Photosensitive resin composition, resin film, substrate with resin film, organic el display device, and method for producing substrate with resin film

Abstract

To provide a photosensitive resin composition that has an adequate light shielding property and can form a resin film having a small range of transmittance fluctuation in the visible light region.SOLUTION: A photosensitive resin composition comprises (A) a black pigment containing carbon black and / or titanium black, (B) an alkali soluble resin having an unsaturated group(s), (C) a photopolymerizable compound having two or more ethylenic unsaturated groups, (D) a photo initiator, and (E) a solvent. A substrate with a resin film, obtained by coating the composition on a glass substrate so that the thickness of the resin film becomes 3.0 μm and, after subjecting the film to a heat treatment at 85°C for 1 min and thereafter at 85°C for 60 minutes, has an average transmittance of 30.0%-80.0% at a wavelength of 440 nm to 650 nm, and a difference between the maximum value and the minimum value in the transmittance at a wavelength of 440 nm to 650 nm is 20.0% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a resin film, a substrate with a resin film, an organic EL display device, and a method for producing a substrate with a resin film. [Background technology]

[0002] Organic EL display devices equipped with organic EL panels, which are advantageous in terms of thinness and flexibility compared to conventional liquid crystal panels and have high light utilization efficiency, have attracted attention and are being put to practical use. In such organic EL display devices, in order to prevent a decrease in visibility due to reflection of external light, etc., a configuration has been proposed in which a circular polarizer is provided as an anti-reflection film on the viewing side of the organic EL panel (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-226842 Summary of the Invention [Problem to be solved by the invention]

[0004] However, circular polarizers cut off more than half of the light emitted by organic EL devices, significantly reducing light utilization efficiency. Therefore, there is a need for the development of organic EL display devices that offer good visibility and low power consumption without using circular polarizers.

[0005] Therefore, organic EL display devices using an overcoat (OC) layer with a suitable light-blocking property that can transmit light emitted by the organic EL while blocking light reflected by the organic EL panel when external light enters the organic EL display device are being considered. In designing such an OC layer, it is required that the transmittance of the OC layer be uniform across the visible light range in order to improve the color reproducibility of the organic EL display device.

[0006] The present invention has been made in view of the above points, and aims to provide a photosensitive resin composition having an appropriate light-shielding property and a small fluctuation range of transmittance in the visible light region. Another aim of the present invention is to provide a resin film, a substrate with a resin film, an organic EL display device, and a method for manufacturing a substrate with a resin film, using the photosensitive resin composition. [Means for solving the problem]

[0007] The above problem can be solved by the following configuration.

[0008] [1] (A) a black pigment containing carbon black and / or titanium black; (B) an unsaturated group-containing alkali-soluble resin; (C) a photopolymerizable compound having two or more ethylenically unsaturated groups; (D) a photopolymerization initiator; (E) a solvent; A photosensitive resin composition comprising: The photosensitive resin composition comprises The resin film-coated substrate obtained by applying the resin film to a glass substrate so that the film thickness is 3.0 μm has an average transmittance of 30.0% to 80.0% at wavelengths of 440 nm to 650 nm, and the difference between the maximum and minimum transmittance at wavelengths of 440 nm to 650 nm is 20.0% or less. Photosensitive resin composition.

[0009] [2] (F) An epoxy compound having at least two epoxy groups; [1] The photosensitive resin composition according to [1].

[0010] [3] The (B) unsaturated group-containing alkali-soluble resin includes a resin represented by the following general formula (B-1): The photosensitive resin composition according to [1] or [2]. [ka] (In formula (B-1), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; R5 independently represents a hydrogen atom or a methyl group; A independently represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y independently represents a tetravalent carboxylic acid residue; and Z independently represents a hydrogen atom or a substituent represented by general formula (B-2), with the proviso that at least one Z is a substituent represented by general formula (B-2); and n is a number from 1 to 20.) [ka] (In formula (B-2), W is a divalent or trivalent carboxylic acid residue, m is the number 1 or 2, and * indicates a bonding site.)

[0011] [4] The (A) black pigment contains carbon black and titanium black, The photosensitive resin composition has a difference between the maximum and minimum transmittance of the resin film-coated substrate in the wavelength range of 440 nm to 650 nm of 10.0% or less. The photosensitive resin composition according to any one of [1] to [3].

[0012] [5] When the (A) black pigment contains carbon black, the average secondary particle diameter of the carbon black is 250 nm or less, When the (A) black pigment contains titanium black, the average particle size of the titanium black is 150 nm or less. The photosensitive resin composition according to any one of [1] to [4].

[0013] [6] A resin film formed from the photosensitive resin composition according to any one of [1] to [5].

[0014] [7] A substrate with a resin film, comprising the resin film according to [6].

[0015] [8] An organic electroluminescence display device comprising the resin film according to [6].

[0016] [9] A step of applying the photosensitive resin composition according to any one of [1] to [5] to a substrate to form a coating film; a heat treatment step of heat treating the coating film at 100°C or less; A method for producing a resin film-attached substrate, comprising:

[0017]

[10] an exposure step of irradiating a part of the coating film formed on the substrate with radiation through a photomask; a developing step of developing the irradiated coating film and removing the unexposed portions of the coating film; Including, The developing step is carried out before the heat treatment step. [9] A method for producing a resin film-coated substrate according to [9]. [Effects of the Invention]

[0018] The present invention aims to provide a photosensitive resin composition having an appropriate light-shielding property and a small fluctuation range of transmittance in the visible light region. It is also an object of the present invention to provide a resin film, a substrate with a resin film, an organic electroluminescence display device, and a method for producing a substrate with a resin film, using the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the present invention, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0020] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0021] 1. Photosensitive resin composition The photosensitive resin composition according to this embodiment comprises: (A) a black pigment containing carbon black and / or titanium black (hereinafter also referred to simply as "component (A)"); (B) an unsaturated group-containing alkali-soluble resin (hereinafter also referred to simply as "component (B)"); (C) a photopolymerizable compound having two or more ethylenically unsaturated groups (hereinafter also referred to simply as "component (C)"); (D) a photopolymerization initiator (hereinafter also referred to simply as "component (D)"); (E) Solvent (hereinafter simply referred to as "Component (E)"). The photosensitive resin composition is applied to a glass substrate so that the thickness of the resin film is 3.0 μm, and the photosensitive resin composition is heat-treated at 85° C. for 1 minute and then heat-treated at 85° C. for 60 minutes, so that the transmittance of the resin film-coated substrate obtained satisfies the following two requirements: (Requirement 1) The average transmittance in the wavelength range of 440 nm to 650 nm is 30.0% to 80.0%. (Requirement 2) The difference between the maximum and minimum transmittance values ​​in the wavelength range of 440 nm to 650 nm is 20.0% or less.

[0022] Each component will be described below.

[0023] 1-1. (A) Black pigments containing carbon black and / or titanium black Component (A) is added to control the transmittance of the resin film to a desired level.

[0024] The reason why component (A) being a black pigment containing carbon black and / or titanium black provides adequate light-blocking properties and a small transmittance fluctuation range in the visible light region is not entirely clear, but is thought to be as follows: Black pigments containing carbon black or titanium black tend to maintain an adequate dispersion state when mixed with component (B). In a resin film formed from such a resin composition, the average transmittance in the visible light region can be easily adjusted, and the difference between the maximum and minimum transmittance values ​​(transmittance fluctuation range) tends to be small. As a result, when a resin film having a predetermined thickness is formed, the average transmittance in the visible light region can be kept within a desired range, while the transmittance fluctuation range can be easily reduced, thereby realizing a photosensitive resin composition that has adequate light-blocking properties and a small transmittance fluctuation range.

[0025] Furthermore, component (A) is preferably a black pigment containing carbon black and titanium black. When carbon black is mixed with component (B), the transmittance at the short wavelength side of the visible light range tends to be relatively lower than the transmittance at the long wavelength side. On the other hand, when titanium black is mixed with component (B), the transmittance at the long wavelength side of the visible light range tends to be relatively lower than the transmittance at the short wavelength side. Therefore, by mixing a black pigment containing both carbon black and titanium black with component (B), the transmittance at wavelengths of 440 nm to 650 nm tends to be flattened, and the transmittance fluctuation range tends to be narrowed.

[0026] When component (A) is a black pigment containing carbon black and titanium black, the mass ratio of the carbon black to titanium black, where the mass of the carbon black is the numerator and the mass of the titanium black is the denominator, is preferably 95 / 5 to 5 / 95, more preferably 85 / 15 to 10 / 90, even more preferably 70 / 30 to 15 / 85, even more preferably 65 / 35 to 20 / 80, and most preferably 50 / 50 to 20 / 80. By setting the ratio within the above range, the transmittance fluctuation range is easily suppressed.

[0027] The component (A) is not particularly limited as long as it is a black pigment containing carbon black and / or titanium black, and may contain any known black pigment.

[0028] Examples of black pigments other than carbon black and titanium black include organic black pigments such as perylene black, cyanine black, aniline black, and lactam black; inorganic black pigments such as chromium oxide and iron oxide; and mixed-color organic pigments that are pseudo-black by mixing two or more pigments selected from red, blue, green, purple, yellow, cyan, magenta, etc.

[0029] Examples of mixed-color organic pigments include pigments in which at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed.

[0030] Furthermore, examples of organic pigments that can be used when a mixed color organic pigment is used as part of component (A) include those with the following color index names: Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81 etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

[0031] Furthermore, a dispersant can be added to component (A) as another compounding component to promote dispersion of component (A) or stabilize its dispersibility. The dispersant used in the dispersion of component (A) can be any known compound used in pigment dispersions (compounds commercially available under the names of dispersant, dispersing wetting agent, dispersion promoter, etc.) without any particular limitation.

[0032] Examples of dispersants used in the dispersion of component (A) include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersing aids). In particular, cationic polymer dispersants having cationic functional groups such as imidazolyl groups, pyrrolyl groups, pyridyl groups, or primary, secondary, or tertiary amino groups as adsorption sites for colorants are preferred. Furthermore, the cationic polymer dispersants preferably have an amine value of 1 mgKOH / g to 100 mgKOH / g. Furthermore, the cationic polymer dispersants preferably have a number-average molecular weight (Mn) of 1,000 to 100,000. The amount of dispersant blended is preferably 1% to 35% by mass, more preferably 2% to 25% by mass, based on the total mass of component (A).

[0033] The content of component (A) is preferably 0.5% by mass to 10.0% by mass relative to the total mass of the solid contents of the photosensitive resin composition. When the content is 0.5% by mass or more, reflected light is more easily blocked even when external light incident on an organic EL panel is reflected by the organic EL panel, which tends to improve the visibility of the organic EL display device. When the content is 10.0% by mass or less, light emitted by the organic EL panel is more easily transmitted, which tends to reduce the amount of emitted light, which tends to reduce the power consumption of the organic EL display device. From the same viewpoint, the total mass of component (A) is more preferably 0.7% by mass to 4.5% by mass, and even more preferably 1.2% by mass to 3.5% by mass relative to the total mass of the solid contents.

[0034] The total content of carbon black and titanium black (excluding other components such as the dispersant) is preferably 70.0 to 100.0% by mass relative to the total mass of the black pigment, which tends to reduce the fluctuation range of transmittance in the wavelength range of 440 to 650 nm.

[0035] In this specification, the contents of component (A), carbon black, and titanium black refer to the contents after surface treatment when the surface has been treated with a surface-coating dye or the like as described below.

[0036] 1-1-1. Carbon black Carbon black preferably has acidic functional groups on its surface through oxidation treatment. In particular, it is preferable to have two or more types of acidic functional groups on its surface through multiple oxidation treatments. The acidic functional groups can improve the dispersibility of carbon black. Examples of oxidation treatments include treatments using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitric oxide gas, nitrogen dioxide gas, sulfuric anhydride, fluorine gas, concentrated sulfuric acid, nitric acid, and various peroxides. Examples of the acidic functional groups include hydroxyl, oxo, hydroperoxy, carbonyl, carboxy, peroxycarboxylic acid, aldehyde, ketone, nitro, nitroso, amide, imide, sulfonic acid, sulfinic acid, sulfenic acid, thiocarboxylic acid, chlorosyl, chloryl, perchloryl, iodosyl, and iodyl groups.

[0037] The carbon black may be surface-treated by coating the surface with a dye. The carbon black having a surface coated with a dye enhances the developability of the photosensitive resin composition and also facilitates enhancing the adhesion to the substrate, fine line reproducibility, and light-shielding properties of the resin film obtained by curing the composition, thereby facilitating increasing the resistance value of the resin film.

[0038] The dye may be any dye capable of adsorbing to the surface of carbon black, and may be a basic dye, acid dye, direct dye, reactive dye, or the like. When acidic functional groups are added to the surface of carbon black (oxidation treatment is performed) to enhance dispersibility, acid dyes (especially acid dyes having sulfonic acid groups or carboxy groups) that readily interact with the acidic functional groups are preferred. Furthermore, acid dyes or nonionic dyes are preferred over dyes having amino groups, etc., from the viewpoint of suppressing reaction with the acidic groups of component (B). Furthermore, dark-colored dyes are preferred from the viewpoint of further enhancing the light-blocking properties of the resin film.

[0039] Specific examples of the dyes include food coloring dyes such as Food Black No. 1, Food Black No. 2, Food Red No. 40, Food Blue No. 1, and Food Yellow No. 7; acid dyes of various colors such as Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (manufactured by BASF), Kayanol Red 3BL (manufactured by Nippon Kayaku Company), Dermacarbon 2GT (manufactured by Sandoz); Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (manufactured by BASF), Basacid Blue 750 (manufactured by BASF), Bernacid Red (manufactured by Bemcolors, Poughkeepsie, NY), and BASF Basacid Black SE 0228 (manufactured by BASF); Pontamine Brilliant Bond Blue A and other Pontamine Brilliant dyes. Bond Blue A and other Pontamine® dyes (Bayer Chemicals Corporation, Pittsburgh, PA), Cartasol Yellow GTF Presscake (Sandoz, Inc.); Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc.); Yellow Shade 16948 (Tricon), Direct Brilliant Pink B (Crompton & Knowles), Carta Black 2GT (Sandoz, Inc.), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz), Pergasol Yellow CGP (Ciba-Geigy), Pyrazol Black BG (JCI), Diazol Black RN Quad (JCJ), Pontamine Brilliant Bond Blue; Berncolor AYDirect dyes of various colors such as Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Pylam Products, Inc., Tempe, AZ), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA, and similar dyes available from Levafix® dyes Dystar LP (Charlotte, NC), reactive dyes of various colors such as Procion Red H8B (Reactive Red 31) (JCI America), Neozapon Red 492 (BASF), Orasol Red G (Ciba-Geigy), Aizen Spilon Red C-BH (Hodogaya Chemical Company), Spirit Fast Yellow 3G, and Aizen Spilon Yellow Examples of suitable dyes include oil-soluble dyes such as C-GNH (manufactured by Hodogaya Chemical Company), Orasol Black RL (manufactured by Ciba-Geigy), Orasol Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by Ciba-Geigy), Luxol Blue MBSN (manufactured by Morton-Thiokol), and Morfast Black Concentrate A (manufactured by Morton-Thiokol). These may be used alone or in combination of two or more.

[0040] The content of the dye is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 7% by mass, based on the total mass of the carbon black. The greater the amount of dye, the higher the resistance value of the resin film. By ensuring that the amount of dye is not excessive, it is possible to prevent thickening of the photosensitive resin composition due to excess dye and aggregation due to the excess dye inhibiting the dispersibility of other components.

[0041] The dye may also be laked with a metal or metal salt. By laked, the dye can be fixed to the surface of the carbon black via the metal or metal salt, thereby preventing the dye from being released from the carbon black surface, thereby preventing the above-mentioned effects from being reduced. Examples of the metal include aluminum, magnesium, calcium, strontium, barium, and manganese. Examples of the metal salt include the hydrochlorides and sulfates of these metals. The content of the metal or metal salt is preferably 0.3 times or more by mole, more preferably 0.5 times by mole, and even more preferably 0.8 times by mole, relative to the dye.

[0042] The average secondary particle size of carbon black can be adjusted by dispersing the carbon black in a bead mill together with a dispersant, such as a polymeric dispersant, and a dispersion medium containing a solvent. The average secondary particle size of carbon black is preferably 250 nm or less, more preferably 50 to 250 nm, and even more preferably 70 to 200 nm. An average secondary particle size within the above range is believed to facilitate the suppression of carbon black sedimentation and aggregation, ensuring good dispersion stability, making it easier to adjust the average transmittance in the visible light range and reducing the difference between the maximum and minimum transmittance values ​​(transmittance fluctuation range). In the present invention, the term "average secondary particle size" refers to the average particle size measured by dynamic light scattering after dilution with a dispersion solvent or an equivalent solvent and then calculated by the cumulant method. For example, it refers to the value measured in a propylene glycol monomethyl ether acetate (PGMEA) dispersion with a particle concentration of 0.1% by mass. In the case of particles in which tiny primary particles are connected together like a bunch of grapes, the particle size in that form (average secondary particle size) is important for expressing physical properties. Also, even if particles are not connected together like a bunch of grapes, the smaller the particle size (average primary particle size), the more likely they are to aggregate in a dispersion, and the particle size in that aggregated state (average secondary particle size) becomes important.

[0043] The DBP oil absorption of the carbon black is preferably 100 ml / 100 g or less. DBP oil absorption refers to the amount of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (JIS K 6217-4 (2017)). When the DBP oil absorption of the carbon black is within the above range, the resistivity and blackness of the resin film can be increased, and the decrease in coatability due to the increased viscosity of the photosensitive resin composition can be suppressed.

[0044] The carbon black preferably has a pH of 2 to 10, more preferably 5 to 9, and even more preferably 4 to 8. The pH value refers to the value measured using a glass electrode pH meter on a mixture of carbon black and distilled water. The higher the pH of the carbon black, the more stable the carbon black. By keeping the pH of the carbon black within a range that is not excessive, the adhesion of the resin film to the substrate can be further improved.

[0045] Furthermore, the carbon black preferably has an ash content of 1.0% or less, which can further increase the resistance value of the resin film.

[0046] Carbon black has a specific surface area of ​​20m 2 / g~300m 2 / g. The specific surface area is preferably 20m 2 / g or more, the shape of the resin film is likely to be stable. 2 When the content is 1 / g or less, the amounts of dispersants, dyes, etc. required can be reduced, thereby further reducing costs.

[0047] 1-1-2.Titanium Black Titanium black is black particles containing titanium atoms, and is preferably a low-order titanium oxide, titanium oxynitride, or titanium nitride.

[0048] The surface of titanium black may be chemically modified as needed to improve dispersibility and inhibit aggregation. Specifically, the surface of titanium black may be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Alternatively, the surface may be treated with a water-repellent substance as disclosed in JP 2007-302836 A. Furthermore, to adjust dispersibility, colorability, etc., titanium black may contain one or a combination of two or more black pigments, such as composite oxides of Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, or aniline black.

[0049] Methods for producing titanium black include, but are not limited to, a method in which a mixture of titanium dioxide and metallic titanium is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), a method in which ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride is reduced in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method in which titanium dioxide or titanium hydroxide is reduced at high temperatures in the presence of ammonia (Japanese Patent Laid-Open Nos. 60-65069 and 61-201610), and a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and then reduced at high temperatures in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610).

[0050] The average particle size of titanium black can be adjusted by dispersing titanium black in a bead mill with a dispersant such as a polymeric dispersant and a dispersion medium containing a solvent. The average particle size of titanium black is preferably 150 nm or less, more preferably 50 nm to 150 nm, and even more preferably 60 nm to 150 nm. An average particle size within the above range is thought to facilitate the suppression of sedimentation and aggregation of titanium black and ensure good dispersion stability, making it easier to adjust the average transmittance in the visible light range and reducing the difference between the maximum and minimum transmittance values ​​(transmittance fluctuation range). In the present invention, the term "average particle size" refers to a value determined by the same measurement method as for the average secondary particle size of carbon black.

[0051] 1-2. (B) Unsaturated group-containing alkali-soluble resin Component (B) contains a polymerizable unsaturated group and an acidic group that provides alkali solubility. The polymerizable unsaturated group provides the photosensitive resin composition with excellent photocurability, and the molecular weight increases upon curing, allowing the component to function as a binder. Furthermore, the acidic group in component (B) improves the physical properties of the resin film, such as developability and patterning characteristics (pattern line width, pattern linearity).

[0052] The component (B) is not particularly limited as long as it is such a resin, and various types of resins can be used.

[0053] Examples of the acidic group that component (B) has for imparting alkali solubility include a carboxy group, a phosphate group, a sulfonic acid group, etc. From the viewpoint of easily improving developability and patterning properties, a carboxy group is preferred.

[0054] Component (B) is preferably an unsaturated group-containing alkali-soluble resin obtained by further reacting a reaction product of an epoxy compound having two or more epoxy groups with (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. During the production of the unsaturated group-containing alkali-soluble resin, a polyester is produced by the reaction of a hydroxy group with a polybasic carboxylic acid. Component (A) is preferably a low-molecular-weight resin in which the polyester has an average degree of polymerization of about 2 to 500. Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and "(meth)acrylate" is a general term for acrylate and methacrylate, and each refers to one or both of these.

[0055] Examples of the epoxy compound having two or more epoxy groups include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, (o, m, p-) cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company), phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds having an aromatic structure such as tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, (meth)acrylates containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, copolymers of monomers having a methyl group, epoxy compounds having a glycidyl group such as hydrogenated bisphenol A diglycidyl ether (e.g., Rikaresin HBE-100, manufactured by New Japan Chemical Co., Ltd., "Rikaresin" is a registered trademark of the company), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175, manufactured by Huntsman Chemical Co., Ltd., "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl)adipate (e.g., CYRACURE UVR-6128, manufactured by The Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celloxide 2021P, manufactured by Daicel Corporation, "Celloxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,Examples of epoxy compounds include 4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401, manufactured by Daicel Corporation; "Epolead" is a registered trademark of the company), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1, manufactured by Shikoku Chemical Industry Co., Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), alicyclic epoxy compounds such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.; "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone skeleton.

[0056] Other preferred examples of resins for component (B) include alkali-soluble resins that are acrylic copolymers.

[0057] Examples of the acrylic copolymer include a copolymer of (meth)acrylic acid, a (meth)acrylic acid ester, etc., and a resin having a (meth)acryloyl group and a carboxy group. Examples of the resin include an alkali-soluble resin containing a polymerizable unsaturated group, which is obtained by copolymerizing a (meth)acrylic acid ester containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting the copolymer with (meth)acrylic acid, and finally reacting the copolymer with an anhydride of a dicarboxylic acid or tricarboxylic acid. Examples of the copolymer include a copolymer disclosed in Japanese Patent Application Laid-Open No. 2014-111722, which is composed of 20 to 90 mol% of repeating units derived from diester glycerol in which the hydroxyl groups at both ends are esterified with (meth)acrylic acid, and 10 to 80 mol% of repeating units derived from one or more polymerizable unsaturated compounds copolymerizable therewith, and which has a number average molecular weight (Mn) of 2,000 to 20,000 and an acid value of 35 to 120 mgKOH / g; and a polymerizable unsaturated group-containing alkali-soluble resin disclosed in Japanese Patent Application Laid-Open No. 2018-141968, which is a polymer having a weight average molecular weight (Mw) of 3,000 to 50,000 and an acid value of 30 to 200 mg / KOH, and which includes units derived from (meth)acrylic acid ester compounds and units having a (meth)acryloyl group and a di- or tricarboxylic acid residue.

[0058] The content of component (B) is preferably 40% by mass to 90% by mass, and more preferably 50% by mass to 90% by mass, based on the total mass of components (B) and (C). By setting the content of component (B) within this range, it is possible to easily improve substrate adhesion and expand the development margin.

[0059] Component (B) is preferably a compound having a weight-average molecular weight (Mw) of 1,000 to 40,000, and more preferably a compound having a weight-average molecular weight (Mw) of 2,000 to 20,000. When component (B) has an Mw of 1,000 or more, adhesion to the substrate is likely to be enhanced, and the development margin during alkaline development is likely to be extended. On the other hand, when component (B) has an Mw of 40,000 or less, resolution in an alkaline developer is likely to be enhanced, and pattern formation is facilitated. In this specification, the weight-average molecular weight (Mw) of component (B) refers to the styrene-equivalent value determined by gel permeation chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh Corporation)).

[0060] Component (B) may also be a mixture of two or more unsaturated group-containing alkali-soluble resins. In this case, it is preferable to include an unsaturated group-containing alkali-soluble resin with an Mw of 1,000 or more but less than 4,000 and an unsaturated group-containing alkali-soluble resin with an Mw of 4,000 to 40,000. Furthermore, when the total mass of the unsaturated group-containing alkali-soluble resins with an Mw of 1,000 or more but less than 4,000 is used as the numerator, the mass ratio between the total mass of the unsaturated group-containing alkali-soluble resins with an Mw of 4,000 to 40,000 is more preferably 10 / 90 to 95 / 5, and even more preferably 50 / 50 to 95 / 5. By mixing components with different dissolution rates in an alkaline developer, it is possible to more easily control the pattern development time and pattern shape.

[0061] The acid value of component (B) is preferably 10 mgKOH / g to 120 mgKOH / g, and more preferably 20 mgKOH / g to 110 mgKOH / g. An acid value of 10 mgKOH / g or more facilitates improving resolution, while an acid value of 120 mgKOH / g or less facilitates reducing development residues.

[0062] In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of each component can be a styrene-equivalent value determined by gel permeation chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh Corporation)). The acid value can be a value determined using a potentiometric titrator (for example, "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.)). However, for compounds such as monomers whose molecular weight can be calculated from their structure, the value calculated from their structure can also be used as the molecular weight of the compound.

[0063] 1-2-1. Alkali-soluble resin containing an unsaturated group represented by the following general formula (B-1): From the viewpoint of facilitating the enhancement of the resolution of the resin film and the control of the pattern shape, it is preferable that the component (B) contains an unsaturated group-containing alkali-soluble resin represented by the following general formula (B-1) (hereinafter also simply referred to as "component (B-1)").

[0064] [ka]

[0065] In formula (B-1), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; R5 independently represents a hydrogen atom or a methyl group; A independently represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y independently represents a tetravalent carboxylic acid residue; and Z independently represents a hydrogen atom or a substituent represented by general formula (B-2), provided that at least one Z is a substituent represented by general formula (B-2), and n is a number from 1 to 20.

[0066] [ka]

[0067] In formula (B-2), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0068] Next, a method for producing the alkali-soluble resin represented by the above general formula (B-1) will be described in detail.

[0069] First, an epoxy compound (b-1) having two epoxy groups in one molecule, represented by general formula (B-3) (hereinafter simply referred to as "epoxy compound (b-1)"), is reacted with an unsaturated group-containing monocarboxylic acid (e.g., (meth)acrylic acid) to obtain an epoxy (meth)acrylate.

[0070] [ka]

[0071] In formula (B-3), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and X independently represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.

[0072] The epoxy compound (b-1) is an epoxy compound having two glycidyl ether groups, which is obtained by reacting a bisphenol with epichlorohydrin.

[0073] Examples of the bisphenols include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3,5-dimethylphenyl) sulfone, bis(4-hydroxy-3,5-dichlorophenyl) sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3 ,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3 -chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, and the like.Among these, from the viewpoint of further improving heat resistance, bisphenols having a fluorene-9,9-diyl group are preferred. These may be used alone or in combination of two or more.

[0074] Examples of the unsaturated group-containing monocarboxylic acid compound include acrylic acid, methacrylic acid, and compounds obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride.

[0075] The reaction between the epoxy compound (b-1) and (meth)acrylic acid can be carried out by a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 discloses that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid per mole of an epoxy compound having two epoxy groups. In this embodiment, the compound obtained by the reaction is a diol compound containing a polymerizable unsaturated group, and is a diol (d) containing a polymerizable unsaturated group represented by general formula (B-4) (hereinafter, also simply referred to as "diol (d) represented by general formula (B-4)").

[0076] [ka]

[0077] In formula (B-4), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; R5 independently represents a hydrogen atom or a methyl group; and X independently represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.

[0078] In the production of the alkali-soluble resin represented by general formula (B-1) by synthesizing the diol (d) represented by general formula (B-4), followed by an addition reaction of a polycarboxylic acid or an anhydride thereof, and further reacting with a monofunctional epoxy compound having a polymerizable unsaturated group reactive with a carboxy group, the reaction is usually carried out in a solvent using a catalyst as necessary.

[0079] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. Note that the reaction conditions, such as the solvent and catalyst used, are not particularly limited, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0080] Furthermore, it is preferable to use a catalyst in the reaction between a carboxy group and an epoxy group. For example, Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0081] Next, the diol (d) represented by general formula (B-4), obtained by the reaction of the epoxy compound (b-1) with (meth)acrylic acid, is reacted with a dicarboxylic acid or tricarboxylic acid or its acid anhydride (b), and a tetracarboxylic acid or its acid dianhydride (c), to obtain an alkali-soluble resin represented by general formula (B-1) having a carboxy group and a polymerizable unsaturated group in one molecule.

[0082] [ka]

[0083] In formula (B-1), R1, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; R5 independently represents a hydrogen atom or a methyl group; A independently represents -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y independently represents a tetravalent carboxylic acid residue; and Z independently represents a hydrogen atom or a substituent represented by general formula (B-2), provided that at least one Z is a substituent represented by general formula (B-2), and n is a number from 1 to 20.

[0084] [ka]

[0085] In formula (B-2), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0086] The acid component used to synthesize the alkali-soluble resin represented by general formula (B-1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by general formula (B-4). It is necessary to use a dicarboxylic acid or tricarboxylic acid or its monoanhydride (b) in combination with a tetracarboxylic acid or its dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated or unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, or carbonyl groups.

[0087] As the dicarboxylic acid or tricarboxylic acid or their acid monoanhydrides (b), chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their acid monoanhydrides, etc. can be used.

[0088] Examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0089] Examples of the alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-3,6-endomethylenetetrahydrophthalic acid, norbornanedicarboxylic acid, chlorendic acid, hexahydrotrimellitic acid, and the like, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0090] Examples of aromatic dicarboxylic acids or tricarboxylic acids include phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and the like, as well as dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0091] Among the dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred.Furthermore, among the dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, it is preferred to use the acid monoanhydrides.The above-mentioned dicarboxylic acid or tricarboxylic acid acid monoanhydrides may be used alone or in combination of two or more.

[0092] As the tetracarboxylic acid or its dianhydride (c), a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or their dianhydrides can be used.

[0093] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced.

[0094] Examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids having a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group introduced therein.

[0095] Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0096] Among the tetracarboxylic acids, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferred. Furthermore, among the tetracarboxylic acids or their acid dianhydrides, it is preferred to use the acid dianhydrides. The above-mentioned tetracarboxylic acids or their acid dianhydrides may be used alone or in combination of two or more.

[0097] The method for reacting the diol (d) with the acid components (b) and (c) is not particularly limited, and any known method can be used. For example, JP-A-9-325494 describes a method in which an epoxy (meth)acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0098] In this case, it is preferable to react the epoxy (meth)acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), and tetracarboxylic acid dianhydride (c) in such a molar ratio that (d):(b):(c) = 1.0:0.01-1.0:0.2-1.0, so that the terminals of the compounds become carboxy groups.

[0099] For example, when using acid monoanhydride (b) and acid dianhydride (c), it is preferable to react them so that the molar ratio [(b) / 2 + (c)] / (d)] of the amount of acid component relative to diol (d) [(b) / 2 + (c)] is greater than 0.5 and less than 1.0. When this molar ratio is 1.0 or less, the terminals of the unsaturated group-containing curable resin represented by general formula (B-1) do not become acid anhydrides, thereby suppressing an increase in the content of unreacted acid dianhydrides and improving the stability of the curable composition over time. Furthermore, when this molar ratio is greater than 0.5, an increase in the amount of unreacted components remaining in diol (d) containing a polymerizable unsaturated group is suppressed, thereby improving the stability of the curable composition over time. The molar ratios of components (b), (c), and (d) can be arbitrarily changed within the above-mentioned ranges in order to adjust the acid value and molecular weight of the unsaturated group-containing curable resin represented by general formula (B-1).

[0100] The synthesis of the diol (d) and the subsequent reaction with the polycarboxylic acid or anhydride thereof are usually carried out in a solvent, if necessary, using a catalyst.

[0101] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions, such as the solvent and catalyst used, are not particularly limited, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0102] The reaction between the epoxy group and the carboxy group or the hydroxy group is preferably carried out using a catalyst, and examples of the catalyst described in JP-A-9-325494 include ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0103] The content of the component (B-1) is preferably 50% by mass to 100% by mass relative to the total mass of the component (B). By setting the content within this range, it becomes easier to improve resolution and control the pattern shape.

[0104] 1-3. (C) Photopolymerizable compounds having two or more ethylenically unsaturated groups Component (C) enhances the exposure sensitivity of the photosensitive resin composition, and upon curing forms an appropriate crosslinked structure, thereby enhancing the adhesion of the resin film to the substrate and improving the developability (resolution, e.g., linearity of the pattern) of the resin film. Component (C) does not have a free carboxy group.

[0105] Specific examples of component (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipe Examples of the ethylenic double bond-containing compound include (meth)acrylic acid esters such as dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; and compounds having an ethylenic double bond such as dendritic polymers having a (meth)acrylic group.

[0106] Examples of the dendritic polymer include dendrimer acrylates, which are spherical macromolecules formed by radially assembling branch molecules having acrylic groups, hyperbranched acrylic polymers, hyperbranched acrylic oligomers, and dendritic polymers obtained by adding a polyvalent mercapto compound to part of the carbon-carbon double bonds in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specific examples include dendritic polymers obtained by reacting the (meth)acryloyl group of a polyfunctional (meth)acrylate represented by the following general formula (C-1) with a polyvalent mercapto compound represented by the following general formula (C-2). From the viewpoint of facilitating the photopolymerization reaction, it is also preferable to use such polyfunctional dendritic polymers.

[0107] [ka]

[0108] In formula (C-1), R6 is a hydrogen atom or a methyl group, and R7 is R8(OH). k The remaining portion is obtained by donating r hydroxy groups out of k hydroxy groups to the ester bond in the formula. Preferred R8(OH) k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking multiple molecules of the polyhydric alcohol via ether bonds resulting from dehydration condensation of the alcohol, or an ester of such a polyhydric alcohol or polyhydric alcohol ether with a hydroxy acid. k and r independently represent integers of 2 to 20, provided that k≧r.

[0109] [ka]

[0110] In formula (C-2), R9 is a single bond or a divalent to hexavalent hydrocarbon group having 1 to 6 carbon atoms, and s is 2 when R9 is a single bond, and is the same as the valence of R9 when R9 is a divalent to hexavalent group.

[0111] Examples of the polyfunctional (meth)acrylate represented by general formula (C-1) include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate.

[0112] Examples of the polyvalent mercapto compound represented by general formula (C-2) include trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), and the like.

[0113] From the viewpoint of increasing the crosslink density of the resin film and facilitating an improvement in resolution, component (C) preferably has two or more ethylenically unsaturated groups, and more preferably has three or more ethylenically unsaturated groups. Increasing the number of ethylenically unsaturated groups makes it easier to increase the degree of curing of the resin film and to improve resolution.

[0114] From the same viewpoint, the acrylic equivalent of the component (C) is preferably 80 g / eq to 1100 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0115] The content of component (C) is preferably 10% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass, based on the total mass of components (B) and (C). When the content of component (C) is 10% by mass or more, not only is the pattern resolution likely to be improved, but the degree of curing of the resin film is also likely to be increased, making it easier to improve adhesion. Furthermore, when the content of component (C) is 60% by mass or less, it is easier to suppress the generation of residues and further to control the pattern shape.

[0116] The component (C) may be used alone or in combination of two or more types.

[0117] 1-4.(D) Photopolymerization initiator There are no particular limitations on the component (D), so long as it is a compound that can initiate polymerization of an addition-polymerizable compound having a polymerizable unsaturated bond upon stimulation with light.

[0118] Examples of component (D) include acetophenone-based photopolymerization initiators, triazine-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, imidazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, etc. In this specification, the term "photopolymerization initiator" is used to include sensitizers.

[0119] Component (D) preferably contains an oxime ester photopolymerization initiator. Oxime ester photopolymerization initiators have high sensitivity, so even when component (D) is contained, sufficient photosensitivity can be ensured, and the developability (resolution) of the resin film can be sufficiently improved.

[0120] Examples of the acetophenone-based photopolymerization initiator include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one. Examples of commercially available products include Omnirad 127, Omnirad 369, Omnirad 1173, Omnirad 184, and Omnirad 651 (the Omnirad series is manufactured by IGM Resins BV).

[0121] Examples of triazine-based photopolymerization initiators include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0122] Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-tert-butyl ether.

[0123] Examples of the benzophenone-based photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(N,N-diethylamino)benzophenone.

[0124] Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxane, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0125] Examples of the imidazole-based photopolymerization initiator include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triarylimidazole dimer.

[0126] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Examples of commercially available products include Omnirad TPO H and Omnirad 819 (the Omnirad series is manufactured by IGM Resins BV).

[0127] Examples of oxime ester photopolymerization initiators include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)- 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-tetrahydrofuranylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-thiophenylmethane-1- 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-morphonylmethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-bicycloheptanecarboxylate 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethan-1-one oxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethan-1-one oxime-O-adamantane carboxylate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione 2-o-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-Dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone, 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2-octanediene, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanol Non-, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, etc.

[0128] Commercially available oxime ester photopolymerization initiators include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (IRGACURE OXE-03, BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (IRGACURE OXE-04, BASF, and Lunar 6, DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-305, Changzhou Powerful Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (TR -PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-831E (ADEKA Corporation), Omnirad 1312 (IGM Resins BV), and DFI-020 (Daito Chemix Co., Ltd.).

[0129] Examples of the oxime ester photopolymerization initiator include oxime ester compound photopolymerization initiators represented by general formula (D-1) or general formula (D-2).

[0130] [ka]

[0131] In formula (D-1), R 10 , R 11 are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms, and R 12 is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Furthermore, the alkyl group may be a straight-chain, branched, or cyclic alkyl group.

[0132] [ka]

[0133] In formula (D-2), R 13 and R 14 R are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 15 are independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. 13 ~R 15 Some of the hydrogen atoms in the group may be substituted with halogen atoms.

[0134] The content of component (D) is 1% by mass to 40% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 10% by mass to 40% by mass, based on the total mass of components (B) and (C). When the resin film absorbs light to a certain extent, the exposure dose tends to decrease from the surface of the resin film facing the exposure light source toward the interface on the opposite side of the resin film from the light source. A content within the above range facilitates photocuring at the interface on the opposite side of the coating film from the light source, making the coating film less likely to peel even in a highly alkaline developer, and ensuring good patterning properties. Furthermore, particularly when a strongly basic developer using a hydroxide such as tetramethylammonium hydroxide (TMAH) is used, the content of component (D) is most preferably 15% by mass to 40% by mass, based on the total mass of components (B) and (C). By ensuring a content of 15% by mass or more, good patterning properties are easily obtained even when a strongly basic developer is used.

[0135] The total content of the oxime ester photopolymerization initiators is preferably 20% by mass to 100% by mass, and more preferably 25% by mass to 100% by mass, based on the total mass of component (D). By ensuring that the total content of the oxime ester photopolymerization initiators is 20% by mass or more based on the total mass of component (D), it is possible to facilitate the progress of the curing reaction upon exposure, even in a resin film that absorbs light to a certain extent, such as one that has a reflected light blocking function, and to make it easier to control the curability and patterning characteristics of the resin film.

[0136] Component (D) may contain only one photopolymerization initiator or may contain two or more types, but preferably contains two or more types of photopolymerization initiators. For example, by using two or more types of photopolymerization initiators that differ in i-line absorbance, reaction efficiency, reaction rate, etc., it becomes easier to control the exposure sensitivity, and it becomes easier to control the pattern shape.

[0137] When component (D) contains two or more photopolymerization initiators, it preferably contains a photopolymerization initiator with an absorbance of less than 0.04 at 365 nm and an oxime ester-based photopolymerization initiator with an absorbance of 0.04 to 0.60 at 365 nm. Using two or more photopolymerization initiators with different absorbances and different reaction efficiencies and reaction rates facilitates control of exposure sensitivity and pattern shape. Herein, the absorbance of component (D) is measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) in a quartz cell with an optical path length of 1 cm using a 0.001 wt% acetonitrile solution.

[0138] Alternatively, compounds that do not function as photopolymerization initiators or sensitizers by themselves but can enhance their photopolymerization initiator or sensitizer capabilities when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0139] 1-5.(E) Solvent The component (E) dissolves or disperses each component contained in the photosensitive resin composition and adjusts the viscosity of the photosensitive resin composition, thereby making it easier to apply the photosensitive resin composition to a substrate or the like.

[0140] Examples of component (E) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and 3-methoxy-3-methyl-1-butanol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol. Examples of the (E) component include glycol ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, and 3-methoxy-3-methyl-1-butyl acetate. The (E) component may be used alone or in combination of two or more. From the viewpoint of safety, ester-based solvents and ester-based or ether-based solvents having a propylene glycol skeleton are preferred, with 3-methoxybutyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate being more preferred.

[0141] The content of component (E) varies depending on the target viscosity, but is preferably 30% to 90% by mass relative to the total mass of the photosensitive resin composition. When the content of component (E) is 30% by mass or more, the viscosity can be made to be such that the photosensitive resin composition can be easily applied to a substrate, and when the content is 90% by mass or less, not only can the pigment dispersion stability be ensured but also a film can be formed without unevenness, repelling, or bumping during drying after the photosensitive resin composition has been applied to a substrate.

[0142] 1-6.(F) Epoxy compounds having at least two epoxy groups (F) An epoxy compound having at least two epoxy groups (hereinafter also referred to as "component (F)") reacts with the alkali-soluble groups of component (B) and facilitates curing. In particular, it is preferable to include component (F) from the viewpoint that the curing reaction proceeds more easily at a relatively low temperature even when using a substrate with a low heat resistance temperature or when a layer with low heat resistance, such as an organic EL element, is included.

[0143] Examples of the component (F) include bisphenol A type epoxy compounds (e.g., jER 828: manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols (e.g., Epolite 100MF: manufactured by Kyoeisha Chemical Co., Ltd.), glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acrylic group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celloxide Examples of epoxy compounds include butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401, manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups, such as HiREM-1 manufactured by Shikoku Chemicals Corporation, multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton.

[0144] The epoxy equivalent of the epoxy compound of component (F) is preferably 100 g / eq to 300 g / eq, and more preferably 100 g / eq to 250 g / eq. When the epoxy equivalent is 300 g / eq or less, the curing reaction at low temperatures proceeds more easily, making it easier to improve solvent resistance. These compounds may be used alone or in combination of two or more types.

[0145] The content of component (F) is preferably 5% by mass to 35% by mass relative to the total mass of component (B). By making it 5% by mass or more, the curing reaction can proceed sufficiently even at low temperatures, making it easier to improve the solvent resistance of the resin film. Furthermore, by making it 35% by mass or less, the content of component (B) can be ensured, making it easier to improve patterning properties.

[0146] 1-7.(G) Heat curing agent The (G) thermosetting agent (hereinafter also referred to as "component (G)") can facilitate the curing reaction of component (F).

[0147] Even when a substrate with a low heat resistance temperature is used or when a layer with low heat resistance, such as an organic EL element, is included, it is preferable to include the component (G) from the viewpoint that the curing reaction of the component (F) is likely to proceed at a relatively low temperature.

[0148] Examples of component (G) include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc. Among these, polycarboxylic acid compounds and dicyandiamide are preferred. Examples of such polycarboxylic acid compounds include polycarboxylic acids, anhydrides of polycarboxylic acids, and thermally decomposable esters of polycarboxylic acids. Polycarboxylic acids are compounds having two or more carboxy groups in one molecule, and specific examples thereof include succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, and butane-1,2,3,4-tetracarboxylic acid. Examples of polycarboxylic acid anhydrides include the polycarboxylic acid anhydrides exemplified above. While intermolecular acid anhydrides may be used as such polycarboxylic acid anhydrides, acid anhydrides that undergo intramolecular ring closure are generally used. Examples of the thermally decomposable ester of a polycarboxylic acid include the thermally decomposable esters of the polycarboxylic acids exemplified above (e.g., t-butyl ester, 1-(alkyloxy)ethyl ester, 1-(alkylsulfanyl)ethyl ester, etc. (wherein the alkyl is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have any of a linear, branched, or cyclic structure and may have any substituent). Furthermore, a polymer or copolymer having two or more carboxy groups can also be used as the polycarboxylic acid compound, and the carboxy groups may form an anhydride group or a thermally decomposable ester group. There are no particular limitations on such polymers or copolymers having two or more carboxy groups, but examples include polymers or copolymers containing (meth)acrylic acid as a constituent component, copolymers containing maleic anhydride as a constituent component, and compounds obtained by reacting tetracarboxylic dianhydride with a diamine or diol to open the acid anhydride ring.Among these polycarboxylic acid compounds, anhydrides of polycarboxylic acids such as phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid are preferred.

[0149] The content of the (G) component can be appropriately set to adjust the thermosetting property, but from the viewpoint of easily improving the curing property at low temperatures, it is preferably 10 to 50 mass % relative to the content of the (F) component.

[0150] 1-8.(H) Surfactants The surfactant (H) (hereinafter also referred to as "component (H)") can facilitate increasing the smoothness of the resin film.

[0151] Examples of the component (H) include compounds containing hydrocarbon chains in the side chains, silicone-containing compounds, and fluorine-based compounds.

[0152] Examples of compounds containing a hydrocarbon chain in the side chain include polymers obtained by polymerizing (meth)acrylic acid alkyl esters. Examples of (meth)acrylic acid alkyl esters include (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid t-butyl ester, (meth)acrylic acid n-octyl ester, (meth)acrylic acid 2-ethylhexyl ester, and (meth)acrylic acid isononyl ester.

[0153] Examples of silicone-containing compounds include the reaction product of (meth)acrylic acid with a hydroxy group-containing silicone (e.g., α,ω-polydimethylsilicone diol) and the reaction product of (meth)acrylic acid with an epoxy group-containing silicone (e.g., polydimethylsilicone containing pendant epoxy groups).

[0154] Examples of the fluorine-based compound include perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkyl ammonium salt, oligomer containing a perfluoroalkyl group and a hydrophilic group, oligomer containing a perfluoroalkyl group and a lipophilic group, oligomer containing a perfluoroalkyl group, a hydrophilic group and a lipophilic group, urethane containing a perfluoroalkyl and a hydrophilic group, perfluoroalkyl ester, perfluoroalkyl phosphate ester, fluorine-containing organic compounds such as compounds containing a fluorine atom in the side chain, and the like.

[0155] Component (H) may also contain a crosslinking group, preferably an epoxy group or an ethylenically unsaturated group.

[0156] Examples of commercially available products of component (H) include DOWSIL SH 3775 M Fluid (manufactured by Dow-Toray Industries, Inc.), MEGAFACE EFS-131, MEGAFACE EFS-321, MEGAFACE EFS-521, and MEGAFACE EFS-801 (manufactured by DIC Corporation).

[0157] Among these, component (H) is preferably a silicone-containing compound. Use of such component (H) makes it easier to suppress cissing when the photosensitive resin composition is applied to a substrate and also makes it easier to improve smoothness.

[0158] The content of component (H) is preferably 0.01% by mass to 10.00% by mass, more preferably 0.01% by mass to 5.00% by mass, and even more preferably 0.01% by mass to 1.00% by mass, based on the total solid content of the photosensitive resin composition. By setting the content of component (H) to 0.01% by mass or more, smoothness tends to be improved, and by setting it to 10.00% by mass or less, component (H) becomes less likely to aggregate, making it easier to improve smoothness.

[0159] The component (H) may be used alone or in combination of two or more types.

[0160] 1-9. Other additives In addition to these components, the photosensitive resin composition may contain additives such as other resin components, coupling agents, fillers, ultraviolet absorbers, and rheology modifiers.

[0161] Examples of the other resin components include vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, and melamine resin.

[0162] Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0163] Examples of fillers include glass fiber, mica, and the like.

[0164] Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.

[0165] The photosensitive resin composition can be obtained by mixing the above-mentioned components.

[0166] 1-10.Transmittance when made into a resin film The photosensitive resin composition according to this embodiment is applied to a glass substrate so that the resin film has a thickness of 3.0 μm, and is then heat-treated at 85°C for 1 minute, followed by heat-treatment at 85°C for 60 minutes, to obtain a resin film-coated substrate whose transmittance satisfies the following two requirements: (Requirement 1) The average transmittance in the wavelength range of 440 nm to 650 nm is 30.0% to 80.0%. (Requirement 2) The difference between the maximum and minimum transmittance values ​​in the wavelength range of 440 nm to 650 nm is 20.0% or less.

[0167] The transmittance is measured by coating a photosensitive resin composition on a glass substrate so that the resin film has a thickness of 3.0 μm, pre-baking at 85° C. for 1 minute, and post-baking at 85° C. for 60 minutes to obtain a resin film-coated substrate, measuring the transmittance spectrum from the resin film side using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) under conditions of Illuminant C, an incident angle of 0°, and a wavelength range of 440 to 650 nm, and calculating the average value. Note that the transmittance does not depend on the pre-bake temperature and post-bake temperature, so the transmittance may be measured using resin film-coated substrates obtained by changing the pre-bake temperature and post-bake temperature.

[0168] The transmittance fluctuation range is calculated as the difference between the maximum and minimum transmittance values ​​for the transmittance spectrum in the wavelength range of 440 to 650 nm obtained above.

[0169] A configuration that satisfies the above (Requirement 1) can be achieved by adjusting the content of component (A), adding pigments other than black, such as red, blue, green, purple, yellow, cyan, and magenta, or, when carbon black and titanium black are included, adjusting the addition ratio of carbon black to titanium black. Among these, from the viewpoint of making it easier to increase the addition ratio of component (B) by keeping the addition amount of pigments including component (A) relatively low and improving patterning properties, it is preferable to achieve (Requirement 1) by adjusting the content of component (A) or adjusting the addition ratio of carbon black to titanium black.

[0170] The configuration that satisfies the above (Requirement 2) can be realized by using a black pigment containing carbon black and / or titanium black, adding a pigment other than black, such as red, blue, green, purple, yellow, cyan, or magenta, or, when carbon black and titanium black are included, adjusting the ratio of the carbon black and titanium black added. Among these, from the viewpoint of making it easier to increase the ratio of the component (B) added by relatively reducing the amount of the pigment containing component (A) added, and thus improving patterning properties, it is preferable to realize (Requirement 2) by using a black pigment containing carbon black and / or titanium black or adjusting the ratio of the carbon black and titanium black added.

[0171] The average transmittance is 30% to 80%, and more preferably 40% to 70%. If the transmittance is 30% or more, even when external light incident on the organic EL panel is reflected by the organic EL panel, the reflected light is easily blocked, which tends to improve the visibility of the organic EL display device. If the transmittance is 80% or less, the light emitted by the organic EL panel is easily transmitted, which tends to reduce the amount of emitted light, which tends to reduce the power consumption of the organic EL display device.

[0172] The transmittance fluctuation range is preferably 12.0% or less, more preferably 10.0% or less, even more preferably 7.5% or less, and most preferably 5.0% or less. By setting the transmittance fluctuation range to a smaller value, light emitted by the organic EL element is more likely to be transmitted uniformly regardless of wavelength, which tends to improve the color reproducibility of the organic EL display device.

[0173] 2. Manufacturing method of resin film and resin film-coated substrate The resin film-coated substrate according to this embodiment can be manufactured through the following steps: (a) applying the photosensitive resin composition to a substrate to form a coating film; (b) exposing a portion of the coating film to radiation through a photomask to cure it; (c) developing the radiation-irradiated coating film and removing the unexposed portions of the coating film to form a pattern; and (d) heat treating (post-curing) the patterned coating film.

[0174] The above steps show a manufacturing method for obtaining a patterned resin film, but when obtaining a non-patterned resin film, the resin film-coated substrate may be manufactured through only the step (a) of forming a coating film, or may be manufactured through the step (a) of forming a coating film and the step (d) of heat treating (post-curing) the non-patterned coating film.

[0175] In the present application, the term "resin film" refers to a film obtained by drying component (E) from a photosensitive resin composition at least to the extent that the film does not flow, after undergoing the aforementioned step (A) of forming a coating film, and is not particularly limited as long as it is such a film. The "resin film" may also be a film obtained by undergoing the aforementioned steps (B) of exposing, (C) of developing, and (D) of heat treatment, in addition to the aforementioned step (A) of forming a coating film.

[0176] In this application, the term "coating film" refers to a "resin film" that has not yet been heat-treated under the preferred heat treatment conditions (temperature, time) for promoting the crosslinking reaction described below in "2-3. Heat treatment step for coating film." The term "cured film" refers to a "resin film" that has been heat-treated under the preferred heat treatment conditions (temperature, time) for promoting the crosslinking reaction described below.

[0177] 2-1. Process of forming the coating film The photosensitive resin composition can be applied by a known application method. Examples of the application method include a known solution immersion method, a spray method, and methods using a roller coater, a land coater, a slit coater, or a spinner. By using these methods, the photosensitive resin composition can be applied to a desired thickness.

[0178] The coating film thus formed is preferably dried before exposure. The coating film can be dried by a known drying method. Examples of the drying method include heating with an oven, a hot air blower, a hot plate, an infrared heater, etc., vacuum drying, and combinations thereof. The heating temperature and heating time during drying can be appropriately selected depending on the solvent used, and is preferably performed at 60°C to 120°C for 0.5 to 5.0 minutes (pre-baking).

[0179] 2-2. Exposure and development process of coating film The exposure step can be carried out by irradiating a part of the coating film with radiation through a photomask, and this exposure photocures the part of the coating film that corresponds to the pattern.

[0180] A known photomask can be used as the photomask. Examples of photomasks include multi-tone masks such as half-tone masks and gray-tone masks. A gray-tone mask has a light-shielding portion and a diffraction grating formed on a light-transmitting substrate. The diffraction grating has light-transmitting regions such as slits, dots, and meshes spaced at intervals equal to or less than the resolution limit of the light used for exposure, and this configuration controls the light transmittance. A half-tone mask has a light-shielding portion and a semi-transmitting portion formed on a light-transmitting substrate. The semi-transmitting portion controls the transmittance of the light used for exposure.

[0181] The exposure device used for exposure and its exposure irradiation conditions can be selected appropriately. Examples of radiation to be irradiated include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among the above-mentioned radiation, ultraviolet light is preferred. Furthermore, known exposure devices (ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, far ultraviolet lamps, etc.) can be used as the device for irradiating radiation. Furthermore, it is preferred that the wavelength of the irradiated radiation is an emission line including 365 nm. The radiation exposure dose is 10 mJ / cm. 2 ~1000mJ / cm 2 It is preferable that:

[0182] The development step can be carried out by a method in which the radiation-irradiated coating film is subjected to alkali development to remove the unexposed portions of the coating film.

[0183] Examples of the method for developing the coating film include shower development, spray development, dip (immersion) development, puddle (puddle) development, etc. The development can be carried out using a commercially available developing machine, ultrasonic cleaner, etc.

[0184] Examples of developers suitable for development include aqueous solutions of alkali metal or alkaline earth metal carbonates, and aqueous solutions of quaternary ammonium ions or alkali metal hydroxides. Alkaline conditions can be appropriately selected depending on the intended use, the required development rate, the pattern shape, and other factors. When development is performed under weakly alkaline conditions, development is preferably carried out at a temperature of 23°C to 30°C using a weakly alkaline aqueous solution containing 0.04% to 5.00% by mass of a carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate. When development is performed under strongly alkaline conditions, development is preferably carried out at a temperature of 23°C to 30°C using a strongly alkaline aqueous solution containing 0.04% to 5.00% by mass of a hydroxide such as tetramethylammonium hydroxide (TMAH). Commercially available developing machines, ultrasonic cleaners, and the like can be used in the development process.

[0185] 2-3. Heat treatment process for coating film In the heat treatment step, the exposed portion (coating film) after development is heat treated for full curing (post-baking) to obtain a cured film.

[0186] The exposed area (coating film) after development can be heated by a known method (heating with an oven, hot air blower, hot plate, infrared heater, etc., vacuum drying, or a combination of these). The heating temperature is not particularly limited as long as it is a temperature at which the coating film undergoes main curing (post-baking), but it is preferably performed at a temperature of 250°C or less for 20 to 60 minutes.

[0187] For example, from the viewpoint of facilitating the use of substrates made of resins with low heat resistance such as polyethylene terephthalate, or substrates containing layers with low heat resistance such as organic EL elements, it is more preferable to perform heat treatment at a temperature of 100°C or less for 20 to 60 minutes, and even more preferable to perform heat treatment at a temperature of 60°C to 100°C for 20 to 60 minutes.

[0188] After heat curing, the resin film may be washed with short-wave radiation to remove organic contaminants from the surface of the resin film.

[0189] The cleaning can be carried out by irradiating ultraviolet rays with wavelengths of 184.9 nm and 253.7 nm using a low-pressure mercury lamp, for example, at a dose of 250 to 1000 mJ.

[0190] 3. Substrate with resin film The resin film-attached substrate according to this embodiment includes the resin film and a substrate.

[0191] Examples of the substrate include glass, polyimide film, polyethylene terephthalate, etc. The substrate may also be provided with an organic EL element or the like.

[0192] 4.Organic EL display device The organic EL display device according to this embodiment includes an organic EL panel and the resin film, and the resin film is provided on the viewer side of the organic EL panel.

[0193] Known organic EL panels can be used as the organic EL panel, and examples of the organic EL panel include a panel configured using an organic EL element in which an organic EL layer is sandwiched between electrodes.

[0194] The organic EL display device according to this embodiment may include a touch panel. A known touch panel can be used as the touch panel. Examples of the touch panel include various types of touch panels, such as resistive film type, capacitive type, surface acoustic wave type, infrared type, electromagnetic induction type, image recognition type, and optical sensor type. [Example]

[0195] Hereinafter, the embodiments of the present invention will be specifically described based on examples, comparative examples, and a reference comparative example, but the present invention is not limited to these.

[0196] The synthesis examples of polymerizable resins will be explained first. The resins in these synthesis examples were evaluated as follows unless otherwise specified.

[0197] When the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place. In the examples, all glass substrates used to prepare the resin film-coated substrates for measurement are subjected to the same treatment. When the first decimal place of the content of each component is 0, the decimal point may be omitted.

[0198] [Solid content concentration] The resin content was calculated using the following formula from the weight [W1(g)] after 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0(g)] and the weight [W2(g)] after heating at 160°C for 2 hours. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0199] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0200] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0201] The abbreviations used in the synthesis examples are as follows. BPFE: Bisphenolfluorene type epoxy compound (a reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane. A compound of the general formula (B-3) in which A is a fluorene-9,9-diyl group and R1 to R4 are hydrogen.) AA: acrylic acid BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate DCPMA: dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: styrene AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine PTMA: Pentaerythritol tetra(mercaptoacetate) DPHA: A mixture of dipentaerythritol pentaacrylate and hexaacrylate BzDMA: benzyldimethylamine

[0202] [Synthesis Example 1] A 500 ml four-neck flask equipped with a reflux condenser was charged with BPFE (50.0 g, 0.10 mol), AA (14.1 g, 0.20 mol), PGMEA (67 g), and TPP (0.26 g) and stirred at 100-105°C for 12 hours to react. Next, BPDA (14.4 g, 0.05 mol) and THPA (7.4 g, 0.05 mol) were added to the flask and stirred at 120-125°C for 6 hours to obtain unsaturated group-containing alkali-soluble resin (B)-1. The solids concentration of the resulting resin solution was 56% by mass, the acid value (solids equivalent) was 96 mg KOH / g, and the Mw by GPC analysis was 3600.

[0203] [Synthesis Example 2] A 500 ml four-neck flask equipped with a reflux condenser was charged with BPFE (50.0 g, 0.10 mol), AA (14.1 g, 0.20 mol), PGMEA (67 g), and TPP (0.26 g) and stirred at 100-105°C for 12 hours to react. Next, BPDA (20.9 g, 0.07 mol) and THPA (0.23 g, 0.015 mol) were added to the flask and stirred at 120-125°C for 6 hours to obtain unsaturated group-containing alkali-soluble resin (B)-2. The solids concentration of the resulting resin solution was 56% by mass, the acid value (solids equivalent) was 102 mg KOH / g, and the Mw by GPC analysis was 7000.

[0204] [Synthesis Example 3] 300.0 g of PGMEA was placed in a 1 L four-neck flask equipped with a reflux condenser, and the atmosphere in the flask was replaced with nitrogen, and then the temperature was raised to 120° C. A monomer mixture (a mixture of 66.1 g (0.30 mol) of DCPMA, 85.3 g (0.60 mol) of GMA, and 10.4 g (0.10 mol) of St dissolved in 10 g of AIBN) was added dropwise to the flask from a dropping funnel over 2 hours, and the mixture was stirred at 120° C. for an additional 2 hours to obtain a copolymer solution.

[0205] Next, the atmosphere in the flask was replaced with air, and then 43.2 g (0.6 mol) of AA, 0.8 g of TDMAMP, and 0.15 g of HQ were added to the resulting copolymer solution, which was then stirred for 6 hours under heating at 120°C to obtain a copolymer solution containing polymerizable unsaturated groups.

[0206] Furthermore, 59.3 g (0.39 mol) of THPA and 0.5 g of TEA were added to the resulting polymerizable unsaturated group-containing copolymer solution and reacted at 120 °C for 4 hours to obtain polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (B)-3. PGMEA was added to adjust the solids concentration of the resin solution to 42% by mass. The acid value (solids equivalent) was 79 mg KOH / g, and the Mw by GPC analysis was 8500.

[0207] [Synthesis Example 4] 300.0 g of PGMEA was placed in a 1 L four-neck flask equipped with a reflux condenser, and the atmosphere in the flask was replaced with nitrogen, after which the temperature was raised to 120° C. A monomer mixture (a mixture of 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 31.2 g (0.30 mol) of St dissolved in 10 g of AIBN) was added dropwise to the flask from a dropping funnel over 2 hours, followed by stirring at 120° C. for an additional 2 hours to obtain a copolymer solution.

[0208] Next, the atmosphere in the flask was replaced with air, and then 24.0 g (0.33 mol) of AA, 0.8 g of TDMAMP, and 0.15 g of HQ were added to the resulting copolymer solution, followed by stirring for 6 hours under heating at 120°C to obtain a polymerizable unsaturated group-containing copolymer solution.

[0209] Furthermore, 30.0 g (0.30 mol) of SA and 0.5 g of TEA were added to the obtained polymerizable unsaturated group-containing copolymer solution and reacted at 120 °C for 4 hours to obtain polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (B)-4. PGMEA was added to adjust the solids concentration of the resin solution to 39 mass%. The acid value (solids equivalent) was 76 mg KOH / g, and the Mw by GPC analysis was 5300.

[0210] [Synthesis Example 5] PTMA (20 g, 0.19 mol of mercapto groups), DPHA (212 g (2.12 mol of acrylic groups)), PGMEA (58 g), HQ (0.1 g), and BzDMA (0.01 g) were added to a 1 L four-neck flask and reacted at 60°C for 12 hours to obtain dendritic polymer solution (C)-2. The solids concentration of the dendritic polymer solution was 50% by mass, and the Mw was 10,000 as determined by GPC analysis. The disappearance of the mercapto groups from the resulting dendritic polymer was confirmed by iodometry.

[0211] [Preparation of Photosensitive Resin Composition] Photosensitive resin compositions of Examples 1 to 32 and Comparative Examples 1 to 4 were prepared by blending the components in the compositions shown in Tables 1 to 4. The numerical values ​​in Tables 1 to 4 indicate the amount added (parts by mass). The amount of component (A) added includes the amount of the dispersant described below. The amounts of components (A), (B), and (C) added include the amount of the solvent described below when added as a solution. The amount of component (E) added in Tables 1 to 4 does not include the solvent carried over from component (A), component (B), and component (C). The total amount of component (E) contained in the photosensitive resin composition is the sum of the amount of component (E) added shown in Tables 1 to 4 and the amount of solvent carried over from component (A), component (B), and component (C).

[0212] The components used in the formulation are as follows. For components (A), (B), and (C) that contain a solvent, the solids concentration is listed. (black pigment) (A)-1: PGMEA dispersion with a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 6.0% by mass (solids concentration 31.0% by mass, average secondary particle diameter of carbon black 170 nm) (A)-2: PGMEA dispersion with a titanium black (TiN) concentration of 15.0% by mass and a dispersant concentration of 5.0% by mass (solid concentration 20.0%, average particle size of titanium black 82 nm) (A)-3: PGMEA dispersion with a titanium black (TiN) concentration of 15.0% by mass and a dispersant concentration of 5.0% by mass (solid concentration 20.0%, average particle size of titanium black 98 nm)

[0213] (Alkali-soluble resin containing unsaturated groups) (B)-1: Unsaturated group-containing alkali-soluble resin solution (solid content concentration: 56% by mass) obtained in Synthesis Example 1 above (B)-2: Unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 2 (solid content concentration: 56% by mass) (B)-3: Unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 3 (solid content concentration: 42% by mass) (B)-4: Unsaturated group-containing alkali-soluble resin solution obtained in Synthesis Example 4 (solid content concentration: 39% by mass)

[0214] (Photopolymerizable compound) (C)-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA) (C)-2: Dendritic polymer solution obtained in Synthesis Example 5 (solid content concentration: 50% by mass)

[0215] (Photopolymerization initiator) (D)-1: OXE-01 (BASF Japan Ltd., oxime ester photopolymerization initiator), absorbance at 365 nm: 0.05 (D)-2: Omnirad 819 (IGM Resins BV, acylphosphine oxide photopolymerization initiator), absorbance at 365 nm: 0.002

[0216] (solvent) (E)-1: Propylene glycol monomethyl ether acetate (PGMEA) (E)-2: Cyclohexanone (ANON) (E)-3: 3-Methoxybutyl acetate (MBA)

[0217] (epoxy compounds) (F)-1: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (Daicel Corporation "EHPE3150", epoxy equivalent 180) (F)-2: 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (Daicel Corporation "Celloxide 2021P", epoxy equivalent 130)

[0218] (thermosetting agent) (G)-1: Benzene-1,2,4-tricarboxylic acid-1,2-anhydride (G)-2: Dicyandiamide (DICY7, manufactured by Mitsubishi Chemical Corporation)

[0219] (surfactant) (H)-1: DOWSIL SH 3775 M Fluid (Dow Toray Industries, Inc.) (H)-2: MEGAFACE EFS-801 (DIC Corporation)

[0220] [Table 1]

[0221] [Table 2]

[0222] [Table 3]

[0223] [Table 4]

[0224] [Evaluation using photosensitive resin composition] The following evaluations were carried out using resin films formed from the photosensitive resin compositions of Examples 1 to 32 and Comparative Examples 1 to 4. The evaluation results are shown in Tables 5 to 8.

[0225] (Preparation of resin film for transmittance and reflectance evaluation) The photosensitive resin composition was applied to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) using a spin coater so that the resin film had a thickness of 3.0 μm. Pre-baking was performed at 85°C for 1 minute. Subsequent post-baking was performed in an oven at 85°C for 60 minutes to obtain an evaluation substrate. The obtained evaluation substrate was measured for the step height between the glass substrate surface and the resin film surface using a step height meter (manufactured by KLA-Tencor Corporation, "Tencor P-17") under conditions of a measurement range of 500 μm, a scanning speed of 50 μm / sec, and a sampling rate of 20 Hz. The average value was calculated, and it was confirmed that the resin film had a thickness of 3.0 μm.

[0226] <Average transmittance evaluation> (Evaluation method) Using the obtained evaluation substrate, the transmittance spectrum was measured from the resin film side using a UV-Vis-Infrared Spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) under the conditions of light source C, incident angle 0°, and wavelength range 440 to 650 nm, and the average value was taken as the average transmittance.

[0227] <Transmittance fluctuation range evaluation> (Evaluation method) For the transmittance spectrum obtained above in the wavelength range of 440 to 650 nm, the difference between the maximum and minimum transmittance values ​​was calculated and used as the transmittance fluctuation range. Note that a smaller transmittance fluctuation range indicates better performance.

[0228] <Reflectance evaluation> (Evaluation method) Using the obtained evaluation substrate, the SCI reflectance of the resin film side was measured using a UV-Vis-Infrared Spectrophotometer "UH4150" (Hitachi High-Tech Science Corporation) under the conditions of a C light source, an incident angle of 2°, and a wavelength range of 380 to 780 nm. Note that a smaller SCI reflectance value indicates better performance.

[0229] <Refractive index evaluation> (Preparation of resin film for evaluation) The above photosensitive resin composition was applied to a 125 mm diameter silicon wafer "5-inch P-type wafer 1-100" (manufactured by Advantec Co., Ltd.) using a spin coater so that the film thickness after post-baking would be 1.0 μm. Pre-baking was carried out at 85°C for 1 minute. Subsequent post-baking was carried out using an oven at 85°C for 60 minutes to obtain a substrate for refractive index evaluation. The thickness of the resin film on the obtained evaluation substrate was measured using the method described above, and it was confirmed that the resin film thickness was 1.0 μm.

[0230] (Evaluation method) Using the obtained substrate for refractive index evaluation, the refractive index of the resin film after post-baking was measured with a spectroscopic ellipsometry "Alpha-SE" (manufactured by JA Woollam).

[0231] <Hole resolution evaluation> (Preparation of resin film for evaluation) The above photosensitive resin composition was applied to a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Inc.) using a spin coater so that the film thickness after post-baking would be 3.0 μm. Pre-baking was carried out at 85° C. for 1 minute.

[0232] Next, a negative photomask was placed on the coating film, and the i-line irradiance was 30 mW / cm 2 100mJ / cm with an ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating the film with ultraviolet light.

[0233] The exposed resin film was then developed at 23°C with a 2.38% tetramethylammonium hydroxide (TMAH) developer at 1 kgf / cm 2 After developing for 10 seconds from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm. 2 The unexposed portions of the resin film were removed to form a resin film pattern on the glass substrate, which was then post-cured (post-baked) at 85°C for 60 minutes using a hot air dryer to obtain a substrate for hole resolution evaluation.

[0234] (Evaluation method) The development was confirmed with a microscope (XD-1000, manufactured by Nikon Corporation) to confirm that the openings were square. The results were judged according to the following criteria based on the opening size of the negative photomask corresponding to the opening. A grade of △ or better was considered to be acceptable. ○: Negative photomask opening size is less than 20 μm △: Negative photomask opening size is 20 to less than 100 μm ×: The opening size of the negative photomask is 100 μm or more

[0235] [Table 5]

[0236] [Table 6]

[0237] [Table 7]

[0238] [Table 8]

[0239] As is clear from the results of Examples 1 to 32 and Comparative Examples 1 to 4, it was found that by using the photosensitive resin composition according to this embodiment, a resin film having appropriate light-shielding properties and a small fluctuation range of transmittance in the visible light region can be produced. Therefore, this resin film is suitable as a resin film for use in an organic EL display device that does not have a circular polarizer. [Industrial Applicability]

[0240] The photosensitive resin composition according to the present embodiment can provide a resin film that can easily block light reflected by an organic EL panel and can easily transmit light emitted by the organic EL panel uniformly regardless of wavelength, even without using a circular polarizer. Such a resin film is useful as a component of an organic EL display device. In particular, the resin film according to the present embodiment is suitable when an organic EL display device that has good color reproducibility and visibility and can be used with low power consumption is required.

Claims

1. (A) a black pigment containing carbon black and / or titanium black; (B) an unsaturated group-containing alkali-soluble resin; (C) a photopolymerizable compound having two or more ethylenically unsaturated groups; (D) a photopolymerization initiator; (E) a solvent; A photosensitive resin composition comprising: The photosensitive resin composition comprises a resin film-coated substrate obtained by applying the resin film to a glass substrate so that the film thickness is 3.0 μm has an average transmittance of 30.0% to 80.0% at wavelengths of 440 nm to 650 nm, and a difference between the maximum and minimum transmittance at wavelengths of 440 nm to 650 nm of 20.0% or less; Photosensitive resin composition.

2. (F) an epoxy compound having at least two epoxy groups; The photosensitive resin composition according to claim 1 .

3. The unsaturated group-containing alkali-soluble resin (B) includes a resin represented by the following general formula (B-1): The photosensitive resin composition according to claim 1 . 【Chemical 1】 (In formula (B-1), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and R ５ are independently a hydrogen atom or a methyl group, and A is independently -CO-, -SO ２ -, -C(CF ３ ) ２ -, -Si(CH ３ ) ２ -, -CH ２ -, -C(CH ３ ) ２ -, -O-, a fluorene-9,9-diyl group, or a direct bond; Y is independently a tetravalent carboxylic acid residue; and Z is independently a hydrogen atom or a substituent represented by general formula (B-2), provided that at least one Z is a substituent represented by general formula (B-2), and n is a number from 1 to 20. 【Chemistry 2】 (In formula (B-2), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.)

4. The black pigment (A) contains carbon black and titanium black, The photosensitive resin composition has a difference between the maximum and minimum transmittance of the resin film-coated substrate in the wavelength range of 440 nm to 650 nm of 10.0% or less. The photosensitive resin composition according to claim 1 .

5. When the (A) black pigment contains carbon black, the average secondary particle diameter of the carbon black is 250 nm or less, When the (A) black pigment contains titanium black, the average particle size of the titanium black is 150 nm or less. The photosensitive resin composition according to claim 1 .

6. A resin film formed from the photosensitive resin composition according to any one of claims 1 to 5.

7. A resin film-coated substrate comprising the resin film according to claim 6.

8. An organic electroluminescence display device comprising the resin film according to claim 6 .

9. A step of applying the photosensitive resin composition according to any one of claims 1 to 5 to a substrate to form a coating film; a heat treatment step of heat treating the coating film at 100°C or less; A method for producing a resin film-attached substrate, comprising:

10. an exposure step of irradiating a portion of the coating film formed on the substrate with radiation through a photomask; a developing step of developing the irradiated coating film and removing the unexposed portions of the coating film; Including, The developing step is carried out before the heat treatment step. The method for producing a resin film-coated substrate according to claim 9 .

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