Polysiloxane, photosensitive resin composition, cured product, semiconductor device, and organic el display device

Abstract

This invention was made with the objective of providing a polysiloxane capable of manufacturing a photosensitive resin composition that can be processed with high precision and yields a highly flexible cured product. This invention is a polysiloxane comprising one or more structures selected from the group consisting of structures shown in formulas (1) to (3). In formulas (1) to (3), R 1 Each group is represented independently as shown in formula (4). R 2 R represents a hydrocarbon group with 1 to 4 carbon atoms. 3 represents a monovalent hydrocarbon group with 1 to 6 carbon atoms. represents the bonding site with an oxygen atom, and represents the bonding site with a hydrogen or silicon atom. In formula (4), represents the bonding site with a silicon atom. R 4 R represents a divalent hydrocarbon group with 1 to 6 carbon atoms. 5 and R 6 Each can be independently represented as a group consisting of 1 to 6 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms. Among them, R... 5 and R 6 At least one of them is a group containing an aliphatic carbon-carbon unsaturated bond.

Description

Technical Field

[0001] This invention relates to polysiloxanes, photosensitive resin compositions, cured products using the same, semiconductor devices, and organic EL display devices. Background Technology

[0002] In addition to heat resistance and electrical insulation, polysiloxanes also possess excellent transparency. Therefore, they are used as surface protective layers for semiconductor devices, interlayer insulating layers, insulating layers for organic electroluminescence (EL) displays, and planarization layers for thin-film transistor (TFT) substrates. In recent years, with the diversification of electronic device designs, the increasing precision and flexibility of display devices, and the miniaturization and high integration of semiconductor devices, there is a growing demand for corresponding technological development in the materials used in these insulating or protective films. In particular, there is a strong need for highly precise and flexible materials.

[0003] For example, Patent Document 1 describes a polysiloxane containing vinyl and styrene groups in its side chains as a positive photosensitive resin composition. Patent Document 2 describes a curable polysiloxane having an isocyanurate ring structure and epoxy groups in its side chains as a hard coating material.

[0004] Existing technical documents Patent documents Patent Document 1: International Publication No. 2020 / 196601 Patent Document 2: International Publication No. 2019 / 123731 Summary of the Invention

[0005] The problem that the invention aims to solve However, when processing the materials described in Patent Documents 1 and 2, fractures occur at the processed curved surfaces, therefore, the materials described in Patent Documents 1 and 2 are still not sufficiently flexible.

[0006] Therefore, the object of the present invention is to provide a polysiloxane capable of manufacturing a photosensitive resin composition that can be processed with high precision and yields a highly flexible cured product, a photosensitive resin composition comprising the polysiloxane, a cured product obtained from the photosensitive resin composition, a semiconductor device having the cured product, and an organic EL display device.

[0007] Methods for solving problems To address the aforementioned issues, the present invention and its preferred embodiments include the following configuration.

[0008] [1] A polysiloxane comprising one or more of the structures shown in any of formulas (1) to (3).

[0009] [Chemical Formula 1] In equations (1) to (3), R 1 Each group is represented independently as shown in formula (4). R 2 R represents a hydrocarbon group with 1 to 4 carbon atoms. 3 It represents a monovalent hydrocarbon group with 1 to 6 carbon atoms. This indicates the bonding site where the oxygen atom is bonded. This indicates the bonding site that is bonded to a hydrogen or silicon atom.

[0010] [Chemical Formula 2] In equation (4), This indicates the bonding site where the silicon atom is bonded. R 4 R represents a divalent hydrocarbon group with 1 to 6 carbon atoms. 5 and R 6 Each can be independently represented as a group consisting of 1 to 6 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms. Among them, R... 5 and R 6 At least one of them is a group containing an aliphatic carbon-carbon unsaturated bond.

[0011] [2] The polysiloxane as described in [1], wherein the total content of the structure shown by any of the aforementioned formulas (1) to (3) is more than 5 mol% and less than 50 mol% relative to 100 mol% of the total amount of silicon atoms in the aforementioned polysiloxane.

[0012] [3] The polysiloxane as described in [1] or [2], wherein the aforementioned polysiloxane further comprises one or more of the structures shown in any one of formulas (5) to (7).

[0013] [Chemical Formula 3] In equations (5) to (7), R 7 The group represented by any of formulas (8) to (10). R 8 R represents a monovalent hydrocarbon group with 1 to 4 carbon atoms. 9 It represents a monovalent hydrocarbon group with 1 to 6 carbon atoms. This indicates the bonding site where the oxygen atom is bonded. This indicates the bonding site that is bonded to a hydrogen or silicon atom.

[0014] [Chemical Formula 4] In equations (8) to (10), This represents the bonding site where the silicon atom bonds. n represents an integer from 0 to 8, and m represents an integer from 1 to 8. R 10 A group representing a hydrogen atom, or a group consisting of 1 to 4 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms.

[0015] [4] The polysiloxane as described in [3], wherein the total content of the structure shown in any of the aforementioned formulas (5) to (7) is more than 20 mol% and less than 50 mol% relative to 100 mol% of the total amount of silicon atoms in the aforementioned polysiloxane.

[0016] [5] The polysiloxane as described in [3] or [4], wherein at least one R in the structure shown in any of the aforementioned formulas (5) to (7) 7 The group is shown in formula (8).

[0017] [6] The polysiloxane as described in any one of [3] to [5], wherein the total number of moles X of the structure represented by any one of formulas (5) to (7) and the total number of moles Y of the structure represented by any one of formulas (1) to (3) of the aforementioned polysiloxane satisfy the following relationship.

[0018] 0.4 ≤ (X / Y) ≤ 4.0 [7] A photosensitive resin composition comprising a photoacid generator and any one of [1] to [6] a polysiloxane.

[0019] [8] The photosensitive resin composition as described in [7], wherein the aforementioned photoacid generator comprises at least naphthoquinone diazide.

[0020] [9] A cured product which is formed by curing the photosensitive resin composition described in [7] or [8].

[0021]

[10] A semiconductor device comprising the cured material described in [9].

[0022]

[11] An organic EL display device having the cured material described in [9].

[0023] Invention Effects According to the present invention, a polysiloxane is provided that enables the manufacture of a photosensitive resin composition capable of being processed with high precision and yielding a highly flexible cured material. Attached Figure Description

[0024] [ Figure 1 [This is a cross-sectional view of an example of a TFT substrate.]

[0025] [ Figure 2[A magnified cross-sectional view of an example of the pad portion of a semiconductor device with bumps.]

[0026] [ Figure 3 [Illustration] is a schematic diagram illustrating an example of a method for manufacturing a semiconductor device with bumps. Detailed Implementation

[0027] The embodiments of the present invention will be described in detail.

[0028] <Polysiloxane> The polysiloxane of the present invention comprises one or more of the structures shown in any of formulas (1) to (3). By making the aforementioned polysiloxane comprise the structures shown in any of formulas (1) to (3), preferably the structure shown in formula (1) and / or the structure shown in formula (3), it is possible to suppress reflow during heating in pattern processing and obtain a highly fine pattern when preparing a photosensitive resin composition comprising the aforementioned polysiloxane. In addition, the flexibility of the cured product of the photosensitive resin composition comprising the aforementioned polysiloxane can be improved.

[0029] [Chemical Formula 5] In equations (1) to (3), R 1 Each group is represented independently as shown in formula (4). R 2 R represents a hydrocarbon group with 1 to 4 carbon atoms. 3 It represents a monovalent hydrocarbon group with 1 to 6 carbon atoms. This indicates the bonding site where the oxygen atom is bonded. This indicates the bonding site that is bonded to a hydrogen or silicon atom.

[0030] As R 2 Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, or methoxyethyl.

[0031] As R 3 Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, or phenyl.

[0032] [Chemical Formula 6] In equation (4), This indicates the bonding site where the silicon atom is bonded. R 4 R represents a divalent hydrocarbon group with 1 to 6 carbon atoms. 5 and R 6Each of these terms independently represents a group consisting of 1 to 6 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms. Specifically, a group consisting of 1 to 6 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms refers to a group that can be represented by the chemical formula C. w H x N y O z The groups are represented by w, where w represents an integer from 1 to 6, and x, y, and z each independently represent any arbitrary integer. Where R... 5 and R 6 At least one of them is a group containing an aliphatic carbon-carbon unsaturated bond.

[0033] As R 4 Examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, phenylene, or cyclohexylene. 4 Preferred to be propylidene.

[0034] As R 5 and R 6 Examples of groups having 1 to 6 carbon atoms, excluding aliphatic carbon-carbon unsaturated bonds, include ethyl, propyl, glycidyl, or hydroxyethyl groups. Examples of groups containing aliphatic carbon-carbon unsaturated bonds include vinyl, allyl, acryloyl, acryloyloxyethylidene, methacryloyl, or methacryloyloxyethylidene, with allyl being preferred. R is preferred. 5 and R 6 All of them are groups containing aliphatic carbon-carbon unsaturated bonds.

[0035] The aforementioned polysiloxane may contain only one or more of the structures shown in any of the aforementioned formulas (1) to (3).

[0036] The total content of the structures shown in any of the aforementioned formulas (1) to (3), relative to 100 mol% of the total silicon atoms in the aforementioned polysiloxane, is preferably 5 mol% or more and 50 mol% or less. The total content of the structures shown in any of the aforementioned formulas (1) to (3) refers to the total content of the structures shown in formula (1), formula (2), and formula (3), and is not counted repeatedly if multiple of the aforementioned structures are involved. By making this content 5 mol% or more, more preferably 15 mol% or more, the flexibility can be improved more effectively. In addition, by making this content 50 mol% or less, more preferably 30 mol% or less, when preparing the photosensitive resin composition, reflow during heating during pattern processing can be suppressed more effectively, resulting in a highly detailed pattern.

[0037] In order to make the aforementioned polysiloxane contain the structure shown by any of the aforementioned formulas (1) to (3), the aforementioned polysiloxane may be manufactured, for example, by using at least the following alkoxysilane compounds.

[0038] [Chemical Formula 7] These alkoxysilane compounds can be used alone or in combination of two or more. In particular, the alkoxysilane compounds shown in formula (11) are preferred.

[0039] [Chemical Formula 8] In formula (11), Me represents methyl, and X represents an alkoxy or alkyl group having 1 to 4 carbon atoms. X is preferably any one of methoxy, ethoxy, methyl, or ethyl.

[0040] These alkoxysilane compounds can be obtained by reacting isocyanurates having carbon-carbon unsaturated bonds with trialkoxysilanes or alkyldialkoxysilanes using a platinum catalyst. Examples of alkoxysilane compounds represented by formula (11) include 1-(3-(trimethoxysilyl)propyl)3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and 1-(3-(ethyldimethoxysilyl)propyl)3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. Additionally, examples of commercially available alkoxysilane compounds represented by formula (11) include Shin-Etsu Chemical Industry Co., Ltd.'s x-12-1290. Commercially available alkoxysilane compounds are preferred due to their easy availability.

[0041] The aforementioned polysiloxane preferably further comprises one or more of the structures shown in any of formulas (5) to (7). Thus, when preparing a photosensitive resin composition comprising the aforementioned polysiloxane, reflow during heating in pattern processing can be more effectively suppressed, resulting in highly detailed patterns.

[0042] [Chemical Formula 9] In equations (5) to (7), R 7 The group represented by any of formulas (8) to (10). R 8 R represents a monovalent hydrocarbon group with 1 to 4 carbon atoms. 9 It represents a monovalent hydrocarbon group with 1 to 6 carbon atoms. This indicates the bonding site where the oxygen atom is bonded. This indicates the bonding site that is bonded to a hydrogen or silicon atom.

[0043] By making R 7The group is any one of the formulas (8) to (10), more preferably the group shown in formula (8), so that when making a photosensitive resin composition, the reflow during heating during pattern processing can be more effectively suppressed, and a high-precision pattern can be obtained.

[0044] As R 8 Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxyethyl, etc.

[0045] As R 9 Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and phenyl.

[0046] [Chemical Formula 10] In equations (8) to (10), This represents the bonding site where the silicon atom bonds. n represents an integer from 0 to 8, and m represents an integer from 1 to 8. R 10 A group representing a hydrogen atom, or a group consisting of 1 to 4 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms.

[0047] As R 10 Examples include hydrogen atoms, methyl, ethyl, propyl, butyl, methoxymethyl, ethoxymethyl, propoxymethyl, ethyleneoxymethyl, allyloxymethyl, etc.

[0048] The aforementioned polysiloxane may contain only one or more of the structures shown in any of the aforementioned formulas (5) to (7).

[0049] The total content of the structures shown in any of the aforementioned formulas (5) to (7), relative to 100 mol% of the total silicon atoms in the aforementioned polysiloxane, is preferably 20 mol% or more and 50 mol% or less. The total content of the structures shown in any of the aforementioned formulas (5) to (7) refers to the total content of the structures shown in formula (5), formula (6), and formula (7), and is not counted repeatedly if multiple of the aforementioned structures are involved. By making this content 20 mol% or more, reflow during heating in pattern processing can be more effectively suppressed when preparing the photosensitive resin composition, resulting in highly detailed patterns. In addition, by making this content 50 mol% or less, flexibility can be more effectively improved.

[0050] In order to make the aforementioned polysiloxane contain the structure shown by any of the aforementioned formulas (5) to (7), the aforementioned polysiloxane may be manufactured, for example, by using at least the following alkoxysilane compounds.

[0051] Specific examples of alkoxysilane compounds in which the aforementioned polysiloxanes contain the structures shown in any of formulas (5) to (7) include styrenetrimethoxysilane, styrenetriethoxysilane, styrenetri(methoxyethoxy)silane, styrenetri(propoxy)silane, styrenetri(butoxy)silane, styrenemethyldimethoxysilane, styreneethyldimethoxysilane, styrenemethyldiethoxysilane, styrenemethyldi(methoxyethoxy)silane, vinyltrimethoxysilane, etc. Vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldi-1-propoxysilane, vinylethyldimethoxysilane, vinylmethyldiethoxysilane, vinylethyldi-n-propoxysilane, vinylethyldi-1-propoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, ethylene 1-Acrylphenyl-1-propoxysilane, vinylphenyl-1-propoxysilane, 7-octenyltrimethoxysilane, 5-hexenyltrimethoxysilane, 7-octenyltriethoxysilane, 5-hexenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane, 7-Acryloyloxyoctyltrimethoxysilane, 5-Acryloyloxyhexyltrimethoxysilane, 7-Acryloyloxyoctyltriethoxysilane, 5-Acryloyloxyhexyltriethoxysilane, 7-Methacryloxyoctyltrimethoxysilane, 5-Methacryloxyhexyltrimethoxysilane, 7-Methacryloxyoctyltriethoxysilane, 5-Methacryloxyhexyltriethoxysilane, etc. Styrenetrimethoxysilane, Styrenetriethoxysilane, Styrenetri(methoxyethoxy)silane, Styrenetri(propoxy)silane, Styrenetri(butoxy)silane, Styrenemethyldimethoxysilane, Styreneethyldimethoxysilane, Styrenemethyldiethoxysilane, Styrenemethyldi(methoxyethoxy)silane, etc.

[0052] These alkoxysilane compounds can be used alone or in combination of two or more.

[0053] The total number of moles X of the structure represented by any of formulas (5) to (7) in the aforementioned polysiloxane and the total number of moles Y of the structure represented by any of formulas (1) to (3) preferably satisfy the following relationship.

[0054] 0.4 ≤ (X / Y) ≤ 4.0 By setting the X / Y ratio to 0.4 or higher, more preferably 1.0 or higher, reflow during heating in pattern processing can be more effectively suppressed when manufacturing the photosensitive resin composition, resulting in highly detailed patterns. Furthermore, by setting the X / Y ratio to 4.0 or lower, more preferably 2.0 or lower, flexibility can be improved more effectively.

[0055] The structural ratio of functional groups in polysiloxanes can be calculated based on the amount of alkoxysilane compounds in the raw materials, or it can be determined specifically for polysiloxanes. 29 The proportion of silicon atoms in various alkoxysilane compounds is calculated by Si-NMR determination relative to the total silicon atom content.

[0056] The aforementioned polysiloxane may further comprise structures derived from alkoxysilane compounds, other than those shown in any of formulas (1) to (3) and any of formulas (5) to (7). Examples of such alkoxysilane compounds include: Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, di Phenyl diethoxysilane, methyl phenyl dimethoxysilane, γ-epoxypropoxypropylmethyl dimethoxysilane, γ-aminopropylmethyl dimethoxysilane, γ-aminopropylmethyl diethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl dimethoxysilane, trifluoropropylmethyl dimethoxysilane, trifluoropropylmethyl diethoxysilane, trifluoropropylethyl dimethoxysilane, trifluoropropylethyl diethoxysilane, cyclohexylmethyl dimethoxysilane, octadecylmethyl dimethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, 3-trimethoxysilylpropyl cyclohexanedicarboxylic anhydride, etc.

[0057] In the manufacture of the aforementioned polysiloxanes, these alkoxysilane compounds can be used alone or in combination of two or more. From the viewpoint of improving flexibility, the weight-average molecular weight of the aforementioned polysiloxane is preferably 2000 or more, more preferably 10000 or more, and even more preferably 20000 or more. Furthermore, from the viewpoint of obtaining highly detailed patterns during pattern processing when preparing a photosensitive resin composition, a weight-average molecular weight of 100000 or less is preferred. Here, the weight-average molecular weight is the weight-average molecular weight converted from polystyrene, and the weight-average molecular weight of the polysiloxane can be easily determined using a GPC (gel permeation chromatography) apparatus. Specifically, for example, using a GPC (gel permeation chromatography) apparatus (Nihon Waters Co., Ltd. AllianceHPLC / GPCe695), the polysiloxane is diluted with tetrahydrofuran (hereinafter referred to as THF) as the developing solvent to a concentration of 0.1% by mass, and the weight-average molecular weight (Mw) converted from polystyrene is determined. It should be noted that, for example, by connecting Tosoh TSKgel (registered trademark) G4000HXL / G1000HXL in series and using a photodiode array (PDA) as a detector, measurements can be performed under conditions of 30°C, flow rate of 1.0 mL / min, detection wavelength of 254 nm, and injection volume of 100 μL.

[0058] <The aforementioned method for manufacturing polysiloxanes> The method for manufacturing the aforementioned polysiloxane will be described.

[0059] The aforementioned polysiloxane can be obtained by hydrolyzing or condensing alkoxysilane compounds used as raw materials.

[0060] The hydrolysis reaction involves adding an acid catalyst and water to the aforementioned alkoxysilane compound in a solvent to generate a silanol group. Preferably, after adding the acid catalyst and water to the aforementioned alkoxysilane compound for 1 to 180 minutes, the reaction is carried out at 10 to 130°C for 1 to 180 minutes. Conducting the hydrolysis reaction under these conditions helps to suppress vigorous reactions. A more preferred reaction temperature for the hydrolysis reaction is 40 to 110°C.

[0061] In addition, after the hydrolysis reaction, a condensation reaction is carried out to obtain the aforementioned polysiloxane. For the condensation reaction, it is preferable to heat the reaction solution at 50°C or above, below the boiling point of the solvent, for 1 to 100 hours.

[0062] Regarding the various conditions in hydrolysis and condensation reactions, considering the reaction scale, the size and shape of the reaction vessel, etc., by setting the acid concentration, reaction temperature, reaction time, etc., it is possible to obtain physical properties suitable for the target application.

[0063] Examples of acid catalysts used in hydrolysis reactions include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Formic acid, acetic acid, or phosphoric acid are particularly preferred as acid catalysts for hydrolysis reactions.

[0064] The preferred content of the acid catalyst used in the hydrolysis reaction is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the total polysiloxane compound before the hydrolysis reaction. Furthermore, the preferred content of the acid catalyst used in the hydrolysis reaction is 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the total polysiloxane compound before the hydrolysis reaction. Here, "total polysiloxane compound" refers to compounds containing silicon atoms, specifically the total amount of polysiloxane including alkoxysilane compounds used as raw materials for polysiloxanes, their hydrolysates, and their condensates. The definition remains the same below. By setting the amount of acid catalyst to 0.05 parts by mass or more, hydrolysis proceeds smoothly; furthermore, by setting it to 10 parts by mass or less, the hydrolysis reaction is easily controlled.

[0065] There are no particular limitations on the solvent used in the hydrolysis-condensation reaction; any appropriate solvent can be selected. Not only one solvent can be used, but two or more can also be used. Specific examples of solvents include the following substances: For example, alcohols such as 3-methyl-3-methoxy-1-butanol and diacetone alcohol; diols such as propylene glycol; ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and propylene glycol monotert-butyl ether; ketones such as methyl ethyl ketone and cyclopentanone; amides such as dimethylacetamide; acetates such as ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; and others such as γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.

[0066] Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monotert-butyl ether, and γ-butyrolactone can be preferred.

[0067] Furthermore, preferably, after the hydrolysis and condensation reaction is completed, a solvent is added to adjust the concentration or viscosity to a suitable level for the photosensitive resin composition. Alternatively, after hydrolysis, all or part of the generated vaporizable hydrolysis products, such as alcohols, can be distilled off by heating and / or under reduced pressure, followed by the addition of a suitable solvent.

[0068] The amount of solvent used in the hydrolysis reaction is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and preferably 500 parts by mass or less, more preferably 200 parts by mass or less, relative to 100 parts by mass of the total polysiloxane compound. By setting the amount of solvent to 50 parts by mass or more, gel formation can be suppressed. In addition, by setting it to 500 parts by mass or less, the hydrolysis reaction proceeds rapidly.

[0069] Furthermore, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be chosen arbitrarily, but it is preferably used in the range of 1.0 to 4.0 moles relative to 1 mole of the alkoxysilane compound.

[0070] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention contains the aforementioned polysiloxane and a photoacid generator. By containing the aforementioned polysiloxane, high-precision photolithography processing is possible, and a highly flexible cured product can be obtained.

[0071] Regarding the aforementioned polysiloxane contained in the aforementioned photosensitive resin composition, as described above.

[0072] From the viewpoint of easily adjusting the film thickness during processing, the content of the aforementioned polysiloxane in the aforementioned photosensitive resin composition is preferably 10 parts by mass or more relative to 100 parts by mass of the total components of the aforementioned photosensitive resin composition. Furthermore, from the same viewpoint, it is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.

[0073] <Photo-acid generator> The photosensitive resin composition of the present invention contains a photoacid-generating agent. By appropriately selecting the photoacid-generating agent, the aforementioned photosensitive resin composition can be formulated into a chemically amplified negative photosensitive resin composition or a positive photosensitive resin composition.

[0074] Examples of photoacid generators used in the aforementioned negative photosensitive resin compositions include onium salts. Examples include iodonium salts, sulfonium salts, diazonium salts, ammonium salts, and pyridinium salts.

[0075] Examples of photoacid generators used in the aforementioned positive-type photosensitive resin composition include halogen-containing compounds, diazonium ketone compounds, and sulfone compounds. For example, examples of halogen-containing compounds include alkyl-halogenated hydrocarbon compounds and heterocyclic compounds containing alkyl haloside (such as halomethyltriazine derivatives); examples of diazonium ketone compounds include 1,3-diketone-2-diazo compounds, diazobenzoquinone compounds, and naphthoquinone diazide compounds (hereinafter sometimes also referred to as naphthoquinone diazide); examples of sulfone compounds include β-ketosulfonates and β-sulfonylsulfonates; and examples of sulfonic acid compounds include alkyl sulfonates, haloalkyl sulfonates, aryl sulfonates, and imino sulfonates. From the viewpoint of obtaining highly detailed patterns, the aforementioned photoacid generator preferably includes the aforementioned naphthoquinone diazide. These aforementioned photoacid generators may be contained individually or in two or more forms in the aforementioned photosensitive resin composition.

[0076] The aforementioned naphthoquinone diazide will be described in detail. Preferably, the aforementioned naphthoquinone diazide contains a substance obtained by esterifying a phenolic compound with naphthoquinone diazide sulfonic acid. In this invention, the naphthoquinone diazide preferably used is a compound obtained by esterifying the phenolic hydroxyl group of the compound shown in formula (12) with naphthoquinone diazide-4-sulfonic acid and / or naphthoquinone diazide-5-sulfonic acid.

[0077] [Chemical Formula 11] In equation (12), R 11 This refers to a monovalent organic group containing 1 to 3 hydrogen or carbon atoms. As mentioned above, R... 11 Examples include methyl, ethyl, and propyl. R 12 ~R 14 Each of these groups independently represents a monovalent organic group with 1 to 20 hydrogen or carbon atoms. As mentioned above, R... 12 ~R 14 Examples include methyl, ethyl, propyl, hydroxyphenylmethylene, hydroxymethylphenylmethylene, and hydroxyphenylpropylidene. Among these, R... 12 ~R 14 In the case of a monovalent organic group having 1 to 20 carbon atoms, (5-a) R 12 (5-b) R 13 and (5-c) R 14 At least one of them is a monovalent organic group containing a phenolic hydroxyl group and having 6 to 20 carbon atoms. Examples of monovalent organic groups containing a phenolic hydroxyl group and having 6 to 20 carbon atoms include hydroxyphenylmethylene, hydroxymethylphenylmethylene, and hydroxyphenylpropylidene. Here, a and b each independently represent integers from 1 to 4, and c represents an integer from 0 to 4.

[0078] Examples of phenolic compounds represented by formula (12) include the compounds shown below. Phenolic compounds represented by formula (12) can also be used in combination of two or more of them.

[0079] [Chemical Formula 12] The compound obtained by esterifying the phenolic hydroxyl group of the compound shown in formula (12) with naphthoquinone diazido-5-sulfonic acid and / or naphthoquinone diazido-4-sulfonic acid can be obtained by subjecting part or all of the phenolic hydroxyl group of the compound shown in formula (12) to, for example, 1,2-naphthoquinone diazido-5- (and / or -4-)sulfonyl chloride in the presence of a basic catalyst via a conventional esterification reaction. That is, a specified amount of the compound shown in formula (12) and the aforementioned 1,2-naphthoquinone diazido-5- (and / or -4-)sulfonyl chloride, dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone, or other solvents are added to a flask, and a basic catalyst such as sodium hydroxide, sodium bicarbonate, or triethylamine is added dropwise and condensation is carried out. The temperature of the condensation reaction is generally -20 to 60°C, preferably 0 to 40°C. The obtained product is preferably purified and dried after washing with water.

[0080] The above esterification reactions can yield mixtures with different esterification rates and esterification positions. The esterification rate referred to in this invention is defined as the average value of the mixture. It should be noted that the esterification rate of the phenolic compound can be calculated based on the peak area ratio obtained by high-performance liquid chromatography (HPLC). The esterification rate can be adjusted by the mixing ratio of the phenolic compound as a raw material with 1,2-naphthoquinone diazido-5- (and / or -4-)sulfonyl chloride. That is, the added 1,2-naphthoquinone diazido-5- (and / or -4-)sulfonyl chloride substantially all undergoes the esterification reaction; therefore, to obtain a mixture with the desired esterification rate, the molar ratio of the raw materials can be adjusted.

[0081] From the viewpoint of pattern formation with practical sensitivity, the content of the aforementioned photoacid-generating agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the aforementioned polysiloxane. From the viewpoint of obtaining a highly detailed pattern, it is preferably 50 parts by mass or less, more preferably 15 parts by mass or less.

[0082] <Other Ingredients> [solvent] To improve operability during coating, the photosensitive resin composition of the present invention may also include a solvent as another component. Examples of such solvents include the following substances.

[0083] For example, the photosensitive resin composition may contain ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monotert-butyl ether, and ethylene glycol dimethyl ether; acetate compounds such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; and lactic acid. The photosensitive resin composition may contain lactate esters such as methyl lactate, ethyl lactate, and butyl lactate; ketone compounds such as acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, and isopropylidene acetone; alcohol compounds such as methanol, ethanol, propanol, butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; aromatic hydrocarbon compounds such as toluene and xylene; γ-butyrolactone; and N-methylpyrrolidone. These compounds may be present individually or in combination with two or more of them.

[0084] The preferred solvents contained in the photosensitive resin composition are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monotert-butyl ether, diacetone alcohol, and γ-butyrolactone. The photosensitive resin composition may contain only one of these solvents or two or more of them.

[0085] Relative to the aforementioned 100 parts by weight of polysiloxane, the content of all solvents in the photosensitive resin composition of the present invention is preferably 100 parts by weight or more and 9900 parts by weight or less, more preferably 100 parts by weight or more and 5000 parts by weight or less.

[0086] [Photoradical polymerization initiator] The photosensitive resin composition of the present invention may also contain a photoradical polymerization initiator. The aforementioned photoradical polymerization initiator can be any substance, as long as it decomposes and / or reacts to generate free radicals upon irradiation by light (including ultraviolet light and electron beams). Examples include α-aminoalkylphenyl ketone compounds, acylphosphine oxide compounds, oxime ester compounds, α-hydroxy ketone compounds, acetophenone compounds, etc. The aforementioned photosensitive resin composition may also contain two or more of these.

[0087] From the viewpoint of effectively carrying out free radical curing, the content of the aforementioned photoradical polymerization initiator in the photosensitive resin composition of the present invention is preferably 1 part by mass or more relative to 100 parts by mass of the aforementioned polysiloxane. On the other hand, from the viewpoint of suppressing the dissolution of residual photoradical polymerization initiator, the content of the aforementioned photoradical polymerization initiator is preferably 10 parts by mass or less relative to 100 parts by mass of the aforementioned polysiloxane.

[0088] [Photopolymerizable compounds] The photosensitive resin composition of the present invention may also contain photopolymerizable compounds. The photopolymerizable compound in the present invention refers to a compound with a molecular weight of 1,000 or less having one or more vinyl unsaturated double bonds in its molecule. Considering the ease of free radical polymerization, the aforementioned photopolymerizable compound preferably has a (meth)acryloyl group. Examples of the aforementioned photopolymerizable compounds include pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. The aforementioned photosensitive resin composition may also contain two or more of the aforementioned photopolymerizable compounds.

[0089] From the viewpoint of effectively performing free radical curing, the content of the aforementioned photopolymerizable compound in the photosensitive resin composition of the present invention is preferably 1 part by mass or more relative to 100 parts by mass of the aforementioned polysiloxane. On the other hand, from the viewpoint of suppressing excessive free radical reaction and improving resolution, the content of the aforementioned photopolymerizable compound is preferably 50 parts by mass or less relative to 100 parts by mass of the aforementioned polysiloxane.

[0090] [surfactant] To improve flowability and film thickness uniformity during coating, the photosensitive resin composition of the present invention may also contain a surfactant. There are no particular limitations on the type of surfactant; for example, fluorinated surfactants, silicone surfactants, polyalkylene oxide surfactants, and poly(meth)acrylate surfactants may be used. However, from the viewpoint of flowability and film thickness uniformity, the aforementioned photosensitive resin composition preferably contains the aforementioned silicone surfactant. The photosensitive resin composition may contain one or more of the aforementioned surfactants.

[0091] Commercially available products that are organosilicon surfactants include, for example, “SH28PA”, “SH7PA”, “SH21PA”, “SH30PA”, “ST94PA” (all manufactured by Dow Corning Toray Silicone Co., Ltd.), “BYK-333”, “BYK-352” (manufactured by BYK-Chemie Japan Co., Ltd.), “KL-700”, “LE-302”, “LE-303”, and “LE-304” (Kyoeisha Chemical Co., Ltd.).

[0092] Other examples of the aforementioned surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene distearate.

[0093] The content of the aforementioned surfactant is typically between 0.001 and 1 part by mass relative to 100 parts by mass of the total components of the aforementioned photosensitive resin composition.

[0094] [Other Additives] Furthermore, the photosensitive resin composition of the present invention may contain known viscosity modifiers, thermal crosslinking agents, stabilizers, colorants, photosensitizers, ultraviolet absorbers, adhesion modifiers, etc., as needed.

[0095] <Cured product> The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. As a curing method, heat curing is preferred. By heat curing the aforementioned photosensitive resin composition, components with low heat resistance can be removed, thereby further improving heat resistance and chemical resistance. Alternatively, the aforementioned cured product can also be prepared by patterning the aforementioned photosensitive resin composition using known methods such as photolithography followed by heat curing.

[0096] Regarding the temperature for heating and curing the aforementioned photosensitive resin composition, from the viewpoint of improving heat resistance and chemical resistance, 150°C or higher is preferred, and 200°C or higher is more preferred. On the other hand, from the viewpoint of improving the toughness of the cured product, 350°C or lower is preferred, and 250°C or lower is more preferred. Within this temperature range, the temperature can be increased in stages or continuously.

[0097] Regarding the time for heating and curing the aforementioned photosensitive resin composition, from the viewpoint of further reducing gas escape, 30 minutes or more is preferred. Furthermore, from the viewpoint of improving the toughness of the cured product, 3 hours or less is preferred.

[0098] Examples of combinations of temperature and time for heating and curing the aforementioned photosensitive resin composition include heat treatment at 150°C and 250°C for 30 minutes each, and heat treatment by linearly increasing the temperature from room temperature to 300°C for 2 hours. From the viewpoint of reducing process time, linearly increasing the temperature to the set temperature is preferred.

[0099] The cured product of the present invention is suitable for use as, for example, a surface protective layer for semiconductor devices, an interlayer insulating layer, an insulating layer for organic EL display devices and micro-LED display devices, a planarization layer for TFT substrates used in driving organic EL display devices and micro-LED display devices, a wiring protective insulating layer for circuit boards, an on-chip microlens for solid-state imaging elements, and a planarization layer for various displays and solid-state imaging elements. For example, it is suitable as a surface protective layer and interlayer insulating layer for MRAM with low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM), phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), etc., which are expected to become next-generation memory. In addition, it can also be used as an insulating layer for display devices, such as LCD, ECD, ELD, organic EL display devices, etc., which include a first electrode formed on a substrate and a second electrode disposed opposite to the aforementioned first electrode. Hereinafter, organic EL display devices and semiconductor devices will be described as examples.

[0100] Organic EL Display Device The organic EL display device of the present invention includes the cured material of the present invention.

[0101] As a specific example of the aforementioned organic EL display device, it is preferable that the cured material of the present invention is provided in the planarization layer and / or insulating layer of the organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on the substrate. Organic EL light-emitting materials are prone to deterioration due to moisture, which can sometimes lead to adverse effects such as a decrease in the area ratio of the light-emitting portion relative to the area of ​​the light-emitting pixel. However, the cured material of the present invention has a low water absorption rate, thus achieving stable driving and light-emitting characteristics. Taking an active matrix type display device as an example, a TFT and wiring located on the side of the TFT and connected to the TFT are provided on a substrate such as glass or various plastics. A planarization layer is provided on the substrate in a manner that covers unevenness, and a display element is further disposed on the planarization layer. The display element and the wiring are connected through contact holes formed in the planarization layer.

[0102] When the cured material of the present invention is used as the aforementioned planarization layer, the thickness is preferably 1.0 μm or more and 5.0 μm or less, more preferably 2.0 μm or more. By keeping the planarization layer within the aforementioned range, the flatness of the densely packed TFTs and wiring due to high precision can be improved. If the planarization layer is thick, the escape gas increases, which is a cause of reduced light emission reliability of the organic EL display device. However, the cured material of the present invention has low escape gas, thus achieving high light emission reliability. In addition, for high precision, TFTs and wiring can be arranged in the film thickness direction, therefore, the aforementioned planarization layer is preferably multilayered.

[0103] Figure 1 A cross-sectional view of an example TFT substrate is shown. On substrate 6, bottom-gate or top-gate TFTs (thin-film transistors) 1 are arranged in rows and columns, and a TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2, which connects to the TFTs 1, is also provided on the TFT insulating layer 3. Furthermore, a planarization layer 4 is provided on the TFT insulating layer 3 to embed the wiring 2. Contact holes 7, reaching the wiring 2, are provided in the planarization layer 4. Then, ITO (transparent electrode) 5 is formed on the planarization layer 4 through the contact holes 7, connecting to the wiring 2. Here, ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is then formed to cover the periphery of the ITO 5. The organic EL element can be a top-emitting type that emits light from the side opposite to substrate 6, or a bottom-emitting type that extracts light from the side of substrate 6. As described above, an active matrix type organic EL display device can be obtained, in which TFTs 1 for driving each organic EL element are connected to it.

[0104] The aforementioned TFT insulating layer 3, planarization layer 4, and / or insulating layer 8 can be formed as described above through the following steps: a step of forming a photosensitive resin film from the photosensitive resin composition of the present invention; a step of exposing the aforementioned photosensitive resin film; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film. By means of this manufacturing method having these steps, an organic EL display device having the cured product of the present invention can be obtained.

[0105] Semiconductor Devices The semiconductor device of the present invention includes the cured material of the present invention.

[0106] As a specific example of the aforementioned semiconductor device, it is preferable that the cured material of the present invention is present in the interlayer insulating layer and / or surface protective layer of the semiconductor device having electrodes, metal wiring, interlayer insulating layer and / or surface protective layer on the substrate.

[0107] Figure 2 The diagram shows an enlarged cross-sectional view of an example of a pad portion of a semiconductor device with bumps. A passivation layer 11, comprising Al pads 10 for input / output and vias, is formed on a silicon wafer 9. An insulating layer 12 is formed on the passivation layer 11, and a metal layer 13, formed from Cr, Ti, etc., is formed to connect with the Al pads 10. Metal wiring 14, formed from Al, Cu, etc., is formed by electroplating or the like. Insulation between the pads is achieved by etching the metal layer 13 surrounding the solder bumps 18. A barrier metal 16 and solder bumps 18 are formed on the insulated pads. During the processing of the insulating film 15, dicing grooves 17 are formed.

[0108] Next, the method for manufacturing the aforementioned semiconductor device will be described using the accompanying drawings. Figure 3 An example of a method for manufacturing the aforementioned semiconductor device with bumps is shown. In step 3a, the photosensitive resin composition of the present invention is coated onto a silicon wafer 9 on which Al pads 10 and passivation layer 11 are formed, and the aforementioned cured material, i.e., the insulating layer 12, is formed by a photolithography process. Next, in step 3b, a metal layer 13 is formed by sputtering. In step 3c, metal wiring 14 is deposited on the metal layer 13 by a plating process. Next, in step 3d', the photosensitive resin composition of the present invention is coated, and in step 3d, the pattern of the aforementioned cured material, i.e., the insulating layer 15, is formed by a photolithography process. At this time, the photosensitive resin composition constituting the insulating layer 15 is subjected to thick film processing at the dicing groove 17. Wiring (so-called rewiring) can be further formed on the insulating layer 15. In the case of forming a multilayer wiring structure with two or more layers, by repeating the above steps, a multilayer wiring structure in which two or more rewiring layers are separated from the interlayer insulating layer formed by the cured material of the present invention can be formed. There is no upper limit to the number of layers in a multilayer wiring structure, but multilayer wiring with fewer than 10 layers is commonly used. Next, in process 3e, a barrier metal 16 is formed, and in process 3f, solder bumps 18 are formed. Then, the semiconductor device with bumps is obtained by dicing along the final dicing groove 17 to cut the semiconductor into individual chips.

[0109] Example The present invention will be further illustrated by the following embodiments, but the present invention is not limited to the embodiments disclosed herein.

[0110] [Abbreviations and corresponding compound names] PSX: Polysiloxane (Alkoxysilane compounds) MeTMS: Methyltrimethoxysilane PhTMS: Phenylacetyltrimethoxysilane StTMS: Styrene-trimethoxysilane VnTMS: Vinyltrimethoxysilane AcTMS: 3-Acryloyloxypropyltrimethoxysilane MAcTMS: 3-Methacryloyloxypropyltrimethoxysilane ISOTMS: 1-(3-(trimethoxysilyl)propyl)3,5-bis-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione ISODMS: 1-(3-(ethyldimethoxysilyl)propyl)3,5-di-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione IAtrisTMS: Tris(3-(trimethoxysilyl)propyl)isocyanurate.

[0111] (solvent) PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether.

[0112] [Determination Method] (1) Concentration of solid components The concentration of the solid component in a polysiloxane solution is determined using the following method: Weigh 1.5g of the polysiloxane solution into an aluminum cup, and heat it at 250°C for 30 minutes using a heating plate to evaporate the liquid component. Weigh the remaining solid component in the aluminum cup after heating, and determine the concentration of the solid component in the polysiloxane solution.

[0113] (2) Determination of weight-average molecular weight For the weight-average molecular weight, a gel permeation chromatography (GPC) apparatus (Nihon Waters Corporation Alliance HPLC / GPCe695) was used. The obtained polysiloxane solution was diluted with tetrahydrofuran (THF) as the developing solvent to a concentration of 0.1% by weight, and the weight-average molecular weight (Mw) of polystyrene was determined. Columns (Tosoh TSKgel (registered trademark) G4000HXL / G1000HXL) were connected in series, and a photodiode array (PDA) was used as the detector. The determination was performed at a temperature of 30°C, a flow rate of 1.0 mL / min, a detection wavelength of 254 nm, and an injection volume of 100 μL.

[0114] (3) Ratio of functional groups conduct 29 In Si-NMR determination, the proportion of silicon atoms in various alkoxysilane compounds relative to the total silicon atom count is calculated, and the corresponding silicon atom ratio is determined. The sample (liquid) is injected into a 10 mm diameter Teflon (registered trademark) NMR sample tube for determination. 29 The determination conditions for Si-NMR are shown below.

[0115] Device: JNM GX-270 manufactured by Nippon Electronics Co., Ltd. Measurement method: Gated decoupling method Nuclear frequency measured: 53.6693MHz 29 Si core) Spectral width: 20000Hz Pulse width: 12μsec (45° pulse) Pulse repetition time: 30.0 sec Solvent: Acetone-d6 Reference material: Tetramethylsilane Measurement temperature: room temperature Sample rotation speed: 0.0 Hz.

[0116] (4) Resolution When the photosensitive resin composition is negative, at an exposure dose of 300 mJ / cm 2 For the exposed areas, a coating is applied to achieve a cured film thickness of 2 μm, and the area is heated at 100°C for 3 minutes using a heating plate. If the photosensitive resin composition is positive, a coating is applied to the unexposed areas to achieve a cured film thickness of 2 μm, and the area is heated at 100°C for 3 minutes using a heating plate.

[0117] Then, using a Mask aligner (Union Optical Co., Ltd. PEM-6M) with a high-pressure mercury lamp as the light source, the exposure dose was increased from 10 mJ / cm². 2 Up to 300mJ / cm 2 Up to 10 mJ / cm 2 The changes were made and the substrate was exposed. It should be noted that during exposure, a photomask with square patterns of 15μm, 20μm, 25μm, 30μm, 40μm, and 50μm side lengths was used. For the exposed substrate, an automatic developing apparatus (manufactured by Takizawa Sangyo Co., Ltd.) was used with a 2.38% by weight aqueous solution of TMAH as the developing solution for 90 seconds. The developed substrate was then rinsed with pure water for 30 seconds and directly immersed in a hot air oven heated to 230°C (Inert Oven DN43HI, manufactured by Yamato Scientific Co., Ltd.) in the presence of air for 60 minutes to obtain a cured material approximately 2μm thick. For the cured material, the square patterns under all exposures were observed, and the smallest pattern size (the side size of the square) of the smallest pattern among the blank patterns that was not damaged by reflow during heating and was fully processed was taken as the resolution x. The evaluation criteria are as follows.

[0118] A: x < 20μm B: 20μm≤x<40μm C: 40μm≤x≤50μm D: 50μm <x。

[0119] (5) Bending test On a 20 μm thick Kapton film, a photosensitive resin composition was coated to obtain a 2 μm thick cured product, following the same method as the aforementioned resolution evaluation, and then heated using a hot plate. Then, in the negative case, an exposure of 300 mJ / cm² was applied without the use of a photomask. 2The entire surface of the coated film was exposed. In the positive case, no exposure was performed, followed by development and heating in a hot air oven to obtain a 2μm thick cured material. The cured material was cut into strips of 1cm × 2cm. These strips were used as test pieces, and the bending radius was varied to 0.50mm, 0.75mm, 1.00mm, and 1.50mm with the coated surface facing outwards. Each strip was bent and left to stand for approximately 1 minute. After bending, the film was observed under a microscope at 10x magnification to confirm the presence of cracks or fissures. The minimum bending radius without cracks or fissures was recorded.

[0120] The evaluation criteria for bending tests are specified as follows.

[0121] S: No cracks or splits occurred even when bent with a bending radius of 0.50mm.

[0122] A: Cracks and fissures appeared at a bending radius of 0.50 mm. No cracks or fissures appeared at a bending radius of 0.75 mm.

[0123] B: Cracks or fissures occurred at a bending radius of 0.75 mm. No cracks or fissures occurred at a bending radius of 1.00 mm.

[0124] C: Cracks or fissures occurred at a bending radius of 1.00 mm. No cracks or fissures occurred at a bending radius of 1.50 mm.

[0125] D: Cracks or fissures occur when the bending radius is 1.50 mm.

[0126] [Synthetic Example 1] Synthesis of PGMEA solution P-1 of polysiloxane Add 21.79 g (0.16 mol) MeTMS, 26.92 g (0.12 mol) StTMS, 44.58 g (0.12 mol) ISOTMS, and 80.28 g PGMEA to a 500 mL three-necked flask. While stirring at 25 °C, add a mixture of 21.60 g of deionized water and 0.10 g of phosphoric acid over 30 minutes. Then, while introducing air at a flow rate of 0.2 L / min, immerse the flask in a 70 °C oil bath and stir for 1 hour. After 30 minutes, raise the oil bath temperature to 120 °C. After 1 hour of heating, when the internal temperature of the solution reaches 100 °C, continue heating and stirring for 3 hours. Maintain the internal temperature of the flask at 100–110 °C. Distill off and remove methanol and water, which are byproducts of the reaction. The remaining polysiloxane PGMEA solution in the flask is designated as polysiloxane PGMEA solution P-1. Its solid content is 45.6% by mass. The weight-average molecular weight (Mw) of polystyrene is 75,000. 29The molar ratio of polysiloxane of formula (1) in P-1 determined by Si-NMR is 30 mol%, the molar ratio of styrene is 30 mol%, and the molar ratio of methyl is 40 mol%.

[0127] [Synthetic Examples 2-29] Synthesis of PGMEA Solutions of Polysiloxanes P-2-29 As shown in Tables 1 and 2, the input amounts of each raw material were changed. Otherwise, the same procedure as in Synthesis Example 1 was followed to synthesize PGMEA solutions P-2 to 29 of polysiloxane.

[0128] [Table 1] [Table 2] [Synthetic Example 30] Synthesis of photoacid generator B-1 15.32 g (0.05 mol) of 1,1,1-tris(4-hydroxyphenyl)ethane and 22.84 g (0.085 mol) of naphthoquinone diazido-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the system was kept at room temperature. 15.18 g of triethylamine, mixed with 50 g of 1,4-dioxane, was added dropwise while adjusting the dropping rate to prevent the system temperature from exceeding 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain photoacid generator B-1 as shown in the following formula.

[0129] [Chemical Formula 13] [Example 1] Photosensitive resin composition (J-1) To 21.05 g of the polysiloxane PGMEA solution P-1 synthesized in Synthesis Example 1, 0.10 g of photoacid generator B-1, 0.29 g of photoradical polymerization initiator (BASF Japan Co., Ltd. Irgacure (registered trademark) OXE-01), 13.53 g of PGMEA, 14.00 g of PGME, and 0.02 g of surfactant BYK-333 (trade name, BYK-Chemie Japan Co., Ltd.) were added to obtain photosensitive resin composition J-1. The obtained photosensitive resin composition has a resolution x of 25 μm and is rated B. The minimum bending radius R evaluated in the bending test is 0.50 mm and is rated S.

[0130] [Examples 2-28] Photosensitive resin compositions J-2-J-28 The PGMEA solution of polysiloxane, photoacid generator, solvent, surfactant, and their amounts were added as described in Tables 3 and 4 to obtain photosensitive resin compositions J-2 to J-28. The results of resolution evaluation and bending test evaluation for the obtained photosensitive resin compositions are shown in Tables 5 to 7.

[0131] [Comparative Example 1] Photosensitive resin composition J-29 To 19.86 g of the synthesized polysiloxane PGMEA solution P-28, 0.91 g of photoacid generator B-1, 14.17 g of PGMEA, 14.00 g of PGME, and 0.02 g of surfactant BYK-333 were added to obtain the photosensitive resin composition J-29. In the resolution evaluation of the obtained photosensitive resin composition, all sizes of patterns experienced reflow and pattern destruction after heating, resulting in a rating of D. In the bending test evaluation, cracking occurred at all levels, also resulting in a rating of D.

[0132] [Comparative Example 2] Photosensitive Resin Composition J-30 To 19.78 g of the synthesized polysiloxane PGMEA solution P-29, 0.91 g of photoacid generator B-1, 14.25 g of PGMEA, 14.00 g of PGME, and 0.02 g of surfactant BYK-333 were added to obtain the photosensitive resin composition J-30. In the resolution evaluation of the obtained photosensitive resin composition, patterns of all sizes experienced reflow and pattern destruction after heating, resulting in a rating of D. In the bending test evaluation, cracking occurred at all levels, also resulting in a rating of D.

[0133] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] Explanation of reference numerals in the attached figures 1: TFT (Thin Film Transistor) 2: Wiring 3: TFT insulating layer 4: Planarization layer 5: ITO (Transparent Electrode) 6: Substrate 7: Contact hole 8: Insulation layer 9: Silicon wafers 10: Al pads 11: Passivation layer 12: Insulation layer 13: Metallic (Cr, Ti, etc.) layer 14: Metallic wiring (Al, Cu, etc.) 15: Insulation layer 16: Barrier Metals 17: Grating groove 18: Solder bump

Claims

1. A polysiloxane comprising one or more of the structures shown in any of formulas (1) to (3), [Chemical Formula 1] In equations (1) to (3), R 1 Each group is independently represented by the group shown in formula (4); R 2 R represents a hydrocarbon group with 1 to 4 carbon atoms; 3 Represents a monovalent hydrocarbon group with 1 to 6 carbon atoms; This indicates the bonding site where the oxygen atom is bonded. Indicates the bonding site where a hydrogen or silicon atom bonds. [Chemical Formula 2] In equation (4), Indicates the bonding site where the silicon atom is bonded; R 4 R represents a divalent hydrocarbon group with 1 to 6 carbon atoms; 5 and R 6 Each of these groups independently represents a group consisting of 1 to 6 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms; among which, R 5 and R 6 At least one of them is a group containing an aliphatic carbon-carbon unsaturated bond.

2. The polysiloxane as described in claim 1, wherein, The total content of the structure shown by any of the formulas (1) to (3) is more than 5 mol% and less than 50 mol% relative to the total amount of silicon atoms in the polysiloxane of 100 mol%.

3. The polysiloxane as described in claim 1 or 2, wherein, The polysiloxane further comprises one or more of the structures shown in any of formulas (5) to (7). [Chemical Formula 3] In equations (5) to (7), R 7 Represents the group shown in any of formulas (8) to (10); R 8 R represents a monovalent hydrocarbon group with 1 to 4 carbon atoms; 9 Represents a monovalent hydrocarbon group with 1 to 6 carbon atoms; This indicates the bonding site where the oxygen atom is bonded. Indicates the bonding site where a hydrogen or silicon atom bonds. [Chemical Formula 4] In equations (8) to (10), Indicates the bonding site with silicon atoms; n represents an integer from 0 to 8, m represents an integer from 1 to 8; R 10 A group representing a hydrogen atom, or a group consisting of 1 to 4 carbon atoms formed solely of hydrogen, carbon, oxygen, and nitrogen atoms.

4. The polysiloxane according to claim 3, wherein, The total content of the structure shown by any one of the formulas (5) to (7) is more than 20 mol% and less than 50 mol% relative to the total amount of silicon atoms in the polysiloxane of 100 mol%.

5. The polysiloxane as described in claim 3, wherein, At least one R in the structure shown by any of equations (5) to (7) 7 The group is shown in formula (8).

6. The polysiloxane according to claim 3, wherein, The total number of moles X of the structures represented by any of formulas (5) to (7) in the polysiloxane and the total number of moles Y of the structures represented by any of formulas (1) to (3) satisfy the following relationship: 0.4≤(X / Y)≤4.

0.

7. A photosensitive resin composition comprising a photoacid generator and the polysiloxane as described in claim 1 or 2.

8. The photosensitive resin composition of claim 7, wherein, The photoacid-producing agent contains at least naphthoquinone diazide.

9. A cured product, which is formed by curing the photosensitive resin composition of claim 7.

10. A semiconductor device comprising the cured material of claim 9.

11. An organic EL display device comprising the cured material as described in claim 9.

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