Cured film and organic el display device

Abstract

[Problem] To provide a cured film excellent in long-term reliability and capable of suppressing a decrease in light emission luminance during high-temperature continuous operation in particular when used in an organic EL display device. [Solution] The cured film of the present invention contains a polyimide and / or a polybenzoxazole. The molar ratio F (fluorine atoms) / C (carbon atoms) of fluorine atoms and carbon atoms, obtained when a cross-section of the cured film is measured with an electron probe microanalyzer, is 0-0.05.

Description

Cured film and organic EL display device

[0001] The present invention relates to a cured film and an organic EL display device using the same.

[0002] 2. Description of the Related Art Many display devices having thin displays, such as smartphones, tablet PCs, and televisions, have been developed that use organic electroluminescence (hereinafter, "organic EL") display devices.

[0003] In general, an organic EL display device has a drive circuit, a planarization layer, a first electrode, a pixel division layer, an organic EL layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes or by passing a current between them. Of these, the material for the planarization layer and the material for the pixel division layer are generally cured films of photosensitive resin compositions that can be patterned by ultraviolet irradiation.

[0004] On the other hand, the demand for higher reliability of organic EL display devices is becoming stricter every year, and materials for the planarization layer and the pixel dividing layer are also required to be materials that do not suffer from a decrease in luminance or pixel shrinkage even after reliability tests under accelerated conditions such as high temperature, high humidity, light irradiation, and continuous driving. Here, pixel shrinkage refers to a phenomenon in which luminance decreases or the edges of pixels do not light up.

[0005] Cured films of positive-type photosensitive resin compositions that have been proposed so far include cured films using a composition in which an alkali-soluble resin is mixed with a naphthoquinone diazide sulfonic acid ester compound as a photosensitive component, and examples thereof include those using a polyimide precursor as the resin before curing (see, for example, Patent Document 1) and those using a polybenzoxazole precursor (see, for example, Patent Document 2).

[0006] JP 2002-91343 A JP 2002-116715 A International Publication No. 2016-047483

[0007] However, the materials proposed in the above-mentioned patent documents are difficult to say have sufficient performance in terms of long-term reliability. On the other hand, a positive-type photosensitive resin composition (see, for example, Patent Document 3) has also been proposed as a material for pixel dividing layers in organic EL display devices, in which the sulfur concentration in the cured film is set within a certain range, thereby improving long-term reliability. However, while the cured film made from the resin composition described in Patent Document 3 has improved long-term reliability against light irradiation, it cannot be said that the decrease in luminance during high-temperature continuous operation is sufficiently suppressed. In view of the above problems, the present invention aims to provide a cured film that has excellent long-term reliability and, particularly when used in an organic EL display device, suppresses the decrease in luminance during high-temperature continuous operation.

[0008] In order to solve the above problems, the cured film of the present invention has the following configuration.

[0009] [1] A cured film comprising a polyimide and / or polybenzoxazole, wherein the molar ratio of fluorine atoms to carbon atoms, F (fluorine atoms) / C (carbon atoms), obtained when a cross section of the cured film is measured with an electron probe microanalyzer is 0 or more and 0.05 or less.

[0010] [2] The cured film according to [1], further comprising one or more compounds selected from the group consisting of a carboxylic acid having an indene structure, a carboxylic acid ester having an indene structure, a sulfonic acid having an indene structure, and a sulfonic acid aryl ester having an indene structure.

[0011] [3] The cured film according to [1] or [2], further comprising polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer.

[0012] [4] The cured film according to any one of [1] to [3], further comprising an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups in one aromatic ring.

[0013] [5] The cured film according to any one of [1] to [4], further comprising β-alkoxypropionamide.

[0014] [6] The cured film according to any one of [1] to [5], further comprising one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5), or sulfonate ions derived from one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5):

[0015]

[0016] In formula (3), R ５ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5; in formula (4), R ６ represents a monovalent organic group having 1 to 10 carbon atoms.

[0017] [7] The cured film according to any one of [1] to [6], wherein the polyimide and / or polybenzoxazole has a repeating unit composed of an acid component and an amine component, and when the acid component and the amine component in all the repeating units are each 100 mol %, the total of the acid component having a fluorene structure and the amine component having a fluorene structure is 0 mol % or more and 50 mol % or less out of a total of 200 mol % of the acid component and the amine component.

[0018] [8] The cured film according to any one of [1] to [7], wherein the polyimide and / or polybenzoxazole has a residue represented by formula (6):

[0019]

[0020] In formula (6), X １ each independently represents a direct bond, a divalent group represented by formula (7), or a divalent group represented by formula (8), X ２ is a divalent group represented by formula (9) or formula (10), R ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and each d independently represents an integer of 0 to 4;

[0021]

[0022] In formula (7) and formula (8), R ９each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, each e independently represents an integer of 0 to 4; * represents * in formula (6), and ** represents the point of attachment to the aromatic ring;

[0023]

[0024] In formula (9) and formula (10), R １１ are each independently an alkyl group having 1 to 4 carbon atoms, R １２ and R １３ are each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, * represents a bonding point to the aromatic ring; each f is independently an integer of 1 to 4, and g is 1 or 2; provided that R １２ and R １３ represents different substituents.

[0025] [9] The cured film according to any one of [1] to [8], wherein the polyimide and / or polybenzoxazole has repeating units each composed of an acid component and an amine component, and when the acid component and the amine component in all repeating units are each taken as 100 mol %, the total of the acid component having an alicyclic structure and the amine component having an alicyclic structure is 0 mol % to 40 mol % out of a total of 200 mol % of the acid component and the amine component.

[0026]

[10] The cured film according to any one of [1] to [9], wherein the polyimide and / or polybenzoxazole contains a repeating unit having a fluorine atom directly bonded to an sp2 carbon.

[0027]

[11] The cured film according to

[10] , wherein the polyimide and / or polybenzoxazole has a repeating unit composed of an acid component and an amine component, and when the acid component and the amine component in all the repeating units are each taken as 100 mol %, the total of the acid component having a fluorine atom directly bonded to the sp2 carbon and the amine component having a fluorine atom directly bonded to the sp2 carbon is 5 mol % or more and 100 mol % or less out of a total of 200 mol % of the acid component and the amine component.

[0028]

[12] The cured film according to any one of [1] to

[11] , wherein the molar ratio of silicon atoms to carbon atoms, Si (silicon atoms) / C (carbon atoms), obtained when a cross section of the cured film is measured with an electron probe microanalyzer, is 0.001 or more and 0.005 or less.

[0029]

[13] The cured film according to any one of [1] to

[12] , which has a transmittance of 30% or less for light with a wavelength of 450 nm at a film thickness of 2.0 μm.

[0030]

[14] The cured film according to any one of [1] to

[13] , which has an OD value of 0.5 to 1.5 in visible light per 1 μm of film thickness.

[0031]

[15] An organic EL display device having the cured film according to any one of [1] to

[14] .

[0032]

[16] The organic EL display device according to

[15] , further comprising a color filter having a black matrix.

[0033]

[17] An electronic component having the cured film according to any one of [1] to

[14] .

[0034] The cured film of the present invention has excellent long-term reliability, and when used in organic EL display devices in particular, it can suppress a decrease in luminance during continuous operation at high temperatures.

[0035] It is a cross-sectional view of an example of an organic EL display device.It is a cross-sectional view of an example of a display device.It is a schematic diagram of a manufacturing procedure of an organic EL display device.

[0036] The cured film of the present invention is a cured film containing polyimide and / or polybenzoxazole, and when a cross section of the cured film is measured with an electron probe microanalyzer, the molar ratio of fluorine to carbon, F (fluorine atoms) / C (carbon atoms) (hereinafter, sometimes referred to as F / C ratio), is from 0 to 0.05.

[0037] The cured film of the present invention is a film of a cured product obtained by curing a composition.

[0038]

[0009] As a result of extensive research, the present inventors have discovered that by setting the molar ratio of fluorine atoms to carbon atoms (F / C ratio) in the cured film within the above-mentioned range, the long-term reliability of the cured film can be improved, and particularly when used in an organic EL display device, a decrease in luminance during high-temperature continuous operation can be suppressed. Although the mechanism is unclear, it is believed that when the F / C ratio in the cured film is within the above-mentioned range, gasification of fluorine components from the cured film and fluorine contamination of openings during processing are suppressed, thereby preventing fluorine components from seeping into the inside of pixels and fluorine contamination of electrode surfaces, particularly in organic EL display devices, and thereby suppressing a decrease in luminance during high-temperature continuous operation.

[0039] From the viewpoint of improving the long-term reliability of the cured film and suppressing a decrease in luminance during continuous high-temperature operation, particularly when used in an organic EL display device, the F / C ratio obtained when a cross section of the cured film of the present invention is measured with an electron beam microanalyzer is from 0 to 0.05, preferably from 0 to 0.03, more preferably from 0 to 0.02, even more preferably from 0 to 0.01, and particularly preferably 0. Furthermore, from the viewpoint of improving reworkability during production of the cured film, the F / C ratio is from 0 to 0.05, preferably from 0.01 to 0.05, more preferably from 0.02 to 0.05, and even more preferably from 0.03 to 0.05. As a method for measuring the F / C ratio, for example, in the case of an organic EL display device having a cured film, the display device was disassembled and polished to expose the cured film, and the peak intensities of fluorine and carbon were measured using an electron beam microanalyzer by quantitative analysis using a standard sample.

[0040] Furthermore, the cured film of the present invention preferably has a molar ratio of silicon atoms to carbon atoms, Si (silicon atoms) / C (carbon atoms) (hereinafter sometimes referred to as the Si / C ratio), of 0.001 or more and 0.005 or less, as determined by measuring a cross section of the cured film with an electron beam microanalyzer. An Si / C ratio of 0.001 or more can improve the bending resistance of the cured film. While the mechanism is unclear, an Si / C ratio of 0.001 or more is thought to improve adhesion to the polyimide film substrate, thereby suppressing peeling during bending and thereby improving bending resistance. On the other hand, an Si / C ratio of 0.005 or less improves the long-term reliability of the cured film, and suppresses a decrease in luminance during continuous high-temperature operation, particularly when used in an organic EL display device. From the viewpoint of improving the bending resistance of the cured film, the Si / C ratio is preferably 0.001 or more, more preferably 0.002 or more, and even more preferably 0.003 or more. On the other hand, from the viewpoint of improving the long-term reliability of the cured film and suppressing a decrease in luminance during continuous operation at high temperatures, particularly when used in an organic EL display device, the Si / C ratio is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. The Si / C ratio can be measured in the same manner as the F / C ratio measured using an electron beam microanalyzer described above. To obtain a cured film having an Si / C ratio of 0.001 or more and 0.005 or less when a cross section of the cured film containing polyimide and / or polybenzoxazole is measured using an electron beam microanalyzer, methods include, but are not limited to, a method of adjusting the content of a silicon-containing acid component and a silicon-containing amine component in the polyimide and / or polybenzoxazole, as described below, and a method of adjusting the content of a silane coupling agent, as described below.

[0041] The cured film of the present invention preferably has a transmittance of 30% or less at a wavelength of 450 nm at a film thickness of 2.0 μm. When the cured film of the present invention is used in an organic EL display device having an oxide semiconductor thin film transistor, malfunctions due to the intrusion of ultraviolet light into the thin film transistor (hereinafter referred to as TFT) can be prevented. To prevent ultraviolet light from intruding into the TFT, the transmittance of light at a wavelength of 450 nm is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The lower limit of the transmittance of light at a wavelength of 450 nm is not particularly limited, but is 0.01% or more. When the film thickness of the cured film is other than 2.0 μm, the transmittance was converted to absorbance, corrected to the absorbance at a film thickness of 2.0 μm, and then the absorbance was converted back to transmittance to determine the transmittance of light at a wavelength of 450 nm at a film thickness of 2.0 μm.

[0042] The cured film of the present invention preferably has an OD value (optical density) of 0.5 to 1.5 in visible light per 1 μm of film thickness. When the OD value is 0.5 or more, the light-blocking properties can be improved by the cured film. Therefore, when the cured film of the present invention is used in a display device such as an organic EL display device or a liquid crystal display device, external light reflection can be further reduced, and the contrast in image display can be improved. From the viewpoint of reducing reflection, the OD value in visible light per 1 μm of film thickness is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more. Furthermore, when the OD value in visible light per 1 μm of film thickness is 1.5 or less, the exposure sensitivity during production of the cured film can be improved. From the viewpoint of increasing sensitivity, the OD value in visible light per 1 μm of film thickness is preferably 1.5 or less, more preferably 1.0 or less.

[0043] The thickness of the cured film of the present invention is not particularly limited, but from the viewpoint of ensuring insulating properties, it is preferably 1.0 μm or more, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. Furthermore, from the viewpoint of reducing outgassing from the cured film, the thickness of the cured film of the present invention is preferably 5.0 μm or less, more preferably 4.0 μm or less, and even more preferably 3.0 μm or less.

[0044] The cured film of the present invention is preferably patterned. When the cured film of the present invention is patterned, it can be suitably used in the application examples of the cured film described below.

[0045] Specific examples of methods for obtaining a patterned cured film containing polyimide and / or polybenzoxazole, which has an F / C ratio of 0 or more and 0.05 or less when a cross section of the cured film is measured with an electron beam microanalyzer, include the following.

[0046] [Method 1] A resin film (hereinafter sometimes referred to as resin film 1) made of a resin composition containing one or more polymers selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, having an F / C ratio of 0 or more and 0.05 or less, is formed, and a photosensitive resin film of photoresist (hereinafter sometimes referred to as photosensitive resin film 1) is formed on the resin film 1, and then the photosensitive resin film 1 is exposed to light, developed, etched, removed, and heat-treated. [Method 2] A photosensitive resin composition containing one or more polymers selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, and a photosensitive compound, wherein the F / C ratio in the solid content excluding the solvent from the photosensitive resin composition is 0 or more and 0.05 or less, and a photosensitive resin film made of the photosensitive resin composition is formed, and the photosensitive resin film is exposed, developed, and then heat-treated.

[0047] Here, the polyimide precursor refers to a resin that can be converted into a polyimide by heat treatment or chemical treatment, such as polyamic acid, polyamic acid ester, etc. The polybenzoxazole precursor refers to a resin that can be converted into a polybenzoxazole by heat treatment or chemical treatment, such as polyhydroxyamide, etc.

[0048] The method for adjusting the F / C ratio of the cured film to 0 or more and 0.05 or less is not particularly limited, but Method 1 and Method 2 are preferred, and Method 2 is preferred in terms of simplifying the production process.

[0049] <Polyimide and / or Polybenzoxazole> The cured film of the present invention contains a polyimide and / or a polybenzoxazole (hereinafter, sometimes referred to as component (a)). By containing component (a), the cured film of the present invention can improve the long-term reliability of the cured film, and in particular, when used in an organic EL display device, can suppress a decrease in luminance during continuous operation at high temperatures.

[0050] Component (a) has a repeating unit composed of an acid component and an amine component. The acid component and amine component referred to here refer to the repeating units derived from the acid component and the amine component, respectively, which are the synthetic raw materials for component (a) among the repeating units constituting component (a). As the repeating units composed of the acid component and the amine component, polyimide has a repeating unit represented by the following formula (1), and polybenzoxazole has a repeating unit represented by the following formula (2). The cured film of the present invention may contain two or more types of resins each having a repeating unit represented by formula (1) and a repeating unit represented by formula (2), or may contain a resin in which the repeating unit represented by formula (1) and the repeating unit represented by formula (2) are copolymerized.

[0051]

[0052] In formula (1), E represents a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and G represents a divalent to octavalent organic group having 6 to 40 carbon atoms. １ and R ２ each independently represents a carboxy group, a sulfonic acid group, or a hydroxyl group, and x and y each independently represent an integer of 0 to 6, provided that x+y>0.

[0053]

[0054] In formula (2), X represents a divalent to octavalent organic group having 4 to 40 carbon atoms, and Y represents a tetravalent to decavalent organic group having 6 to 40 carbon atoms. ３ and R ４ each independently represents a carboxy group, a hydroxyl group, or a sulfonic acid group, and s and t each independently represent an integer of 0 to 6.

[0055] From the viewpoint of reducing the F / C ratio to 0.05 or less and improving the long-term reliability of the cured film, when the contents of the acid component and the amine component in all repeating units in the component (a) are each 100 mol%, the total content of the acid component and the amine component is 200 mol%, and the total content of the fluorine atom-containing acid component and the fluorine atom-containing amine component is preferably 0 mol% or more and 50 mol% or less, more preferably 0 mol% or more and 40 mol% or less, even more preferably 0 mol% or more and 20 mol% or less, particularly preferably 0 mol% or more and 10 mol% or less, and most preferably 0 mol%.

[0056] From the viewpoint of setting the Si / C ratio at 0.001 or more and 0.005 or less, improving the bending resistance of the cured film, and improving the long-term reliability of the cured film, when the contents of the acid component and the amine component in all repeating units in component (a) are each taken as 100 mol%, the total content of the acid component having a silicon atom and the amine component having a silicon atom is preferably 2.5 mol% or more and 12.5 mol% or less, more preferably 3 mol% or more and 11 mol% or less, even more preferably 4 mol% or more and 10 mol% or less, and particularly preferably 5 mol% or more and 8 mol% or less, out of the total content of the acid component and the amine component (200 mol%).

[0057] From the viewpoint of improving the reworkability during the preparation of the cured film while maintaining the long-term reliability of the cured film, it is preferable that component (a) contains a repeating unit having a fluorine atom directly bonded to sp2 carbon. In addition, the reworkability is improved along with the improvement in solvent solubility due to the inclusion of a repeating unit having a fluorine atom in component (a), and although the mechanism is not clear, it is thought that even when the F / C ratio of the cured film is approximately the same, the case where a fluorine atom is directly bonded to sp2 carbon is more effective in suppressing gasification of the fluorine component from the cured film and fluorine contamination of openings during processing than the case where a fluorine atom is directly bonded to sp3 carbon such as a CF3 group.

[0058] When the contents of the acid component and the amine component in all repeating units in component (a) are each 100 mol%, the total content of the acid component and the amine component is 200 mol%, and the total content of the acid component having a fluorine atom directly bonded to the sp2 carbon and the amine component having a fluorine atom directly bonded to the sp2 carbon is preferably 5 mol% or more and 100 mol% or less. From the viewpoint of improving reworkability during production of a cured film, the total content of the acid component having a fluorine atom directly bonded to the sp2 carbon and the amine component directly bonded to the sp2 carbon is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. From the viewpoint of improving the long-term reliability of the cured film, the total content of the acid component having a fluorine atom directly bonded to the sp2 carbon and the amine component directly bonded to the sp2 carbon is preferably 100 mol% or less, preferably 80 mol% or less, and even more preferably 60 mol% or less.

[0059] From the viewpoint of improving the bending resistance of cured film, when the content of acid component and amine component in all repeating units in component (a) is 100 mol%, respectively, in the total content of acid component and amine component of 200 mol%, the total content of acid component having fluorene structure and amine component having fluorene structure is preferably 0 mol% or more and 50 mol% or less.From the viewpoint of improving the bending resistance of cured film, the total content of acid component having fluorene structure and amine component having fluorene structure is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 10 mol% or less, particularly preferably 0 mol%.On the other hand, from the viewpoint of improving the reworkability when preparing cured film, the content of repeating unit having fluorene structure is preferably 10 mol% or more.

[0060] From the viewpoint of improving the solvent solubility of the component (a) and improving the reworkability during production of a cured film, the component (a) preferably has a residue represented by formula (6).

[0061]

[0062] In formula (6), X １each independently represents a direct bond, a divalent group represented by formula (7), or a divalent group represented by formula (8), X ２ is a divalent group represented by formula (9) or (10), R ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group; each d independently represents an integer of 0 to 4;

[0063]

[0064] In formula (7) and formula (8), R ９ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and each e independently represents an integer of 0 to 4. * represents * in formula (6), and ** represents the point of attachment to the aromatic ring.

[0065]

[0066] In formulas (9) and (10), R １１ are each independently an alkyl group having 1 to 4 carbon atoms, R １２ and R １３ are each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, * is a bonding point to the aromatic ring, f is each independently an integer of 1 to 4, and g is 1 or 2. However, R １２ and R １３ represents different substituents.

[0067] The residue represented by formula (6) contained in component (a) may be contained in either the acid component or the amine component, but is preferably contained in the amine component because the raw material is easily available.

[0068] When the contents of the acid component and the amine component in all repeating units in the component (a) are each taken as 100 mol%, the content of the residue represented by the formula (6) is preferably 5 mol% or more and 100 mol% or less. From the viewpoint of improving reworkability during production of a cured film, the content of the residue represented by the formula (6) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more. From the viewpoint of improving the bending resistance of the cured film, the content of the residue represented by the formula (6) is preferably 90 mol% or less, preferably 80 mol% or less, and more preferably 60 mol% or less.

[0069] From the viewpoint of improving the bending resistance of the cured film, when the contents of the acid component and the amine component in all repeating units in component (a) are each 100 mol%, the total content of the acid component and the amine component is 200 mol%, and the total content of the acid component having an alicyclic structure and the amine component having an alicyclic structure is preferably 0 mol% or more and 40 mol% or less. From the viewpoint of improving the bending resistance of the cured film, the total content of the acid component having an alicyclic structure and the amine component having an alicyclic structure is preferably 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 10 mol% or less. On the other hand, from the viewpoint of improving the reworkability during the production of the cured film, the total content of the acid component having an alicyclic structure and the amine component having an alicyclic structure is preferably 10 mol% or more, more preferably 20 mol% or more.

[0070] The method for determining whether cured film contains polyimide and / or polybenzoxazole can be, for example, by analyzing cured film by infrared spectroscopy.In addition, the total content of the acid component of the fluorine atom that is directly bonded to sp2 carbon and the amine component of the fluorine atom that is directly bonded to sp2 carbon relative to the total content of acid component and amine component in all repeating units of the cured film that contains polyimide and / or polybenzoxazole, the total content of the acid ...ene structure and the amine component of the fluorene structure relative to the total content of acid component and amine component in all repeating units of the cured film that contains polyimide and / or polybenzoxazole, the content of the residue represented by above-mentioned formula (6) relative to the total content of acid component and amine component in all repeating units of the acid component of the alicyclic structure and the amine component of the alicyclic structure relative to the total content of acid component and amine component in all repeating units of the acid component of the alicyclic structure, for example, can be determined by pyrolysis GC / MS, which is carried out pyrolysis of cured film at 600 ℃, and then measures by gas chromatography.

[0071] Component (a) preferably contains 5 to 100,000 repeating units represented by formula (1) or formula (2). Furthermore, component (a) may contain other repeating units in addition to the repeating units represented by formula (1) or formula (2). In this case, component (a) preferably contains 50 mol % or more of repeating units represented by formula (1) or formula (2) out of 100 mol % of all repeating units.

[0072] In the above formula (2), X(R ３ ) ｓ represents an acid residue. X is a divalent to octavalent organic group having 4 to 40 carbon atoms, and among these, a divalent to octavalent organic group containing an aromatic ring or a cyclic aliphatic group is preferred. Examples of acid residues are shown below, but component (a) is X(R ３ ) ｓ The alkyl group may have two or more kinds of residues of the following acids.

[0073] Examples of the residue of an acid containing a fluorine atom include residues of dicarboxylic acids such as 2,2-bis(4-carboxyphenyl)hexafluoropropane, tetrafluoroterephthalic acid, and tetrafluoroisophthalic acid, as well as residues of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,4-difluoro-2,3,4,5-benzenetetracarboxylic acid, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzoic acid, hexafluorooxydiphthalic acid, and aromatic tetracarboxylic acids having the structures shown below.

[0074]

[0075] R ２１ and R ２２ each independently represents a hydrogen atom or a hydroxyl group.

[0076] Examples of the acid residues not containing fluorine atoms include residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; residues of tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; residues of pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, and 1,1-bis(3,4-dicarboxyphenyl) Examples of the tetracarboxylic acid residues include tetracarboxylic acid residues such as 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid.

[0077]

[0078] R ２０ is an oxygen atom, SO ２ or C(CH ３ ) ２ Represents R ２１ and R ２２ each independently represents a hydrogen atom or a hydroxyl group.

[0079] In the above formula (1), E(R １ ) ｘ represents a residue of an acid dianhydride. E is a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and among these, an organic group containing an aromatic ring or a cyclic aliphatic group is preferred. Examples of the residue of an acid dianhydride are shown below, and the component (a) is represented by E(R １ )ｘ The carboxylic acid may have two or more types of acid dianhydride residues shown below.

[0080] Examples of the residue of an acid dianhydride containing a fluorine atom include residues of aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,4-difluoro-2,3,4,5-benzenetetracarboxylic acid dianhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene acid dianhydride, hexafluorooxydiphthalic acid dianhydride, and acid dianhydrides having the structures shown below.

[0081]

[0082] R ２１ and R ２２ each independently represents a hydrogen atom or a hydroxyl group.

[0083] Examples of the residue of an acid dianhydride that does not contain a fluorine atom include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic 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, and bis(2,3-dicarboxyphenyl)methane dianhydride. Examples of the dianhydride include aromatic tetracarboxylic acid dianhydrides such as hydrates, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, and acid dianhydrides having the structures shown below; aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride; and residues of aliphatic tetracarboxylic acid dianhydrides containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride.

[0084]

[0085] R ２０ is an oxygen atom, SO ２ or C(CH ３ ) ２ Represents R ２１ and R ２２ each independently represents a hydrogen atom or a hydroxyl group.

[0086] Y(R ４ ) ｔ and G(R ２ )ｙ represents a residue of a diamine or dihydroxydiamine. Y is a tetravalent to decavalent organic group having 6 to 40 carbon atoms, and among these, a tetravalent to decavalent organic group containing an aromatic ring or a cyclic aliphatic group is preferred. G is a divalent to octavalent organic group having 6 to 40 carbon atoms, and among these, a divalent to octavalent organic group containing an aromatic ring or a cyclic aliphatic group is preferred. Examples of diamine and dihydroxydiamine residues are shown below, and component (a) is represented by Y(R ４ ) ｔ and G(R ２ ) ｙ As the amino acid residue, the amino acid residue may have two or more of the following residues:

[0087] Examples of the residues of diamines and dihydroxydiamines containing fluorine atoms include 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,4'-diaminooctafluorobiphenyl, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 2-fluoro-1,4-phenylenediamine ...4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,4-phenylenediamine, 2,4,5,6-tetrafluoro- It may contain residues of aromatic diamines such as phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 4,4'-diamino-2,2'-difluorobiphenyl, 4,4'-diamino-3,3'-difluorobiphenyl, 4,4'-diamino-2,5,2',5'-tetrafluorobiphenyl, 4,4'-diamino-2,6,2',6'-tetrafluorobiphenyl, 4,4'-diaminooctafluorodiphenyl ether, and compounds in which at least a portion of the hydrogen atoms on these aromatic rings have been substituted with alkyl groups or halogen atoms, as well as residues of diamines having the structures shown below.

[0088]

[0089] R ２１ ~R ２２ each independently represents a hydrogen atom or a hydroxyl group.

[0090] Examples of the residues of diamines and dihydroxydiamines that do not contain fluorine atoms include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1, 4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-di Residues of aromatic diamines and dihydroxydiamines such as aminobenzoic acid, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4,6-diaminoresorcinol, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 3,3'-diamino-[1,1'-biphenyl]-4,4'-diol, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings are substituted with alkyl groups or halogen atoms, cyclohexyldiamine, methylenebiscyclohexyldiamine, residues of aliphatic diamines containing a cyclic aliphatic group such as amine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, α,ω-bisaminopolydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, bis(10-aminodecamethylene)tetramethyldisiloxane, bis(3-aminophenoxymethyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polymethylphenylsiloxane, α,It may contain residues of silicon atom-containing diamines such as ω-bis(3-aminopropyl)poly(dimethylsiloxane-diphenylsiloxane) copolymer, residues of diamines having the structure shown below, and residues of diamines having the residue represented by the above formula (6).

[0091]

[0092] R ２０ is an oxygen atom, SO ２ or C(CH ３ ) ２ Represents R ２１ ~R ２４ each independently represents a hydrogen atom or a hydroxyl group.

[0093] From the viewpoint of improving the solvent solubility of the component (a) and improving the reworkability during the production of a cured film, X in formula (6) １ On the other hand, from the viewpoint of improving the sensitivity during the preparation of a cured film, X is preferably a direct bond. １ is preferably a divalent group represented by formula (7) or a divalent group represented by formula (8), and more preferably a divalent group represented by formula (7). ２ represents a divalent group represented by formula (9) or (10), and preferably has a divalent group represented by formula (10) from the viewpoint of improving the bending resistance of the cured film. ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and from the viewpoint of improving the solvent solubility of component (a), an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is preferred. Each d independently represents an integer of 0 to 4, and from the viewpoint of improving the solvent solubility of component (a), d is preferably an integer of 1 to 4.

[0094] In formulas (7) and (8), R ９ are each independently an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and are preferably a methyl group from the viewpoint of enhancing the heat resistance of component (a). Each e is independently an integer from 0 to 4, and from the viewpoint of enhancing the solvent solubility of component (a), d is preferably an integer from 1 to 4. * represents * in formula (6), and ** represents the point of attachment to the aromatic ring.

[0095] In formula (9), R１１ are each independently an alkyl group having 1 to 4 carbon atoms, and are preferably a methyl group in that the heat resistance of component (a) can be improved. When g is 1 or 2 and f is an integer of 1 to 4, both heat resistance and solvent solubility of component (a) can be achieved, which is preferable. In formula (10), R １２ and R １３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. From the viewpoint of enhancing the heat resistance of component (a), R １２ , R １３ are each independently preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 6 carbon atoms. １２ and R １３ represents different substituents. The "different substituents" shown here are １２ and R １３ In addition to the relationship where the composition formula is different, the relationship also includes structural isomers where the composition formula is the same but the bonding state between atoms is different. １２ and R １３ By using different substituents, it is possible to improve the solvent solubility of the component (a). １２ and R １３ The difference in the number of carbon atoms between these is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Examples of the substituents represented by formulae (9) and (10) include the substituents shown below.

[0096]

[0097] The terminals of these resins may also be blocked with known monoamines, acid anhydrides, acid chlorides, monocarboxylic acids, or active ester compounds having an acidic group.

[0098] Component (a) may be synthesized by a known method, but it is preferable to use a solvent containing a β-alkoxypropionamide as the polymerization solvent. When the polymerization solvent for component (a) contains a β-alkoxypropionamide, component (a) containing a β-alkoxypropionamide is obtained, and when the resin composition is subjected to heat treatment, a cured film containing a β-alkoxypropionamide can be obtained. When the cured film contains a β-alkoxypropionamide, the long-term reliability of the cured film can be improved.

[0099] The cured film of the present invention may contain a resin other than component (a), such as, but not limited to, a polymer of a radically polymerizable monomer having an acidic group, a cardo resin, a phenolic resin, or a siloxane resin.

[0100] Examples of polymers of radically polymerizable monomers having an acidic group include acrylic resins, polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymers, etc. Known materials can be used as radically polymerizable monomers having an acidic group, and examples thereof include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and alkyl- or alkoxy-substituted derivatives thereof, methacrylic acid, acrylic acid, and haloalkyl-, alkoxy-, halogen-, nitro-, or cyano-substituted derivatives thereof at the α-position.

[0101] From the viewpoint of improving the long-term reliability of the cured film and suppressing a decrease in luminance during continuous high-temperature operation, particularly when used in an organic EL display device, the cured film of the present invention preferably contains polyhydroxystyrene and / or a polyhydroxystyrene / polystyrene copolymer. In the present invention, the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of component (a). By adjusting the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer to 5 parts by mass or more, per 100 parts by mass of component (a), the long-term reliability of the cured film can be improved. Furthermore, the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, per 100 parts by mass of component (a). By setting the content of polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer to 60 parts by mass or less per 100 parts by mass of component (a), the chemical resistance of the cured film can be maintained.

[0102] Methods for confirming whether or not a cured film contains polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer include, for example, a method of analyzing the cured film by infrared spectroscopy, a method of pyrolyzing the cured film at 600°C and then analyzing it by pyrolysis GC / MS in which the cured film is measured by gas chromatography, a method of extracting the components in the cured film with an organic solvent or the like and measuring the extract by liquid chromatography, and a method of measuring the components in the cured film using time-of-flight secondary ion mass spectrometry.

[0103] Cardo resins include resins having a cardo structure, i.e., a backbone structure in which two rings are bonded to a quaternary carbon atom that constitutes a ring. A typical cardo structure is a fluorene ring bonded to a benzene ring.

[0104] Examples of phenolic resins include known novolak phenolic resins and resol phenolic resins obtained by polycondensing various phenols alone or a mixture of several of them with aldehydes such as formalin.

[0105] Examples of the siloxane resin include known siloxane resins obtained by hydrolyzing and dehydrating condensation of one or more organosilanes selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0106] <Aromatic Hydrocarbon Compound Having at Least Three Phenolic Hydroxyl Groups in One Aromatic Ring> The cured film of the present invention preferably contains an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups in one aromatic ring (hereinafter, sometimes referred to as component (b)). By containing component (b), the cured film of the present invention can improve the long-term reliability of the cured film and, particularly, can suppress a decrease in luminance during continuous high-temperature operation when used in an organic EL display device.

[0107] Methods for confirming whether or not the cured film contains component (b) include, for example, a method in which the cured film is pyrolyzed at 600°C and then analyzed by pyrolysis GC / MS, in which measurement is made by gas chromatography; a method in which the components in the cured film are extracted with an organic solvent or the like and the extract is measured by liquid chromatography; and a method in which the components in the cured film are measured using time-of-flight secondary ion mass spectrometry.

[0108] The aromatic hydrocarbon structure of component (b) includes known monocyclic structures or fused polycyclic structures. Furthermore, the aromatic hydrocarbon has at least three phenolic hydroxyl groups in one aromatic ring. In the present invention, "having at least three phenolic hydroxyl groups in one aromatic ring" refers to a state in which at least three phenolic hydroxyl groups are present in a single aromatic ring. For example, a compound having three aromatic rings each with one phenolic hydroxyl group is not included in component (b) of the present invention. Specific examples of component (b) include, but are not limited to, compounds having the structure shown below:

[0109]

[0110] R ７ are independently a monovalent organic group having 1 to 20 carbon atoms, k is an integer of 0 to 2, l is an integer of 0 to 7, and m is an integer of 3 to 10, provided that {(2k+6)-(l+m)}≧0.

[0111] Examples of aromatic hydrocarbons having at least three phenolic hydroxyl groups in one aromatic ring include phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, gallacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-isopropylidenedipyrogallol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin.

[0112] From the viewpoint of further reducing the transmittance of light of 300 nm to 500 nm of the cured film in combination with a thermal crosslinking agent described below, that is, from the viewpoint of reducing the transmittance of light of a wavelength of 450 nm to 30% or less, in component (b), it is preferable that the substitution position of at least one phenolic hydroxyl group other than any one of the phenolic hydroxyl groups in component (b) is the ortho-position or para-position, and more preferably the para-position.

[0113] Among the component (b), examples of the compound (b1) in which at least one substitution position of a phenolic hydroxyl group other than one of the phenolic hydroxyl groups is the ortho position include pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, gallacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-isopropylidenedipyrogallol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and 1,2,4,5-tetrahydroxybenzene. Pyrogallol or 1,2,4-trihydroxybenzene is preferred from the viewpoint of further reducing the transmittance of light in the 300 nm to 500 nm range of the cured film when combined with a thermal crosslinking agent described below. Examples of the compound (b2) of component (b) in which at least one substitution position of a phenolic hydroxyl group other than one of the phenolic hydroxyl groups is para-positioned include 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin. 1,2,4-trihydroxybenzene is preferred from the viewpoint of further reducing the transmittance of light in the 300 nm to 500 nm range of the cured film when combined with a thermal crosslinking agent described below.

[0114] The upper limit of the molecular weight of component (b) is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. The lower limit of the molecular weight of component (b) is 126 or more.

[0115] In the present invention, the content of component (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (a). By making the content of component (b) 1 part by mass or more, per 100 parts by mass of component (a), the long-term reliability of the cured film of the present invention can be improved. Furthermore, the content of component (b) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, per 100 parts by mass of component (a). By making the content of component (b) 50 parts by mass or less, per 100 parts by mass of component (a), the chemical resistance of the cured film can be maintained.

[0116] <Compound derived from photosensitive compound> The cured film of the present invention preferably contains a compound derived from a photosensitive compound (hereinafter, may be referred to as component (c)). When the cured film of the present invention contains a compound derived from a photosensitive compound, the manufacturing process of the cured film can be simplified. Examples of component (c) include a photopolymerization initiator (hereinafter, may be referred to as component (c1)), a naphthoquinone diazide compound (hereinafter, may be referred to as component (c2)), etc.

[0117] Examples of the component (c1) include known photopolymerization initiators. Examples include benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine oxide compounds, biimidazole compounds, oxime ester compounds, acridine compounds, titanocene compounds, benzophenone compounds, acetophenone compounds, aromatic ketoester compounds, and benzoic acid ester compounds. From the viewpoint of improving sensitivity during cured film production, the cured film of the present invention is preferably an α-hydroxyketone compound, α-aminoketone compound, acylphosphine oxide compound, biimidazole compound, or oxime ester compound. From the viewpoints of improving sensitivity during exposure, improving halftone characteristics, and suppressing residues after development, oxime ester compounds are more preferred.

[0118] Methods for confirming whether or not the cured film contains a compound derived from component (c) include, for example, a method in which the cured film is pyrolyzed at 600°C and then analyzed by pyrolysis GC / MS, in which measurement is made by gas chromatography; a method in which the components in the cured film are extracted with an organic solvent or the like and the extract is measured by liquid chromatography; and a method in which the components in the cured film are measured using time-of-flight secondary ion mass spectrometry.

[0119] From the viewpoint of improving sensitivity during the production of the cured film of the present invention, the content of the compound derived from the component (c1) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the component (a). On the other hand, from the viewpoint of suppressing residue during the production of the cured film of the present invention, the content of the compound derived from the component (c1) is preferably 50 parts by mass or less, per 100 parts by mass of the component (a).

[0120] Examples of the component (c2) include known naphthoquinone diazide compounds, such as 1,2-naphthoquinone diazide-5-sulfonic acid ester compounds and / or 1,2-naphthoquinone diazide-4-sulfonic acid ester compounds.

[0121] From the viewpoint of improving the long-term reliability of the cured film of the present invention, the compound derived from the photosensitive compound contained in the cured film of the present invention is preferably a compound derived from component (c2). Specific examples of the compound derived from a naphthoquinone diazide compound include one or more compounds selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and sulfonic acid aryl esters containing an indene structure. One or more compounds selected from the group consisting of carboxylic acids containing an indene structure, carboxylic acid esters containing an indene structure, sulfonic acids containing an indene structure, and sulfonic acid aryl esters containing an indene structure are preferred.

[0122] From the viewpoint of improving sensitivity during the production of the cured film of the present invention, the content of the compound derived from component (c2) is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 25 parts by mass or more, per 100 parts by mass of component (a). On the other hand, from the viewpoint of suppressing residue during the production of the cured film of the present invention, the content of the compound derived from component (c2) is preferably 100 parts by mass or less, per 100 parts by mass of component (a).

[0123] <β-Alkoxypropionamide> The cured film of the present invention preferably contains a β-alkoxypropionamide. By containing a β-alkoxypropionamide in the cured film of the present invention, the long-term reliability of the cured film can be improved, and in particular, when used in an organic EL display device, a decrease in luminance during continuous operation at high temperatures can be suppressed.

[0124] Specific methods for obtaining a cured film containing a β-alkoxypropionamide include a method in which a β-alkoxypropionamide is added to a resin composition for obtaining the cured film of the present invention and the resin composition is heat-treated to obtain a cured film, a method in which a β-alkoxypropionamide is used as a polymerization solvent for component (a) and a resin composition containing component (a) containing a β-alkoxypropionamide is heat-treated to obtain a cured film, etc. From the viewpoint of suppressing volatilization of the β-alkoxypropionamide during heat treatment and improving the long-term reliability of the cured film, a method in which a β-alkoxypropionamide is used as a polymerization solvent for component (a) and a resin composition containing component (a) containing a β-alkoxypropionamide is heat-treated to obtain a cured film is preferred.

[0125] As a method for confirming whether or not the cured film contains a β-alkoxypropionamide, for example, a method can be mentioned in which components generated from the cured film are adsorbed and collected by a purge-and-trap method, subjected to thermal decomposition at 600°C, and then analyzed by purge-and-trap GC / MS, in which the components are measured by gas chromatography.

[0126] Examples of β-alkoxypropionamides include β-methoxypropionamide, β-methoxy-N-methylpropionamide, β-methoxy-N,N-dimethylpropionamide, β-methoxy-N-ethylpropionamide, β-methoxy-N,N-diethylpropionamide, β-methoxy-(N-propyl)propionamide, β-methoxy-(N,N-dipropyl)propionamide, β-methoxy-N-butylpropionamide, β-methoxy-N,N-dibutylpropionamide, β-ethoxy-N,N-dimethylpropionamide, β-propoxy-N,N-dimethylpropionamide, β-butoxy-N,N-dimethylpropionamide, etc. From the viewpoint of versatility, β-methoxy-N,N-dimethylpropionamide or β-butoxy-N,N-dimethylpropionamide is preferred as the β-alkoxypropionamide.

[0127] From the viewpoint of improving the long-term reliability of the cured film, the content of β-alkoxypropionamide in the cured film is preferably from 0.01% by mass to 5% by mass, more preferably from 0.05% by mass to 1% by mass, and even more preferably from 0.1% by mass to 0.5% by mass.

[0128] <Sulfonic Acid and / or Sulfonate Ion> The cured film of the present invention preferably contains one or more sulfonic acids selected from the group represented by any one of formulas (3) to (5), or sulfonate ions derived from the sulfonic acids (hereinafter, may be referred to as specific sulfonic acids and / or sulfonate ions).

[0129]

[0130] In formula (3), R ５ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5. ６ represents a monovalent organic group having 1 to 10 carbon atoms.

[0131] The cured film of the present invention contains a specific sulfonic acid and / or sulfonate ion, which improves the long-term reliability of the cured film and, particularly, when used in an organic EL display device, can suppress a decrease in luminance during continuous operation at high temperatures.

[0132] Specific methods for obtaining a cured film containing a specific sulfonic acid and / or sulfonate ions include a method of obtaining a cured film by heat-treating a composition using a compound containing a specific sulfonic acid and / or sulfonate ions, and a method of obtaining a cured film by heat-treating a composition containing a thermal acid generator that generates a specific sulfonic acid and / or sulfonate ions during heat treatment. From the viewpoint of improving the long-term reliability of the cured film, the method of obtaining a cured film by heat-treating a composition containing a thermal acid generator that generates a specific sulfonic acid and / or sulfonate ions during heat treatment is preferred.

[0133] Methods for confirming whether a cured film contains a specific sulfonic acid and / or sulfonate ion include, for example, a method in which the cured film is pyrolyzed at 600°C and then analyzed by pyrolysis GC / MS, in which measurement is made by gas chromatography; a method in which components in the cured film are extracted with an organic solvent or the like and the extract is measured by liquid chromatography; and a method in which the components in the cured film are measured using time-of-flight secondary ion mass spectrometry.

[0134] As the thermal acid generator that generates a specific sulfonic acid and / or sulfonate ions during heat treatment, a thermal acid generator having a sulfonate ester structure is preferred, and specific examples thereof include "Irgacure" (registered trademark) PAG103, PAG121 (trade names, manufactured by BASF Japan Ltd.), PA-411, PA-480 (trade names, manufactured by Heraeus K.K.), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, PAI-1004 (trade names, manufactured by Midori Chemical Co., Ltd.), and SP-082. , SP-601, SP-606, SP-607, SP-612 (trade names, manufactured by ADEKA CORPORATION), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade names, manufactured by Heraeus K.K.), NAI-105, NAI-106, NAI-109 (trade names, manufactured by Midori Chemical Co., Ltd.), as well as sulfonate esters synthesized by known methods using one or more sulfonic acids selected from the group represented by formulas (3) to (5) and alcohols or phenols.

[0135] In formula (3), R ５ are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and n is an integer of 1 to 5. Examples of the monovalent organic group having 1 to 10 carbon atoms include an alkyl group, an alkynyl group, an alkenyl group, an aryl group, and CF ３ From the viewpoint of easy availability of raw materials, R5 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group. From the viewpoint of easy availability of raw materials, n is preferably an integer of 1 to 3, and more preferably 1. Examples of sulfonic acids represented by formula (3) include benzenesulfonic acid, toluenesulfonic acid, and styrenesulfonic acid.

[0136] In formula (4), R ６ represents a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include an alkyl group, an alkynyl group, an alkenyl group, a benzyl group, and CF ３ From the viewpoint of easy availability of raw materials, ５ is an alkyl group having 1 to 10 carbon atoms or CF ３ is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples of sulfonic acids represented by formula (4) include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, trifluoromethanesulfonic acid, benzylsulfonic acid, and vinylsulfonic acid.

[0137] From the viewpoint of improving the long-term reliability of the cured film, the content of the specific sulfonic acid and / or sulfonate ion is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, per 100 parts by mass of component (a). On the other hand, from the viewpoint of improving the heat resistance of the cured film, the content of the specific sulfonic acid and / or sulfonate ion is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, per 100 parts by mass of component (a).

[0138] <Colorant (d)> The cured film of the present invention preferably further contains a colorant (d) (hereinafter, sometimes referred to as component (d)). By including component (d) in the cured film of the present invention, the light-blocking properties of the cured film can be improved, thereby suppressing external light reflection when used in a display device. Furthermore, by including component (d) in the cured film of the present invention, the transmittance of light at a wavelength of 450 nm can be reduced. When the cured film of the present invention is used in an organic EL display device having an oxide semiconductor TFT, malfunctions due to UV light entering the TFT can be prevented. From the viewpoint of improving the visible light-blocking properties of the cured film and increasing the OD value of visible light per μm of film thickness, component (d) preferably has a maximum absorption wavelength anywhere in the wavelength range of 300 nm to 850 nm. Furthermore, from the viewpoint of achieving a transmittance of 450 nm light of 30% or less, component (d) preferably has a maximum absorption wavelength anywhere in the range of 300 nm to 600 nm, and more preferably has a maximum absorption wavelength anywhere in the range of 400 nm to 500 nm.

[0139] The component (d) preferably contains a dye (d1) and / or a pigment (d2). The component (d) preferably contains at least one type. For example, the component (d) may contain one type of dye (d1) or pigment (d2), or two or more types of dyes (d1) or pigments (d2), or may contain one or more types of dyes (d1) and one or more types of pigments (d2). The component (d) is preferably a black agent and / or a mixture of two or more colorants.

[0140] From the viewpoint of solvent solubility, the component (d) contained in the cured film of the present invention preferably contains a dye (d1). Furthermore, from the viewpoint of improving sensitivity during the preparation of the cured film of the present invention, the dye (d1) is preferably an ionic dye that forms an ion pair between organic ions. Furthermore, from the viewpoint of increasing sensitivity and reducing residues, the component (d) preferably has a sulfonic acid group and / or a sulfonate group.

[0141] Examples of the skeletal structure of dye (d1) include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, and xanthene-based skeletal structures. Among these, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based skeletal structures are preferred from the viewpoints of solubility in solvents and heat resistance. Furthermore, a xanthene-based skeletal structure is more preferred from the viewpoint of improving heat resistance. Furthermore, each of these dyes may be used alone or as a metal-containing complex salt system.

[0142] The component (d) contained in the cured film of the present invention preferably contains a pigment (d2) from the viewpoint of improving the heat resistance of the cured film. The pigment (d2) is particularly preferably an organic black pigment, and preferably contains one or more pigments selected from the group consisting of benzofuranone-based black pigments, perylene-based black pigments, and azo-based black pigments.

[0143] The content of component (d) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of component (a). By ensuring that the content of component (d) is 0.1 parts by mass or more per 100 parts by mass of component (a), light of the corresponding wavelength can be absorbed. Furthermore, by ensuring that the content of component (d) is 300 parts by mass or less, light of the corresponding wavelength can be absorbed while maintaining the heat resistance and mechanical properties of the cured film.

[0144] <Compound Derived from Thermal Crosslinking Agent> The cured film of the present invention may contain a compound derived from a thermal crosslinking agent. A thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group, in the molecule. When the cured film of the present invention contains a compound derived from a thermal crosslinking agent, crosslinking occurs between the thermal crosslinking agent and component (a) or between the thermal crosslinking agents themselves, thereby improving the heat resistance, chemical resistance, and bending resistance of the cured film. When used in combination with the aforementioned component (b), from the viewpoint of reducing the transmittance of light in the 300 nm to 500 nm range after curing, an alkoxymethyl group or a methylol group is preferred as the thermal crosslinking agent, and it is more preferred that the thermal crosslinking agent has an alkoxymethyl group or a methylol group directly substituted on the nitrogen atom. When used in combination with the aforementioned component (b), from the viewpoint of reducing the transmittance of light in the 300 nm to 500 nm range after curing, the compound derived from the thermal crosslinking agent preferably has a triazine ring.

[0145] The content of the compound derived from the thermal crosslinking agent is preferably 1% by mass or more and 30% by mass or less based on 100% by mass of the cured film. If the content of the compound derived from the thermal crosslinking agent is 1% by mass or more, the chemical resistance and bending resistance of the cured film can be further improved. Furthermore, if the content of the compound derived from the thermal crosslinking agent is 30% by mass or less, the amount of outgassing from the cured film can be further reduced.

[0146] <Compounds derived from adhesion improvers> The cured film of the present invention may contain a compound derived from an adhesion improver. Examples of compounds derived from adhesion improvers include known silane coupling agents, titanium chelating agents, aluminum chelating agents, and compounds derived from compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. By containing these compounds derived from adhesion improvers, the adhesion of the cured film to underlying substrates such as silicon wafers, indium tin oxide (ITO), SiO2, silicon nitride, and polyimide film substrates can be improved.

[0147] From the viewpoints of setting the Si / C ratio at 0.001 or more and 0.005 or less and improving the bending resistance and long-term reliability of the cured film, the cured film of the present invention preferably contains a known silane coupling agent as an adhesion improver. Known silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- ... Examples thereof include aryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.Among these, from the viewpoint of improving storage stability, one or more silane coupling agents selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane are preferred, and 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane is more preferred.

[0148] The content of the adhesion improver is preferably 0.01 to 10% by mass based on 100% by mass of the cured film. When the cured film of the present invention contains a known silane coupling agent as an adhesion improver from the viewpoints of improving the bending resistance and long-term reliability of the cured film by setting the Si / C ratio at 0.001 or more and 0.005 or less, the content of the known silane coupling agent is preferably 0.6 to 6.0% by mass, more preferably 1.0 to 5.0% by mass, and particularly preferably 2.0 to 4.0% by mass based on 100% by mass of the cured film.

[0149] <Inorganic Particles> The cured film of the present invention may contain inorganic particles. Specific preferred examples of inorganic particles include particles made of silicon oxide, titanium oxide, barium titanate, alumina, talc, etc. The primary particle diameter of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0150] The content of the inorganic particles is preferably 5 to 90% by mass based on 100% by mass of the cured film.

[0151] <Method for Producing Cured Film> The method for producing the cured film of the present invention will be described taking as an example a method in which a photosensitive resin film made of a photosensitive resin composition is formed on a substrate, and the photosensitive resin film is exposed to light, developed, and then subjected to a heat treatment.

[0152] First, the process of forming a photosensitive resin film made of a photosensitive resin composition on a substrate will be described.

[0153] The photosensitive resin composition used in producing the cured film of the present invention can be obtained by mixing and dissolving, for example, one or more polymers selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, component (c), and, if necessary, component (b), β-alkoxypropionamide, a thermal acid generator that generates a specific sulfonic acid and / or sulfonate ions, component (d), a thermal crosslinking agent, an adhesion improver, a surfactant, inorganic particles, a solvent, etc.

[0154] Subsequently, the photosensitive resin composition is applied to a base substrate to obtain a coating film of the photosensitive resin composition, and the coating film is dried to obtain a photosensitive resin film. A known substrate such as a glass substrate can be used as the base substrate. Examples of methods for applying the photosensitive resin composition of the present invention include spin coating, slit coating, dip coating, spray coating, and printing.

[0155] After coating the photosensitive resin composition, a reduced-pressure drying process is performed as needed. The reduced-pressure drying rate depends on the vacuum chamber volume, vacuum pump capacity, and piping diameter between the chamber and the pump. For example, it is preferable to set conditions such that the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate. After coating or reduced-pressure drying, the resulting coating film is typically heated and dried. This process is also known as pre-baking. A hot plate, oven, infrared light, or the like is used for drying. When using a hot plate, the coating film is heated directly on the plate or while held on a jig such as a proxy pin placed on the plate. The heating time is preferably from one minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but is preferably 80°C or higher, more preferably 90°C or higher, from the viewpoint of accelerating solvent drying during pre-baking. On the other hand, the heating temperature is preferably 150°C or lower, more preferably 140°C or lower, from the viewpoint of reducing the progress of curing during pre-baking.

[0156] Next, the step of exposing the photosensitive resin film will be described. For example, the photosensitive resin film can be exposed to actinic rays through a photomask having a desired pattern, and then developed to form a desired pattern.

[0157] Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the photosensitive resin film has positive photosensitivity, the exposed areas dissolve in a developer. When the photosensitive resin film has negative photosensitivity, the exposed areas harden and become insoluble in a developer.

[0158] Next, the process of developing the exposed photosensitive resin film will be described.

[0159] After exposure, the desired pattern is formed by removing the exposed areas with a developer if the photosensitive resin film is positive-tone, or the unexposed areas if the photosensitive resin film is negative-tone. Examples of the developer include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. These alkaline aqueous solutions may contain one or more of the following: polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Examples of the developing method include spray, puddle, immersion, and ultrasonic methods.

[0160] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.

[0161] Next, a process of heat treating the developed photosensitive resin film to obtain a cured film will be described.

[0162] A cured film can be obtained by heat-treating the photosensitive resin film developed as described above. When the photosensitive resin composition used for producing the cured film of the present invention contains a polyimide precursor or a polybenzoxazole precursor, a cured film containing polyimide or polybenzoxazole can be obtained by heat-treating.

[0163] The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured film. On the other hand, from the viewpoint of improving the film toughness of the cured film, the heat treatment temperature is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured film, the heat treatment time is preferably 3 hours or shorter. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours may be mentioned.

[0164] The atmosphere during the heat treatment is preferably a low oxygen concentration of less than 5% from the viewpoints of improving the long-term reliability of the cured film and suppressing a decrease in luminance during continuous high-temperature operation, particularly when used in an organic EL display device. Examples of inert gases for achieving an oxygen concentration of less than 5% include nitrogen and argon. The oxygen concentration in the inert gas atmosphere is preferably less than 5%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably less than 0.01%.

[0165] <Application Examples of Cured Film> The cured film of the present invention is suitable for use as a surface protection layer or interlayer insulating layer for semiconductor elements, a pixel dividing layer for organic EL elements, a planarizing layer for a TFT substrate of a display device using an organic EL element, a wiring protection insulating layer for a circuit board, an on-chip microlens for a solid-state imaging element, and a planarizing layer for various display devices and solid-state imaging elements. For example, the cured film is suitable as a surface protection layer or interlayer insulating layer for MRAM, which has low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), which are promising next-generation memories, and the like.

[0166] <Organic EL display device> The organic EL display device of the present invention has the cured film of the present invention. An organic EL display device using the cured film of the present invention includes at least a substrate, a first electrode, a second electrode, an organic EL layer, a planarizing layer, and a pixel dividing layer, and it is preferable that the cured film is contained in the planarizing layer and / or the pixel dividing layer. By containing the cured film of the present invention in the planarizing layer and / or the pixel dividing layer, it is possible to provide an organic EL display device with excellent long-term reliability.

[0167] The organic EL display device using the cured film of the present invention is an organic EL display device having multiple pixels formed on a matrix. The driving methods of organic EL display devices are broadly classified into passive matrix types, in which electrodes are divided into columns and rows and only the pixels sandwiched between the electrodes emit light, and active matrix types, in which several TFTs are provided for each pixel for switching, but are not particularly limited thereto. An organic EL display device is formed on a substrate in the following order: a planarization layer, a first electrode, a pixel division layer, an organic EL layer, and a second electrode. An active matrix organic EL display device has a substrate such as glass on which a drive circuit consisting of TFTs and wiring located on the sides of the TFTs and connected to the TFTs is formed. A planarization layer is formed on the drive circuit to cover the unevenness, and an organic EL layer is further formed on the planarization layer. The organic EL layer and the wiring are connected via contact holes formed in the planarization layer. Furthermore, in the organic EL display device of the embodiment of the present invention, a pixel division layer is formed on the first electrode.

[0168] FIG. 1 shows a cross-sectional view of an organic EL display device provided on a substrate 1. Bottom-gate or top-gate TFTs 2 are arranged in a matrix on the substrate 1, and a TFT insulating layer 3 is formed to cover the TFTs 2. Wiring 4 connected to the TFTs 2 is provided below the TFT insulating layer 3. A planarization layer 5 is further provided on the TFT insulating layer 3. Contact holes 6 are formed in the planarization layer 5 so that the wiring 4 is exposed. A first electrode 7 is formed on the planarization layer 5, connected to the wiring 4 via the contact holes 6. A pixel division layer 8 is then formed to cover the periphery of the first electrode 7. An organic EL layer 9 and a second electrode 10 are further formed thereon. This organic EL display device may be a top-emission type, in which emitted light is emitted from the opposite side of the substrate 1, or a bottom-emission type, in which light is extracted from the substrate 1 side.

[0169] In addition, in this organic EL display device, a color display can be obtained by arranging organic EL elements having emission peak wavelengths in the red, green, and blue regions as the organic EL layer, or by providing a white organic EL layer on the entire surface and using it in combination with a color filter. In color displays, the peak wavelength of light displayed in the red region is usually in the range of 560 to 700 nm, the green region is 500 to 560 nm, and the blue region is 420 to 500 nm.

[0170] In an organic EL element, the area where the opposing first and second electrodes intersect and overlap, and each area defined by the pixel division layer on the first electrode, is called a light-emitting pixel. The shape of the light-emitting pixel is not particularly limited and may be, for example, rectangular or circular, and can be easily changed depending on the shape of the pixel division layer. In an active matrix display, the part where the switching means is formed may be arranged to occupy part of the light-emitting pixel, so the shape of the light-emitting pixel may not be rectangular but may have a shape with a missing part.

[0171] In the fabrication of the organic EL device of the present invention, the organic EL layer is formed by a mask vapor deposition method. The mask vapor deposition method is a method of vapor-depositing and patterning an organic compound using a vapor deposition mask. The vapor deposition mask has openings of the desired pattern and is placed on the vapor deposition source side of the substrate. To obtain a highly accurate vapor deposition pattern, it is important to use a highly flat vapor deposition mask in close contact with the substrate. Generally, a technique for applying tension to the vapor deposition mask or a technique for closely contacting the vapor deposition mask with the substrate using a magnet placed on the backside of the substrate is used.

[0172] Methods for manufacturing a vapor deposition mask having openings of a desired pattern include etching, mechanical polishing, sandblasting, sintering, laser processing, and the use of photosensitive resins. When a fine pattern is required, etching or electroforming, which have excellent processing accuracy, are often used.

[0173] The configuration of the organic EL layer included in the organic EL element of the present invention is not particularly limited, and may be, for example, any of (1) a hole transport layer / a light emitting layer, (2) a hole transport layer / a light emitting layer / a electron transport layer, and (3) a light emitting layer / a electron transport layer.

[0174] Next, the second electrode is formed. In active matrix type LCDs, the second electrode is often formed solid over the entire light-emitting area. The second electrode is required to function as a cathode that can efficiently inject electrons, so metal materials are often used to ensure electrode stability. It is also possible to use the first electrode as a cathode and the second electrode as an anode.

[0175] After forming the second electrode, sealing is performed to obtain an organic EL display device. Generally, organic EL elements are considered to be vulnerable to oxygen and moisture, and therefore, in order to obtain a highly reliable display device, it is preferable to perform sealing in an atmosphere with as little oxygen and moisture as possible. It is also preferable to select a material with high gas barrier properties for use in sealing.

[0176] In order to enhance the effect of reducing external light reflection, the organic EL display device of the present invention preferably further comprises a color filter having a black matrix. The black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a siloxane resin.

[0177] The black matrix contains a colorant. Examples of colorants that can be used include black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among these, carbon black, titanium nitride, titanium carbide, and composite particles of these with metals such as silver, which have high light-shielding properties, are preferred.

[0178] The OD value of the black matrix is ​​preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 4.5 or more.

[0179] <Display Device Other Than Organic EL Display Device> Another embodiment of a display device having the cured film of the present invention will be described with reference to Fig. 2. This display device has at least metal wiring, the cured film of the present invention, and a plurality of light-emitting elements, each of which has a pair of electrode terminals on one surface thereof, the pair of electrode terminals being connected to a plurality of metal wirings extending in the cured film, and the plurality of metal wirings being electrically insulated by the cured film.

[0180] In FIG. 2, the display device 11 has a plurality of light-emitting elements 12 arranged on a counter substrate 15, and a cured film 13 arranged on the light-emitting elements 12. Here, "on the light-emitting elements" does not necessarily mean the surface of the light-emitting elements, but may also mean the upper side of the supporting substrate or the light-emitting elements. The embodiment shown in FIG. 2 illustrates a configuration in which a plurality of cured films 13 are laminated on a cured film 13 arranged so as to contact at least a portion of the light-emitting elements 12, resulting in a total of three cured film layers. However, the cured film 13 may also be a single layer. The light-emitting element 12 has a pair of electrode terminals 16 on the surface opposite to the surface contacting the counter substrate 15, and each electrode terminal 16 is connected to a metal wiring 14 extending through the cured film 13. Note that if the plurality of metal wirings 14 extending through the cured film 13 are covered with the cured film 13, the cured film 13 also functions as an insulating layer, thereby maintaining electrical insulation. The term "metal wiring maintaining electrical insulation" means that the portions of the metal wiring that require electrical insulation are covered with a cured film containing component (a). In the present invention, the insulating layer is in an electrically insulating state when the volume resistivity of the insulating layer is 10 １２ This means a state in which the electrical resistance is equal to or greater than Ω cm. Furthermore, the light emitting element 12 is electrically connected to a driving element 18 attached to a light emitting element driving substrate 17 provided at a position opposite to the counter substrate 15 via metal wiring 14 or 14c, thereby controlling the light emission of the light emitting element 12. Furthermore, the light emitting element driving substrate 17 is electrically connected to the metal wiring 14 via, for example, solder bumps 20. Furthermore, a barrier metal 19 may be provided to prevent diffusion of metal such as the metal wiring 14.

[0181] <Electronic Components> The electronic components of the present invention are electronic components having the cured film of the present invention. The cured film of the present invention can be used in electronic components such as semiconductor devices. Examples of electronic components include active components having semiconductors, such as transistors, diodes, integrated circuits (ICs), and memories, and passive components, such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices or semiconductor packages. In the present invention, the term "semiconductor device" refers to any device that can function by utilizing the characteristics of semiconductor elements. Semiconductor devices include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices containing these. Semiconductor devices also include electronic components such as interposers for connecting semiconductor elements to a substrate. Specifically, the cured film of the present invention has excellent electrical insulation, mechanical strength, adhesion, and heat resistance, and can be used as surface protection films such as passivation films and buffer coat films for semiconductor elements, interlayer insulating films between rewirings formed on the surface of semiconductor elements, insulating films between elements when multiple semiconductor elements are bonded, and insulating films between wiring layers in multilayer wiring boards for high-density packaging and interposers.

[0182] More preferably, the cured film of the present invention is disposed as a semiconductor surface protective film or an interlayer insulating film between rewirings in a semiconductor device. By disposing the cured film of the present invention as a semiconductor surface protective film or an interlayer insulating film between rewirings, a highly reliable semiconductor device can be obtained.

[0183] More preferably, the semiconductor device has the rewiring and the interlayer insulating film repeatedly arranged in 2 to 10 layers. By repeatedly arranging the rewiring and the interlayer insulating film in 2 to 10 layers, the semiconductor device can be miniaturized.

[0184] The electronic component of the present invention preferably comprises a substrate on which the cured film of the present invention is formed. The substrate on which the cured film is formed can be appropriately selected depending on the application and process, and examples thereof include a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, ceramics, gallium arsenide, a metal, and an epoxy resin. A silicon substrate, a silicon carbide substrate, or a gallium nitride substrate is preferred, and a silicon carbide substrate or a gallium nitride substrate is more preferred.

[0185] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Evaluations in the examples were carried out by the following methods.

[0186] (1) Electron Probe Microanalyzer Measurement of Cured Films The varnishes obtained in each of the Examples and Comparative Examples were spin-coated onto a 5 cm square glass substrate so that the film thickness after heat treatment (curing) would be 2.0 μm, and the substrate was pre-baked at 120°C for 120 seconds to produce a pre-baked film. Thereafter, without UV exposure, the substrate was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) so that the film thickness reduction in the unexposed areas was approximately 0.5 μm. Next, the substrate was cured at 250°C for 60 minutes in a nitrogen atmosphere using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. to produce a cured film.

[0187] The thickness of the cured film was measured using a stylus profiler (P-15, manufactured by KLA Tencor Corporation).

[0188] The cross section of the cured film thus obtained was exposed by oblique polishing and ion milling. Carbon deposition was performed on the exposed cross section of the cured film, and elemental analysis was then performed using an electron beam microanalyzer JXA-8530F (manufactured by JEOL Ltd.). The measurement conditions were an acceleration voltage of 6 kV, a probe current of 25 nA, and a measurement time of 10 seconds. C (carbon atoms) had a Kα peak intensity of 44.00 Å using an LDE2H analyzing crystal, Si (silicon atoms) had a Kα peak intensity of 7.12 Å using a PETH analyzing crystal, N (nitrogen atoms) had a Kα peak intensity of 31.60 Å using an LDE1 analyzing crystal, O (oxygen atoms) had a Kα peak intensity of 23.71 Å using an LDE1 analyzing crystal, and F (fluorine atoms) had a Kα peak intensity of 18.31 Å using an LDE1 analyzing crystal. As a standard sample for each element, BaSO ４ , SiO ２ , AlN, CaF ２ , and SiC were used, and ZAF correction (Z: atomic number correction, A: absorption correction, F: fluorescence excitation correction) was performed. Each sample was measured three times, and the mole percentage of each element in the cured film was calculated from the average value, and the F / C ratio, which is the molar ratio of fluorine atoms to carbon atoms, and the Si / C ratio, which is the molar ratio of silicon atoms to carbon atoms, were calculated.

[0189] (2) Evaluation of reworkability during preparation of cured film A glass substrate with a resin film after development, prepared in the same manner as in (1), was immersed in propylene glycol monomethyl ether and left at room temperature for 30 minutes. Thereafter, the glass substrate was taken out of the propylene glycol monomethyl ether, and the presence or absence of residue on the glass substrate was visually observed. When no residue was observed on the glass substrate, it was judged as "A", when only a small amount of residue was observed on the glass substrate, it was judged as "B", and when a large amount of residue was observed on the glass substrate, it was judged as "C".

[0190] (3) Evaluation of bending resistance of cured films The varnishes obtained in each example and comparative example were spin-coated onto a polyimide film substrate so that the film thickness after heat treatment (curing) would be 2.0 μm, and the varnishes were pre-baked at 120°C for 120 seconds to produce pre-baked films. Subsequently, without UV exposure, the films were developed with a 2.38% TMAH aqueous solution so that the film thickness in the unexposed areas was approximately 0.5 μm. Next, the films were cured at 250°C for 60 minutes in a nitrogen atmosphere using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. to produce cured films.

[0191] Next, 10 polyimide film substrates with a size of 50 mm length x 10 mm width were cut out. Next, with the cured film surface facing outward, the polyimide film substrate was bent along a 25 mm vertical line with a curvature radius of 0.1 to 1.0 mm and held in this state for 30 seconds. After 30 seconds, the bent polyimide film substrate was returned to its original state, and the bent portion along the 25 mm vertical line on the cured film surface was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation) to evaluate changes in the appearance of the cured film surface. The bending test was performed with varying curvature radii in the range of 0.1 to 1.0 mm, and the minimum curvature radius at which the cured film did not peel from the polyimide film substrate or cause changes in appearance such as cracks on the cured film surface was recorded. If the minimum radius of curvature was less than 0.2 mm, it was rated as "S", if it was 0.2 mm or more but less than 0.4 mm, it was rated as "A", if it was 0.4 mm or more but less than 0.6 mm, it was rated as "B", and if it was 0.6 mm or more, it was rated as "C".

[0192] (4) Calculation of the β-alkoxypropionamide content in the cured film. 10 mg of the cured film prepared in the same manner as in (1) was sampled, and components containing β-alkoxypropionamide were adsorbed and collected using a purge-and-trap method. Specifically, the sampled cured film was heated at 400°C for 60 minutes using helium as a purge gas, and the components desorbed from the cured film were collected in an adsorption tube. The collected components were desorbed from the adsorption tube by heating at 320°C for 5 minutes, and GC-MS analysis was performed using a GC-MS system 7890 / 5975C (manufactured by Agilent) under the following conditions: column temperature: 40 to 300°C, carrier gas: helium (1.5 mL / min), and scan range: m / Z 29 to 600. The same β-alkoxypropionamide as the detected β-alkoxypropionamide was used as a standard substance and subjected to GC-MS analysis under the same conditions as above to create a calibration curve, from which the amount of β-alkoxypropionamide gas generated was calculated.The content (mass%) of β-alkoxypropionamide in the cured film was calculated from the amount of β-alkoxypropionamide gas generated thus determined and the mass of the sample used in the measurement.

[0193] (5) Long-Term Reliability Evaluation of Organic EL Display Devices (Brightness Evaluation During Continuous Operation at High Temperatures) A ​​schematic diagram of the fabrication procedure for an organic EL display device is shown in Figure 3. First, a 10-nm thick ITO transparent conductive film was formed over the entire surface of a 38 mm x 46 mm alkali-free glass substrate 21 by sputtering, and then etched into the desired shape to form a first electrode (transparent electrode) 22. Simultaneously, an auxiliary electrode 23 for connecting the second electrode was also formed (Figure 3(1)). The resulting electrode-attached substrate was ultrasonically cleaned for 10 minutes using Semicoclean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then washed with ultrapure water. Next, the photosensitive resin composition obtained in each example and comparative example was applied to the entire surface of the substrate by spin coating, and the substrate was prebaked for 2 minutes on a hot plate at 120°C. The resulting prebaked film was exposed to the minimum exposure dose for each photosensitive resin composition using a high-pressure mercury lamp as a light source through a photomask having the desired pattern. The resulting film was then developed with a 2.38% by mass TMAH aqueous solution to dissolve unnecessary portions and rinsed with pure water to obtain a resin pattern. The resulting resin pattern was then cured by heating at 230°C for 60 minutes in air or nitrogen using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. In this manner, a pixel division layer 24 was formed in the effective substrate area, with openings measuring 70 μm in width and 260 μm in length arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, each opening exposing the first electrode. In this manner, a pixel division layer with an aperture ratio of 25% was formed in the effective substrate area, which was a rectangle with sides of 16 mm. The pixel division layer had a thickness of approximately 1.5 μm (Figure 3(2)).

[0194] Next, an organic EL layer 25 including a light-emitting layer was formed by vacuum deposition on the substrate on which the pixel dividing layer was formed. Note that the degree of vacuum during deposition was 1×10 －３The pressure was below 1 Pa, and the substrate was rotated relative to the evaporation source during evaporation. First, compound (HT-1) was evaporated to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was evaporated to a thickness of 50 nm as a hole transport layer. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were evaporated to a thickness of 40 nm as an emitting layer so that the doping concentration was 10%. Next, compound (ET-1) and compound (LiQ) were laminated to a thickness of 40 nm as electron transport materials at a volume ratio of 1:1. In this way, an organic EL layer 25 consisting of a hole injection layer / hole transport layer / emitting layer / electron transport was formed (Figure 3 (3)). The structures of the compounds used in the organic EL layer are shown below.

[0195]

[0196] Next, a compound (LiQ) was vapor-deposited to a thickness of 2 nm, followed by vapor deposition of 10 nm of Mg and Ag at a volume ratio of 10:1 to form a second electrode (non-transparent electrode) 26 (FIG. 3(4)). Finally, a cap-shaped glass plate was attached to the substrate in a low-humidity nitrogen atmosphere using an epoxy resin adhesive to seal the substrate. Four top-emission organic EL display devices, each 5 mm square, were fabricated on a single substrate. The film thickness referred to here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0197] The organic EL display device fabricated by the above method was subjected to a current of 10 mA / cm ２ The same organic EL display device was then driven with a DC current of 10 mA / cm at 85°C and the initial luminance was measured. ２ The device was continuously driven with a direct current at 100 Hz, and the time it took for the brightness to decrease to half of the initial brightness was measured as the brightness half-life. A brightness half-life of 400 hours or more was rated as "S," a brightness half-life of 380 hours or more but less than 400 hours was rated as "A," a brightness half-life of 360 hours or more but less than 380 hours was rated as "B," and a brightness half-life of less than 360 hours was rated as "C."

[0198] (6) Evaluation of Light-Shielding Property at 450 nm (Transmittance at 450 nm) For cured films prepared in the same manner as in (1), the transmission spectrum of light with wavelengths of 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance of light with a wavelength of 450 nm at a film thickness of 2.0 μm after curing was determined.

[0199] When the thickness of the cured film was other than 2.0 μm, the transmittance was converted to absorbance, corrected to the absorbance at a film thickness of 2.0 μm, and then the absorbance was converted back to transmittance, thereby determining the transmittance at a wavelength of 450 nm at a film thickness of 2.0 μm.

[0200] (7) Evaluation of visible light blocking ability (OD value per 1 μm) For the cured films prepared in the same manner as in (1), the OD value was measured using an optical densitometer (361T; manufactured by X-Rite Corporation). The obtained OD value was divided by the film thickness of the cured film to determine the OD value per 1 μm (hereinafter referred to as OD / μm) (OD value per 1 μm = OD value / film thickness of cured film).

[0201] Synthesis Example 1 Synthesis of Quinone Diazide Compound (c-1) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was removed by filtration, and the resulting filtrate was poured into water, and the resulting precipitate was collected by filtration. The resulting precipitate was dried in a vacuum dryer to obtain quinone diazide compound (c-1) represented by the following formula:

[0202]

[0203] Synthesis Example 2 Synthesis of Polyhydroxystyrene (p-1) 2,400 g of tetrahydrofuran was mixed with 2.56 g (0.04 mol) of sec-butyllithium as an initiator, and 105.75 g (0.6 mol) of p-t-butoxystyrene was added to the mixture. After polymerization with stirring for 3 hours, 12.82 g (0.4 mol) of methanol was added to carry out a polymerization termination reaction. Next, to purify the polymer, the reaction mixture was poured into 3 L of methanol, and the precipitated polymer was dried. The obtained polymer was dissolved in 1.6 L of acetone, and 2 g of concentrated hydrochloric acid was added at 60 ° C. and stirred for 7 hours to deprotect the p-t-butoxy group, converting p-t-butoxystyrene to hydroxystyrene. After completion of the reaction, the solution was poured into water to precipitate the polymer. The resulting precipitate was washed three times with water and then dried in a vacuum dryer at 50 ° C. for 24 hours to obtain the desired polyhydroxystyrene (p-1).

[0204] Synthesis Example 3 Synthesis of diamine compound (α) 18.3 g (0.05 mol) of 6FAP was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the solution was cooled to −15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise to the solution. After the addition was completed, the mixture was reacted at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0205] 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2 g of 5 mass % palladium on carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a fluorine atom-containing diamine compound (α) represented by the following formula:

[0206]

[0207] Synthesis Example 4 Synthesis of diamine compound (β) 25.66 g (0.086 mol) of 4,4'-(2-ethylhexylidene)diphenol and 100 ml of glacial acetic acid were placed in a 500 ml four-neck flask equipped with a stirrer, a thermocouple, and a dropping funnel, and the internal temperature was raised to 50°C in a water bath. 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour, followed by ice cooling to lower the internal temperature to 13°C, and 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was continued for 3 hours, and the precipitated yellow crystals were collected by filtration, washed successively with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain a dinitro compound.

[0208] Next, 52.44 g (0.135 mol) of the dinitro compound, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were placed in a 2 L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and the mixture was stirred under ice cooling. 0.9 g of 5% palladium-carbon (Wako Pure Chemical Industries, Ltd.) suspended in 30 ml of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 ml of ethanol. All of the solvent was removed by heating under reduced pressure, and the residue was washed with 75 ml of ice-cold ethanol, filtered, and then washed with 75 ml of deionized water and 150 ml of diethyl ether, followed by drying under reduced pressure, to obtain diamine (β).

[0209]

[0210] Synthesis Example 5 Synthesis of diamine compound (γ) Diamine compound (γ) was obtained in the same manner as in Synthesis Example 3, except that 16.4 g (0.05 mol) of diamine compound (β) obtained in Synthesis Example 4 was used instead of 6FAP.

[0211]

[0212] Synthesis Example 6 Synthesis of diamine compound (δ) A dinitro compound was synthesized using 26.70 g (0.086 mol) of 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol) instead of 4,4'-(2-ethylhexylidene)diphenol, and diamine compound (δ) was obtained in the same manner as in Synthesis Example 4 except that 54.06 g (0.135 mol) of the dinitro compound was used.

[0213]

[0214] Synthesis Example 7 Synthesis of Alkali-Soluble Resin (a-1) Under a dry nitrogen stream, 31.02 g (0.10 mol) of ODPA was dissolved in 500 g of MPA. To this solution, 21.96 g (0.085 mol) of BAP and 1.24 g (0.005 mol) of SiDA were added along with 50 g of MPA, and the mixture was allowed to react at 40°C for 2 hours. Next, 2.18 g (0.02 mol) of 3-aminophenol as an end-capping agent was added along with 5 g of MPA, and the mixture was allowed to react at 50°C for 2 hours. Subsequently, a solution prepared by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of MPA was added. After addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water, yielding a white precipitate. The resulting precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide precursor (a-1) which is an alkali-soluble resin.

[0215] Synthesis Example 17: Synthesis of Alkali-Soluble Resin (a-11) Under a dry nitrogen stream, 12.92 g (0.050 mol) of BAP, 12.82 g (0.035 mol) of 6FAP, 1.24 g (0.005 mol) of SiDA, 2.18 g (0.02 mol) of MAP, and 52.8 g (0.6 mol) of glycidyl methyl ether were dissolved in 500 g of MPA, and the solution was cooled to -15°C. To this solution, a solution prepared by dissolving 29.51 g (0.10 mol) of OBBC in 50 g of MPA was added dropwise so that the internal temperature did not exceed 0°C. After completion of the dropwise addition, stirring was continued for 6 hours at -15°C. After completion of the reaction, the solution was poured into 3 L of water containing 10 wt% methanol, and the white precipitate was collected. The resulting precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polybenzoxazole precursor (a-11) which is an alkali-soluble resin.

[0216] Synthesis Examples 8 to 16, 18 to 25, Comparative Synthesis Examples 1 to 4 Polyimide precursors (a-2) to (a-10), (a-12) to (a-19), and (a'-1) to (a'-4) were obtained in the same manner as in Synthesis Example 7, except that the amine component, acid component, and polymerization solvent were changed as shown in Table 1.

[0217] Comparative Synthesis Example 5 A polybenzoxazole precursor (a'-5) was obtained in the same manner as in Synthesis Example 17, except that the amine component, acid component and polymerization solvent were changed as shown in Table 1.

[0218] The names of the compounds used in each of the Examples and Comparative Examples are shown below. Compounds other than commercially available products were synthesized using known methods. GBL: γ-butyrolactone MPA: 3-methoxy-N,N-dimethylpropanamide NMP: N-methylpyrrolidone BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane (diamine not containing a fluorine atom) ABPS: bis(3-amino-4-hydroxyphenyl)sulfone (diamine not containing a fluorine atom) BAHF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (diamine not containing a fluorine atom and having a fluorene structure) SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane (diamine not containing a fluorine atom and containing a silicon atom) 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (diamine containing a fluorine atom) 8FBZ: 4,4'-diaminooctafluorobiphenyl (diamine containing a fluorine atom directly bonded to an sp2 carbon) MAP: 3-aminophenol ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (an acid dianhydride containing no fluorine atoms) TDA: tetralin dianhydride (an acid dianhydride containing no fluorine atoms and containing an alicyclic structure) 6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (an acid dianhydride containing a fluorine atom) OBBC: diphenyl ether dicarboxylic acid dichloride (an acid chloride containing no fluorine atoms) b-1: 1,2,4-trihydroxybenzene (an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups in one aromatic ring) b'-1: 1,1,1-tris(4-hydroxyphenyl)ethane BTS: p-butyl toluenesulfonate (a thermal acid generator that generates specific sulfonic acid and / or sulfonate ions during heat treatment) s-1: 3-glycidoxypropyltrimethoxysilane (a silane coupling agent) e-1: a thermal crosslinking agent represented by the structure shown below e-2: A thermal crosslinking agent represented by the structure shown below d1-1: A dye represented by the structure shown below d1-2: A dye represented by the structure shown below

[0219]

[0220] Example 1 10.0 g of polyimide precursor (a-1), 2.0 g of photosensitive compound (c-1), and 2.0 g of (e-1) were dissolved in 50 g of GBL, and the solution was then filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a positive photosensitive resin composition, varnish A-1. Using the obtained varnish A-1, the cured film was measured with an electron probe microanalyzer, the reworkability during cured film preparation was evaluated, the bending resistance of the cured film was evaluated, the content of β-alkoxypropionamide in the cured film was calculated, and the long-term reliability of the organic EL display device was evaluated, and the 450 nm light-blocking property and visible light-blocking property were evaluated, as described above.

[0221] The cured film contains at least one compound derived from the quinone diazide compound (c-1), i.e., at least one selected from the group consisting of a carboxylic acid having an indene structure, a carboxylic acid ester having an indene structure, a sulfonic acid having an indene structure, and an aryl sulfonate ester having an indene structure. This can be confirmed by analyzing the cured film using methods such as proton nuclear magnetic resonance spectroscopy, infrared spectroscopy, pyrolysis-gas chromatography-mass spectrometry, reactive pyrolysis-gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, and time-of-flight secondary ion mass spectrometry.

[0222] Examples 2 to 33 and Comparative Examples 1 to 5: Photosensitive resin composition varnishes were obtained in the same manner as in Example 1, except that component (a), component (b), component (c), other components, and solvents were changed as shown in Tables 2 and 3. Using the obtained varnishes, the cured films were measured with an electron beam microanalyzer, the reworkability during cured film preparation was evaluated, the bending resistance of the cured films was evaluated, the content of β-alkoxypropionamide in the cured films was calculated, the long-term reliability of the organic EL display devices was evaluated, and the 450 nm light-blocking ability and visible light-blocking ability were evaluated, as described above. The compound derived from the quinone diazide compound (c-1) in the cured film was the same as in Example 1.

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229] 1: Substrate 2: TFT 3: TFT insulating layer 4: Wiring 5: Planarization layer 6: Contact hole 7: First electrode 8: Pixel dividing layer 9: Organic EL layer 10: Second electrode 11: Display device 12: Light-emitting element 13: Hardened film 14, 14c: Metal wiring 15: Counter substrate 16: Electrode terminal 17: Light-emitting element driving substrate 18: Driving element 19: Barrier metal 20: Solder bump 21: Non-alkali glass substrate 22: First electrode (transparent electrode) 23: Auxiliary electrode 24: Pixel dividing layer 25: Organic EL layer 26: Second electrode (non-transparent electrode)

Claims

1. A cured film comprising polyimide and / or polybenzoxazole, wherein the molar ratio of fluorine atoms to carbon atoms, F (fluorine atoms) / C (carbon atoms), obtained when a cross section of the cured film is measured with an electron beam microanalyzer is 0 or more and 0.05 or less.

2. The cured film according to claim 1, further comprising one or more compounds selected from the group consisting of a carboxylic acid having an indene structure, a carboxylic acid ester having an indene structure, a sulfonic acid having an indene structure, and a sulfonic acid aryl ester having an indene structure.

3. The cured film according to claim 1 or 2, further comprising polyhydroxystyrene and / or polyhydroxystyrene / polystyrene copolymer.

4. The cured film according to claim 1 or 2, further comprising an aromatic hydrocarbon compound having at least three phenolic hydroxyl groups in one aromatic ring.

5. The cured film according to claim 1 or 2, further comprising a β-alkoxypropionamide.

6. The cured film according to claim 1 or 2, further comprising one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5), or sulfonate ions derived from one or more sulfonic acids selected from the group consisting of compounds represented by any one of formulas (3) to (5): In formula (3), R ５ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5; in formula (4), R ６ represents a monovalent organic group having 1 to 10 carbon atoms.

7. The cured film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole has a repeating unit composed of an acid component and an amine component, and when the acid components and the amine components in all the repeating units are each taken as 100 mol %, the total of the acid components having a fluorene structure and the amine components having a fluorene structure is 0 mol % or more and 50 mol % or less out of a total of 200 mol % of the acid components and the amine components.

8. The cured film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole has a residue represented by formula (6): In formula (6), X １ each independently represents a direct bond, a divalent group represented by formula (7), or a divalent group represented by formula (8), X ２ is a divalent group represented by formula (9) or formula (10), R ８ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and each d independently represents an integer of 0 to 4; In formula (7) and formula (8), R ９ each independently represents an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, each e independently represents an integer of 0 to 4; * represents * in formula (6), and ** represents a bonding point to bond to the aromatic ring; In formula (9) and formula (10), R １１ each independently represents an alkyl group having 1 to 4 carbon atoms; R １２ and R １３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, * represents a bonding point to the aromatic ring, each f independently represents an integer of 1 to 4, and g represents 1 or 2; １２ and R １３ represent different substituents.

9. The cured film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole has a repeating unit composed of an acid component and an amine component, and when the acid components and the amine components in all the repeating units are each taken as 100 mol %, the total of the acid components having an alicyclic structure and the amine components having an alicyclic structure is 0 mol % or more and 40 mol % or less out of a total of 200 mol % of the acid components and the amine components.

10. The cured film according to claim 1 or 2, wherein the polyimide and / or polybenzoxazole contains a repeating unit having a fluorine atom directly bonded to an sp2 carbon.

11. The cured film according to claim 10, wherein the polyimide and / or polybenzoxazole has a repeating unit composed of an acid component and an amine component, and when the acid components and the amine components in all the repeating units are each taken as 100 mol %, the total of the acid component having a fluorine atom directly bonded to the sp2 carbon and the amine component having a fluorine atom directly bonded to the sp2 carbon is 5 mol % or more and 100 mol % or less out of a total of 200 mol % of the acid components and the amine components.

12. The cured film according to claim 1 or 2, wherein the molar ratio of silicon atoms to carbon atoms, Si (silicon atoms) / C (carbon atoms), obtained when a cross section of the cured film is measured with an electron probe microanalyzer, is 0.001 or more and 0.005 or less.

13. The cured film according to claim 1 or 2, which has a transmittance of 30% or less for light with a wavelength of 450 nm at a film thickness of 2.0 μm.

14. The cured film according to claim 1 or 2, which has an OD value of 0.5 to 1.5 in visible light per 1 μm of film thickness.

15. An organic EL display device having the cured film according to claim 1 or 2.

16. The organic EL display device according to claim 15, further comprising a color filter having a black matrix.

17. An electronic component having the cured film according to claim 1 or 2.