TW201700301A - Resin laminated film, laminated body containing the same, TFT substrate, organic EL element, color filter, and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide a resin laminated film having a low irradiation energy required for laser peeling using ultraviolet light. The resin laminated film is a resin laminated film having a polyimide film on at least one surface of the resin film, and the polyimine resin film is a polyimine resin film A below. Polyimine resin film A: a polyimide film having a thickness of 300 nm in a wavelength range of 300 to 400 nm, and a minimum of light transmittance of less than 50%.

Description

A resin laminated film, a laminated body containing the same, a TFT substrate, an organic EL element, a color filter, and a method of manufacturing the same.

The present invention relates to a resin laminated film, a laminate including the same, a TFT substrate, an organic EL device, and a method for producing the same.

The resin film is more flexible than glass, is not easily broken, and is lightweight. Recently, a review has been made on the use of a resin film on a substrate of a flat panel display to make the display flexible.

In general, examples of the resin film include polyester, polyamine, polyimine, polyamidimide, and polybenzoene. Oxazole, polycarbonate, polyether oxime, acrylic acid, epoxy resin, and the like. In order to use a resin film in an alternative material for a glass substrate such as a display device or an optical element, heat resistance or transparency in a visible light region or the like is required. Examples of the display device include an organic electroluminescence (organic EL) display, a liquid crystal display, and electronic paper. A color filter is mentioned as an optical element, and a touch panel is mentioned as another member.

An example of a method of producing a flexible substrate by using a resin film is a step of forming a resin film by applying a resin varnish on a support substrate, forming a display device or an optical element on the resin film, and the like. A method of the step of peeling the resin film from the support substrate.

As a method of peeling off a resin film as a self-supporting substrate, a laser peeling technique using ultraviolet light is disclosed (for example, refer to Patent Documents 1 and 2). In this method, the resin generated by absorbing the laser light in the resin is thermally decomposed in the vicinity of the interface with the support substrate, and the resin film is peeled off from the support substrate.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Publication No. 2007-512568

Patent Document 2: Japanese Special Table 2010-500609

However, in the heat resistant resin film typified by polyimine, there is a problem that the irradiation energy required for peeling is high and the laser peeling property is poor.

It is considered that this is because the heat resistance of the resin film is high and it is difficult to thermally decompose by laser irradiation. Further, the irradiation energy required for the peeling of the transparent polyimine which has a high light transmittance in the visible light region is higher than that of the colored polyimide. It is considered that this is because of the heat resistance, and the absorbance in the ultraviolet range is low.

Accordingly, it is an object of the present invention to provide a resin laminated film having a low irradiation energy required for laser peeling using ultraviolet light in this wavelength range.

That is, the present invention is a resin laminated film which is a resin laminated film having a polyimide film on at least one surface of a resin film, The polyimine resin film is the following polyimine resin film A.

Polyimine resin film A: A polyimide film having a minimum transmittance of less than 50% in a wavelength range of 300 to 400 nm when a film having a thickness of 100 nm is formed.

The resin laminated film of the present invention can reduce the irradiation energy required for laser peeling of the self-supporting substrate.

1‧‧‧Support substrate

2, 2'‧‧‧ resin laminated film

2A, 2A'‧‧‧ Polyimine resin film A

2B, 2B'‧‧‧ resin film

3‧‧‧Black matrix

4R‧‧‧Red coloring pixels

4G‧‧‧Green coloring pixels

4B‧‧‧Blue coloring pixels

5‧‧‧gas barrier

6‧‧‧TFT

7‧‧‧Flating layer

8‧‧‧First electrode

9‧‧‧Insulation

10‧‧‧second electrode

11R‧‧‧Red Organic EL Light Emitting Layer

11G‧‧‧Green Organic EL Light Emitting Layer

11B‧‧‧Blue organic EL luminescent layer

11W‧‧‧White Organic EL Light Emitting Layer

12‧‧‧Closed film

13‧‧‧Next layer

20‧‧‧CF

30‧‧‧Organic EL components

Fig. 1 is a cross-sectional view showing an example of a color filter substrate.

Fig. 2 is a cross-sectional view showing an example of a TFT substrate.

Fig. 3 is a cross-sectional view showing an example of an organic EL element display.

Fig. 4 is a cross-sectional view showing an example of an organic EL element display.

[Formation of the Invention]

Hereinafter, the form of carrying out the invention will be described in detail. Furthermore, the present invention is not limited by the following embodiments.

<Resin laminated film>

The resin laminated film of the present invention is a resin laminated film having a polyimide film on at least one surface of the resin film, and the polyimine resin film is the following polyimide film A.

Polyimine resin film A: A polyimide film having a minimum transmittance of less than 50% in a wavelength range of 300 to 400 nm when a film having a thickness of 100 nm is formed.

The polyimide film A is preferably formed to have a thickness of 100 nm. In the case of at least one of the wavelengths of 308 nm, 343 nm, 351 nm, and 355 nm, the light transmittance is less than 50%.

Hereinafter, when a film having a thickness of 100 nm is formed, in the wavelength range of 300 to 400 nm, the minimum value of the light transmittance is less than 50%, which is called "physical property (A)". Further, when a film having a thickness of 100 nm is formed, the wavelength at which the minimum value of the light transmittance is given in the wavelength range of 300 to 400 nm is λ ₁ .

Since the polyimine resin film A satisfies the physical property (A), the light absorption of the laser of the wavelength near λ _{1 is} large. Therefore, the heat generated by the light absorption is large, and as a result, the irradiation energy required for the laser peeling is lower than that of the polyimide film which does not satisfy the physical property (A). Hereinafter, the decrease in the irradiation energy required for the laser peeling is expressed as the laser peeling property is improved.

The smoothness of the peeling surface of the resin film can be improved by reducing the irradiation energy required for the laser peeling. For example, the lower the irradiation energy, the more the maximum height (Rz) of the peeling surface can be reduced. By increasing the smoothness of the peeling surface, for example, the film forming property of the inorganic film on the peeling surface can be improved. When the peeling surface has irregularities, the coverage of the inorganic film on the peeling surface is lowered, or pinhole defects occur in the inorganic film. These are causes of a decrease in gas barrier properties of the inorganic film, and the like, and are associated with a decrease in the characteristics of the inorganic film. Therefore, the smoothness of the peeling surface is preferably high. Further, the smoothness of the peeling surface can be evaluated by a surface roughness meter or AFM. Further, as an index of smoothness, in addition to Rz, arithmetic mean roughness (Ra), maximum mountain height (Rp) of the roughness curve, maximum valley depth (Rv) of the roughness curve, and the like can be used.

The polyimine which is contained in the polyimide film A is not particularly limited, but is preferably a main component of the diamine residue in the polyimide. The component is a (B) diamine derivative derived from the following.

(B) The maximum absorbance at a wavelength of 300 to 400 nm in the wavelength range of 300 to 400 nm when the solution has a concentration of 1 × 10 ^-4 mol/L of N-methyl-2-pyrrolidone It is a diamine derivative of more than 0.6.

(B) The diamine derivative is more preferably at least one of wavelengths of 308 nm, 343 nm, 351 nm, and 355 nm when a solution of N-methyl-2-pyrrolidone having a concentration of 1 × 10 ^-4 mol/L is prepared. The diamine derivative having an absorbance of more than 0.6 under the condition of a light path length of 1 cm.

The diamine derivative may, for example, be a diamine compound obtained by reacting a diamine compound, a diisocyanate compound or a decylating agent (a guanamine-based decylating agent).

In order for the polyimide film A to satisfy the physical property (A), at least one of the acid dianhydride derivative or the diamine derivative of the raw material monomer of the polyimide may have an absorbance in the wavelength range of 300 to 400 nm. High. Since the degree of freedom in molecular design of the diamine derivative is higher than that of the acid dianhydride derivative, it is easy to obtain a diamine derivative having a high absorbance in the wavelength range of 300 to 400 nm.

Hereinafter, the polyimine which has a diamine residue derived from (B) a diamine derivative as a main component is called "polyimine B". The term "main component" as used herein means that the ratio of the diamine residue occupied by all the diamine residues of the polyimine is higher than the total ratio of all other diamine residues. Further, the wavelength at which the (B) diamine derivative is given the maximum value of the absorbance in the wavelength range of 300 to 400 nm is λ ₂ .

To polyimide B, in the vicinity of the wavelength [lambda] ₂ to give the minimum value of the light transmittance, the wavelength [lambda] ₂ of the vicinity of the laser light absorption becomes larger. Therefore, the heat generated by the light absorption is large, and as a result, the irradiation energy required for the laser peeling becomes lower than that of the polyimine other than the polyimide.

The method for producing the resin laminated film of the present invention is not particularly limited, but it is preferably produced by a two-stage film forming process as will be described later. For example, a polyimide film A is produced as a first resin film (hereinafter referred to as "resin film 1") on a support substrate such as a glass substrate, and a second resin film is produced on the resin film 1 (hereinafter) The "resin film 2" is irradiated with a laser from the side of the glass substrate, and the resin laminated film is peeled off from the glass substrate. Since the resin film 1 is present on the glass substrate, the resin laminated film exhibits good laser peeling properties regardless of the kind of the resin film 2.

The wavelength of the irradiation laser is not particularly limited, and examples thereof include 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm. Moreover, as long as the resin laminated film is peeled off, the light source is not limited to a laser, and a high pressure mercury lamp, an LED, or the like can also be used.

In such a resin laminated film, it is preferable to laminate at least the resin film 1 and the resin film 2 in this order. Further, the number of layers of the resin film 2 is not particularly limited, and the resin film 2 may be a single layer or a laminated film of two or more layers. For example, the resin film 2 may be composed of a polyimide resin, similar to the resin film 1. Resin layer. However, the number of layers of the resin laminated film is preferably 2 from the viewpoint of transparency of the resin laminated film or adhesion between the layers. That is, the resin film 2 is preferably a single layer.

Further, in the resin laminated film of the present invention, an inorganic film may be interposed between the resin film 1 and the resin film 2. When the inorganic film is inserted, the gas barrier property of the laminated film is increased, which is preferable.

The gas barrier layer on the resin film is such as to prevent water vapor or oxygen The task of penetrating. In particular, in the organic EL device, deterioration of the device due to moisture is remarkable, and it is required to impart gas barrier properties to the resin laminated film used as the substrate.

Whether or not the resin film present on the surface of the resin laminated film of the present invention satisfies the physical property A, and the resin laminated body can be etched to a thickness of 100 nm from the side opposite to the surface to be measured, and the residual film can be measured. Confirmed by light transmittance.

As a specific method thereof, for example, it can be measured by the following procedure. First, the film thickness of the resin laminated film is measured by a height difference meter, a scanning electron microscope (SEM), a micrometer, or the like. At this time, the film thickness of each resin layer in the resin laminated film can also be measured by observing the fracture surface of the resin laminated film by SEM. Then, the surface to be measured is fixed to the glass substrate by an adhesive tape or the like, and a glow discharge luminescence analyzer (GD-OES), reactive ion etching (RIE), gas cluster ion beam (GCIB), or the like is used. The surface of the resin laminated film on the side opposite to the measurement target faces the measurement target side, and etching is performed until the film thickness becomes 100 nm. The etching method is not particularly limited, but is preferably GD-OES or GCIB from the viewpoint of elemental analysis of the resin film. The etching was performed until the film thickness became 100 nm, and then the light transmission spectrum was measured using a microscopic spectroscope. The same etching and transmittance measurement were performed at five places, and the average value of these was set as the light transmittance.

The resin composition (for example, the molecular structure of the diamine residue of the resin film 1) or the film thickness of each layer in the resin laminated film of the present invention can be analyzed by using TPD-MS, TOF-SIMS or IR. Spectrometry and precision tilt cutting were used for analysis.

The minimum value of the light transmittance of the polyimide film A is not particularly limited as long as it is less than 50%, but is preferably less than 40%, more preferably less than 30%, and still more preferably less than 20%. As the light transmittance becomes lower, the irradiation energy required for laser peeling is lowered, and when it is less than 20%, the effect of reducing the irradiation energy is particularly large.

The maximum value of the absorbance of the (B) diamine derivative is not particularly limited as long as it exceeds 0.6, but is preferably 0.8 or more, and more preferably 1.0 or more. As the absorbance becomes higher, the irradiation energy required for laser peeling is lowered, and when it is 1.0 or more, the effect of reducing the irradiation energy is particularly large.

The thickness of the resin film 1 and the resin film 2 is not particularly limited, but the thickness of the resin film 1 is preferably from the viewpoints of transparency, heat resistance, linear thermal expansion coefficient (hereinafter also referred to as CTE) of the resin laminated film. It is 100 nm to 1 μm, more preferably 100 nm to 0.5 μm. When the thickness of the resin film 1 is 1 μm or less, the transparency of the resin film 1 in the visible light range is high. Therefore, the transparency of the resin laminated film in the visible light range is not impaired. Further, the thickness of the resin film 1 is preferably thinner than the thickness of the resin film 2.

Further, the ratio of the resin film 1 in the resin laminated film is not particularly limited, but the ratio of the resin film 1 is preferably 50% or less, more preferably 10% or less. By setting the ratio of the resin film 1 to 10% or less, it is possible to prevent the CTE of the entire resin laminated film from becoming large. Specifically, the difference in CTE between the resin laminated film and the resin film 2 can be considerably reduced, and is, for example, 5 ppm/° C. or less.

The CTE system of the resin laminated film of the present invention is not particularly limited, but is preferably in the range of -10 to 30 ppm/°C in the range of 50 ° C to 200 ° C. In this range, resin formation on the support substrate can be reduced When the substrate is warped by laminating the film, it is possible to form an element such as a TFT on the resin laminated film with high precision. In particular, when used as a TFT substrate, it is more preferably in the range of -10 to 20 ppm/°C, and still more preferably in the range of -10 to 10 ppm/°C.

The glass transition temperature (Tg) of the resin laminated film of the present invention is not particularly limited, but is preferably 300 ° C or higher. In this range, the film formation temperature of the inorganic film on the resin laminated film can be increased, for example, the performance of the gas barrier layer or the TFT can be improved. In particular, when a TFT is formed, a temperature of 350 ° C or higher is generally used. Therefore, the Tg of the resin laminated film is more preferably 350 ° C or higher, and still more preferably 400 ° C or higher.

The transparency of the resin laminated film of the present invention is not particularly limited, but is required to be transparent in the visible light range of the substrate such as a substrate of a bottom emission type organic EL display, a color filter substrate, or a touch panel substrate. In the case, it is preferred that the resin laminated film be transparent.

The term "transparent" as used herein means that the transmitted light that is visually recognized by the resin laminated film is a color close to white, and more specifically, the transmitted chromaticity of the above-mentioned resin laminated film in the XYZ color system chromaticity diagram. The coordinates (x, y) are (x-x0)/2+(y-y0)/2≦0.01 for the chromaticity coordinates (x0, y0) of the light source.

Here, the "transmitting chromaticity coordinate" means a coordinate of the transmitted chromaticity in the CIE 1931 color system measured by a 2 degree field of view. Examples of the type of the light source include a C light source and the like.

Specific examples of the relational expression satisfying the above (x-x0)/2+(y-y0)/2≦0.01 include, for example, a transmittance of 80% at a wavelength of 400 nm to 800 nm in the resin laminated film. The above situation, etc. Furthermore, The resin laminated film of the present invention can be formed on a glass substrate through a chromaticity coordinate and a light transmittance, and can be measured using an ultraviolet-visible spectrophotometer or a colorimeter.

(resin film 1)

The resin film 1 is not particularly limited as long as it is a polyimide film which satisfies the physical property A. However, it is preferable to contain a polyimine component B in the polyimine component, and the polyimine component is more preferably Polyimine B is composed of. (B) The diamine derivative has a concentration of 1×10 ^-4 mol/L of N-methyl-2-pyrrolidone solution in the wavelength range of 300 to 400 nm, and absorbance at a light path length of 1 cm. The diamine derivative having a maximum value exceeding a wavelength of 0.6 is not particularly limited, and examples thereof include bis[4-(4-aminophenoxy)phenyl]anthracene and 9,9-bis(4-amine). Phenyl) guanidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]indole, bis[ 3-(3-Aminophenoxy)phenyl]anthracene, bis[3-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl] Ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(4-aminophenoxy)biphenyl, 2,2 - bis[3-(3-aminobenzoguanamine)-4-hydroxyphenyl]hexafluoropropane, bis[3-(3-aminobenzoguanamine)-4-hydroxyphenyl]indole , 2,2-bis[2-(3-aminophenyl)-5-benzo Azoyl]hexafluoropropane, bis[2-(3-aminophenyl)-5-benzo Azolyl] oxime and the like.

In particular, the absorbance of light of 308 nm which is generally used for a light source which is used as a laser light source is high, and it is preferable that the polyimide film of the resin film 1 has a main component having a formula (1) or (2). The diamine residue of the diamine derivative of the structure shown.

In the formulae (1) to (2), A represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, a fluorenyl group, a divalent organic group having a carbon number of 1 to 5 which may be substituted by a halogen atom, Or a two-valent organic group formed by two or more of them. R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 10 carbon atoms and having at least one amine group.

The formula (1) contains a hydroxyguanamine structure, and the formula (2) contains benzo The azole structure, which is effective for increasing the absorbance in the wavelength range of 300 to 400 nm.

As will contain benzo The first method of introducing a diamine residue of an azole structure into a molecular chain of a polyimine, and a diamine compound having a hydroxyguanamine structure represented by the formula (1) or a derivative thereof and an acid dianhydride or The closed-loop or chemical ring-closing reaction of the polyamidiamine precursor synthesized by the reaction of the derivative thereof, and the ruthenium ring closure A azole ring closure. The second method is exemplified by having a benzoic acid represented by the formula (2) The poly-imine precursor synthesized by the reaction of the diamine compound or its derivative with an azole structure and an acid dianhydride or a derivative thereof is subjected to a heating ring closure or a chemical ring closure reaction to form a ring closure of the quinone.

The heating temperature for the ruthenium ring closure is not particularly limited, but is preferably 250 ° C or higher, more preferably 300 ° C or higher. Further, by adding an alkaline catalyst such as imidazole, the temperature of the ring closure of the quinone imine can be lowered. Used for The heating temperature of the azole ring is not particularly limited, but is preferably 300 ° C or higher, more preferably 350 ° C or higher. Furthermore, by adding an acidic catalyst such as a thermal acid generator, it is possible to reduce The temperature of the azole ring closure.

From the viewpoint of the laser releasability of the resin film 1, the diamine residue of the polyimine of the resin film 1 preferably contains the benzoic acid of the formula (2). The azole structure or A of the formulae (1) and (2) is hexafluoroisopropylidene. Benzo Since the azole structure has a higher absorbance at a wavelength of 300 to 400 nm than that of a hydroxyguanamine structure, it is effective in reducing the irradiation energy required for laser lift-off. Further, when A is hexafluoroisopropylene, since it is easily thermally decomposed than a single bond, a mercapto group or a sulfonyl group, it is effective in reducing the irradiation energy required for the laser to be peeled off.

From the viewpoint of transparency of the resin film 1 in the visible light range, A is preferably a hexafluoroisopropylidene group or a sulfonyl group. The diamine derivative containing the structure represented by the formula (1) or (2), for example, the polyimine which is particularly preferably the resin film 1 has a main component having the following chemical formulas (3) to (6). A diamine residue derived from a diamine compound.

Since the diamine residue derived from the diamine compound represented by the general formulae (3) to (6) is a main component of the polyimine of the resin film 1, the transparency of the resin film 1 in the visible light range can be further improved. . Therefore, the transparency of the resin laminated film is not deteriorated, and it is applicable to applications requiring transparency in the visible light range. Examples of such a use include a base material of a bottom emission type organic EL display, a color filter substrate, and a touch panel substrate.

Further, from the viewpoint of heat resistance of the resin film 1, A is preferably a single bond or a phenyl group. Since A is a main component of a polyamine of the diamine compound-based resin film 1 of a single bond or a phenyl group, and the heat resistance of the resin laminated film is further increased, it can be suitably used as a device requiring a high temperature in a process. Substrate. Specifically, it can be mentioned that there is a high temperature between the substrate and the component. The base material of the organic EL display in the case of forming a barrier layer, and the base material of the TFT which is annealed at a high temperature in order to ensure mobility or reliability.

When the polyimine of the resin film 1 contains a diamine residue derived from the (B) diamine derivative as a main component, a diamine residue derived from another diamine derivative may be contained. The term "main component" as used herein means that the ratio of the diamine residue in all the diamine residues of the polyimine is higher than the total ratio of all other diamine residues.

The other diamine derivative is not particularly limited, and examples thereof include an aromatic diamine compound, an alicyclic diamine compound, and an aliphatic diamine compound.

Examples of the aromatic diamine compound include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenylmethane. , 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene , 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2, 2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2',3,3'-tetramethylbenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,2',3,3'-tetrachlorobenzidine , m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, or a hydrogen atom of such an aromatic ring is replaced by an alkyl group, an alkoxy group, a halogen atom or the like The diamine compound is not limited by these.

Examples of the alicyclic diamine compound include cyclobutanediamine, isophoronediamine, bicyclo[2,2,1]heptane dimethylamine, and tricyclo[3,3,1,13. 7] decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyl Diamine, 1,4-cyclohexyldiamine, trans-1,4-cyclohexyldiamine, cis-1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3, 3'-Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5 '-Tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5- Diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4 , 4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4, 4'-Diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5 '-Dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-amino ring Hexyl)propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2,2 - bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3',5'-dimethyl a 4,4'-diaminodicyclohexyl)propane; or a diamine compound in which the hydrogen atom of the alicyclic structure is substituted with an alkyl group, an alkoxy group, a halogen atom or the like, but is not subject to such limited.

Examples of the aliphatic diamine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diamino group. Alkanediamines such as hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane; Ethylene glycol diamines such as (aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether; and 1,3-bis(3-aminopropyl) Tetramethyldioxane, 1,3-bis(4-aminobutyl)tetramethyldioxane, α,ω-bis(3-aminopropyl)polydimethyloxime Alkane diamines such as alkanes are not limited by these.

These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds may be used alone or in combination of two or more.

As the acid dianhydride used for the production of the polyimine in the resin film 1, a known one can be used. The acid dianhydride is not particularly limited, and examples thereof include aromatic acid dianhydride, alicyclic acid dianhydride, and aliphatic acid dianhydride.

Examples of the aromatic acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetra Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-triphenyltetracarboxylic dianhydride, 3,3',4 , 4'-hydroxydiphthalic dianhydride, 2,3,3',4'-hydroxydiphthalic dianhydride, 2,3,2',3'-hydroxydiphthalic dianhydride, diphenyl碸-3,3',4,4'-tetracarboxylic dianhydride, diphenyl ketone-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4- Dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, 1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1, 4-(3,4-dicarboxyphenoxy)benzene dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene -2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dihydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenic anhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-nonanedicarboxylic acid Anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane Dianhydride, 1,6-difluorobenzenetetracarboxylic dianhydride, 1-trifluoromethylbenzenetetracarboxylic dianhydride, 1,6-fluorene trifluoromethylbenzenetetracarboxylic dianhydride, 2,2'- Bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane II Anhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl] Hexafluoropropane dianhydride; or an acid dianhydride compound in which a hydrogen atom of the aromatic ring is substituted with an alkyl group, an alkoxy group, a halogen atom or the like, is not limited thereto.

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S. 1,2,4,5-cyclohexanetetracarboxylic dianhydride such as 5R-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1- Cyclohexyl succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [ 3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [ 4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]nonane-2,4,8,10-tetracarboxylic dianhydride, tricyclic [6,3,0,0<2,6>]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6 -tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,1]heptane tetracarboxylic dianhydride Bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1] Alkane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecano-1,2,8,9-tetracarboxylic acid Anhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-hydroxydicyclohexanetetracarboxylic dianhydride, 5-(2,5- Dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, "Rikacid" (registered trademark) TDA-100 (trade name, New Japan Physical and Chemical Co., Ltd. And their derivatives; or the hydrogen atom of such an alicyclic structure via an alkyl group, an alkoxy group, or a halogen atom The acid dianhydride compound substituted by the sub-group is not limited by these.

Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and "Rikacid" (registered trademark) BT. -100 (product name, Nippon Chemical and Chemical Co., Ltd.), "Rikacid" (registered trademark) TMEG-100 (trade name, Nippon Chemical and Chemical Co., Ltd.), "Rikacid" (registered trademark) TMTA-C (product) The name, the new Japanese physicochemical (share) system, and their derivatives, etc., are not subject to these restrictions.

These aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides can be used individually or in combination of 2 or more types.

The polyimine contained in the polyimide film A is preferably a polyimine having a main component of an aromatic acid dianhydride as a main component from the viewpoint of improving heat resistance. In particular, if the aromatic acid dianhydride residue is a residue derived from pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride, in addition to heat resistance, It is also preferable to obtain a low CTE effect.

In addition, the polyimine contained in the polyimide film A is preferably an alicyclic acid from the viewpoints of transparency in the visible light range and irradiation intensity required for laser peeling. The dianhydride residue is a main component, or an aliphatic acid dianhydride residue as a main component, or a polyimine which has a total of an alicyclic acid dianhydride residue and an aliphatic acid dianhydride residue as a main component. In particular, as the polyiminoimine B, it is preferred to use an alicyclic acid dianhydride residue as a main component, or an aliphatic acid dianhydride residue as a main component, or an alicyclic acid dianhydride residue and A polyimine which has a total of aliphatic acid dianhydride residues as a main component. By having such an acid dianhydride residue, the charge shifting is one of the reasons for suppressing the coloring of the polyimide. The transparency of the resin film 1 in the visible light range is increased. Further, since these acid dianhydride residues are more easily thermally decomposed than the aromatic acid dianhydride residues, the effect of reducing the irradiation intensity required for laser peeling becomes large.

In addition, the term "the aromatic acid dianhydride residue as a main component" means that the ratio of the aromatic acid dianhydride residue in all the acid dianhydride residues of the polyimine is higher than that of the other The total ratio of acid dianhydride residues is higher.

The phrase "the alicyclic acid dianhydride residue as a main component" means that the ratio of the alicyclic acid dianhydride residue in all the acid dianhydride residues of the polyimine is higher than that of all other acids. The total proportion of dianhydride residues is higher.

The phrase "the aliphatic acid dianhydride residue as a main component" means that the ratio of the aliphatic acid dianhydride residue in the entire acid dianhydride residue of the polyimine is higher than that of all other acid dianhydrides. The total proportion of residues is higher.

The term "the total of the alicyclic acid dianhydride residue and the aliphatic acid dianhydride residue as a main component" means the alicyclic acid group occupied by all the acid dianhydride residues of the polyiminimide. The total ratio of the anhydride residue and the aliphatic acid dianhydride residue is higher than the total ratio of all other acid dianhydride residues.

The ratio of the total of the acid dianhydride is not limited as long as the residue is a main component, but it is preferably 75% or more from the viewpoint of laser peelability.

Among the alicyclic acid dianhydride and the aliphatic acid dianhydride, from the viewpoint of easiness of availability, cyclobutane tetracarboxylic dianhydride, 1S, 2S, 4R, 5R-cyclohexane 4 is preferred. Carboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane Carboxylic acid dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, "Rikacid" (registered trademark) BT-100 (above, trade name, Nippon Chemical and Chemical Co., Ltd.), "Rikacid" (registered trademark) TMEG-100 (above, trade name, Nippon Chemical and Chemical Co., Ltd.), "Rikacid" (registered trademark) TMTA-C (above, trade name, Nippon Chemical and Chemical Co., Ltd.), "Rikacid" (registered trademark) TDA-100 (above, trade name, New Japan Physical and Chemical Co., Ltd.).

Among these, from the viewpoint of reactivity with a diamine derivative, cyclobutane tetracarboxylic dianhydride represented by the chemical formulas (7) to (10), 1S, 2S, 4R, 5R are more preferable. - cyclohexanetetracarboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride. That is, the alicyclic acid dianhydride residue in the polyimine is preferably a tetracarboxylic dianhydride represented by any one of the formulas (7) to (10).

Polyimine imine resin, polypyridic acid or polyamidomate, polydecyl phthalate precursor resin, etc., in order to adjust the molecular weight to a better range, the terminal blocking agent Both ends are closed. Make The terminal blocking agent which reacts with the acid dianhydride may, for example, be a monoamine or a monohydric alcohol. Further, examples of the terminal blocking agent to be reacted with the diamine compound include an acid anhydride, a monocarboxylic acid, a monofluorene compound, a mono-active ester compound, a dicarbonate compound, and a vinyl ether compound. Further, by reacting the terminal blocking agent, various organic groups can be introduced as a terminal group.

Examples of the monoamine used as the blocking agent at the acid anhydride group terminal include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, and 1-hydroxyl group. -7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxyl 2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxyl 4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxyl -6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amine 7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxyl 3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4 -Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, cyanuramide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2 -Aminobenzenesulfonic acid, 3-amino group Sulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-fluorenyl Quinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-indolyl-7-aminonaphthalene, 1-indolyl-6-aminonaphthalene, 1-indolyl-5- Aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-nonylnaphthalene, 2-mercapto-7- Amino naphthalene, 2- Mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-indenylnaphthalene, 3- Amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-Diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl- 2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4 - aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3 , 5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2 - amino naphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8 -Diethynyl-2-aminonaphthalene, etc. As defined by this other.

Examples of the monohydric alcohol used as the blocking agent at the acid anhydride group terminal include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, and 3 -pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1 - decyl alcohol, 2-nonanol, 1-nonanol, 2-nonanol, 1-undecyl alcohol, 2-undecyl alcohol, 1-dodecyl alcohol, 2-dodecanol, 1-tridecyl alcohol, 2 -Tridecyl alcohol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-ten Heptaol, 1-octadecyl alcohol, 2-octadecyl alcohol, 1-nonadecanol, 2-nonadecanol, 1-eicosanol, 2-methyl-1-propanol, 2-methyl-2- Propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1- Pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2, 6-Dimethyl-4-heptanol, isodecyl alcohol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptyl undecyl alcohol, B Glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, two Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol , tricyclodecane monomethylol, drop Alcohol, terpineol, etc., but are not limited by these.

Examples of the acid anhydride, monocarboxylic acid, monoterpene chlorine compound and mono-active ester compound used as the blocking agent for the amine terminal include phthalic anhydride, maleic anhydride, nadic acid anhydride, and cyclohexane. Anhydride such as dicarboxylic anhydride or 3-hydroxyphthalic anhydride; 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1- Hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxyl Naphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-fluorenyl 4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzene Formic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diacetylenebenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4- Diacetylene benzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-B 1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-acetylene 2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-acetylene a monocarboxylic acid such as benzyl-2-naphthoic acid or 8-ethynyl-2-naphthoic acid; and a monofluorinated chlorine compound in which the carboxyl group is fluorinated; and terephthalic acid, phthalic acid, maleic acid, Cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-nor Alkene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, Only one carboxyl group of a dicarboxylic acid such as 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene or 2,7-dicarboxynaphthalene Chlorinated monochloro compounds; from monoterpene chloride compounds to N-hydroxybenzotriazole or N-hydroxy-5- An active ester compound obtained by the reaction of a ene-2,3-dicarboxy quinone imine.

Examples of the dicarbonate compound used as the blocking agent for the amine terminal include di-tertiary butyl dicarbonate, diphenyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

Examples of the vinyl ether compound used as the blocking agent for the amine terminal include butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, and ethyl chloroformate. , chloroformate chloroformate, chloromethyl chloroformate, chloroformate such as 2,2,2-trichloroethyl chloroformate; butyl isocyanate, 1-naphthyl isocyanate, isocyanic acid Isocyanate compounds such as octadecyl ester and phenyl isocyanate; butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, N-propyl vinyl ether, tertiary butyl vinyl ether, benzyl vinyl ether, and the like.

Other compounds used as a blocking agent for the amine terminal include benzamidine chloride, methanesulfonium chloride, p-toluenesulfonium chloride, and isocyanide. Benzene ester and the like.

The introduction ratio of the blocking agent at the acid anhydride group terminal is preferably in the range of 0.1 to 60 mol%, particularly preferably 1 to 50 mol%, based on the acid dianhydride component. Further, the ratio of introduction of the blocking agent at the amine terminal is preferably in the range of 0.1 to 60 mol%, particularly preferably 1 to 50 mol%, based on the diamine component. Further, a plurality of terminal groups can be introduced by reacting a plurality of terminal blocking agents.

The molecular structure of the repeating unit of the polyimide resin or the structure of the terminal blocking agent to be introduced can be confirmed by the following method. For example, it can be easily detected by thermal decomposition gas chromatography (PGC) or infrared spectroscopy and ¹³ C NMR spectroscopy. Further, the polymer into which the terminal blocking agent is introduced is dissolved in an acidic solution, and is decomposed into an amine component and an acid anhydride component of a constituent unit of the polymer, and is measured by gas chromatography (GC) or NMR. The terminal blocking agent is easily detected.

(resin film 2)

In the resin laminated film of the present invention, the kind of the resin of the resin film 2 is not particularly limited, and examples thereof include polybenzonitrile resin and polyphenylene. An azole resin, a polyamidoximine resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyether oxime resin, an acrylic resin, an epoxy resin, or the like. Among them, from the viewpoints of heat resistance, mechanical properties, and the like, it is preferred to contain a polybenzazole resin and a polybenzoic acid. The resin of at least one of the group consisting of an azole resin, a polyamidoximine resin, and a polyamide resin is more preferably a polyimide resin from the viewpoint of chemical resistance or low CTE.

The acid dianhydride and the diamine used for the synthesis of the polyimide resin in the resin film 2 can be used.

The acid dianhydride is not particularly limited, and examples thereof include the aromatic acid dianhydride, the alicyclic acid dianhydride, and the aliphatic acid dianhydride. These aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides can be used individually or in combination of 2 or more types. Further, the diamine is not particularly limited, and examples thereof include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine. These aromatic diamines, alicyclic diamines, or aliphatic diamines may be used alone or in combination of two or more. Further, the aforementioned terminal blocking agent can also be used.

When a polyimide resin is used for a substrate of a TFT substrate, a top emission type organic EL display, and a base material of an electronic paper, heat resistance and low CTE property are particularly required. In this case, the acid dianhydride used as the polyimide resin in the resin film 2 preferably contains pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride. At least one type of the diamine is preferably at least one selected from the group consisting of 4,4'-diaminodiphenyl ether, p-phenylenediamine, and 3,3'-dimethylbenzidine.

On the other hand, when a polyimide resin is used for a base material of a bottom emission type organic EL display, a color filter substrate, a touch panel substrate, or the like, heat resistance and high transparency in a visible light region are required. At this time, at least one of the acid dianhydride or the diamine used in the polyimide resin in the resin film 2 preferably has an alicyclic structure or a fluorinated alkyl group. At this time, the polyimide resin of the resin film 2 has an alicyclic structure or a fluorinated alkyl group.

The alicyclic structure or the fluorinated alkyl group can be used for both the acid dianhydride and the diamine, and can also be used for one. The diamine having an alicyclic structure is not particularly limited, and examples thereof include trans-1,4-diaminocyclohexane and 4,4'-dicyclohexylmethane. As an acid dianhydride having an alicyclic structure There is no particular limitation, and examples thereof include 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride and the like. The diamine having a fluorinated alkyl group is not particularly limited, and examples thereof include 2,2'-bis(trifluoromethyl)benzidine. The acid dianhydride having a fluorinated alkyl group is not particularly limited, and examples thereof include 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

Among the polyimine resin films using these compounds, from the viewpoint of transparency and low CTE, the acid dianhydride preferably contains 3,3',4,4'-biphenyl four. The carboxylic acid dianhydride, as the diamine, preferably contains trans-1,4-diaminocyclohexane.

(Manufacturing method of polyimine precursor)

Hereinafter, a general production method of a polyimide intermediate precursor will be described. In general, the polyimine resin represented by the following formula (11) is subjected to a ruthenium imine ring by a polyimine precursor resin represented by the following formula (12). Reaction). The method for the ruthenium imidization reaction is not particularly limited, and examples thereof include thermal sulfiliation or chemical ruthenium. Among them, from the viewpoint of heat resistance of the polyimide film and transparency in the visible light region, it is preferred to be imidized.

In the general formulae (11) and (12), R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group. X ¹ and X ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms or a monovalent alkyl fluorenyl group having 1 to 10 carbon atoms.

Polyimine precursors such as polyamine or polyamidomate or polydecyl phthalate can be synthesized by reaction of a diamine compound or a derivative thereof with an acid dianhydride or a derivative thereof. Examples of the derivative of the acid dianhydride include a tetracarboxylic acid, a phosphonium chloride, and a mono-, di-, tri- or tetra-ester of the tetracarboxylic acid, and specific examples thereof include a methyl group and an ethyl group. An esterified structure of n-propyl, isopropyl, n-butyl, secondary butyl, tert-butyl or the like. The reaction method of the polymerization reaction is not particularly limited as long as it is a polyimide precursor which can be produced, and a well-known reaction method can be used.

Specific reaction methods include adding a predetermined amount of all diamine components and a reaction solvent to a reactor and dissolving them. A predetermined amount of the acid dianhydride component is added, and the mixture is stirred at room temperature to 120 ° C for 0.5 to 30 hours.

As the reaction solvent, two or more kinds of N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide may be used alone or in combination. a polar aprotic solvent such as N,N-dimethylpropylpropylurea, 1,3-dimethyl-2-imidazolidinone or dimethylhydrazine; tetrahydrofuran, An ether such as an alkane or a propylene glycol monomethyl ether; a ketone such as acetone, methyl ethyl ketone, diisobutyl ketone or diacetone; ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate Esters such as esters; aromatic hydrocarbons such as toluene and xylene;

The content of the solvent in the polyimide composition of the polyimide precursor is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 2,000 parts by weight based on 100 parts by weight of the polyimide precursor. It is more preferably 1,500 parts by weight or less. When it is in the range of 50 to 2,000 parts by weight, the viscosity is suitable for coating, and the film thickness after coating can be easily adjusted.

(Method of Manufacturing Resin Laminate Film)

The resin laminated film of the present invention can be produced by a production method including at least the following steps (1) to (3).

(1) A step of producing a polyimide film A on a support substrate.

(2) A step of forming a resin laminated film by further laminating a resin film on the resin film.

(3) a step of irradiating ultraviolet light on the side of the self-supporting substrate and peeling off the resin laminated film.

Hereinafter, the use of a polyimide-containing precursor and a solvent will be described. The polyimine precursor solution, the resin film 1 and the resin film 2 are all a method of producing a resin laminated film of polyimide.

(1) Step of producing a polyimide film A on a support substrate

The polyimine precursor resin solution is applied onto a support substrate to form a polyimide film precursor composition film of the polyimide film A. As the support substrate, for example, tantalum, ceramics, gallium arsenide, soda lime glass, alkali-free glass, or the like is used, but it is not limited thereto. The coating method may be, for example, a slit coating method, a spin coating method, a spray coating method, a roll coating method, or a bar coating method, or may be applied by a combination of these methods. Among these, coating by spin coating or slit coating is preferred.

Next, the polyimide composition precursor resin composition coated on the support substrate was dried to obtain a polyimide polyimide precursor resin composition film. The drying system uses a hot plate, an oven, an infrared ray, a vacuum chamber, or the like. When the hot plate is used, the support substrate coated with the polyimide composition of the polyimide precursor is held on the plate directly or on a jig such as a proxy pin provided on the plate, and heated. As a material for the proximity pin, there are a metal material such as aluminum or stainless steel, or a synthetic resin such as a polyimide resin or a Teflon (registered trademark), and a proximity pin of any material can be used. The height of the proximity pin is various depending on the size of the support substrate, the kind of the resin composition, the purpose of heating, etc., for example, the resin composition applied on a glass support substrate of 300 mm × 350 mm × 0.7 mm is applied. When heating, the height of the proximal pin is preferably about 2 to 12 mm.

Preferably, it is preferably vacuum-dried using a vacuum chamber, more preferably heating for drying after vacuum drying, or vacuuming The drying is carried out while drying. Thereby, it is possible to shorten the drying treatment time and form a uniform coating film system. The heating temperature for drying is various depending on the kind and purpose of the support substrate or the polyimide precursor, and it is preferably carried out in the range of room temperature to 170 ° C for 1 minute to several hours. Further, the drying step can be carried out plural times under the same conditions or under different conditions.

Next, heating for hydrazine imidization is carried out. The polyimine precursor resin composition film is heated in a range of 170 ° C to 650 ° C to be converted into a polyimide film. Further, the enthalpy imidization step may be carried out after any of the steps after the above drying step.

The gas atmosphere of the thermal imidization step is not particularly limited, and may be an inert gas such as air, nitrogen or argon, or may be in a vacuum. However, when calcination is carried out in an environment having a high oxygen concentration, the calcined film becomes brittle due to oxidative degradation, and the mechanical properties are lowered. In order to suppress such deterioration of mechanical properties, it is preferred to calcine in a gas atmosphere having an oxygen concentration of 5% or less. On the other hand, ppm level oxygen concentration management is often difficult in the manufacturing site. The resin film of the present invention is preferable because it can maintain a higher mechanical property as long as the oxygen concentration in the thermal imidization step is 5% or less. Further, when colorless transparency is required, it is also preferred to heat and imidize in an environment having an oxygen concentration of 5% or less. In general, by lowering the oxygen concentration, the coloration of the polyimide film in the thermal imidization step can be reduced, and a polyimide film exhibiting high transparency can be obtained.

Further, in the hot hydrazine imidization step, a temperature rising method in accordance with the heating form of the oven of the production line may be selected, but it is preferred to heat up to the maximum heating temperature in 5 to 300 minutes. For example, in an oven, The film of the polyimide film of the polyimide precursor formed on the substrate is heated to a maximum heating temperature for 5 to 300 minutes from room temperature to be imidized to form a polyimide film; The polyimine precursor resin film formed on the substrate is suddenly placed in an oven heated to a temperature in the range of 170 ° C to 650 ° C or less, and heat-treated to carry out hydrazine imidization to form a polyfluorene. Amine resin film. Further, the number of steps of the temperature rising process is not particularly limited, and the temperature may be increased in one step from the substrate input temperature to the maximum heating temperature, or the temperature may be increased in two stages of two or more stages.

(2) a step of further laminating a resin film on the resin film to form a resin laminated film

Then, the second polyimine precursor resin solution was applied and dried in the same manner as in the first layer to produce a resin film 2 to form a resin laminated film.

Moreover, from the viewpoint of improving the glass transition temperature of the resin laminated film, it is preferred that the resin film used in at least one of the steps (1) or (2) has a baking temperature of 400 ° C or higher.

(3) a step of irradiating ultraviolet light on the side of the self-supporting substrate and peeling off the resin laminated film

The self-supporting substrate side is irradiated with ultraviolet light, and the resin laminated film is peeled off from the support substrate. Since the resin film 1 is present on the support substrate, the resin laminated film exhibits excellent laser peeling properties regardless of the type of the resin film 2.

The wavelength of the ultraviolet light is not particularly limited, and examples thereof include 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm. Further, the light source is not particularly limited as long as it is peeled off by a resin, a high pressure mercury lamp, an LED, or the like.

Further, the polyimide film precursor solution resin solution or the polyimide film of the resin films 1 and 2 may further contain a surfactant, an internal mold release agent, a decane coupling agent, and a thermal crosslinking. Agent, inorganic particles, ultraviolet absorber, photoacid generator, and the like. Further, these may be contained in the resin films 1 and 2 within a range not impairing the required physical properties.

Fluoride-based interfacial activity such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC), and Sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.) Agent. In addition, KP341 (trade name, Shin-Etsu Chemical Co., Ltd.), DBE (trade name, CHISSO (share) system), Glanol (product name, Kyoeisha Chemical Co., Ltd.), BYK (BYK Chemical) An organic oxoxane surfactant such as a (stock) system. In addition, polyoxyalkylene lauryl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, or Polyflow (e.g., Emulmin (manufactured by Sanyo Chemical Industries Co., Ltd.)) may be mentioned. An acrylic polymer surfactant such as the trade name, Kyoeisha Chemical Co., Ltd.).

As the thermal crosslinking agent, an epoxy compound or a compound having at least two alkoxymethyl groups or a methylol group is preferred. Since at least two of these groups are present, and a resin and a molecule of the same type are subjected to a condensation reaction to form a crosslinked structure, mechanical strength or chemical resistance of the cured film after the heat treatment can be improved.

Preferable examples of the epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, propylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, and polymethyl ( An epoxy group-containing polyfluorene oxide or the like such as glycidoxypropyl)oxane, but the present invention is not limited at all. Specifically, Epiclon 850-S and Epiclon can be cited. HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA-1514, Epiclon EXA-4880, Epiclon EXA-4850-150 , Epiclon EXA-4850-1000, Epiclon EXA-4816, Epiclon EXA-4822 (above trade name, Dainippon Ink Chemical Industry Co., Ltd.), Rikaresin BEO-60E, Rikaresin BPO-20E, Rikaresin HBE-100, Rikaresin DME- 100 (above trade name, New Japan Physical and Chemical Co., Ltd.), EP-4003S, EP-4000S (above trade name, ADEKA (share) system), PG-100, CG-500, EG-200 (above trade name, Osaka Gas Chemical Co., Ltd., NC-3000, NC-6000 (above trade name, Nippon Chemical Co., Ltd.), EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (trade name, manufactured by PRINTEC Co., Ltd.), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085 (trade name, manufactured by DAICEL Chemical Industries Co., Ltd.).

Examples of the compound having at least two alkoxymethyl groups or hydroxymethyl groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, and DML. -OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM -BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290 , NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (above, trade name, Sanwa Chemical Co., Ltd.). It is also possible to contain two or more of these. The thermal crosslinking agent is preferably contained in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the resin.

Examples of the internal mold release agent include long-chain fatty acids such as lauric acid, stearic acid, and myristic acid; long-chain alcohols such as stearyl alcohol and myristyl alcohol; polyoxyalkylene alkyl ethers and fluoroalkyl epoxy resins; Alkane adducts, etc.

Examples of the decane coupling agent include 3-aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, vinyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like. . From the viewpoint of preservation stability, it is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polyimine precursor resin.

Examples of the inorganic particles include vermiculite fine particles, alumina fine particles, titanium oxide fine particles, and zirconia fine particles.

The shape of the inorganic particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a rod shape, and a fiber shape.

The particle diameter of the inorganic particles to be contained is not particularly limited, but the particle diameter is preferably small in order to prevent scattering of light. The average particle diameter is from 0.5 to 100 nm, preferably from 0.5 to 30 nm.

The content of the inorganic particles is preferably from 1 to 200% by weight, and the lower limit is more preferably 10% by weight or more based on the resin. The upper limit is better 150 weight % or less is more preferably 100% by weight or less, and particularly preferably 50% by weight or less. As the content increases, the flexibility or folding endurance decreases.

As a method of mixing the inorganic particles, various well-known methods can be used. For example, those in which inorganic particles or an organic inorganic filler sol and a resin solution are mixed may be mentioned. The organic inorganic filler sol is dispersed in an organic solvent in an organic solvent at a ratio of about 30% by weight. Examples of the organic solvent include methanol, isopropanol, n-butanol, ethylene glycol, methyl ethyl ketone, and methyl group. Isobutyl ketone, propylene glycol monomethyl acetate, propylene glycol monomethyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidine Ketone, 1,3-dimethylimidazolidinone, γ-butyrolactone, and the like.

The organic inorganic filler sol is surface-treated by using a decane coupling agent, and the dispersibility of the inorganic filler in the resin is increased.

In the present invention, inorganic particles may be contained from the viewpoint of low CTE of the resin laminated film. When the resin film containing the inorganic particles formed on the glass substrate is subjected to laser peeling, the inorganic particles are not thermally decomposed by the laser irradiation, and thus the laser peeling property is remarkably lowered. Therefore, in the resin laminated film of the present invention, it is preferred that the resin film 1 does not contain inorganic particles, and the resin film 2 contains inorganic particles. In this case, since the polyimide film having excellent laser releasability is formed on the interface with the glass substrate, the resin laminated film containing the inorganic particles in the resin film 2 can be easily peeled off by laser peeling.

Examples of the ultraviolet absorber include a diphenylketone ultraviolet absorber, a benzotriazole ultraviolet absorber, and three It is a UV absorber, a benzoate type ultraviolet absorber, a hindered amine type light stabilizer, etc. In the resin laminated film of the present invention, it is particularly preferred that the resin film 1 contains an ultraviolet absorber. At this time, since the light absorption when the resin film 1 is irradiated with ultraviolet light is higher than that of the case where the ultraviolet absorber is not contained, the irradiation energy required for the laser peeling can be reduced.

Examples of the photoacid generator include a quinonediazide compound, a phosphonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, and the like. Among them, a quinonediazide compound is preferably used from the viewpoint of exhibiting an excellent dissolution inhibiting effect and obtaining a positive photosensitive resin composition having high sensitivity and low film thinning. Further, two or more kinds of photoacid generators may be contained. Thereby, exposure by i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm) of a general ultraviolet mercury lamp can be used, and the dissolution rate of the exposed portion and the unexposed portion can be further increased. In comparison, a positive photosensitive resin composition having high sensitivity can be obtained. The photoacid generator is preferably contained in an amount of from 3 to 40 parts by weight based on 100 parts by weight of the polyimine precursor. By setting the content of the photo-acid generator to this range, it is possible to achieve higher sensitivity. Further, a sensitizer or the like may be contained as needed. Further, as the developing liquid for removing the exposed portion, it is preferably alkaline, such as tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or diethylaminoethanol. An aqueous solution of the compound. Further, as the case may be, an alkali metal solution such as N-methyl-2-pyrrolidone or an alcohol such as propanol or ethyl lactate may be added alone or in combination. A ketone such as an ester or a cyclohexanone or a lactone such as γ-butyrolactone.

(Use of resin laminated film)

The resin laminated film of the present invention can be used as a TFT substrate provided with a TFT on the resin film 2, or an organic EL element substrate provided with an organic EL element on the resin film 2, or on the resin film 2 Color filter Color filter substrate. These may also be provided with a support substrate on the resin film 1 side.

The resin laminated film of the present invention can be used for display elements such as liquid crystal displays, organic EL displays, and electronic papers, optical elements such as color filters or optical waveguides, light-receiving elements such as solar cells and CMOS, touch panels, and circuit boards. Wait. In particular, in order to use such a display element or a light-receiving element as a bendable flexible element, the polyimide film of the present invention can be preferably used as a flexible substrate. In addition, a display element or an optical element (such as a color filter) when the polyimide resin laminated film of the present invention is used as a flexible substrate, such as a flexible display element or a flexible optical element ( In the case of a flexible color filter or the like, there is a case where "flexibility" is described before the component name. For example, the resin laminated film of the present invention can be produced on a support substrate such as glass, and the flexible TFT substrate provided with the TFT on the resin film 2 and the organic EL element can be provided on the resin film 2 An organic EL element substrate, a flexible color filter substrate provided with a color filter, or the like.

In the production of a display element, a light-receiving element, a circuit board, a TFT substrate, or the like, the resin laminated film of the present invention may be formed on a support substrate, and the resin laminated film may be peeled off from the support substrate, or the resin laminated film may be peeled off from the support substrate. . The type of the resin film 2 is not particularly limited, but from the viewpoint of heat resistance and mechanical properties, polyimine is preferred.

In the case of the former manufacturing method, the display element, the light receiving element, the TFT circuit, and the like may be formed on either of the resin film 1 and the resin film 2, or may be formed on both resin films. In the case of the latter manufacturing method, since the display element, the light receiving element, and the TFT are manufactured After the road or the like, the self-supporting substrate is peeled and peeled off, so that it is advantageous in that a conventional one-piece manufacturing process can be utilized. Moreover, since the resin laminated film is fixed to the support substrate, it is suitable for manufacturing a display element, a light receiving element, a circuit board, a TFT substrate, a touch panel, and the like with high positional accuracy. In the following description, many methods will be described as representative examples, but any of them may be the former method.

In the resin laminated film of the present invention, an inorganic film can be produced on at least one surface to form a gas barrier layer, and the substrate having the gas barrier layer can be suitably used for a substrate of a display element.

The gas barrier layer on the resin film serves to prevent penetration of water vapor, oxygen, or the like. In particular, in the organic EL device, deterioration of the device due to moisture is remarkable, and therefore it is preferable to impart gas barrier properties to the substrate.

The substrate containing the resin laminated film of the present invention has flexibility and has a characteristic of being greatly bendable. This flexible substrate is referred to as a flexible substrate. The flexible substrate can be produced by at least the following steps (1), (2), and (4). Further, the flexible substrate having an inorganic film on the polyimide film can be produced by at least the following steps (1) to (4).

(1) A step of producing a polyimide film A on a support substrate.

(2) A step of forming a resin laminated film by further laminating a resin film on the resin film.

(3) a step of forming an inorganic film on the above-mentioned resin laminated film.

(4) a step of irradiating ultraviolet light on the side of the self-supporting substrate and peeling off the resin laminated film.

The steps (1), (2), and (4) above are as described in (1) to (3) above (in the method for producing a resin laminated film).

The step (3) in the manufacturing step of the flexible substrate is a step of forming an inorganic film on at least one surface of the resin laminated film. The resin laminated film can be peeled off from the support substrate to produce a flexible substrate.

Further, in the step (3), an inorganic film may be formed directly above the resin laminated film, or an inorganic film may be formed therebetween via another layer. A method of forming an inorganic film directly above the resin laminated film is preferred. Further, the place where the inorganic film is formed is not particularly limited. For example, the inorganic film may be formed on the resin film 1 after the step (1), or may be formed on the resin film 2 after the step (2), or may be formed on the resin film 1 after the step (4). The peeling surface is formed on both of the resin film 1 and the resin film 2.

The support substrate in the case of producing a flexible substrate is preferably a rigid one having a self-standing property, and the surface on which the resin composition is applied is a smooth and heat-resistant substrate. The material is not particularly limited, and examples thereof include ceramics such as soda glass or alkali-free glass, barium, quartz, alumina, or sapphire; metals such as gallium arsenide, iron, tin, zinc, copper, aluminum, and stainless steel; Yttrium or polybenzo A heat-resistant plastic film such as azole; a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride; a substrate such as epoxy resin, polyethylene terephthalate or polyethylene naphthalate. Among these, glass is preferable from the viewpoints of smoothness of the surface, laser peeling, and the like. The type of the glass is not particularly limited, but from the viewpoint of reducing metal impurities, alkali-free glass is preferred.

As described above, when a flexible substrate is used for the substrate of the display element, since the substrate is required to have gas barrier properties, it is preferable to form an inorganic film on the resin laminated film. As the material of the inorganic film constituting the gas barrier layer, metal oxides, metal nitrides, and metal oxynitrides can be preferably used. . For example, aluminum (Al), bismuth (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), niobium (Nb), molybdenum (Mo), Metal oxides such as tungsten (Ta), calcium (Ca), metal nitrides, and metal oxynitrides. In particular, a gas barrier layer containing at least a metal oxide of Zn, Sn, and In, a metal nitride, and a metal oxynitride is preferred because of high bending resistance. Further, a gas barrier layer having an atomic concentration of Zn, Sn, and In of 20 to 40% is preferable because the bending resistance is higher. It is preferable that the composition in which the ceria and alumina coexist in the gas barrier layer is also excellent in bending resistance.

These inorganic gas barrier layers can be produced, for example, by a vapor phase deposition method in which a material is deposited in a gas phase by a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method or the like to form a film. Among them, in the sputtering method, by performing reactive sputtering on a metal target in an oxygen-containing environment, the film formation speed can be improved.

The gas barrier layer may be formed on the laminate formed of the support substrate and the resin laminate film, or may be formed on the self-supporting film from which the self-supporting substrate is peeled off.

The film forming temperature of the gas barrier layer is preferably set to 80 to 400 ° C. In order to improve the gas barrier performance, it is advantageous to select a high film forming temperature. However, if the film forming temperature is high, the bending resistance is lowered. Therefore, in the application where the bending resistance is important, the film forming temperature of the gas barrier layer is preferably 100 to 300 °C. In the resin laminated film of the present invention, when the resin film 2 is a polyimide, since the heat resistance of the resin laminated film is high, the temperature of the substrate can be increased to form a gas barrier layer. Further, even if a gas barrier layer is formed at a high temperature (for example, 300 ° C), defects such as wrinkles do not occur in the film.

The number of layers of the gas barrier layer is not limited and can be only one layer. It is a multilayer of 2 or more layers. Examples of the multilayer film include SiO in the first layer, a gas barrier layer made of SiN in the second layer, or SiO/AlO/ZnO in the first layer, and a gas barrier composed of SiO in the second layer. Floor.

A layer having various functions such as an organic EL light-emitting layer is formed on the gas barrier layer of the flexible substrate, and various organic solvents are used in the steps of producing a display element or an optical element. For example, when a color filter (hereinafter also referred to as CF) is formed, a gas barrier layer is formed on the resin laminated film, and a color pixel or a black matrix or the like is formed to form CF. At this time, when the solvent resistance of the gas barrier layer is poor, the gas barrier properties are lowered. Therefore, it is preferable to impart solvent resistance to the gas barrier layer of the uppermost layer. For example, the uppermost gas barrier layer is preferably made of ruthenium oxide.

The composition analysis of the gas barrier layer was carried out by quantitatively analyzing each element by X-ray photoelectron spectroscopy (XPS method).

The total thickness of the gas barrier layer is preferably from 20 to 600 nm, more preferably from 30 to 300 nm.

The thickness of the gas barrier layer is usually measured by a cross-sectional observation of a transmission electron microscope (TEM).

When the composition of the boundary layer between the upper layer and the lower layer of the gas barrier layer is changed obliquely, and a clear interface cannot be recognized by TEM, first, the composition analysis in the thickness direction is performed, and the concentration distribution of the elements in the thickness direction is obtained. Based on the information of the concentration distribution, the boundary of the layer and the thickness of the layer are obtained. The procedure of composition analysis in the thickness direction and the definition of the boundary of each layer and the thickness of the layer are described below.

First, the cross section of the gas barrier layer was observed by a transmission electron microscope, and the thickness of the entire layer was measured. Second, use elements in the depth direction The composition analysis is a possible measurement, and the concentration distribution (concentration profile in the thickness direction) of the element corresponding to the thickness position of the gas barrier layer is obtained. Examples of the composition analysis method that can be used at this time include electron energy loss spectroscopy (hereinafter referred to as EELS analysis) and energy-dispersive X-ray spectroscopy (hereinafter referred to as "energy-dispersive X-ray spectroscopy" (hereinafter referred to as EDX analysis), secondary ion mass spectrometry (hereinafter referred to as SIMS analysis), X-ray photoelectron spectroscopy (described as XPS analysis), and Auger electron spectroscopy (Aug) Erelectron spectroscopy (described below as AES analysis), but from the viewpoint of sensitivity and accuracy, the best is EELS analysis. Therefore, the EELS analysis is first performed, and the analysis is performed by the following sequence (EELS analysis → EDX analysis → SIMS analysis → XPS analysis → AES analysis). For the components that cannot be identified by the higher-level analysis, the data of the lower analysis can be used.

CF is obtained by providing a black matrix or a colored pixel on the flexible substrate using the resin laminated film of the present invention. This CF is characterized by being lightweight, not easily broken, and flexible because a resin film is used for the substrate. The resin used in at least one of the black matrix and the colored pixel layer preferably contains a polyimide resin. Further, from the viewpoint of a decrease in reflectance and heat resistance, it is preferred that the black matrix is composed of a low optical density layer and a high optical density layer formed on the low optical density layer, and the low optical density layer is high. The resin used in at least one layer of the optical concentration layer contains a polyimide resin.

In the resin laminated film of the present invention, when the resin film 2 is a polyfluorene In the case of an imine, since the solvent of the polyimide precursor is highly chemically resistant to a general polar aprotic solvent, a polyimide resin can be used in the black matrix or the colored pixel layer. Further, even when a gas barrier layer is formed on the black matrix or the colored pixel layer, the gas is generated during the formation of the gas barrier layer because the polyimide matrix of the black matrix and the colored pixel layer is high in heat resistance. Less, it can produce a gas barrier layer with high gas barrier properties. Further, in the pattern processing of the black matrix or the colored pixel layer, since a polyimine precursor which is soluble in an aqueous alkali solution can be used, it is advantageous for fine pattern formation.

A configuration example of CF will be described with reference to the drawings. Fig. 1 is a view showing the basic configuration of CF of the resin laminated film of the present invention formed on a support substrate. From this, the support substrate (symbol: 1) was peeled off by the above-described peeling method, and CF having the resin laminated film of the present invention as a substrate was obtained.

A resin laminated film (symbol: 2) composed of a polyimide film A (symbol: 2A) and a resin film (symbol: 2B) was formed on a support substrate (symbol: 1), and a black matrix was formed thereon ( Symbol: 3), red coloring pixels (symbol: 4R), green coloring pixels (symbol: 4G), and blue coloring pixels (symbol: 4B). Furthermore, on the coloring pixels, a jacket layer can also be formed. Further, it may be formed as a gas barrier layer of an inorganic film. The place where the gas barrier layer is formed is not particularly limited, and may be formed, for example, on the resin laminated film (symbol: 2) or on the black matrix (symbol: 3) or the layer of the colored pixel, or may be formed. Both the overcoat layer (symbol: 2) and the overcoat layer may be formed on the overcoat layer present on the surface of the color filter. Further, the number of layers of the gas barrier layer is not limited, and may be only one layer or two or more layers. Examples of the multilayer film include a first layer of SiO, a second layer of a gas barrier layer composed of SiN, or a first layer of SiO/AlO/ZnO, the second layer is a gas barrier layer composed of SiO.

The black matrix is preferably a black matrix composed of a resin in which a black pigment is dispersed in a resin. Examples of the black pigment include carbon black, titanium black, titanium oxide, titanium oxynitride, titanium nitride or iron oxide. In particular, it is preferably carbon black or titanium black. Further, a red pigment, a green pigment, or a blue pigment may be mixed and used as a black pigment.

In the manufacture of the black matrix, a black composition containing a black pigment as described above, preferably a resin, more preferably a solvent is used. Further, it is preferable to form a black matrix by patterning the black resin composition. The black composition may be non-photosensitive or photosensitive. Examples of the method of patterning include mechanical processing, dry etching, sand blasting, photolithography, etc., and high-definition patterning is preferred. Lithography. As a method of patterning the photolithography, the black resin composition itself may be patterned as a photosensitive material, or may be formed by laminating a black resin by laminating a photoresist different from the black resin composition. The objects are patterned to form a black matrix. In the photolithography, an exposure step and an imaging step are performed to perform patterning.

The resin used for the resin black matrix is preferably a polyimide resin from the viewpoint of heat resistance and ease of formation of the fine pattern. The polyimine resin is preferably a polyamiled acid synthesized from an acid dianhydride and a diamine, which is thermally hardened after pattern processing to form a polyimide resin. Further, as an example of the acid dianhydride, the diamine, and the solvent, those listed under the above-mentioned "resin film 1" can be used.

In order to form a black matrix containing a polyimide resin, it is generally a photosensitive material composed of at least a polyamic acid, a black pigment, and a solvent. After the black composition is applied onto the substrate, it is dried by air drying, heat drying, vacuum drying, or the like to form a non-photosensitive polyphthalic acid black film, and a positive resist is used to form a desired pattern, and then the alkali peeling resist is formed. Finally, the method of hardening (polyimidization) of the colored pixels by heating at 200 to 300 ° C for 1 minute to 3 hours.

As the resin used for the resin black matrix, a photosensitive acrylic resin can also be used. In the manufacture of the black matrix, an alkali-soluble acrylic resin containing a black pigment dispersed therein, a photopolymerizable monomer, a polymerization initiator, and a solvent black are used. Composition.

As an example of the alkali-soluble acrylic resin, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is mentioned. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or an acid anhydride.

Examples of the photopolymerizable monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tripropylenesulfenyl formaldehyde, and pentaerythritol IV (A) Acrylate, dipentaerythritol hexa(meth) acrylate or dipentaerythritol penta (meth) acrylate.

Examples of the photopolymerization initiator include diphenyl ketone, N, N'-tetraethyl-4,4'-diaminodiphenyl ketone, and 4-methoxy-4'-dimethyl hydride. Aminodiphenyl ketone, 2,2-diethoxyacetophenone, α-hydroxyisobutylbenzophenone, thioxanthone or 2-chlorothioxanthone.

Examples of the solvent for dissolving the photosensitive acrylic resin include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetate ethyl acetate, and methyl-3-methoxypropionate. Ethyl-3-ethoxypropionate, methoxybutyl acetate or 3-methyl-3-methoxybutylacetic acid ester.

In order to suppress a decrease in visibility due to external light reflection, the black matrix is preferably a laminated resin black matrix composed of a low optical density layer and a high optical density layer formed on the low optical density layer. Further, the term "low optical density layer" means a layer having an optical density of not 0 and substantially opaque, and the value of the optical density per unit thickness is smaller than the optical density per unit thickness of the high optical density layer. The resin constituting the black matrix of the laminated resin is not particularly limited. However, from the viewpoint of batch patterning the low optical density layer and the high optical density layer, the low optical density layer is preferably a polyimide resin. The optical concentration layer is preferably an acrylic resin. Further, in order to lower the reflectance, it is more preferable to include fine particles in the resin black matrix.

After forming a black matrix, a color pixel is formed. The coloring pixels are composed of three coloring pixels of red, green, and blue. Further, in addition to the three-color colored pixels, the brightness of the white display of the display device can be improved by forming a pixel of the fourth color which is colorless or extremely lightly colored.

As the coloring matter of CF, a resin containing a pigment or a dye as a coloring agent can be used.

Examples of the pigment used in the red coloring element include PR254, PR149, PR166, PR177, PR209, PY138, PY150, or PYP139. Examples of the pigment used in the green coloring pixel include PG7. PG36, PG58, PG37, PB16, PY129, PY138, PY139, PY150 or PY185, examples of the pigment used in the blue coloring element include PB15:6 or PV23.

As an example of the blue dye, C.I. Basic Blue (BB) 5 can be cited. BB7, BB9 or BB26, examples of the red dye include C.I. Acid Red (AR) 51, AR87 or AR289. Examples of the green dye include C.I. Acid Green (AG) 25 and AG27.

Examples of the resin used in the red, green and blue coloring elements include an acrylic resin, an epoxy resin or a polyimide resin. From the viewpoint of heat resistance, a polyimide resin is preferable, and a photosensitive acrylic resin can also be used in order to reduce the production cost of CF.

In order to form a color pixel composed of a polyimide resin, a non-photosensitive color paste composed of at least a polyphthalic acid, a colorant, and a solvent is generally applied onto a substrate, and then dried by air drying, heating, and drying. Drying by vacuum drying or the like to form a non-photosensitive polyphthalic acid colored film, using a positive photoresist to form a desired pattern, alkali stripping the photoresist, and finally heating at 200 to 300 ° C for 1 minute to 3 hours. A method of hardening a colored pixel (polyimidization).

The photosensitive acrylic resin generally contains an alkali-soluble acrylic resin, a photopolymerizable monomer, and a photopolymerization initiator.

As an example of the alkali-soluble acrylic resin, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is mentioned. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid or an acid anhydride.

Examples of the photopolymerizable monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tripropylenesulfenyl formaldehyde, and pentaerythritol IV (A) Acrylate, dipentaerythritol hexa(meth) acrylate or dipentaerythritol penta (meth) acrylate.

Examples of the photopolymerization initiator include diphenyl ketone, N,N'-tetraethyl-4,4'-diaminodiphenyl ketone, 4-methoxy-4'-dimethylaminodiphenyl ketone, 2,2-diethoxybenzene Ethyl ketone, α-hydroxyisobutyl benzophenone, thioxanthone or 2-chlorothioxanthone.

Examples of the solvent for dissolving the photosensitive acrylic resin include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetate ethyl acetate, and methyl-3-methoxypropionate. Ethyl-3-ethoxypropionate, methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.

In order to planarize the surface of the CF on which the black matrix and the color pixel are formed, a jacket layer may be further formed on the surface of the CF. Examples of the resin used for the formation of the overcoat layer include an epoxy resin, an acrylic modified epoxy resin, an acrylic resin, a decane resin, or a polyimide resin. As the thickness of the overcoat layer, the surface is preferably a flat thickness, more preferably 0.5 to 5.0 μm, still more preferably 1.0 to 3.0 μm.

The CF system containing the resin laminated film of the present invention can be produced by at least the following steps.

(1) A step of producing a polyimide film A on a support substrate.

(2) A step of forming a resin laminated film by further laminating a resin film on the resin film.

(3) a step of forming a black matrix on the aforementioned resin laminated film.

(4) a step of forming a color pixel on the above-mentioned resin laminated film.

(5) a step of irradiating the self-supporting substrate side with ultraviolet light and peeling off the resin laminated film.

The steps (1), (2), and (5) above are as described in (1) to (3) in the (method of manufacturing a resin laminated film).

The steps (3) and (4) in the above-described CF manufacturing step are steps of forming a black matrix and a colored pixel on the resin laminated film. As described above, photolithography is used in the patterning of black matrices or colored pixels. At present, as a liquid crystal display or an organic EL display, high precision of 300 ppi or more is required, and equivalent performance is required in a flexible display panel. In order to achieve such high resolution, high-precision pattern formation is required. When a black matrix or a colored pixel is formed on a resin laminated film formed on a support substrate to form CF, since a conventional technique of producing CF using a glass substrate as a supporting substrate can be employed, a case where CF is formed on the self-standing film can be used. In contrast, a high-definition pattern can be formed.

Further, in the steps (3) and (4), a black matrix or a colored pixel may be formed directly above the resin laminated film, or may be formed therebetween with another layer interposed therebetween.

In the manufacturing step of the CF described above, a step of producing an inorganic film such as a gas barrier layer may be further included. The place where the inorganic film is formed is not particularly limited. For example, it may be formed on the resin laminated film, may be formed on the black matrix or the colored pixel layer, or may be formed on the outer layer of the surface of the color filter, or may be formed on the resin laminated film and the outer cover. Both on the layer. Further, the number of layers of the inorganic film is not limited, and may be one layer or two or more layers. Examples of the multilayer film include a first layer of SiO, a second layer of an inorganic film made of SiN, or a first layer of SiO/AlO/ZnO, and a second layer of an inorganic film made of SiO.

Next, an example of the method for producing CF of the present invention will be described more specifically. The resin laminated film of the present invention and the gas barrier layer were formed on the support substrate by the above method. On top of it, using a spin coater or a mouth mode coater In the method, the black matrix paste composed of polyamic acid, which is a black pigment composed of carbon black or titanium black, is applied so as to have a thickness of 1 μm after curing, and dried under reduced pressure to 60 Pa or less. Semi-curing with a hot air oven or hot plate at 110~140 °C.

Applying a positive photoresist to a thickness of 1.2 μm after prebaking by a spin coater or a die coater, and then drying under reduced pressure until 80 Pa, using a hot air oven at 80 to 110 ° C or The hot plate is pre-baked to form a photoresist film. Then, after selective exposure by ultraviolet light through a photomask by a proximity exposure machine or a projection exposure machine or the like, an alkali imaging solution such as potassium hydroxide or tetramethylammonium hydroxide is used in an amount of 1.5 to 3% by weight. Immerse for 20 to 300 seconds to remove the exposed portion. After stripping the positive photoresist using a stripping solution, the mixture is heated in a hot air oven or hot plate at 200 to 300 ° C for 10 to 60 minutes to convert the polyaminic acid into a polyimine to form a resin black matrix.

The coloring pixels are produced using a coloring agent and a resin. When a pigment is used as a coloring agent, a polymer dispersing agent and a solvent are mixed with the pigment, and polyglycine is added to the dispersion liquid which has been subjected to dispersion treatment. On the other hand, when a dye is used as a coloring agent, it is produced by adding a solvent and poly-proline to a dye. The total solid content at this time is a total of a polymer dispersant of a resin component, a polyamine acid, and a coloring agent.

The obtained coloring agent composition is applied to a resin laminated film on which a resin black matrix is formed by a method such as a spin coater or a die coater, and the thickness after heat treatment is 0.8 to 3.0 μm. After coating, it is dried under reduced pressure, and prebaked in a hot air oven or hot plate at 80 to 110 ° C to form a coating film of a coloring agent.

Next, a positive-type photoresist is applied so as to have a thickness of 1.2 μm after prebaking by a spin coater or a die coater, and then dried under reduced pressure, using a hot air oven of 80 to 110 ° C or heat. The board is pre-baked to form a photoresist film. Then, after selective exposure by ultraviolet light through a photomask by a proximity exposure machine or a projection exposure machine or the like, an alkali imaging solution such as potassium hydroxide or tetramethylammonium hydroxide is used in an amount of 1.5 to 3% by weight. Immerse for 20 to 300 seconds to remove the exposed portion. After the positive photoresist is peeled off using a stripping solution, it is heated by a hot air oven or a hot plate at 200 to 300 ° C for 10 to 60 minutes to convert the polyaminic acid into a polyimine to form a color pixel. The coloring agent composition was used for each color of the coloring pixels, and the red coloring pixels, the green coloring pixels, and the blue coloring pixels were sequentially subjected to the patterning step as described above. Furthermore, the patterning order of the coloring pixels is not particularly limited.

Then, the polysiloxane resin is applied by a spin coater or a mouth coater, and then vacuum-dried, and pre-baked with a hot air oven or a hot plate at 80 to 110 ° C, using a hot air of 150 to 250 ° C. The oven or hot plate is heated for 5 to 40 minutes to form a jacket layer, whereby the CF of the present invention can be produced.

As described above, since the resin film 1 of the present invention has a large light absorption in the ultraviolet light range, the irradiation energy required for the peeling can be reduced. Moreover, when the CTE of the resin laminated film of the present invention is low, for example, 30 ppm/° C. or less, the warpage of the substrate when the resin laminated film is formed on the support substrate can be reduced. Therefore, the focus shift in the photolithography step at the time of formation of the black matrix or the colored pixel can be reduced, and as a result, CF can be produced with high precision. Furthermore, by reducing the CTE, the color filter after peeling can be reduced. Curl can suppress the pixel defect after peeling.

The resin laminated film of the present invention can be applied to a substrate of a TFT substrate. That is, a TFT substrate provided with a TFT on the resin laminated film of the present invention can be obtained. Since this TFT substrate uses a resin film in a base material, it is characterized by being lightweight and not easily broken.

An example of the configuration of the TFT will be described with reference to the drawings. Fig. 2 is a view showing the basic configuration of a TFT including the resin laminated film of the present invention formed on a support substrate. From this, the support substrate (symbol: 1) is peeled off by the above-described peeling method, and a TFT having the resin laminated film (symbol: 2') of the present invention as a substrate can be obtained. A resin laminated film (symbol: 2') composed of a polyimide film A (symbol: 2A') and a resin film (symbol: 2B') is formed on a support substrate (symbol: 1), and further thereon A gas barrier layer (symbol: 5) formed of an inorganic film was formed thereon, and a TFT (symbol: 6) and a planarization layer (symbol: 7) were formed thereon.

The TFT substrate using the resin laminated film of the present invention can be produced by at least the following steps.

(1) A step of producing a polyimide film A on a support substrate.

(2) A step of forming a resin laminated film by further laminating a resin film on the resin film.

(3) a step of forming a gas barrier layer on the aforementioned resin laminated film

(4) a step of forming a TFT on the above-mentioned resin laminated film.

(5) a step of irradiating the self-supporting substrate side with ultraviolet light and peeling off the resin laminated film.

The steps (1), (2), and (5) above are as described in (1) to (3) in the (method of manufacturing a resin laminated film).

The steps (3) and (4) in the manufacturing steps of the TFT substrate are a step of forming a gas barrier layer on the resin laminated film and then forming a TFT. Further, in the step (3) or (4), a gas barrier layer or a TFT may be formed directly above the resin laminated film, or may be formed therebetween with another layer interposed therebetween. A method of forming a gas barrier layer directly above the resin laminated film and forming a TFT thereon is preferred.

Examples of the semiconductor layer for forming a TFT include an amorphous germanium semiconductor, a polycrystalline germanium semiconductor, an oxide semiconductor represented by In-Ga-ZnO ^- ₄ , an organic semiconductor represented by condensed pentabenzene or polythiophene, and carbon nanoene. Carbon material such as rice pipe. For example, using the resin laminated film of the present invention as a substrate, a gas barrier layer, a gate electrode, a gate insulating film, a semiconductor layer, an etch stop film, and a source are sequentially formed by a well-known method. The bottom electrode is fabricated to form a bottom gate type TFT.

Through the above steps, a TFT substrate using the resin laminated film of the present invention can be produced. Such a TFT substrate can be used as a drive substrate of a display element such as a liquid crystal element, an organic EL element, or an electronic paper.

The manufacturing temperature of the TFT depends on the type of the semiconductor layer. However, in the case of a polycrystalline germanium semiconductor or an oxide semiconductor, it is advantageous to select a high manufacturing temperature in order to improve mobility or reliability. In general, it is necessary to be 500 ° C or more in the polycrystalline germanium semiconductor and 300 ° C or more in the oxide semiconductor. In the resin laminated film of the present invention, when the resin film 2 is polyimide, since the heat resistance of the resin laminated film is high, high-temperature TFT production is possible. In addition, when the acid dianhydride residue in the polyimine contained in the polyimide film A of the resin film 1 is an aromatic acid dianhydride residue, the heat resistance of the resin film 1 becomes high, and Less Since the exhaust gas at the time of the high-temperature semiconductor manufacturing step is less passed, a high-quality TFT substrate having a small component defect can be obtained. Further, when the aromatic acid dianhydride residue is a group derived from pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride, heat resistance is further increased. good.

As described above, since the resin film 1 of the present invention has high light absorption in the ultraviolet light range, the irradiation energy required for the peeling can be reduced. In the manufacture of TFT substrate, in the gate electrode, gate insulating film, semiconductor layer, etching stop film, source. In the formation of tantalum electrodes, photolithography is mainly used. When the CTE of the resin laminated film of the present invention is low, for example, 30 ppm/° C. or lower, preferably 10 ppm/° C. or less, the warpage of the substrate when the resin laminated film is formed on the support substrate can be reduced as described above. Therefore, since the focus shift in the photolithography step can be reduced, the TFT can be fabricated with high precision. As a result, a TFT substrate having good driving performance can be obtained. Moreover, since the curl of the TFT substrate after peeling can be reduced, damage of the TFT element after peeling can be prevented.

The flexible substrate using the resin laminated film of the present invention can be used as a substrate for a touch panel. For example, a transparent conductive film can be formed on at least one surface of the resin laminated film of the present invention to form a transparent conductive film, and a transparent conductive film can be laminated on each other by using an adhesive or an adhesive to form a touch panel.

As the transparent conductive layer, a carbon material such as a well-known metal film, a metal oxide film, or the like, a carbon nanotube or graphene can be used, but from the viewpoints of transparency, conductivity, and mechanical properties, it is preferably employed. Metal oxide film. Examples of the metal oxide film include tin, antimony, cadmium, molybdenum, tungsten, fluorine, zinc, antimony, and the like as inclusions. Indium oxide, cadmium oxide, and tin oxide of the material, and a metal oxide film such as zinc oxide or titanium oxide to which aluminum is contained as an inclusion. Among them, a film containing 2 to 15% by mass of tin oxide or zinc oxide indium oxide is preferably used because of its excellent transparency and electrical conductivity.

The film forming method of the transparent conductive layer may be any method as long as it can form a target film, but is preferably a gas phase such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method. A vapor phase deposition method in which a material is deposited to form a film. Among them, particularly excellent conductivity can be obtained. From the viewpoint of transparency, it is preferred to form a film by a sputtering method. Further, the film thickness of the transparent conductive layer is preferably from 20 to 500 nm, more preferably from 50 to 300 nm.

Further, the patterning method of the transparent conductive layer is not particularly limited, and examples thereof include wet etching using a photoresist and an etching liquid, dry etching using a laser, and the like.

The flexible substrate using the resin laminated film of the present invention can be used for a display element such as a liquid crystal display, an organic EL display or an electronic paper, or a light receiving element such as a solar cell or a CMOS. In particular, the flexible substrate of the present invention is preferably used in the use of such a display element or a light-receiving element as a flexible device that can be bent.

An example of a manufacturing step of the display element or the light-receiving element is a circuit and a functional layer required for forming a display element or a light-receiving element on a resin laminated film formed on a substrate, and further irradiating ultraviolet light to peel the resin from the substrate. Laminated film.

An organic EL element as an example of a display element, an organic EL element is shown in FIG. 3 (top emission mode, red green blue light organic EL). A resin laminated film (symbol: 2') composed of a polyimide film A (symbol: 2A') and a resin film (symbol: 2B') is formed on a support substrate (symbol: 1), and further thereon A gas barrier layer (symbol: 5) formed of an inorganic film, a circuit of the TFT (symbol: 6) and an organic EL light-emitting layer (symbol: 11R, 11G, 11B) and the like are formed thereon. The circuit of the TFT (symbol: 6) and the organic EL light-emitting layer (symbol: 11R, 11G, and 11B) are composed of a TFT composed of an amorphous germanium, a low-temperature polysilicon, an oxide semiconductor, or the like (symbol: 6). And a planarization layer (symbol: 7); a first electrode (symbol: 8) composed of Al/ITO or the like; an insulating layer (symbol: 9) covering the end of the first electrode (symbol: 8); Red, green, and blue organic EL light-emitting layers (symbols: 11R, 11G, and 11B) composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer; and a second electrode made of ITO or the like (symbol: 10), and is enclosed by a closed film (symbol: 12). The resin laminated film (symbol: 2') is peeled off from the support substrate (symbol: 1) by irradiation with ultraviolet light, and can be used as an organic EL device.

The organic EL device containing the resin laminated film of the present invention can be produced by at least the following steps.

(1) A step of producing a polyimide film A on a support substrate.

(2) A step of forming a resin laminated film by further laminating a resin film on the resin film.

(3) a step of forming an organic EL element on the above-mentioned resin laminated film.

(4) a step of irradiating ultraviolet light on the side of the self-supporting substrate and peeling off the resin laminated film.

The steps (1), (2), and (4) above are as described in (1) to (3) above (in the method for producing a resin laminated film).

The step (3) in the manufacturing step of the organic EL device is formed by forming a TFT composed of an amorphous germanium, a low-temperature polysilicon, an oxide semiconductor or the like (symbol: 6); and a planarization layer (symbol: 7). a first electrode (symbol: 8) composed of Al/ITO or the like; an insulating layer (symbol: 9) covering the end of the first electrode (symbol: 8); a hole injection layer, a hole transport layer, An organic EL light-emitting layer (symbol: 11W, 11R, 11G, 11B) of white or various colors (red, green, blue, etc.) composed of a light-emitting layer, an electron transport layer, and an electron injection layer; and a second layer composed of ITO or the like Electrode (symbol: 10). In this case, it is preferable to form a gas barrier layer (symbol: 5) of the inorganic film on the resin laminated film (symbol: 2'), and then form a circuit of the TFT and the organic EL light-emitting layer, and it is also preferable to After the organic EL light-emitting layer was formed, it was blocked with a sealing film (symbol: 12).

Further, the light extraction method may be either a bottom emission mode in which light is taken out on the TFT substrate side, or a top emission mode in which light is taken out on the closed film side.

The organic EL device containing the resin laminated film of the present invention and/or the CF containing the resin laminated film of the present invention can be preferably used as an organic EL display having them. For example, an organic EL display having a full color display can be obtained by combining a white light-emitting organic EL element using the resin laminated film of the present invention on a substrate and CF containing the resin laminated film of the present invention. Further, for the purpose of improving the color purity, a red-green blue light-emitting organic EL element using the resin laminated film of the present invention in the substrate and CF containing the resin laminated film of the present invention may be combined.

Fig. 4 shows an example of an organic EL display formed by bonding CF and white light-emitting organic EL elements of the present invention. As its manufacture An example of the procedure is the following method. The CF 20 of the present invention is formed on the first support substrate (not shown) by the above-described manufacturing method. In addition, the organic EL element 30 having a resin laminated film as a substrate is formed on the second supporting substrate (not shown) by the above method. Then, CF (symbol: 20) and an organic EL element (symbol: 30) are bonded via the adhesive layer 13. Then, each of the first and second support substrates is irradiated with ultraviolet light from the side of the support substrate, and the first and second support substrates are peeled off.

The layer system is not particularly limited, and examples thereof include those in which an adhesive, an adhesive, and an adhesive are cured by light or heat. The resin of the layer is not particularly limited, and examples thereof include an acrylic resin, an epoxy resin, a urethane resin, a polyamide resin, a polyimide resin, and a polyoxymethylene resin.

[Examples]

The invention is illustrated by the following examples and the like, but the invention is not limited by the examples.

(1) Production of a polyimide film (on a glass substrate)

A glass substrate (manufactured by AN-100 Asahi Glass Co., Ltd.) having a thickness of 100 mm × 100 mm × 0.7 mm was used as a supporting substrate, and a spin coater MS-A200 manufactured by MIKASA Co., Ltd. was used for a preheating at 140 ° C × 4 minutes. The thickness after baking was set to a predetermined thickness (0.15, 0.75, 1.5, 3.0, 7.5, 15.0 μm), and the number of rotations was adjusted to spin-coat varnish (Synthesis Examples 1 to 19). Then, a pre-baking treatment at 140 ° C for 4 minutes was carried out using a large Japanese SCREEN hot plate D-SPIN. The coating film after the prebaking treatment was heated to 300 ° C or 400 ° C at 3.5 ° C / min under a nitrogen flow (in an oxygen concentration of 20 ppm or less) using a blunt oven (INH-21CD manufactured by Koko Thermal Systems Co., Ltd.). , keep it for 30 minutes, The resin film 1 was produced by cooling to 50 ° C at 5 ° C / min. Then, the varnish was spin-coated on the resin film 1 so that the thickness after prebaking was 15.0 μm (Synthesis Examples 20 to 22, Preparation Examples 1 and 2). Then, in the same manner as described above, the prebaking treatment/baking in a passive oven is performed, and the resin film 2 is produced on the resin film 1.

(2) Production of polyimine resin film (on glass substrate)

A glass substrate (manufactured by AN-100 Asahi Glass Co., Ltd.) having a thickness of 100 mm × 100 mm × 0.7 mm was used as a supporting substrate, and a spin coater MS-A200 manufactured by MIKASA Co., Ltd. was used for a preheating at 140 ° C × 4 minutes. The thickness after baking was 15.0 μm, the number of rotations was adjusted, and the varnish was spin-coated (Synthesis Examples 1 to 22, Preparation Examples 1 and 2). Then, a pre-baking treatment at 140 ° C for 4 minutes was carried out using a large Japanese SCREEN hot plate D-SPIN. The coating film after the prebaking treatment was heated to 3.5 ° C at 3.5 ° C / min under a nitrogen flow (in an oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD manufactured by Koko Thermal Systems Co., Ltd.). The film was kept at 400 ° C for 30 minutes, and cooled to 50 ° C at 5 ° C / min to prepare a polyimide film. The thickness of the obtained polyimide resin film was 10.0 μm.

(3) Determination of light transmittance of polyimine resin laminated film

The light transmittance at 400 nm was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). Further, the polyimide film laminate film on the glass substrate produced in (1) was measured.

(4) Determination of absorbance of diamine solution

The absorbance at 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). Further, a diamine solution (solvent: NMP) having a concentration of 1 × 10 ^-4 mol/L was measured using a quartz cell having a light path length of 1 cm.

(5) Measurement of Light Transmittance of Resin Film 1 in Polyimide Resin Film

A GD-OES analyzer (GD-Profiler 2 manufactured by Horiba, Ltd.) was used for the polyimide film laminated film formed on the glass substrate by the method described in (1), and the resin film 2 was oriented toward the resin film. 1 etching (diameter 5mm A resin film 1 having a film thickness of 100 nm was produced. The light transmittance of the resin film 1 at a thickness of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when a film having a thickness of 100 nm was measured using a micro ultraviolet-visible near-infrared spectrophotometer (MSV-5100 manufactured by JASCO Corporation). The same etching and transmittance measurement were performed at 5 places, and the average value of these was set as the light transmittance.

(6) Laser peeling test

The polyimine resin laminated film obtained by the method described in (1), the polyimine resin film obtained by the method described in (2), and the CF, TFT substrate, and organic EL produced by the method described later. The display was irradiated with a 308 nm excimer laser (shape: 21 mm × 1.0 mm) from the side of the glass substrate, and subjected to a laser peeling test. The laser system is irradiated with a 0.5 mm offset every time in the short-axis direction. When the slit was introduced along the edge of the irradiation region, the irradiation energy required for the peeling was measured as the energy of the film peeling, and the evaluation was performed based on the following criteria.

A: The irradiation energy is 230 mJ/cm ² or less.

B: Irradiation energy exceeds 230 mJ/cm ² and is 250 mJ/cm ² or less.

C: The irradiation energy exceeds 250 mJ/cm ² and is 270 mJ/cm ² or less.

D: The irradiation energy exceeds 270 mJ/cm ² and is 290 mJ/cm ² or less.

E: Irradiation energy exceeds 290 mJ/cm ² .

(7) Determination of linear thermal expansion coefficient (CTE) and glass transition temperature (Tg)

The measurement was carried out under a nitrogen flow using a thermomechanical analyzer (EXSTAR 6000 TMA/SS6000 manufactured by SII Nanotech Co., Ltd.). The heating method was carried out under the following conditions. In the first stage, the adsorbed water of the sample was removed by raising the temperature to 150 ° C at a temperature increase rate of 5 ° C / min, and was air-cooled to room temperature at a temperature lowering rate of 5 ° C / min in the second stage. In the third stage, the measurement was carried out at a temperature increase rate of 5 ° C / min, and CTE and Tg were determined. Further, CTE is an average value of 50 ° C to 200 ° C in the third stage. Further, in the measurement, the polyimide substrate on the glass substrate prepared by the laser peeling method (1) and the (poly) imide resin film on the glass substrate produced by the method described in (6) were used. The obtained polyimide film laminate film (Examples 1 to 29, Comparative Examples 1 to 3) and the polyimide film (synthesis examples 1 to 23, Preparation Examples 1 and 2). In addition, the difference between the CTE of the polyimide film laminate film (resin film 1 + resin film 2) and the CTE of the resin film 2 (the CTE of the polyethylenimine resin laminate film and the CTE of the resin film 2) is obtained. The change in CTE due to the stratification with the resin film 1.

(8) Determination of chromaticity coordinates

The transmission chromaticity coordinates (x, y) in the chromaticity diagram of the XYZ color system were measured using a microscopic spectrophotometer (MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.). Further, a polyimide film on the glass substrate produced in (1) was used for the measurement. Further, a C light source (x0 = 0.310, y0 = 0.316) was used for the light source.

(9) Determination of surface roughness

The peeling surface of the polyimide film laminated film peeled by (6) was performed using an atomic force microscope (AFM) (DIMENSION Icon manufactured by BRUKER) Determination of surface roughness (maximum height (Rz)).

(10) Determination of 1% weight loss temperature (heat resistance)

The measurement was carried out under a nitrogen flow using a thermogravimetric measuring apparatus (TGA-50 manufactured by Shimadzu Corporation). The heating method was carried out under the following conditions. In the first stage, the adsorbed water of the sample was removed by raising the temperature to 350 ° C at a temperature increase rate of 3.5 ° C / min, and was cooled to room temperature at a temperature decreasing rate of 10 ° C / min in the second stage. In the third stage, the measurement was carried out at a temperature increase rate of 10 ° C / min, and a 1% hot weight reduction temperature was obtained. Further, a polyimide film laminate film obtained by using a polyimide film on a glass substrate prepared by laser stripping (1) by the method described in (6) was used for the measurement (Examples 1 to 29). ).

(11) Film formation of indium tin oxide (ITO) film

The ITO layer having a thickness of 150 nm is deposited by using a composite oxide target of indium oxide and tin oxide on the peeled surface of the polyimide film laminated film peeled off from the glass substrate by the method described in (6). Make a film. The pressure at this time was 6.7 × 10 ^-1 Pa, the substrate temperature was 150 °, and sputtering was performed using a DC power supply of 3 kW.

(12) Determination of water vapor transmission rate

The polyimine resin laminated film with an ITO film produced by the method described in (11) was measured at a temperature of 40 ° C, a humidity of 90% RH, and a measurement area of 50 cm ² using a water vapor transmission rate. A device (PERMATRAN (registered trademark) manufactured by MOCON) was used to measure the water vapor transmission rate. The number of samples was set to 2 samples per level, and the number of measurements was set to 10 times for the same sample, and the average value was set as the water vapor transmission rate (g/(m ² .day)) as the gas barrier property. Indicator of evaluation.

(13) Measurement of warpage of glass substrate after film formation of resin laminated film

The warpage measurement was carried out on a 300 × 350 × 0.7 mm thick glass substrate (manufactured by AN-100 Asahi Glass Co., Ltd.), and a polyimide film was laminated as described in (1), and placed on MITUTOYO. On the precision stone platform (1000 mm × 1000 mm) made up, the amount (distance) of the floating from the platform was measured using a gap gauge for each of the four midpoints of the four sides of the test panel and the apexes. The average value of these is set as the amount of warpage. The measurement was carried out at room temperature (25 ° C).

(14) Curl evaluation of TFT substrate and color filter substrate

The crimp of the TFT substrate and the color filter substrate was evaluated as follows.

The TFT substrate or the color filter substrate peeled off from the glass substrate by the method described in (6) was allowed to stand at room temperature for 30 minutes. The TFT substrate or the color filter substrate which had been stored in a static state was cut out to 30 mm square, and was allowed to stand still at room temperature for 30 minutes on the smooth glass plate so that the substrate side became downward. Then, the maximum amount of the 50 mm square TFT substrate or the color filter substrate floating from the glass plate was measured as the amount of curl, and the evaluation was performed based on the following criteria.

A (very good): the amount of curl is 2mm or less

B (good): the amount of curl exceeds 2 mm and is less than 5 mm

C (may): the amount of curl exceeds 5 mm and is less than 10 mm

D (bad): The amount of curl exceeds 10 mm or is cylindrical.

(15) Evaluation of defect of TFT substrate and color filter substrate

Evaluation of the TFT base stripped from the glass substrate by the method described in (6) The component defect of the board or the number of pixel defects of the color filter substrate. In the evaluation, an optical microscope (Nikon PHOT300 manufactured by Nikon Co., Ltd.) was used, and 1000 elements or pixel observations were visually observed.

(recorded using raw materials, etc.)

The abbreviations of the substances and the like used in the examples are summarized below.

PMDA: pyromellitic dianhydride

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

ODPA: 3,3',4,4'-hydroxydiphthalic dianhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

BSAA: 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride

CBDA: cyclobutane tetracarboxylic dianhydride

PMDA-HS: 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride

BPDA-H: 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride

PDA: p-phenylenediamine

3,3'-DDS: 3,3'-diaminodiphenylanthracene

TFMB: 2,2'-bis(trifluoromethyl)benzidine

HFHA: structure of chemical formula (3)

BABOHF: Structure of chemical formula (5)

BABODS: Structure of Chemical Formula (6)

BABOHA: Structure of chemical formula (13)

BABOBA: Structure of Chemical Formula (14)

BAPS: bis[4-(3-aminophenoxy)phenyl]indole

CHDA: trans-1,4-diaminocyclohexane

BABB: Structure of Chemical Formula (15)

DAE: 4,4'-diaminodiphenyl ether

SiDA: bis(3-aminopropyl)tetramethyldioxane

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

Synthesis Example 1: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 5.0505 g (21.2 mmol) of PMDA, 13.9591 g (23.2 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 2: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 6.2357 g (21.2 mmol) of BPDA, 12.811 g (21.2 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 3: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 6.4597 g (20.8 mmol) of ODPA, 12.5879 g (20.8 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 4: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 8.0685 g (18.2 mmol) of 6FDA, 10.9792 g (18.2 mmol) of HFHA and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 5: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 8.8126 g (16.9 mmol) of BSAA, 10.2350 g (16.9 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 6: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 4.6657 g (23.8 mmol) of CBDA, 14.3819 g (23.8 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 7: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 5.1527 g (23.0 mmol) of PMDA-HS, 13.8944 g (23.0 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 8: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 6.4058 g (20.9 mmol) of BPDA-H, 12.6811 g (20.9 mmol) of HFHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 9: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 5.3869 g (24.0 mmol) of PMDA-HS, 13.60607 g (24.0 mmol) of BABOHF, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 10: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 6.0422 g (27.0 mmol) of PMDA-HS, 13.005 g (27.0 mmol) of BABODS, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 11: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 5.2923 g (23.6 mmol) of PMDA-HS, 13.7554 g (23.6 mmol) of BABOHA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 12: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 7.8637 g (26.7 mmol) of BPDA, 11.184 g (26.7 mmol) of BABOBA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 13: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 6.6445 g (29.6 mmol) of PMDA-HS, 12.4031 g (29.6 mmol) of BABOBA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 14: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 7.9558 g (25.6 mmol) of ODPA, 11.091 g (25.6 mmol) of BAPS, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 15: Synthesis of Polyimine Precursor Solution

4.7698 g (16.2 mmol) of BPDA, 1.2114 g (5.4 mmol) of PMDA-HS, 13.0665 g (21.6 mmol) of HFHA, 100 g of NMP were added to a 200 mL four-necked flask under a dry nitrogen stream, and heated and stirred at 65 ° C. . After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 16: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 3.2443 g (11.0 mmol) of BPDA, 2.4719 g (11.0 mmol) of PMDA-HS, 13.3331 g (22.0 mmol) of HFHA, 100 g of NMP were added to a 200 mL four-necked flask, and the mixture was heated and stirred at 65 ° C. . After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 17: Synthesis of Polyimine Precursor Solution

1.6557g (5.6mmol) of BPDA, 3.7846g (16.8mmol) of PMDA-HS, 13.8603g (22.5mmol) of HFHA, 100g of NMP were added to a 200mL four-necked flask under a dry nitrogen stream, and heated and stirred at 65 °C. . After 6 hours, it was cooled to form a polyaminic acid solution.

Synthesis Example 18: Synthesis of polyaminic acid solution

Under a dry nitrogen stream, 9.0374 g (40.3 mmol) of PMDA-HS, 10.0102 g (40.3 mmol) of 3,3'-DDS, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 19: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 14.00776 g (46.0 mmol) of BPDA-H, 4.9700 g (46.0 mmol) of PDA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 20: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 13.7220 g (46.6 mmol) of BPDA, 5.3256 g (46.6 mmol) of CHDA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 21: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 9.3724 g (30.2 mmol) of ODPA, 9.6752 g (30.2 mmol) of TFMB, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 22: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 13.9283 g (47.3 mmol) of BPDA, 5.1193 g (47.3 mmol) of PDA, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Synthesis Example 23: Synthesis of Polyimine Precursor Solution

Under a dry nitrogen stream, 7.3799 g (25.1 mmol) of BPDA, 11.0443 g (25.1 mmol) of BABB, and 100 g of NMP were placed in a 200 mL four-necked flask, and the mixture was stirred under heating at 65 °C. After 6 hours, it was cooled to form a polyimide precursor solution.

Preparation Example 1: Adjustment of Polyimine Precursor / Vermiculite Nanoparticle Solution

The organic vermiculite was added to the polyamidene precursor solution in such a manner that 100 parts by weight of the vermiculite particles were obtained in 100 parts by weight of the polyfluorene imide precursor in the polyimine precursor solution obtained in Synthesis Example 2. Sol (manufactured by Nissan Chemical Industry Co., Ltd., trade name: PMA-ST, particle size: 10 to 30 nm), and obtained a polybendimimine precursor - vermiculite nanoparticle varnish.

Preparation Example 2: Adjustment of Polyimine Precursor / Vermiculite Nanoparticle Solution

The organic vermiculite was added to the polyamidene precursor solution in such a manner that the vermiculite fine particles were 50 parts by weight based on 100 parts by weight of the polyimine precursor in the polyimine precursor solution obtained in Synthesis Example 22. Sol (manufactured by Nissan Chemical Industry Co., Ltd., trade name: PMA-ST, particle size: 10 to 30 nm), and obtained a polybendimimine precursor - vermiculite nanoparticle varnish.

Using the polyimide precursor solution of each of the synthesis examples and the preparation examples, a polyimide film was formed by the method described in (2), and the laser peeling property was evaluated by the method described in (6). The maximum absorbance of the diamine solution in the wavelength range of 300 to 400 nm, the absorbance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm, and the CTE of the polyimide film were shown in Table 1.

Example 1

The resin film 1 (baking at 300 ° C) having a film thickness of 1 μm and the resin film 2 having a film thickness of 10 μm (300 ° C) were prepared by the method described in (1) using the polyimide precursor solution of Synthesis Example 1 and Synthesis Example 20. Roasting). Using the obtained polyimide film laminate film, the transmittance of the resin laminated film, the laser peeling test, and the CTE method were measured by the methods described in (3), (6) to (10), and (12). Measurement, measurement of Tg, measurement of change in CTE due to stratification, measurement of chromaticity coordinates, measurement of Rz on the peeling surface, measurement of 1% weight loss temperature, and water vapor after film formation of the ITO film on the peeling surface Determination of penetration rate. The results are shown in Table 2. In addition, the minimum value of the light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm when the film is a film having a thickness of 100 nm produced by the method described in the above (5), and the wavelengths of 266 nm, 308 nm, and 343 nm are measured. Light transmittance at 351 nm and 355 nm. The results are shown in Table 6.

Example 2~11

A polyimide film laminate film was produced in the same manner as in Example 1 except that the polyimide film precursor solution used in the production of the resin film 1 was changed as described in Tables 2 to 3. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the Tg, the measurement of the change in the CTE due to the stratification, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeling surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Tables 2~3. Further, in Table 6, the minimum value of the light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm when the film is a film having a thickness of 100 nm, and the wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm are shown. Light transmittance.

Example 12

A polyimide film laminate film was produced in the same manner as in Example 1 except that the polyimide film precursor solution of Synthesis Example 12 was used in the production of the resin film 1 and the baking temperature was changed to 400 °C. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the Tg, the measurement of the change in the CTE due to the stratification, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeling surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Table 3. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Examples 13~17

A polyimide film laminate film was produced in the same manner as in Example 1 except that the polyimide film precursor solution used in the production of the resin film 1 was changed as described in Table 3. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the Tg, the measurement of the change in the CTE due to the stratification, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeling surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Table 3. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Example 18~22

The polymerization was carried out in the same manner as in Example 1 except that the polyimine precursor solution of Synthesis Example 7 was used instead of the polyimide precursor solution of Synthesis Example 1 and the film thickness of the resin film 1 was changed as shown in Table 4.醯Imine resin laminated film. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the change in the CTE due to the stratification, the measurement of the Tg, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeled surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Table 4. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Example 23~25

The polyimine precursor solution described in Table 4 was used for the production of the resin film 1, and the polyimine precursor solution described in Table 4 was used for the production of the resin film 2, and the baking temperature was set to A polyimide film laminate film was produced in the same manner as in Example 1 except for 400 ° C. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the Tg, the measurement of the change in the CTE due to the stratification, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeling surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Table 4. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Example 26~27

The polyimine precursor solution described in Table 4 was used in the production of the resin film 1, and the baking temperature was changed to 400 ° C, and the polyimine precursor of Synthesis Example 22 was used in the production of the resin film 2. The solution was prepared in the same manner as in Example 1 except that the baking temperature was 400 ° C, and a polyimide film laminate film was produced. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the Tg, the measurement of the change in the CTE due to the stratification, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeling surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Table 4. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Example 28~29

A polyimide film laminate film was produced in the same manner as in Example 23, except that the polyimide film precursor solution described in Table 4 was used for the production of the resin film 2. In the same manner as in the first embodiment, the measurement of the light transmittance, the laser peeling test, the measurement of the CTE, the measurement of the Tg, the measurement of the change in the CTE due to the stratification, the measurement of the chromaticity coordinates, and the measurement of the Rz of the peeling surface were carried out. The measurement of the 1% weight loss temperature and the measurement of the water vapor transmission rate after the film formation of the ITO film on the peeling surface. The results are shown in Table 4. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Comparative example 1~2

A polyimide film laminate film was produced in the same manner as in Example 1 except that the polyimide film precursor solution used in the production of the resin film 1 was changed as described in Table 5. In the same manner as in Example 1, the measurement of the light transmittance, the laser peeling test, and the measurement of the chromaticity coordinates were carried out. The results are shown in Table 5. Even if it is the maximum irradiation energy (400 mJ/cm ² ) of the apparatus used in the laser peeling test, the resin laminated film cannot be peeled off. Therefore, measurement of CTE measurement, change of CTE by lamination, measurement of Rz of a peeling surface, measurement of a 1% weight reduction temperature, film formation of an ITO film, and measurement of a water vapor transmission rate were not performed. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Comparative example 3

A polyimide film of a polyimide film was produced in the same manner as in Example 24 except that the polyimide film precursor solution used in the production of the resin film 1 was changed as described in Table 5. In the same manner as in Example 1, the measurement of the light transmittance, the laser peeling test, and the measurement of the chromaticity coordinates were carried out. The results are shown in Table 5. Even if it is the maximum irradiation energy (400 mJ/cm ² ) of the apparatus used in the laser peeling test, the resin laminated film cannot be peeled off. Therefore, measurement of CTE measurement, change of CTE by lamination, measurement of Rz of a peeling surface, measurement of a 1% weight reduction temperature, film formation of an ITO film, and measurement of a water vapor transmission rate were not performed. Further, in Table 6, the minimum transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittance at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm in the case of a film having a thickness of 100 nm are shown.

Adjustment Example 3: Synthesis of polyaminic acid solution

DAE (0.30 mol), PDA (0.65 mol), and SiDA (0.05 mol) were added together with 850 g of GBL and 850 g of NMP, ODPA (0.9975 mol) was added, and the reaction was carried out at 80 ° C for 3 hours. Add maleic anhydride (0.02 mol), further The reaction was carried out at 80 ° C for 1 hour to obtain a polyaminic acid solution (concentration of the resin: 20% by weight).

Preparation Example 4; Production of a Black Resin Composition for Forming a Black Matrix

50 g of carbon black (manufactured by MA100 Mitsubishi Chemical Corporation) and 200 g of NMP were mixed in 250 g of the polyaminic acid solution of the adjustment example 3, and yttrium oxide beads having a diameter of 0.3 mm were used using Dyno-Mill KDL-A. The dispersion treatment was carried out at 3,200 rpm for 3 hours to obtain a black resin dispersion.

To 50 g of this black dispersion, 49.9 g of NMP and 0.1 g of a surfactant (manufactured by LC951 Nippon Chemical Co., Ltd.) were added to obtain a non-photosensitive black resin composition.

Modification Example 5: Production of photosensitive color resist

8.05 g of Pigment Red PR177 was added together with 50 g of 3-methyl-3-methoxybutanol, and after dispersing at 7000 rpm for 5 hours using a homogenizer, the glass beads were filtered and removed. 134.75 g of a photosensitive acrylic resin solution (AC) having a concentration of 20% by weight was added to obtain a photosensitive red photoresist. The photosensitive acrylic resin solution (AC) is based on 70.00 g of an acrylic copolymer solution ("Cyclomer" P manufactured by DAICEL Chemical Industry Co., Ltd., ACA-250, 43 wt% solution), and 30.00 g of a new monomer as a polyfunctional monomer. Tetraol tetramethacrylate and 15.00 g of "Irgacure" 369 as a photopolymerization initiator were added with 260.00 g of cyclopentanone. In the same manner, a photosensitive green photoresist composed of Pigment Green PG38 and Pigment Yellow PY138 and a photosensitive blue resistance composed of Pigment Blue PB15:6 were obtained.

Example 30 Production of Color Filters (Fig. 1)

[1] Production of polyimine resin laminated film

A glass substrate (manufactured by AN100 Asahi Glass Co., Ltd.) having a thickness of 300 mm × 350 mm × 0.7 mm was used as a support substrate (symbol: 1), and a baking temperature of the polyimide film A was set to 300 ° C, and Example 18 was used. In the same manner, a resin laminated film (symbol: 2) of a polyimide film laminate film composed of a polyimide film A (symbol: 2A) and a resin film (symbol: 2B) was produced.

[2] Production of resin black matrix

The black resin composition prepared in the adjustment example 4 was spin-coated on the polyimide film laminated film formed on the glass substrate prepared above, and dried at 130 ° C for 10 minutes on a hot plate to form a black resin coating film. Spin-coated positive resist ("SRC-100", manufactured by SHIPLEY Co., Ltd.), prebaked at 120 °C for 5 minutes using a hot plate, and irradiated with 100 mJ/cm ^{2 of} ultraviolet light using an ultrahigh pressure mercury lamp. After mask exposure, use 2.38. % of aqueous solution of tetramethylammonium hydroxide was simultaneously etched by photoresist and black resin coating to form a pattern, which was stripped with methyl cellosolve acetate and heated at 280 ° C with a hot plate. In a minute, the oxime is imidized to form a black matrix (symbol: 3) in which carbon black is dispersed in the polyimide resin. The thickness of the black matrix was measured and found to be 1.4 μm.

[3] Production of colored layers

On the polyimide film laminate film on the black matrix patterned glass substrate produced in [1] and [2], the film thickness of the black matrix opening was 2.0 μm after heat treatment, and the spin coating was adjusted. The number of rotations of the machine was applied to the photosensitive red photoresist adjusted in Preparation Example 5, and prebaked at 100 ° C for 10 minutes by a hot plate to obtain a red colored layer. Next, using a CANON ultraviolet exposure machine "PLA-5011", a chrome mask that penetrates a portion of the black matrix opening portion and the black matrix by light in an island shape at 100 mJ/cm ² (365 nm) UV intensity) exposure. After the exposure, the film was immersed in a developing solution composed of a 0.2% aqueous solution of tetramethylammonium hydroxide, and then washed with pure water, and then heat-treated in an oven at 230 ° C for 30 minutes to prepare a red color. Picture (symbol: 4R). In the same manner, a green colored pixel (symbol: 4G) composed of a photosensitive green photoresist adjusted in the preparation example 5 and a blue colored pixel composed of a photosensitive blue resist (symbol: 4B were obtained). Polyimine substrate color filter produced on a glass substrate (Fig. 1).

Examples 31 to 33 and Comparative Example 4

The production of the polyimide film of the polyimide film was carried out in the same manner as in Example 30 except that the conditions were the same as those in the example described in Table 6, and the color was produced in the same manner as in Example 30. Filter.

The color filter of each of the examples and the comparative examples was subjected to a laser peeling test by the method described in (6), and the curl of the color filter was evaluated by the method described in (14). The method described is used to evaluate the pixel defect. Moreover, in each of the examples and the comparative examples, after the polyimide film was laminated on the glass substrate supporting the substrate, the amount of warpage of the glass substrate was measured by the method described in (13). The results are shown in Table 7.

In Examples 30 to 33, there was no particular problem of rejection or color mixing, and a good color filter was obtained. However, in comparison with the color filter of Example 30, the color filters of Examples 31 to 33 were curled greatly, and the pixel defects were also increased. The reason for this is considered to be an increase in the CTE of the polyimide film laminate film. In Comparative Example 4, the color filter could not be peeled off from the glass substrate.

Example 34 Production of TFT Substrate (Fig. 2)

[1] Production of polyimine resin laminated film

A glass substrate (AN100 (Asahi Glass)) having a thickness of 300 mm × 400 mm × 0.7 mm was used as a support substrate (symbol: 1), and the baking temperature of the polyimide film A was set to 300 ° C, and Example 26 was used. In the same manner, a resin laminated film (symbol: 2') of a polyimide film laminate film composed of a polyimide film A (symbol: 2A') and a resin film (symbol: 2B') was produced.

[2] Fabrication of TFT substrate

A gas barrier layer (symbol: 5) made of SiO was formed by a plasma CVD method on a polyimide film laminated film (on a glass substrate) produced by the above method. Then, a bottom gate type TFT (symbol: 6) is formed to cover the TFT, and an insulating film (not shown) made of Si ₃ N ₄ is formed. Next, after a contact hole was formed in the insulating film, a wiring (having a height of 1.0 μm, not shown) connected to the TFT through the contact hole was formed on the insulating film. This wiring is used to connect the organic EL element and the TFT formed in the steps between the TFTs or later.

In addition, in order to planarize the unevenness due to the formation of the wiring, a planarization layer is formed on the insulating film in a state in which the unevenness due to the wiring is buried (symbol: 7). The formation of the planarization layer is performed by spin coating a photosensitive polyimide varnish on a substrate, prebaking on a hot plate (120 ° C × 3 minutes), and then exposing and developing the image through a mask of a desired pattern. The air flow was carried out by heat treatment at 230 ° C for 60 minutes. The coating property at the time of applying a varnish was good, and after exposure, development, and heat treatment, no wrinkles or cracks were observed in the obtained planarization layer. Furthermore, the wiring is flat The average step was 500 nm, and a 5 μm square contact hole was formed in the flattened layer to be formed, and the thickness was about 2 μm.

Example 35~36

The TFT was produced in the same manner as in Example 34 except that the same conditions as in the example described in Table 8 were carried out except that the polyimide film was laminated under the same conditions as in Example 26. Substrate.

The obtained TFT substrate (Fig. 2) was subjected to a laser peeling test by the method described in (6), and the curl of the TFT substrate was evaluated by the method described in (14), and the method described in (15) was carried out. Evaluation of component defects. Further, after a polyimide film was formed on a glass substrate, the amount of warpage of the glass substrate was measured by the method described in (13). The results are shown in Table 8.

Example 37 Production of Polyimine Substrate Organic EL Display (Fig. 3)

[1] Production of polyimine resin laminated film

A resin laminated film (symbol) of a polyimide film laminated film composed of a polyimide film A (symbol: 2A') and a resin film (symbol: 2B') was produced by the method described in Example 34. :2').

[2] Fabrication of TFT substrate

A TFT substrate was produced by the method described in Example 34.

[3] Production of top emission type organic EL element

On the planarization layer (symbol: 7) of the TFT obtained by the above method, the following respective portions were formed, and a top emission type organic EL device was produced. First, a first electrode (symbol: 8) composed of Al/ITO (Al: reflective electrode) is formed on the planarization layer (symbol: 7) by connection to a wiring through a contact hole. Then, the photoresist is applied, pre-baked, exposed by a mask of a desired pattern, and developed. This photoresist pattern was used as a mask, and pattern processing of the first electrode (symbol: 8) was performed by wet etching using ITO etching. Then, the photoresist pattern was peeled off using a photoresist stripping solution (a mixture of monoethanolamine and diethylene glycol monobutyl ether). The substrate after washing and peeling was heated and dehydrated at 200 ° C for 30 minutes to obtain an electrode substrate with a planarization layer. The thickness change of the planarization layer was less than 1% after heating and dehydration before the treatment with the stripping solution. The first electrode (symbol: 8) thus obtained corresponds to the anode of the organic EL element.

Next, an insulating layer (symbol: 9) covering the shape of the end portion of the first electrode (symbol: 8) is formed. In the insulating layer, the same photosensitive polyimide varnish was used. By providing this insulating layer, a short circuit between the first electrode and the second electrode (symbol: 10) formed in the subsequent step can be prevented.

Further, in the vacuum vapor deposition apparatus, the hole transport layer, the organic light-emitting layer, and the electron transport layer are sequentially deposited by a desired pattern mask, and a red organic EL light-emitting layer (symbol: 11R) and green organic EL light are provided. Layer (symbol: 11G), blue organic EL light-emitting layer (symbol: 11B). Next, a second electrode (symbol: 10) composed of Mg/ITO was formed over the entire substrate. Furthermore, a SiON sealing film is formed by CVD film formation. No.: 12).

Next, the organic EL device was peeled off from the glass substrate by the method described in (6) to prepare an organic EL display (Fig. 3). With respect to the obtained active matrix type organic EL display, a voltage was applied through the driving circuit, and as a result, good light emission was exhibited. Further, the obtained organic EL device is inferior to the organic EL device produced by using a glass substrate.

Example 38 Production of Polyimine Substrate Organic EL Display (Fig. 4)

[1] Production of polyimine resin laminated film

A resin laminated film (symbol) of a polyimide film laminated film composed of a polyimide film A (symbol: 2A') and a resin film (symbol: 2B') was produced by the method described in Example 34. :2').

[2] Fabrication of TFT substrate

A TFT substrate was produced by the method described in Example 34.

[3] Production of top emission type organic EL element

A top emission type organic EL device was produced by the method described in Example 34 except that the organic light-emitting layer was changed to a white organic EL light-emitting layer (symbol: 11 W).

[4] Production of organic EL display

The color filter with a glass substrate obtained in Example 30 and the top emission type organic EL element with the glass substrate obtained in the above [3] were bonded to each other via the adhesive layer (symbol: 13). Next, the color filter and the organic EL element were peeled off from the glass substrate by the method described in (6) to produce an organic EL display (Fig. 4). With respect to the obtained active matrix type organic EL display, a voltage was applied through the driving circuit, and as a result, good light emission was exhibited. Again The organic EL element obtained was inferior to the organic EL element produced by using a glass substrate.

Claims (22)

A resin laminated film which is a resin laminated film having a polyimide film on at least one surface of a resin film, the polyimine resin film being the following polyimine resin film A, a polyimide resin Film A: A polyimide film having a minimum transmittance of less than 50% in a wavelength range of 300 to 400 nm when formed into a film having a thickness of 100 nm. The resin laminated film according to claim 1, wherein the main component of the diamine residue in the polyimine contained in the polyimide film A is derived from the following (B) diamine derivative, (B) When the concentration is 1×10 ^-4 mol/L N-methyl-2-pyrrolidone solution, the maximum absorbance at a wavelength of 1 cm in the wavelength range of 300 to 400 nm exceeds 0.6. Diamine derivative. The resin laminated film according to claim 1 or 2, wherein the maximum value of the absorbance of the (B) diamine derivative is 1.0 or more. The resin laminated film according to any one of claims 1 to 3, wherein the polyimide film has a thickness of from 100 nm to 1 μm. The resin laminated film according to any one of claims 1 to 4, wherein the (B) diamine derivative comprises the structure represented by the formula (1) or (2), (In the formulae (1) to (2), A represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, a fluorenyl group, or a divalent organic group having a carbon number of 1 to 5 which may be substituted by a halogen atom. Or a divalent organic group formed by linking two or more of them; and R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 10 carbon atoms and having at least one amine group. The resin laminated film according to any one of claims 1 to 5, wherein the acid dianhydride residue in the polyimine contained in the polyimide film A is mainly composed of an aromatic acid dianhydride residue ingredient. The resin laminated film according to claim 6, wherein the aromatic acid dianhydride residue is derived from pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride. The resin laminated film according to any one of claims 1 to 5, wherein the acid dianhydride residue in the polyimine contained in the polyimide film A is an alicyclic acid dianhydride residue The main component is either a main component of an aliphatic acid dianhydride residue or a total of an alicyclic acid dianhydride residue and an aliphatic acid dianhydride residue. The resin laminated film of claim 8, wherein the acid dianhydride residue in the polyimine contained in the polyimide film A is mainly composed of an alicyclic acid dianhydride residue or a lipid The total of the cyclic acid dianhydride residue and the aliphatic acid dianhydride residue as a main component, and the alicyclic acid dianhydride residue is a tetracarboxylic acid represented by any one of the formulas (3) to (6). Diacetate compound, The resin laminated film according to any one of claims 1 to 9, wherein the resin product The linear thermal expansion coefficient of the film is from -10 to 30 ppm/°C in the range of 50 ° C to 200 ° C. The resin laminated film according to any one of claims 1 to 10, wherein the resin laminated film has a glass transition temperature of 400 ° C or higher. The resin laminated film according to any one of claims 1 to 11, wherein the number of laminated layers of the resin laminated film is 2. The resin laminated film according to any one of claims 1 to 12, wherein, in the resin laminated film, the resin film other than the polyimide film comprises a polybenzazole resin, polyphenylene At least one resin of the group consisting of an azole resin, a polyamidoximine resin, and a polyamide resin. A laminate comprising a support substrate on the polyimide film A of the resin laminated film according to any one of claims 1 to 13. A TFT substrate provided with a TFT on the resin laminated resin film according to any one of claims 1 to 13. An organic EL element which is provided with an organic EL element on a resin laminated film according to any one of claims 1 to 13. A color filter provided with a color filter on the resin laminated film according to any one of claims 1 to 13. A method for producing a resin laminated film comprising at least the following steps (1) to (3): (1) a step of producing the following polyimide film A on a support substrate; and (2) a resin a step of further laminating a resin film on the film to form a resin laminated film; (3) irradiating ultraviolet light on the side of the self-supporting substrate, and peeling off the resin laminated film In the step of the polyimine resin film A, a polyimide film having a thickness of 100 nm is a polyimide film having a minimum light transmittance of less than 50% in a wavelength range of 300 to 400 nm. The method for producing a resin laminated film according to claim 18, wherein the resin film used in at least one of the steps (1) or (2) has a baking temperature of 400 ° C or higher. A method for producing a TFT substrate, comprising at least the following steps (1) to (4): (1) a step of producing the following polyimide film A on a support substrate; and (2) a resin film a step of further laminating a resin film to form a resin laminated film; (3) a step of forming a TFT on the resin laminated film; (4) a step of irradiating ultraviolet light on the side of the support substrate, and peeling off the resin laminated film, polyimine Resin film A: a polyimide film having a minimum transmittance of less than 50% in a wavelength range of 300 to 400 nm when it is a film having a thickness of 100 nm. A method for producing an organic EL device, comprising at least the following steps (1) to (4): (1) a step of producing the following polyimide film A on a support substrate; and (2) a resin a step of further laminating a resin film on the film to form a resin laminated film; (3) a step of forming an organic EL element on the resin laminated film; (4) a step of irradiating ultraviolet light on the side of the support substrate, and peeling off the resin laminated film, and a polyimide film A: a film having a thickness of 100 nm A polyimide film having a minimum transmittance of less than 50% in a wavelength range of 300 to 400 nm. A method for producing a color filter comprising at least the following steps (1) to (5): (1) producing the following polyimide film A on a support substrate; and (2) a step of further laminating a resin film on the resin film to form a resin laminated film; (3) a step of forming a black matrix on the resin laminated film; (4) a step of forming a color pixel on the resin laminated film; (5) The step of irradiating the support substrate side with ultraviolet light and peeling off the resin laminated film, the polyimine resin film A: as a film having a thickness of 100 nm, the minimum value of the light transmittance in the wavelength range of 300 to 400 nm is less than 50%. Polyimine resin film.