KR102392962B1 - Method of manufacturing laminated member - Google Patents

Abstract

(Project) In obtaining a laminated member having a functional layer on a thin resin film, a method for manufacturing a laminated member by suppressing the influence on the quality of the functional layer while considering handling properties in the manufacturing process to provide.
(Solution means) A method of manufacturing a lamination member by feeding a long base film wound in roll shape in the longitudinal direction, processing it, patterning if necessary, and forming a functional layer on the base film, the base film comprising: A polyimide layer imidized by coating a polyamic acid solution on a support material is provided, and after forming a functional layer on the polyimide layer side, the support material is separated and removed using the interface between the polyimide layer and the support material This is a method of manufacturing a laminated member to thin the base film.

Description

Method of manufacturing a laminated member {METHOD OF MANUFACTURING LAMINATED MEMBER}

The present invention relates to a method for manufacturing a lamination member, specifically, a long base film is drawn out in the longitudinal direction to form a predetermined functional layer, a part of the base film is separated and removed, and a lamination member is obtained by thinning It relates to a method of manufacturing a laminated member to be

For example, display apparatuses, such as a liquid crystal display device and an organic electroluminescent display, are used for various display uses, including a large display like a television, and small displays, such as a cellular phone, a personal computer, and a smart phone. Among these, for example, in an organic EL display device, a thin film transistor (hereinafter, TFT) is formed on a glass substrate, an electrode, a light emitting layer, and an electrode are sequentially formed, and finally, hermetically sealed with a separate glass substrate or a multilayer thin film. is made

In these display devices, by replacing a glass substrate with a resin substrate, thinner, lighter, and more flexible than before can be realized, and the use and variations of the display device can be further expanded. However, in general, resins are inferior to glass in dimensional stability, transparency, heat resistance, moisture resistance, gas barrier properties, and the like, and various studies have been made to improve them.

For example, Patent Document 1 proposes a polyimide useful as a resin substrate for a flexible display, and an invention related to a precursor thereof, using tetracarboxylic acids having an alicyclic structure such as cyclohexylphenyltetracarboxylic acid. It is disclosed that the polyimide made to react with various diamines is excellent in transparency. Further, in Non-Patent Documents 1 and 2, an organic EL display device in which a resin material with high transparency is applied to a support substrate is proposed.

On the other hand, by using a resin substrate excellent in flexibility, it is possible to enable manufacturing by a roll-to-roll method. For example, in Patent Document 2, in the manufacture of an organic EL display device, a roll-to-roll method using a roll-like film substrate having barrier layers on both surfaces of a transparent plastic substrate such as polycarbonate is used, and the roll-like film is transferred by a sputtering device. The formation of an active layer of a thin film transistor on a substrate is described (see Fig. 6). By using such a long resin substrate, continuous operation is possible, and productivity improvement of the display device can be expected.

Japanese Patent Laid-Open No. 2008-231327 Japanese Patent Laid-Open No. 2011-181590

S. An et. al., “2.8-inch WQVGA Flexible AMOLED Using High Performance Low Temperature Polysilicon TFT on Plastic Substrates”, SID2010 DIGEST, p706 (2010) Oishi et. al., "Transparent PI for flexible display", IDW '11 FLX2/FMC4-1

As described above, by substituting a resin substrate (resin film) for a glass substrate used in a display device or the like, thinness, light weight, and flexibility can be achieved. In particular, in mobile devices including smart phones, competition for thin and light weight development is fierce, and the demand is very strong. However, in order to make the thickness of the resin substrate thin, it is necessary to sufficiently consider handling properties. In particular, when transporting a long resin film like a roll-to-roll method, if the film is extremely thin, its elongation becomes a problem during winding, etc. In some cases, there exists a possibility that a wrinkle may arise in a film or a tear may generate|occur|produce. In addition, even when wrinkles or tears do not occur in the film itself, various functional layers formed on the film such as TFTs, electrodes, and light emitting layers may be affected by the quality of the film during the manufacturing process by stretching the film.

Therefore, the present invention has been made in view of these problems, and in obtaining a laminated member having a functional layer on a thin resin film, it is possible to suppress the influence on the quality of the functional layer while considering handling properties in the manufacturing process. An object of the present invention is to provide a method for manufacturing a laminated member.

In order to solve the above problems, the present inventors have studied diligently. As a result, a base film having a polyimide layer on a support material is used, and after forming a functional layer on the polyimide layer side, the interface between the polyimide layer and the support material is used Thus, by separating, removing, and thinning the support material, it is possible to obtain a laminated member having a functional layer on a resin film made of a polyimide layer by suppressing the decrease in handling properties during the manufacturing process and the influence on the quality of the functional layer. found and completed the present invention.

That is, the present invention is a method of manufacturing a lamination member by feeding a long base film wound in roll shape in the longitudinal direction and forming a film, patterning if necessary, and forming a functional layer on the base film, the base film A polyimide layer imidized by coating a polyamic acid solution on this support material is provided. After forming a functional layer on the polyimide layer side, the support material is separated using the interface between the polyimide layer and the support material. It is a method of manufacturing a lamination member, characterized in that removing and thinning the base film.

In the present invention, a long base film wound in roll shape is fed out in the longitudinal direction to form a film, and if necessary, the film forming process is patterned to form a functional layer on the base film, then part of the base film is separated and removed and thinned to obtain a laminated member having a functional layer on a thin resin film (polyimide layer).

In general, when the roll-to-roll method is adopted, the long resin film wound on the roll winding mechanism on the delivery side is conveyed by the roll while being fed in the longitudinal direction by the delivery mechanism, and processes such as film formation are performed, and through the winding mechanism. It is wound by the roll winding mechanism on the winding side.

Here, in Patent Document 2, a transparent plastic film such as polysulfone-based resin, olefin-based resin, cyclic polyolefin-based resin, etc. other than polycarbonate can be used as a long resin film, and the thickness thereof is about 50 to 200 μm. (See paragraph 0083). However, at least when the resin film is wound by the roll winding mechanism on the take-up side, tensile stress is applied, so if the thickness of the resin film becomes thinner, elongation or contraction naturally becomes a problem. Therefore, if it does not have a thickness of at least about 100 micrometers, when it actually winds up with a roll winding mechanism, the problem that a wrinkle will generate|occur|produce or a film will tear will generate|occur|produce. In addition, when multiple layers of film are formed to form a functional layer, or a metal formed into a film is patterned while feeding a resin film wound up once again by a roll-to-roll method after film formation, when passing through a plurality of steps, the film is stretched and contracted. If this exists, dimensional accuracy may not be maintained but the quality of the functional layer obtained may be affected.

Therefore, in the present invention, a base film provided with a polyimide layer imidized by coating a polyamic acid solution on a support material is used, and at least while forming the functional layer by a roll-to-roll method, etc., depending on the thickness of the base film After the functional layer is formed to ensure mechanical strength and the support material is separated and removed using the interface between the polyimide layer and the support material, a laminated member having a functional layer on a thin resin film made of a polyimide layer is obtained. let it be In addition, the manufacturing method of the lamination|stacking member in this invention can be applied to the roll-to-roll system provided with the roll winding mechanism on the sending side and the roll winding mechanism on the winding side, and of course, for example, the roll winding mechanism on the winding side. It can also be applied to an incomplete roll-to-roll method, such as cutting the base film roll conveyed by the winding mechanism in front of it into a sheet shape, and is particularly effective when tension is applied to the film in any one scene.

In the present invention, in order to separate and remove the support material using the interface between the polyimide layer and the support material to reduce the thickness of the base film, it is necessary to make the interface between the polyimide layer and the support material easy to peel. As the means, it is preferable to use a polyimide having a specific chemical structure at the interface between the polyimide layer and the support material.

In general, polyimide is obtained by polymerizing an acid anhydride and diamine, which are raw materials, and can be represented by the following general formula (1).

In the formula, Ar ₁ represents a tetravalent organic group that is an acid anhydride residue, Ar ₂ is a divalent organic group that is a diamine residue, and from the viewpoint of heat resistance, at least one of Ar ₁ and Ar ₂ is preferably an aromatic residue.

The polyimide (polyimide resin) preferably used in the present invention is a polyimide having the following repeating structural unit (a) as a first example thereof. More preferably, it is good to contain the following repeating units in a ratio of 80 mol% or more.

Among these repeating structural units, polyimide having the following repeating structural unit (b) is more preferable.

If it is a polyimide having a repeating structural unit (a) or (b) as in the first example, a heat-resistant polyimide surface having a glass transition temperature (Tg) of 300° C. or higher can be formed. Separation at the interface between the polyimide layer and the support material can be facilitated by forming the polyimide layer or by making the surface of the support material have a heat-resistant polyimide surface made of such polyimide.

Here, when the polyimide shown as the first example is used, other polyimides that may be added in a ratio of up to 20 mol% other than the polyimide are not particularly limited, and general acid anhydrides as described later and diamines can be used.

Moreover, as a 2nd example of the polyimide (polyimide resin) used preferably, a fluorine-containing polyimide is mentioned. That is, separation at the interface between the polyimide layer and the support material can be facilitated by allowing the polyimide layer to be formed of such polyimide or by making the surface of the support material have a heat-resistant polyimide surface made of such polyimide. Here, a fluorine-containing polyimide refers to what has a fluorine atom in a polyimide structure, and has a fluorine-containing group in at least one component among the acid anhydride and diamine which are polyimide raw materials. As such a fluorine-containing polyimide, for example, among those represented by the general formula (1), Ar ₁ in the formula is a tetravalent organic group, and Ar ₂ is a divalent group represented by the following general formula (2) or (3). What is represented by an organic group is exemplified.

R ₁ to R ₈ in the general formula (2) or (3) are each independently a hydrogen atom, a fluorine atom, an alkyl or alkoxy group having 1 to 5 carbon atoms, or a fluorine-substituted hydrocarbon group, In (2), at least one of R ₁ to R ₄ is a fluorine atom or a fluorine-substituted hydrocarbon group, and in the general formula (3), at least one of R ₁ to R ₈ is a fluorine atom or a fluorine-substituted hydrocarbon group. Among these, -H, _-CH3 , -OCH3, -F, -CF3 etc. are mentioned as a preferable specific example of R1 _{- R8} , At least ₁ substituent in Formula (2) or Formula ( ₃ ) It is preferable that is any one of -F or -CF ₃ .

As a specific example of Ar< ₁ > in General formula (1) at the time of forming a fluorine-containing polyimide, the following tetravalent acid anhydride residues are mentioned, for example.

The fluorine-containing polyimide as described above includes those having excellent transparency. For example, when obtaining a laminated member that is used in display devices such as a liquid crystal display device or an organic EL display device and requires transparency, a polyimide layer is formed. Although it is preferable as a thing to do, when the transparency is made more excellent, or when the peelability at the interface of a polyimide layer and a support material is improved more, etc. are considered, as a specific diamine residue which gives Ar2 in General formula ( ₁ ), Preferably, it is good to use the following.

In addition, in such a fluorine-containing polyimide, when either of the structural units represented by the following general formulas (4) or (5) is contained in a ratio of 80 mol% or more, transparency and peelability are excellent and thermal expansion is excellent. It is more preferable from the viewpoint of low property and excellent dimensional stability. That is, if it is a polyimide having a structural unit represented by the following general formula (4) or (5), the transmittance in the wavelength range of 440 nm to 780 nm is 70% or more, preferably 80% or more, as in a display device, etc. It is more advantageous as forming a polyimide layer in a laminated member requiring transparency. In addition, while having a glass transition temperature (Tg) of 300 ° C. or higher, the coefficient of thermal expansion may be 25 ppm/K or less, preferably 10 ppm/K or less. Therefore, by using such a polyimide for both the polyimide layer and the support material, it is possible to prevent overturning or wrinkling because the thermal expansion coefficients of both are close even if a temperature change is received during the process.

Here, when the polyimide is a polyimide having the structure of the general formula (4) or (5), other polyimides that may be added in a ratio of less than 20 mol% at most other than the polyimide are particularly limited. No, general acid anhydrides and diamines can be used. Among them, examples of the acid anhydride preferably used include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4-cyclohexanedicarboxylic acid, 1,2,3 , 4-cyclobutanetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc. are mentioned. As one diamine, 4,4'-diaminodiphenylsulfone, trans-1,4-diaminocyclohexane, 4,4'-diaminocyclohexylmethane, 2,2'-bis(4-aminocyclohexyl) -hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'- diaminobicyclohexane, etc. are mentioned.

The various polyimides including the said 1st and 2nd examples can be obtained by imidating a polyamic acid. Here, the resin solution of polyamic acid is preferably obtained by using substantially equimolar diamine and acid dianhydride as raw materials, and reacting in an organic solvent. More specifically, it can be obtained by dissolving diamine in an organic polar solvent such as N,N-dimethylacetamide under a nitrogen stream, adding tetracarboxylic dianhydride, and reacting at room temperature for about 5 hours. As for the weight average molecular weight of the polyamic acid obtained from a viewpoint of the film thickness uniformity at the time of application|coating and the mechanical strength of the polyimide film obtained, 10,000-300,000 are preferable. Moreover, the preferable molecular weight range of the polyimide layer obtained is also the same molecular weight range as this polyamic acid. In addition, the polyimide layer may be formed in a single layer, and may be formed in multiple layers. In the case of being formed in a plurality of layers, at least for the layer forming the interface with the support material, the polyimides listed as the first and second examples above may be used.

Then, in order to obtain a base film having a polyimide layer on the support material, the polyamic acid solution is applied to the support material, and then, for example, heat-treated at about 150 to 160° C. to remove the solvent contained in the resin solution. , to imidize the polyamic acid by further heat treatment at a high temperature. As for the heat treatment performed in imidization, for example, the temperature may be increased continuously or stepwise from a temperature of about 160°C to a temperature of about 350°C. At this time, it is preferable to employ a casting method in which a long support material is prepared and a resin solution of polyamic acid for forming a polyimide layer is applied while conveying this in a roll-to-roll manner.

About the support material which forms the base film in this invention, while having flexibility, it should just be equipped with heat resistance which can withstand the heat processing at least at the time of apply|coating and imidating a polyamic-acid solution and forming a polyimide layer. . Specific examples thereof include metal foils such as copper foil and SUS foil, metal foil-resin laminates such as copper clad laminates (CCL), and resin films such as polyimide. Among them, as described above, in order to have the surface of the support material to have a heat-resistant polyimide surface made of polyimide as listed in the first and second examples, a metal foil-polyimide laminate having these polyimides, such as You may use it as a support material, or you may make it use individually as a support material the polyimide film which consists of these polyimides. In addition, in order to most easily separate the polyimide layer and the support material at the interface, it is preferable that both the polyimide layer and the support material interface be formed of the polyimides listed in the first and second examples.

Further, for the support material in the present invention, from the viewpoint of facilitating separation at the interface between the polyimide layer and the support material, preferably the surface of the support material at the interface between the polyimide layer and the support material has a surface roughness (Ra). ) is preferably less than 100 nm. In addition, if the support material has electrical conductivity or an electrically conductive layer on the back side opposite to the polyimide layer, the film can be fed out like a roll-to-roll method and static electricity generated when winding it can be prevented. There is an advantage.

In the present invention, by using the polyimide exemplified above, the adhesive strength at the interface between the polyimide layer and the support material is preferably 1 N/m or more and 500 N/m or less, more preferably 5 N/m or more and 300 N/m Hereinafter, more preferably, it can be set to 10 N/m or more and 200 N/m or less, and for example, it can be easily peeled off by human hands.

As mentioned above in this invention, since the thickness of a base film is ensured by presence of a support material, even if it makes the thickness of a polyimide layer thin, the mechanical strength at the time of forming a functional layer is maintained. In the case of feeding and winding a film as in the roll-to-roll method, since tensile stress is applied to the film by the feeding mechanism or the roll of the winding mechanism, and also the roll winding mechanism on the winding side, the film thickness of about 100 μm is generally Although necessary, in the present invention, together with the support material, at least the thickness thereof may be reached. Therefore, the thickness of a polyimide layer can be made into 100 micrometers or less, Preferably it is 50 micrometers or less, More preferably, it can be made thin to 30 micrometers or less. In addition, in consideration of ensuring insulation in forming a laminated member having a functional layer, the lower limit of the thickness of the polyimide layer is preferably 2 µm, preferably 5 µm.

On the other hand, about the thickness of a support material, what is necessary is just to be able to maintain the thickness required as a base film including a polyimide layer, and it can set arbitrarily. That is, if the role as a support material, winding property, etc. are considered, although thickness of 10-200 micrometers can be illustrated, for example, there is no restriction|limiting in particular. However, it is preferable to make the polyimide layer thinner than the support material.

The lamination member in the present invention can be used as a liquid crystal display device or an organic EL display device, as well as a display device such as electronic paper and a touch panel or a component thereof, and is used in an organic EL lighting device, or is laminated with ITO or the like. It is used as a functional material having various functions, such as an electrically conductive film, a gas barrier film that prevents penetration of moisture or oxygen, and a component of a flexible circuit board. That is, the functional layer as used in the present invention constitutes various functional materials including these display devices, lighting devices, or constituent parts thereof, and specifically, an electrode layer, a light emitting layer, a gas barrier layer, an adhesive layer, a thin film transistor, a wiring layer, and a transparent conductive material. It is a generic term for one type or a combination of two or more types such as layers.

In addition, these functional layers can be obtained using well-known methods, such as patterning into a predetermined shape or heat-processing as needed after forming a metal etc. into a film. That is, the means for forming these functional layers is not particularly limited, and for example, sputtering, vapor deposition, CVD, printing, exposure, immersion, etc. are appropriately selected. If necessary, these processes are performed in a vacuum chamber or the like. You can do it. In addition, the separation and removal of the support material may be immediately after forming the functional layer through various process treatments, or may be integrated with the support material for a certain period of time, for example, immediately before use as a display device or a functional material. You may separate it and remove it.

(Effects of the Invention)

According to the present invention, in obtaining a laminated member having a functional layer on a thin resin film, mechanical strength is secured by the thickness of the substrate film at least during the formation of the functional layer, and after the functional layer is formed, the substrate By using the interface between the polyimide layer and the support material in the film to separate and remove the support material and reduce the thickness, a laminated member having a functional layer on a thin resin film made of a polyimide layer can be efficiently produced without any problem. .

In addition, since the laminate member obtained by the present invention can reduce the thickness of the resin film, it is preferably used for display devices and various functional materials, and further reduction in thickness, weight and flexibility can be realized.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the roll-to-roll apparatus for forming a functional layer in a long base film.
It is a schematic diagram which shows the base film in the shape of a long roll.
3 : shows the cross-sectional schematic diagram of a base film.
4 : shows a cross-sectional schematic diagram after forming a functional layer on a base film.
It is a schematic diagram which shows the mode which isolate|separates and removes a support material from a base film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely, using drawings. In addition, the present invention is not limited to these contents.

1 shows a pattern of forming a functional layer on a base film by a roll-to-roll method. In this roll-to-roll apparatus, a long base film 10 wound around a roll winding mechanism 14 on the delivery side is fed out in the longitudinal direction by the delivery mechanism 12, and a predetermined The metal is formed into a film, a functional layer is formed, and it winds up by the roll winding mechanism 15 of the winding side via the winding mechanism 13. Here, when a vacuum environment is required for process processing, the entire roll-to-roll apparatus is installed in a vacuum chamber.

In addition, the base film 10 in the shape of a long roll is shown in FIG. This base film 10 is provided with a polyimide layer 2 imidized by coating a polyamic acid solution on a support material 1 as shown in the longitudinal cross-sectional views of Figs. After forming the functional layer 3 on the surface of 2), the support material 1 can be isolate|separated using the interface of the polyimide layer 2 and the support material 1, and can be removed and made thin.

The functional layer formed on the base film 10 can be appropriately selected according to the use of the lamination member 20 obtained by the present invention, for example, an electrode layer, a light emitting layer, a gas barrier layer, an adhesive layer, a thin film transistor, a wiring layer. , one type or a combination of two or more types such as a transparent conductive layer can be exemplified. Hereinafter, a specific example for obtaining a functional layer according to the use of some lamination|stacking member is demonstrated.

(Manufacture of transparent conductive film)

A transparent conductive film can be obtained by laminating|stacking a transparent conductive layer on the elongate roll-shaped base film 10 provided with the polyimide layer 2 on the support material 1 . That is, in this case, the transparent conductive layer corresponds to the functional layer 3 . In obtaining the transparent conductive film, for example, a polyimide film made of polyimide having either of the structural units represented by the general formula (4) or (5) in the second example in a ratio of 80 mol% or more. is used as the support material 1, and the polyimide layer 2 is also formed of the same polyimide, and a long transparent base film 10 wound up in roll shape is prepared. Here, the polyimide film of the support material 1 may be a polyimide having the structural unit (a) shown in the first example above.

This transparent base film 10 is set in the roll-to-roll apparatus shown in FIG. As shown in FIG. 1 , the transparent base film 10 is held by the roll winding mechanism 14 on the delivery side, the delivery mechanism 12 , the winding mechanism 13 , and the roll winding mechanism 15 on the winding side, , A transparent conductive layer is laminated on the surface of the polyimide layer 2 of the transparent base film 10 fed out in the longitudinal direction by means such as a vapor deposition method in the process processing unit 11 . In that case, when a vacuum environment is required for lamination of the transparent conductive layer, the entire roll-to-roll apparatus may be installed in a vacuum chamber to perform the process treatment.

Here, when the polyimide layer 2 is formed of polyimide having any one of the structural units represented by the general formula (4) or (5) in a ratio of 80 mol% or more, low thermal expansibility and visible light region It has high transmittance and excellent transparency. Moreover, it has the characteristics that it is excellent also in dimensional stability, heat resistance is high, surface smoothness is favorable, and retardation in an in-plane direction is small. In addition, by using the polyimide film made of the same polyimide for the support material 1, the polyimide layer 2 and the support body 1 formed by the casting method are integrated by a certain amount of adhesive force, and the roll-to-roll device is used. A transparent conductive layer can be formed, and after forming a transparent conductive layer, using the interface of the support material 1 and the polyimide layer 2, it can separate easily and can reduce thickness.

By the way, when ITO is used as a transparent conductive layer, it is an amorphous state at the time of vapor-depositing on the base film 10, and the resistance value is high. For example, when a transparent conductive film is applied to a touch panel, it is necessary to reduce the resistance. Therefore, after patterning the electrode pattern for a touch panel, an annealing treatment of about 200°C to 300°C is performed to lower the resistance value. It has sufficient heat resistance, and it is possible to achieve sufficient low resistance by annealing treatment.

In addition, if it is possible to consider providing a transparent conductive film for a touch panel or the like, it is preferable that the thickness be thin. For example, when a film having a thickness of 50 μm is applied to a roll-to-roll device alone, handling difficulties or elongation of the film in the conveying process become a problem. By the way, if the base film 10 like this embodiment is used, for example, if the thickness of the support material 1 and the polyimide layer 2 is 50 micrometers respectively, while solving these problems, the thickness is about 50 A transparent conductive film having a thickness of mu m (the thickness of the transparent conductive layer is about 100 nm) can be industrially manufactured with good productivity.

(Manufacture of gas barrier film)

For example, ingress of moisture or oxygen into the organic EL light emitting layer of an organic EL device causes deterioration of properties, so a gas barrier layer for preventing the intrusion of moisture or oxygen is essential. Therefore, in the process processing unit 11, for example, an inorganic oxide film of silicon oxide, aluminum oxide, silicon carbide, silicon oxide carbide, silicon carbide nitride, silicon nitride, silicon nitride oxide, or the like is formed by a CVD method to form a functional layer. and, other than that, it is possible to obtain a thin gas barrier film in the same manner as in the case of the transparent conductive film.

However, if the difference between the coefficient of thermal expansion (CTE) of the gas barrier layer made of the inorganic oxide film and the CTE of the polyimide film made of the polyimide layer 2 becomes large, curl occurs, and dimensional stability deteriorates, or In some cases, there is a risk that cracks may occur. In particular, when a large-area film is manufactured, the problem of warpage becomes more remarkable. By the way, when the polyimide layer 2 is formed of polyimide having either of the structural units represented by the general formula (4) or (5) in a ratio of 80 mol% or more, the CTE is preferably 15 ppm/K or less. In general, since the difference with the inorganic oxide film having a CTE of 10 ppm/K or less can be reduced, the occurrence of such problems is eliminated. In addition, a gas barrier layer may be formed by 1 type of the above inorganic membranes, and may be formed so that 2 or more types may be included.

(Manufacturing of thin film transistors)

First, thin film transistors (TFTs) are roughly divided into amorphous silicon TFTs (a-Si TFTs) and polysilicon TFTs. In polysilicon TFTs, low-temperature polysilicon TFTs (LTPS-TFTs) capable of lowering the process temperature have become mainstream. Hereinafter, a method of obtaining an a-Si TFT having a bottom gate structure in obtaining a thin film transistor (TFT) used for a backplane of a liquid crystal display device or the like will be described.

In advance, a gas barrier layer is provided on the base film 10 in the same manner as in the manufacturing method of the gas barrier film described above in order to prevent intrusion of oxygen, water vapor, or the like from the outside. Then, a material for forming the gate electrode and wiring is deposited. As a film-forming material, Al-type material is mainly used and it laminates|stacks by means, such as sputtering. After the film formation, the gate and wiring patterns are transferred in a photolithography process, and formed (patterned) into a predetermined shape by an etching process.

Next, a gate insulating film (SiN, SiO2, etc.) and a _{semiconductor} layer (a-Si) are similarly formed into a film by methods, such as CVD, and are shape|molded into a predetermined shape. Hereinafter, a drain wiring, a source electrode, an interlayer insulating film, etc. are formed by repeating processing processes, such as a film-forming process, a photolitho process, and an etching process, similarly, and can obtain an a-Si TFT. In addition, in order to obtain the a-Si TFT as described above, the process processing units 11 for various process treatments may be arranged horizontally, respectively, and the base film 10 may be continuously processed, or the resin film wound up once again You may make it feed|feed out by a roll-to-roll system, and divide a process process into several processes and make it perform.

(Manufacture of organic EL display device)

For example, in order to obtain the organic electroluminescent display which has a bottom emission structure, first, it carries out similarly to the method mentioned above with respect to the polyimide layer 2 side of the base film 10, and provides a gas barrier layer, It has a structure that blocks the permeation of oxygen. Next, a circuit component layer including the above-described thin film transistor (TFT) is also formed on the upper surface of the gas barrier layer. In this case, LTPS-TFT is mainly selected as the thin film transistor. In this circuit structure layer, an anode electrode made of, for example, a transparent conductive film of ITO is formed for each of the pixel regions arranged in a matrix on the upper surface thereof. Further, an organic EL light emitting layer is formed on the upper surface of the anode electrode, and a cathode electrode is formed on the upper surface of the light emitting layer. This cathode electrode is formed in common in each pixel area. Then, a gas barrier layer is formed again to cover the surface of the cathode electrode, and a sealing substrate is further provided on the outermost surface to protect the surface. It is preferable that a gas barrier layer for blocking moisture and oxygen permeation is also laminated on the surface of the sealing substrate on the cathode electrode side.

In this way, in the organic EL display device, it is common to form various thin films on the polyimide layer 2 of the base film 10 in the above order, and finally seal it with a sealing substrate. In addition, although the organic EL light emitting layer is formed of a multilayer film (anode electrode - light emitting layer - cathode electrode) such as hole injection layer - hole transport layer - light emitting layer - electron transport layer, in particular, since the organic EL light emitting layer is deteriorated by moisture or oxygen, it is formed by vacuum deposition It is common to continuously form in a vacuum including electrode formation.

(Manufacture of organic EL lighting device)

When obtaining organic electroluminescent illumination, the bottom emission structure except the TFT layer in the organic electroluminescent display mentioned above about the functional layer is common. Here, as the anode electrode, a transparent electrode such as ITO is generally used, and the electrode resistance becomes low as the high temperature treatment is performed. As described above, in the case of ITO, heat treatment at about 200 to 300°C is common. In addition, organic EL lighting has increased in size, and the resistance value of the ITO electrode has become insufficient, and various alternative electrode materials are being searched for. In that case, there is a high possibility that the temperature of the annealing treatment will be higher than 200 to 300°C. However, if the base film using the polyimide as described above has sufficient heat resistance, it can respond to various alternative electrode materials.

(Manufacture of other functional layers)

In addition to the above examples, for example, various functional layers necessary for obtaining electronic paper or a touch panel are formed on the base film 10, and then the interface between the polyimide layer 2 and the support material 1 is formed. When the support material 1 is separated and removed using the slab and a laminated member with a reduced thickness is obtained, it is possible to achieve a thinner and lighter weight than the conventional one.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated, based on a test example.

First, the abbreviation of a raw material monomer and a solvent at the time of synthesizing a polyimide in the following, and the measuring method of various physical properties in an Example, and the conditions are shown below.

[About abbreviations]

DMAc:N,N-dimethylacetamide

PDA: 1,4-phenylenediamine

TFMB: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl

DADMB: 4,4'-diamino-2,2'-dimethylbiphenyl

1,3-BAB: 1,3-bis(4-aminophenoxy)benzene

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

6FDA: 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride

PMDA: pyromellitic dianhydride

[Surface Roughness (Ra)]

The surface observation was performed in tapping mode using the atomic force microscope (AFM) "Multi Mode8" manufactured by Bluka Corporation. The visual field observation of 10 micrometers x 10 micrometers was performed 4 times, and these average values were calculated|required. The surface roughness (Ra) represents the arithmetic mean roughness (JIS B0601-1991).

[Peel strength]

T-shaped peeling test method about the interface in the support material and polyimide layer in the sample which cut|disconnected the polyimide laminated body into the rectangular shape of width 10mm using the Toyo Seiki Seisakusho company strograph R-1 It was evaluated by measuring the peeling strength by.

[Transmittance (%)]

About the polyimide film (50 mm x 50 mm) which consists of a polyimide layer for forming a functional layer, the average value of the light transmittance in 440 nm - 780 nm was calculated|required using the U4000 type|mold spectrophotometer.

[Glass Transition Temperature Tg]

The glass transition temperature of the polyimide film which consists of a polyimide layer for forming a functional layer was measured as follows. Loss tangent when heating from room temperature to 400°C at a rate of 10°C/min using a 10 mm wide sample using a viscoelasticity analyzer (RSA-II manufactured by Rheometric Science &amp; Co., Ltd.) and applying a vibration of 1 Hz It was calculated|required from the maxima of (Tanδ).

[Coefficient of Thermal Expansion (CTE)]

A sample of 3 mm x 15 mm was cut out from each of the polyimide film and the support material comprising the polyimide layer for forming the functional layer, and a load of 5.0 g was applied with a thermomechanical analysis (TMA) apparatus at a constant temperature increase rate (20 ° C.) /min), a tensile test was performed in a temperature range of 30°C to 260°C, and the coefficient of thermal expansion (×10 ⁻⁶ /K) was measured from the elongation amount of the sample with respect to temperature.

Synthesis Example 1 (Polyimide A)

While stirring in a 300 ml separable flask under a nitrogen stream, 8.00 g of PDA was dissolved in DMAc as a solvent. Then, 22.00 g of this solution BPDA was added. After that, the solution was stirred at room temperature for 5 hours to carry out polymerization reaction, and was maintained overnight. A viscous polyamic acid solution was obtained, and it was confirmed that polyamic acid A having a high degree of polymerization was produced.

Synthesis Example 2 (Polyimide B)

12.08 g of TFMB was dissolved in DMAc as a solvent while stirring in a 300 ml separable flask under a nitrogen stream. Then, 6.20 g of PMDA and 4.21 g of 6FDA were added to this solution. After that, the solution was stirred at room temperature for 5 hours to carry out polymerization reaction, and was maintained overnight. A viscous polyamic acid solution was obtained, and it was confirmed that polyamic acid B having a high degree of polymerization was produced.

Synthesis Example 3 (Polyimide C)

13.30 g of TFMB was dissolved in DMAc as a solvent while stirring in a 300 ml separable flask under a nitrogen stream. Then, 9.20 g of PMDA was added to this solution. After that, the solution was stirred at room temperature for 5 hours to carry out polymerization reaction, and was maintained overnight. A viscous polyamic acid solution was obtained, and it was confirmed that polyamic acid C having a high degree of polymerization was produced.

Example 1 [Production of laminated member I]

After apply|coating the resin solution of the polyamic acid A obtained in Synthesis Example 1 on an 18-micrometer-thick long electrolytic copper foil, it heat-dried at 130 degreeC, and the solvent was removed. Then, imidized by heat treatment at a temperature increase rate of about 4 °C/min from 160 °C to 360 °C, and a copper clad laminate (thermal expansion) having a polyimide (surface roughness (Ra) = 1.3 nm, Tg = 355 °C) having a thickness of 25 µm. Coefficient of 17.5 ppm/K) was obtained, and it was set as the support material.

To the polyimide surface of the obtained copper clad laminate, the resin solution of polyamic acid B obtained in Synthesis Example 2 was uniformly applied to a thickness of 25 µm after curing, and then dried by heating at 130°C to remove the solvent in the resin solution. . Next, the polyamic acid was imidized by heat-processing from 160 degreeC to 360 degreeC at the temperature increase rate of about 20 degreeC/min, and the elongate base film I provided with the polyimide layer for forming a functional layer was obtained.

About the elongate base film I obtained above, it is attached to the testing machine which imitates the roll-to-roll apparatus shown in FIG. 1, and the elongate base film I wound up in roll shape is fed out longitudinally from the sending roll, and the vacuum chamber is passed through the conveyance roll. It was introduced into the process processing unit provided inside, and ITO with a thickness of 100 nm was formed into a film by continuous processing by the sputtering method on the polyimide layer of the elongate base film I in the said process processing part. Next, after being cut to a predetermined length, annealing was performed at 250° C. to crystallize the ITO film, thereby completing a test piece according to Example 1.

With respect to the test piece obtained above, the support material was separated and removed while measuring the peel strength at the interface between the copper clad laminate as the support material and the polyimide layer, and a transparent conductive layer made of ITO was formed on the polyimide layer having a thickness of 25 µm. I got The peeling strength at that time was 8.7 N/m, and it was a value of the grade which can peel easily manually. Moreover, about the polyimide layer in the base film I used when obtaining this lamination|stacking member I, the transmittance|permeability and thermal expansion coefficient are put together and are shown in Table 1.

Example 2 [Production of laminated member II]

A 25 µm-thick long polyimide film (Kapton H, manufactured by Toray DuPont Co., Ltd.: surface roughness Ra = 70 nm, Tg = 428 ° C., coefficient of thermal expansion 28.5 ppm/K) was used as a support material, and on this, a synthesis example The resin solution of polyamic acid B obtained in 2 was uniformly applied so that the thickness after hardening might be set to 25 micrometers, After that, the solvent in the resin solution was removed by heating and drying at 130 degreeC. Next, heat treatment is performed from 160°C to 360°C at a temperature increase rate of about 20°C/min to imidize polyamic acid to form a polyimide layer, and a long substrate having a polyimide layer on a support material (polyimide film) Film II was obtained.

Using the obtained base film II, it carried out similarly to Example 1, the ITO film|membrane was formed into a film, it annealed and completed the test piece by Example 2. The peeling strength in the interface of the support material (polyimide film) and polyimide layer in this test piece was 130 N/m, and it was a value of the grade which can peel easily by human hand. In addition, about the polyimide layer in base film II used when obtaining this lamination|stacking member II, the transmittance|permeability and thermal expansion coefficient are put together and shown in Table 1.

Example 3 [Production of laminated member III]

As a support material, a 25 µm-thick long polyimide film (Upirex S, manufactured by Ube Kyosan Co., Ltd.: surface roughness Ra = 15 nm, Tg = 359 ° C., coefficient of thermal expansion 12.5 ppm/K) was used, and on this, a synthesis example was used. A long base film III was obtained in the same manner as in Example 2 except that the resin solution of polyamic acid C obtained in 3 was uniformly applied so that the thickness after curing was set to 25 µm.

Using the obtained base film III, it carried out similarly to Example 1, the ITO film|membrane was formed into a film, it annealed and completed the test piece by Example 3. The peeling strength in the interface of the support material (polyimide film) and polyimide layer in this test piece was 53 N/m, and it was a value of the grade which can peel easily by human hand. In addition, the transmittance|permeability and thermal expansion coefficient are put together and shown in Table 1 about the polyimide layer in base film III used when obtaining the lamination|stacking member III.

1: support material 2: polyimide layer
3: functional layer 10: base film
11: process processing unit 12: sending mechanism
13: winding mechanism 14: roll winding mechanism on the delivery side
15: roll winding mechanism on the winding side 20: lamination member

Claims (11)

A method for continuously manufacturing a lamination member by feeding a long base film wound into a roll shape in the longitudinal direction by a roll-to-roll method, forming a film, and forming a functional layer on the base film,
The base film is provided with a polyimide layer imidized by coating a polyamic acid solution on a support material, and after forming a functional layer on the polyimide layer side, using the interface between the polyimide layer and the support material Separating and removing the support material to thin the base film,
The surface of the support material at the interface between the polyimide layer and the support material is formed of a heat-resistant polyimide surface having a glass transition temperature of 300°C or higher,
The method for manufacturing a lamination member, characterized in that the adhesive strength at the interface between the polyimide layer and the support material is 1N/m or more and 300N/m or less. The method of claim 1,
The method for manufacturing a lamination member, characterized in that the polyimide layer is formed of a single layer or a plurality of layers, and at least an interface with the support material is formed of fluorine-containing polyimide. 3. The method according to claim 1 or 2,
The polyimide layer has a transmittance of 70% or more in a wavelength range of 440 nm to 780 nm. 3. The method according to claim 1 or 2,
A method of manufacturing a lamination member, characterized in that the surface of the support material at the interface between the polyimide layer and the support material has a surface roughness (Ra) of 100 nm or less. The method of claim 1,
The method for manufacturing a laminate member, characterized in that the heat-resistant polyimide surface is formed of polyimide having the following structural unit.

delete 3. The method according to claim 1 or 2,
The method of manufacturing a laminate member, characterized in that the coefficient of thermal expansion of the polyimide layer is 25 ppm/K or less, and the thermal expansion coefficient of the support material is 25 ppm/K or less. 3. The method according to claim 1 or 2,
The thickness of the polyimide layer is 2 to 100 μm, the thickness of the support material is 10 to 200 μm, and the thickness of the polyimide layer is thinner than the support material. 3. The method according to claim 1 or 2,
The method for manufacturing a laminate member, characterized in that the support material has electrical conductivity or an electrically conductive layer on a rear side opposite to the polyimide layer. 3. The method according to claim 1 or 2,
The functional layer is a layer comprising any one or a combination of two or more selected from the group consisting of an electrode layer, a light emitting layer, a gas barrier layer, an adhesive layer, a thin film transistor, a wiring layer, and a transparent conductive layer. 3. The method according to claim 1 or 2,
A method of manufacturing a laminated member, characterized in that the patterning process is additionally performed after the film forming process.

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