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

Abstract

The present invention addresses the problem of providing a polysiloxane which enables the production of a photosensitive resin composition yielding a cured product that can be processed with high resolution and has high flexibility. The present invention is a polysiloxane that includes one or more structures selected from the group consisting of structures represented by formulae (1) to (3). In formulae (1) to (3), R1s each independently represent a group represented by formula (4); R2 represents a hydrocarbon group having 1-4 carbon atoms; R3 represents a monovalent hydrocarbon group having 1-6 carbon atoms; *1 represents a bonding point bonded to an oxygen atom; and *2 represents a bonding point bonded to a hydrogen atom or a silicon atom. In formula (4), *3 represents a bonding point bonded to a silicon atom; R4 represents a divalent hydrocarbon group having 1-6 carbon atoms; and R5 and R6 each independently represent a group having 1-6 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms and nitrogen atoms, wherein at least one of R5 and R6 represents a group containing an aliphatic carbon-carbon unsaturated bond.

Description

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

[0001] The present invention relates to a polysiloxane, a photosensitive resin composition, a cured product using the same, a semiconductor device, and an organic EL display device.

[0002] Polysiloxanes have excellent transparency in addition to heat resistance and electrical insulation. Therefore, they are used in surface protection layers and interlayer insulating layers of semiconductor devices, insulating layers of organic electroluminescence (EL) display devices, and planarization layers of thin film transistor (TFT) substrates for display devices. With the recent diversification of electronic device designs, display devices have become increasingly high-definition and flexible, and semiconductor devices have become smaller and more highly integrated. Therefore, technological developments are required for materials used in these insulating films, protective films, and the like to meet these needs. High-definition and flexible materials are particularly in demand.

[0003] For example, Patent Document 1 describes a polysiloxane containing a vinyl group or a styryl group in the side chain as a positive-type photosensitive resin composition, and Patent Document 2 describes a curable polysiloxane having an isocyanurate ring structure and an epoxy group in the side chain as a hard coating material.

[0004] International Publication No. 2020 / 196601 International Publication No. 2019 / 123731

[0005] However, when the materials described in Patent Documents 1 and 2 are processed, breakage occurs at the processed curved surface, and therefore the flexibility of the materials described in Patent Documents 1 and 2 is still insufficient.

[0006] Therefore, an object of the present invention is to provide a polysiloxane that can be used to produce a photosensitive resin composition that can be processed with high precision and that gives a highly flexible cured product; a photosensitive resin composition containing the polysiloxane; a cured product obtained from the photosensitive resin composition; and a semiconductor device and an organic EL display device that include the cured product.

[0007] In order to solve the above problems, the present invention and its preferred embodiments comprise the following: [1] A polysiloxane containing one or more structures represented by any one of formulas (1) to (3).

[0008]

[0009] In formulas (1) to (3), R １ R each independently represents a group represented by formula (4). ２ represents a hydrocarbon group having 1 to 4 carbon atoms. ３ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. １ is the point of attachment to the oxygen atom, * ２ represents a point of attachment to a hydrogen atom or a silicon atom.

[0010]

[0011] In formula (4), * ３ represents the point of attachment to the silicon atom. ４ represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ５ and R ６ each independently represents a group having 1 to 6 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms, and nitrogen atoms. ５ and R ６ at least one of which is a group containing an aliphatic carbon-carbon unsaturated bond. [2] The polysiloxane according to [1], wherein the total content of structures represented by any one of formulas (1) to (3) is 5 mol % or more and 50 mol % or less relative to 100 mol % of the total amount of silicon atoms in the polysiloxane. [3] The polysiloxane according to [1] or [2], wherein the polysiloxane further contains one or more structures represented by any one of formulas (5) to (7).

[0012]

[0013] In formulas (5) to (7), R ７ represents a group represented by any one of formulas (8) to (10). ８ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. ９ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. １is the bond point to the oxygen atom, and * ２ represents a bond point to a hydrogen atom or a silicon atom.

[0014]

[0015] In formulas (8) to (10), * ３ represents the point of attachment to the silicon atom, n represents an integer of 0 to 8, and m represents an integer of 1 to 8. R １０ represents a hydrogen atom or a group having 1 to 4 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms, and nitrogen atoms. [4] The polysiloxane according to [3], wherein the total content of the structures represented by any one of the formulas (5) to (7) is 20 mol % or more and 50 mol % or less relative to 100 mol % of the total amount of silicon atoms in the polysiloxane. [5] At least one R in the structure represented by any one of the formulas (5) to (7) ７ is a group represented by formula (8). [6] The polysiloxane according to any one of [3] to [5], wherein the total number of moles X of the structures represented by any one of formulas (5) to (7) and the total number of moles Y of the structures represented by any one of formulas (1) to (3) in the polysiloxane satisfy the following relationship: 0.4≦(X / Y)≦4.0. [7] A photosensitive resin composition comprising the polysiloxane according to any one of [1] to [6] and a photoacid generator. [8] The photosensitive resin composition according to [7], wherein the photoacid generator contains at least naphthoquinone diazide. [9] A cured product obtained by curing the photosensitive resin composition according to [7] or [8].

[10] A semiconductor device comprising the cured product according to [9].

[11] An organic EL display device comprising the cured product according to [9].

[0016] According to the present invention, it is possible to provide a polysiloxane that can be used to produce a photosensitive resin composition that can be processed with high precision and gives a highly flexible cured product.

[0017] It is a cross-sectional view of an example of a TFT substrate, an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having bumps, and a schematic diagram showing an example of a method for manufacturing a semiconductor device having bumps.

[0018] An embodiment of the present invention will now be described in detail.

[0019] <Polysiloxane> The polysiloxane of the present invention contains one or more structures represented by any one of formulas (1) to (3). When the polysiloxane contains a structure represented by any one of formulas (1) to (3), preferably a structure represented by formula (1) and / or a structure represented by formula (3), a photosensitive resin composition containing the polysiloxane can be formed, suppressing reflow during heating during pattern processing, thereby enabling the production of a high-resolution pattern. In addition, the flexibility of a cured product of the photosensitive resin composition containing the polysiloxane can be improved.

[0020]

[0021] In formulas (1) to (3), R １ R each independently represents a group represented by formula (4). ２ represents a hydrocarbon group having 1 to 4 carbon atoms. ３ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. １ is the point of attachment to the oxygen atom, * ２ represents a point of attachment to a hydrogen atom or a silicon atom.

[0022] R ２ Examples of the alkyl group include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, an isobutyl group, a tertiary butyl group, and a methoxyethyl group.

[0023] R ３ Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and a phenyl group.

[0024]

[0025] In formula (4), * ３ represents the point of attachment to the silicon atom. ４ represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ５ and R ６each independently represents a group having 1 to 6 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms, and nitrogen atoms. Here, the group having 1 to 6 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms, and nitrogen atoms is a group represented by the chemical formula C ｗ H ｘ N ｙ O ｚ where w is an integer of 1 to 6, and x, y, and z each independently represent any integer. ５ and R ６ At least one of the groups is a group containing an aliphatic carbon-carbon unsaturated bond.

[0026] R ４ Examples of R include a methylene group, an ethylene group, a propylene group, a butylene group, a pentene group, a hexylene group, a phenylene group, and a cyclohexylene group. ４ is preferably a propylene group.

[0027] R ５ and R ６ Examples of the group having 1 to 6 carbon atoms include groups that do not contain an aliphatic carbon-carbon unsaturated bond, such as an ethyl group, a propyl group, a glycidyl group, or a hydroxyethyl group. Examples of groups that contain an aliphatic carbon-carbon unsaturated bond include a vinyl group, an allyl group, an acryloyl group, an acryloyloxyethylene group, a methacryloyl group, or a methacryloyloxyethylene group, with an allyl group being preferred. ５ and R ６ and are preferably groups containing an aliphatic carbon-carbon unsaturated bond.

[0028] The polysiloxane may contain only one type of structure represented by any one of the formulas (1) to (3), or may contain two or more types.

[0029] The total content of the structures represented by any one of formulas (1) to (3) relative to 100 mol% of the total amount of silicon atoms in the polysiloxane is preferably 5 mol% to 50 mol%. The total content of the structures represented by any one of formulas (1) to (3) refers to the total content of the structure represented by formula (1), the structure represented by formula (2), and the structure represented by formula (3). When a structure corresponds to multiple of these structures, they are not counted together. By setting the content to 5 mol% or more, more preferably 15 mol% or more, flexibility can be more effectively improved. Furthermore, by setting the content to 50 mol% or less, more preferably 30 mol% or less, when used as a photosensitive resin composition, reflow upon heating during pattern processing can be more effectively suppressed, allowing for the production of high-resolution patterns.

[0030] In order to make the polysiloxane contain a structure represented by any one of the formulas (1) to (3), the polysiloxane may be produced using, for example, at least the following alkoxysilane compounds.

[0031]

[0032] These alkoxysilane compounds may be used alone or in combination of two or more. In particular, it is preferable to use the alkoxysilane compound represented by formula (11).

[0033]

[0034] In formula (11), Me represents a methyl group, and X represents an alkoxy group or an alkyl group having 1 to 4 carbon atoms. X is preferably any one of a methoxy group, an ethoxy group, a methyl group, and an ethyl group.

[0035] These alkoxysilane compounds can be obtained by reacting an isocyanurate having a carbon-carbon unsaturated bond with a trialkoxysilane or alkyldialkoxysilane using a platinum catalyst. Examples of the alkoxysilane compound 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. A commercially available alkoxysilane compound represented by formula (11) is X-12-1290 manufactured by Shin-Etsu Chemical Co., Ltd. Because of its ease of availability, it is preferable to use a commercially available alkoxysilane compound.

[0036] The polysiloxane preferably further contains one or more structures represented by any one of formulas (5) to (7). By doing so, when a photosensitive resin composition containing the polysiloxane is prepared, reflow upon heating during pattern processing can be more effectively suppressed, and a high-definition pattern can be obtained.

[0037]

[0038] In formulas (5) to (7), R ７ represents a group represented by any one of formulas (8) to (10). ８ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. ９ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. １ is the bond point to the oxygen atom, and * ２ represents a bond point to a hydrogen atom or a silicon atom.

[0039] R ７ is a group represented by any one of formulas (8) to (10), more preferably a group represented by formula (8), when the photosensitive resin composition is prepared, reflow upon heating during pattern processing can be more effectively suppressed, and a high-definition pattern can be obtained.

[0040] R ８Examples of the alkyl group include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, an isobutyl group, a tertiary butyl group, and a methoxyethyl group.

[0041] R ９ Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and a phenyl group.

[0042]

[0043] In formulas (8) to (10), * ３ represents the point of attachment to the silicon atom, n represents an integer of 0 to 8, and m represents an integer of 1 to 8. R １０ represents a hydrogen atom or a group having 1 to 4 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms and nitrogen atoms.

[0044] R １０ Examples of the aryl group include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methyloxymethyl group, an ethyloxymethyl group, a propyloxymethyl group, a vinyloxymethyl group, and an allyloxymethyl group.

[0045] The polysiloxane may contain only one type of structure represented by any one of the formulas (5) to (7), or may contain two or more types.

[0046] The total content of the structures represented by any one of formulas (5) to (7) relative to the total amount of silicon atoms in the polysiloxane (100 mol%) is preferably 20 mol% or more and 50 mol% or less. The total content of the structures represented by any one of formulas (5) to (7) refers to the total content of the structure represented by formula (5), the structure represented by formula (6), and the structure represented by formula (7). When multiple structures are present, they are not counted. By setting this content to 20 mol% or more, when a photosensitive resin composition is formed, reflow during heating during pattern processing can be more effectively suppressed, allowing for the production of high-resolution patterns. Furthermore, by setting this content to 50 mol% or less, flexibility can be more effectively improved.

[0047] In order to make the polysiloxane contain a structure represented by any one of the formulas (5) to (7), the polysiloxane may be produced using, for example, at least the following alkoxysilane compounds.

[0048] Specific examples of the alkoxysilane compound having a structure represented by any one of the formulas (5) to (7) in the polysiloxane include styryltrimethoxysilane, styryltriethoxysilane, styryltri(methoxyethoxy)silane, styryltri(propoxy)silane, styryltri(butoxy)silane, styrylmethyldimethoxysilane, styrylethyldimethoxysilane, styrylmethyldiethoxysilane, styrylmethyldi(methoxyethoxy)silane, vinyltrimethoxysilane, and vinyltriethoxysilane. Sisilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldi-1-propoxysilane, vinylethyldimethoxysilane, vinylmethyldiethoxysilane, vinylethyldi-n-propoxysilane, vinylethyldi-1-propoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, vinylphenyl-n-propoxysilane vinylphenyl-1-propoxysilane, 7-octenyltrimethoxysilane, 5-hexenyltrimethoxysilane, 7-octenyltriethoxysilane, 5-hexenyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 7-acryloxyoctyltrimethoxysilane, 5-acryloxyhexyltrimethoxysilane, 7-acryloxyoctyltriethoxysilane, 5-acryloxyhexyltriethoxysilane, 7-methacryloxyoctyltrimethoxysilane, 5-methacryloxyhexyltrimethoxysilane, 7-methacryloxyoctyltriethoxysilane, 5-methacryloxyhexyltriethoxysilane, and the like.Examples thereof include styryltrimethoxysilane, styryltriethoxysilane, styryltri(methoxyethoxy)silane, styryltri(propoxy)silane, styryltri(butoxy)silane, styrylmethyldimethoxysilane, styrylethyldimethoxysilane, styrylmethyldiethoxysilane, and styrylmethyldi(methoxyethoxy)silane.

[0049] These alkoxysilane compounds may be used alone or in combination of two or more.

[0050] The total number of moles X of the structures represented by any one of Formulas (5) to (7) and the total number of moles Y of the structures represented by any one of Formulas (1) to (3) in the polysiloxane preferably satisfy the following relationship: 0.4≦(X / Y)≦4.0 When X / Y is 0.4 or more, and more preferably 1.0 or more, a photosensitive resin composition can be obtained that more effectively suppresses reflow during heating during pattern processing, thereby enabling the production of a high-resolution pattern. Furthermore, when X / Y is 4.0 or less, and more preferably 2.0 or less, flexibility can be more effectively improved.

[0051] The structural ratio of functional groups in polysiloxane can be calculated from the blending amount of the raw material alkoxysilane compound, or ２９ It is also possible to carry out Si-NMR measurement and calculate the ratio of the integral value of silicon atoms of various alkoxysilane compounds to the integral value of all silicon atoms.

[0052] The polysiloxane may contain a structure derived from an alkoxysilane compound other than the structure represented by any one of formulas (1) to (3) and the structure represented by any one of formulas (5) to (7). Examples of the alkoxysilane compound include the following: 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-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, di Phenyldiethoxysilane, methylphenyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, and the like.

[0053] When producing the polysiloxane, these alkoxysilane compounds may be used alone or in combination of two or more.

[0054] The weight-average molecular weight of the polysiloxane is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more, from the viewpoint of improving flexibility. Furthermore, when used as a photosensitive resin composition, it is preferably 100,000 or less, from the viewpoint of obtaining a high-resolution pattern during pattern processing. Here, the weight-average molecular weight is the weight-average molecular weight in terms of polystyrene, and the weight-average molecular weight of the polysiloxane can be easily determined using a GPC (gel permeation chromatography) device. Specifically, for example, using a GPC (gel permeation chromatography) device (Alliance HPLC / GPCe695 manufactured by Nihon Waters K.K.), the polysiloxane is diluted with the developing solvent tetrahydrofuran (hereinafter referred to as THF) to adjust the concentration to 0.1% by mass, and the weight-average molecular weight (Mw) in terms of polystyrene is measured. The columns may be, for example, TSKgel (registered trademark) G4000HXL / G1000HXL manufactured by Tosoh Corporation, connected in series, and a photodiode array (PDA) may be used as a detector. Measurements may be performed under the following conditions: temperature 30°C, flow rate 1.0 mL / min, detection wavelength 254 nm, and injection volume 100 μL.

[0055] <Method for Producing the Polysiloxane> A method for producing the polysiloxane will be described.

[0056] The polysiloxane can be obtained by subjecting an alkoxysilane compound serving as a raw material to a hydrolysis reaction and a condensation reaction.

[0057] The hydrolysis reaction is carried out by adding an acid catalyst and water to the alkoxysilane compound in a solvent to generate silanol groups. The acid catalyst and water are preferably added to the alkoxysilane compound over a period of 1 to 180 minutes, and then the reaction is carried out at 10 to 130°C for 1 to 180 minutes. Carrying out the hydrolysis reaction under these conditions can prevent a rapid reaction. A more preferred reaction temperature for the hydrolysis reaction is 40 to 110°C.

[0058] After the hydrolysis reaction, a condensation reaction is carried out to obtain the polysiloxane. The condensation reaction is preferably carried out by heating the reaction solution at a temperature of 50° C. or higher and lower than the boiling point of the solvent for 1 to 100 hours.

[0059] Various conditions for the hydrolysis reaction and condensation reaction, such as acid concentration, reaction temperature, and reaction time, can be set in consideration of the reaction scale, size and shape of the reaction vessel, etc., to obtain physical properties suitable for the intended application.

[0060] Examples of the acid catalyst used in the hydrolysis reaction include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, ion exchange resins, etc. As the acid catalyst used in the hydrolysis reaction, it is particularly preferable to use formic acid, acetic acid or phosphoric acid.

[0061] The preferred content of the acid catalyst used in the hydrolysis reaction is preferably 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 compounds before the hydrolysis reaction. The preferred content of the acid catalyst used in the hydrolysis reaction is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the total polysiloxane compounds before the hydrolysis reaction. Here, the total amount of polysiloxane compounds refers to the amount of silicon-containing compounds, including alkoxysilane compounds, which are raw materials for polysiloxanes, their hydrolysates, and polysiloxanes, which are condensates thereof. The same definition applies hereinafter. By using an amount of acid catalyst of 0.05 parts by mass or more, the hydrolysis proceeds smoothly, and by using an amount of acid catalyst of 10 parts by mass or less, the hydrolysis reaction can be easily controlled.

[0062] The solvent used in the hydrolysis and condensation reaction is not particularly limited and can be selected appropriately. One or more types of solvents may be used. Specific examples of solvents include the following: alcohols such as 3-methyl-3-methoxy-1-butanol and diacetone alcohol; glycols 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 mono-t-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 other solvents such as γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.

[0063] Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, and γ-butyrolactone can be preferably used.

[0064] It is also preferable to add a solvent after the completion of the hydrolysis and condensation reaction to adjust the concentration or viscosity to an appropriate level for the photosensitive resin composition. Alternatively, after the hydrolysis, all or part of the volatile hydrolysis products such as alcohols produced may be distilled and removed by heating and / or under reduced pressure, and then a suitable solvent may be added.

[0065] The amount of solvent used during 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 using a solvent amount of 50 parts by mass or more, gel formation can be suppressed. Furthermore, by using a solvent amount of 500 parts by mass or less, the hydrolysis reaction proceeds quickly.

[0066] The water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be selected arbitrarily, but it is preferable to use 1.0 to 4.0 moles of water per mole of the alkoxysilane compound.

[0067] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention contains the polysiloxane and a photoacid generator. By containing the polysiloxane, it is possible to obtain a cured product that can be processed with high precision by photolithography and that is highly flexible.

[0068] The polysiloxane contained in the photosensitive resin composition is as described above.

[0069] The content of the polysiloxane in the photosensitive resin composition is preferably 10 parts by mass or more, and more preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of all components of the photosensitive resin composition, from the viewpoint of facilitating adjustment of the film thickness during processing.

[0070] <Photoacid Generator> The photosensitive resin composition of the present invention contains a photoacid generator. By appropriately selecting the photoacid generator, the photosensitive resin composition may be a chemically amplified negative-type photosensitive resin composition or a positive-type photosensitive resin composition.

[0071] Examples of the photoacid generator used in the negative photosensitive resin composition include onium salts, such as iodonium salts, sulfonium salts, diazonium salts, ammonium salts, and pyridinium salts.

[0072] Examples of photoacid generators used in the positive-type photosensitive resin composition include halogen-containing compounds, diazoketone compounds, and sulfone compounds. Examples of halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds (e.g., halomethyltriazine derivatives). Examples of diazoketone compounds include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, and naphthoquinone diazide compounds (hereinafter sometimes referred to as naphthoquinone diazide). Examples of sulfone compounds include β-ketosulfones and β-sulfonylsulfones. Examples of sulfonic acid compounds include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, and iminosulfonates. Among these, naphthoquinone diazide is preferred as the photoacid generator from the viewpoint of obtaining high-resolution patterns. These photoacid generators may be contained in the photosensitive resin composition singly or in combination of two or more.

[0073] The naphthoquinone diazide will be described in detail. The naphthoquinone diazide preferably contains a compound obtained by esterifying a phenol compound with naphthoquinone diazide sulfonic acid. In the present invention, the naphthoquinone diazide preferably used is a compound represented by the following formula (12), in which the phenolic hydroxyl group is esterified with 4-naphthoquinone diazide sulfonic acid and / or 5-naphthoquinone diazide sulfonic acid:

[0074]

[0075] In formula (12), R １１ represents a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. １１ Examples of R include a methyl group, an ethyl group, and a propyl group. １２ ~R １４ Each of R independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. １２ ~R １４Examples of R include a methyl group, an ethyl group, a propyl group, a hydroxyphenylmethylene group, a hydroxymethylphenylmethylene group, and a hydroxyphenylpropylene group. １２ ~R １４ represents 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 the groups is a monovalent organic group having 6 to 20 carbon atoms and containing a phenolic hydroxyl group. Examples of the monovalent organic group having 6 to 20 carbon atoms and containing a phenolic hydroxyl group include a hydroxyphenylmethylene group, a hydroxymethylphenylmethylene group, and a hydroxyphenylpropylene group. Here, a and b each independently represent an integer of 1 to 4, and c represents an integer of 0 to 4.

[0076] Specific examples of the phenol compound represented by formula (12) include the compounds shown below. Two or more of the phenol compounds represented by formula (12) may be used in combination.

[0077]

[0078] A compound in which the phenolic hydroxyl groups of a compound represented by formula (12) are esterified with 5-naphthoquinone diazide sulfonyl acid and / or 4-naphthoquinone diazide sulfonyl acid can be obtained by subjecting some or all of the phenolic hydroxyl groups of a compound represented by formula (12) to a conventional esterification reaction with, for example, 1,2-naphthoquinone diazide-5-(and / or -4-)sulfonyl chloride in the presence of a basic catalyst. That is, predetermined amounts of the compound represented by formula (12), the 1,2-naphthoquinone diazide-5-(and / or -4-)sulfonyl chloride, and a solvent such as dioxane, acetone, methyl ethyl ketone, or N-methylpyrrolidone are charged into a flask, and a basic catalyst such as sodium hydroxide, sodium bicarbonate, or triethylamine is added dropwise to cause condensation. The temperature of the condensation reaction is generally −20 to 60°C, preferably 0 to 40°C. The resulting product is preferably washed with water, purified, and dried.

[0079] In the above esterification reaction, mixtures with various different esterification rates and esterification positions are obtained. The esterification rate referred to in the present invention is defined as the average value of this mixture. The esterification rate of a phenolic compound can be calculated from the peak area ratio obtained by high-performance liquid chromatography (HPLC). The esterification rate can be adjusted by the mixing ratio of the raw material phenolic compound and 1,2-naphthoquinonediazide-5-(and / or -4-)sulfonyl chloride. In other words, since substantially all of the added 1,2-naphthoquinonediazide-5-(and / or -4-)sulfonyl chloride undergoes esterification, a mixture with the desired esterification rate can be obtained by adjusting the molar ratio of the raw materials.

[0080] The content of the photoacid generator is preferably 1 part by mass or more, and more preferably 2 parts by mass or more, per 100 parts by mass of the polysiloxane, from the viewpoint of forming a pattern with practical sensitivity, and is preferably 50 parts by mass or less, and more preferably 15 parts by mass or less, from the viewpoint of obtaining a high-definition pattern.

[0081] <Other Components> [Solvent] The photosensitive resin composition of the present invention may contain a solvent as another component to improve the handling property during application. Examples of the solvent include the following.

[0082] 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 mono-t-butyl ether, and ethylene glycol dimethyl ether; 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; The photosensitive resin composition may contain acetate compounds such as acetate, lactic acid 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 mesityl oxide, alcohol compounds such as methanol, ethanol, propanol, butanol, isobutyl alcohol, 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, N-methylpyrrolidinone, etc. The photosensitive resin composition may contain these compounds alone or in combination of two or more.

[0083] Among these, more preferred solvents that the photosensitive resin composition contains are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, diacetone alcohol, and γ-butyrolactone. The photosensitive resin composition may contain these alone or in combination of two or more.

[0084] The total solvent content in the photosensitive resin composition of the present invention is preferably 100 parts by mass or more and 9900 parts by mass or less, and more preferably 100 parts by mass or more and 5000 parts by mass or less, relative to 100 parts by mass of the polysiloxane.

[0085] [Photoradical Polymerization Initiator] The photosensitive resin composition of the present invention may contain a photoradical polymerization initiator. The photoradical polymerization initiator may be any one that decomposes and / or reacts upon irradiation with light (including ultraviolet light and electron beams) to generate radicals. Examples of the photoradical polymerization initiator include α-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, α-hydroxyketone compounds, and acetophenone compounds. The photosensitive resin composition may contain two or more of these.

[0086] The content of the 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 polysiloxane from the viewpoint of effectively promoting radical curing, while the content of the photoradical polymerization initiator is preferably 10 parts by mass or less relative to 100 parts by mass of the polysiloxane from the viewpoint of suppressing elution of the remaining photoradical polymerization initiator.

[0087] [Photopolymerizable Compound] The photosensitive resin composition of the present invention may contain a photopolymerizable compound. The photopolymerizable compound in the present invention refers to a compound having one or more ethylenically unsaturated double bonds in the molecule and a molecular weight of 1,000 or less. Considering the ease of radical polymerization, the photopolymerizable compound preferably has a (meth)acryloyl group. Examples of the photopolymerizable compound include pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. The photosensitive resin composition may contain two or more of the photopolymerizable compounds.

[0088] The content of the 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 polysiloxane from the viewpoint of effectively promoting radical curing, while the content of the photopolymerizable compound is preferably 50 parts by mass or less relative to 100 parts by mass of the polysiloxane from the viewpoint of suppressing excessive radical reaction and improving resolution.

[0089] [Surfactant] The photosensitive resin composition of the present invention may contain a surfactant to improve flowability and film thickness uniformity during application. There are no particular limitations on the type of surfactant, and for example, fluorine-based surfactants, silicone-based surfactants, polyalkylene oxide-based surfactants, poly(meth)acrylate-based surfactants, etc. can be used. Among these, from the viewpoint of flowability and film thickness uniformity, it is preferable that the photosensitive resin composition contains the silicone-based surfactant. The photosensitive resin composition may contain one or more of the surfactants.

[0090] Commercially available examples of the silicone surfactant include "SH28PA", "SH7PA", "SH21PA", "SH30PA", and "ST94PA" (all manufactured by Toray Dow Corning Silicone Co., Ltd.), "BYK-333", "BYK-352" (manufactured by BYK Japan KK), and "KL-700", "LE-302", "LE-303", and "LE-304" (manufactured by Kyoeisha Chemical Co., Ltd.).

[0091] Other examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene distearate.

[0092] The content of the surfactant is usually 0.001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of all components of the photosensitive resin composition.

[0093] [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 improvers, etc., as necessary.

[0094] <Cured Product> The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. Heat curing is preferred as a curing mode. By heat curing the photosensitive resin composition, components with low heat resistance can be removed, thereby further improving heat resistance and chemical resistance. Alternatively, the photosensitive resin composition may be patterned by a known method such as photolithography, and then heat cured to obtain the cured product.

[0095] The temperature at which the photosensitive resin composition is heat-cured is preferably 150° C. or higher, more preferably 200° C. or higher, from the viewpoint of improving heat resistance and chemical resistance. On the other hand, from the viewpoint of improving toughness of the cured product, the temperature is preferably 350° C. or lower, more preferably 250° C. or lower. Within this temperature range, the temperature may be increased stepwise or continuously.

[0096] The time for heat curing the photosensitive resin composition is preferably 30 minutes or more from the viewpoint of further reducing the amount of outgassing, and is preferably 3 hours or less from the viewpoint of improving the toughness of the cured product.

[0097] Examples of the combination of temperature and time for heat-curing the photosensitive resin composition include a method of heat-treating at 150° C. and 250° C. for 30 minutes each, and a method of heat-treating while linearly increasing the temperature from room temperature to 300° C. over 2 hours. From the viewpoint of reducing the process time, it is preferable to linearly increase the temperature to the set temperature.

[0098] The cured product of the present invention is suitable for use as, for example, a surface protection layer or interlayer insulating layer in a semiconductor device, an insulating layer in an organic electroluminescent (EL) display device or a micro LED display device, a planarizing layer in a TFT substrate for driving an organic electroluminescent (EL) display device or a micro LED display device, a wiring protection insulating layer in a circuit board, an on-chip microlens in a solid-state imaging device, or a planarizing layer for various displays and solid-state imaging devices. For example, the cured product is suitable as a surface protection layer or an interlayer insulating layer in MRAM, which has low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM), which is a promising next-generation memory, and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM). It can also be used as an insulating layer in a display device including a first electrode formed on a substrate and a second electrode disposed opposite the first electrode, such as an LCD, an ECD, an ELD, or an organic electroluminescent (EL) display device. The following description will be given using an organic electroluminescent (EL) display device and a semiconductor device as examples.

[0099] <Organic EL Display Device> The organic EL display device of the present invention comprises the cured product of the present invention.

[0100] A specific example of the organic EL display device is an organic EL display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and the planarizing layer and / or insulating layer preferably comprises the cured product of the present invention. Organic EL light-emitting materials are susceptible to degradation by moisture, which can have adverse effects such as a decrease in the area ratio of the light-emitting portion to the area of ​​the light-emitting pixel. However, the cured product of the present invention has low water absorption, thereby achieving stable driving and light-emitting characteristics. Taking an active matrix display device as an example, a display device has a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or various plastics, a planarizing layer on top of the TFT to cover the irregularities, and a display element is further provided on the planarizing layer. The display element and the wiring are connected via contact holes formed in the planarizing layer.

[0101] When the cured product of the present invention is used as the planarizing layer, the thickness is preferably 1.0 μm or more and 5.0 μm or less, more preferably 2.0 μm or more. By making the planarizing layer within the above-mentioned range, the planarization layer can be made higher in definition and the planarization degree of densely packed TFTs and wiring can be improved. If the planarizing layer becomes thick, outgassing increases, causing a decrease in the light-emitting reliability of the organic EL display device. However, the cured product of the present invention has low outgassing, and therefore high light-emitting reliability can be obtained. Furthermore, since TFTs and wiring can be arranged in the film thickness direction in order to achieve high definition, the planarizing layer is preferably multi-layered.

[0102] FIG. 1 shows a cross-sectional view of an example of a TFT substrate. Bottom-gate or top-gate thin film transistors (TFTs) 1 are arranged in a matrix on a substrate 6, with a TFT insulating layer 3 covering the TFTs 1. Wiring 2 connected to the TFTs 1 is provided on the TFT insulating layer 3. A planarization layer 4 is provided on the TFT insulating layer 3, burying the wiring 2. Contact holes 7 are provided in the planarization layer 4, reaching the wiring 2. An ITO (transparent electrode) 5 is formed on the planarization layer 4, connected to the wiring 2 via the contact holes 7. The ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is formed to cover the periphery of the ITO 5. The organic EL element may be a top-emission type that emits light from the side opposite the substrate 6, or a bottom-emission type that extracts light from the substrate 6. In this manner, an active matrix organic EL display device is obtained, in which TFTs 1 for driving each organic EL element are connected to the corresponding TFTs 1.

[0103] The TFT insulating layer 3, the planarizing layer 4, and / or the insulating layer 8 can be formed by the steps of forming a photosensitive resin film made of the photosensitive resin composition of the present invention, exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heat-treating the developed photosensitive resin film, as described above. An organic EL display device comprising the cured product of the present invention can be obtained by a manufacturing method including these steps.

[0104] <Semiconductor Device> The semiconductor device of the present invention comprises the cured product of the present invention.

[0105] A specific example of the semiconductor device is preferably a semiconductor device having electrodes, metal wiring, an interlayer insulating layer and / or a surface protective layer on a substrate, in which the interlayer insulating layer and / or the surface protective layer comprises the cured product of the present invention.

[0106] Figure 2 shows an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having bumps. A passivation layer 11 having an input / output Al pad 10 and via holes is formed on a silicon wafer 9. An insulating layer 12 is then formed on the passivation layer 11. A metal layer 13 made of Cr, Ti, or the like is then formed to connect to the Al pad 10, and metal wiring 14 made of Al, Cu, or the like is then formed by electrolytic plating or the like. The metal layer 13 located around the solder bumps 18 is etched to provide insulation between the pads. A barrier metal 16 and the solder bumps 18 are formed on the insulated pads. A scribe line 17 is formed when the insulating film 15 is processed.

[0107] Next, a method for manufacturing the semiconductor device will be described with reference to the drawings. FIG. 3 shows an example of a method for manufacturing the semiconductor device having bumps. In step 3a, a photosensitive resin composition of the present invention is applied to a silicon wafer 9 on which an Al pad 10 and a passivation layer 11 have been formed, and a patterned cured insulating layer 12 is formed through a photolithography process. Next, in step 3b, a metal layer 13 is formed by sputtering. In step 3c, metal wiring 14 is formed on the metal layer 13 by plating. Next, in step 3d', a photosensitive resin composition of the present invention is applied, and in step 3d, a pattern of the cured insulating layer 15 is formed through a photolithography process. During this process, the photosensitive resin composition constituting the insulating layer 15 is processed into a thick film along scribe lines 17. Further wiring (so-called rewiring) can be formed on the insulating layer 15. When forming a multilayer wiring structure of two or more layers, the above steps can be repeated to form a multilayer wiring structure in which two or more rewiring layers are separated by an interlayer insulating layer made of the cured product of the present invention. Although there is no upper limit to the number of layers in the multilayer wiring structure, those with 10 layers or less are often used. Next, in step 3e, barrier metal 16 is formed, and in step 3f, solder bumps 18 are formed. Finally, the substrate is diced along scribe lines 17 to separate into individual chips, thereby obtaining the semiconductor device having bumps.

[0108] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the embodiments disclosed in these examples.

[0109] [Abbreviations and compound names] PSX: Polysiloxane (alkoxysilane compound) MeTMS: Methyltrimethoxysilane PhTMS: Phenyltrimethoxysilane StTMS: Styryltrimethoxysilane VnTMS: Vinyltrimethoxysilane AcTMS: 3-Acryloxypropyltrimethoxysilane MAcTMS: 3-Methacryloxypropyltrimethoxysilane ISOTMS: 1-(3-(trimethoxysilyl)propyl)3,5-di-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.

[0110] (Solvent) PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether.

[0111] [Measurement Method] (1) Solids Concentration The solids concentration of the polysiloxane solution was determined by the following method. 1.5 g of the polysiloxane solution was weighed into an aluminum cup and heated at 250°C for 30 minutes using a hot plate to evaporate the liquid. The solids remaining in the aluminum cup after heating were weighed to determine the solids concentration of the polysiloxane solution.

[0112] (2) Measurement of Weight Average Molecular Weight The weight average molecular weight of the obtained polysiloxane solution was measured using a gel permeation chromatography (GPC) apparatus (Alliance HPLC / GPCe695 manufactured by Nihon Waters Co., Ltd.) by diluting the developing solvent with tetrahydrofuran (hereinafter referred to as THF) to 0.1 wt % and measuring the weight average molecular weight (Mw) in terms of polystyrene. Columns (TSKgel (registered trademark) G4000HXL / G1000HXL manufactured by Tosoh Corporation) were connected in series, and a photodiode array (PDA) was used as a detector. Measurements were performed under the following conditions: temperature 30 ° C, flow rate 1.0 mL / min, detection wavelength 254 nm, and injection volume 100 μL.

[0113] (3) Functional group ratio２９ Si-NMR measurements were performed, and the ratio of the integral value of the silicon atoms of various alkoxysilane compounds to the integral value of all silicon atoms was calculated to calculate the ratio of the corresponding silicon atoms. The sample (liquid) was injected into a 10 mm diameter Teflon (registered trademark) NMR sample tube and used for the measurement. ２９ The Si-NMR measurement conditions are as follows: Apparatus: JNM GX-270 manufactured by JEOL Ltd. Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( ２９ Si nucleus) Spectral width: 20,000 Hz Pulse width: 12 μsec (45° pulse) Pulse repetition time: 30.0 sec Solvent: acetone-d6 Reference substance: tetramethylsilane Measurement temperature: room temperature Sample rotation speed: 0.0 Hz.

[0114] (4) Resolution When the photosensitive resin composition is a negative type, the exposure dose is 300 mJ / cm ２ The photosensitive resin composition was applied to a thickness such that a cured product having a thickness of 2 μm was obtained in the exposed area, and heated on a hot plate at 100° C. for 3 minutes. When the photosensitive resin composition was a positive type, the composition was applied to a thickness such that a cured product having a thickness of 2 μm was obtained in the unexposed area, and heated on a hot plate at 100° C. for 3 minutes.

[0115] Thereafter, a mask aligner (PEM-6M manufactured by Union Optical Co., Ltd.) using a high-pressure mercury lamp as a light source was used to expose the mask to a light source of 10 mJ / cm. ２ to 300 mJ / cm ２ up to 10 mJ / cm ２The exposure was performed with the exposure dose changed every time. During exposure, a photomask with square patterns measuring 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, or 50 μm on a side was used. The exposed substrate was developed for 90 seconds using an automatic developing device (manufactured by Takizawa Sangyo Co., Ltd.) with a 2.38 wt % aqueous solution of TMAH as the developer. The developed substrate was washed with pure water for 30 seconds and directly placed in a hot air oven (Inert Oven DN43HI, manufactured by Yamato Scientific Co., Ltd.) heated to 230°C in the presence of air, and heated for 60 minutes to obtain a cured product with a thickness of approximately 2 μm. For the cured product, square patterns at all exposure doses were observed, and the smallest pattern dimension (size of the square side) that could be processed without collapsing due to reflow during heating was defined as the resolution x. The evaluation criteria were defined as follows: A: x<20 μm B: 20 ​​μm≦x<40 μm C: 40 μm≦x≦50 μm D: 50 μm<x.

[0116] (5) Bending test: The photosensitive resin composition was applied to a 20 μm thick Kapton film in the same manner as in the evaluation of resolution, and heated on a hot plate to obtain a cured product having a thickness of 2 μm. After that, in the case of a negative type, the exposure dose was 300 mJ / cm. ２ The entire coated film was exposed to light without using a photomask. In the case of a positive type, no exposure was performed, and development and heating in a hot air oven were performed to obtain a 2 μm thick cured product. The obtained cured product was cut into 1 cm x 2 cm strips, and the cut strips were used as test pieces. The bending radius was changed to 0.50 mm, 0.75 mm, 1.00 mm, and 1.50 mm so that the coated surface was on the outside, and the test pieces were bent and left to stand for about 1 minute. After bending, the test pieces were observed under a microscope at 10x magnification to check for the occurrence of cracks or breaks. The minimum bending radius at which no cracks or breaks occurred was recorded.

[0117] The evaluation criteria for the bending test were set as follows: S: No cracks or breaks occurred when bent with a bending radius of 0.50 mm. A: Cracks or breaks occurred with a bending radius of 0.50 mm. No cracks or breaks occurred with a bending radius of 0.75 mm. B: Cracks or breaks occurred with a bending radius of 0.75 mm. No cracks or breaks occurred with a bending radius of 1.00 mm. C: Cracks or breaks occurred with a bending radius of 1.00 mm. No cracks or breaks occurred with a bending radius of 1.50 mm. D: Cracks or breaks occurred with a bending radius of 1.50 mm.

[0118] Synthesis Example 1 Synthesis of Polysiloxane PGMEA Solution P-1 21.79 g (0.16 mol) of MeTMS, 26.92 g (0.12 mol) of StTMS, 44.58 g (0.12 mol) of ISOTMS, and 80.28 g of PGMEA were charged into a 500 mL three-neck flask, and a mixture of 21.60 g of ion-exchanged water and 0.10 g of phosphoric acid was added over 30 minutes while stirring at 25 ° C. Thereafter, the flask was immersed in a 70 ° C. oil bath while introducing air at a flow rate of 0.2 L / min and stirred for 1 hour, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 3 hours. The temperature inside the flask was 100-110 ° C. During the reaction, the by-products methanol and water were removed by distillation. The polysiloxane PGMEA solution remaining in the flask was designated as polysiloxane PGMEA solution P-1. The solids content was 45.6% by mass. The weight average molecular weight (Mw) in terms of polystyrene was 75,000. ２９ As measured by Si-NMR, the molar ratio of the structure of formula (1) in the polysiloxane in P-1 was 30 mol %, the molar ratio of styryl groups was 30 mol %, and the molar ratio of methyl groups was 40 mol %.

[0119] Synthesis Examples 2 to 29 Synthesis of PGMEA Solutions of Polysiloxane P-2 to 29 Polysiloxane PGMEA solutions P-2 to 29 were synthesized in the same manner as in Synthesis Example 1, except that the amounts of each raw material were changed as shown in Tables 1 and 2.

[0120]

[0121]

[0122] Synthesis 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 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the temperature of the system was brought to room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, adjusting the dropping rate so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain Photoacid Generator B-1 represented by the following formula:

[0123]

[0124] [Example 1] Photosensitive resin composition (J-1) To 21.05 g of the PGMEA solution P-1 of polysiloxane synthesized in Synthesis Example 1, 0.10 g of photoacid generator B-1, 0.29 g of photoradical polymerization initiator (Irgacure (registered trademark) OXE-01 manufactured by BASF Japan Ltd.), 13.53 g of PGMEA, 14.00 g of PGME, and 0.02 g of surfactant BYK-333 (trade name, manufactured by BYK-Chemie Japan Co., Ltd.) were added to obtain photosensitive resin composition J-1. The resolution x of the obtained photosensitive resin composition was 25 μm, and the evaluation was B. The minimum bending radius R in the bending test evaluation was 0.50 mm, and the evaluation was S.

[0125] [Examples 2 to 28] Photosensitive resin compositions J-2 to J-28 Photosensitive resin compositions J-2 to J-28 were obtained by adding a PGMEA solution of polysiloxane, a photoacid generator, a solvent, a surfactant, and the amounts thereof as shown in Tables 3 and 4. The results of the resolution evaluation and bending test evaluation of the obtained photosensitive resin compositions are shown in Tables 5 to 7.

[0126] [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 photosensitive resin composition J-29. In the evaluation of the resolution of the obtained photosensitive resin composition, patterns of all dimensions reflowed after heating and were crushed, and the composition was evaluated as D. In the bending test evaluation, cracks occurred at all levels, and the composition was evaluated as D.

[0127] [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 photosensitive resin composition J-30. In the evaluation of the resolution of the obtained photosensitive resin composition, patterns of all dimensions reflowed after heating and were crushed, and the evaluation was D. In the bending test evaluation, cracks occurred at all levels, and the evaluation was D.

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] 1: TFT (thin film transistor) 2: Wiring 3: TFT insulating layer 4: Planarization layer 5: ITO (transparent electrode) 6: Substrate 7: Contact hole 8: Insulating layer 9: Silicon wafer 10: Al pad 11: Passivation layer 12: Insulating layer 13: Metal (Cr, Ti, etc.) layer 14: Metal wiring (Al, Cu, etc.) 15: Insulating layer 16: Barrier metal 17: Scribe line 18: Solder bump

Claims

1. Polysiloxane containing one or more structures represented by any one of formulas (1) to (3). In formulas (1) to (3), R １ R each independently represents a group represented by formula (4). ２ represents a hydrocarbon group having 1 to 4 carbon atoms. ３ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. １ is the point of attachment to the oxygen atom, * ２ represents a point of attachment to a hydrogen atom or a silicon atom. In formula (4), * ３ represents the point of attachment to the silicon atom. ４ represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ５ and R ６ each independently represents a group having 1 to 6 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms, and nitrogen atoms. ５ and R ６ At least one of the groups is a group containing an aliphatic carbon-carbon unsaturated bond.

2. The polysiloxane according to claim 1, wherein the total content of structures represented by any one of formulas (1) to (3) is 5 mol % or more and 50 mol % or less relative to 100 mol % of the total amount of silicon atoms in the polysiloxane.

3. The polysiloxane according to claim 1 or 2, further comprising one or more structures represented by any one of formulas (5) to (7). In formulas (5) to (7), R ７ represents a group represented by any one of formulas (8) to (10). ８ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. ９ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. １ is the bond point to the oxygen atom, and * ２ represents a bond point to a hydrogen atom or a silicon atom. In formulas (8) to (10), * ３ represents the point of attachment to the silicon atom, n represents an integer of 0 to 8, and m represents an integer of 1 to 8. R １０ represents a hydrogen atom or a group having 1 to 4 carbon atoms and consisting only of hydrogen atoms, carbon atoms, oxygen atoms and nitrogen atoms.

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

5. At least one R in the structure represented by any one of the formulas (5) to (7) ７ The polysiloxane according to claim 3 , wherein is a group represented by formula (8):

6. The polysiloxane according to claim 3, wherein the total number of moles X of the structures represented by any one of formulas (5) to (7) and the total number of moles Y of the structures represented by any one of formulas (1) to (3) in the polysiloxane satisfy the following relationship: 0.4≦(X / Y)≦4.0 7. A photosensitive resin composition comprising the polysiloxane of claim 1 or 2 and a photoacid generator.

8. The photosensitive resin composition according to claim 7, wherein the photoacid generator comprises at least naphthoquinone diazide.

9. A cured product obtained by curing the photosensitive resin composition according to claim 7.

10. A semiconductor device comprising the cured product according to claim 9.

11. An organic EL display device comprising the cured product according to claim 9.

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