JP6746888B2 - Display support substrate, color filter using the same, manufacturing method thereof, organic EL element and manufacturing method thereof, and flexible organic EL display - Google Patents

Description

The present invention relates to a support substrate for a display, a color filter using the same, a manufacturing method thereof, an organic EL element and a manufacturing method thereof, and a flexible organic EL display.

Compared with glass, organic films are more flexible, less likely to break, and lighter in weight. Recently, studies on making a display flexible by forming a substrate of a flat panel display with an organic film have become active.

In general, examples of the resin used for the organic film include polyester, polyamide, polyimide, polycarbonate, polyether sulfone, acryl and epoxy. In particular, polyimide has higher heat resistance than other resins, as well as excellent mechanical properties such as high mechanical strength, abrasion resistance, dimensional stability, and chemical resistance, and excellent electrical properties such as insulation. Since it has both, the development of a flexible substrate using a polyimide film is being promoted.

Examples of the flexible substrate include a display substrate such as a flexible TFT (Thin Film Transistor) substrate, a flexible organic EL element substrate, and a flexible color filter substrate. The color filter is a member necessary for displaying a color on an organic electroluminescence display device or a liquid crystal display device using white light as a light source. A three-color color filter in which three colored pixels of a red colored pixel, a green colored pixel and a blue colored pixel are finely patterned is common. In the three-color filter, white is obtained by the additive color mixture of three colored pixels of red, green and blue.

The flat panel display substrate and the color filter substrate exemplified above are required to have high light transmittance in the visible light region. Further, in order to prevent deterioration of alignment accuracy due to heating at the time of forming display elements/light receiving elements such as TFTs and color filters, it is required that the coefficient of linear thermal expansion (CTE) is low and the substrate does not warp. Further, low birefringence is required in order to prevent color shift when viewed from an oblique direction and to suppress reflection of external light when using a circularly polarizing film.

As a transparent polyimide showing a high light transmittance in the visible light region, a polyimide comprising a fluorine-containing and/or alicyclic acid dianhydride and a fluorine-containing and/or alicyclic diamine is disclosed (for example, Patent Document 1-4).

Further, as a method of manufacturing an organic EL device having a small warp even if the difference in CTE is large, a shape retention layer is laminated on the side opposite to the high CTE layer laminated on the low CTE layer, and the shape retention layer is generated on both sides of the low CTE layer. There is disclosed a method of canceling the applied stress and suppressing the warp of the substrate (for example, refer to Patent Document 5). Further, as a flexible substrate having both low CTE and low birefringence, a polyimide prepared by a specific method using a specific dianhydride and diamine is disclosed. (For example, see Patent Document 6)

JP 2005-338394 A JP2012-146905A JP, 2008-045054, A JP, 2010-100674, A JP, 2013-157228, A JP, 2011-111596, A

When a transparent substrate is formed using a polyimide resin as described in Patent Documents 1 to 4, CTE shows a large value of 50 ppm/° C. or more. When a TFT or a color filter is manufactured using such a polyimide resin, there is a problem that a substrate is warped, alignment accuracy is poor, and it is difficult to manufacture a high-definition display.

Moreover, when an organic EL element is produced using such a polyimide resin, it is common to form an oxide or nitride of silicon as a gas barrier film on the polyimide. Generally, the CTE of silicon oxides and nitrides is as low as 3.5 ppm/°C. Therefore, in such a case, in addition to the above-mentioned problems, cracks and wrinkles are generated in the gas barrier film in the subsequent heating step due to the CTE difference between the polyimide resin and the gas barrier film, and deterioration of the organic EL element is likely to occur. There is a problem.

Further, in the method described in Patent Document 5, in order to suppress the warp of the substrate, it is necessary to attach the shape retention layer to the low CTE layer via the adhesive layer, which makes the manufacturing process complicated. There's a problem.

Further, Patent Document 6 discloses a method of obtaining a polyimide film having both low CTE and low birefringence by using a specific method using a specific acid anhydride and diamine, but the monomer is limited. Therefore, there is a problem that the degree of freedom in polymer design is rather low. In addition, low molecular compounds (imidizing agent, dehydration catalyst) are used for chemical imidization, but these compounds may cause degassing in the heating process during module manufacturing, which may cause defects. ..

In view of the above problems, the present invention can be applied to a color filter, an organic EL element, or the like without performing a complicated operation, can manufacture a high-definition display, has a small CTE, a small birefringence, and has flexibility. An object of the present invention is to provide a supporting substrate for a display provided.

That is, the present invention is a supporting substrate for a display having a layer B comprising a polysiloxane resin on one surface of the film A containing a polyimide resin, a support for a display which comprises an inorganic oxide particles to the membrane B The substrate.

According to the present invention, it can be applied to a color filter, an organic EL element, or the like without complicated operations, a high-definition display can be manufactured, CTE is small, birefringence is small, and flexibility is provided. A support substrate for a display can be provided.

Schematic perspective view for evaluation of flex resistance of color filters Schematic perspective view for evaluation of flex resistance of color filters Sectional view showing an example of a color filter Sectional drawing which shows an example of the array which consists of organic EL elements. Sectional drawing which shows an example of a flexible organic EL display.

Hereinafter, modes for carrying out the present invention will be described in detail. It should be noted that the present invention is not limited to the following embodiments and can be variously modified and implemented within the scope of the gist thereof.

The present invention relates to a display support substrate having a film B containing a polysiloxane resin on at least one surface of a film A containing a polyimide resin, wherein the film B contains inorganic oxide particles. Is.

Hereinafter, a structure having a film B containing a polysiloxane resin on at least one surface of a film A containing a polyimide resin, which is used for the supporting substrate for a display of the present invention, is referred to as a “resin laminate”.

The support substrate for a display here includes not only a substrate that supports the display itself, but also any support substrate that is used as a member that constitutes the display. For example, a black matrix, a color filter support substrate having colored pixels, a TFT, an electrode, an organic EL device support substrate having an organic layer, an electronic paper support substrate having an electrode, an ink layer, an electrode, a phosphor, etc. A supporting substrate for a plasma display having the above, an on-chip type supporting substrate having a color filter directly formed on an organic EL element, a supporting substrate for a sealing resin having a gas barrier film on the resin laminated body, and at least one surface of the resin laminated body. At least a touch screen support substrate having a transparent conductive layer, a touch device support substrate having a transparent conductive layer on at least one surface of the resin laminate, a circuit support substrate having some circuit formed on the resin laminate, and a resin laminate Examples thereof include a liquid crystal display support substrate having a liquid crystal layer on one side, an LED display support substrate having an LED element on at least one side of a resin laminate, and a see-through display support substrate in which the opposite side of the screen can be seen through.

In the supporting substrate for a display according to the present invention, at least one of the film containing a polyimide resin (film A) has a film containing a polysiloxane resin (film B), and the film containing a polysiloxane resin is an inorganic oxide. Since the material particles are included, even if the CTE of the polyimide is large, it is possible to reduce the CTE as a laminate. The linear expansion coefficient of the display support substrate is preferably 40 ppm/° C. or less. In this case, a color filter is formed on the opposite side of the display support substrate from the side in contact with the support substrate, or an organic layer is formed. When forming a gas barrier layer to form an EL element, a high-definition color filter or an organic EL element in which deterioration of the element is suppressed without deterioration of processing accuracy or generation of cracks in the gas barrier layer is produced. It is possible to

Further, .DELTA.N _A birefringence of the film A, it is preferable birefringence film B is (ΔN _A -ΔN _B) ≦ 0.065 when the .DELTA.N _B. In this case, for example, when an attempt is made to prevent reflection of external light by using a circularly polarizing film, the reflection can be suppressed predominantly, and the visibility of the display can be improved.

The thickness of the resin laminate in the present invention is not particularly limited, but the film thickness ratio of the film A and the film B is preferably film A/film B=25/1 to 1.5/1. Above all, it is more preferable that film A/film B=10/1 to 5/3. When the film thickness ratio of each layer is within the above range, it is possible to further reduce the CTE while maintaining the flexibility of the display support substrate.

Regarding the film thickness of each layer, from the viewpoint of transparency and low CTE, the film thickness of the film A is preferably 5.0 μm or more and 20 μm or less, and the film thickness of the film B is 0.2 μm or more and 3.0 μm or less. Preferably. From the viewpoint of transparency, the thickness of the entire laminate is preferably 5.0 μm or more and 20 μm or less.

The film thickness of the film A is more preferably 5.0 μm or more and 15 μm or less, and further preferably 5 μm or more and 10 μm or less. Within the above range, the transparent color tone of the display support substrate becomes better. The lower limit of the thickness of the film B is more preferably 0.4 μm or more, and the upper limit thereof is more preferably 2.0 μm or less. Within the above film thickness range, it is possible to produce a resin film laminate having a lower CTE, no warp of the substrate, and particularly excellent transparency and crack resistance.

The film thickness can be measured by observing the cross section with a scanning electron microscope (SEM). In the present invention, five points are set at intervals of 1 mm in the cross-sectional direction of the laminate, the measurement points are determined, the thickness of each layer is measured, and the average value is taken as the film thickness of each layer.

Further, the transparency of the resin laminate in the present invention is not particularly limited, but when the substrate is required to have transparency such as a color filter or a see-through display, the resin laminate is preferably transparent. The term “transparent” as used herein means that the resin laminate has a visible light transmittance of 65% or more at a wavelength of 400 nm. Since it has transparency in the visible light region, it can be effectively used for a flexible display substrate or the like that requires high transparency. The visible light transmittance at a wavelength of 400 nm is more preferably 75% or more. The visible light transmittance can be measured by forming the resin film laminate of the present invention on a glass substrate and using an ultraviolet-visible spectrophotometer.

<Polyimide resin>
In the present invention, the polyimide resin contained in the film A is not particularly limited, and a polyimide resin represented by the following general formula (11) can be generally used. This is obtained, for example, by subjecting a polyimide precursor resin represented by the following general formula (12) to imide ring closure (imidization reaction). The imidization reaction method is not particularly limited, and examples thereof include thermal imidization and chemical imidization. Among them, thermal imidization is preferable from the viewpoint of heat resistance of the polyimide resin film and transparency in the visible light region.

In general formulas (11) and (12), R ² represents a tetravalent organic group, and R ³ 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 alkylsilyl group having 1 to 10 carbon atoms.

Polyimide precursor resins such as polyamic acid, polyamic acid ester, and polyamic acid silyl ester can be synthesized by reacting a diamine compound with an acid dianhydride or a derivative thereof. Examples of the derivative include tetracarboxylic acid of the acid dianhydride, mono-, di-, tri-, or tetra-esters of the tetracarboxylic acid, acid chlorides, and the like, and specifically include a methyl group, an ethyl group, and n-propyl. Examples thereof include structures esterified with groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, and the like. The reaction method of the polymerization reaction is not particularly limited as long as the desired polyimide precursor resin can be produced, and a known reaction method can be used.

As a specific reaction method, a predetermined amount of all diamine components and a solvent are charged and dissolved in a reactor, then a predetermined amount of acid dianhydride component is charged, and stirred at room temperature to 80° C. for 0.5 to 30 hours. There is a method for doing so.

Known acid dianhydrides and diamines can be used for the synthesis of the polyimide precursor resin.

The acid dianhydride is not particularly limited, and examples thereof include aromatic acid dianhydride, alicyclic acid dianhydride, and aliphatic acid dianhydride.

As the aromatic dianhydride, 4,4′-oxydiphthalic anhydride, pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis( 4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid Dianhydride, 3,3',4,4'-terphenyltetracarboxylic dianhydride, 3,3',4,4'-oxyphthalic dianhydride, 2,3,3',4'-oxyphthal Acid dianhydride, 2,3,2′,3′-oxyphthalic dianhydride, diphenylsulfone-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-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-dihydroisobenzfuran -5-carboxylic acid) 1,4-phenylene-2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,3 6,7-Naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4 ,9,10-Perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyl) Oxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2 ,2'-bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2'-bis[(Zical Boxyphenoxy)phenyl]hexafluoropropane dianhydride, 9,9′-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride or an aromatic group thereof having an alkyl group, an alkoxy group or a halogen atom. Examples thereof include, but are not limited to, substituted acid dianhydride compounds.

As the alicyclic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-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, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3 ,4,5-Tetrahydrofuran tetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic acid 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[4,3,4] 0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,4] 0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[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 Acid dianhydride, bicyclo[2,2,1]heptanetetracarboxylic acid dianhydride, bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic acid dianhydride, 7- Oxabicyclo[2,2,1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene- 1,2,8,9-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-oxydicyclohexanetetracarboxylic Acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic sunanhydride, and "Ricacid" BT-100 ( As mentioned above, trade names, manufactured by Shin Nippon Rika Co., Ltd. and their derivatives, or these Examples thereof include acid dianhydride compounds having an alicyclic ring substituted with an alkyl group, an alkoxy group, a halogen atom and the like, but are not limited thereto.

Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-pentanetetracarboxylic acid dianhydride and derivatives thereof, It is not limited to these.

These aromatic dianhydrides, alicyclic dianhydrides, or aliphatic dianhydrides can be used alone or in combination of two or more.

Among these, from the viewpoints of being commercially available and easily available, and from the viewpoint of reactivity, pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′, 4,4'-oxyphthalic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride ,2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride Preference is given to using the anhydride.

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

As the aromatic diamine compound, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylmethane 4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 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-naphthalene Diamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis(4-aminophenoxy) Biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis[3 -(3-Aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4-aminophenyl-4-aminobenzenesulfonate, 3- Aminophenyl-4-aminobenzenesulfonate, 1,4-phenylene-bis(4-aminobenzenesulfonate) or a diamine compound in which an aromatic ring thereof is substituted with an alkyl group, an alkoxy group, a halogen atom or the like can be given. However, the present invention is not limited to these.

As the alicyclic diamine compound, cyclobutanediamine, isophoronediamine, bicyclo[2,2,1]heptanebismethylamine, tricyclo[3,3,1,13,7]decane-1,3-diamine, 1,2 -Cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, trans-1,4-diaminocyclohexane, 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-aminocyclohexyl)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-4,4 Examples thereof include, but are not limited to,'-diaminodicyclohexyl)propane and diamine compounds obtained by substituting an alicyclic ring with an alkyl group, an alkoxy group, a halogen atom or the like.

Examples of the aliphatic diamine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane. , Alkylenediamines such as 1,9-diaminononane and 1,10-diaminodecane, ethylene glycol diamines such as bis(aminomethyl)ether, bis(2-aminoethyl)ether and bis(3-aminopropyl)ether, And siloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane Examples include, but are not limited to, diamines.

These aromatic diamines, alicyclic diamines, or aliphatic diamines can be used alone or in combination of two or more.

The polyimide resin of the supporting substrate for a display used for a color filter or a touch screen is required to have heat resistance, low water absorption and high transparency in the visible light region. It is preferable that the component has a trifluoromethyl group as a bulky fluorine substituent or an alicyclic monomer component. That is, it is preferable that the polyimide resin has at least one group selected from a trifluoromethyl group and an alicyclic hydrocarbon group. Further, in order to impart low water absorption, it is preferable that the acid dianhydride or diamine component has a trifluoromethyl group. The trifluoromethyl group-containing monomer and the alicyclic monomer component may be used for both the acid dianhydride and the diamine component, or may be used for one of them, but it is preferable to use the diamine component from the viewpoint of availability of the monomer. preferable. Further, in order to exhibit sufficient transparency and low water absorption, it has at least one group selected from a trifluoromethyl group and an alicyclic hydrocarbon group with respect to the total amount of diamine residues contained in the polyimide resin. It is preferable that the diamine residue is contained in an amount of 50 mol% or more.

In this case, 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-(hexafluoro) Isopropylidene)diphthalic anhydride (6FDA), 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), 1,2,3,4-cyclobutanetetracarboxylic acid It is preferable to include dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (PMDA-H). As diamine, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HFHA), trans-1,4-diaminocyclohexane (t-DACH), 2,2′ -Bis(trifluoromethyl)benzidine (TFMB) is preferred.

On the other hand, the polyimide resin of the display support substrate used for the organic EL element is required to have heat resistance and low water absorption. As the acid dianhydride in this case, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 4,4′-oxydiphthalic anhydride (ODPA), 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride (PMDA-H), 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), 4,4'-(hexafluoroisopropyl) Ridene) diphthalic anhydride (6FDA) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) are preferably contained, and the diamine is 4,4′-diaminodiphenyl ether or p-phenylenediamine. , 3,3′-Dimethylbenzidine, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HFHA), trans-1,4-diaminocyclohexane, 2,2 It is preferred to include'-bis(trifluoromethyl)benzidine (TFMB). Further, since it is required to be transparent when extracting light from the display supporting substrate side, when extracting light from the display supporting substrate side, a trifluoromethyl group or an alicyclic monomer component is added to the acid dianhydride or diamine component. It is effective to introduce The acid dianhydride in this case is 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2-bis(4- (3,4-Dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), 4,4′-oxydiphthalic anhydride (ODPA), 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) , 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride (CBDA) is preferable. As diamine, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HFHA), trans-1,4-diaminocyclohexane, 2,2′-bis(trifluoro) It is preferred to include methyl)benzidine (TFMB).

As a particularly preferable polyimide resin, a polyimide containing as a main component at least one of the repeating structural units represented by the general formulas (1) to (3) can be mentioned.

In general formulas (1) to (3), R ¹ is at least one kind of groups represented by (4) to (9).

Here, the main component means that the structural units represented by the general formulas (1) to (3) have 50 mol% or more of all the structural units of the polymer. By having the structure represented by the general formulas (1) to (3) in the diamine portion of the polyimide, it is possible to improve low water absorption, transparency, and heat resistance of the polyimide resin. In addition, a polyimide resin having high heat resistance and good flexibility can be obtained by having an aromatic or alicyclic acid anhydride represented by the general formulas (4) to (9) in the acid anhydride portion. It is possible.

Further, as a particularly preferable polyimide resin, a polyimide containing a repeating structural unit represented by the general formula (10) as a main component can be mentioned.

In the general formula (10), R ¹ is at least one kind of groups represented by (4) to (9).

Here, the main component means that the structural unit represented by the general formula (10) has 50 mol% or more of all the structural units of the polymer.

By having the structure represented by the general formula (10) at the diamine portion of the polyimide, it is possible to improve the transparency and heat resistance of the polyimide resin. In addition, a polyimide resin having high heat resistance and good flexibility can be obtained by having an aromatic or alicyclic acid anhydride represented by the general formulas (4) to (9) in the acid anhydride portion. It is possible.

Both ends of the polyimide and the polyimide precursor resin may be capped with a capping agent in order to adjust the molecular weight to a preferable range. Examples of the terminal blocking agent that reacts with the acid dianhydride include monoamines and monohydric alcohols. Examples of the terminal blocking agent that reacts with the diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds, dicarbonic acid esters, vinyl ethers and the like. Moreover, various organic groups can be introduced as terminal groups by reacting the terminal blocking agent.

Examples of monoamines used as the acid anhydride group terminal sealing agent include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, and 1-hydroxy-7-amino. Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino -7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene , 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy- 4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-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, amide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline , 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto- 4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mer Capto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercapto Naphthalene, 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-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene However, the present invention is not limited to these.

Examples of the monohydric alcohol used as a sealant for the acid anhydride group end 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-nonanol, 2-nonanol, 1- Decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2- Pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-icosanol , 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, isononyl alcohol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether. , Propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norboneol, terpineol, etc. However, the present invention is not limited to these.

Acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as amino group terminal sealing agents include phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3- Acid anhydrides such as 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-carboxynaphthalene, 1- Hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxy Naphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynyl Benzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2 -Ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1- Naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6- Monocarboxylic acids such as ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds obtained by acid chloride of these carboxyl groups, and terephthalic acid and phthalic acid. , Maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxyna Phthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, Monoacid chloride compounds in which only monocarboxylic groups of dicarboxylic acids such as 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene are converted into acid chlorides, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5 And active ester compounds obtained by reaction with norbornene-2,3-dicarboximide.

Examples of the dicarbonate ester compound used as the amino group terminal sealant include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

Examples of the vinyl ether compound used as a sealing agent for the amino group terminal include tert-butyl chloroformate, -n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, isopropyl chloroformate and the like. Isocyanate compounds such as chloroformates, butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, 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, tert-butyl vinyl ether, benzyl vinyl ether and the like.

Other compounds used as a sealing agent for the amino group terminal include benzyl chloroformate, benzoyl chloride, fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, allyl chloroformate, methanesulfonic acid chloride, Examples thereof include p-toluenesulfonic acid chloride and phenyl isocyanate.

The introduction ratio of the sealing agent at the acid anhydride group terminal is preferably in the range of 0.1 to 60 mol %, particularly preferably 0.5 to 50 mol% with respect to the acid dianhydride component. The introduction ratio of the amino group end capping agent is preferably in the range of 0.1 to 100 mol %, particularly preferably 0.5 to 70 mol% with respect to the diamine component. A plurality of different end groups may be introduced by reacting a plurality of end capping agents.

The polyimide precursor resin or the terminal blocking agent introduced into the polyimide resin can be easily detected by the following method. For example, by dissolving the polymer into which the terminal blocking agent is introduced into an acidic solution and decomposing it into an amine component and an acid anhydride component, which are the constitutional units of the polymer, and subjecting this to gas chromatography (GC) or NMR measurement, The end-capping agent can be easily detected. In addition, the polymer into which the terminal blocking agent has been introduced can also be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum, ¹ H NMR spectrum measurement and ¹³ C NMR spectrum measurement.

<Thermal crosslinking agent>
The film A may contain a thermal crosslinking agent. The thermal crosslinking agent is preferably an epoxy compound or a compound having at least two alkoxymethyl groups or methylol groups. By having at least two of these groups, a cross-linked structure is formed by condensation reaction with the resin and the same type of molecule, and the mechanical strength and chemical resistance of the cured film after heat treatment can be improved.

Preferred examples of the epoxy compound include epoxy group-containing silicones such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl), and siloxane. However, the present invention is not limited thereto. Specifically, Epiclon 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514,. Epiclon EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (these trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Rekaresin BEO-60E, Rekaresin BPO-20E, lycaredine HBE-100, lycaredine DME-100 (trade name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA CORPORATION), PG-100, CG-500, EG-200 (all trade names, manufactured by Osaka Gas Chemicals Co., Ltd.), NC-3000, NC-6000 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (trade name, manufactured by Printec Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085 (trade name, Daicel Chemical Industries, Ltd.). Manufactured).

Examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, 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 (trade names, 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, brand name, Sanwa Chemical Co., Ltd. make) are mentioned. You may contain 2 or more types of these.

The thermal crosslinking agent is preferably contained in 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin.

<Coupling agent>
A coupling agent such as a silane coupling agent or a titanium coupling agent can be added to the film A in order to improve the adhesion to the substrate. The coupling agent is preferably contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin.

<Inorganic filler>
The film A may contain an inorganic filler. Examples of the inorganic filler include silica fine particles, alumina fine particles, titania fine particles, and zirconia fine particles. The shape of the inorganic filler is not particularly limited, and examples thereof include spherical shape, elliptical shape, flat shape, rod shape, and fibrous shape. The contained inorganic filler preferably has a small particle size in order to prevent light scattering. The average particle size is 0.5 to 100 nm, preferably 0.5 to 30 nm, and the inorganic filler is preferably contained in 1 to 100 parts by weight with respect to 100 parts by weight of the resin. By adding 1 to 100 parts by weight of the inorganic filler having the above particle size range to 100 parts by weight of the resin, it is possible to reduce the CTE and birefringence of the polyimide resin without impairing the flexibility.

<Polysiloxane resin>
In the present invention, the polysiloxane resin contained in the film B is not particularly limited. When the polysiloxane resin composition used for forming the film B is non-photosensitive or positive-type photosensitive, it is preferable to have a phenyl group or a naphthyl group from the viewpoint of storage stability of the coating liquid, and from the viewpoint of chemical resistance. Those having an epoxy group or an amino group are preferable. Further, when the polysiloxane resin composition used for forming the film B is negative-type photosensitive, from the viewpoint of storage stability of the coating liquid, those having a phenyl group or a naphthyl group are preferable, and from the viewpoint of curability ( Those having a (meth)acrylic group or a vinyl group are preferable, and those having a carboxyl group or a phenolic hydroxyl group are preferable from the viewpoint of pattern processability.

As a method for synthesizing a polysiloxane resin, a method of hydrolyzing and condensing an organosilane compound is generally used. Examples of the organosilane compound used in the synthesis of polysiloxane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and phenyl. Trimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 2-naphthyltriethoxysilane, 4-hydroxyphenyl Trimethoxysilane, 4-hydroxyphenyltriethoxysilane, 4-hydroxybenzyltrimethoxysilane, 4-hydroxybenzyltriethoxysilane, 2-(4-hydroxyphenyl)ethyltrimethoxysilane, 2-(4-hydroxyphenyl)ethyl Triethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane Silane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β- Glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β- Glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane Orchid, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltri Propoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4- Epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane Silane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropyl Methyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glyce Sidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetra Ethoxysilane, methyl silicate, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyl Ropyltriethoxysilane, 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilyl Phosphoric acid, 4-dimethylmethoxysilylphosphoric acid, 4-dimethylethoxysilylvaleric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 5-dimethylmethoxysilylvaleric acid, 5-dimethylethoxysilylvaleric acid , 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, 3-dimethylethoxysilylpropyl succinic anhydride, 3-trimethoxysilyl Propylcyclohexyldicarboxylic acid anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-trimethoxysilylpropylphthalate Acid anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethylethoxysilylpropylphthalic anhydride, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxy Silane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ -Acryloylpropylmethyldimethoxysilane or γ-acryloylpropylmethyldiethoxysilane.

The conditions for the hydrolysis reaction of the organosilane compound may be appropriately set. For example, after adding the acid catalyst and water to the organosilane compound in a solvent over 1 to 180 minutes, the reaction is performed at room temperature to 110°C for 1 to 180 minutes. Preferably. By carrying out the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is preferably 30 to 105°C. Further, the hydrolysis reaction is preferably performed in the presence of an acid catalyst. The acid catalyst is preferably an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid. The content of these acid catalysts is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of all the organosilane compounds used in the hydrolysis reaction. By setting the content of the acid catalyst within the above range, the hydrolysis reaction can be easily controlled so that the hydrolysis reaction is necessary and sufficient. As conditions for the condensation reaction, it is preferable to obtain the silanol compound by the hydrolysis reaction of the organosilane compound and then heat the reaction solution as it is at 50° C. to the boiling point of the solvent for 1 to 100 hours. Further, reheating or addition of a base catalyst may be performed in order to increase the degree of polymerization of polysiloxane. In addition, after the hydrolysis reaction, an appropriate amount of the produced alcohol or the like may be distilled and removed by heating and/or reduced pressure, if desired, and then an optional solvent may be added.

The weight average molecular weight (Mw) of the polysiloxane resin contained in the film B is preferably 1,000 to 100,000 in terms of polystyrene measured by GPC. By setting the Mw within the above range, the coating properties and the solubility in the developing solution at the time of pattern formation are improved.

<Inorganic oxide particles>
The film B containing the polysiloxane resin contains inorganic oxide particles. By containing the inorganic oxide particles, the CTE of the film B can be lowered, and by forming the film B on at least one of the films A, the CTE of the resin laminate can be lowered.

The number average particle diameter of the inorganic oxide particles is preferably 1 to 200 nm, and more preferably 1 to 70 nm in order to obtain a cured film having high transmittance. Here, the number average particle diameter of the inorganic oxide particles can be calculated as follows. The surface of the film B is observed with a SEM (scanning electron microscope) at a magnification of 10,000 times, and the image of the particles is connected to an image analyzer (for example, QTM900 manufactured by Cambridge Instruments). Data is taken in at different observation points, and when the total number of particles reaches 5000 or more, the following numerical processing is carried out, and the number average diameter d thus obtained is taken as the average particle diameter (diameter).

d=Σdi /N
Here, di is the equivalent circular diameter of the particle (diameter of a circle having the same area as the cross-sectional area of the particle), and N is the number.

There are various types of inorganic oxides, and they are not particularly limited, but are preferably silicon oxide (silica), hollow silica, aluminum oxide (alumina), titanium oxide, antimony oxide, zinc oxide, tin oxide, zirconium oxide. Etc. are used. Of these, silicon dioxide is preferred from the viewpoints of transparency when dispersed in a polysiloxane resin, CTE reduction, price, and availability.

One kind or two or more kinds of these inorganic oxides are appropriately selected and used. The form of the inorganic oxide to be added is not particularly limited, but a form such as powder or sol is preferable.

The inorganic oxide particles can be pulverized or dispersed by procuring an appropriate nanoparticle powder and using a dispersing machine such as a bead mill. Examples of commercially available nanoparticle powders include REA200, RA200SH, RA200H (silica; manufactured by Nippon Aerosil Co., Ltd.), T-BTO-020RF (barium titanate; manufactured by Toda Kogyo Co., Ltd.), UEP-100 (zirconium oxide; Daiichi Rare Element Chemical Industry Co., Ltd.) or STR-100N (titanium oxide; manufactured by Sakai Chemical Industry Co., Ltd.). It can also be procured as a dispersion. As silica particles, IPA-ST and MIBK-ST having a number average particle diameter of 12 nm, IPA-ST-L having a number average particle diameter of 45 nm, IPA-ST-ZL having a number average particle diameter of 100 nm, and PGM- having a number average particle diameter of 15 nm. ST (above, trade name, manufactured by Nissan Chemical Industries, Ltd.), "Oscar (registered trademark)" 101 having a number average particle size of 12 nm, "Oscar" 105 having a number average particle size of 60 nm, "Oscar" having a number average particle size of 120 nm "106, "Cataloid (registered trademark)" having a number average particle size of 5 to 80 nm-S (above, trade name, manufactured by Catalysts & Chemicals Co., Ltd.), "Quatron (registered trademark)" PL- having a number average particle size of 16 nm. 2L-PGME, “Quatron” PL-2L-BL with a number average particle size of 17 nm, “Quatron” PL-2L-DAA, “Quatron” PL-2L with a number average particle size of 18 to 20 nm, GP-2L (above, product Name: Fuso Chemical Industry Co., Ltd.), silica (SIO ₂ ) SG-SO100 (trade name, manufactured by Kyoritsu Material Co., Ltd.) having a number average particle diameter of 100 nm, and “Roleoseal (registered trademark) having a number average particle diameter of 5 to 50 nm. )” (trade name, manufactured by Tokuyama Corp.) and the like. Further, “Thruria” 4110, which is a hollow silica particle having a number average particle diameter of 60 nm, can be mentioned. Examples of the silicon oxide-titanium oxide particles include “Optlake” (registered trademark) TR-502, “Optlake” TR-503, “Optlake” TR-504, “Optlake” TR-513, and “Optlake”. "TR-520,"Optraque" TR-527, "Optlake" TR-528, "Optlake" TR-529, "Optlake" TR-544 or "Optlake" TR-550 (all are JGC Catalysis Industrial Co., Ltd. is mentioned. As zirconium oxide, for example, Bairar Zr-C20 (average particle size = 20 nm; manufactured by Taki Chemical Co., Ltd.), ZSL-10A (average particle size = 60-100 nm; manufactured by Daiichi Rare Element Co., Ltd.), Nanouse OZ -30M (average particle size = 7 nm; manufactured by Nissan Chemical Industries, Ltd.), SZR-M or SZR-K (all manufactured by Sakai Chemical Co., Ltd.) or HXU-120JC (manufactured by Sumitomo Osaka Cement Co., Ltd.). To be

The content of the inorganic oxide particles is not particularly limited, but is preferably in the range of 20 to 80% by weight in the film B. Further, from the viewpoint of crack resistance, 20 to 65% by weight is more preferable. When the content is within this range, cracking of the film B can be further suppressed, and the CTE of the laminated body can be further reduced.

<Polysiloxane resin composition used for forming film B>
The solid content concentration of the polysiloxane resin composition used for forming the film B is preferably 5 to 35 wt% because the film thickness can be easily controlled.

The polysiloxane resin composition may contain a photosensitizer. By sensitizing the polysiloxane resin composition, it is possible to obtain a resin laminate comprising the films A and B by patterning the same at once by exposure and development. More specifically, the photosensitive polysiloxane resin composition for forming the film B'is applied onto the film A'(a film containing a polyimide precursor resin), and the pattern is processed by exposing, developing and curing. A film A and a film B can be obtained. When the photosensitive resin composition is a positive type, a quinonediazide compound is preferable as a component that imparts photosensitivity. The mixture of the quinonediazide compound and the alkali-soluble resin forms a positive type by exposure and alkali development. The quinonediazide compound is preferably a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid ester-bonded thereto, and hydrogen or the following general formula (13) is independently present at the ortho position and the para position of the phenolic hydroxyl group of the compound. A compound having a substituent represented by is used.

R ^{4 to} R ^{6, which} may be the same or different, each represents an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group, or R ⁴ and R ⁵ , R ⁴ And R ⁶ or R ⁵ and R ⁶ may form a ring.

In the substituent represented by the general formula (13), R ^{4 to} R ⁶ may be the same or different, and a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. Indicates either Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group. Group, a trifluoromethyl group or a 2-carboxyethyl group. A hydroxyl group is mentioned as a substituent which substitutes the hydrogen of a phenyl group. Moreover, examples of the ring formed by R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

When the ortho and para positions of the phenolic hydroxyl group are other than hydrogen or a substituent represented by the general formula (13), oxidative decomposition occurs by thermosetting to form a conjugated compound represented by a quinoid structure, and a cured film. Will be colored and the transparency will be reduced. The quinonediazide compound can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.

Examples of the compound having a phenolic hydroxyl group include the following compounds (manufactured by Honshu Chemical Industry Co., Ltd.).

Examples of the naphthoquinone diazide sulfonic acid include 4-naphthoquinone diazide sulfonic acid and 5-naphthoquinone diazide sulfonic acid. The 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region and is therefore suitable for i-line exposure. Further, the 5-naphthoquinonediazide sulfonic acid ester compound has absorption in a wide wavelength range, and is therefore suitable for exposure in a wide wavelength range. It is preferable to appropriately select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.

300-1500 are preferable and, as for the molecular weight of a naphthoquinone diazide compound, 350-1200 are more preferable. If the molecular weight of the naphthoquinonediazide compound is larger than 1500, pattern formation may not be possible with an addition amount of 4 to 10% by weight. On the other hand, when the molecular weight of the naphthoquinonediazide compound is less than 300, the colorless transparency may decrease.

When the photosensitive polysiloxane composition is a negative type, a photopolymerization initiator and a polyfunctional monomer are preferable as the component that imparts photosensitivity.

The photopolymerization initiator that is a component that imparts photosensitivity is preferably one that decomposes and/or reacts with light (including ultraviolet rays and electron beams) to generate radicals. Examples of the photopolymerization initiator that decomposes and/or reacts with light to generate a radical include, for example, 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-dimethylamino- 2-(4-Methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1,2,4,6-Trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethyl Pentyl)-phosphine oxide, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl) Oxime)], 1-phenyl-1,2-butadion-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, Ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone , Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'- Methyl-diphenyl sulfide, alkylated benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 4-benzoyl-N,N-dimethyl -N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N , N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3-(3,3. 4-Dimethyl-9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2,2'-bis(o-chlorophenyl)-4,5,4 ',5'-Tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester , Η5-cyclopentadienyl-η6-cumenyl-iron(1+)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis(η5-2,4-cyclopentadien-1-yl)-bis(2, 6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2, 3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyldichloroacetophenone, benzylmethoxyethylacetal, anthraquinone, 2-t. -Butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis( p-azidobenzylidene)-4-methylcyclohexanone, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenyl sulfone, benzoyl peroxide or eosin or Photoreducing dyes such as methylene blue and ascorbic acid Examples include a combination with a reducing agent such as triethanolamine. Moreover, you may contain 2 or more types of these. In order to further enhance the curability of the cured film, an α-aminoalkylphenone compound, an acylphosphine oxide compound, an oxime ester compound, a benzophenone compound having an amino group or a benzoic acid ester compound having an amino group is preferable.

Examples of the α-aminoalkylphenone compound include 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-. (4-morpholin-4-yl-phenyl)-butan-1-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide or bis(2,6-dimethoxybenzoyl)-(2 , 4,4-Trimethylpentyl)-phosphine oxide. Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O- Benzoyl oxime)], 1-phenyl-1,2-butadion-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime or ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime). Examples of the benzophenone compound having an amino group include 4,4-bis(dimethylamino)benzophenone and 4,4-bis(diethylamino)benzophenone. Examples of the benzoic acid ester compound having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate or ethyl p-diethylaminobenzoate.

Examples of the polyfunctional monomer that is a component that imparts photosensitivity include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylol. Propane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4- Butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetra Pentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, penta Pentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2- Methacryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-methacryloyloxyethoxy)-3-methylphenyl]fluorene, (2-acryloyloxypropoxy)-3-methylphenyl]fluorene Ren, 9,9-bis[4-(2-acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene or 9,9-bis[4-(2-methacryloyloxyethoxy)-3,5-dimethylphenyl] Fluorene, but from the viewpoint of improving sensitivity, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate or tripentaerythritol octaacrylate is preferable, and from the viewpoint of improving hydrophobicity. , Dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene are preferred.

Examples of other polyfunctional monomers include epoxy (meth)acrylates obtained by reacting a polyfunctional epoxy compound with (meth)acrylic acid. Examples of the polyfunctional epoxy compound include the following compounds.

The 3% weight loss temperature (Td3) of the film B used in the present invention is preferably 300°C or higher. As a result, degassing is suppressed, for example, when a gas barrier film is formed on the resin laminate of the present invention, cracking in the gas barrier film due to degassing is suppressed, and the display performance of the display is improved. The 3% weight loss temperature (Td3) referred to here means that the adsorbed water of the sample is removed by raising the temperature to 150° C. at a heating rate of 3.5° C./min in the first step, and the temperature is lowered in the second step. It was cooled to 40° C. at a rate of 10° C./min, and the weight when cooled to 40° C. was measured. When the weight was measured at the temperature rising rate of 10° C./min in the third step, the weight was 3%. It means the temperature when it decreases by %.

<Transmission chromaticity coordinates of film B>
The transmission chromaticity coordinates of the resin layer of the film B are preferably in the range of 0.300≦x≦0.325 and 0.305≦y≦0.325. Thereby, the transmitted light visually recognized through the resin laminate can have a color tone close to white. This transmission chromaticity coordinate is more preferably in the range of 0.300≦x≦0.310 and 0.305≦y≦0.315. Here, the “transmissive chromaticity coordinates” refer to the coordinates of the transparent chromaticity in the CIE1931 color system measured with a C light source and a 2-degree visual field.

<Colorant>
The resin layer of the film B preferably contains a coloring agent in order to set the transmission chromaticity coordinate within the above range. Examples of the colorant include organic pigments, inorganic pigments, and dyes, and blue pigments, blue dyes, violet pigments, or violet dyes are preferable for adjusting the color tone of transmitted light.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 or 79, but C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 or 60 is preferable, and C.I. I. Pigment Blue 15:6 is more preferable.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 or 50, and C.I. I. Pigment Violet 19 or 23 is preferable, and C.I. I. Pigment Violet 23 is more preferable.

These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment or basic treatment, if necessary, and a pigment derivative may be added as a dispersant.

Examples of the form of the dye include those having any form of various dyes such as an oil-soluble dye, an acid dye, a direct dye, a basic dye, a mordant dye, and an acid mordant dye. Further, the dye may be used in the form of lake, or may be in the form of a salt-forming compound of the dye and a nitrogen-containing compound.

The dye is not particularly limited as long as it is generally called a dye, but among them, triphenylmethane dye, diphenylmethane dye, quinoline dye, thiazine dye, thiazole dye, xanthene dye, flavin Series dyes, auramine series dyes, safranine series dyes, phloxine series dyes, methylene blue series dyes, rhodamine series dyes and the like can be preferably used. Specifically, C.I. I. Solvent Blue 2, 3, 4, 5, 718, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59:1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139, 143, C. I. Acid Blue 22, 25, 40, 78, 78, 92, 113, 129, 167, 230, C.I. I. Basic Blue 3, 7, 9, 17, 41, 66, C.I. I. Solvent Violet 2, 8, 9, 11, 13, 14, 21, 21:1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60, 61, C.I. I. Acid Red 52, 87, 91, 92, 94, 289 and the like.

In the case of a basic dye, it is preferably a salt-forming compound that is salified by using an organic acid or perchloric acid. The organic acid is preferably organic sulfonic acid or organic carboxylic acid. Of these, naphthalenesulfonic acid such as tobiasic acid and perchloric acid are preferable in terms of resistance.

In the case of an acid dye or a direct dye, a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., and a resin component having these functional groups were used for salinization. From the viewpoint of resistance, a salt-forming compound or a salt-forming compound obtained by sulfonamidation into a sulfonic acid amide compound is preferable.

These colorants may be used alone, but it is preferable to use two or more kinds in combination because it is easy to bring transmitted light close to white. Examples of the combination of colorants include C.I. I. Pigment Blue 15:6, C.I. I. Pigment Violet 23, C.I. A combination of colorants selected from the group consisting of I Acid Red 289 is preferred.

In addition to these blue pigment, blue dye, violet pigment or violet dye, the film B may contain other pigments or dyes for adjusting the transmission tone more accurately. Examples of other pigments include red pigments, green pigments, yellow pigments, and orange pigments.

The proportion of the colorant in the film B is preferably 0.0001 to 10% by weight, more preferably 0.001 to 1% by weight, based on the solid content, because the color tone can be easily adjusted.

The film B preferably contains a pigment derivative or a polymer dispersant as a dispersant.

<Production of resin laminate>
The method for producing the resin laminate of the present invention is not particularly limited, but preferably includes the following steps.
(1) A step of applying a resin solution containing a polyimide precursor resin on a supporting substrate to obtain a film A′.
(2) A step of applying a polysiloxane resin composition on the film A′ to obtain a film B′.
(3) A step of heating the film A′ and the film B′ to obtain a resin laminate.

Each step will be described. First, in the step (1), the supporting substrate is not particularly limited, but non-alkali glass, silicon wafer, ceramics, gallium arsenide, soda lime glass, etc. can be used.

The coating method includes, for example, a slit coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and the like, and these methods may be combined and coated.

Next, the solvent in the resin varnish is removed by drying. For drying, a hot plate, oven, infrared ray, vacuum chamber or the like is used. When a hot plate is used, the object to be heated is heated directly on the plate or on a jig such as a proxy pin installed on the plate. As the material of the proxy pin, there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or "Teflon" (registered trademark), and the proxy pin of any material may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer that is the object to be heated, the purpose of heating, etc., but for example, heating the resin layer applied on a glass substrate of 300 mm × 350 mm × 0.7 mm. In that case, the height of the proxy pin is preferably about 2 to 12 mm.

Above all, it is preferable to perform vacuum drying using a vacuum chamber, and it is more preferable to further perform heating for drying after vacuum drying, or to perform heating for drying while vacuum drying. As a result, the drying treatment time can be shortened and a uniform coating film can be obtained. The heating temperature for drying varies depending on the type and purpose of the object to be heated, and it is preferable to perform heating in the range of room temperature to 170° C. for 1 minute to several hours. Room temperature is usually 20 to 30°C, preferably 25°C. Further, the drying step may be performed multiple times under the same condition or different conditions. In this way, the film A'is formed.

Subsequently, in the step (2), the polysiloxane resin composition is applied onto the film A'by the same method as that of the film A', and a drying step is performed to form the film B'on the film A'.

Next, in the step (3), the resin coating film is heated in a range of 180° C. or higher and 500° C. or lower to obtain a resin laminate including the film A and the film B. Note that the heating step may be performed after some step after the drying step.

The atmosphere of the heating step is not particularly limited, and may be air or an inert gas such as nitrogen or argon. However, if heating is performed in an atmosphere with a high oxygen concentration, mechanical properties are deteriorated, such as the film A and the film B becoming brittle due to oxidative deterioration. In order to suppress such deterioration of mechanical properties, it is preferable to perform heat curing by heating in an atmosphere having an oxygen concentration of 5% or less. On the other hand, it is often difficult to manage the oxygen concentration in the ppm order at the manufacturing site. The resin film of the present invention is preferable if the oxygen concentration during heating is 5% or less because higher mechanical properties can be maintained.

When the resin composition used for forming the film B′ is a photosensitive resin composition and patterning is performed after forming the coating film B′, the film B′ is exposed and exposed after the step of obtaining the film B′. A step of developing can be added. Using a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), or other exposure device, the light of 10 mJ/m ² or more and 1000 mJ or less/m ² or less (wavelength 365 nm exposure amount conversion) is used as a desired mask. Irradiate with or without. The light source is not limited, and ultraviolet rays such as i-ray, g-ray, and h-ray, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

Next, the unexposed area or the exposed area can be dissolved by development to form a pattern. As a developing method, it is preferable to immerse in a developing solution for 5 seconds or more and 10 minutes or less by a method such as showering, dipping or paddle.

As the developing solution, a known alkaline developing solution can be used. Specific examples thereof include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-dimethylaminoethanol, monoethanolamine and diethanolamine, and tetramethylammonium. Examples include aqueous solutions containing one or more quaternary ammonium salts such as hydroxide and choline. After development, it is preferable to rinse with water, and then dry baking can be performed at a temperature of 50° C. or higher and 150° C. or lower.

The above-described laminated body composed of the film A containing the polyimide resin and the film B containing the polysiloxane resin may be produced through the following two-stage film forming process. First, as a step (1), a resin solution containing a polyimide precursor resin is applied on a supporting substrate, and then heating is performed as a step (3) to form a film A. Then, in the step (2), the polysiloxane resin composition is applied onto the film A, and heating is performed in the step (3) as in the case of the first layer.

The resin laminate described above is used as a display support substrate applicable to color filters, organic EL elements, on-chip type substrates, sealing resins, touch panels, circuit boards, liquid crystal panels, PDP panels, electronic paper, see-through displays, and the like. Used.

The linear thermal expansion coefficient (CTE) of the resin laminate of the present invention is preferably 40 ppm/° C. or less. This not only can reduce the amount of BM misalignment when creating a color filter, but can also prevent cracks from forming in the gas barrier layer when the gas barrier layer is formed on the present resin laminate, The display performance of the display can be improved. More preferably, the coefficient of linear expansion (CTE) is 35 ppm/° C. or less.

The linear expansion coefficient here means that the adsorbed water of the sample is removed by raising the temperature to 150° C. at the temperature rising rate of 5° C./min in the first stage, and air cooling to room temperature at the temperature lowering rate of 5° C./min in the second stage. Then, in the third stage, the main measurement is performed at a temperature rising rate of 5° C./min, and indicates a value obtained from the average of linear expansion coefficients of 50 to 200° C.

<Color filter>
When the resin laminate is used for a color filter, it is a color filter including at least a black matrix and colored pixels on the film B. When the resin laminated body is used for an organic EL element, the film B is provided with at least a TFT, an electrode and an organic layer to form an organic EL element. Each of these may have a supporting substrate on the side of the film A.

A color filter using the supporting substrate for a display of the present invention can be manufactured through the following steps in addition to the steps (1) to (3).
(4) A step of forming a black matrix on the resin laminate.
(5) A step of forming colored pixels on the resin laminate.
(6) A step of peeling the resin laminate from the supporting substrate.

The black matrix is preferably a resin black matrix in which a black pigment is dispersed in resin. Examples of black pigments include carbon black, titanium black, titanium oxide, titanium oxynitride, titanium nitride or iron tetroxide. Particularly, carbon black and titanium black are preferable. Further, a red pigment, a green pigment and a blue pigment can be mixed and used as a black pigment.

As a resin used for the resin black matrix, a polyimide resin is preferable because a thin pattern is easily formed. It is preferable that the polyimide resin is a polyamic acid synthesized from an acid anhydride and a diamine, which is thermally cured after patterning to obtain a polyimide resin.
As the examples of the acid anhydride, diamine and solvent, those mentioned above for the polyimide resin can be used.

A photosensitive acrylic resin is also preferable as the resin used for the resin black matrix. The resin black matrix using this contains an alkali-soluble acrylic resin in which a black pigment is dispersed, a photopolymerizable monomer, a polymer dispersant and an additive.

Examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or acid anhydrides.

Examples of the photopolymerizable monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylic formal, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate or dipentaerythritol. Examples include penta(meth)acrylate.

Examples of the photopolymerization initiator include benzophenone, N,N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone. , 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 acetoacetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, Methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate may be mentioned.

A black resin composition for a resin black matrix composed of polyamic acid in which a black pigment is dispersed is applied on the resin film by a method such as a spin coater or a die coater so that the film thickness after curing is 1 μm and 60 Pa or less. After drying under reduced pressure, semi-cure is performed in a hot air oven or hot plate at 110 to 140°C.

A positive resist is applied by a method such as a spin coater or a die coater so that the film thickness after prebaking is 1.2 μm, and then dried under reduced pressure to 80 Pa, and prebaked in a hot air oven or hot plate at 80 to 110° C. Then, a resist film is formed. Then, after selectively exposing with ultraviolet rays through a photomask with a proximity exposure machine or a projection exposure machine, 1.5-3.0% by weight of potassium hydroxide or tetramethylammonium hydroxide The exposed area is removed by immersing in an alkaline developer for 20 to 300 seconds. After removing the positive resist using a stripping solution, the black pigment was dispersed in the resin film by converting the polyamic acid into polyimide by heating in a hot air oven or a hot plate at 200 to 300° C. for 10 to 60 minutes. Form a resin black matrix. When the photosensitive resin is used, exposure and development can be performed without applying a positive resist.

After forming the resin black matrix, colored pixels are formed. The colored pixel is generally composed of three colored pixels of red, green and blue. Further, in addition to the three colored pixels, the pixels of the fourth color, which are colorless and transparent or which are thin and thin, are formed, so that the brightness of white display of the display device can be improved.

For the colored pixel of the color filter, a resin containing a pigment or a dye as a colorant is used.

Examples of pigments used for red colored pixels include PR254, PR149, PR166, PR177, PR209, PY138, PY150 or PYP139, and examples of pigments used for green colored pixels include PG7, PG36, PG58. , PG37, PB16, PY129, PY138, PY139, PY150 or PY185, and examples of pigments used for blue colored pixels include PB15:6 or PV23.

Examples of blue dyes include C.I. I. Basic Blue (BB) 5, BB7, BB9 or BB26 may be mentioned, and examples of the red dye include C.I. I. Acid red (AR) 51, AR87 or AR289 is mentioned.

Examples of the resin used for the red, green, and blue colored pixels include acrylic resins, epoxy resins, and polyimide resins, but photosensitive acrylic resins are preferable because the manufacturing cost of the color filter can be reduced. The photosensitive acrylic resin generally contains an alkali-soluble resin, a photopolymerizable monomer and a photopolymerization initiator.

Examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid or acid anhydrides.

Examples of the photopolymerizable monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylic formal, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate or dipentaerythritol. Examples include penta(meth)acrylate.

Examples of the photopolymerization initiator include benzophenone, N,N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone. , 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 acetoacetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate. , Methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.

The colored pixel of the color filter is manufactured using a colorant and a resin. When a pigment is used as a colorant, it is prepared by mixing a polymer dispersant and a solvent with the pigment for dispersion treatment, and then adding an alkali-soluble resin, a monomer, a photopolymerization initiator and the like. On the other hand, when a dye is used as the colorant, it is prepared by adding a solvent, an alkali-soluble resin, a monomer, a photopolymerizable initiator and the like to the dye. In this case, the total solid content is the total of the polymer dispersant, the alkali-soluble resin and the monomer which are the resin components, and the colorant.

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

Next, a proximity exposure machine, a projection exposure machine, or the like is used to selectively expose with ultraviolet light or the like through a photomask. After that, the unexposed portion is removed by immersing for 20 to 300 seconds in an alkaline developer such as 0.02 to 1.0 wt% potassium hydroxide aqueous solution or tetramethylammonium hydroxide aqueous solution. The obtained coating film pattern is heat-treated in a hot air oven or a hot plate at 180 to 250° C. for 5 to 40 minutes to form colored pixels. Using the colorant composition prepared for each color of the colored pixel, the patterning process as described above is sequentially performed on the red colored pixel, the green colored pixel and the blue colored pixel.

The above-mentioned gas barrier film may be formed between the resin film and the black matrix/colored pixel layer.

Further, a flattening layer may be provided on the color filter. Examples of the resin used for forming the flattening layer include an epoxy resin, an acrylic epoxy resin, an acrylic resin, a siloxane resin, or a polyimide resin. The thickness of the flattening layer is preferably such that the surface becomes flat, more preferably 0.5 to 5.0 μm, and even more preferably 1.0 to 3.0 μm.

As a method of peeling off the color filter, it is preferable to make a cut in the periphery of the resin laminate and peel it off.

Through the above steps, a color filter using the display support substrate can be manufactured. The order of patterning the colored pixels is not particularly limited.

<Organic EL device>
The organic EL device using the supporting substrate for a display of the present invention can be manufactured through the following steps in addition to the steps (1) to (3).
(4) A step of forming an organic EL element on the resin laminate.
(5) A step of peeling the resin laminate from the supporting substrate.

The organic EL element can be formed, for example, as follows. First, a gas barrier film for suppressing the permeation of gas such as water vapor and oxygen is formed on the film B of the resin laminate described above. Preferred gas barrier films include, for example, metal oxides containing at least one metal selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium, and tantalum, silicon, and aluminum. , Metal nitrides of boron or mixtures thereof. Above all, it is preferable that the main component is an oxide, nitride, or oxynitride of silicon from the viewpoints of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like.

These gas barrier films can be produced by a vapor deposition method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma CVD method or the like in which a material is deposited from a vapor phase to form a film. Among them, the sputtering method is preferable from the viewpoint that a particularly excellent gas barrier property can be obtained.

The thickness of the gas barrier film is preferably 10 to 300 nm, more preferably 30 to 200 nm. In order to obtain high gas barrier properties, the film forming temperature of the gas barrier film is preferably high, preferably 300° C. or higher, more preferably 400° C. or higher, still more preferably 500° C. or higher.

A TFT is formed on the gas barrier film. Examples of the semiconductor layer for forming the TFT include an amorphous silicon semiconductor, a polycrystalline silicon semiconductor, an oxide semiconductor typified by InGaZnO, and an organic semiconductor typified by pentacene or polythiophene. For example, using the laminate of the present invention as a base material, a gas barrier film, a gate electrode, a gate insulating film, a polycrystalline silicon semiconductor layer, an etching stopper film, and a source/drain electrode are sequentially formed by a known method to form a bottom gate type TFT. Create.

Next, a planarization layer is provided on the TFT. Examples of the resin used for forming the flattening layer include an epoxy resin, an acrylic epoxy resin, an acrylic resin, a polysiloxane resin, or a polyimide resin. Further, an electrode and an organic layer are formed on it. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, which has a first electrode made of Al/ITO or the like and an insulating film covering the end of the first electrode, A white organic EL light emitting layer made of is formed, a second electrode made of ITO or the like is formed, and a sealing film is formed. An organic EL element can be obtained by peeling the resin film from the supporting substrate after the fabrication through the above steps.

Further, an on-chip type substrate can be produced by directly forming a color filter on the thus obtained organic EL element by the method described above.
<Device>
The support substrate for a display of the present invention can be used for a display device such as a liquid crystal display, an organic EL display, an electronic paper, a PDP display, an LED display and a see-through display, a color filter, a touch panel, a solar cell, a light receiving device such as a CMOS. it can. In particular, the display supporting substrate of the present invention is preferably used for utilizing these display devices and light receiving devices as flexible devices that can be bent.

An example of a flexible device manufacturing process is to form a circuit necessary for a display device or a light-receiving device on a resin film formed on a substrate, make a cut as described above, and physically peel it to form a resin laminate. Is peeled from the substrate.

Since the color filter and the organic EL element manufactured in the present invention have a flexible resin laminate as a base material, they can be used as a flexible color filter and a flexible organic EL element. A flexible organic EL display can be manufactured using these flexible color filters and flexible organic EL elements. For example, a flexible display device for full-color display can be obtained by attaching a light emitting device to a color filter using the flexible substrate of the present invention. In particular, a flexible organic EL display in which an organic EL element using the flexible substrate of the present invention and a color filter are combined is preferable.

The present invention is described below with reference to examples and the like, but the present invention is not limited to these examples.

(1) Preparation of resin laminate (on glass substrate) (transmittance measurement)
Using a spin coater MS-A200 manufactured by Mikasa Co., Ltd., a glass substrate (Tempax) having a thickness of 50 mm×50 mm×1.1 mm was used, and the thickness after pre-baking at 140° C.×4 minutes was as shown in Table 1. The polyimide precursor resin solution was spin-coated so that Then, 140 degreeC x 4 minute prebaking process was performed using Dainippon Screen Co., Ltd. hotplate D-SPIN. Subsequently, the spin coater MS-A200 manufactured by Mikasa Co., Ltd. was also used to spin-coat the polysiloxane resin composition so that the thickness after prebaking at 100° C. for 2 minutes would be the thickness described in Table 1. did. The coating film after the pre-baking treatment is heated to 300° C. at 3.5° C./min for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) It was held and cooled to 50° C. at 5° C./min to prepare a resin laminate (on a glass substrate).

(2) Preparation of heat resistant resin film (on silicon substrate) (birefringence measurement)
Using a spin coater MS-A200 manufactured by Mikasa Co., Ltd., on a 4-inch silicon substrate cut into quarters, a polyimide precursor resin or polysiloxane resin composition was prepared so that the film thickness after prebaking would be 5±0.5 μm. The article was spin coated. After that, prebaking treatment was performed using a hot plate D-SPIN manufactured by Dainippon Screen Co., Ltd. (The polyimide precursor resin was prebaked under the conditions of 140° C.×4 minutes, and the polysiloxane resin composition was 100° C.×2 minutes.) The prebaked film was formed using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.). Under a nitrogen stream (oxygen concentration of 20 ppm or less), the temperature is raised to 300° C. or 350° C. at 3.5° C./min, held for 30 minutes, and cooled to 50° C. at 5° C./min to form a heat resistant resin film (silicon substrate). Above) was prepared.

(3) Preparation of resin laminate (TMA measurement)
On a 6-inch silicon substrate, using a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Ltd., a polyimide precursor is prepared so that the thickness after prebaking at 140° C. for 4 minutes becomes the thickness described in Table 1. The resin solution was spin coated. After that, a prebaking process was performed at 140° C. for 4 minutes using the same Mark-7 hot plate. Subsequently, a spin coater MS-A200 manufactured by Mikasa Co., Ltd. was used to spin-coat the polysiloxane resin composition so that the thickness after prebaking at 100° C. for 2 minutes would be the thickness described in Table 1. The coating film after the pre-baking treatment is heated to 300° C. at 3.5° C./min for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) It was held and cooled to 50° C. at 5° C./min to prepare a resin laminate. Subsequently, a cut was made around the obtained resin laminate, and the resin laminate was peeled from the substrate by physically pulling it by immersing it in hot water at 65° C. for 1 to 4 minutes, and air-drying.

(4) Measurement of light transmittance (T) The light transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation). The resin laminate on the glass substrate prepared in (1) was used for the measurement.

(5) Measurement of linear thermal expansion coefficient (CTE) Using a thermomechanical analyzer (EXSTAR6000 TMA/SS6000 manufactured by SII Nano Technology Co., Ltd.), measurement was performed under a nitrogen stream. The temperature raising method was performed under the following conditions. In the first step, the temperature was raised to 150° C. at a heating rate of 5° C./min to remove the adsorbed water of the sample, and in the second step, it was air-cooled to room temperature at a temperature dropping rate of 5° C./min. In the third step, the main measurement was performed at a temperature rising rate of 5° C./min, and the linear expansion coefficient (CTE) was determined from the average of the linear expansion coefficients of 50 to 200° C. In addition, the resin laminated body produced by (3) was used for the measurement, and it evaluated by the following evaluation methods.
Excellent (A): 35 ppm/° C. or less Good (B): Over 35 ppm/° C. 40 ppm/° C. or less Poor (C): Over 40 ppm/° C.

(6) Measurement of Birefringence Using a prism coupler (PC2010 manufactured by METRICON), TE refractive index (n(TE)) and TM refractive index (n(TM)) at a wavelength of 632.8 nm were measured. n(TE) and n(TM) are the refractive indices in the parallel and vertical directions with respect to the film surface, respectively. Birefringence is calculated as the n difference (TE) and n (TM) (n (TE ) -n (TM)), the birefringence of the film A was .DELTA.N _A, .DELTA.N _B birefringence film B. The resin film produced in (2) was used for the measurement.

(7) Measurement of 3% weight loss temperature (Td3) The polysiloxane resin film prepared in (2) was scraped off and placed in an aluminum cell in an amount of about 15 mg, and nitrogen was added using a thermogravimetric measuring device (TGA-50 manufactured by Shimadzu Corporation). The measurement was performed under airflow. The temperature raising method was performed 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 raising rate of 3.5° C./min, and in the second stage, it was cooled to 40° C. at the temperature lowering rate of 10° C./min and the third stage The main measurement was carried out at a temperature rising rate of 10° C./min to determine the temperature (Td3) when the weight was reduced by 3%.

(8) Measurement of chromaticity The transmission chromaticity coordinate in the XYZ color system chromaticity diagram of the film B formed on non-alkali glass (glass thickness 0.7 mm) is a microspectrophotometer manufactured by Otsuka Electronics Co., Ltd. It was measured using "MCPD-2000".

In addition, a resin laminate substrate was prepared in which the film A containing a polyimide resin was provided with non-alkali glass (glass thickness 0.7 mm). The C light source (L ^* a ^* b ^* ) color space of the resin laminate substrate was measured using a microspectrophotometer "MCPD-2000" manufactured by Otsuka Electronics Co., Ltd., and the transmission color tone was determined as follows. ..
A (very good: ◎): a ^* and b ^* values are 0≦|a ^* |≦0.5 and 0≦|b ^* |≦1.0
B (good): a ^* and b ^* values are 0≦|a ^* |≦1.0 and 1.0<|b ^* |≦1.8.
C (possible: Δ): The values of a ^* and b ^* are 0≦|a ^* |≦1.5 and 1.8<|b ^* |≦2.5.
D (defective: x): The values of a ^* and b ^* are |a ^* |>1.5 or |b ^* |>2.5.
(9) Flexing resistance evaluation of the flexible color filter The bending resistance of the flexible color filter was measured by the following method. First, the color filter separated from the glass substrate was sampled to 100 mm×140 mm, a metal cylinder having a diameter of 30 mm was fixed at the center of the surface, and the holding angle of the cylinder was 0° (the sample was in a flat state along this cylinder. ) (See FIG. 1), and 100 bending bending operations were performed within a range (see FIG. 2) where the holding angle to the cylinder was 180° (state folded by the cylinder). The flex resistance was evaluated by visually observing 100 sheets using an optical microscope (Nikon (manufactured by OPTIPHOT300)) after the test, using the presence or absence of cracks in the film B before and after the bending operation as an index.

(10) Evaluation of Position Accuracy of Black Matrix (BM) The amount of deviation of the BM from the ideal lattice in the color filter with a glass substrate was measured as follows using SMIC-800 (manufactured by Sokia Topcon). First, a BM pattern was formed on a glass substrate in the same manner as described in Example 1[2] except that the formation location was on the glass substrate. The amount of deviation from the ideal lattice was measured at 24 points in the BM pattern. Next, the deviation amount from the ideal lattice was measured at 24 positions of the BM pattern in the color filters obtained in each of the examples and the comparative examples. In both cases, the average of the absolute values of the deviation amounts obtained by the measurement was calculated, and the obtained value was taken as the deviation amount of the BM from the ideal lattice at that level. The value of the amount of deviation in each of the examples and comparative examples was evaluated, and how much the amount of deviation was different between when the BM pattern was formed on the glass substrate and when it was formed on the resin laminate, The evaluation was made by the following evaluation method.
Excellent (A): BM misalignment amount is 1.8 μm or less Good (B): BM misalignment amount is over 1.8 μm 2.4 μm or less Poor (C): BM misalignment amount is over 2.4 μm

(11) Measurement of Luminous Efficiency Current efficiency (cd) at a luminance of 1000 cd/m ² in an organic EL element immediately after fabrication, an organic EL element after a high temperature and high humidity test, and an organic EL element after a high temperature and high humidity test following a bending test /A) was measured. In the bending test, the organic EL element peeled from the glass substrate was sampled to 100 mm×140 mm, a metal cylinder having a diameter of 30 mm was fixed at the center of the surface, and the holding angle of the cylinder was 0° (sample Is in a flat state) (see FIG. 1), and is bent 100 times within a range (see FIG. 2) where the holding angle to the cylinder is 180° (state folded by the cylinder). The high temperature and high humidity test was carried out by placing the organic EL element separated from the glass substrate in a high temperature and high humidity tank having an internal temperature of 85° C. and a humidity of 85% for 24 hours.

Synthesis Example 1: Synthesis of transparent polyimide precursor resin solution (I) 16.66 g (53.7 mmol) of 4,4'-oxydiphthalic anhydride (ODPA), 2,2- in a 200 mL four-necked flask under a dry nitrogen stream. 32.46 g (53.7 mmol) of bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HFHA) and 100 g of N-methyl-2-pyrrolidone were added and the mixture was heated with stirring at 65°C. After 6 hours, it was cooled to obtain a transparent polyimide precursor resin solution (I).

Synthesis Example 2: Synthesis of transparent polyimide precursor resin solution (II) 11.3 g (39) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) in a 200 mL four-necked flask under a dry nitrogen stream. .2 mmol), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) 1.92 g (9.79 mmol), trans-1,4-diaminocyclohexane (CHDA) 5.59 g (49. 0 mmol) and N-methyl-2-pyrrolidone (100 g) were added, and the mixture was heated with stirring at 65°C. After 6 hours, it was cooled to obtain a transparent polyimide precursor resin solution (II).

Synthesis Example 3: Synthesis of Transparent Polyimide Precursor Resin Solution (III) 7.90 g (26) of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) in a 200 mL four-necked flask under a dry nitrogen stream. .4 mmol), 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride (BSAA) 14.01 g (26.4 mmol), trans-1,4-diaminocyclohexane ( CHDA) 6.1375 g (53.7 mmol) and N-methyl-2-pyrrolidone 100 g were added and the mixture was heated with stirring at 65°C. After 6 hours, it was cooled to obtain a transparent polyimide precursor resin solution (III).

Synthesis Example 4: Synthesis of transparent polyimide precursor resin solution (IV) In a 200 mL four-neck flask under a dry nitrogen stream, 3,72'(46,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was added. .6 mmol), trans-1,4-diaminocyclohexane (CHDA) 5.33 g (46.6 mmol), and N-methyl-2-pyrrolidone 100 g were put and stirred with heating at 65°C. After 6 hours, it was cooled to obtain a transparent polyimide precursor resin solution (IV).

Synthesis Example 5: Synthesis of transparent polyimide precursor resin solution (V) 7.23 g (36.9 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) in a 200 mL four-necked flask under a dry nitrogen stream. ), 2,2′-bis(trifluoromethyl)benzidine (TFMB) 11.81 g (36.9 mmol) and N-methyl-2-pyrrolidone 100 g were added and the mixture was heated with stirring at 65° C. After 6 hours, it was cooled to obtain a transparent polyimide precursor resin solution (V).

Synthesis Example 6: Synthesis of Transparent Polyimide Precursor Resin Solution (VI) 12.4 g (53) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (PMDA-HS) in a 200 mL four-neck flask under a stream of dry nitrogen. 0.7 mmol), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HFHA) 32.46 g (53.7 mmol), and N-methyl-2-pyrrolidone 100 g were added. The mixture was heated and stirred at 65°C. After 6 hours, it was cooled to obtain a transparent polyimide precursor resin solution (VI).

Synthesis Example 7: Synthesis of Polyimide Precursor Resin Solution (VII) 7.03 g (32.2 mmol) of pyromellitic dianhydride (PMDA) and 4,4′-biphthalic anhydride in a 200 mL four-necked flask under a stream of dry nitrogen. 6.32 g (21.5 mmol) of (BPDA), 5.81 g (53.7 mmol) of 1,4-phenylenediamine (PDA) and 100 g of N-methyl-2-pyrrolidone were added and the mixture was heated with stirring at 65°C. After 6 hours, it was cooled to obtain a polyimide precursor resin solution (VII).

Synthesis Example 8 Synthesis of Polyimide Precursor Resin Solution (VIII) Under a dry nitrogen stream, 4,21'-biphthalic anhydride (BPDA) 10.21 g (34.7 mmol), trans-1,4-in a 200 mL four-necked flask. 1.59 g (13.9 mmol) of diaminocyclohexane (CHDA), 7.26 g (20.8 mmol) of 9,9-bis(4-aminophenyl)fluorene (FDA), and 100 g of N-methyl-2-pyrrolidone were put in 65. The mixture was heated and stirred at ℃. After 6 hours, it was cooled to obtain a polyimide precursor resin solution (VIII).

Synthesis Example 9: Synthesis of Polyimide Precursor Resin Solution (VIIII) 4,4′-Diaminophenyl ether (ODA) 60.07 g (300.0 mmol), 1,4-phenylenediamine (PDA) 70. Charge 33 g (650.4 mmol) and 12,3-bis(3-aminopropyl)tetramethyldisiloxane 12.43 g (50.0 mmol) with 850 g γ-butyrolactone and 850 g N-methyl-2-pyrrolidone, 309.43 g (997.5 mmol) of 3,3′,4,4′-oxydiphthalcarboxylic acid dianhydride (ODPA) was added, and the mixture was reacted at 80° C. for 3 hours. 1.96 g (20.0 mmol) of maleic anhydride was added, and the mixture was further reacted at 80° C. for 1 hour to obtain a polyimide precursor resin solution (VIIII).

Synthesis Example 10: Synthesis of Polysiloxane Resin Solution (I) Into a 500 ml three-necked flask, 46.05 g (0.34 mo) of methyltrimethoxysilane was added.
l), 83.79 g (0.42 mol) of phenyltrimethoxysilane, (2-(3,3
20.82 g (0.08mo of 4-epoxycyclohexyl)ethyltrimethoxysilane
l), 151.681136.51 g of propylene glycol monomethyl ether acetate (PGMEA) and 15.17 g of methanol were charged, and 0.45 g of phosphoric acid (charged) was added to 47.21 g of water (theoretical amount necessary for hydrolysis) while stirring at room temperature. An aqueous solution of phosphoric acid in which 0.3% by weight of the monomer) was dissolved was added with a dropping funnel over 10 minutes. Then, the flask was immersed in an oil bath at 40° C. and stirred for 30 minutes, and then the oil bath was heated to 115° C. over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100° C., and the mixture was heated and stirred for 2 hours (internal temperature is 100 to 110° C.) to obtain a polysiloxane solution (I). During the heating and stirring, 0.05 l (liter)/min of nitrogen was flowed. During the reaction, a total of 105 g of by-products, methanol, water, and a solvent, was distilled. PGMEA was added to the obtained polysiloxane PGMEA solution so that the polymer concentration was 40 wt %, to obtain a polysiloxane solution (I) (Mw=5500 (in terms of polystyrene)). For the solid content concentration, 1 g of the polysiloxane resin solution was weighed in an aluminum cup, heated at 250° C. for 30 minutes using a hot plate to evaporate the liquid content, and the solid content remaining in the aluminum cup after heating was measured. I asked. Moreover, the weight average molecular weight was determined by GPC (410 type RI detector manufactured by Waters, fluidized bed: tetrahydrofuran) in terms of polystyrene.

Synthesis Example 11: Synthesis of polysiloxane resin solution (II) In a 500 mL flask, 47.67 g (0.35 mol) of methyltrimethoxysilyl, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 82.04 g (0 .35 mol) of γ-acryloylpropyltrimethoxysilane, 26.23 (0.1 mol) of 3-trimethoxysilylpropylsuccinic anhydride and 195.6 g of diacetone alcohol (DAA) were charged, and an oil bath at 40° C. A phosphoric acid aqueous solution prepared by dissolving 0.39 g of phosphoric acid (0.2 parts by weight with respect to the charged monomer) in 55.8 g of water (theoretical amount necessary for hydrolysis) was stirred with the dropping funnel. Added over minutes. After stirring at 40° C. for 1 hour, the oil bath temperature was set to 70° C. and stirring was performed for 1 hour, and the oil bath was further heated to 115° C. over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature is 100 to 110°C). During the reaction, a total of 127 g of by-products, methanol and water, were distilled off. DAA was added to the obtained polysiloxane resin DAA solution so that the polymer concentration was 40 wt %, to obtain a polysiloxane resin solution (II) (Mw=4500 (polystyrene conversion)).

Preparation Example 1: Preparation of Polysiloxane Resin Composition 1 7.42 g of the polysiloxane solution (I) obtained in Synthesis Example 10 and PMA-ST as inorganic oxide particles (manufactured by Nissan Chemical Industries, Ltd.; silicon dioxide propylene glycol) Monimethyl ether acetate dispersion liquid; solid content concentration=30 wt %) 2.66 g, Megafac F-477 (manufactured by DIC) 0.01 g as a leveling agent, PGMEA 4.94 g as solvent, diethylene glycol ethyl methyl ether (EDM) 4.80 g Was mixed and stirred to form a uniform solution, which was then filtered through a 0.45 μm filter to prepare a polysiloxane resin composition 1 in which the content of silica particles in the varnish solid content was 20 wt %.

Preparation Example 2: Preparation of Polysiloxane Resin Composition 2 1.995 g of PMA-ST (manufactured by Nissan Chemical Industries, Ltd.; silicon dioxide propylene glycol monomethyl ether acetate dispersion liquid) under yellow light; solid content concentration=30 wt% ), 0.0898 g of Irgacure OXE-02 and 0.0299 g of hydroquinone methyl ether (HQME) were added and dissolved in 6.00 g of DAA and 1.44 g of PGMEA and stirred. 1.257 g of a 50 wt% PGMEA solution of dipentaerythritol hexaacrylate (DPHA), 4.115 g of a polysiloxane solution (II), and 0.075 g of a 1 wt% PGMEA solution of BYK-333 were added thereto and stirred. .. Then, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive polysiloxane resin composition 2 in which the content of silica particles in the varnish solid content was 20 wt %.

Adjustment Example 3: Under yellow light, 1.995 g of PMA-ST (manufactured by Nissan Chemical Industries, Ltd.; silicon dioxide propylene glycol monomethyl ether acetate dispersion; solid content concentration=30 wt %), 0.1197 g of Irgacure OXE -02 and 0.0299 g of hydroquinone methyl ether (HQME) were added, dissolved in 6.00 g of DAA and 2.38 g of PGMEA and stirred. 0.599 g of 50 wt% PGMEA solution of dipentaerythritol hexaacrylate (DPHA), 2.24 g of polysiloxane solution (II), and 50% PGMEA solution of epoxy ester 3002A (manufactured by Kyoeisha Co., Ltd.) were added thereto. 018 g, 0.539 g of a 50 wt% PGMEA solution of M-510 (manufactured by Toagosei Co., Ltd.) and 0.075 g of a 1 wt% PGMEA solution of BYK-333 were added and stirred. Then, filtration was performed with a 0.45 μm filter to obtain a negative photosensitive polysiloxane resin composition 3 in which the content of silica particles in the varnish solid content was 20 wt %.

Preparation Example 4; Preparation of Black Resin Composition for Forming Black Matrix In 250 g of the polyimide precursor resin solution (VIIII) of Synthesis Example 9, 50 g of carbon black (MA100; manufactured by Mitsubishi Chemical Corporation) and 200 g of N were added. -Methyl-2-pyrrolidone was mixed, and dyno mill KDL-A was used to carry out dispersion treatment at 3200 rpm for 3 hours using zirconia beads having a diameter of 0.3 mm to obtain a black resin dispersion liquid.

To 50 g of this black dispersion, 49.9 g of N-methyl-2-pyrrolidone and 0.1 g of a surfactant (LC951; manufactured by Kusumoto Chemical Co., Ltd.) were added to give a non-photosensitive black resin composition. Got

Preparation Example 5: Preparation of Photosensitive Color Resist Pigment Red PR177 (8.05 g) was charged together with 3-methyl-3-methoxybutanol (50 g) and dispersed using a homogenizer at 7,000 rpm for 5 hours, and then the glass beads were removed by filtration. 70.00 g of acrylic copolymer solution ("Cyclomer" P, ACA-250, 43 wt% solution manufactured by Daicel Chemical Industries, Ltd.), 30.00 g of pentaerythritol tetramethacrylate as a polyfunctional monomer, and "Irgacure" as a photopolymerization initiator A photosensitive red resist was obtained by adding 134.75 g of a photosensitive acrylic resin solution (AC) having a concentration of 20% by weight to 369, 15.00 g and 260.00 g of cyclopentanone. Similarly, a photosensitive green resist containing Pigment Green PG38 and Pigment Yellow PY138 and a photosensitive blue resist containing Pigment Blue PB15:6 were obtained.

Preparation Example 6: Preparation of Resin Composition for Forming Transparent Protective Film To 65.05 g of trimellitic acid, 280 g of GBL and 74.95 g of γ-aminopropyltriethoxysilane were added, and at 120° C. for 2 hours. Heated. To 20 g of the obtained solution, 7.00 g of bisphenoxyethanol full orange glycidyl ether and 15.00 g of diethylene glycol dimethyl ether were added to obtain a resin composition.

Preparation Example 7: Preparation of pigment dispersion (d1) PB15:6 65 g, PV23 35 g, as a dispersant, "BYK2001" 40 g of bi chemie company and propylene glycol monomethyl acetate 860 g were used together with 1000 g of zirconia beads having a diameter of 0.3 mm using a homogenizer. After the dispersion treatment at 7,000 rpm for 30 minutes, the zirconia beads were removed by filtration to obtain a pigment dispersion liquid (d1).

Example 1 Preparation of color filter and organic EL element using support substrate for display (FIGS. 3 and 4)
[1] Production of Resin Laminated Body A glass substrate 1 (AN100 (manufactured by Asahi Glass Co., Ltd.)) having a thickness of 300 mm×400 mm×0.7 mm is coated with the transparent polyimide precursor resin solution (I) obtained in Synthesis Example 1. Spin coating was performed so that the thickness after prebaking at 140° C. for 10 minutes was 15±0.5 μm. After that, prebaking treatment was performed at 140° C. for 10 minutes using a blower dryer. Subsequently, the polysiloxane resin composition 1 obtained in Preparation Example 1 was spin-coated on the polyimide resin film at 100° C. for 2 minutes to a thickness of 1.2 μm after prebaking. After that, a prebaking treatment was performed at 100° C. for 2 minutes using a blow dryer. Then, it is heated for 30 minutes in an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) heated to 300° C. under a nitrogen stream (oxygen concentration of 20 ppm or less), and a film A containing a polyimide resin A 10 μm and a film containing a polysiloxane resin B 1 μm. A resin laminated body was manufactured. When the visible light transmittance and CTE at a wavelength of 400 nm of the obtained resin laminate were measured, the transmittance was 87.8% and the CTE was 30 ppm/°C. The birefringence was measured, the flex resistance was evaluated, the 3% weight loss temperature was measured, and the chromaticity was measured by the methods described above. The results are shown in Table 1.

[2] Preparation of resin black matrix The black resin composition prepared in Preparation Example 4 was spin-coated on the film B containing the polysiloxane resin of the laminate prepared in [1], and the hot plate was applied thereto at 130° C. for 10 minutes. It was dried to form a black resin coating film. A positive photoresist ("SRC-100" manufactured by Shipley Co., Ltd.) was spin-coated, prebaked at 120°C for 5 minutes on a hot plate, and irradiated with ultraviolet rays of 100 mJ/cm ² (i-line conversion) using an ultra-high pressure mercury lamp to form a mask. After the exposure, using a 2.38% tetramethylammonium hydroxide aqueous solution, the photoresist is developed and the black resin coating film is etched at the same time to form a pattern, and the resist is peeled off with methyl cellosolve acetate, and then a hot plate is used. It was imidized by heating at 280° C. for 10 minutes to form a resin black matrix in which carbon black was dispersed in polyimide resin. When the thickness of the black matrix was measured, it was 1.4 μm. Further, when the positional accuracy of the black matrix was evaluated by the above-mentioned method, the BM positional deviation amount was 1.7 μm.

[3] Preparation of Colored Layer The photosensitive red resist prepared in Preparation Example 5 was added to the resin laminate having the black matrix patterned prepared in [1] and [2] in the black matrix opening after heat treatment. Was spin-coated to a film thickness of 2.0 μm and prebaked on a hot plate at 100° C. for 10 minutes to obtain a red colored layer. Next, using an ultraviolet light exposure device "PLA-5011" manufactured by Canon Inc., 100 mJ is applied through a chrome photomask that transmits light in an island shape with respect to a black matrix opening and a partial area on the black matrix. /Cm ² (i-line conversion) was used for exposure. After the exposure, the film was immersed in a developing solution containing a 0.2% tetramethylammonium hydroxide aqueous solution for development, followed by washing with pure water, and then heat treatment in an oven at 230° C. for 30 minutes to prepare a red pixel 7R. Similarly, a green pixel 7G made of a photosensitive green resist and a blue pixel 7B made of a photosensitive blue resist prepared in Preparation Example 4 were produced, and a color filter (FIG. 3) was obtained. Subsequently, the rotation number of the spinner was adjusted so that the thickness of the colored layer portion after the heat treatment was 2.5 μm, and the resin composition prepared in Adjustment Example 6 was applied. Then, it heat-processed for 30 minutes in the oven of 230 degreeC, and produced the overcoat layer.

[4] Preparation of TFT substrate On the film B containing the polysiloxane resin of the resin laminate (on the glass substrate) prepared by the method of [1], an inorganic gas barrier film made of SiO was formed by plasma CVD method. .. After that, a bottom gate type TFT was formed, and an insulating film made of Si ₃ N ₄ was formed so as to cover the TFT. Next, after forming a contact hole in this insulating film, a wiring (height 1.0 μm) connected to the TFT through this contact hole was formed on the insulating film. This wiring is for connecting between the TFTs or between the organic EL element formed in a later step and the TFT.

Further, in order to flatten the unevenness due to the formation of the wiring, a flattening layer was formed on the insulating film in a state of filling the unevenness due to the wiring. The flattening layer is formed by spin-coating a photosensitive polyimide varnish on a substrate, pre-baking it on a hot plate (120° C. for 3 minutes), exposing it through a mask with a desired pattern, developing it, and then air-flowing it. At 230° C. for 60 minutes. The coating property when applying the varnish was good, and wrinkles and cracks were not found in the flattening layer obtained after exposure, development and heat treatment. Further, the average level difference of the wiring was 500 nm, 5 μm square contact holes were formed in the produced flattening layer, and the thickness was about 2 μm.

[5] Preparation of White Light Emitting Organic EL Element (FIG. 4) A top emission type organic EL element was formed on the flattening layer of the TFT obtained by the above method. First, a first electrode made of Al/ITO (Al: reflective electrode) was formed on the flattening layer by connecting to a wiring through a contact hole. Then, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, the first electrode was patterned by wet etching using an ITO etchant. Then, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and heated and dehydrated at 200° C. for 30 minutes to obtain an electrode substrate with a flattening layer. The change in the thickness of the flattening layer was less than 1% after heat dehydration as compared with before the stripping solution treatment. The first electrode thus obtained corresponds to the anode of the organic EL element.

Next, an insulating layer having a shape covering the end portion of the first electrode was formed. Similarly, a photosensitive polyimide varnish was used for the insulating layer. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent step.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially vapor-deposited through a desired pattern mask in a vacuum vapor deposition apparatus to provide a white organic EL light emitting layer. Then, a second electrode made of Mg/ITO was formed on the entire surface above the substrate. Further, a SiON sealing film was formed by CVD film formation to obtain an organic EL device (FIG. 4).

When the luminous efficiency of the obtained organic EL device was measured by the above-mentioned method, the luminous efficiency was 5 cd/A immediately after the production and after the high temperature and high humidity test.

Example 2
A resin laminate, a color filter, and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (II) obtained in Synthesis Example 2 was used instead of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 85.5% and 20 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 3
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (III) obtained in Synthesis Example 3 was used instead of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 91.0% and 32 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 4
A resin laminate, a color filter, and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (IV) obtained in Synthesis Example 4 was used instead of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 86.8% and 9.0 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 5
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (V) obtained in Synthesis Example 5 was used instead of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 95.3% and 19 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 6
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (VI) obtained in Synthesis Example 6 was used instead of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 96.1% and 29 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 7
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (VII) obtained in Synthesis Example 7 was used instead of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 2.4% and 6.0 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 8
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the polyimide precursor resin solution (VIII) obtained in Synthesis Example 8 was used in place of the polyimide precursor resin solution (I). did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 65.2% and 23 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 9
The polysiloxane resin composition 2 obtained in Preparation Example 2 was used in place of the polysiloxane resin composition 1, the polysiloxane resin composition 2 was applied and prebaked. -5011″ was used to expose the entire surface of the coating film at 150 mJ/cm ² (converted to i-line) to photocure the film B′, and then to form a developer containing a 0.2% tetramethylammonium hydroxide aqueous solution. A resin laminate, a color filter, and an organic EL element were produced in the same manner as in Example 1 except that immersion was performed for 1 minute for development, followed by washing with pure water. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 87.4% and 30 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 10
A resin laminate, a color filter and an organic EL device were produced in the same manner as in Example 1 except that 0.1 g of the pigment dispersion liquid (d1) was added in Preparation Example 1. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 87.7% and 30 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 1.

Example 11
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 20 μm and the thickness of the film B was changed to 3 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 76.3% and 29 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 12
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 5 μm and the thickness of the film B was changed to 3 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 91.1% and 25 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 13
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 10 μm and the thickness of the film B was changed to 2.5 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 85.6% and 28 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 14
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 15 μm and the thickness of the film B was changed to 1.5 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 82.2% and 31 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 15
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 19 μm in Example 1. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 77.1% and 36 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 16
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 24 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 75.8% and 38 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 17 The polysiloxane resin composition 2 obtained in Preparation Example 3 was used in place of the polysiloxane resin composition 1, the polysiloxane resin composition 2 was applied and prebaked, followed by UV exposure by Canon Inc. Machine "PLA-5011" is used to expose the entire surface of the coating film at 150 mJ/cm ² (i-line conversion) to photocure the film B′, and then a 0.2% tetramethylammonium hydroxide aqueous solution is used. A resin laminate, a color filter and an organic EL device were produced in the same manner as in Example 1 except that the film was immersed in a developing solution for 1 minute for development, followed by washing with pure water. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 87.6% and 30 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 18
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the content of silica particles in the varnish solid content in Preparation Example 1 was changed to 65 wt %. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 88.0% and 29 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 19
A resin laminate, a color filter and an organic EL device were produced in the same manner as in Example 1 except that the content of silica particles in the varnish solid content in Preparation Example 1 was changed to 80 wt %. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 88.1% and 27 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 20 A resin was prepared in the same manner as in Example 1 except that PMA-ST was changed to TR-513 (manufactured by JGC Catalysts &Chemicals; titanium dioxide γ-butyrolactone dispersion; solid content concentration=30 wt %). A laminate, a color filter and an organic EL device were produced. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 83.5% and 36 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 21
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film B was changed to 0.4 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 88.5% and 39 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Example 22
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the content of silica particles in the varnish solid content in Preparation Example 1 was changed to 90 wt %. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 86.2% and 25 ppm/° C., respectively. It was 88.5% and 25 ppm. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Comparative Example 1
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the film B was not formed in Example 1. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 88.0% and 48 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Comparative example 2
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that PMA-ST was not added in Preparation Example 1. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 87.7% and 53 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Comparative Example 3
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the film thickness of the film A was changed to 25 μm and the film thickness of the film B was changed to 0.5 μm. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 73.4% and 42 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Comparative Example 4
A resin laminate, a color filter and an organic EL element were produced in the same manner as in Example 1 except that the thickness of the film A was changed to 4.0 μm and the thickness of the film B was changed to 3.0 μm. did. The visible light transmittance and CTE at a wavelength of 400 nm of the resin laminate were 92.1% and 23 ppm, respectively. Further, the birefringence was measured, the bending resistance was evaluated, the 3% weight loss temperature was measured, the chromaticity was measured, the positional accuracy of the black matrix was evaluated, and the luminous efficiency was measured by the methods described above. The results are shown in Table 2.

Results of transmittance, CTE, birefringence, bending resistance test, transmission chromaticity coordinates, BM position shift amount of color filters, and luminous efficiency of organic EL elements of the supporting substrates for displays of Examples 1 to 22 and Comparative Examples 1 to 4. Are shown in Tables 1 and 2. By having the film B containing the inorganic oxide fine particles on the film A, the CTE of the resin laminate is reduced without impairing the transmittance and the bending resistance, the BM position accuracy is improved, and the high temperature and high humidity test is performed. It can be seen that the reduction of the light emission efficiency of the organic EL element is suppressed when it is carried out. In Comparative Example 4, since the film thickness ratio of the film B in the laminate was large, many cracks were observed when the bending resistance test was performed, and sufficient flexibility could not be confirmed.

Example 23 Preparation of organic EL display (FIG. 5)
[1] Preparation of Color Filter with Glass Substrate and White Light Emitting Organic EL Element The color filter and white light emitting organic EL element were produced on the glass substrate by the method described in Example 1.

[2] Production of Organic EL Display The color filter with a glass substrate and the white light emitting organic EL element with a glass substrate obtained in the above [1] were bonded together via an adhesive layer. Subsequently, the color filter and the white light emitting organic EL element were peeled from the glass substrate by irradiating the glass substrate with an excimer laser (wavelength 308 nm). Then, a circularly polarizing film was attached to the film A on the color filter side to produce an organic EL display (FIG. 5).

Example 24
An organic EL display was produced in the same manner as in Example 23 except that the color filter produced in Example 10 was used.

Example 25
An organic EL display was produced in the same manner as in Example 23 except that the color filter produced in Example 4 was used.

Example 26
An organic EL display was produced in the same manner as in Example 23 except that the color filter produced in Example 8 was used.

Reference Example 1: Preparation of Polyimide Resin Film A glass substrate 1 (AN100 (Asahi Glass Co., Ltd.)) having a thickness of 300 mm×400 mm×0.7 mm was charged with the polyimide precursor resin solution (VII) obtained in Synthesis Example 7 at 140° C. Was spin-coated so that the thickness after prebaking for 10 minutes was 15±0.5 μm. After that, prebaking treatment was performed at 140° C. for 10 minutes using a blower dryer. After the temperature of the substrate dropped to room temperature, it was heated for 30 minutes in an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) heated to 300° C. under a nitrogen stream (oxygen concentration of 20 ppm or less) to prepare a polyimide resin film. .. When the visible light transmittance at a wavelength of 400 nm and the CTE of the obtained resin film were measured, the transmittance was 2.5% and the CTE was 6 ppm/°C.

Example 27 Production of Organic EL Display [1] Production of Color Filter with Glass Substrate By the method described in Example 1, a color filter was produced on a glass substrate.

[2] Production of White Light Emitting Organic EL Element with Glass Substrate (1) Production of Polyimide Resin Film A resin film was produced on the glass substrate by the method described in Reference Example 1.

(2) Preparation of TFT supporting substrate A TFT supporting substrate was prepared on the polyimide resin film prepared in (1) above in the same manner as in [4] of Example 1.

(3) Preparation of White Light Emitting Organic EL Element A white light emitting organic EL element was prepared on the TFT substrate prepared in (2) above in the same manner as in [5] of Example 1.

[3] Preparation of Organic EL Display The color filter with a glass substrate obtained in [1] above and the white light emitting organic EL element with a glass substrate obtained in [2] were bonded together via an adhesive layer. Then, by irradiating an excimer laser (wavelength 308 nm) from the glass substrate side, the color filter and the white light emitting organic EL element were peeled off from the glass substrate to produce an organic EL display.

Example 28
An organic EL display was produced in the same manner as in Example 23 except that the color filter produced in Example 16 was used.

Example 29
An organic EL display was produced in the same manner as in Example 23 except that the color filter produced in Example 20 was used.

Comparative Example 5
An organic EL display was produced in the same manner as in Example 23 except that the color filter produced in Comparative Example 1 was used.

Comparative Example 6
An organic EL display was produced in the same manner as in Example 23 except that the white light emitting organic EL element produced in Comparative Example 1 was used.

The following evaluations were performed on the displays of each of the examples and comparative examples. The results are shown in Table 3.

(Visibility evaluation of organic EL display)
The color when the organic EL display was displayed in white was visually observed and the visibility was determined as follows.
Excellent (A): Appearing white Good (B): Appearing to be slightly colored, but not so noticeable as white (C): Clearly colored and cannot be said to be white.

(External light reflection suppression performance evaluation of organic EL display)
A voltage was applied to each of the displays of Examples and Comparative Examples via a drive circuit, and the visibility of the displays outdoors on a sunny day was confirmed.
Excellent (A): External light reflection was sufficiently suppressed and visibility was excellent.
Good (B): The visibility is good, although the effect of reducing the reflection of external light is slightly inferior.
Bad (C): External light reflection is not reduced and visibility is poor.

(Display performance evaluation of organic EL display)
A voltage was applied to the display of each of the examples and comparative examples via a drive circuit, and the clarity and contrast of the display were confirmed.
Excellent (A): A display that is clear and has excellent contrast.
Good (B): A display with good display as a whole, although the display is inferior.
Bad (C): A display having many defects and inferior display performance.

In the organic EL displays of Examples 23, 24, and 27, it was possible to produce clear and high-contrast displays with little displacement of the color filters and no deterioration of the organic EL elements. In Example 24, by adjusting the transmission chromaticity of the resin film used for the film B, coloring of the display support substrate was reduced, and a display with good visibility could be produced.

In Example 25, although the effect of reducing external light reflection was slightly inferior, it was possible to create a display having good visibility and display performance.

In Examples 28 and 29, some of the color filters had defects, but the display was good as a whole.

In Example 26, the display was good as a whole, although the clarity was inferior because the transparency of the color filter support substrate was slightly low.

In the organic EL display of Comparative Example 5, many pixel defects were observed due to the poor positional accuracy of the color filters. In the organic EL display of Comparative Example 6, the white light emitting element had deterioration and defects, and the display was inferior in sharpness. Since many defects were observed in Comparative Examples 5 and 6, the visibility (color and external light reflection reducing effect) could not be confirmed.

1 Metal Cylinder 2 Flexible Color Filter 3 Glass Substrate 4 Film A
5 Membrane B
6 Black Matrix 7R Red Pixel 7G Green Pixel 7B Blue Pixel 8 Overcoat Layer 9 Flattening Layer 10 First Electrode 11 Insulating Layer 12 White EL Element 13 Second Electrode 14 Sealing Layer 15 TFT Layer 16 Gas Barrier Layer 17 Adhesive Layer 18 Yen Polarizing film 19 Flexible color filter 20 Flexible organic EL device

Claims (16)

A support substrate for a display having a film B containing a polysiloxane resin on one surface of a film A containing a polyimide resin, wherein the film B contains inorganic oxide particles, and the film thickness of the film A is 5.0 μm or more and 20 μm or less. And the film thickness of the film B is 0.2 μm or more and 3.0 μm or less, and the film thickness ratio between the film A and the film B is film A/film B=25/1 to 1.5/1. The support substrate for a display, wherein the polyimide resin has at least one group selected from a trifluoromethyl group and an alicyclic hydrocarbon group. The support substrate for a display according to claim 1, wherein the linear expansion coefficient of the support substrate for a display is 40 ppm/° C. or less. .DELTA.N _A birefringence of the film A, the film for a display support substrate according to claim 1 or 2 which is (ΔN _A -ΔN _B) ≦ 0.065 When the birefringence was .DELTA.N _B of B. The support substrate for a display according to claim 1, wherein the content of the inorganic oxide particles in the film B is 20 to 80% by weight. The support substrate for a display according to claim 1, wherein the inorganic oxide particles are silicon dioxide. It is transparent, The support substrate for displays in any one of Claims 1-5. 50 mol% or more of diamine residues having at least one kind of group selected from a trifluoromethyl group and an alicyclic hydrocarbon group are contained with respect to the total amount of diamine residues contained in the polyimide resin. The support substrate for a display according to any one of claims 1 to 6. The support substrate for a display according to claim 1, wherein the polyimide resin is a polyimide containing, as a main component, at least one of the repeating structural units represented by the general formulas (1) to (3).

(In the general formulas (1) to (3), R ¹ is at least one kind of groups represented by (4) to (9).)

The support substrate for a display according to claim 1, wherein the polyimide resin is a polyimide containing a repeating structural unit represented by the general formula (10) as a main component.

(In the general formula (10), R ¹ is at least one kind of groups represented by (4) to (9).)

The support substrate for a display according to claim 1, wherein the 3% weight loss temperature of the film B is 300° C. or higher. 11. The transmission chromaticity coordinates in the XYZ color system chromaticity diagram of the film B are in the range of 0.300≦x≦0.325 and 0.305≦y≦0.325. Display support substrate. A color filter comprising a black matrix and colored pixels on the film B of the support substrate for a display according to claim 1. The color filter according to claim 12, further comprising a support substrate on the side of the film A of the color filter. An organic EL device comprising an organic EL device on the film B of the support substrate for a display according to claim 1. The organic EL device according to claim 14 , wherein a support substrate is provided on the film A side of the previous organic EL device. A flexible organic EL display comprising the color filter according to claim 12 and/or the organic EL element according to claim 14 .

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