Silicone resin composition for curing film formation and curing film

Abstract

The object of this invention is to provide a relatively inexpensive silicone resin composition for curing films, which yields a curing film with excellent storage stability and solvent resistance. Furthermore, even without a catalyst removal step, polysiloxanes with good storage stability can be manufactured. The silicone resin composition for curing films of this invention is a resin composition containing polysiloxane, an organic salt, and a solvent, and specifically, the organic salt has a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution. Additionally, the method for manufacturing the polysiloxane of this invention uses alkoxysilanes as raw materials and an organic salt as a catalyst for hydrolysis and / or thermal condensation, and is characterized in that the organic salt has a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution.

Description

[Technical Field]

[0001] This invention relates to a silicone resin composition for forming a hardened film, a hardened film, and a method for manufacturing a polysiloxane. [Previous Technology]

[0002] Resin compositions containing polysiloxanes are widely used in optical lenses, such as microlens arrays for solid-state imaging elements, planarization films for thin film transistors (TFTs) in liquid crystal or organic electroluminescent (EL) displays, protective and insulating films for touch panels, anti-reflective films, optical filters, and other applications due to their excellent heat resistance, weather resistance, and transparency.

[0003] In these applications, a curing film with excellent solvent resistance is generally required. In order to achieve the required properties, the curing degree of the film needs to be improved by promoting the reaction between the polysiloxanes in the film (condensation reaction of silanol groups) during the formation of the curing film.

[0004] To promote this reaction, it is effective to contain polysiloxane condensation catalysts such as acid catalysts or alkali catalysts in the resin composition. However, if both such catalysts and polysiloxanes are present, the reaction between the silanol groups will proceed over time, resulting in problems such as thickening or gelation, and deterioration of storage stability. Therefore, a method for promoting film curing by using acid-generating materials or alkali-generating materials, through the acid or alkali generated during the exposure step and / or heating step, has been reported (e.g., Patent Document 1, Patent Document 2).

[0005] Furthermore, most industrially used polysiloxanes are synthesized via the sol-gel method using alkoxysilane compounds as raw materials, utilizing hydrolysis and polycondensation reactions. Generally, in the sol-gel method, acid or alkali catalysts are used to promote the hydrolysis and condensation reactions. However, if these catalysts remain in the polysiloxane solution after the reaction, problems such as thickening or gelation over time, as described above, occur. Therefore, in practice, a catalyst removal step (or neutralization reaction) is usually required after the reaction. However, the introduction of these steps not only increases costs but also leads to reduced yields or increased impurities.

[0006] In order to obtain polysiloxanes with excellent storage stability even without removing the catalyst, a method of using a fluoride salt, which is a neutral compound, as a catalyst is reported in Patent Document 3.

[0007] Furthermore, Patent Document 4 proposes a method for synthesis using a neutral salt as a catalyst. [Prior Art Documents] [Patent Documents]

[0008] Patent Document 1: Japanese Patent Application Publication No. 2004-107562; Patent Document 2: Japanese Patent Application Publication No. 2006-154037; Patent Document 3: Japanese Patent Application Publication No. Hei 7-292108; Patent Document 4: International Publication No. 2016 / 098596; Patent Document 5: Japanese Patent Application Publication No. 2006-106311; Patent Document 6: Japanese Patent No. 645892 [Summary of the Invention]

[0009] [Problems to be Solved by the Invention] However, in the technologies of Patent Document 1 and Patent Document 2, effective acid-generating materials or alkali-generating materials are generally expensive, which can be listed as a problem. In addition, when there are metal wirings on the substrate, there are also problems such as wiring corrosion.

[0010] In the technology of Patent Document 3, it is known that most fluoride salts produce highly toxic hydrofluoric acid in acidic aqueous solutions, which raises concerns about safety or substrate corrosion.

[0011] In the technology of Patent Document 4, magnesium chloride or sodium chloride are cited as preferred examples as neutral salt catalysts. However, when used in semiconductor applications, there is a concern that alkali metal impurities originating from the catalyst may become a problem. In addition, since these neutral salt catalysts are salts of strong acids and strong bases, the pH of the aqueous solution is around 7, which may make it difficult for the hydrolysis of alkoxysilane compounds to proceed, and the subsequent polycondensation reaction may also be difficult to carry out.

[0012] The object of the present invention is to provide, relatively inexpensively, a silicone resin composition for forming a hardened film that yields a hardened film with excellent storage stability and excellent solvent resistance. Furthermore, the object is to manufacture a polysiloxane that exhibits good storage stability even without a catalyst removal step. [Means for Solving the Problem]

[0013] The present invention is described below. [1] A resin composition for forming a hardened film is a resin composition containing (a) a polysiloxane, (b) an organic salt, and (c) a solvent, wherein the pH value of the organic salt (b) in a 1.0% by mass aqueous solution is 3.0 to 5.5. [2] The silicone resin composition for forming a hardened film as described in [1], wherein the content of the organic salt (b) is 0.01 to 5.00 parts by mass relative to 100 parts by mass of the polysiloxane (a). [3] The silicone resin composition for forming a hardened film as described in [1] or [2], wherein the organic salt (b) is an organic salt containing an organic acid or an amine having a structure represented by any one of the general formulas (1) to (3) described below. [4] The silicone resin composition for forming a hardened film as described in [3], wherein the amine is a heterocyclic amine or an aromatic amine. [5] The silicone resin composition for forming a curing film as described in [3] or [4], wherein the organic acid having a structure represented by any one of general formulas (1) to (3) is an organic acid selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, trifluoropropanesulfonic acid, and trifluoroacetic acid. [6] The silicone resin composition for forming a curing film as described in [4], wherein the heterocyclic amine or aromatic amine is an amine selected from the group consisting of pyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, and aniline. [7] The silicone resin composition for forming a curing film as described in any one of [1] to [6] further contains (d) a photosensitizer. [8] A silicone resin composition for forming a hardened film as described in any one of [1] to [7], wherein the (a) polysiloxane has an aromatic group and / or a substituted aromatic group in the side chain group, and the contents of benzene, toluene, xylene, aniline, styrene and naphthalene in the resin composition are each less than 1 ppm. [9] A silicone resin composition for forming a hardened film as described in any one of [1] to [8], wherein the hardened film is a permanent film.

[10] A hardened film is formed by hardening the resin composition for forming a hardened film as described in any one of [1] to [9].

[11] A hardened film wherein the atomic ratio of N to Si, as determined by scanning electron microscopy (SEM-EDX), is 0.005 or more and 0.200 or less, and the atomic ratio of at least one of S, P, and F to Si is 0.005 or more and 0.200 or less.

[12] The hardened film as described in

[10] , wherein the atomic ratio of N to Si, as determined by scanning electron microscopy (SEM-EDX), is 0.005 or more and 0.200 or less, and the atomic ratio of at least one of S, P, and F to Si is 0.005 or more and 0.200 or less.

[13] A method for manufacturing a polysiloxane, using an alkoxysilane as a raw material and an organic salt as a catalyst for hydrolysis and / or thermal condensation, wherein the method for manufacturing the polysiloxane is characterized in that the pH value of the organic salt in a 1.0% by mass aqueous solution is 3.0 to 5.5. [Effects of the Invention].

[0014] This invention provides a silicone resin composition for forming a hardened film, which yields a hardened film with excellent storage stability and excellent solvent resistance. Furthermore, this invention provides a hardened film with excellent solvent resistance. Moreover, it provides a method for manufacturing a polysiloxane that produces a polysiloxane with good storage stability even without a catalyst removal step.

Implementation Method

[0016] Hereinafter, preferred embodiments of the silicone resin composition for forming a hardened film, the hardened film, and the method for manufacturing polysiloxane according to the present invention will be specifically described. However, the present invention is not limited to the following embodiments and can be implemented with various modifications depending on the purpose or use.

[0017] The resin composition for forming a hardened film of the present invention contains (a) a polysiloxane, (b) an organic salt, and (c) a solvent.

[0018] (a) Polysiloxane (a) Polysiloxane is a hydrolysis and dehydration condensate of an alkoxysilane compound. (a) Polysiloxane preferably contains at least a repeating unit represented by the following general formula (4) and / or a repeating unit represented by the following general formula (5). In the case of forming a thick film with a thickness of 10 μm or more, it is preferable to contain a repeating unit derived from a difunctional alkoxysilane compound represented by general formula (4). By containing a repeating unit derived from a difunctional alkoxysilane compound represented by general formula (4), excessive thermal polymerization (condensation) of polysiloxane caused by heating can be suppressed, and the crack resistance of the hardened film can be improved. In addition, by containing a repeating unit derived from a trifunctional alkoxysilane compound represented by general formula (5), the crosslinking density of polysiloxane after film formation is increased, and the hardness of the hardened film can be improved.

[0019] [Chemical 1]

[0020] In the general formula (4), R4 and R5 may be the same or different, representing monovalent organic groups with 1 to 20 carbon atoms. A portion of R4 and R5 may be substituted by a free radical polymerizable group. In this case, the free radical polymerizable group can undergo free radical polymerization in the cured resin composition. Examples of free radical polymerizable groups include vinyl, (meth)acrylate, and styrene groups. In addition, the polysiloxane may contain two or more repeating units represented by general formula (4) with different R4 and R5.

[0021] In the general formula (5), R6 represents a monovalent organic group having 1 to 20 carbon atoms. A portion of R6 may be substituted by a free radical polymerizable group. In this case, the free radical polymerizable group can undergo free radical polymerization in the cured resin composition. Examples of free radical polymerizable groups include vinyl, (meth)acrylate, and styrene groups. In addition, the polysiloxane may contain two or more repeating units represented by general formula (5) with different R6s.

[0022] The repeating units represented by general formulas (4) and (5) are derived from alkoxysilane compounds represented by general formulas (6) and (7) respectively. That is, polysiloxanes containing repeating units represented by general formulas (4) and (5) can be obtained by hydrolyzing and polycondensing alkoxysilane compounds containing alkoxysilane compounds represented by general formulas (6) and (7). Other alkoxysilane compounds may also be used.

[0023] [Chemical 2]

[0024] In the general formulas (6) and (7), R4 to R6 represent the same groups as R4 to R6 in general formulas (4) and (5), respectively. R7 may be the same or different, representing hydrogen or a monovalent organic group having 1 to 20 carbon atoms, preferably hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0025] Examples of alkoxysilane compounds represented by general formula (6) include: dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, vinylmethyldimethoxysilane, vinyl Methyldiethoxysilane, allylmethyldiethoxysilane, allylmethyldiethoxysilane, styrylmethyldiethoxysilane, styrylmethyldiethoxysilane, γ-methacrylpropylmethyldiethoxysilane, γ-methacrylpropylmethyldiethoxysilane, γ-acrylpropylmethyldiethoxysilane, γ-acrylpropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane (-Epoxycyclohexyl)ethylethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride, 5-dimethylmethoxysilylvaleric acid, 5-dimethylethoxysilylvaleric acid, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethyl... Ethoxysilylpropyl phthalic anhydride, 3-dimethylmethoxysilylpropyl phthalic anhydride, 3-dimethylethoxysilylpropyl phthalic anhydride, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropyl)diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, diphenylsilanediol, etc. Two or more of these compounds may also be used.

[0026] As an alkoxysilane compound represented by general formula (7), examples include: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and other trifunctional alkoxysilane compounds; 3-glycidyl Alkoxysilane compounds containing epoxy groups or oxetyl groups, such as oxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane; phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, toluene Alkoxysilane compounds containing aromatic rings, such as trimethoxysilane, tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride, and 3-triethoxysilylpropylphthalic anhydride; styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ-acrylpropyltrimethoxysilane, γ-acrylpropyltriethoxysilane, and γ-methacrylpropyltrimethoxysilane. Alkoxysilane compounds containing free radical polymerizable groups, such as γ-methacrylpropyltriethoxysilane; alkoxysilane compounds containing carboxyl groups, such as 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, and 3-triethoxysilylpropylphthalic anhydride.Fluorine-containing alkoxysilane compounds such as trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane. Two or more of these compounds may also be used.

[0027] When the silicone resin composition for forming a curing film of the present invention has photocurability, the alkoxysilane compound represented by general formula (6) and / or general formula (7) is preferably an alkoxysilane compound containing at least one free radical polymerizable group. Furthermore, when the silicone resin composition for forming a curing film of the present invention has negative photosensitivity, the alkoxysilane compound represented by general formula (6) and / or general formula (7) is preferably an alkoxysilane compound containing at least one free radical polymerizable group and at least one carboxyl-containing alkoxysilane compound. By containing an alkoxysilane compound containing a free radical polymerizable group, the crosslinking reaction can be carried out using free radicals generated in the exposed portion, thereby improving the curing degree of the exposed portion. In addition, by containing a carboxyl-containing alkoxysilane compound, the solubility of the unexposed portion is improved, thereby improving the resolution during pattern processing.

[0028] When the silicone resin composition for forming the hardened film of the present invention has positive photosensitivity, the alkoxysilane compound represented by general formula (6) and / or general formula (7) is preferably an alkoxysilane compound containing at least an aromatic group. By containing an alkoxysilane compound containing an aromatic group, the compatibility between (a) the polysiloxane and the photosensitizer can be improved.

[0029] Other alkoxysilane compounds include, for example, tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetraethoxysilane oligomer); and monofunctional alkoxysilane compounds such as trimethylmethoxysilane, triphenylmethoxysilane, trimethylsilanol, and triphenylsilanol. Two or more of these compounds may also be used.

[0030] From the viewpoint of coatability, (a) the weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the polysiloxane is preferably 200,000 or less, more preferably 150,000 or less. Here, the Mw of the polysiloxane in this invention refers to the polystyrene equivalent value determined by gel permeation chromatography (GPC).

[0031] (a) The polysiloxane can be obtained by hydrolyzing the alkoxysilane compound and then subjecting the hydrolysate to a dehydration condensation reaction.

[0032] Various conditions for hydrolysis can be considered, such as the reaction scale, the size and shape of the reaction vessel, and set according to the physical properties suitable for the target application. Examples of various conditions include oxygen concentration, reaction temperature, and reaction time.

[0033] To promote the hydrolysis and dehydration condensation reactions, it is preferable to add a catalyst. As a catalyst, the following can be used: hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, or monoethanolamine, diethanolamine, triethanolamine, 3,3-dimethylbutylamine, methylpentylamine, n-butylethylamine, dibutylamine, n-butylamine, pentylamine, isopentylamine, cyclopentylamine, hexylamine, cyclohexylamine, dimethylhexylamine, N,N-dimethylbutylamine, N,N-dimethylhexadecylamine, N,N-dimethyl- Bases such as n-octylamine or organic salts such as pyridinium methanesulfonate, pyridinium ethanesulfonate, pyridinium propanesulfonate, pyridinium benzenesulfonate, pyridinium p-toluenesulfonate, pyridinium xylenesulfonate, pyridinium trifluoromethanesulfonate, pyridinium trifluoroethanesulfonate, pyridinium trifluoropropanesulfonate, pyridinium trifluoroacetate, 2,4,6-trimethylpyridinium p-toluenesulfonate, aniline p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetraethylammonium p-toluenesulfonate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide.

[0034] Preferably, an organic salt with a pH of 3.0 to 5.5 in a 1.0% by weight aqueous solution is used. That is, the method for manufacturing polysiloxane of the present invention uses an alkoxysilane compound as a raw material, uses an organic salt as a catalyst for hydrolysis and / or thermal condensation, and in the method for manufacturing polysiloxane, the organic salt has a pH of 3.0 to 5.5 in a 1.0% by weight aqueous solution.

[0035] Examples of organic salts with a pH of 3.0 to 5.5 in a 1.0% by mass aqueous solution include: pyridinium benzenesulfonate, pyridinium methanesulfonate, pyridinium p-toluenesulfonate, pyridinium xylenesulfonate, pyridinium trifluoromethanesulfonate, pyridinium trifluoroethanesulfonate, pyridinium trifluoropropanesulfonate, pyridinium trifluoroacetate, 2,4,6-trimethylpyridinium p-toluenesulfonic acid, and aniline p-toluenesulfonic acid. By using an organic salt with a pH of 3.0 to 5.5 in a 1.0% by mass aqueous solution, polysiloxanes with good preservation stability can be manufactured even without the catalyst removal or neutralization steps described later. The pH of the organic salt in a 1.0% by mass aqueous solution is preferably 3.0 to 5.0, and more preferably 3.0 to 4.5.

[0036] In hydrolysis and dehydration condensation reactions, when a catalyst is used, from the viewpoint of making the reaction proceed more rapidly, the amount of catalyst added 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 all alkoxysilane compounds used in the reaction. On the other hand, from the viewpoint of appropriately adjusting the reaction proceeding, the amount of catalyst added is preferably 5.00 parts by mass or less, more preferably 3.00 parts by mass or less, relative to 100 parts by mass of all alkoxysilane compounds. Here, the amount of "all alkoxysilane compounds" refers to the total amount including the alkoxysilane compounds, their hydrolysates, and their condensates. The same applies below.

[0037] Hydrolysis and dehydration condensation reactions are preferably carried out in a solvent. The solvent should be selected appropriately, taking into account factors such as the stability, wettability, and volatility of the resin composition. Alternatively, if a solvent is generated through the hydrolysis reaction, hydrolysis can also be carried out without a solvent. When used in a resin composition, it is preferable to add a solvent after the hydrolysis reaction is complete, thereby adjusting the resin composition to an appropriate concentration. Alternatively, after hydrolysis, the total amount or a portion of the alcohols generated can be distilled off by heating and / or reducing pressure, and then a suitable solvent can be added.

[0038] When a solvent is used in the hydrolysis reaction, from the viewpoint of suppressing gel formation caused by overreaction, the amount of solvent added is preferably 20 parts by mass or more, and more preferably 40 parts by mass or more, relative to 100 parts by mass of all alkoxysilane compounds. On the other hand, from the viewpoint of making the hydrolysis proceed more rapidly, the amount of solvent added is preferably 500 parts by mass or less, and more preferably 200 parts by mass or less, relative to 100 parts by mass of all alkoxysilane compounds.

[0039] In addition, the water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be set arbitrarily, but is preferably 1.0 mol to 4.0 mol relative to 1 mol of all alkoxysilane compounds.

[0040] As a method for dehydration condensation reaction, for example, a method of directly heating a solution of a silanol compound obtained by the hydrolysis reaction of an alkoxysilane compound can be listed. The heating temperature is preferably 50°C or higher and below the boiling point of the solvent, and the heating time is preferably 1 hour to 100 hours. Alternatively, depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the generated alcohol can be distilled off under heating and / or reduced pressure, and then a suitable solvent can be added.

[0041] From the viewpoint of the preservation stability of the resin composition, a catalyst removal or neutralization step may be performed as needed. From the viewpoint of ease of operation and removability, the preferred catalyst removal methods are water washing, treatment with ion exchange resin, etc. Water washing refers to a method of diluting the polysiloxane solution with a suitable hydrophobic solvent, washing it several times with water, and then concentrating the obtained organic layer using an evaporator or the like. Treatment with ion exchange resin refers to a method of contacting the polysiloxane solution with a suitable ion exchange resin. (b) Organic salt (b) Organic salt is an organic salt compound containing both acid and base. (b) Organic salt acts as a condensation catalyst that promotes the condensation reaction of residual silanol groups in the polysiloxane. By including (a) polysiloxane and (b) organic salt in the resin composition, the reaction between the silanol groups in the polysiloxane can be promoted, thereby increasing the crosslinking density in the film, improving the hardening degree of the hardened film, and improving the solvent resistance of the film.

[0042] Furthermore, Patent Document 5 provides an example of using p-toluenesulfonic acid pyridinium salt as an organic salt in the resist composition. This is added for the purpose of suppressing the diffusion rate of acid generated by the photoacid generator into the resist film, which is significantly different from the role of (b) organic salt in the silicone resin composition for forming a hardened film used in this invention to form a permanent film.

[0043] As a method for introducing (b) organic salt into the resin composition, examples include using (b) organic salt as a catalyst in the step of manufacturing (a) polysiloxane as described above, and using a polysiloxane solution obtained without a catalyst removal step, and adding (b) organic salt by post-addition to (a) polysiloxane after catalyst removal. From the viewpoint of simplicity of procedure, the former method is preferred.

[0044] In the silicone resin composition for forming a hardened film of the present invention, (b) the pH value of the organic salt in a 1.0% by mass aqueous solution is 3.0 to 5.5. By setting the pH value within this range, both the storage stability of the resin composition and the degree of film hardening can be achieved. Examples of organic salts described as preferred catalysts include those with a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution. (b) The pH value of the organic salt in a 1.0% by mass aqueous solution is preferably 3.0 to 5.0, more preferably 3.0 to 4.5.

[0045] From the viewpoint of improving the curing degree of the membrane, the content of the organic salt in the resin composition for forming the curing membrane of the present invention is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polysiloxane. On the other hand, from the viewpoint of improving storage stability and inhibiting membrane yellowing, the content of the organic salt in the resin composition for forming the curing membrane of the present invention is preferably 5.00 parts by mass or less, more preferably 3.00 parts by mass or less, relative to 100 parts by mass of the polysiloxane.

[0046] In order to make the pH value of the 1.0% by mass aqueous solution within the preferred range, (b) the organic salt is preferably a salt containing both a strong acid and a weak base. Therefore, (b) the organic salt is preferably an organic salt containing an organic acid or an amine having a structure represented by any one of the following general formulas (1) to (3).

[0047] [Chemical 3]

[0048] In general formulas (1) to (2), R1 to R2 independently represent a monovalent organogroup with 1 to 30 carbon atoms or a divalent organogroup with 1 to 30 carbon atoms. Examples of monovalent organogroups include: substituted or unsubstituted linear or branched alkyl groups, substituted or unsubstituted cyclic alkyl groups, substituted or unsubstituted aryl groups, perfluoroalkyl groups, etc. Examples of divalent organogroups include: substituted or unsubstituted enylalkyl groups, substituted or unsubstituted enylenyl groups, substituted or unsubstituted enylphenyl groups, etc.

[0049] In general formula (3), n represents 0, 1 or 2. When n=1, R3 in general formula (3) represents a monovalent organic group with 1 to 30 carbons or a divalent organic group with 1 to 30 carbons. When n=2, R3 in general formula (3) can be the same or different, representing hydrogen, a monovalent organic group with 1 to 30 carbons, or a divalent organic group with 1 to 30 carbons.

[0050] Organic acids represented by general formula (1) can be listed as follows: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, heptadecanic acid, stearic acid, trifluoroacetic acid, benzoic acid, phthalic acid, terephthalic acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, etc.

[0051] The organic acids represented by the general formula (2) can be listed as follows: methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, o-toluenesulfonic acid, xylenesulfonic acid, 10-camphorsulfonic acid, malonic acid, taurine, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, trifluoropropanesulfonic acid, etc.

[0052] The organic acids represented by the general formula (3) can be listed as follows: phosphoric acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, cyclohexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, eicosylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, phenylphosphonic acid, tolylphosphonic acid, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dihexyl phosphate, diphenyl phosphate, etc.

[0053] Among these, from the viewpoint of ease of salt formation or ease of acquisition, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, trifluoropropanesulfonic acid, or trifluoroacetic acid are preferred.

[0054] The structure of the amine is not particularly limited, but as described above, it is preferably a weakly basic amine compound. The amine is preferably a heterocyclic amine or an aromatic amine.

[0055] As heterocyclic amines, examples include: pyrrole, oxazole, isoxazole, thiazole, imidazole, pyrazole, 1,2,3-thiadiazole, pyridine, piperidine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, purine, pteridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, etc.

[0056] As aromatic amines, examples include: aniline, o-toluidine, 2,4,6-trimethylaniline, methoxyaniline, 3-(trifluoromethyl)aniline, etc.

[0057] Among these, from the viewpoint of ease of salt formation and ease of acquisition, pyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, and aniline are preferred.

[0058] (b) The organic salt is preferably an organic salt comprising the preferred organic acids and preferred amines described above. Among these, from the viewpoint of ease of salt formation and ease of acquisition, pyridinium methanesulfonate, pyridinium ethanesulfonate, pyridinium propanesulfonate, pyridinium benzenesulfonate, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, pyridinium trifluoropropanesulfonate, pyridinium trifluoroacetate, pyridinium xylenesulfonate, p-toluenesulfonic acid, and 2,4,6-trimethylpyridinium salt are preferred. Among these, from the viewpoint of reducing the color of the hardened film, pyridinium methanesulfonate, pyridinium benzenesulfonate, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, or trifluoroacetic acid are preferred, and pyridinium methanesulfonate is particularly preferred. In addition, when using the siloxane resin composition of the present invention for use in low refractive index films, from the viewpoint of reducing the refractive index, it is preferable to use pyridine trifluoromethanesulfonate, pyridine trifluoroethanesulfonate, pyridine trifluoropropanesulfonate, or pyridine trifluoroacetate, and more preferably pyridine trifluoromethanesulfonate or pyridine trifluoroacetate.

[0059] (b) The organic salt may be commercially available or synthesized. As a synthesis method, it may be obtained, for example, by filtration of the salt precipitated by stirring the organic acid and dehydrated tetrahydrofuran (THF) under nitrogen, while cooling in an ice bath and adding the amine dropwise, followed by vacuum drying. (c) Solvent (c) The solvent has the function of adjusting the viscosity of the resin composition to a suitable range for coating and improving the coating uniformity.

[0060] As solvents, examples include: alcohols such as ethanol, propanol, isopropanol, and diacetone alcohol; diols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; ketones such as methyl ethyl ketone, acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclopentanone; dimethylformamide, dimethyl ethyl ketone ... Acetamides such as methyl acetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc.; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, etc. Two or more of these compounds may also be contained. From the viewpoint of coatability, a combination of a solvent with a boiling point exceeding 150°C and below 250°C at atmospheric pressure and a solvent with a boiling point below 150°C is preferred; more preferably, a combination of diacetone alcohol as a solvent with a boiling point exceeding 150°C and below 250°C at atmospheric pressure and propylene glycol monomethyl ether as a solvent with a boiling point below 150°C is preferred.

[0061] The content of the solvent can be set arbitrarily according to the coating method, etc. For example, when the film is formed by spin coating, the content of the solvent is generally set to be 50% by mass or more and 95% by mass or less in the resin composition for forming the hardened film of the present invention.

[0062] (d) Photosensitive agent: When photosensitivity is required, the silicone resin composition for forming the curing film of the present invention preferably contains a (d) photosensitive agent. When imparting negative photosensitivity, it is preferable to contain a photopolymerization initiator as the (d) photosensitive agent, which can form highly detailed patterns. When imparting negative photosensitivity, it is preferable to further contain a photopolymerizable compound. On the other hand, when imparting positive photosensitivity, it is preferable to contain a quinone diazide compound as the (d) photosensitive agent.

[0063] A photopolymerization initiator can be any photoradioactive polymerization initiator, as long as it generates free radicals through decomposition and / or reaction by light (including ultraviolet light and electron beams). Examples include: 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-4-yl-phenyl)-butane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and other α-aminophenylalkyl ketone compounds; 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-oxy Phosphine oxides such as phosphine oxyphosphates; oxime compounds such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butanone-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetylated oxime); benzyl ketals such as benzyl dimethyl ketal; 2-hydroxy α-hydroxy ketone compounds such as 2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, and 1-hydroxycyclohexylphenyl ketone; benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, and alkylated compounds. Benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and other benzophenone compounds; acetophenone compounds such as 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzyl acetophenone, and 4-azidobenzylidene acetophenone; aromatic ketone ester compounds such as methyl 2-phenyl-2-oxyacetate; benzoic acid ester compounds such as ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate, etc. It may also contain two or more of these compounds.

[0064] From the viewpoint of effectively performing free radical curing, the content of the photopolymerization initiator in the silicone resin composition for forming the curing film of the present invention is preferably 0.01% by mass or more, and more preferably 1% by mass or more in the solid components. On the other hand, from the viewpoint of suppressing the dissolution of residual photopolymerization initiator, the content of the photopolymerization initiator in the solid components is preferably 20% by mass or less, and more preferably 10% by mass or less.

[0065] The photopolymerizable compound in this invention refers to a compound having two or more vinyl unsaturated double bonds in its molecule. Considering the ease of free radical polymerization, the photopolymerizable compound is preferably one having (meth)acrylic acid groups.

[0066] Examples of photopolymerizable compounds include: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, and 1,10-decanediol dimethylpropylene. Acetic acid esters, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, etc. It may also contain two or more of these compounds.

[0067] From the viewpoint of effectively performing free radical curing, the content of the photopolymerizable compound in the silicone resin composition for forming the curing film of the present invention is preferably 1% by mass or more in the solid component. On the other hand, from the viewpoint of suppressing excessive free radical reaction and improving resolution, the content of the photopolymerizable compound in the solid component is preferably 50% by mass or less.

[0068] As a quinone diazide compound, it is preferably a compound formed by ester bonding of a quinone diazide sulfonic acid to a compound having a phenolic hydroxyl group. Examples of compounds having a phenolic hydroxyl group used herein include BIs-Z, TekP-4HBPA (tetra-P-DO-BPA), TrIsP-HAP, TrIsP-PA, BIsRS-2P, BIsRS-3P (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (trade names, manufactured by Asahi Organic Materials Co., Ltd.), 4,4'-sulfonyldiphenol, BPFL (trade name, manufactured by JFE Chemical Co., Ltd.), etc. As quinone diazide compounds, it is preferable to introduce 4-naphthoquinone diazidesulfonic acid or 5-naphthoquinone diazidesulfonic acid into these compounds having phenolic hydroxyl groups via ester bonds, such as THP-17, TDF-517 (trade name, manufactured by Toyo Gosei Kogyo Co., Ltd.), SBF-525 (trade name, manufactured by AZ Electronic Materials Co., Ltd.), etc.

[0069] From the viewpoint of improving sensitivity, the content of the quinone diazide compound in the silicone resin composition for forming the hardened film of the present invention is preferably 0.5% by mass or more, and more preferably 1% by mass or more in the solid component. On the other hand, from the viewpoint of improving resolution, the content of the quinone diazide compound is preferably 25% by mass or less, and more preferably 20% by mass or less in the solid component.

[0070] In addition, the resin composition of the present invention may contain ultraviolet absorbers, polymerization inhibitors, surfactants, adhesion modifiers, nanoparticles, pigments, etc., as needed.

[0071] By including an ultraviolet absorber in the silicone resin composition for forming the hardened film of the present invention, light resistance can be improved. From the viewpoint of transparency and non-coloring properties, benzotriazole compounds such as 2-(2H-benzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-terpentylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol, and 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol are preferred as ultraviolet absorbers.

[0072] By including a polymerization inhibitor in the silicone resin composition for forming the hardened film of the present invention, the resolution can be further improved. Examples of polymerization inhibitors include: di-tertiary butylhydroxytoluene, butylhydroxyanisole, 4-methoxyphenol, 1,4-benzoquinone, and tertiary butylcatechol. Commercially available polymerization inhibitors include: IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (these are trade names, manufactured by Japan BASF). Two or more of these compounds may also be included.

[0073] By including a surfactant in the silicone resin composition for forming the hardened film of the present invention, the fluidity during coating can be improved. Examples of surfactants include: fluorinated surfactants such as "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (trade names, manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), NBX-15, FTX-218 (trade names, manufactured by Neos Co., Ltd.); silicone surfactants such as "BYK" (registered trademark) F-333, 301, 331, 345, 307 (trade names, manufactured by BYK-Chemie Japan Co., Ltd.); polyoxyalkylene surfactants; and poly(meth)acrylate surfactants. It may also contain two or more of these compounds.

[0074] By including an adhesion modifier in the silicone resin composition for forming the curing film of the present invention, the adhesion to the substrate can be improved. Examples of adhesion modifiers include alicyclic epoxy compounds and silicone coupling agents. Among these, alicyclic epoxy compounds are preferred from the viewpoint of heat resistance.

[0075] Examples of alicyclic epoxy compounds include: 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinylcyclohexane, and butane. Tetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol A bis(propylene glycol glycidyl ether), hydrogenated bisphenol A bis(ethylene glycol glycidyl ether), 1,4-cyclohexanedicarboxylic acid diglycidyl ester, 1,4-cyclohexanediethanol diglycidyl ether, etc. It may also contain two or more of these compounds.

[0076] From the viewpoint of further improving adhesion to the substrate, the content of the adhesion modifier in the silicone resin composition for forming the curing film of the present invention is preferably 0.1% by mass or more, and more preferably 1% by mass or more, of the solid components. On the other hand, from the viewpoint of pattern processingability, the content of the adhesion modifier is preferably 20% by mass or less, and more preferably 10% by mass or less, of the solid components.

[0077] By including nanoparticles in the silicone resin composition for forming the hardened film of the present invention, the refractive index of the hardened film can be adjusted. Examples of nanoparticles include silicon dioxide particles, magnesium fluoride particles, titanium dioxide particles, and zirconium oxide particles. Two or more of these particles may also be included. To reduce the refractive index, it is preferable to include silicon dioxide particles and magnesium fluoride particles; to increase the refractive index, it is preferable to include titanium dioxide particles and zirconium oxide particles.

[0078] By including pigments in the silicone resin composition for forming the hardened film of the present invention, the reflectivity or opacity of the hardened film can be adjusted.

[0079] When it is desired to improve the reflectivity of the hardened film, it is preferable to contain a white pigment. Examples of white pigments include titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof. It may also contain two or more of these compounds.

[0080] When it is desired to improve the light-blocking properties of the hardened film at a specific wavelength, it is preferable to contain light-blocking pigments such as red pigment, blue pigment, black pigment, green pigment, and yellow pigment. Furthermore, when it is desirable to balance reflectivity and light-blocking properties, it is preferable to contain both white pigment and light-blocking pigment.

[0081] As a red pigment, examples include: pigment red (hereinafter referred to as PR) PR177, PR179, PR180, PR192, PR209, PR227, PR228, PR240, PR254, etc. It may also contain two or more of these compounds.

[0082] As a blue pigment, examples include: Pigment Blue (hereinafter referred to as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, PB64, etc. It may also contain two or more of these compounds.

[0083] Examples of black pigments include black organic pigments, mixed organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments. These can also be coated with resin. Examples of mixed organic pigments include pigments that simulate blackness by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, and cyan. Among these, a mixed pigment of red and blue pigments is preferred from the viewpoint of having both a moderately high OD value and pattern processing properties. The mass ratio of red pigment to blue pigment in the mixed pigment is preferably 20 / 80 to 80 / 20, more preferably 30 / 70 to 70 / 30. Examples of black inorganic pigments include: graphite; microparticles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zirconium, zinc, calcium, silver, gold, platinum, and palladium; metal oxides; metal complex oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. They may also contain two or more of these compounds.

[0084] Examples of green pigments include: CI pigment green (hereinafter referred to as PG) 7, PG36, PG58, PG37, PG59, etc. It may also contain two or more of these compounds.

[0085] As a yellow pigment, examples include: pigment yellow (hereinafter referred to as PY) PY150, PY153, PY154, PY166, PY168, PY185, etc. It may also contain two or more of these compounds.

[0086] The silicone resin composition for forming the hardened film of the present invention may also contain resins other than polysiloxanes. By containing resins other than polysiloxanes, for example, the film properties that are insufficient in polysiloxanes can be supplemented, such as improving the degummability after pre-baking. Examples of resins other than polysiloxanes include: polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, (meth)acrylic acid polymer, calomel resin, etc.

[0087] In the case where the (a) polysiloxane contains aromatic groups and / or substituted aromatic groups in the side chain groups, the silicone resin composition for forming the curing film of the present invention preferably has a content of less than 1 ppm for benzene, toluene, xylene, aniline, styrene and naphthalene in the resin composition.

[0088] Previously, when polysiloxanes containing aromatic groups and / or substituted aromatic groups in their side chains were obtained by condensation reaction using strong acid catalysts such as phosphoric acid or strong base catalysts, or when used with acid-generating materials / base-generating materials that generate strong acids / bases, a portion of the bond between the Si atoms in the polysiloxane and the side chain groups was cleaved, resulting in the generation of trace amounts of impurities originating from the side chain groups. For example, when polysiloxanes containing phenyl, toluene, xylene, phenylamino, styrene, or naphthyl groups in their side chains were obtained by condensation reaction using a phosphoric acid catalyst, there was a problem that they contained more than 1 ppm of benzene, toluene, xylene, aniline, styrene, or naphthalene as impurities.

[0089] On the other hand, the silicone resin composition for forming the hardened film of the present invention uses a polysiloxane formed by condensation using an organic salt (b) with a pH of 3.0 to 5.5 in a 1.0% by mass aqueous solution as a catalyst, or uses an organic salt (b) instead of an acid-generating material / alkali-generating material. Therefore, the side chain cleavage reaction described above is not caused, and the content of the impurity can be suppressed to less than 1 ppm.

[0090] Preferably, the silicone resin composition for forming the hardened film of the present invention is a permanent film, i.e., a resin composition for forming a permanent film. A permanent film is not a film that is removed during the manufacturing process, like a typical resist layer, but rather a hardened film that permanently remains on the product.

[0091] Next, the hardened film of the present invention will be described.

[0092] The curing film of the present invention is formed by curing the resin composition for forming the curing film of the present invention. Furthermore, the curing film of the present invention is preferably used as a permanent film.

[0093] Another aspect of the hardened film of the present invention is a hardened film in which the atomic ratio of N to Si, as measured by scanning electron microscopy (SEM-EDX), is 0.005 or more and 0.200 or less, and the atomic ratio of at least one of S, P, and F to Si is 0.005 or more and 0.200 or less. By having the atomic ratio within these ranges, both solvent resistance and permeability of the film can be achieved. The atomic ratio of N to Si and the atomic ratio of at least one of S, P, and F to Si are preferably 0.010 or more and 0.150 or less, more preferably 0.015 or more and 0.100 or less.

[0094] The hardened film of the present invention can be obtained by hardening the silicone resin composition for forming the hardened film by the method described later.

[0095] In addition to being preferably used as a protective film for touch panels and other hard coating films, the hardened film of the present invention is also preferably used as an insulating film for touch sensors, a planarization film for TFTs of liquid crystal or organic EL displays, a metal wiring protection film, an insulating film, an anti-reflective film, an outer coating for optical filters and color filters, a column, etc.

[0096] The thickness of the hardened film varies depending on the application, but is preferably 0.1 μm to 100 μm, and even more preferably 0.5 μm to 50 μm.

[0097] Next, the method for forming the hardened film of the present invention will be described by way of example.

[0098] The preferred method for forming the hardened film of the present invention comprises: a film-forming step of coating a silicone resin composition for forming the hardened film of the present invention onto a substrate and drying it to obtain a dry film; and a heating step of hardening the dry film by heating it. After the film-forming step, an exposure step of exposing the obtained dry film may also be included.

[0099] Examples of coating methods for the silicone resin composition used in the film-forming step include slot coating, spin coating, and spray coating. Examples of drying apparatus include hot air ovens or heating plates. The drying time is preferably 80°C to 130°C and preferably 1 minute to 30 minutes.

[0100] The exposure apparatus used in the exposure step can be, for example, a proximity exposure machine. The active light source used for illumination in the exposure step can be, for example, near-infrared light, visible light, or ultraviolet light, with ultraviolet light being preferred. Furthermore, the light source for ultraviolet light can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, or a germicidal lamp, but an ultra-high-pressure mercury lamp is preferred.

[0101] The exposure conditions can be selected appropriately according to the thickness of the dried film to be exposed. Generally, it is preferable to use an ultra-high pressure mercury lamp with an output power of 1 W / cm2 to 100 mW / cm2 and an exposure dose of 1 mJ / cm2 to 10,000 mJ / cm2.

[0102] The heating step is a step of heating and hardening the film. Examples of heating devices include heating plates and ovens. From the viewpoint of suppressing crack formation in the heated film, the heating temperature during the heating step is preferably 250°C or lower, more preferably 240°C or lower. On the other hand, from the viewpoint of the degree of hardening of the film, it is preferably 100°C or higher, and even more preferably 120°C or higher. The heating time is preferably 15 minutes to 2 hours. [Example]

[0103] Hereinafter, examples and comparative examples will be provided to describe the present invention in more detail, but the present invention is not limited to these scopes. Furthermore, the names of compounds used in this invention, which are referred to by abbreviations, will be shown below. PGMEA: Propylene glycol monomethyl ether acetate; DAA: Diacetone alcohol; BHT: Butylated hydroxytoluene.

[0104] The solid content concentration of the polysiloxane solution in Synthesis Examples 1 to 26 was determined by the following method: 1.0 g of polysiloxane solution was weighed into an aluminum cup, and heated at 250°C for 30 minutes using a heating plate to evaporate the liquid component. The mass of the solid component remaining in the aluminum cup after heating was weighed, and the solid content concentration was determined based on the ratio of the mass to the mass before heating.

[0105] The weight-average molecular weight of the polysiloxane solutions in Synthetic Examples 1 to 26 was determined by converting the polystyrene values ​​using the following method. Apparatus: GPC measuring apparatus (2695) with RI detector manufactured by Waters Corporation Column: PLgel MIXED-C column (manufactured by Polymer Laboratories, 300 mm) × two (connected in series) Measurement temperature: 40°C Flow rate: 1 mL / min Solvent: 0.5% by mass solution of tetrahydrofuran (THF) Standard substance: polystyrene Detection mode: RI.

[0106] The content ratio of each repeating unit in the polysiloxanes of Synthetic Examples 1 to 26 was determined by the following method. A polysiloxane solution was injected into a nuclear magnetic resonance (NMR) sample tube made of Teflon (registered trademark) with a diameter of 10 mm, and 29Si-NMR measurements were performed. The content ratio of each repeating unit was calculated based on the ratio of the integral value of Si derived from a specific organosilane to the total integral value of Si derived from the organosilane. The 29Si-NMR measurement conditions are shown below. Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by Nippon Electron Ltd.) Measurement method: gated decoupling method Nuclear frequency: 53.6693 MHz (29Si nucleus) Spectral width: 20000 Hz Pulse width: 12 μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: acetone-d6 Standard material: tetramethylsilane Measurement temperature: 23℃ Sample rotation speed: 0.0 Hz.

[0107] Synthesis Example 1: A polysiloxane (A-1) solution was placed in a 1000 ml three-necked flask containing 203.13 g (0.831 mol) of diphenyldimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.475 g of BHT, and 308.45 g of PGMEA. 76.39 g of water was added while stirring at 40°C for 30 minutes. A catalyst aqueous solution containing 3.887 g of p-toluenesulfonic acid pyridinium salt (1.0% by mass relative to the monomer content) was dissolved in a flask. The flask was then immersed in an oil bath at 70°C and stirred for 60 minutes, followed by a 30-minute heating process to 115°C. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C, and this was continued for 2 hours with heating and stirring (internal temperature 100°C–110°C) to obtain a polysiloxane solution. Furthermore, during heating and stirring, a mixture of 95% by volume nitrogen and 5% by volume oxygen was passed through at 0.05 L / min. A total of 173.99 g of methanol and water, as byproducts, were distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 50% by mass, specifically without removing the catalyst, to obtain a polysiloxane (A-1) solution. Furthermore, the obtained polysiloxane (A-1) has a weight-average molecular weight of 5,000. Additionally, the molar ratios of the repeating units derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-1) are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0108] Synthesis Example 2: The polysiloxane (A-2) solution was prepared by using an aqueous catalyst solution containing 3.887 g of pyridinium methanesulfonate (1.0% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-2) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-2) was 5,000. In addition, in polysiloxane (A-2), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0109] Synthesis Example 3: The polysiloxane (A-3) solution was prepared by using an aqueous catalyst solution containing 3.887 g of pyridinium trifluoromethanesulfonate (1.0% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-3) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the obtained polysiloxane (A-3) had a weight average molecular weight of 5,000. In addition, in polysiloxane (A-3), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0110] Synthesis Example 4: The polysiloxane (A-4) solution was prepared by using an aqueous catalyst solution containing 3.887 g of pyridinium trifluoroacetate (1.0% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-4) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-4) was 5,000. In addition, in polysiloxane (A-4), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0111] Synthesis Example 5: The polysiloxane (A-5) solution was prepared by using an aqueous catalyst solution containing 3.887 g of pyridinium benzenesulfonate (1.0% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-5) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the obtained polysiloxane (A-5) had a weight average molecular weight of 5,000. In addition, in polysiloxane (A-5), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0112] Synthesis Example 6: A polysiloxane (A-6) solution was obtained by using an aqueous catalyst solution containing 3.887 g of aniline benzenesulfonate salt (1.0% by mass relative to the monomer) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-6) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-6) was 5,000. In addition, in polysiloxane (A-6), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0113] Synthesis Example 7: A polysiloxane (A-7) solution was obtained by using an aqueous catalyst solution containing 3.887 g of tetraethylammonium p-toluenesulfonate (1.0% by mass relative to the monomer charge) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-7) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-7) was 1,200. In addition, in polysiloxane (A-7), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0114] Synthesis Example 8: A polysiloxane (A-8) solution was prepared by adding 213.82 g (0.875 mol) of diphenyldimethoxysilane, 43.12 g (0.175 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 68.86 g (0.263 mol) of tetraethoxysilane, 59.59 g (0.438 mol) of methyltrimethoxysilane, 1.413 g of BHT and 298.06 g of PGMEA to 76.39 g of an aqueous catalyst solution containing 3.887 g of pyridine p-toluenesulfonate (1.0% by mass relative to the monomers) in 76.39 g of water over 30 minutes while stirring at 40°C. Subsequently, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes. Then, over a period of 30 minutes, an aqueous solution of phosphoric acid containing 2.265 g of dissolved phosphoric acid (1.0% by mass relative to the monomer) was added to 52.65 g of water. The flask was then immersed in an oil bath at 70°C and stirred for 90 minutes. The oil bath temperature was then increased to 115°C over a period of 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C, and then heated and stirred for 2 hours (internal temperature 100°C–110°C) to obtain a polysiloxane solution. Furthermore, during the heating and stirring, a mixture of 95% nitrogen and 5% oxygen was passed through at a rate of 0.05 L / min. A total of 282.58 g of methanol and water were distilled off as byproducts during the reaction. PGMEA was added to the obtained polysiloxane solution at a solid content concentration of 50% by mass to obtain a polysiloxane (A-8) solution. Furthermore, the obtained polysiloxane (A-8) had a weight-average molecular weight of 8,000. Additionally, the molar ratios of repeating units derived from diphenyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, tetraethoxysilane, and methyltrimethoxysilane in polysiloxane (A-8) were 50 mol%, 10 mol%, 15 mol%, and 25 mol%, respectively.

[0115] Synthesis Example 9: A polysiloxane (A-9) solution was obtained by using an aqueous catalyst solution containing 3.887 g of phosphoric acid (1.0% by mass relative to the monomers) dissolved in 76.39 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-9) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-9) was 4,200. In addition, the molar ratios of the repeating units derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-9) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0116] Synthesis Example 10: A polysiloxane (A-10) solution was prepared by adding 2.00 g of a weakly basic ion exchange resin ("Amberlite" (registered trademark) A21, manufactured by Organo (stock) (hereinafter "A21")) and 2.00 g of a weakly acidic ion exchange resin ("Amberlite" (registered trademark) 15JWET, manufactured by Organo (stock) (hereinafter "15J"))) to 100 g of a polysiloxane (A-9) solution and stirring at room temperature for 12 hours. The ion exchange resin was then removed by filtration to obtain a polysiloxane (A-10) solution. Furthermore, the obtained polysiloxane (A-10) had a weight-average molecular weight of 4,500. In addition, in polysiloxane (A-10), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0117] Synthesis Example 11: A polysiloxane (A-11) solution was prepared by using an aqueous catalyst solution containing 0.389 g of pyridinium p-toluenesulfonate (1.0% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. The amount of PGMEA added was set to 311.95 g. Otherwise, the polysiloxane (A-11) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-11) was 2,500. In addition, in polysiloxane (A-11), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0118] Synthesis Example 12: A polysiloxane (A-12) solution was prepared by using an aqueous catalyst solution containing 11.66 g of pyridinium p-toluenesulfonate (3.0% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. The amount of PGMEA added was set to 300.68 g. Otherwise, the polysiloxane (A-12) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-12) was 6,500. In addition, in polysiloxane (A-12), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0119] Synthesis Example 13: A polysiloxane (A-13) solution was prepared by using an aqueous catalyst solution containing 0.039 g of pyridinium p-toluenesulfonate (0.01% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. The amount of PGMEA added was set to 312.30 g. Otherwise, the polysiloxane (A-13) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-13) was 6,500. In addition, in polysiloxane (A-13), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0120] Synthesis Example 14: A polysiloxane (A-14) solution was prepared by using an aqueous catalyst solution containing 21.38 g of pyridinium p-toluenesulfonate (5.5% by mass relative to the monomer content) dissolved in 76.39 g of water as the catalyst aqueous solution. The amount of PGMEA added was set to 290.96 g. Otherwise, the polysiloxane (A-14) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-14) was 6,500. In addition, in polysiloxane (A-14), the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0121] Synthesis Example 15 A polysiloxane (A-15) solution was prepared by adding 47.67 g (0.350 mol) of methyltrimethoxysilane, 152.11 g (0.613 mol) of 3-methacryloxypropyltrimethoxysilane, 152.74 g (0.700 mol) of trifluoropropyltrimethoxysilane, 22.95 g (0.088 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.282 g of BHT and 275.65 g of PGMEA to 96.08 g of an aqueous catalyst solution containing 3.755 g of p-toluenesulfonic acid pyridine salt (1.0% by mass relative to the monomers added) to 96.08 g of water for 30 minutes while stirring at 40°C. Subsequently, a polysiloxane (A-15) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight-average molecular weight of the obtained polysiloxane (A-15) was 4,500. Additionally, the molar ratios of the repeating units derived from methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, trifluoropropyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-15) were 35 mol%, 20 mol%, 40 mol%, and 5 mol%, respectively.

[0122] Synthesis Example 16: A polysiloxane (A-16) solution was obtained by using an aqueous catalyst solution containing 3.755 g of trifluoroacetic acid pyridinium salt (1.0% by mass relative to the monomers) dissolved in 96.08 g of water as the catalyst aqueous solution. Otherwise, the polysiloxane (A-16) solution was obtained in the same manner as in Synthesis Example 15. Furthermore, the weight average molecular weight of the obtained polysiloxane (A-16) was 4,500. In addition, the molar ratios of the repeating units derived from methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, trifluoropropyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-16) were 35 mol%, 20 mol%, 40 mol%, and 5 mol%, respectively.

[0123] Synthesis Example 17: A polysiloxane (A-17) solution was placed in a 1000 ml three-necked flask containing 176.49 g (0.831 mol) of p-tolyltrimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.245 g of BHT, and 267.12 g of PGMEA. The solution was stirred at 40°C for 30 minutes and then added to 91.35 g of water. A catalyst aqueous solution containing 3.621 g of pyridinium methanesulfonate (1.0% by mass relative to the monomers) was then prepared. Subsequently, a polysiloxane (A-17) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight-average molecular weight of the obtained polysiloxane (A-17) was 4,500. In addition, the molar ratios of the repeating units derived from p-tolyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-17) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0124] Synthesis Example 18: A polysiloxane (A-18) solution was placed in a 1000 ml three-necked flask containing 188.15 g (0.831 mol) of 3,5-dimethylphenyltrimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.245 g of BHT, and 278.67 g of PGMEA. The solution was stirred at 40°C for 30 minutes and then added to 91.35 g of water. A catalyst aqueous solution containing 3.738 g of pyridinium methanesulfonate salt (1.0% by mass relative to the monomers) was then prepared. Subsequently, a polysiloxane (A-18) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight-average molecular weight of the obtained polysiloxane (A-18) was 4,000. In addition, the molar ratios of the repeating units derived from 3,5-dimethylphenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-18) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0125] Synthesis Example 19: A polysiloxane (A-19) solution was placed in a 1000 ml three-necked flask containing 177.31 g (0.831 mol) of M-aminophenyltrimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.249 g of BHT, and 267.94 g of PGMEA. The solution was stirred at 40°C for 30 minutes and then added to 91.35 g of water. A catalyst aqueous solution containing 3.629 g of pyridinium methanesulfonate (1.0% by mass relative to the monomers) was then prepared. Subsequently, a polysiloxane (A-19) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight-average molecular weight of the obtained polysiloxane (A-19) was 5,000. In addition, the molar ratios of the repeating units derived from M-aminophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-19) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0126] Synthesis Example 20: A polysiloxane (A-20) solution was placed in a 1000 ml three-necked flask containing 186.45 g (0.831 mol) of p-styryltrimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.295 g of BHT, and 276.98 g of PGMEA. The solution was stirred at 40°C for 30 minutes and then added to 91.35 g of water. A catalyst aqueous solution containing 3.721 g of pyridinium methanesulfonate (1.0% by mass relative to the monomers) was then prepared. Subsequently, a polysiloxane (A-20) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight-average molecular weight of the obtained polysiloxane (A-20) was 6,600. In addition, the molar ratios of the repeating units derived from p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-20) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0127] Synthesis Example 21: A polysiloxane (A-21) solution was placed in a 1000 ml three-necked flask containing 206.44 g (0.831 mol) of 1-naphthyltrimethoxysilane, 76.06 g (0.306 mol) of 3-methacryloxypropyltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 42.08 g (0.350 mol) of dimethyldimethoxysilane, 45.91 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.396 g of BHT, and 296.77 g of PGMEA. The solution was stirred at 40°C for 30 minutes and then added to 91.35 g of water. An aqueous catalyst solution containing 3.920 g of pyridinium methanesulfonate (1.0% by mass relative to the monomers) was then prepared. Subsequently, a polysiloxane (A-21) solution was obtained in the same manner as in Synthesis Example 1. Furthermore, the weight-average molecular weight of the obtained polysiloxane (A-21) was 3,000. In addition, the molar ratios of the repeating units derived from 1-naphthyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-21) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0128] Synthesis Example 22: A polysiloxane (A-22) solution was prepared by adding 3.621 g of phosphoric acid (1.0% by mass relative to the monomer content) to 91.35 g of water as a catalyst aqueous solution. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 17. 2.00 g of A21 (as an ion exchange resin) and 2.00 g of 15JWET were added to 100 g of the obtained solution and stirred at room temperature for 12 hours. Subsequently, the ion exchange resin was removed by filtration to obtain a polysiloxane (A-22) solution. Furthermore, the obtained polysiloxane (A-22) had a weight-average molecular weight of 4,500. In addition, in polysiloxane (A-22), the molar ratios of each repeating unit derived from p-tolyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0129] Synthesis Example 23: A polysiloxane (A-23) solution was prepared by adding 3.621 g of phosphoric acid (1.0% by mass relative to the monomer content) to 91.35 g of water as a catalyst aqueous solution. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 18. 2.00 g of A21 (as an ion exchange resin) and 2.00 g of 15JWET were added to 100 g of the obtained solution and stirred at room temperature for 12 hours. Subsequently, the ion exchange resin was removed by filtration to obtain a polysiloxane (A-23) solution. Furthermore, the obtained polysiloxane (A-23) had a weight-average molecular weight of 4,500. In addition, in polysiloxane (A-23), the molar ratios of each repeating unit derived from 3,5-dimethylphenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0130] Synthesis Example 24: A polysiloxane (A-24) solution was prepared by adding 3.621 g of phosphoric acid (1.0% by mass relative to the monomer content) to 91.35 g of water as a catalyst aqueous solution. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 19. 2.00 g of A21 (as an ion exchange resin) and 2.00 g of 15JWET were added to 100 g of the obtained solution and stirred at room temperature for 12 hours. Subsequently, the ion exchange resin was removed by filtration to obtain a polysiloxane (A-24) solution. Furthermore, the obtained polysiloxane (A-24) had a weight-average molecular weight of 4,500. In addition, in polysiloxane (A-24), the molar ratios of each repeating unit derived from M-aminophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0131] Synthesis Example 25: A polysiloxane (A-25) solution was prepared by adding 3.621 g of phosphoric acid (1.0% by mass relative to the monomer content) to 91.35 g of water as a catalyst aqueous solution. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 20. 2.00 g of A21 (as an ion exchange resin) and 2.00 g of 15JWET were added to 100 g of the obtained solution and stirred at room temperature for 12 hours. Subsequently, the ion exchange resin was removed by filtration to obtain a polysiloxane (A-25) solution. Furthermore, the obtained polysiloxane (A-25) had a weight-average molecular weight of 6,500. In addition, in polysiloxane (A-25), the molar ratios of each repeating unit derived from p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0132] Synthesis Example 26: A polysiloxane (A-26) solution was prepared by adding 3.621 g of phosphoric acid (1.0% by mass relative to the monomer content) to 91.35 g of water as a catalyst aqueous solution. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 21. 2.00 g of A21 (as an ion exchange resin) and 2.00 g of 15JWET were added to 100 g of the obtained solution and stirred at room temperature for 12 hours. Subsequently, the ion exchange resin was removed by filtration to obtain a polysiloxane (A-26) solution. Furthermore, the obtained polysiloxane (A-26) had a weight-average molecular weight of 3,000. In addition, in polysiloxane (A-26), the molar ratios of each repeating unit derived from 1-naphthyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride are 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0133] The composition of Synthetic Examples 1 to 26 is summarized in Tables 1 to 4.

[0134] [Table 1] Raw materials (mol%) Condensation catalyst (Relative to the weight % of silane feedstock) catalyst Remove step Formula (4) Alkoxysilane Formula (5) Alkoxysilane other Alkoxy silane Catalyst types 1.0 wt% aqueous solution pH value Synthesis example 1 Polysiloxane (A-1) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - p-Toluene sulfonic acid Pyridine salts (1.0) 3.6 none Synthesis example 2 Polysiloxane (A-2) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - mesylate Pyridine salts (1.0) 3.3 none Synthesis example 3 Polysiloxane (A-3) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - Trifluoromethane sulfonic acid Pyridine salts (1.0) 3.5 none Synthesis example 4 Polysiloxane (A-4) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - Trifluoroacetic acid Pyridine salts (1.0) 3.3 none Synthesis example 5 Polysiloxane (A-5) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - benzenesulfonic acid Pyridine salts (1.0) 3.5 none Synthesis example 6 Polysiloxane (A-6) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - benzenesulfonic acid Aniline salts (1.0) 3.7 none Synthesis example 7 Polysiloxane (A-7) Solution Diphenyldimethoxysilane (47.5) Dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - p-Toluene sulfonic acid Tetraethylammonium (1.0) 5.9 none Synthesis example 8 Polysiloxane (A-8) Solution Diphenyldimethoxysilane (50) Methyltrimethoxysilane (25) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (10) Tetraethoxysilane (15) p-Toluene sulfonic acid Pyridine salts (1.0) 3.6 none

[0135] [Table 2] Raw materials (mol%) Condensation catalyst (Relative to the weight % of silane feedstock) catalyst Remove step Formula (4) Alkoxysilane Formula (5) Alkoxysilane other Alkoxy silane Catalyst types 1.0 wt% Aqueous solution pH value Synthesis example 9 Polysiloxane (A-9) Solution Diphenyldimethoxysilane (47.5) dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - Phosphoric acid (1.0) 1.5 none Synthesis example 10 Polysiloxane (A-10) Solution Diphenyldimethoxysilane (47.5) dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - Phosphoric acid (1.0) 1.5 have Synthesis example 11 Polysiloxane (A-11) Solution Diphenyldimethoxysilane (47.5) dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - p-Toluene sulfonic acid Pyridine salts (0.1) 3.6 none Synthesis example 12 Polysiloxane (A-12) Solution Diphenyldimethoxysilane (47.5) dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - p-Toluene sulfonic acid Pyridine salts (3.0) 3.6 none Synthesis example 13 Polysiloxane (A-13) Solution Diphenyldimethoxysilane (47.5) dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - p-Toluene sulfonic acid Pyridine salts (0.01) 3.6 none Synthesis example 14 Polysiloxane (A-14) Solution Diphenyldimethoxysilane (47.5) dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) - p-Toluene sulfonic acid Pyridine salts (5.5) 3.6 none

[0136] [Table 3] Raw materials (mol%) Condensation catalyst (Relative to the weight % of silane feedstock) catalyst Remove step Formula (4) Alkoxysilane Formula (5) Alkoxysilane other Alkoxy silane Catalyst types 1.0 wt% Aqueous solution pH value Synthesis example 15 Polysiloxane (A-15) Solution - 3-Methylpropenyloxypropyltrimethoxysilane (35) Methyltrimethoxysilane (20) Trifluoropropyltrimethoxysilane (40) 3-Trimethoxysilylpropylsuccinic anhydride (5) - p-Toluene sulfonic acid Pyridine salts (1.0) 3.6 none Synthesis example 16 Polysiloxane (A-16) Solution - 3-Methylpropenyloxypropyltrimethoxysilane (35) Methyltrimethoxysilane (20) Trifluoropropyltrimethoxysilane (40) 3-Trimethoxysilylpropylsuccinic anhydride (5) - Trifluoroacetic acid Pyridine salts (1.0) 3.3 none Synthesis example 17 Polysiloxane (A-17) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) p-Tolyltrimethoxysilane (47.5) - mesylate Pyridine salts (1.0) 3.3 none Synthesis example 18 Polysiloxane (A-18) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) 3,5-Dimethylphenyltrimethoxysilane (47.5) - mesylate Pyridine salts (1.0) 3.3 none Synthesis example 19 Polysiloxane (A-19) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) M-Aminophenyltrimethoxysilane (47.5) - mesylate Pyridine salts (1.0) 3.3 none Synthesis example 20 Polysiloxane (A-20) solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) p-Styryltrimethoxysilane (47.5) - mesylate Pyridine salts (1.0) 3.3 none Synthesis example twenty one Polysiloxane (A-21) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) 1-Naphthyltrimethoxysilane (47.5) - mesylate Pyridine salts (1.0) 3.3 none

[0137] [Table 4] Raw materials (mol%) Condensation catalyst (Relative to the weight % of silane feedstock) catalyst Remove step Formula (4) Alkoxysilane Formula (5) Alkoxysilane other Alkoxy silane Catalyst types 1.0 wt% Aqueous solution pH value Synthesis example twenty two Polysiloxane (A-22) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) p-Tolyltrimethoxysilane (47.5) - Phosphoric acid (1.0) 1.5 have Synthesis example twenty three Polysiloxane (A-23) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) 3,5-Dimethylphenyltrimethoxysilane (47.5) - Phosphoric acid (1.0) 1.5 have Synthesis example twenty four Polysiloxane (A-24) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) M-Aminophenyltrimethoxysilane (47.5) - Phosphoric acid (1.0) 1.5 have Synthesis example 25 Polysiloxane (A-25) solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) p-Styryltrimethoxysilane (47.5) - Phosphoric acid (1.0) 1.5 have Synthesis example 26 Polysiloxane (A-26) Solution dimethyldimethoxysilane (20) 3-Methylpropenyloxypropyltrimethoxysilane (17.5) 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane (5) 3-Trimethoxysilylpropylsuccinic anhydride (10) 1-Naphthyltrimethoxysilane (47.5) - Phosphoric acid (1.0) 1.5 have

[0138] Example 1 Silicone Resin Composition for Curing Film Formation (P-1) Under a yellow light, 65.7 g of a polysiloxane (A-1) solution containing p-toluenesulfonic acid pyridinium salt as an organic salt, 0.750 g of 1,2-octanedione as a photosensitizer (photopolymerization initiator), 1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime) ("Irgacure" (registered trademark) OXE-01, 0.750 g of BASF Japan (hereinafter "OXE-01")), 0.250 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure" 819, BASF Japan (hereinafter "IC-819")), 15.0 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure" 819, BASF Japan (hereinafter "IC-819")), 15.0 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide g of dipentaerythritol hexaacrylate as a photopolymerizable compound ("KAYARAD" (registered trademark) DPHA, manufactured by Shin Nippon Pharmaceutical Co., Ltd. (hereinafter "DPHA")), 0.150 g of ethyl bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] as an additive ("Irganox" (registered trademark) 1010, manufactured by BASF Japan Co., Ltd. (hereinafter "IRGANOX")), 1.00 g of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter "KBM-5103")), and acrylic surfactant ("BYK" (registered trademark) 352, manufactured by BYK-Chemie Chemical Co., Ltd.). 0.300 g (equivalent to a concentration of 300 ppm) of a 10% mass dilution solution of PGMEA manufactured by Japan (stock) (hereinafter referred to as "BYK-352") was dissolved in 6.90 g of PGMEA and 10.0 g of DAA solvents and stirred at room temperature. The resulting mixture was filtered through a 0.45 μm filter to obtain a silicone resin composition (P-1) for curing film formation.

[0139] Examples 2 to 6: Silicone Resin Compositions for Curing Film Formation (P-2) to (P-6) The polysiloxane (A-1) solution was replaced with polysiloxane (A-2) solution to polysiloxane (A-6) solution, and otherwise, the silicone resin compositions for curing film formation (P-2) to (P-6) were obtained in the same manner as in Example 1.

[0140] Example 7 Silicone Resin Composition for Curing Film Formation (P-7) Under yellow light, 92.9 g of a polysiloxane (A-8) solution containing p-toluenesulfonic acid pyridinium salt as an organic salt, 2.50 g of THP-17 (trade name, manufactured by Toyo Gosei Kogyo Co., Ltd.) as a photosensitizer (quinone diazide compound), 1.00 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter "KBM-303")), and 0.300 g (equivalent to a concentration of 300 ppm) of a 10% by mass diluted solution of PGMEA ("BYK" (registered trademark) 352, manufactured by BYK-Chemie Japan (hereinafter "BYK-352")) were dissolved in solvent PGMEA 0.258 g and DAA 3.00 g was stirred at room temperature. The resulting mixture was filtered through a 0.45 μm filter to obtain a silicone resin composition (P-7) for hardening film formation.

[0141] Example 8 Silicon oxane resin composition for curing film formation (P-8) The polysiloxane (A-1) solution was replaced with a polysiloxane (A-10) solution, and 0.657 g of p-toluenesulfonic acid pyridine salt was added as an organic salt. Otherwise, the silicone resin composition for curing film formation (P-8) was obtained in the same manner as in Example 1.

[0142] Examples 9 to 12 Silicone resin composition for curing film formation (P-9) to silicone resin composition for curing film formation (P-12) The polysiloxane (A-1) solution was changed to a polysiloxane (A-11) solution to a polysiloxane (A-14) solution, and otherwise, silicone resin composition for curing film formation (P-9) to silicone resin composition for curing film formation (P-12) were obtained in the same manner as in Example 1.

[0143] Examples 13 to 19 Silicone resin composition for curing film formation (P-13) to silicone resin composition for curing film formation (P-19) The polysiloxane (A-1) solution was changed to a polysiloxane (A-15) solution to a polysiloxane (A-21) solution, and otherwise, silicone resin composition for curing film formation (P-13) to silicone resin composition for curing film formation (P-19) were obtained in the same manner as in Example 1.

[0144] Example 20 Resin composition for isolation wall (P-20) 50.0 g of titanium dioxide pigment (CR-97; manufactured by Ishihara Sangyo Co., Ltd. (hereinafter "CR-97")) was mixed with 50.0 g of polysiloxane (A-1) solution obtained by Synthesis Example 1, and dispersed using a mill-type disperser filled with zirconia beads to obtain pigment dispersion (MW-1). Next, under a yellow light, 40.25 g of the pigment dispersion (MW-1), 15.70 g of a polysiloxane (A-1) solution containing p-toluenesulfonic acid pyridinium salt as an organic salt, 0.755 g of OXE-01 as a photosensitizer (photopolymerization initiator), 0.252 g of IC-819, 15.1 g of DPHA as a photopolymerizable compound, 0.151 g of IRGANOX 1010 as an additive, 1.01 g of KBM-5103, and 0.302 g (equivalent to a concentration of 300 ppm) of a 10% mass diluted solution of the acrylic surfactant BYK-352 in PGMEA were dissolved in solvents 17.02 g of PGMEA and 10.1 g of DAA, and stirred at room temperature. The obtained mixture was filtered using a 5.0 μm filter to obtain a silicone resin composition (P-20) for hardening membrane formation.

[0145] Example 21 Resin composition for isolation wall (P-21) 50.0 g of titanium dioxide pigment CR-97 and 50.0 g of polysiloxane (A-2) solution obtained by Synthesis Example 2 were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain pigment dispersion (MW-2). 40.25 g of the pigment dispersion (MW-2) was added to replace pigment dispersion MW-1, and 15.70 g of polysiloxane (A-2) solution containing pyridinium methanesulfonate was added to replace polysiloxane (A-1) solution. Otherwise, a silicone resin composition (P-21) for hardening film formation was obtained in the same manner as in Example 20.

[0146] Comparative Example 1 Silicon oxane resin composition for curing film formation (P-22) The polysiloxane (A-1) solution was changed to a polysiloxane (A-7) solution, and otherwise, the silicone resin composition for curing film formation (P-22) was obtained in the same manner as in Example 1.

[0147] Comparative Example 2 Silicone Resin Composition for Curing Film Formation (P-23) The polysiloxane (A-1) solution was replaced with a polysiloxane (A-9) solution containing phosphoric acid. Otherwise, the same silicone resin composition for curing film formation (P-23) was obtained as in Example 1.

[0148] Comparative Example 3 Silicon oxane resin composition for curing film formation (P-24) The polysiloxane (A-1) solution was changed to a polysiloxane (A-10) solution, and otherwise, the silicone resin composition for curing film formation (P-24) was obtained in the same manner as in Example 1.

[0149] Comparative Example 4 Silicone Resin Composition for Hardening Film Formation (P-25) Referring to Patent Document 6, under yellow light, a 20% by mass PGMEA solution of the reactant was prepared by reacting a phosphate derivative compound 2-methacryloxyethyl phosphate (trade name "P-1M", manufactured by Kyoei Chemical Co., Ltd.) with monoethanolamine in a mass ratio of 9.5:0.5. 2.47 g of the solution, 65.0 g of polysiloxane (A-1) solution, 0.742 g of OXE-01 as a photosensitizer (photopolymerization initiator), 0.247 g of IC-819, 14.8 g of DPHA as a photopolymerizable compound, 0.148 g of IRGANOX 1010 as an additive, 0.990 g of KBM-5103, and 0.300 g of a 10% mass diluted solution of BYK-352 PGMEA (equivalent to a concentration of 300 ppm) were dissolved in solvents 5.25 g of PGMEA and 10.0 g of DAA, and stirred at room temperature. The resulting mixture was filtered through a 0.45 μm filter to obtain a silicone resin composition (P-25) for curing film formation.

[0150] Comparative Examples 5 to 9 Silicone Resin Composition for Curing Film Formation (P-26) to Silicone Resin Composition for Curing Film Formation (P-30) The polysiloxane (A-10) solution was changed to a polysiloxane (A-22) solution to a polysiloxane (A-26) solution, and otherwise, the silicone resin composition for curing film formation (P-26) to silicone resin composition for curing film formation (P-30) were obtained in the same manner as in Comparative Example 3.

[0151] The composition of Examples 1 to 21 and Comparative Examples 1 to 9 is summarized in Tables 5 to 7.

[0152] [Table 5] resin Composition (a) Polysiloxane (weight%) (b) Organic salts (relative to (a) polysiloxane by weight %) (c) Solvent (weight%) (d) Photosensitive agent (weight%) additive (weight%) other (weight%) type pH value of 1.0 wt% aqueous solution Example 1 P-1 A-1 (32.5) p-Toluenesulfonic acid pyridine salt (1.0) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 2 P-2 A-2 (32.5) Pyridine Mesylate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 3 P-3 A-3 (32.5) Pyridine trifluoromethanesulfonate (1.0) 3.5 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 4 P-4 A-4 (32.5) Pyridine trifluoroacetate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 5 P-5 A-5 (32.5) Pyridine benzenesulfonate (1.0) 3.5 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 6 P-6 A-6 (32.5) Benzenesulfonate aniline salt (1.0) 3.7 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 7 P-7 A-8 (46.0) p-Toluenesulfonic acid pyridine salt (1.0) 3.6 PGMEA (47) DAA (3) THP-17 (2.5) KBM-303 (1.0) - Example 8 P-8 A-10 (32.5) p-Toluenesulfonic acid pyridine salt (1.0) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 9 P-9 A-11 (32.8) p-Toluenesulfonic acid pyridine salt (0.1) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 10 P-10 A-12 (31.9) p-Toluenesulfonic acid pyridine salt (3.0) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 11 P-11 A-13 (32.8) p-Toluenesulfonic acid pyridine salt (0.01) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 12 P-12 A-14 (31.0) p-Toluenesulfonic acid pyridine salt (5.5) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) -

[0153] [Table 6] resin Composition (a) Polysiloxane (weight%) (b) Organic salts (relative to (a) polysiloxane by weight %) (c) Solvent (weight%) (d) Photosensitive agent (weight%) additive (weight%) other (weight%) type 1.0 wt% pH value of aqueous solution Example 13 P-13 A-15 (32.5) p-Toluenesulfonic acid pyridine salt (1.0) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 14 P-14 A-16 (32.5) Pyridine trifluoroacetate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 15 P-15 A-17 (32.5) Pyridine Mesylate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 16 P-16 A-18 (32.5) Pyridine Mesylate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 17 P-17 A-19 (32.5) Pyridine Mesylate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 18 P-18 A-20 (32.5) Pyridine Mesylate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Example 19 P-19 A-21 (32.5) Pyridine Mesylate (1.0) 3.3 PGMEA (47) DAA (3) THP-17 (2.5) KBM-303 (1.0) - Example 20 P-20 A-1 (12.8) p-Toluenesulfonic acid pyridine salt (1.0) 3.6 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) CR-97 (20) Example twenty one P-21 A-2 (12.8) Pyridine Mesylate (1.0) 3.3 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) CR-97 (20)

[0154] [Table 7] resin composition (a) Polysiloxane (wt%) (b) Organic salts (relative to (a) polysiloxane by weight %) (c) Solvent (weight%) (d) Photosensitive agent (weight%) additive (weight%) other (weight%) type 1.0 wt% pH value of aqueous solution Comparative example 1 P-22 A-7 (32.5) Tetraethylammonium p-toluenesulfonate (1.0) 5.9 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 2 P-23 A-9 (32.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) Phosphoric acid (0.4%) Comparative example 3 P-24 A-10 (33.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 4 P-25 A-10 (32.5) P1-M: Monoethanolamine =9.5:0.5 (1.0) 2.5 PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 5 P-26 A-22 (33.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 6 P-27 A-23 (33.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 7 P-28 A-24 (33.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 8 P-29 A-25 (33.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) - Comparative example 9 P-30 A-26 (33.5) - - PGMEA (40) DAA (10) OXE-01 (0.8) IC-819 (0.3) DPHA (15) Irganox 1010 (0.2) KBM-5103 (1.0) -

[0155] The following shows the evaluation methods in Examples 22 to 42 and Comparative Examples 10 to 18.

[0156] <Storage Stability> For the silicone resin compositions for curing film formation obtained by the various examples and comparative examples, the viscosity (viscosity before storage) was measured after blending. The viscosity measurement was performed at 23°C using an E-type rotational viscometer (VISCOMETER TV-25 (manufactured by TOKI SANGYO)). In addition, the silicone resin compositions for curing film formation obtained by the various examples and comparative examples were placed in sealed containers, and the viscosity was measured after seven days of storage at room temperature (23°C) and three days of storage at room temperature (40°C). Based on the viscosity change rate ({|viscosity after storage - viscosity before storage| / viscosity before storage}×100), the storage stability was evaluated according to the following criteria for each storage condition: A: Viscosity change rate less than 5% B: Viscosity change rate 5% or more and less than 10% C: Viscosity change rate 10% or more.

[0157] <Pattern Processability> Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the silicone resin composition for forming a hardened film obtained by each example and comparative example was spin-coated onto the original glass substrate. A film with a thickness of 10 μm was pre-baked at 100°C for 2 minutes using a heating plate (trade name SCW-636, manufactured by Dainippon Screen Co., Ltd.).

[0158] For the fabricated film, a parallel light mask was aligned with an exposure machine (trade name PLA-501F, manufactured by Canon, Inc.), using an ultra-high pressure mercury lamp as the light source. A grayscale mask with line and spatial patterns of widths of 100 μm, 50 μm, 40 μm, 30 μm, 20 μm, and 10 μm was used, with a gap of 100 μm, and exposure was performed at an exposure dose of 100 mJ / cm2. Subsequently, an automatic developing device (manufactured by Mikasa, Inc., "AD-1200 (trade name)") was used for 60 seconds of spray development with 2.38% TMAH by mass, followed by 30 seconds of rinsing with water.

[0159] The smallest pattern size after exposure and development is used as the resolution. Furthermore, the developed pattern is observed using a microscope adjusted to 50-100x magnification. Based on the degree of dissolution residue in the unexposed areas, the following criteria are used to evaluate the development residue: A: No residue was found in fine patterns smaller than 50 μm. B: No residue was found in patterns larger than 50 μm, but residue was found in patterns smaller than 50 μm. C: Residue was found in patterns larger than 50 μm.

[0160] <Solvent Resistance> Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the silicone resin composition for forming a hardened film obtained by the various examples and comparative examples was spin-coated onto the original glass substrate. A film with a thickness of 11 μm was produced by pre-baking at 100°C for 2 minutes using a heating plate (trade name SCW-636, manufactured by Dainippon Screen Co., Ltd.).

[0161] For the fabricated film, a parallel light mask was used to align with an exposure machine (trade name PLA-501F, manufactured by Canon, Inc.), and an ultra-high pressure mercury lamp was used as the light source for exposure at an exposure dose of 100 mJ / cm². Subsequently, an automatic developing apparatus (Mikasa, Inc., "AD-1200 (trade name)") was used for 60 seconds of spray development with 2.38% TMAH by mass, followed by a 30-second rinse with water. For the developed film, an oven (trade name IHPS-222, manufactured by Espec, Inc.) was used to cure the film in air at 180°C for 1 hour to produce a 10 μm thick hardened film.

[0162] As the solvent for the solvent resistance test, a resist stripping solution, TOK106 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), was selected. The hardened film was immersed in it at 70°C for 5 minutes to conduct the solvent resistance test. The film thickness before and after the solvent resistance test was measured. Based on the film thickness change rate ({|film thickness after solvent resistance test - film thickness before solvent resistance test| / film thickness before solvent resistance test}×100), the solvent resistance was evaluated according to the following criteria: A: Film thickness change rate less than 1% B: Film thickness change rate 1% or more and less than 5% C: Film thickness change rate 5% or more.

[0163] <Transmittance> Using the silicone resin composition for forming the hardened film obtained by the various examples and comparative examples, the hardened film was prepared in the same manner as evaluated for <Substrate Adhesion>. For the obtained glass substrate with the hardened film, the transmittance of ultraviolet and visible light (300 nm to 800 nm) was measured using a spectrophotometer (U-4100 (manufactured by Hitachi High-Tech Co., Ltd.)) with the glass substrate used as a reference. Based on the transmittance value at a wavelength of 400 nm, the transmittance of the hardened film was evaluated according to the following criteria: A: Transmittance ≥ 90% B: Transmittance < 90%.

[0164] <Refractive Index> Using the silicone resin composition for forming the hardened film obtained by the various examples and comparative examples, a hardened film with a thickness of 2 μm was formed on a silicon wafer, in the same manner as the evaluation of <substrate adhesion>. For the obtained silicon wafer with the hardened film, using a prism coupler (PC-2000 (manufactured by Metricon (stock))), under atmospheric pressure and at 20°C, light with a wavelength of 550 nm was irradiated from a direction perpendicular to the surface of the hardened film, and the refractive index was measured and rounded to three decimal places. Furthermore, for Examples 41 and 42, the hardened film was white, and it could not be measured due to reflection of the irradiated light, so it is recorded as "-" in the table.

[0165] <b* value> Using the silicone resin composition for forming the hardened film obtained by the various embodiments and comparative examples, the hardened film was prepared in the same manner as the evaluation of <substrate adhesion>. For the obtained glass substrate with the hardened film, the colorimetry (b* value) was measured from the hardened film side using a spectrophotometer (trade name CM-2600d, manufactured by Konica Minolta, Inc.) in Specular Component Included (SCI) mode. Furthermore, the larger the b* value, the greater the yellowing of the hardened film.

[0166] <SEM-EDX Measurement> Using the silicone resin composition for forming the hardened film obtained by the various examples and comparative examples, the curing temperature was set to 150°C. Otherwise, the hardened film was prepared in the same manner as the evaluation of <substrate adhesion>. The obtained hardened film was observed using a scanning electron microscope, and EDX analysis was performed at an accelerating voltage of 15 kV. Semi-quantitative calculations were performed using ZAF correction calculations. N (moles%) / Si (moles%) was calculated as the atomic ratio of N to Si, S (moles%) / Si (moles%) was calculated as the atomic ratio of S to Si, P (moles%) / Si (moles%) was calculated as the atomic ratio of P to Si, and F (moles%) / Si (moles%) was calculated as the atomic ratio of F to Si.

[0167] <Impurity Analysis> For the silicone resin compositions for curing film formation obtained by the various examples and comparative examples, the contents of benzene, toluene, xylene, aniline, styrene, and naphthalene in the resin compositions were analyzed and quantified by gas chromatography / mass spectrometry (GC / MS). Furthermore, regarding the pretreatment method, the analysis of benzene, toluene, xylene, and styrene was performed according to the EPA 5021A method specified by the U.S. Environmental Protection Agency (EPA). The analysis of aniline was performed according to the European / General Test Method EN14362-1. Furthermore, the analysis of naphthalene was performed according to the AfPS GS 2019:01PAK method of the German Federal Institute for Risk Assessment. The detected values ​​are summarized in the table. Values ​​below the detection limit (1 ppm) are recorded as "<1".

[0168] The evaluation results of each embodiment and comparative example are shown in Tables 8 to 9.

[0169] [Table 8-1] resin Composition Preservation stability Pattern processing Solvent resistance Transparency Refractive index b* value SEM-EDX measurement room temperature 40℃ Resolution (μm) Developing residue N / Si S / Si P / Si F / Si Actual example 22 P-1 A A 20 A A A 1.54 0.4 0.050 0.050 0.002 0 Actual example 23 P-2 A A 20 A A A 1.54 -0.4 0.050 0.050 0.002 0 Actual example 24 P-3 A A 20 A A A 1.52 0.6 0.050 0.050 0.002 0.150 Actual example 25 P-4 A A 20 A A A 1.52 0.6 0.050 0 0.002 0.150 Actual example 26 P-5 A A 20 A A A 1.54 0.5 0.050 0.050 0.002 0 Actual example 27 P-6 A A 30 A A B 1.54 2.5 0.050 0.050 0.002 0 Actual example 28 P-7 A A 10 A A A 1.52 0.2 0.050 0.050 0 0 Actual example 29 P-8 A A 20 A A A 1.54 0.4 0.050 0.050 0.002 0 Actual example 30 P-9 A A 20 A B A 1.54 0.1 0.004 0.004 0.002 0 Example 31 P-10 A B 30 A A B 1.54 0.9 0.140 0.140 0.002 0 Example 32 P-11 A A 20 A B A 1.54 0.1 0.001 0.001 0.002 0 Example 33 P-12 B B 40 B A B 1.54 1.5 0.250 0.250 0.002 0 Example 34 P-13 A A 20 A A A 1.47 0.3 0.050 0.050 0.002 0 Example 35 P-14 A A 20 A A A 1.45 0.4 0.050 0 0.002 0.150 Actual example 36 P-15 A A 20 A A A 1.51 0.1 0.050 0.050 0.002 0 Actual example 37 P-16 A A 20 A A A 1.51 0.1 0.050 0.050 0.002 0 Actual example 38 P-17 B B 40 B A B 1.51 1.5 0.050 0.050 0.002 0 Actual example 39 P-18 A A 20 A A A 1.50 0.1 0.050 0.050 0.002 0 Example 40 P-19 A A 30 A A A 1.57 0.5 0.050 0.050 0.002 0 Example 41 P-20 A A 30 A A B - 2.5 0.050 0.050 0.002 0 Example 42 P-21 A A 30 A A B - 0.5 0.050 0.050 0.002 0

[0170] [Table 8-2] resin Composition Impurity analysis (ppm) benzene Toluene xylene aniline styrene Naphthalene Example 22 P-1 <1 <1 <1 <1 <1 <1 Example 23 P-2 <1 <1 <1 <1 <1 <1 Example 24 P-3 <1 <1 <1 <1 <1 <1 Example 25 P-4 <1 <1 <1 <1 <1 <1 Example 26 P-5 <1 <1 <1 <1 <1 <1 Example 27 P-6 <1 <1 <1 <1 <1 <1 Example 28 P-7 <1 <1 <1 <1 <1 <1 Example 29 P-8 15 <1 <1 <1 <1 <1 Example 30 P-9 <1 <1 <1 <1 <1 <1 Example 31 P-10 <1 <1 <1 <1 <1 <1 Example 32 P-11 <1 <1 <1 <1 <1 <1 Example 33 P-12 <1 <1 <1 <1 <1 <1 Example 34 P-13 <1 <1 <1 <1 <1 <1 Example 35 P-14 <1 <1 <1 <1 <1 <1 Example 36 P-15 <1 <1 <1 <1 <1 <1 Example 37 P-16 <1 <1 <1 <1 <1 <1 Example 38 P-17 <1 <1 <1 <1 <1 <1 Example 39 P-18 <1 <1 <1 <1 <1 <1 Example 40 P-19 <1 <1 <1 <1 <1 <1 Example 41 P-20 <1 <1 <1 <1 <1 <1 Example 42 P-21 <1 <1 <1 <1 <1 <1

[0171] [Table 9-1] resin Composition Preservation stability Pattern processing Solvent resistance Transparency Refractive index b* value SEM-EDX measurement room temperature 40℃ Resolution (μm) Developing residue N / Si S / Si P / Si F / Si Comparative Example 10 P-22 A A 30 A C A 1.54 0.4 0.050 0 0 0 Comparative Example 11 P-23 C C 100 C A A 1.54 0.4 0 0 0.050 0 Comparative Example 12 P-24 A A 20 A C A 1.54 0.4 0 0 0 0 Comparative Example 13 P-25 A C 20 A A A 1.54 0.4 0.050 0 0.050 0 Comparative Example 14 P-26 A A 20 A A A 1.51 0.1 0.050 0.050 0.002 0 Comparative Example 15 P-27 A A 20 A A A 1.51 0.1 0.050 0.050 0.002 0 Comparative Example 16 P-28 B B 40 B A B 1.51 1.5 0.050 0.050 0.002 0 Comparative Example 17 P-29 A A 20 A A A 1.50 0.1 0.050 0.050 0.002 0 Comparative Example 18 P-30 A A 30 A A A 1.57 0.5 0.050 0.050 0.002 0

[0172] [Table 9-2] resin Composition Impurity Analysis benzene Toluene xylene aniline styrene Naphthalene Comparative Example 10 P-22 <1 <1 <1 <1 <1 <1 Comparative Example 11 P-23 12 <1 <1 <1 <1 <1 Comparative Example 12 P-24 15 <1 <1 <1 <1 <1 Comparative Example 13 P-25 3 <1 <1 <1 <1 <1 Comparative Example 14 P-26 <1 10 <1 <1 <1 <1 Comparative Example 15 P-27 <1 <1 12 <1 <1 <1 Comparative Example 16 P-28 <1 <1 <1 8 <1 <1 Comparative Example 17 P-29 <1 <1 <1 <1 5 <1 Comparative Example 18 P-30 <1 <1 <1 <1 <1 15 [Simplified Explanation of the Diagram]

[0015] None

Claims

1. A silicone resin composition for forming a curable film, comprising (a) a polysiloxane, (b) an organic salt, (c) a solvent, and (d) a photosensitizer, wherein, The pH value of the organic salt in a 1.0% by mass aqueous solution is 3.0 to 5.5, and the photosensitizer is a photopolymerizable compound or a quinone diazide compound. The content of the organic salt in (b) is 0.1 to 5.00 parts by mass relative to 100 parts by mass of the polysiloxane in (a).

2. The silicone resin composition for forming a hardened film as described in claim 1, wherein, The content of the organic salt in (b) is 1.0 to 5.00 parts by mass relative to 100 parts by mass of the polysiloxane in (a).

3. The silicone resin composition for forming a hardened film as described in claim 1, wherein, The organic salt (b) is an organic salt containing organic acids and amines having the structure represented by any one of the following general formulas (1) to (3), wherein in general formulas (1) to (2), R1 to R2 independently represent a monovalent organic group having 1 to 30 carbon atoms or a divalent organic group having 1 to 30 carbon atoms. Examples of monovalent organic groups include substituted or unsubstituted linear or branched alkyl groups, substituted or unsubstituted cyclic alkyl groups, substituted or unsubstituted aryl groups, and perfluoroalkyl groups. Examples of divalent organic groups include substituted or unsubstituted enylalkyl groups, substituted or unsubstituted enylene groups, and substituted or unsubstituted enylphenyl groups. In general formula (3), n represents 0, 1 or 2. When n=1, R3 in general formula (3) represents a monovalent organic group with 1 to 30 carbons or a divalent organic group with 1 to 30 carbons. When n=2, R3 in general formula (3) can be the same or different, representing hydrogen, a monovalent organic group with 1 to 30 carbons, or a divalent organic group with 1 to 30 carbons.

4. The silicone resin composition for forming a hardened film as described in claim 3, wherein, The amines are heterocyclic amines or aromatic amines.

5. The silicone resin composition for forming a hardened film as described in claim 3, wherein, The organic acids having a structure represented by any one of general formulas (1) to (3) are organic acids selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, trifluoropropanesulfonic acid, and trifluoroacetic acid.

6. The silicone resin composition for forming a hardened film as described in claim 4, wherein, The heterocyclic or aromatic amines are selected from the group consisting of pyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine and aniline.

7. The silicone resin composition for forming a hardened film as described in claim 1, wherein, The polysiloxane (a) has aromatic groups and / or substituted aromatic groups in its side chain, and the contents of benzene, toluene, xylene, aniline, styrene and naphthalene in the resin composition are each less than 1 ppm.

8. The silicone resin composition for forming a hardened film as described in claim 1, wherein, Hardened films are permanent films.

9. A curing film formed by curing a silicone resin composition for curing a curing film as described in any one of claims 1 to 8.

10. The hardened film as claimed in claim 9, wherein, The atomic ratio of N to Si, as determined by scanning analytical electron microscopy (scanning electron microscopy-energy dispersive X-ray spectroscopy), is 0.005 or more and 0.200 or less, and the atomic ratio of at least one of S, P, and F to Si is 0.005 or more and 0.200 or less.