TW201730255A - Method of fabricating substrate film - Google Patents

Abstract

The invention provides a method for making substrate film which is appropriately adaptable for making a laminated member which has a functional layer on a thin resin membrane; the method is capable of suppressing adverse impacts on the quality of the functional layer while an easy-handling in the manufacturing process is considered. It is a method for making an elongated substrate film which has a supporting member and a polyimide later on the supporting member. A functional layer is formed on the polyimide layer. The supporting member has a heat resisting polyimide face on a surface, the heat resisting face having glass transition temperature of 300 DEG C or higher. A polyimide layer having a transmittance 70% or higher in the wave length range of 440 nm to 780 nm is formed on the heat resisting polyimide face by coating a resin solution of polyamide acid on the heat resisting polyimide face, and imidizing the polyamide acid by heat treating.

Description

Method for producing substrate film

The present invention relates to a method for producing a base film, and more particularly to a method for producing a base film which is suitable for obtaining a laminated member having a functional layer on a thin resin film including a polyimide layer.

For example, a display device such as a liquid crystal display device or an organic EL display device is used in various displays including a large display such as a television and a small display such as a mobile phone, a personal computer, or a smart phone. In the organic EL display device, for example, a thin film transistor (hereinafter abbreviated as TFT) is formed on a glass substrate, and is formed in the order of an electrode, a light-emitting layer, and an electrode, and finally air-tight with another glass substrate or a multilayer film. Made by sealing.

In such a display device, a resin substrate can be used in place of the glass substrate, which is thinner, lighter, and more flexible than the conventional one, and can be used and diversified in the display device. However, in general, when the resin is compared with glass, it is inferior in terms of dimensional stability, transparency, heat resistance, moisture resistance, gas barrier property, and the like, and various reviews have been made in order to improve these disadvantages.

For example, Patent Document 1 proposes an invention in which a polyimine which is a resin substrate for a flexible display and a precursor thereof can be used, and it is disclosed that an alicyclic structure containing, for example, cyclohexylphenyltetracarboxylic acid or the like is used. Tetracarboxylic acids, with various The amine-reacted polyimine has excellent transparency. Further, Non-Patent Documents 1 and 2 disclose an organic EL display device in which a highly transparent resin material is applied to a support substrate.

On the other hand, a resin substrate excellent in flexibility can be manufactured by a roll to roll method. For example, Patent Document 2 discloses that a roll-shaped film substrate having a gas barrier layer on both surfaces of a transparent plastic substrate such as polycarbonate is used in the production of an organic EL display device, and is transported by a reel by sputtering. The apparatus forms an active layer of a thin film transistor on a roll-form film substrate (see Fig. 6). By using such a long resin substrate, it is possible to continuously operate, and it is expected to improve the productivity of the display device.

[Previous Technical Literature] (Patent Literature)

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-231327

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-181590

(Non-patent literature)

[Non-Patent Document 1] S. An et. al., "2.8-inch WQVGA Flexible AMOLED Using High Performance Low Temperature Polysilicon TFT on Plastic Substrates", SID2010 DIGEST, p. 706 (2010)

[Non-Patent Document 2] Oishi et.al., "Transparent PI for flexible display", IDW' 11 FLX2/FMC4-1

As described above, when a glass substrate used for a display device or the like is replaced with a resin substrate (resin film), it can be made thin, lightweight, and bendable. In particular, mobile devices that include smart phones are highly competitive in the development of thin and light, and are eagerly expected to be thin and light. However, when the thickness of the resin substrate is made thin, it is necessary to fully consider the problem of operability, especially when a long resin film is transported by a reel, when the film is extremely thin, it becomes There are extension problems, depending on the situation, there will be wrinkles in the film or cracking. Further, even if the film itself is not wrinkled or broken, various functional layers formed on a film such as a TFT, an electrode or a light-emitting layer may have an influence on quality during the manufacturing process due to expansion and contraction of the film.

Here, the present invention has been made in view of the above problems, and an object of the invention is to provide a functional layer on a thin resin film while suppressing the influence on the quality of the functional layer while considering the operability in the manufacturing process. The laminated member is suitable for a method of producing a substrate film of such a laminated member.

In order to solve the above-mentioned problems, the inventors of the present invention have found that a heat-resistant polyimide surface is coated with a polyamine solvent solution by using a support material having a heat-resistant polyimide surface on the surface. The imidization produces a substrate film having a polyimide layer having excellent transparency, whereby the interface between the support and the polyimide layer is used to separate the support and flaking, and a polyimide layer can be used. The present invention has been completed as a resin substrate.

That is, the present invention is a method for producing a base film, which is a method for producing a long-length base film having a polyimide layer on a support material and forming a functional layer on the polyimide layer. Characterized by a support material attached to the surface with a glass turn a heat-resistant polyimide surface having a temperature of 300 ° C or higher, a resin solution of poly-proline on the surface of the heat-resistant polyimide, and heat treatment to imidize the polyamine to heat resistance A polyimine layer having a transmittance of 70% or more in a wavelength region of 440 nm to 780 nm is formed on the polyimide surface.

Hereinafter, a method of producing a base film of the present invention will be described. In the following, an example in which the base film of the present invention is used as the base film in the laminated member will be described.

In the present invention, a long-length base film wound in a roll shape is sent to a vertical axis direction to perform a film formation process, and if necessary, the film formation is performed, and a functional layer is formed on the base film. A part of the base film is separated and removed to be thin, and a laminated member having a functional layer on a thin resin film (polyimine layer) is obtained.

In general, when the reel type is used, the resin film which is wound in a strip shape is wound in the reel mechanism on the delivery side, and is conveyed by the feeding mechanism in the vertical axis direction, and is processed by film formation, etc., and is interposed. The winding mechanism is wound in a reel mechanism on the winding side.

Therefore, in the above-mentioned Patent Document 2, a transparent plastic film such as a polyfluorene-based resin, an olefin-based resin, or a cyclic polyolefin-based resin which can be used as a long resin film is used. The thickness is about 50 to 200 μm (refer to [0083]). However, at least the resin film is in a state in which tensile stress is generated when the reel mechanism on the winding side is wound. Therefore, when the thickness of the resin film is reduced, the problem of stretching or shrinking naturally occurs. For this reason, if there is no thickness of at least about 100 μm, in fact, when wound by a reel mechanism, there is a problem that wrinkles or film breakage. Further, in order to form a functional layer, a film of a plurality of layers is formed, and the resin film temporarily wound after film formation is again sent out by a reel, and at the same time When the film-forming metal is subjected to pattern processing or the like in a plurality of steps, the dimensional precision is not maintained when the film is stretched and stretched, and the quality of the obtained functional layer is also affected.

Therefore, in the present invention, if a substrate film having a polyimide layer coated with a polyaminic acid solution on a support material and imidized is used, at least between the functional layers is formed by a reel method or the like. The strength of the substrate can be ensured by the thickness of the substrate film. After the functional layer is formed, the support material is separated and removed by the interface between the polyimide layer and the support material, thereby obtaining a thin layer containing the polyimide layer. A laminated member having a functional layer is provided on the resin film. Moreover, the method of manufacturing the laminated member in the present invention can be suitably applied to a reel type including a reel mechanism on the delivery side and a reel mechanism on the winding side, and can be applied to, for example, a roll directly in front of the reel mechanism on the winding side. The winding mechanism cuts the substrate film conveyed by the reel into a sheet-like incomplete reel type, and is particularly effective when the film is subjected to tensile tension in either case.

In the present invention, the support material is separated and removed by the interface between the polyimide layer and the support material, and in order to make the base film thin, it is necessary to make the interface between the polyimide layer and the support material easy to peel off. status. As such a means, it is preferred to use a polyimine having a specific chemical structure in the interface between the polyimide layer and the support.

Usually, the polyimine is obtained by polymerizing an acid anhydride of a raw material and a diamine, and can be represented by the following general formula (1).

In the formula, Ar1 represents a tetravalent organic group of an acid anhydride residue, and Ar2 represents a divalent organic group of a diamine residue, and from the viewpoint of heat resistance, at least one of Ar1 and Ar2 is desirably an aromatic residue.

The polyimine (polyimine resin) which is suitably used in the present invention, as the first example thereof, may be a polyimine having the following repeating structural unit (a). More preferably, it is preferred to include a ratio of the above-mentioned repeating unit at 80 mol% or more.

More preferably, in such a repeating structural unit, the polyimine having the following repeating structural unit (b).

In the case of the polyimine having the repeating structural unit (a) or (b) of the first example, since a heat-resistant polyimide surface having a glass transition temperature (Tg) of 300 ° C or more can be formed, the polyfluorene is formed. The imide layer is formed by such a polyimide, or the surface of the support has a heat-resistant polyimide surface containing such a polyimide. In this case, the interface between the polyimide layer and the support material can be easily separated.

Here, when the polyimine which is the first example described above is used, other polyimides having a ratio of up to 20 mol% may be added to the polyimine, and there is no particular limitation. A general acid anhydride and a diamine as described later can be used.

Further, as a second example of a polyimine (polyimine resin) which is suitably used, a fluorine-containing polyimide may be mentioned. That is, when the polyimide layer is formed by such a polyimide, or when the surface of the support has a heat-resistant polyimide surface containing such a polyimide, The interface between the imine layer and the support material can be easily separated. Therefore, the fluorine-containing polyimine refers to a fluorine-containing atom in the polyimine structure, an acid anhydride of a polyimide raw material, and a fluorine-based group in at least one of the components of the diamine. In the case of the fluorine-containing polyimine, for example, in the above formula (1), Ar1 in the formula may be a tetravalent organic group, and Ar2 is a compound of the following formula (2) or ( 3) The two-valent organic group shown is shown.

R1 to R8 in the above formula (2) or formula (3) are independently of each other and represent a hydrogen atom, a fluorine atom, an alkyl group or alkoxy group having 1 to 5 carbon atoms, or a fluorine-substituted hydrocarbon group. In the formula (2), at least one of R1 to R4 is a fluorine atom or a fluorine-substituted hydrocarbon group, and in the formula (3), at least one of R1 to R8 is a fluorine atom or a fluorine-substituted hydrocarbon group. In the above, preferred examples of R1 to R8 include -H, -CH ₃ , -OCH ₃ , -F, -CF ₃ and the like, and at least one substituent of the formula (2) or the formula (3) is Either -F or -CF ₃ is preferred.

Specific examples of Ar1 in the formula (1) in the case of forming a fluorine-containing polyimine are, for example, the following tetravalent acid anhydride residues.

In the case of the display device including the liquid crystal display device or the organic EL display device, for example, the display device including the liquid crystal display device or the organic EL display device is suitable for forming a polymerized layer. The imide layer is a specific diamine which imparts Ar ₂ of the general formula (1), in consideration of the fact that it is more excellent than the transparency, or the peeling property is improved at the interface between the polyimide layer and the support material. Residues, it is desirable to use the following.

Further, among the fluorine-containing polyimides, any one of the structural units represented by the following formula (4) or formula (5) has a ratio of 80 mol% or more, in addition to transparency and releasability. In addition to being excellent, it is more preferable because it has low thermal expansion property and excellent dimensional stability. In other words, the polyimine having a structural unit represented by the following formula (4) or (5) has a transmittance of 70% or more in a wavelength region of 440 nm to 780 nm, which is desirable. Since it is 80% or more, it is more advantageous to form a polyimine layer in a laminate member which requires transparency such as a display device. Further, in addition to having a glass transition temperature (Tg) of 300 ° C or higher, the coefficient of thermal expansion may be 25 ppm / K or less, or preferably 10 ppm / K or less. For this reason, when such a polyimide is used in both the polyimide layer and the support material, even if subjected to a temperature change during the process, the thermal expansion coefficients of the two are similar, and the aggregation of the wrinkles can be prevented.

Here, when the polyimine is set to the polyimine of the formula (4) or (5), other polyimines having a ratio of up to 20 mol% may be added in addition to the polyimine. There is no particular limitation on this, and a general acid anhydride and a diamine can be used. Among them, as the acid anhydride to be used, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,4-cyclohexanedicarboxylic acid, 1, 2 may be mentioned. 3,4-cyclobutanetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and the like. On the other hand, as the diamine, there may be mentioned 4,4'-diaminodiphenylphosphonium, trans-1,4-diaminocyclohexane, and 4,4'-diaminocyclohexylmethane. 2,2'-bis(4-aminocyclohexyl)-hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diaminobicyclohexane or the like.

Including the first and second examples described above, various polyimine groups can be obtained by imidating polylysine. Here, the resin solution of polylysine is substantially obtained by reacting a diamine and an acid dianhydride using a raw material of a molar amount in an organic solvent. The winner is better. More specifically, after diamine is dissolved in an organic polar solvent such as N,N-dimethylacetamide or the like, a tetracarboxylic dianhydride is added, and the reaction is carried out at room temperature for about 5 hours. . The weight average molecular weight of the obtained polyglycine is preferably from 10,000 to 300,000 from the viewpoint of mechanical strength of the uniform film thickness of the polyimide film obtained after coating. Further, the desired molecular weight range of the obtained polyimine layer is the same as the molecular weight range of the polyamic acid. Further, the polyimide layer may be formed of a single layer or a plurality of layers. When forming a plurality of layers, it is sufficient to use at least the polyimine listed in the first and second examples as described above for the layer forming the interface with the support.

Therefore, the substrate film having the polyimide layer on the support material is coated with a polyaminic acid solution on the support material, for example, heat-treated at about 150 to 160 ° C and removed in the resin solution. The solvent is further heat treated at a high temperature to imidize the polyamic acid. The heat treatment performed in the imidization can be carried out by, for example, raising the temperature at a temperature of about 160 ° C in a continuous or stepwise manner to a temperature of about 350 ° C. At this time, after preparing a long support material, it is suitable to form a polyamidite layer by coating a polyphthalic acid resin solution by a casting method while carrying it on a reel.

The support material for forming the base film in the present invention has flexibility, and at the same time, it is provided with at least heat treatment which can withstand the formation of the polyimide layer by imidization of the polyamic acid solution. Heat resistance can be. Specific examples thereof include a metal foil such as a copper foil or a SUS foil, a metal foil-resin laminate such as a copper clad laminate (CCL), and a resin film such as polyimide. In addition, as described above, the surface of the support material is a heat-resistant polyimide surface having a polyimine which is exemplified in the first and second examples, and is formed into a metal foil having such a polyimide. - Polyimine laminate The support material may be used as a support material only by using a polyimine film containing such a polyimide. Further, the interface between the polyimide layer and the support material is most easily separated, and any of the interfaces between the polyimide layer and the support material can be exemplified by the first and second examples. Amines are formed.

Further, in the support material of the present invention, from the viewpoint of easily separating the interface between the polyimide layer and the support material, it is desirable that the surface of the support material at the interface between the polyimide layer and the support material The roughness Ra is preferably 100 nm or less. Further, when the support material has conductivity, or when the conductive layer is provided on the back surface opposite to the polyimide layer, the film can be fed by a reel, and when it is wound, the generated static electricity can be prevented. The advantages of electricity.

In the present invention, by using the above-exemplified polyimine or the like, the adhesion 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, and more preferably 5 N/ m or more and 300 N/m or less, more preferably 10 N/m or more and 200 N/m or less, for example, can be easily peeled off by hand.

In the present invention, as described above, the thickness of the base film is ensured by the presence of the support material. Therefore, even when the thickness of the polyimide layer is reduced, the mechanical strength at the time of forming the functional layer can be maintained. When the film is fed by a reel, when the film is wound, the roller of the feeding mechanism or the winding mechanism, and the reel mechanism on the winding side have tensile stress on the film, it is generally necessary to have a film thickness of about 100 μm. However, in the present invention, it is sufficient that at least the thickness is achieved in combination with the support member. For this reason, the thickness of the polyimide layer can be made 100 μm or less, and desirably 50 μm or less, and preferably 30 μm or less. Further, in addition to the laminated member having the functional layer, the lower limit of the thickness of the polyimide layer is desirably 2 μm, preferably 5 μm, in consideration of ensuring insulation properties and the like.

On the other hand, the thickness of the support material may be arbitrarily set as long as it contains a polyimide layer and has a required thickness as a base film. In other words, for example, the effect as the support material, the windability, and the like are considered, and for example, a thickness of 10 to 200 μm can be exemplified without particular limitation. However, it is desirable that the side of the polyimide layer be made thinner than the support.

The laminated member of the present invention can be used not only as a display device such as an electronic paper or a touch panel including a liquid crystal display device or an organic EL display device but also as a component, and can also be used in an organic EL illumination device. A conductive film having a laminated layer such as ITO, a gas barrier film that prevents penetration of moisture or oxygen, and a functional component having various functions such as a component of a flexible circuit board are used. That is, the functional layer in the present invention refers to a display device, an illumination device, or a component thereof, and constitutes various functional materials, specifically, an electrode layer, a light-emitting layer, a gas barrier layer, and an adhesive layer. One type of a thin film transistor, a wiring layer, a transparent conductive layer, or the like, or a combination of two or more types.

Then, such a functional layer can be obtained by forming a metal or the like, and then forming a predetermined shape, heat treatment, or the like as necessary, and using a known method. That is, there is no particular limitation on the means for forming the functional layers, for example, sputtering, deposition, CVD, printing, exposure, dipping, etc., if necessary, in a vacuum chamber ( The process is performed in the chamber. Then, the separation and removal of the support material may be performed immediately after the formation of the functional layer by various processes, or may be integrated with the support material within a certain period of time, for example, just as a display device or a functional material. The support material was previously separated and removed.

According to the invention, as long as the surface has a heat-resistant polyimide surface The support material is coated with a polyaminic acid solution on a heat-resistant polyimide surface and imidized to produce a base film having a polyimine layer having excellent transparency, and the support material and the aggregate can be used. The interface of the quinone imine layer separates the support material and is thinned, and a polyimide layer can be used as the resin substrate. Further, in addition to the use of such a base film to obtain a laminated member having a functional layer on a thin resin film, in one form, at least the functional layer is formed by the thickness of the base film. The strength of the machine, after forming the functional layer, using the interface between the polyimide layer and the support material in the base film to separate and remove the support material, and thinning it, can be easily and effectively manufactured in the containing polyphthalate The thin resin film of the amine layer is provided with a laminated member of a functional layer.

Further, the laminated member obtained by the present invention can be used in a display device or various functional materials because the thickness of the resin film can be reduced, and the thickness, the weight, and the bendability can be further reduced. .

1‧‧‧Support material

2‧‧‧polyimine layer

3‧‧‧ functional layer

10‧‧‧Substrate film

11‧‧‧Process Processing Department

12‧‧‧Send agency

13‧‧‧Winding mechanism

14‧‧‧Reel side reel mechanism

15‧‧‧Rolling mechanism on the winding side

20‧‧‧Layered components

Fig. 1 is a schematic view showing a reel device for forming a functional layer on a long substrate film.

Fig. 2 is a schematic view showing a base film of a long roll shape.

Fig. 3 is a schematic cross-sectional view showing a substrate film.

Fig. 4 is a schematic cross-sectional view showing the formation of a functional layer on a substrate film.

Fig. 5 is a schematic view showing a state in which the substrate is separated and the support material is removed.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be specifically described using the drawings, and the present invention is not limited to these.

Fig. 1 is a view showing a state in which a functional layer is formed on a base film by a reel method. In the reel device, the long base film 10 wound on the reel mechanism 14 on the delivery side is fed in the vertical axis direction by the delivery mechanism 12, and is set in the processing unit 11 such as a sputtering apparatus. The metal is formed into a film to form a functional layer, and is wound around the winding side reel mechanism 15 via the winding mechanism 13. Here, when a vacuum environment is required in the process, the entire reel device is disposed in the vacuum chamber.

Moreover, Fig. 2 is a view showing a long roll-shaped base film 10 . The base film 10 is provided with a polyamidene layer 2 which is coated with a polyaminic acid solution on the support material 1 as shown in the longitudinal cross-sectional views of FIGS. 3 to 5 . After the surface of the polyimine layer 2 is formed into the functional layer 3, the interface between the polyimide layer 2 and the support material 1 is separated and the support material 1 is removed to be thinned.

The functional layer formed on the base film 10 can be appropriately selected in accordance with the use of the laminated member 20 obtained by the present invention. For example, an electrode layer, a light-emitting layer, a gas barrier layer, an adhesive layer, and a thin film transistor can be exemplified. One type of the wiring layer, the transparent conductive layer, or the like, or a combination of two or more types. Hereinafter, a specific example for obtaining a functional layer will be described by combining the use of several laminated members.

(Manufacture of transparent conductive film)

A transparent conductive layer is formed by laminating a transparent conductive layer on the long roll-shaped base film 10 having the polyimide layer 2 on the support member 1. That is, the transparent conductive layer at this time is equivalent to the functional layer 3. When a transparent conductive film is obtained, for example, any of the structural units represented by the above formula (4) or (5) shown in the above second embodiment has a polyfluorene-containing polyfluorene in a ratio of 80 mol% or more. Imine film as support material 1 for polythenimine Similarly to the layer 2, the transparent base film 10 which is wound into a roll shape is prepared in the same manner as the polyimide. Here, the polyimide film of the support material 1 may be the polyimine having the structural unit (a) shown in the above first example.

This transparent base film 10 is attached to a reel apparatus as shown in Fig. 1. As shown in Fig. 1, the transparent base film 10 is held by the reel mechanism 14, the delivery mechanism 12, the winding mechanism 13, and the reel mechanism 15 on the winding side, and is fed in the direction of the vertical axis. On the surface of the polyimide layer 2 of the transparent base film 10, a transparent conductive layer is laminated on the process portion 11 by a deposition method or the like. In this case, when a vacuum environment is required for laminating the transparent conductive layer, the entire reel device may be placed in a vacuum chamber to perform a process.

Therefore, when the polyimine layer 2 is formed by the polyimine of any of the structural units represented by the above formula (4) or (5) having a ratio of 80 mol% or more, the thermal expansion property is low. However, the transmittance in the visible light region is high and the transparency is excellent. Further, the dimensional stability is also good, the heat resistance is high, the surface smoothness is good, and the retardation in the in-plane direction is small. Further, in the support material 1, a polyimide film containing polyimine is similarly used, and the polyimide layer 2 formed by the casting method is integrated with the support body 1 to some extent. A transparent conductive layer can be formed in the reel device, and after the transparent conductive layer is formed, the interface between the support member 1 and the polyimide layer 2 can be easily separated and thinned.

However, when ITO is used as the transparent conductive layer, it is in an amorphous state when deposited on the base film 10, and its resistance value is high. For example, when a transparent conductive film is used as a touch panel, it is necessary to reduce the resistance. For this reason, after patterning in the electrode pattern for the touch panel, an annealing treatment of about 200 ° C to 300 ° C is performed in an attempt to reduce the resistance value as long as the substrate film 10 of the present embodiment is provided. In the case of such annealing temperature, sufficient heat resistance can be obtained, and more sufficient resistance can be obtained by annealing treatment.

Further, in consideration of the use of a transparent conductive film for a touch panel or the like, it is preferable to make the thickness as thin as possible. For example, when a film having a thickness of 50 μm is used alone in a reel device, there is a problem in handling difficulty or film stretching during handling. However, when the base film 10 of the present embodiment is used, for example, when the thickness of the support member 1 and the polyimide layer 2 is 50 μm, respectively, the above problems can be solved, and on the one hand, industrial productivity can be improved. A transparent conductive film having a thickness of about 50 μm was produced (the thickness of the transparent conductive layer was about 100 nm).

(Manufacture of gas barrier film)

For example, in the organic EL light-emitting layer of the organic EL device, if moisture or oxygen permeates, characteristic deterioration occurs, and thus a gas barrier layer that prevents penetration of moisture or oxygen is indispensable. Here, in the processing unit 11, for example, an inorganic oxide film such as yttrium oxide, aluminum hydride, tantalum carbide, yttria oxide, tantalum carbide, tantalum nitride, or tantalum nitride is formed by a CVD method. The film is used as a functional layer, and the rest is operated in the same manner as in the case of the above transparent conductive film, and a thinned gas barrier film can be obtained.

However, when the coefficient of thermal expansion (CTE) of the gas barrier layer containing the inorganic oxide film becomes larger than the CTE of the polyimide film containing the polyimide layer 2, in addition to curling, there are also sizes. Stability is worse, and there are concerns about cracks depending on the situation. In particular, the problem of warpage is more pronounced when manufacturing a large-area film. However, when the polyimine layer 2 is formed by a polyimine having a ratio of 80 mol% or more of any of the structural units represented by the above formula (4) or (5), the preferred one is The CTE can be set to 15 ppm/K or less, and the difference from the inorganic oxide film having a CTE of 10 ppm/K or less can be made small, so that such a defect can be eliminated. The phenomenon occurs. Further, the gas barrier layer may be formed of one type of the inorganic film as described above, or may be formed by containing two or more kinds.

(Manufacture of thin film transistor)

First, a thin film transistor (TFT) can be roughly classified into an amorphous silicon TFT (a-Si TFT) and a polysilicon TFT, a polycrystalline germanium TFT, and a low temperature polycrystalline germanium TFT (LTPS-) having a low process temperature. TFT) has become the mainstream. The following is a method for obtaining an a-Si TFT having a bottom gate type structure when a thin film transistor (TFT) used in a substrate or the like of a liquid crystal display device is obtained.

First, in the base film 10, in order to prevent penetration of oxygen or water vapor from the outside, a gas barrier layer is provided in the same manner as in the above-described method for producing a gas barrier film. Next, a material for forming a gate electrode and wiring is formed into a film. As a film-forming material, an Al-based material is mainly used, and a layer is deposited by means of sputtering or the like. After the film formation, the pattern of the gate and the wiring is transferred by a photolithography step, and formed (patterned) into a predetermined shape by an etching process.

Next, a gate insulating film (SiN, SiO ₂ or the like) and a semiconductor layer (a-Si) are formed into a film by a method such as CVD to form a predetermined shape. In the following, the processing steps such as the film formation step, the photolithography step, and the etching step are repeated in the same manner to form a drain wire, a source electrode, an interlayer insulating film, and the like, and an a-Si TFT can be obtained. Further, in the above-described a-Si TFT, the process processing portions 11 for various process processes may be arranged in parallel to continuously process the base film 10, or the temporarily wound resin film may be reused again. The reel method is sent out, and the process processing is divided into several steps.

(Manufacture of organic EL display device)

For example, in obtaining an organic EL having a bottom emission structure In the display device, first, on the side of the polyimide layer 2 of the base film 10, a gas barrier layer is provided in the same manner as the above-described method to form a structure for preventing penetration of moisture or oxygen. Next, a circuit constituent layer containing the above-mentioned thin film transistor (TFT) is also formed on the upper surface of the gas barrier layer. At this time, the LTPS-TFT is mainly selected as the thin film transistor. In this circuit constituent layer, for example, a structure in which a matrix region is arranged in a matrix, for example, a structure in which an anode electrode of a transparent conductive film containing ITO is formed. Further, an organic EL light-emitting layer was formed on the upper surface of the anode electrode, and a cathode electrode was formed on the light-emitting layer. This cathode electrode is formed in common in each pixel region. Then, a gas barrier layer is formed again in such a manner as to cover the surface of the cathode electrode, and a sealing substrate for protecting the surface is provided on the outermost surface. It is desirable to form a gas barrier layer that blocks the penetration of moisture or oxygen on the surface of the cathode electrode side of the sealing substrate.

As described above, in the organic EL display device, various films are formed on the polyimide layer 2 of the base film 10 in the above-described order, and generally, the sealing substrate is finally sealed. Further, the organic EL light-emitting layer is formed by a multilayer film (anode electrode-light-emitting layer-cathode electrode) such as a hole injection layer-hole transport layer-light-emitting layer-electron transport layer, in particular, an organic EL light-emitting layer. It will be degraded by moisture or oxygen, so it is formed by vacuum deposition, and generally also includes electrode formation which is continuously formed in a vacuum.

(Manufacture of organic EL lighting device)

When the organic EL illumination is obtained, the functional layer is generally a bottom emission structure in which the TFT layer is removed in the above-described organic EL display device. Here, the anode electrode is generally a transparent electrode made of ITO or the like, and the electrode resistance is low resistance when subjected to high temperature treatment. As described above, in the case of ITO, heat treatment is generally performed at about 200 to 300 °C. Further, the organic EL illumination is progressing toward the shape of the large form, and in terms of the ITO electrode, the resistance value is always insufficient, and various alternative electrode materials are required. At this time, although the annealing temperature is highly likely to be higher than 200 to 300 ° C, the substrate film using the above polyimine has sufficient heat resistance, so that it can be used in various forms. The need for alternative electrode materials.

(manufacturing of other functional layers)

In addition to the above examples, for example, in order to obtain an electronic paper, a touch panel, or the like, various necessary functional layers are formed on the base film 10, and then the support material 1 is used by the interface of the polyimide layer 2 and the support material 1. Separation and removal can be made thinner and lighter than ever, as long as it can be formed into a thinned laminated member.

[Examples]

Hereinafter, the present invention will be described based on test examples.

First, the abbreviation of the raw material monomer and the solvent in the case of synthesizing the polyimine in the following, and the measurement methods of various physical properties in the examples and the conditions thereof are shown below.

[Related 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)]

Surface observation was performed in a tapping mode using an atomic force micromirror (AFM) "Multi Mode 8" manufactured by Bruker. Perform 4 times 10μm square Observe the field of view and obtain the average of these. The surface roughness (Ra) is an arithmetic mean roughness (JIS B0601-1991).

[peel strength]

Using the STROGRAPHY R-1 manufactured by Toyo Seiki Co., Ltd., the interface between the support material and the polyimide layer in which the polyimide film laminate was cut into a strip sample having a width of 10 mm was subjected to a T-stripping test method. The measured peel strength was evaluated.

[Transmission rate (%)]

For the polyimine film (50 mm × 50 mm) containing the polyimide layer for forming the functional layer, an average value of light transmittance from 440 nm to 780 nm was obtained using a U4000 spectrophotometer.

[Glass transfer temperature Tg]

The glass transition temperature of the polyimide film containing the polyimide layer for forming the functional layer was measured in the following manner. Using a viscoelastic analyzer (Rheometric Science Effie Co., Ltd.; RSA-II), a 10 mm wide sample was used to impart a vibration of 1 Hz while raising the temperature from room temperature to 400 ° C at a rate of 10 ° C/min. The maximum value of the loss tangent (tan δ) is used to determine the glass transition temperature (Tg) of the polyimide film.

[Coefficient of Thermal Expansion (CTE)]

For the polyimide film and the support material comprising the polyimine layer for forming the functional layer, a sample of 3 mm×15 mm was cut out, and a load of 5.0 g was added to one side of the thermomechanical analysis (TMA) device. The heating rate (20 ° C / min) was subjected to a tensile test in a temperature range of 30 ° C to 260 ° C, and the coefficient of thermal expansion (×10 ^-6 /K) was measured from the elongation of the sample.

Synthesis Example 1 (polyimine A)

Under a nitrogen gas stream, stir the side of the PDA in a 300 ml separable flask. 8.00 g was dissolved in the solvent DMAc. Next, this solution BPDA 22.00g was added. Thereafter, the solution was continuously stirred at room temperature for 5 hours to carry out polymerization for a day and night. A viscous polyamine acid solution was obtained, and the formation of polyglycine A having a high degree of polymerization was confirmed.

Synthesis Example 2 (polyimine B)

Under a nitrogen gas stream, 12.08 g of TFMB was dissolved in a solvent DMAc while stirring in a 300 ml separable flask. Next, 6.20 g of PMDA and 4.21 g of 6FDA were added to the solution. Thereafter, the solution was continuously stirred at room temperature for 5 hours to carry out polymerization for a day and night. A viscous polyamine acid solution was obtained, and the formation of polyglycine B having a high degree of polymerization was confirmed.

Synthesis Example 3 (polyimine C)

Under a nitrogen gas stream, 13.30 g of TFMB was dissolved in a solvent DMAc while stirring in a 300 ml separable flask. Next, 9.20 g of PMDA was added to this solution. Thereafter, the solution was continuously stirred at room temperature for 5 hours to carry out polymerization for a day and night. A viscous polyamine acid solution was obtained, and the formation of a polyglycine C having a high degree of polymerization was confirmed.

Example 1

Embodiment 1 [Production of laminated member I]

The resin solution of the polyamic acid A obtained in Synthesis Example 1 was applied onto a strip of electrolytic copper foil having a thickness of 18 μm, and then dried by heating at 130 ° C to remove the solvent. Next, heat treatment was carried out at 160 ° C to 360 ° C at a temperature elevation rate of about 4 ° C / min to imidize, and a polyiminoimine having a thickness of 25 μm (surface roughness Ra = 1.3 nm, Tg = 355 ° C) was obtained. A copper laminate (coefficient of thermal expansion 17.5 ppm/K) was used as a support material.

The polyimine surface of the copper-clad laminate obtained was uniformly coated so that the resin solution of the poly-proline B obtained in Synthesis Example 2 was cured to a thickness of 25 μm, and then dried by heating at 130 ° C to remove Solvent in the resin solution. Secondly, The heat treatment is carried out at 160 ° C to 360 ° C at a temperature elevation rate of about 20 ° C /min to imidize the polyamidated acid to obtain a long-length base film I having a polyimine layer for forming a functional layer.

The long-length base film I obtained as described above is mounted in a testing machine of the reel-like apparatus shown in Fig. 1, and the long-length base film I wound in a roll shape is fed by the conveying roller in the vertical axis direction. The film is introduced into the process chamber of the vacuum chamber via a conveyance roller, and ITO of a thickness of 100 nm is continuously processed by a sputtering method on the polyimide layer of the long substrate film I of the process portion to form a film. Next, an annealing treatment was performed at 250 ° C to crystallization of the ITO film, except that the predetermined length was cut out, and the test piece of Example 1 was completed.

With respect to the test piece obtained above, the peeling strength at the interface between the copper-clad laminate of the support material and the polyimide layer was measured, and the support material was separated and removed to obtain ITO containing the polyimide layer having a thickness of 25 μm. The laminated member I of the transparent conductive layer. The peel strength at this time was 8.7 N/m, which is a value which is easily peeled off by a human hand. Further, the polyimide film of the base film I used in obtaining the laminated member I was combined with the transmittance and the coefficient of thermal expansion and shown in Table 1.

Example 2 [Production of laminated member II]

As a support material, a long-length polyimide film having a thickness of 25 μm (Kapton H, manufactured by Toray DuPont Co., Ltd.: surface roughness Ra = 70 nm, Tg = 428 ° C, thermal expansion coefficient: 28.5 ppm / K) was used. The resin solution of the polyamic acid B obtained in Synthesis Example 2 was uniformly applied so as to have a thickness of 25 μm after hardening, and then dried at 130 ° C to remove the solvent in the resin solution. Next, heat treatment is carried out at a temperature elevation rate of about 20 ° C /min from 160 ° C to 360 ° C to imidize the polyamido acid to form a polyimine layer, and the support material (polyimine film) has a poly Amine layer Long strip substrate film II.

Using the obtained base film II, an ITO film was formed in the same manner as in Example 1, and the test piece of Example 2 was completed after the annealing treatment. In this test piece, the peel strength at the interface between the support material (polyimine film) and the polyimide layer was 130 N/m, which is a value which can be easily peeled off by a human hand. Moreover, the polyimide film of the base film II used when the laminated member II was obtained was shown in Table 1 in combination with the transmittance and the thermal expansion coefficient.

Example 3 [Production of laminated member III]

In addition to the support material, a long strip of polyimide film having a thickness of 25 μm (UPILEX S, manufactured by Ube Industries, Ltd.: surface roughness Ra = 15 nm, Tg = 359 ° C, thermal expansion coefficient 12.5 ppm / K) was used. A long substrate film III was obtained in the same manner as in Example 2 except that the resin solution of the polyamic acid C obtained in Synthesis Example 3 was uniformly applied to a thickness of 25 μm after hardening. .

Using the obtained base film III, an ITO film was formed into a film in the same manner as in Example 1, and an annealing treatment was performed to complete the test piece of Example 3. The peel strength at the interface between the support material (polyimine film) and the polyimide layer in the test piece was 53 N/m, which is a value which can be easily peeled off by a human hand. Further, the polyimide film of the base film III used for obtaining the laminated member III was shown in Table 1 in terms of its transmittance and thermal expansion coefficient.

10‧‧‧Substrate film

11‧‧‧Process Processing Department

12‧‧‧Send agency

13‧‧‧Winding mechanism

14‧‧‧Reel side reel mechanism

15‧‧‧Rolling mechanism on the winding side

Claims (8)

A method for producing a base film, which is a method for producing a long-length base film having a polyimide layer on a support material and forming a functional layer on the polyimide layer, wherein the support is attached to the surface a heat-resistant polyimide surface having a glass transition temperature of 300 ° C or higher, a resin solution of poly-proline on the surface of the heat-resistant polyimide, and heat treatment to imidize the polyamine On the heat-resistant polyimide surface, a polyimide layer having a transmittance of 70% or more in a wavelength region of 440 nm to 780 nm is formed. The method for producing a base film according to the above aspect of the invention, wherein the heat-resistant polyimide film surface is formed of a polyimide having the following structural unit: The method for producing a base film according to claim 1 or 2, wherein the polyimine layer is composed of a single layer or a plurality of layers, and at least the interface with the support material is a fluorine-containing polymerization. Formed by quinone imine. The method for producing a base film according to the first or second aspect of the invention, wherein the polyimine layer is formed of a polyimide having a glass transition temperature of 300 ° C or higher. The method for producing a base film according to claim 1 or 2, wherein the polyimine layer is formed of a polyimine having the following structural unit: The method for producing a base film according to the first or second aspect of the invention, wherein the surface roughness Ra of the surface of the support material at the interface between the polyimide layer and the support material is 100 nm or less. The method for producing a base film according to the first or second aspect of the invention, wherein the adhesive strength of the interface between the polyimide and the support is from 1 N/m to 500 N/m. The method for producing a substrate film according to claim 1 or 2, wherein the polyimine layer has a thickness of 2 to 100 μm, and the support material has a thickness of 10 to 200 μm, and the polycondensation The thickness of the imine layer is thinner than the aforementioned support material.