layer.

This problem can be solved by using a roll for peeling, and peeling the roll along the circumference of the roll. At this time, by setting the diameter of the roll to 50 mm or more, preferably 100 mm or more,
It is possible to prevent an excessive bending force from being applied to the transparent conductive layer and to prevent cracks generated in the transparent conductive layer. However, depending on the material and thickness of the release layer even when peeled off using a roll having a diameter of 100 mm, when the film is transferred from a rigid support onto a film made of a flexible plastic material and peeled off, the release layer or the transparent layer may be used. A phenomenon may occur in which the conductive layer is partially transferred and remains on the support. At this time, it was observed that the transparent conductive layer and the intermediate layer or the interface between the intermediate layer and the adhesive layer, which had much higher adhesiveness than the adhesiveness between the support and the release layer, were peeled off. Further, it was confirmed by experiments that this phenomenon became remarkable when a hard inorganic material such as SiOx was formed before and after the transparent conductive layer as the intermediate layer. This phenomenon tends to remain as the pattern of the transparent conductive layer is larger (the area is larger). Even if the transparent conductive layer is transferred to the film, the peeling direction may be increased by applying a heat treatment or a stress such as a high temperature and high humidity test. Wrinkles occur in the direction perpendicular to This is considered to be due to the fact that the transparent conductive layer, which is harder than the film made of a plastic material at the time of peeling, resists the force against bending at the time of peeling. Therefore, when the transparent conductive layer has an elongated stripe pattern, it is preferable to arrange the rolls in parallel with each other and to rotate the rolls so as to cross each pattern in the width direction.

In the present invention, when a transfer member including a transparent conductive layer is transferred from a rigid support to a film made of a plastic material and peeled off, the transfer member can be separated from the interface between the support and the release layer, and the transparent conductive layer can be separated. As a result of various investigations on a method for preventing cracks from occurring on the surface, it was found through experiments that the film strength of the release layer should be increased. Originally,
To transfer at least the release layer, the transparent conductive layer and the adhesive layer from the rigid support onto a film made of a highly flexible plastic material, peel off the transfer body from the rigid support side and remove the transfer body from the plastic material. When it is transferred to the film side, since it has an integrated structure from the release layer to the film made of the plastic material, it seems that it easily peels off from the interface between the support and the release layer, as described above. In addition, by controlling the material and thickness of the release layer and increasing the strength of the release layer to the extent described above, at least not only the adhesive force (adhesive force) between each of the release layer, the transparent conductive layer and the adhesive layer, The transparent conductive layer can be peeled off by lifting it on a release layer. In this way, by using the release layer having a certain tensile strength, the transparent conductive layer can be transferred regardless of the pattern shape of the transparent conductive layer and the material of the intermediate layer, and further, excessive stress is applied to the transparent conductive layer. Can be transferred without adding
After the transfer, even if a stress such as a heat treatment or a high-temperature and high-humidity test is applied, the transparent conductive layer does not wrinkle and the heat resistance and the high-temperature and high-humidity resistance of the transferred transparent conductive layer can be improved. At this time, the strength required for the release layer affects the adhesion between the support and the release layer, the hardness of the transparent conductive layer, and the area (shape) of the pattern of the transparent conductive layer. The adhesion between the body and the release layer must be suppressed to a certain width in consideration of the process of each layer to be formed thereafter, and the hardness of the transparent conductive layer varies depending on the film forming method, but is within a certain range. Of hardness. In particular, when used for a stripe electrode for an LCD, a line width of 100 μm is required.
It is important that about m transparent conductive layers can be transferred. The strength required for the release layer at this time is 100 g / cm, and in the case of a product including a pattern having a larger line width and a larger area, a strength of 150 g / cm is required.
Further, as disclosed in Japanese Patent Application Laid-Open No. H11-24081, when the release layer is formed as a thin film having a thickness of 100 nm, a film such as ITO formed on a rigid support is made of a flexible material such as plastic. Cannot be transferred to a film. In the case of such a thin release layer, ITO on the support
In the transfer, the peeling interface is determined only by the strength of the adhesion (adhesion) between the layers. In that regard, support and IT
Since the rigidity of O is stronger than the rigidity of the film or adhesive,
This is because the area that receives a force during transfer becomes larger than other interfaces, and as a result, ITO remains on the support.

When a transparent conductive layer or the like is transferred to a film made of a plastic material, a release layer made of a resin material remains on the uppermost layer. At this time, particularly when a transparent conductive layer is used as an electrode for an LCD or the like, it is necessary to remove the release layer in order to improve the driving of the liquid crystal. At this time, as a method for removing the release layer made of polyimide, it is possible to remove with a specific solution such as a mixed solution of hydrazine-ethylenediamine or an aqueous alkaline solution. In addition, for example, since the solution may permeate from the end of each layer of the transparent conductive layer, the adhesive layer, and the film and adversely affect the adhesion (adhesion) between the layers, for example, plasma etching mainly using oxygen It is desirable to remove the release layer using a technique such as reactive ion etching or the like. However, when the thickness of the release layer is increased, the surface smoothness when coated is reduced, and it becomes extremely difficult to remove the release layer. For example, when the peeling layer is removed, the influence of the etching unevenness becomes large, and a portion which is excessively exposed to an etching solution or an etching gas is formed, so that the underlying layer is easily damaged. Technically, there is no damage to the underlying layer, 20 μm
Although it is possible to remove the release layer up to the extent, considering the production tact, the thickness of the release layer is desirably 10 μm or less. When the release layer is removed by a plasma etching method mainly using oxygen, 0.1 μm is provided between the release layer and the transparent conductive layer.
A barrier layer made of SiOx of m or less may be provided, or the intermediate layer may be formed using a material resistant to plasma gas, and the intermediate layer may also serve as a barrier layer. Furthermore, in order to clearly understand the end point when the peeling layer is removed by etching (that is, when to end the etching), instead of forming the peeling layer with a colorless resin, the peeling layer itself is formed with a colored resin. It is preferable to do so. As the colored resin, an aromatic polyimide which is originally colored yellow in terms of molecular structure, or a resin colored by adding a dye or a pigment to a transparent resin can be used. Specific examples of the latter include, for example, acrylic resin, epoxy resin, and polyimide having a specific structure (a resin obtained by adding a silane coupling agent to a polyimide synthesized from pyromellitic anhydride and 4,4′-diaminodiphenyl ether). , As a dye, C.I. I. Solvent Yel
low 63, C.I. I. Solvent Blue 25
And acid rhodamine, and C.I. I. Pi
gment Blue and C.I. I. Pigment Ye
llow 139. Their coloring density is preferably 2 to 4 μm and a minimum transmittance of 5 to 60%.
It is about.

When a transfer member is formed,
When a layer resistant to the above-described plasma gas is formed, when a hue of the color filter layer or a defect that cannot be completely corrected occurs in the stage of forming the color filter layer, only the color filter layer is removed. For example, the transfer body can be regenerated by removing it by a method such as plasma etching mainly using oxygen. At this time, by adding a small amount of gas such as CF4 to oxygen, etching can be performed faster than oxygen alone.
In the initial stage of etching, etching is performed by adding CF4 to oxygen, and pure oxygen is used at the end of etching, so that efficient etching with less damage to the base can be achieved. It is possible. As described above, since the removal of the release layer and the regeneration of the transfer body are performed by a dry process such as a plasma etching method using oxygen as a main component, there is no need to perform a waste liquid treatment as compared with the above-described removal using a solution. Desirable without causing problems such as contamination. At this time, the barrier layer made of SiOx functions as an insulating film of the transparent conductive layer opposed to the panel after the panel formation and a protective film of the transparent conductive film itself, and also improves the gas barrier property and the transparent conductive layer and the color filter. It also has the function of improving the adhesion of the layer.

[0020]

EXAMPLES The tensile strength and releasability of the release layer and the removal of the release layer will be described below. Example 1 A silane coupling agent KBM-573 (manufactured by Shin-Etsu Silicone Co., Ltd.) was added to a polyimide precursor varnish (dimethylacetamide solution, solid content ratio: 10%) produced by reacting pyromellitic anhydride with 4,4′-diaminodiphenyl ether. Was added at 0.05 wt% (solid content ratio),
A blue glass substrate coated with silica is prepared as above, and the substrate 10 is coated with a spin coater at 900 rpm for 1 hour.
A coating film is formed under the condition of 2 seconds, dried, heated at 260 ° C. at a high temperature using a hot plate, heated under a condition of 10 minutes, dehydrated and closed, and a release layer 20 made of a polyimide film having a thickness of 2 μm is formed.
Was formed (FIG. 1). The adhesion strength at the interface between the release layer 20 and the support 10 was 4 g / cm after 2 days of the heat treatment. The tensile strength of this release layer is JIS K
It was 150 g / cm in a test measured using 7127 mutatis mutandis.

Next, a transparent conductive layer 30 of 1500 A (angstrom) was formed on the release layer 10 by sputtering at a substrate temperature of 180 ° C. using ITO, and its surface resistance was 15 Ω / □. (FIG. 2). Next, a commercially available positive resist was applied on the transparent conductive layer 30, and after drying, exposure, development, etching, and the resist were peeled off through a mask having a predetermined pattern to pattern the transparent conductive layer 30. (FIG. 3). A silica-based coating agent ZRS-5PH-3 (manufactured by Catalyst Kasei Co., Ltd.)
m intermediate layer 40 was formed (FIG. 4). Next, a color filter layer 50 is formed on the intermediate layer 40 by using a colored polyimide by a photolithography method (FIG. 5). Then, as an adhesive layer 60 on the color filter layer 50, an ultraviolet curable adhesive KR- 400 (manufactured by Asahi Denka Co., Ltd.) so as to have a thickness of about 8 μm, thereby forming an adhesive layer 60.
Was formed (FIG. 6).

Next, the transfer body 100 is bonded to a film 70 made of a plastic material (polyether sulfone resin (manufactured by Sumitomo Bakelite Co., Ltd.)) having a thickness of 150 μm via an adhesive layer 60, and irradiated with ultraviolet rays to bond the adhesive layer 60. Was cured (FIG. 7). Next, one end on the film 70 side bonded to the transfer body 100 is placed on a roll 8 having a diameter of 200 mm.
0, and the transfer body 1 is
Then, the film 70 was peeled off from 00 (FIG. 8). At this time, the transparent conductive layer 30, the color filter layer 50, and the like are peeled off from the interface between the support 10 and the release layer 20 of the transfer body 100, and are transferred to the film 70 side, and subjected to stress such as heat treatment or a high-temperature high-humidity test. However, no wrinkles occurred in the transparent conductive layer 30. As described above, in the case where the transparent conductive layer 30 has a stripe pattern, the peeling is performed in such a manner that the axis of the roll 80 and the pattern of the transparent conductive layer 30 are arranged in parallel as shown in FIG. Is good. Next, the release layer 20 was removed from the film 70 using a V1000 multi-stage tester (manufactured by Mori Engineering) at a gas flow rate of 4
Oxygen plasma etching was performed under the conditions of 00 sccm, a degree of vacuum of 86 Pa, an RF output of 500 W, and an atmosphere (temperature) of 25 ° C., and the release layer 20 was removed in about 15 minutes (FIG. 9). No problem occurred in ITO adjacent to the release layer 20.

Example 2 A 4 μm-thick release layer of the same material as in Example 1 was formed on a support (silica-coated soda lime glass). The tensile strength of this release layer was 300 g / cm. afterwards,
Each layer was formed under the same conditions as in Example 1 except that an intermediate layer having a thickness of 1.5 μm was formed using a coating agent EXP-1474 (manufactured by Fujikura Kasei Co., Ltd.) to form a second transfer body. This second transfer member was transferred to a film under the same conditions as in Example 1 and peeled off from the roll under the same conditions as in Example 1. However, the second transfer member was peeled off from the interface between the support of the transfer member and the release layer, resulting in a transparent conductive material. Layers, color filter layers, etc. are transferred to the film side,
No wrinkles were generated in the transparent conductive layer even when a stress such as a heat treatment or a high-temperature high-humidity test was applied. Thereafter, the film was immersed in a 1: 1 mixture of hydrazine and ethylenediamine for 11 minutes to remove the peeling layer and washed with water.
Heat treatment was performed at 0 ° C. and drying was performed, but no particular problem occurred.

Example 3 Coating Agent Optomer SS-6917 as Intermediate Layer
Each layer was formed under the same conditions as in Example 1 except that 2 μm (manufactured by JSR) was formed to form a third transfer body. This transfer body was transferred to a film under the same conditions as in Example 1, and peeled off from the roll under the same conditions as in Example 1. However, the transfer body was peeled off from the interface between the support and the release layer of the transfer body, and the transparent conductive layer,
The color filter layer etc. is transferred to the film side,
Alternatively, no wrinkles were generated in the transparent conductive layer even when stress such as a high-temperature high-humidity test was applied. Next, the film was immersed in a warmed 5% aqueous NaOH solution to remove the release layer by swelling. Thereafter, the film was washed with water and heated to 140 ° C. and dried, but there was no problem at all. Further, even if this film was stored at 40 ° C. and 90% for a long time, no problem occurred.

Example 4 ITO which is to become a transparent conductive layer was formed by a vacuum evaporation method at a substrate temperature of 300 ° C. so as to have a thickness of 1500 A (surface resistance: 20 Ω / □), and other layers were the same as in Example 1. To obtain a fourth transcript. This transcript was prepared in Example 1.
The transfer and removal of the peeling layer were performed under the same conditions as in the above, but no problem occurred.

Comparative Example 1 A 1 μm-thick release layer made of the same material as in Example 1 was formed on a support (silica-coated soda lime glass). The tensile strength of the release layer was 75 g / cm. Thereafter, each layer was formed under the same conditions as in Example 1 to form a transfer body e. This transfer body e was transferred to a film under the same conditions as in Example 1, and peeled off from the roll under the same conditions as in Example 1. However, a portion of the transparent conductive layer almost remained on the support side, and the intermediate layer and the color filter were removed. It was peeled off from the interface between the layers or the interface between the color filter layer and the adhesive layer. In addition, when the interface between the intermediate layer and the color filter layer or the interface between the color filter layer and the adhesive layer is independently formed on a glass or the like and the adhesion is evaluated, the cross-cut cellophane tape test (JIS K540)
0-8-5-1 (1990), ISO 2409 (19
92)) did not peel off.

Comparative Example 2 Example 2 was repeated except that the release layer was formed under the same conditions as in Comparative Example 1.
Each layer was formed under the same conditions as described above to obtain a transfer body f. This transfer body f was transferred to a film under the same conditions as in Example 1;
When the transparent conductive layer was peeled off from the roll under the same conditions as described above, a portion having a line width of 100 μm could be transferred,
The portion of mm or more remained on the support side. The transferred film was heat-treated at 100 ° C. Wrinkles occurred in the transparent conductive layer perpendicular to the peeling direction (parallel to the roll at the time of peeling). Furthermore, when left for a long time under the condition of 40 ° C. and 90%, wrinkles were severe and cracks occurred.

Comparative Example 3 Example 3 was repeated except that a release layer was formed under the same conditions as in Comparative Example 1.
Each layer was formed under the same conditions as described above to obtain a transfer body g. This transfer body g was transferred to a film under the same conditions as in Example 1.
When the transparent conductive layer was peeled off from the roll under the same conditions as described above, a portion having a line width of 100 μm of the transparent conductive layer could be transferred, but a portion having a line width of 1 mm remained on the support.

Comparative Example 4 Example 4 except that a release layer was formed under the same conditions as in Comparative Example 1.
Each layer was formed under the same conditions as described above to obtain a transfer body h. This transfer body h was transferred to a film under the same conditions as in Example 1.
When the transparent conductive layer was peeled off from the roll under the same conditions as described above, the transparent conductive layer could hardly be transferred to the film side and remained on the support side.

Experimental Example 1 for Confirming Critical Significance of Numerical Values A release layer having the same material as in Example 1 and having a thickness of 1.5 μm was formed on a support (silica-coated soda lime glass). The tensile strength of this release layer was 110 g / cm. Thereafter, each layer was formed under the same conditions as in Example 1 to obtain a transfer body. This transfer body was transferred to a film under the same conditions as in Example 1, and peeled off from the roll under the same conditions as in Example 1. Observation of the transfer state of the transparent conductive layer including portions having different line widths revealed that a portion having a line width of 100 μm could be transferred, but a portion having a line width of 1 mm or more remained on the support side.

Experimental Example 2 for Confirming the Critical Significance of Numerical Values The release layer was formed under the same conditions as in Experimental Example 1, and the other layers were formed under the same conditions as in Example 2 to obtain a transfer body. Was.
This transfer body was transferred to a film under the same conditions as in Example 1,
When peeled off from the roll under the same conditions as in Example 1,
Although it was a transparent conductive layer having portions with different line widths, transfer was effective.

Experimental Example 3 for Confirming the Critical Significance of Numerical Values The release layer was formed under the same conditions as in Experimental Example 1, and the other layers were formed under the same conditions as in Example 3 to obtain a transfer body. Was.
This transfer body was transferred to a film under the same conditions as in Example 1,
When peeled off from the roll under the same conditions as in Example 1,
Although it was a transparent conductive layer having portions with different line widths, transfer was effective.

Experimental Example 4 for Confirming the Critical Significance of Numerical Values The release layer was formed under the same conditions as in Experimental Example 1, and the other layers were formed under the same conditions as in Example 4 to obtain a transfer body. Was.
This transfer body was transferred to a film under the same conditions as in Example 1,
When peeled off from the roll under the same conditions as in Example 1,
A portion having a line width of 100 μm in the transparent conductive layer could be transferred, but a portion having a line width of 1 mm or more could not be transferred effectively and remained on the support side.

In the following examples, a method for regenerating a supported member will be described. Example 5 Using a colored polyimide under the same conditions as in Example 1, Y, M and C were formed by photolithography so as to have a thickness of about 0.7 μm.
Each color pixel was formed up to the color filter layer 50 (FIGS. 1 to 4). However, since some of the color pixels had defects such as spots and the like, the color filter layer 50 was replaced with a V1000 multi-stage tester (Mori). Engineering), gas flow rate 4
Oxygen plasma etching was performed under the conditions of 00 sccm, a degree of vacuum of 86 Pa, an RF output of 500 W, and an atmosphere (temperature) of 25 ° C., and the color filter layer 50 was removed in about 5 minutes. The color filter layer 50 was completely removed, and no problem occurred in the silica-based intermediate layer 40. Next, using the colored polyimide on the intermediate layer 40, each of the Y, M and C color pixels was formed again by photolithography so as to have a thickness of about 0.7 μm, and the color filter layer 50 was reproduced (FIG. 5). ). Next, as a bonding layer 60 on the color filter layer 50, an ultraviolet curable adhesive KR-400 (manufactured by Asahi Denka Co., Ltd.) was applied to a thickness of about 8 μm.
m to form a transfer body 100 (FIG. 6).

Example 6 A release layer 20 was formed on the support 10 under the same conditions as in Example 1 (FIG. 11).
At a substrate temperature of 80 ° C., a 100 A (angstrom) barrier layer 90 was formed of SiO 2 (FIG. 12). Next, a transparent conductive layer 30 of 1500 A (angstrom) is formed on the barrier layer 90 by ITO at a substrate temperature of 180 ° C. by using the same sputtering method.
It was □. Next, a commercially available positive resist was applied on the transparent conductive layer 30, and after drying, exposure, development, etching, and the resist were peeled off through a mask having a predetermined pattern to pattern the transparent conductive layer 30. (FIG. 13). Next, an alkyd resin coating agent EXP-147
4 (manufactured by Fujikura Kasei Co., Ltd.) and a 1.5 μm thick intermediate layer 4
0 was formed (FIG. 14). Next, using the colored polyimide on the intermediate layer, Y, M, and C color pixels were formed by photolithography so as to have a thickness of about 0.7 μm, and the color filter layer 50 was formed (FIG. 15). However, since some color pixels were defective, the color filter layer 50 was
0 Using a multi-stage tester (Mori Engineering), gas flow rate 400 sccm, degree of vacuum 86 Pa, RF output 50
Oxygen plasma etching was performed under the conditions of 0 W and an atmosphere (temperature) of 25 ° C., and the intermediate layer 40 and the color filter layer 50 were removed in about 10 minutes. The intermediate layer 40 and the color filter layer 50 were completely removed, and no problem occurred in the barrier layer 90. Next, the intermediate layer 40 and the color filter layer 50 were reproduced on the barrier layer 90 as described above (FIG. 15). Next, an ultraviolet curing adhesive KR-400 (manufactured by Asahi Denka Co., Ltd.) was applied on the color filter layer 50 as the adhesive layer 60 so as to have a thickness of about 8 μm, thereby forming the transfer body 100 (FIG. 16).

[0036]

As described above, since the transparent conductive layer and the color filter layer are formed on a rigid support, the alignment between the transparent conductive layer and the color filter layer is easy. Along with providing a fine color filter, a transparent conductive layer or a color filter layer is formed on a conventional heat-resistant plastic sheet, and is then transferred and formed again on the plastic sheet via an adhesive. There is no need to consider the shrinkage of the sheet, which is a problem in
By providing the intermediate layer made of an inorganic material such as l ₂ O ₃ or TiO ₂ , the transfer body can be reproduced, and the transparent conductive layer is not adversely affected when the release layer is removed. The present invention provides a transcript that can solve these problems,
A method for reproducing the transfer body, a method for forming a transparent conductive layer using the transfer body, and a method for manufacturing a color filter using the same can be provided.

[Brief description of the drawings]

FIG. 1 is a view showing a stage in which a release layer is formed.

FIG. 2 is a view showing a stage in which a transparent conductive layer is formed.

FIG. 3 is a diagram showing a stage where a transparent conductive layer is patterned.

FIG. 4 is a view showing a stage in which an intermediate layer is formed.

FIG. 5 is a view showing a stage in which a color filter layer is formed.

FIG. 6 is a view showing a stage in which an adhesive layer is formed.

FIG. 7 is a diagram showing a transfer stage.

FIG. 8 is another diagram showing the transfer stage.

FIG. 9 is a diagram showing a state after transfer.

FIG. 10 is a top view showing a transfer stage.

FIG. 11 is a view showing a stage in which a release layer is formed.

FIG. 12 is a view showing a stage in which a barrier layer is formed.

FIG. 13 is a view showing a stage where a transparent conductive layer is patterned.

FIG. 14 is a view showing a stage in which an intermediate layer is formed.

FIG. 15 is a diagram showing a stage in which a color filter layer is formed.

FIG. 16 is a view showing a stage in which an adhesive layer is formed.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Support 20 Release layer 30 Transparent conductive layer 40 Intermediate layer 50 Color filter layer 60 Adhesive layer 70 Film 80 Roll 90 Barrier layer 100, 100 'Transfer body

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 27, 2000 (2009.2)
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

Further, since a plastic film is used as the temporary support, there is another problem that the long dimension accuracy is not obtained due to the distortion of the film. In particular, when a Kerr filter is formed on the ITO layer, it is necessary to align the color pixels constituting the ITO layer and the color filters, or to align the color pixels, but the pattern accuracy (position accuracy) of the ITO layer is required. If it is not good, it becomes a fatal disadvantage that color pixels cannot be accurately provided on the ITO layer. For example, a typical heat-resistant polymer polyimide (Kapton) has a thermal expansion coefficient of about 4 × 10 ⁻⁵ / ° C. this is,
When the temperature changes by 1 ° C., it means that the length is extended by 12 μm for a length of 30 cm. However, in actual production, it is difficult to control the temperature within a range of 1 ° C. Also, considering that the space width between the lines of the ITO for the liquid crystal is usually 10 to 20 μm,
When color filters and ITO are manufactured on film,
Due to variations in the heat treatment temperature during manufacturing, the color pixels of the color filter layer may overlap
May be straddled between different color pixels. Further, as an example of the change due to humidity, when a film made of polyethersulfone resin is used as an example, if this film is simply immersed in water for washing, it is 30 cm.
Has grown by 150 μm. When this film was treated at 100 ° C. for drying and returned to room temperature, it shrunk by 300 μm as compared to before the washing. This film was stored at a constant temperature and humidity, but it took three days for the dimensions to stabilize. Such a dimensional change makes it difficult not only to align the ITO and the color filter layer during manufacturing, but also to align the ITO with the driver circuit.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

The support of the transfer member used in the present invention includes:
Use a material that has heat resistance, a coefficient of thermal expansion of 1.5 × 10 ⁻⁵ / ° C. or less, and rigidity that does not undergo dimensional change due to humidity.
The most suitable as such a support is a soda lime glass (coefficient of thermal expansion of 9 to 10 X 10 ^-6 / ° C). Further, when the pattern of the transparent conductive layer and the color pixels is fine-pitched, and the alignment accuracy between the transparent conductive layer and the color filter including the color pixels of Y, M, C, R, G, and B becomes severe, etc. low expansion glass (4~5 X ^{10 -6} / ℃)
It is desirable to use

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

As the release layer used in the present invention, a resin material having high heat resistance such as a polyimide resin is used. This release layer is a few g / cm at a 90 degree release between the release layer and the support.
Approximately 100 g / cm of adhesion is required. At this time,
Considering that the transfer body is transferred and peeled off from the film, the smaller the adhesion, the better.However, in order to withstand the manufacturing process such as cleaning and etching accompanying the pattern formation process of the transparent conductive layer, the adhesion should be a certain level or more. Required. The strength of the release layer was 100 g / cm (1 cm in width) in tensile strength.
Per) or more, desirably a strength of 150 g / cm or more (the reason will be described later). In order to increase the tensile strength of the release layer, it is possible to increase the thickness of the release layer. is there. As the function required for the release layer, the temperature at the time of forming the transparent conductive layer and the resistance to the chemical used for patterning the transparent conductive layer are also required. Moreover, it goes without saying that the release layer must have good adhesion to the transparent conductive layer. As described above, polyimide is most suitable as a material suitable for the release layer. This is placed on a support at 1.3 μm or more, preferably
When the film has a thickness of 2 μm or more, necessary tensile strength can be obtained.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

As the transparent conductive layer used in the present invention, ITO (indium-tin-oxide), indium oxide, tin oxide, or the like can be used, and ITO shows the best physical characteristics at present. ITO is deposited by film forming means such as vacuum evaporation, sputtering, ion plating, etc.
When the film is formed under a temperature condition of 50 ° C. or more, a low-resistance film is obtained. It is difficult to lower the resistance, but the sol-gel method
It is also possible to form O. The transparent conductive layer thus formed is patterned to form a transparent electrode. Patterning can be performed by a well-known photolithography process.
At this time, the adhesion between the release layer and the support was determined by a 90 degree peel test.
If it is less than several g / cm, the peeling layer will be peeled off in the step of patterning the transparent conductive layer. Further, at this time, since a support having a small expansion coefficient is used, patterning with excellent dimensional accuracy is possible.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ichiro Besmiya 4-14-12 Koishikawa, Bunkyo-ku, Tokyo Kyodo Printing Co., Ltd. (72) Inventor Kazumi Arai 4- 14-12 Koishikawa, Bunkyo-ku, Tokyo Kyodo Printing Inside the corporation

Claims (16)

[Claims] 1. A transfer member comprising a support, on which at least a release layer, a transparent conductive layer, and an adhesive layer are sequentially laminated, wherein the support has heat resistance enough to withstand heat treatment of each of the layers. Each of them has greater rigidity than the mating side to be transferred, and the peel strength of the release layer is 100%.
g / cm or more. 2. The transfer member according to claim 1, wherein the transparent conductive layer is formed in a pattern. 3. The transfer member according to claim 1, wherein an intermediate layer is provided between the transparent conductive layer and the adhesive layer. 4. The transfer member according to claim 3, wherein a color filter layer is provided between the transparent conductive layer and the intermediate layer or any one of the intermediate layer and the adhesive layer. . 5. The transfer member according to claim 1, wherein the release layer is a polyimide resin, and has a layer thickness of 1.3 μm or more, preferably 2 μm or more. 6. A barrier layer made of an inorganic compound is provided between any one of the release layer and the transparent conductive layer, or between the transparent conductive layer and the color filter layer, or between both layers. The transfer body according to claim 4, characterized in that: 7. A release layer, a transparent conductive layer, and an adhesive layer are sequentially laminated on a support, and a color filter layer is provided between the release layer and the adhesive layer, and a barrier layer is provided between the color filter layer and the release layer. When reproducing the transfer body having the above, the color filter layer is etched and removed up to the interface of the barrier layer by a plasma etching method or an RIE (reactive ion etching) method mainly using oxygen, and thereafter, at least the color filter layer, A method for reproducing a transfer body, comprising sequentially forming an adhesive layer. 8. A laminated structure in which at least a release layer, a transparent conductive layer, and an adhesive layer are sequentially formed on a support, and heat resistance enough to withstand heat treatment of each layer supported by the support, and transfer of each layer. Using transfer members each having greater rigidity than the other side, the transparent conductive layer is bonded to one surface of a film made of a plastic material via the adhesive layer, and then the support is bonded to the interface of the release layer. A transparent conductive layer formed by transferring the transparent conductive layer onto a film made of the plastic material, wherein the tensile strength of the release layer is 100 g / cm or more. The method of forming the used transparent conductive layer. 9. The method for forming a transparent conductive layer using a transfer body according to claim 8, wherein the transparent conductive layer formed in a pattern is formed on the release layer. 10. The method of claim 8, wherein an intermediate layer is formed between the transparent conductive layer and the adhesive layer. 11. The transfer member according to claim 10, wherein a color filter layer is formed between the transparent conductive layer and the intermediate layer or any one of the intermediate layer and the adhesive layer. A method for forming a transparent conductive layer using the method. 12. The transfer of the film made of the plastic material by temporarily fixing the end of the film made of the plastic material to a roll having a diameter of 50 mm or more, preferably 100 mm or more, and then substantially rotating the roll. The transparent body using the transfer body according to claim 8, wherein the transparent conductive layer is transferred to a film made of a plastic material by peeling off the interface between the support and the release layer of the body. A method for forming a conductive layer. 13. A barrier layer made of an inorganic compound is provided between any one of the release layer and the transparent conductive layer, or between the transparent conductive layer and the color filter layer, or between both layers. A method for forming a transparent conductive layer using the transfer body according to any one of claims 8 to 11. 14. The method according to claim 1, wherein after transferring the transparent conductive layer to the film made of the plastic material, the release layer is removed by a plasma etching method or a RIE (reactive ion etching) method mainly using oxygen. Item 14. A method for forming a transparent conductive layer using the transfer body according to Item 13. 15. The release layer is a polyimide resin,
9. The method according to claim 8, wherein the layer thickness is at least 1.3 [mu] m, preferably at least 2 [mu] m. 16. The method for forming a transparent conductive layer using a transfer body according to claim 8, wherein the release layer is made of a colored resin, so that an end point at which the release layer is removed is known. .