Method for producing polysiloxane solution

Abstract

To comparatively inexpensively provide a siloxane resin composition for cured film formation from which a cured film that is excellent in storage stability and solvent resistance can be obtained, and to produce polysiloxane having good storage stability even when eliminating a catalyst removal step.SOLUTION: A resin composition for cured film formation contains polysiloxane, an organic salt and a solvent, wherein a pH value in a 1.0 mass% aqueous solution of the organic salt is 3.0-5.5. There is provided a production method of polysiloxane using alkoxysilane as a raw material and an organic salt as a catalyst of hydrolysis and / or thermal condensation, wherein a pH value in the 1.0 mass% aqueous solution of the organic salt is 3.0-5.5.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a siloxane resin composition for forming a cured film, a cured film, and a method for producing a polysiloxane. [Background technology]

[0002] Resin compositions containing polysiloxanes have excellent heat resistance, weather resistance, and transparency, and are therefore widely used in a variety of applications, including optical lenses such as microlens arrays for solid-state imaging devices, planarizing films for TFTs in liquid crystal and organic electroluminescence displays, protective and insulating films for touch panels, anti-reflection films, and optical filters.

[0003] These applications generally require cured films with excellent properties such as solvent resistance, and in order to achieve the required properties, it is necessary to increase the degree of curing of the film by promoting the reaction between polysiloxanes in the film (condensation reaction between silanol groups) during the formation of the cured film.

[0004] To promote such reactions, it is effective to include a polysiloxane condensation catalyst, such as an acid catalyst or a base catalyst, in the resin composition, but if such a catalyst and polysiloxane are included at the same time, the reaction between silanol groups progresses over time, causing problems such as thickening and gelation, and deteriorating storage stability. Therefore, a method has been reported in which an acid generator or base generator is used to promote the curing of the film by the acid or base generated during the exposure step and / or heating step (e.g., Patent Documents 1 and 2).

[0005] Moreover, such industrially used polysiloxanes are often synthesized by the sol-gel method using an alkoxysilane compound as a raw material, utilizing hydrolysis and polycondensation reactions. In general, in the sol-gel method, an acid or base catalyst is used to promote the hydrolysis and condensation reactions, but if these catalysts remain in the polysiloxane solution after the reaction, problems such as thickening and gelation over time as described above occur. For this reason, in practice, a catalyst removal process (or neutralization reaction) is often required after the reaction. However, the introduction of these processes not only increases costs, but also poses problems such as a decrease in yield and an increase in impurities.

[0006] In order to obtain a polysiloxane having excellent storage stability without removing the catalyst, Patent Document 3 reports a method using a fluoride salt, which is a neutral compound, as a catalyst.

[0007] Moreover, Patent Document 4 proposes a synthesis method using a neutral salt as a catalyst. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2004-107562 A [Patent Document 2] JP 2006-154037 A [Patent Document 3] Japanese Patent Application Publication No. 7-292108 [Patent Document 4] International Publication No. 2016 / 098596 [Patent Document 5] JP 2006-106311 A [Patent Document 6] Patent No. 645892 Summary of the Invention [Problem to be solved by the invention]

[0009] However, the techniques of Patent Documents 1 and 2 have problems in that effective acid generators and base generators are generally expensive. In addition, when there is metal wiring in the base, there is also a problem that the wiring may corrode.

[0010] In the technology of Patent Document 3, many fluoride salts are known to generate highly toxic hydrofluoric acid in an acidic aqueous solution, raising concerns about safety and substrate corrosion.

[0011] In the technology of Patent Document 4, magnesium chloride and sodium chloride are given as suitable examples of neutral salt catalysts, but when used in semiconductor applications, there is concern that alkali metal impurities derived from the catalyst will be a problem. In addition, since these neutral salt catalysts are salts of strong acids and strong bases, the pH of the aqueous solution is about 7, and there is concern that the hydrolysis of the alkoxysilane compound will not proceed easily, and the subsequent polycondensation reaction will also not proceed easily.

[0012] The present invention aims to provide a relatively inexpensive siloxane resin composition for forming a cured film, which can give a cured film having excellent storage stability and excellent solvent resistance, and to produce a polysiloxane having good storage stability without a catalyst removal step. [Means for solving the problem]

[0013] The present invention is as follows. [1] A resin composition for forming a cured film, comprising (a) a polysiloxane, (b) an organic salt, and (c) a solvent, wherein the organic salt (b) has a pH value of 3.0 to 5.5 in a 1.0 mass % aqueous solution. [2] The siloxane resin composition for forming a cured film according to [1], wherein the content of the (b) organic salt is 0.01 to 5.00 parts by mass per 100 parts by mass of the (a) polysiloxane. [3] The cured film-forming polysiloxane resin composition according to [1] or [2], wherein the (b) organic salt is an organic salt composed of an organic acid having a structure represented by any one of general formulas (1) to (3) described below and an amine. [4] The siloxane resin composition for forming a cured film according to [3], wherein the amines are heterocyclic amines or aromatic amines. [5] The siloxane resin composition for forming a cured film according to [3] or [4], wherein the organic acid having a structure represented by any one of the 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 siloxane resin composition for forming a cured film according to [4], wherein the heterocyclic amines 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 siloxane resin composition for forming a cured film according to any one of [1] to [6], further comprising (d) a photosensitizer. [8] The siloxane resin composition for forming a cured film according to any one of [1] to [7], wherein the (a) polysiloxane has an aromatic group and / or a substituted aromatic group in a side chain group, and the content of benzene, toluene, xylene, aniline, styrene and naphthalene in the resin composition is each less than 1 ppm. [9] The siloxane resin composition for forming a cured film according to any one of [1] to [8], wherein the cured film is a permanent film.

[10] A cured film obtained by curing the resin composition for forming a cured film according to any one of [1] to [9].

[11] A cured film in which the atomic ratio of N to Si is 0.005 or more and 0.200 or less, and the atomic ratio of at least one atom selected from S, P and F to Si is 0.005 or more and 0.200 or less, as measured with a scanning electron microscope (SEM-EDX).

[12] The cured film according to

[10] , wherein the atomic ratio of N to Si is 0.005 or more and 0.200 or less, and the atomic ratio of at least one atom selected from S, P and F to Si is 0.005 or more and 0.200 or less, as measured with a scanning electron microscope (SEM-EDX).

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

[0014] The present invention provides a siloxane resin composition for forming a cured film, which can provide a cured film having excellent storage stability and excellent solvent resistance. The present invention also provides a cured film having excellent solvent resistance. Furthermore, the present invention provides a method for producing a polysiloxane having good storage stability, even without a catalyst removal step. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015]

[0043] Preferred embodiments of the siloxane resin composition for forming a cured film, the cured film, and the method for producing a polysiloxane according to the present invention will be specifically described below. However, the present invention is not limited to the following embodiments, and can be modified in various ways depending on the purpose and application.

[0016] The resin composition for forming a cured film of the present invention contains (a) a polysiloxane, (b) an organic salt, and (c) a solvent.

[0017] (a) Polysiloxane The (a) polysiloxane is a hydrolysis / dehydration condensation product of an alkoxysilane compound. The (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). When a thick film having a thickness of 10 μm or more is formed, it is preferable to contain a repeating unit derived from a bifunctional alkoxysilane compound represented by general formula (4). By containing a repeating unit derived from a bifunctional alkoxysilane compound represented by general formula (4), excessive thermal polymerization (condensation) of the polysiloxane due to heating can be suppressed, and the crack resistance of the cured film can be improved. In addition, by containing a repeating unit derived from a trifunctional alkoxysilane compound represented by general formula (5), the crosslink density of the polysiloxane after film formation can be increased, and the hardness of the cured film can be improved.

[0018] [ka]

[0019] In the above general formula (4), R 4 and R 5 R may be the same or different and each represents a monovalent organic group having 1 to 20 carbon atoms. 4 and R 5 may be partially substituted with a radical polymerizable group. In this case, in the cured product of the resin composition, the radical polymerizable group may be radically polymerized. Examples of the radical polymerizable group include a vinyl group, a (meth)acrylic group, and a styryl group. In addition, when different R 4 and R 5 The repeating unit may contain two or more kinds of repeating units represented by general formula (4).

[0020] In the above general formula (5), R 6 R represents a monovalent organic group having 1 to 20 carbon atoms. 6may be partially substituted with a radical polymerizable group. In this case, in the cured product of the resin composition, the radical polymerizable group may be radically polymerized. Examples of the radical polymerizable group include a vinyl group, a (meth)acrylic group, and a styryl group. In addition, when different R 6 The repeating unit may contain two or more kinds of repeating units represented by general formula (5).

[0021] The repeating units represented by the above general formulas (4) and (5) are derived from alkoxysilane compounds represented by the following general formulas (6) and (7), respectively. That is, polysiloxanes containing repeating units represented by the above general formulas (4) and (5) can be obtained by hydrolysis and polycondensation of alkoxysilane compounds containing alkoxysilane compounds represented by the following general formulas (6) and (7). Other alkoxysilane compounds may also be used.

[0022] [ka]

[0023] In the above general formulas (6) and (7), R 4 ~R 6 R in general formulas (4) and (5), respectively. 4 ~R 6 R represents the same group as 7 may be the same or different and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and preferably hydrogen or an alkyl group having 1 to 6 carbon atoms.

[0024] Examples of the alkoxysilane compound represented by the general formula (6) include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, vinylmethyldimethoxysilane, , vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, gamma-methacryloylpropylmethyldimethoxysilane, gamma-methacryloylpropylmethyldiethoxysilane, gamma-acryloylpropylmethyldimethoxysilane, gamma-acryloylpropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-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-dimethylethoxysilylpropyl Examples of the silylsilane include propyl 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, and diphenylsilanediol. Two or more of these may be used.

[0025] Examples of the alkoxysilane compound represented by the general formula (7) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy ... trifunctional alkoxysilane compounds such as propyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane. Epoxy group or oxetane group-containing alkoxysilane compounds such as methyl}oxetane: phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropionate, propylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, and other aromatic ring-containing alkoxysilane compounds; styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, and other radical polymerizable group-containing alkoxysilane compounds;Carboxylic acids 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. alkoxysilane compounds containing a fluorine group, such as trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane, may be used in combination of two or more of these.

[0026] When the siloxane resin composition for forming a cured film of the present invention has photocurability, it is preferable to contain at least one radical polymerizable group-containing alkoxysilane compound as the alkoxysilane compound represented by general formula (6) and / or (7). When the siloxane resin composition for forming a cured film of the present invention has negative photosensitivity, it is preferable to contain at least one radical polymerizable group-containing alkoxysilane compound and at least one carboxyl group-containing alkoxysilane compound as the alkoxysilane compound represented by general formula (6) and / or (7). By containing a radical polymerizable group-containing alkoxysilane compound, a crosslinking reaction proceeds with the radicals generated in the exposed area, and the degree of curing of the exposed area can be increased. In addition, by containing a carboxyl group-containing alkoxysilane compound, the solubility of the unexposed area is improved, and the resolution can be improved during pattern processing.

[0027] When the siloxane resin composition for forming a cured film of the present invention has positive photosensitivity, it is preferable that the alkoxysilane compound represented by the general formula (6) and / or (7) contains at least an aromatic group-containing alkoxysilane compound. By containing an aromatic group-containing alkoxysilane compound, the compatibility of the (a) polysiloxane with the photosensitizer can be improved.

[0028] Other alkoxysilane compounds include, for example, tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetraethoxysilane oligomer); monofunctional alkoxysilane compounds such as trimethylmethoxysilane, triphenylmethoxysilane, trimethylsilanol, and triphenylsilanol. Two or more of these may be used.

[0029] (a) The weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of coatability. 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 the present invention refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0030] (a) Polysiloxane can be obtained by hydrolyzing the above-mentioned alkoxysilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction.

[0031] Various conditions for hydrolysis can be set according to properties suitable for the intended use, taking into consideration the reaction scale, the size and shape of the reaction vessel, etc. Examples of various conditions include acid concentration, reaction temperature, reaction time, etc.

[0032] In order to promote the hydrolysis reaction and the dehydration condensation reaction, it is preferable to add a catalyst. Examples of the catalyst include acids such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids and their anhydrides, bases such as monoethanolamine, diethanolamine, triethanolamine, 3,3-dimethylbutylamine, methylpentylamine, n-butylethylamine, dibutylamine, n-butylamine, pentylamine, isopentylamine, cyclopentylamine, hexylamine, cyclohexylamine, dimethylhexylamine, N,N-dimethylbutylamine, N,N-dimethylhexadecylamine, and N,N-dimethyl-n-octylamine, and bases such as methanesulfonic acid pyridine salt and ethanesulfonic acid pyridine salt. Organic salts that can be used include lysine salt, pyridine propanesulfonate salt, pyridine benzenesulfonate salt, pyridine p-toluenesulfonate salt, pyridine xylenesulfonate salt, pyridine trifluoromethanesulfonate salt, pyridine trifluoroethanesulfonate salt, pyridine trifluoropropanesulfonate salt, pyridine trifluoroacetate salt, 2,4,6-trimethylpyridine p-toluenesulfonate salt, aniline p-toluenesulfonate salt, tetramethylammonium p-toluenesulfonate, tetraethylammonium p-toluenesulfonate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide.

[0033] Among these, it is preferable to use an organic salt having a pH value of 3.0 to 5.5 in a 1.0% by weight aqueous solution. That is, the method for producing a polysiloxane of the present invention is a method for producing a polysiloxane using an alkoxysilane compound as a raw material and an organic salt as a catalyst for hydrolysis and / or thermal condensation, and the pH value of the organic salt in a 1.0% by weight aqueous solution is 3.0 to 5.5.

[0034] Examples of organic salts having a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution include pyridine benzenesulfonate, pyridine methanesulfonate, pyridine p-toluenesulfonate, pyridine xylenesulfonate, pyridine trifluoromethanesulfonate, pyridine trifluoroethanesulfonate, pyridine trifluoropropanesulfonate, pyridine trifluoroacetate, 2,4,6-trimethylpyridine p-toluenesulfonate, and aniline p-toluenesulfonate. By using an organic salt having a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution, a polysiloxane having good storage stability can be produced without the need for a catalyst removal or neutralization step described below. 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.

[0035] In the hydrolysis reaction and dehydration condensation reaction, when a catalyst is used, the amount of catalyst added is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total alkoxysilane compounds used in the reaction, from the viewpoint of making the reaction proceed more quickly. On the other hand, from the viewpoint of appropriately adjusting the progress of the reaction, the amount of catalyst added is preferably 5.00 parts by mass or less, more preferably 3.00 parts by mass or less, based on 100 parts by mass of the total alkoxysilane compounds. Here, the amount of the total alkoxysilane compounds refers to the amount including all of the alkoxysilane compounds, their hydrolyzates and their condensates. The same applies below.

[0036] The hydrolysis reaction and the dehydration condensation reaction are preferably carried out in a solvent. The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. In addition, when a solvent is generated by the hydrolysis reaction, it is also possible to carry out the hydrolysis without a solvent. When used in a resin composition, it is also preferable to adjust the resin composition to an appropriate concentration by further adding a solvent after the completion of the hydrolysis reaction. In addition, it is also possible to distill and remove all or a part of the generated alcohol, etc. by heating and / or under reduced pressure after the hydrolysis, and then add a suitable solvent.

[0037] When a solvent is used in the hydrolysis reaction, the amount of the solvent added is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, based on 100 parts by mass of the total alkoxysilane compounds, from the viewpoint of suppressing the formation of gel due to overreaction, while the amount of the solvent added is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, based on 100 parts by mass of the total alkoxysilane compounds, from the viewpoint of proceeding hydrolysis more rapidly.

[0038] 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 to 4.0 mol per mol of the total alkoxysilane compounds.

[0039] As a method for the dehydration condensation reaction, for example, a method of heating the silanol compound solution obtained by the hydrolysis reaction of the alkoxysilane compound as it is can be mentioned. The heating temperature is preferably 50°C or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the generated alcohol, etc. may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

[0040] From the viewpoint of storage stability of the resin composition, a catalyst removal or neutralization step may be carried out as necessary. As a catalyst removal method, from the viewpoint of ease of operation and removability, washing with water, treatment with ion exchange resin, etc. are preferred. Washing with water is a method in which the polysiloxane solution is diluted with a suitable hydrophobic solvent, washed with water several times, and the obtained organic layer is then concentrated using an evaporator or the like. Treatment with ion exchange resin is a method in which the polysiloxane solution is brought into contact with a suitable ion exchange resin. (b) Organic Salt The (b) organic salt is an organic salt compound consisting of an acid and a base. The (b) organic salt acts as a condensation catalyst that promotes the condensation reaction of the silanol groups remaining in the polysiloxane. By containing the (a) polysiloxane and the (b) organic salt in the resin composition, the reaction between the silanol groups in the polysiloxane is promoted, increasing the crosslink density in the film, improving the degree of curing of the cured film, and improving the solvent resistance of the film.

[0041] Patent Document 5 shows an example of using an organic salt, p-toluenesulfonic acid pyridine salt, in a resist composition. However, this is added for the purpose of suppressing the diffusion rate of the acid generated from the photoacid generator when it diffuses into the resist film. The role of the organic salt (b) in the siloxane resin composition for forming a cured film used to form a permanent film, as in the present invention, is clearly different.

[0042] Methods for introducing the (b) organic salt into the resin composition include, as described above, a method in which the (b) organic salt is used as a catalyst in the step of producing the (a) polysiloxane, and a polysiloxane solution obtained without carrying out a catalyst removal step is used, and a method in which the (b) organic salt is added by post-addition to the (a) polysiloxane after the catalyst has been removed. From the viewpoint of process simplicity, the former method is preferred.

[0043] In the siloxane resin composition for forming a cured film of the present invention, the (b) organic salt has a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution. By setting the pH value within this range, it is possible to achieve both the storage stability of the resin composition and an improvement in the degree of curing of the film. Examples of organic salts having a pH value of 3.0 to 5.5 in a 1.0% by mass aqueous solution include the organic salts described above as suitable catalysts. The pH value of the (b) organic salt in a 1.0% by mass aqueous solution is preferably 3.0 to 5.0, more preferably 3.0 to 4.5.

[0044] The content of the (b) organic salt in the resin composition for forming a cured film 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, based on 100 parts by mass of the (a) polysiloxane, from the viewpoint of improving the degree of curing of the film. On the other hand, the content of the (b) organic salt in the resin composition for forming a cured film of the present invention is preferably 5.00 parts by mass or less, more preferably 3.00 parts by mass or less, based on 100 parts by mass of the (a) polysiloxane, from the viewpoint of improving storage stability and suppressing yellowing of the film.

[0045] The (b) organic salt is preferably a salt composed of a strong acid and a weak base so that the pH value in a 1.0% by mass aqueous solution falls within the above-mentioned preferred range. Therefore, the (b) organic salt is preferably an organic salt composed of an organic acid having a structure represented by any one of the following general formulas (1) to (3) and an amine.

[0046] [ka]

[0047] In general formulas (1) to (2), R 1 ~R 2 each independently represents a monovalent organic group having 1 to 30 carbon atoms or a divalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group include a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted aryl group, a perfluoroalkyl group, etc., and examples of the divalent organic group include a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted phenylene group, etc.

[0048] In the general formula (3), n represents 0, 1 or 2. When n=1, R 3 represents a monovalent organic group having 1 to 30 carbon atoms or a divalent organic group having 1 to 30 carbon atoms. When n=2, R in general formula (3) 3 may be the same or different and represent hydrogen, a monovalent organic group having 1 to 30 carbon atoms, or a divalent organic group having 1 to 30 carbon atoms.

[0049] Examples of organic acids represented by general formula (1) include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric 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, and adipic acid.

[0050] Examples of the organic acid represented by the general formula (2) include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, o-toluenesulfonic acid, xylenesulfonic acid, 10-camphorsulfonic acid, magic acid, taurine, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, and trifluoropropanesulfonic acid.

[0051] Examples of the organic acid represented by general formula (3) include phosphoric acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, cyclohexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, icosylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, phenylphosphinic acid, tolylphosphonic acid, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dihexyl phosphate, and diphenyl phosphate.

[0052] Among these, from the viewpoints of ease of salt formation and availability, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, trifluoropropanesulfonic acid, and trifluoroacetic acid are preferred.

[0053] The structure of the amine is not particularly limited, but is preferably a weakly basic amine compound as described above. The amine is preferably a heterocyclic amine or an aromatic amine.

[0054] Examples of heterocyclic amines 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, and 2,4,6-trimethylpyridine.

[0055] Examples of aromatic amines include aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline.

[0056] Among these, from the viewpoints of ease of salt formation and availability, pyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, and aniline are preferred.

[0057] (b) The organic salt is preferably an organic salt composed of the above-mentioned preferred organic acids and preferred amines. Among these, from the viewpoint of ease of salt formation and availability, methanesulfonic acid pyridine salt, ethanesulfonic acid pyridine salt, propanesulfonic acid pyridine salt, benzenesulfonic acid pyridine salt, p-toluenesulfonic acid pyridine salt, trifluoromethanesulfonic acid pyridine salt, trifluoropropanesulfonic acid pyridine salt, trifluoroacetic acid pyridine salt, xylenesulfonic acid pyridine salt, p-toluenesulfonic acid, and 2,4,6-trimethylpyridine salt are preferred. Among these, from the viewpoint of reducing coloration of the cured film, methanesulfonic acid pyridine salt, benzenesulfonic acid pyridine salt, p-toluenesulfonic acid pyridine salt, trifluoromethanesulfonic acid pyridine salt, or trifluoroacetic acid is preferred, and methanesulfonic acid pyridine salt is particularly preferred. Furthermore, when the siloxane resin composition of the present invention is used for a low refractive index film application, from the viewpoint of lowering the refractive index, pyridine trifluoromethanesulfonate, pyridine trifluoroethanesulfonate, pyridine trifluoropropanesulfonate, or pyridine trifluoroacetate is preferred, and pyridine trifluoromethanesulfonate or pyridine trifluoroacetate is particularly preferred.

[0058] (b) The organic salt may be commercially available or may be synthesized. For example, the organic salt may be synthesized by stirring the organic acid and dehydrated THF under nitrogen, dropping the amine while cooling with ice, filtering the precipitated salt, and then drying it under vacuum. (c) Solvent The (c) solvent has the function of adjusting the viscosity of the resin composition to a range suitable for application and improving the application uniformity.

[0059] Examples of the solvent include alcohols such as ethanol, propanol, isopropanol, and diacetone alcohol; glycols 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; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentane, and the like. Examples of the solvent include ketones such as acetone; amides such as dimethylformamide and dimethylacetamide; 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, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane, γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be contained. From the viewpoint of coating properties, it is preferable to combine a solvent having a boiling point of more than 150° C. and less than 250° C. under atmospheric pressure with a solvent having a boiling point of 150° C. or less, and it is preferable to combine diacetone alcohol as a solvent having a boiling point of more than 150° C. and less than 250° C. under atmospheric pressure with propylene glycol monomethyl ether as a solvent having a boiling point of 150° C. or less.

[0060] The content of the solvent can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating, the content of the solvent is generally set to 50% by mass or more and 95% by mass or less in the resin composition for forming a cured film of the present invention.

[0061] (d) Photosensitizer When photosensitivity is required, the siloxane resin composition for forming a cured film of the present invention preferably contains (d) a photosensitizer. When negative photosensitivity is to be imparted, it is preferable that a photopolymerization initiator is contained as (d) a photosensitizer, and a highly precise pattern can be formed. When negative photosensitivity is to be imparted, it is preferable that a photopolymerizable compound is further contained. On the other hand, when positive photosensitivity is to be imparted, it is preferable that a quinone diazide compound is contained as (d) a photosensitizer.

[0062] The photopolymerization initiator may be any one that decomposes and / or reacts upon irradiation with light (including ultraviolet light and electron beams) to generate radicals. For example, α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. acylphosphine oxide compounds such as bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide; 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, Oxime ester compounds such as ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime); benzil ketal compounds such as benzil dimethyl ketal; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl- α-hydroxyketone compounds such as phenyl ketones; benzophenone compounds such as 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, alkylated benzophenones, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;Examples of the compound include acetophenone compounds such as 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone; aromatic ketoester compounds such as methyl 2-phenyl-2-oxyacetate; and benzoic acid ester compounds such as ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. Two or more of these compounds may be contained.

[0063] The content of the photopolymerization initiator in the siloxane resin composition for forming a cured film of the present invention is preferably 0.01% by mass or more, more preferably 1% by mass or more, based on the solid content, from the viewpoint of effectively promoting radical curing. On the other hand, from the viewpoint of suppressing elution of the remaining photopolymerization initiator, the content of the photopolymerization initiator is preferably 20% by mass or less, more preferably 10% by mass or less, based on the solid content.

[0064] The photopolymerizable compound in the present invention refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. In consideration of the ease of radical polymerization, the photopolymerizable compound preferably has a (meth)acrylic group.

[0065] Examples of the photopolymerizable compound 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, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, and pentaerythritol triacrylate. Examples of the acrylate include 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 undecamethacrylate, pentapentaerythritol dodecamethacrylate, and dimethylol-tricyclodecane diacrylate. Two or more of these may be contained.

[0066] The content of the photopolymerizable compound in the siloxane resin composition for forming a cured film of the present invention is preferably 1% by mass or more based on the solid content in order to effectively promote radical curing, while the content of the photopolymerizable compound is preferably 50% by mass or less based on the solid content in order to suppress excessive radical reaction and improve resolution.

[0067] As the quinone diazide compound, a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group by ester bonding is preferred. Examples of the compound having a phenolic hydroxyl group used here include BIs-Z, TekP-4HBPA (tetrakis P-DO-BPA), TrIsP-HAP, TrIsP-PA, BIsRS-2P, BIsRS-3P (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), 4,4'-sulfonyldiphenol, BPFL (trade name, manufactured by JFE Chemical Co., Ltd.), etc. As the quinone diazide compound, a compound having a phenolic hydroxyl group and 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid introduced via an ester bond is preferred, and examples thereof include THP-17, TDF-517 (trade name, manufactured by Toyo Gosei Co., Ltd.), and SBF-525 (trade name, manufactured by AZ Electronic Materials Co., Ltd.).

[0068] The content of the quinone diazide compound in the siloxane resin composition for forming a cured film of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the solid content, from the viewpoint of improving sensitivity. On the other hand, the content of the quinone diazide compound is preferably 25% by mass or less, more preferably 20% by mass or less, based on the solid content, from the viewpoint of improving resolution.

[0069] Furthermore, the siloxane resin composition for forming a cured film of the present invention may contain an ultraviolet absorber, a polymerization inhibitor, a surfactant, an adhesion improver, nanoparticles, a pigment, and the like, as necessary.

[0070] By including an ultraviolet absorber in the siloxane resin composition for forming a cured film of the present invention, light resistance can be improved.As the ultraviolet absorber, from the viewpoint of transparency and non-coloring, benzotriazole compounds such as 2-(2H-benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-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 preferably used.

[0071] By including a polymerization inhibitor in the siloxane resin composition for forming a cured film of the present invention, the resolution can be further improved. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. In addition, examples of commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (all trade names, manufactured by BASF Japan Ltd.). Two or more of these may be included.

[0072] By including a surfactant in the siloxane resin composition for forming a cured film of the present invention, the flowability during application can be improved. Examples of the surfactant include fluorine-based surfactants such as "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (all trade names, manufactured by Dainippon Ink and Chemicals Co., Ltd.), NBX-15, FTX-218 (all trade names, manufactured by Neos Co., Ltd.); silicone-based surfactants such as "BYK" (registered trademark)-333, 301, 331, 345, 307 (all trade names, manufactured by BYK Japan Co., Ltd.); polyalkylene oxide-based surfactants; poly(meth)acrylate-based surfactants, etc. Two or more of these may be included.

[0073] By including an adhesion improver in the siloxane resin composition for forming a cured film of the present invention, the adhesion to the base substrate can be improved. Examples of the adhesion improver include alicyclic epoxy compounds and silane coupling agents. Among these, alicyclic epoxy compounds are preferred from the viewpoint of heat resistance.

[0074] Examples of the alicyclic epoxy compound include 3',4'-epoxycyclohexymethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic 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) ether, hydrogenated bisphenol A bis(ethylene glycol glycidyl ether) ether, 1,4-cyclohexanedicarboxylate diglycidyl, and 1,4-cyclohexanedimethanol diglycidyl ether. Two or more of these may be contained.

[0075] The content of the adhesion improver in the siloxane resin composition for forming a cured film of the present invention is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the solid content, from the viewpoint of further improving the adhesion to the base substrate. On the other hand, the content of the adhesion improver is preferably 20% by mass or less, more preferably 10% by mass or less, based on the solid content, from the viewpoint of pattern processability.

[0076] The refractive index of the cured film can be adjusted by including nanoparticles in the siloxane resin composition for forming the cured film of the present invention. Examples of nanoparticles include silica particles, magnesium fluoride particles, titania particles, and zirconia particles. Two or more of these may be included. When the refractive index is to be reduced, it is preferable to include silica particles and magnesium fluoride particles, and when the refractive index is to be increased, it is preferable to include titania particles and zirconia particles.

[0077] By incorporating a pigment in the siloxane resin composition for forming a cured film of the present invention, the reflectivity and light blocking properties of the cured film can be adjusted.

[0078] When it is desired to improve the reflectivity of the cured film, it is preferable to contain a white pigment. Examples of the white pigment include titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof. Two or more of these may be contained.

[0079] When it is desired to improve the light-shielding property of the cured film at a specific wavelength, it is preferable to contain a light-shielding pigment such as a red pigment, a blue pigment, a black pigment, a green pigment, a yellow pigment, etc. When it is desired to achieve both reflectivity and light-shielding property, it is preferable to contain both a white pigment and a light-shielding pigment.

[0080] Examples of red pigments include Pigment Red (hereinafter abbreviated as PR), PR177, PR179, PR180, PR192, PR209, PR227, PR228, PR240, PR254, etc. Two or more of these may be contained.

[0081] Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, PB64, etc. Two or more of these may be contained.

[0082] Examples of black pigments include black organic pigments, mixed-color organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. These may be coated with resin. Examples of mixed-color organic pigments include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, and cyan to give a pseudo-black color. Among these, a mixed pigment of a red pigment and a blue pigment is preferred from the viewpoint of achieving both a moderately high OD value and pattern processability. The mass ratio of the red pigment to the blue pigment in the mixed pigment is preferably 20 / 80 to 80 / 20, and more preferably 30 / 70 to 70 / 30. Examples of black inorganic pigments include graphite, fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zirconium, zinc, calcium, silver, gold, platinum, and palladium, metal oxides, metal composite oxides, metal sulfides, metal nitrides, metal oxynitrides, and metal carbides. Two or more of these may be contained.

[0083] Examples of green pigments include CI Pigment Green (hereinafter abbreviated as PG) 7, PG36, PG58, PG37, PG59, etc. Two or more of these may be contained.

[0084] Examples of yellow pigments include Pigment Yellow (hereinafter abbreviated as PY), PYPY150, PY153, PY154, PY166, PY168, PY185, etc. Two or more of these may be contained.

[0085] The siloxane resin composition for forming a cured film of the present invention may contain a resin other than polysiloxane. By using a resin other than polysiloxane, it is possible to complement the film properties that are insufficient with polysiloxane, such as improving the tacklessness after pre-baking. Examples of resins other than polysiloxane include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, (meth)acrylic polymer, and cardo resin.

[0086] In the siloxane resin composition for forming a cured film of the present invention, when the (a) polysiloxane contained therein has an aromatic group and / or a substituted aromatic group in its side chain group, it is preferable that the content of benzene, toluene, xylene, aniline, styrene, and naphthalene in the resin composition is each less than 1 ppm.

[0087] Conventionally, when polysiloxanes containing aromatic and / or substituted aromatic groups in the side chains are obtained by condensation reaction using a strong acid catalyst such as phosphoric acid or a strong base catalyst, or when they are used together with an acid generator or base generator that generates a strong acid or strong base, some of the bonds between the Si atoms in the polysiloxane and the side chains are broken, resulting in the generation of trace amounts of impurities derived from the side chains. That is, for example, when polysiloxanes having phenyl, tolyl, xylyl, phenylamino, styryl, or naphthyl groups in the side chains are obtained by condensation reaction using a phosphoric acid catalyst, there is a problem that they contain 1 ppm or more of benzene, toluene, xylene, aniline, styrene, or naphthalene as impurities, respectively.

[0088] On the other hand, the siloxane resin composition for forming a cured film of the present invention uses, as a catalyst, a polysiloxane condensed with an organic salt (b) having a pH value of 3.0 to 5.5 in a 1.0 mass % aqueous solution, or uses an organic salt (b) instead of an acid generator or base generator, so that the above-mentioned cleavage reaction of the side chain group does not occur and the content of the impurity can be suppressed to less than 1 ppm.

[0089] The siloxane resin composition for forming a cured film of the present invention is preferably a permanent film, i.e., a resin composition for forming a permanent film. A permanent film refers to a cured film that remains on a product permanently, unlike a film that is removed during a manufacturing process like a general resist layer.

[0090] Next, the cured film of the present invention will be described.

[0091] The cured film of the present invention is obtained by curing the resin composition for forming a cured film of the present invention. The cured film of the present invention is preferably used as a permanent film.

[0092] Another embodiment of the cured film of the present invention is a cured film in which the atomic ratio of N to Si measured by scanning electron microscope (SEM-EDX) is 0.005 to 0.200, and the atomic ratio of at least one atom selected from S, P, and F to Si is 0.005 to 0.200. By having the atomic ratio within these ranges, the film can have both solvent resistance and permeability. The atomic ratio of N to Si and the atomic ratio of at least one atom selected from S, P, and F to Si are preferably 0.010 to 0.150, more preferably 0.015 to 0.100.

[0093] The cured film of the present invention can be obtained by curing the above-mentioned siloxane resin composition for forming a cured film by the method described below.

[0094] The cured film of the present invention is suitably used for various hard coat films such as protective films for touch panels, as well as insulating films for touch sensors, planarizing films for TFTs of liquid crystal and organic EL displays, protective films for metal wiring, insulating films, anti-reflection films, optical filters, overcoats for color filters, pillar materials, etc.

[0095] The thickness of the cured film varies depending on the application, but is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

[0096] Next, the method for forming the cured film of the present invention will be described with reference to examples.

[0097] The method for forming a cured film of the present invention preferably includes a film-forming step of applying the siloxane resin composition for forming a cured film of the present invention onto a base substrate and drying the composition to obtain a dry film, and a heating step of heating the dry film to cure the film. After the film-forming step, the method may include an exposure step of exposing the obtained dry film to light.

[0098] Examples of the method for applying the siloxane resin composition for forming a cured film in the film-forming step include slit coating, spin coating, spray coating, etc. Examples of the drying device include a hot air oven and a hot plate, etc. The drying time is preferably 80 to 130° C., and the drying time is preferably 1 to 30 minutes.

[0099] The exposure device used in the exposure step may be, for example, a proximity exposure machine. The actinic ray irradiated in the exposure step may be, for example, near infrared light, visible light, or ultraviolet light, with ultraviolet light being preferred. The light source may 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, with ultra-high-pressure mercury lamp being preferred.

[0100] The exposure conditions can be appropriately selected depending on the thickness of the dry film to be exposed. Generally, the exposure conditions are 1 to 100 mW / cm. 2 Using an ultra-high pressure mercury lamp with an output of 1 to 10,000 mJ / cm 2 It is preferable to expose the film with an exposure amount of 1000 to 1000 nm.

[0101] The heating step is a step of heating and curing the film. Examples of heating devices include a hot plate and an oven. The heating temperature during the heating step is preferably 250° C. or lower, more preferably 240° C. or lower, from the viewpoint of suppressing the occurrence of cracks in the film to be heated. On the other hand, from the viewpoint of the degree of curing of the cured film, it is preferably 100° C. or higher, more preferably 120° C. or higher. The heating time is preferably 15 minutes to 2 hours. EXAMPLES

[0102] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In addition, the names of the compounds used, for which abbreviations are used, are shown below. PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol BHT: dibutylhydroxytoluene.

[0103] The solids concentration of the polysiloxane solution in Synthesis Examples 1 to 26 was determined by the following method. 1.0 g of the polysiloxane solution was weighed out in an aluminum cup and heated at 250° C. for 30 minutes using a hot plate to evaporate the liquid. The mass of the solids remaining in the aluminum cup after heating was weighed, and the solids concentration was determined from the ratio to the mass before heating.

[0104] The weight average molecular weight of the polysiloxane solution in Synthesis Examples 1 to 26 was determined in terms of polystyrene by the following method. Equipment: Waters GPC measurement equipment with RI detector (2695) Column: PLgelMIXED-C column (Polymer Laboratories, 300 mm) x 2 (connected in series) Measurement temperature: 40℃ Flow rate: 1mL / min Solvent: 0.5% by weight solution in tetrahydrofuran (THF) Standard material: polystyrene Detection mode: RI.

[0105] The content ratio of each repeating unit in the polysiloxane in Synthesis Examples 1 to 26 was determined by the following method. The polysiloxane solution was poured into a 10 mm diameter Teflon (registered trademark) NMR sample tube. 29 Si-NMR measurements were performed, and the content ratio of each repeating unit was calculated from the ratio of the integral value of Si derived from a specific organosilane to the integral value of all Si derived from the organosilane. 29 The Si-NMR measurement conditions are as follows. Equipment: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measured nuclear frequency: 53.6693MHz ( 29 Si nucleus) Spectral width: 20000Hz Pulse width: 12μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: Acetone-d6 Reference material: Tetramethylsilane Measurement temperature: 23℃ Sample rotation speed: 0.0Hz.

[0106] Synthesis Example 1 Polysiloxane (A-1) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.887 g (1.0 mass % relative to the charged monomer) of p-toluenesulfonic acid pyridine salt was dissolved in 76.39 g of water was added over 30 minutes while stirring at 40°C. After that, the flask was immersed in a 70°C oil bath and stirred for 60 minutes, and the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110°C) to obtain a polysiloxane solution. During the temperature increase and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. During the reaction, a total of 173.99 g of methanol and water, which are by-products, was distilled out. PGMEA was added to the obtained polysiloxane solution so that the solid concentration was 50% by mass, and a polysiloxane (A-1) solution was obtained without removing the catalyst. The weight average molecular weight of the obtained polysiloxane (A-1) was 5,000. 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 polysiloxane (A-1) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol% and 10 mol%, respectively.

[0107] Synthesis Example 2 Polysiloxane (A-2) solution A polysiloxane (A-2) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution prepared by dissolving 3.887 g of methanesulfonic acid pyridine salt (1.0 mass% based on the charged monomer) in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-2) was 5,000. 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-2) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0108] Synthesis Example 3 Polysiloxane (A-3) solution A polysiloxane (A-3) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 3.887 g of pyridine trifluoromethanesulfonate (1.0 mass% based on the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-3) was 5,000. 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-3) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0109] Synthesis Example 4 Polysiloxane (A-4) solution A polysiloxane (A-3) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 3.887 g of pyridine trifluoroacetate (1.0 mass % relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-4) was 5,000. 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-4) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0110] Synthesis Example 5 Polysiloxane (A-5) Solution A polysiloxane (A-5) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 3.887 g of benzenesulfonic acid pyridine salt (1.0 mass % relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-5) was 5,000. 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-5) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0111] Synthesis Example 6 Polysiloxane (A-6) Solution A polysiloxane (A-6) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 3.887 g of benzenesulfonic acid aniline salt (1.0 mass % relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-6) was 5,000. 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-6) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0112] Synthesis Example 7 Polysiloxane (A-7) Solution A polysiloxane (A-7) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 3.887 g of tetraethylammonium p-toluenesulfonate (1.0 mass% relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-7) was 1,200. 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-7) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0113] Synthesis Example 8 Polysiloxane (A-8) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.887 g of p-toluenesulfonic acid pyridine salt (1.0 mass% relative to the charged monomer) was dissolved in 76.39 g of water was added over 30 minutes while stirring at 40 ° C. Then, the flask was immersed in an oil bath at 70 ° C. and stirred for 60 minutes, and the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of the temperature rise, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane solution. During the temperature rise and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. During the reaction, a total of 282.58 g of by-products, methanol and water, was distilled out. PGMEA was added to the obtained polysiloxane solution so that the solid concentration was 50% by mass, and a polysiloxane (A-8) solution was obtained. The weight average molecular weight of the obtained polysiloxane (A-8) was 8,000. In addition, 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.

[0114] Synthesis Example 9 Polysiloxane (A-9) Solution A polysiloxane (A-9) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 3.887 g of phosphoric acid (1.0 mass% based on the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-9) was 4,200. 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.

[0115] Synthesis Example 10 Polysiloxane (A-10) solution 2.00 g of a weakly basic ion exchange resin ("Amberlite" (registered trademark) A21, manufactured by Organo Corporation (hereinafter "A21")) and 2.00 g of a weakly acidic ion exchange resin ("Amberlite" (registered trademark) 15JWET, manufactured by Organo Corporation (hereinafter "15J")) were added to 100 g of the polysiloxane (A-9) solution and stirred at room temperature for 12 hours. The ion exchange resin was then removed by filtration to obtain a polysiloxane (A-10) solution. The weight average molecular weight of the obtained polysiloxane (A-10) was 4,500. 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 polysiloxane (A-10) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0116] Synthesis Example 11 Polysiloxane (A-11) solution A polysiloxane (A-11) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 0.389 g of p-toluenesulfonic acid pyridine salt (0.1 mass % relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution, and the amount of PGMEA added was 311.95 g. The weight average molecular weight of the obtained polysiloxane (A-11) was 2,500. In addition, the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-11) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0117] Synthesis Example 12 Polysiloxane (A-12) solution A polysiloxane (A-12) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 11.66 g of p-toluenesulfonic acid pyridine salt (3.0% by mass relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution, and the amount of PGMEA added was 300.68 g. The weight average molecular weight of the obtained polysiloxane (A-12) was 6,500. 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-12) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0118] Synthesis Example 13 Polysiloxane (A-13) solution A polysiloxane (A-13) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 0.039 g of p-toluenesulfonic acid pyridine salt (0.01% by mass relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution, and the amount of PGMEA added was 312.30 g. The weight average molecular weight of the obtained polysiloxane (A-13) was 6,500. In addition, the molar ratios of each repeating unit derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in the polysiloxane (A-13) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0119] Synthesis Example 14 Polysiloxane (A-14) solution A polysiloxane (A-14) solution was obtained in the same manner as in Synthesis Example 1, except that a catalyst aqueous solution in which 21.38 g of p-toluenesulfonic acid pyridine salt (5.5% by mass relative to the charged monomer) was dissolved in 76.39 g of water was used as the catalyst aqueous solution, and the amount of PGMEA added was 290.96 g. The weight average molecular weight of the obtained polysiloxane (A-14) was 6,500. 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-14) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 10 mol%, respectively.

[0120] Synthesis Example 15 Polysiloxane (A-15) solution In a 1000ml three-neck flask, 47.67g (0.350mol) of methyltrimethoxysilane, 152.11g (0.613mol) of 3-methacryloxypropyltrimethoxysilane, 152.74g (0.700mol) of trifluoropropyltrimethoxysilane, 22.95g (0.088mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.282g of BHT, and 275.65g of PGMEA were charged, and an aqueous catalyst solution in which 3.755g of p-toluenesulfonic acid pyridine salt (1.0% by mass relative to the charged monomer) was dissolved in 96.08g of water was added over 30 minutes while stirring at 40°C. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a polysiloxane (A-15) solution. The weight average molecular weight of the obtained polysiloxane (A-15) was 4,500. In addition, the molar ratios of repeating units derived from methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, trifluoropropyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-15) were 35 mol%, 20 mol%, 40 mol%, and 5 mol%, respectively.

[0121] Synthesis Example 16 Polysiloxane (A-16) solution A polysiloxane (A-16) solution was obtained in the same manner as in Synthesis Example 15, except that a catalyst aqueous solution prepared by dissolving 3.755 g of pyridine trifluoroacetate (1.0% by mass relative to the charged monomer) in 96.08 g of water was used as the catalyst aqueous solution. The weight average molecular weight of the obtained polysiloxane (A-16) was 4,500. 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.

[0122] Synthesis Example 17 Polysiloxane (A-17) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.621 g of methanesulfonic acid pyridine salt (1.0 mass % relative to the charged monomer) was dissolved in 91.35 g of water was added over 30 minutes while stirring at 40 ° C. Thereafter, a polysiloxane (A-17) solution was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the obtained polysiloxane (A-17) was 4,500. 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.

[0123] Synthesis Example 18 Polysiloxane (A-18) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.738 g of methanesulfonic acid pyridine salt (1.0 mass % relative to the charged monomer) was dissolved in 91.35 g of water was added over 30 minutes while stirring at 40 ° C. Thereafter, a polysiloxane (A-18) solution was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the obtained polysiloxane (A-18) was 4,000. 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.

[0124] Synthesis Example 19 Polysiloxane (A-19) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.629 g of methanesulfonic acid pyridine salt (1.0 mass % relative to the charged monomer) was dissolved in 91.35 g of water was added over 30 minutes while stirring at 40°C. Thereafter, a polysiloxane (A-19) solution was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the obtained polysiloxane (A-19) was 5,000. 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.

[0125] Synthesis Example 20 Polysiloxane (A-20) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.721 g of methanesulfonic acid pyridine salt (1.0 mass % relative to the charged monomer) was dissolved in 91.35 g of water was added over 30 minutes while stirring at 40°C. Thereafter, a polysiloxane (A-20) solution was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the obtained polysiloxane (A-20) was 6,600. 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.

[0126] Synthesis Example 21 Polysiloxane (A-21) solution In a 1000 ml three-neck flask, 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 were charged, and an aqueous catalyst solution in which 3.920 g of methanesulfonic acid pyridine salt (1.0 mass % relative to the charged monomer) was dissolved in 91.35 g of water was added over 30 minutes while stirring at 40°C. Thereafter, a polysiloxane (A-21) solution was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of the obtained polysiloxane (A-21) was 3,000. 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.

[0127] Synthesis Example 22 Polysiloxane (A-22) solution The reaction was carried out in the same manner as in Synthesis Example 17, except that a catalyst aqueous solution in which 3.621 g of phosphoric acid (1.0% by mass relative to the charged monomer) was added to 91.35 g of water was used as the catalyst aqueous solution. 2.00 g of A21 and 2.00 g of 15JWET were added as ion exchange resins to 100 g of the obtained solution, and the mixture was stirred at room temperature for 12 hours. After that, the ion exchange resin was removed by filtration, and a polysiloxane (A-22) solution was obtained. The weight average molecular weight of the obtained polysiloxane (A-22) was 4,500. In addition, the molar ratios of repeating units derived from p-tolyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-22) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol% and 5 mol%, respectively.

[0128] Synthesis Example 23 Polysiloxane (A-23) solution The reaction was carried out in the same manner as in Synthesis Example 18, except that a catalyst aqueous solution in which 3.621 g of phosphoric acid (1.0% by mass relative to the charged monomer) was added to 91.35 g of water was used as the catalyst aqueous solution. 2.00 g of A21 and 2.00 g of 15JWET were added as ion exchange resins to 100 g of the obtained solution, and the mixture was stirred at room temperature for 12 hours. After that, the ion exchange resin was removed by filtration, and a polysiloxane (A-23) solution was obtained. The weight average molecular weight of the obtained polysiloxane (A-23) was 4,500. In addition, the molar ratios of repeating units derived from 3,5-dimethylphenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-23) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0129] Synthesis Example 24 Polysiloxane (A-24) solution The reaction was carried out in the same manner as in Synthesis Example 19, except that a catalyst aqueous solution in which 3.621 g of phosphoric acid (1.0% by mass relative to the charged monomer) was added to 91.35 g of water was used as the catalyst aqueous solution. 2.00 g of A21 and 2.00 g of 15JWET were added as ion exchange resins to 100 g of the obtained solution, and the mixture was stirred at room temperature for 12 hours. After that, the ion exchange resin was removed by filtration, and a polysiloxane (A-23) solution was obtained. The weight average molecular weight of the obtained polysiloxane (A-24) was 4,500. In addition, the molar ratios of repeating units derived from M-aminophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-24) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol% and 5 mol%, respectively.

[0130] Synthesis Example 25 Polysiloxane (A-25) solution The reaction was carried out in the same manner as in Synthesis Example 20, except that a catalyst aqueous solution in which 3.621 g of phosphoric acid (1.0% by mass relative to the charged monomer) was added to 91.35 g of water was used as the catalyst aqueous solution. 2.00 g of A21 and 2.00 g of 15JWET were added as ion exchange resins to 100 g of the obtained solution, and the mixture was stirred at room temperature for 12 hours. After that, the ion exchange resin was removed by filtration, and a polysiloxane (A-23) solution was obtained. The weight average molecular weight of the obtained polysiloxane (A-25) was 6,500. In addition, the molar ratios of repeating units derived from p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-25) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol%, and 5 mol%, respectively.

[0131] Synthesis Example 26 Polysiloxane (A-26) solution The reaction was carried out in the same manner as in Synthesis Example 21, except that a catalyst aqueous solution in which 3.621 g of phosphoric acid (1.0% by mass relative to the charged monomer) was added to 91.35 g of water was used as the catalyst aqueous solution. 2.00 g of A21 and 2.00 g of 15JWET were added as ion exchange resins to 100 g of the obtained solution, and the mixture was stirred at room temperature for 12 hours. After that, the ion exchange resin was removed by filtration, and a polysiloxane (A-23) solution was obtained. The weight average molecular weight of the obtained polysiloxane (A-26) was 3,000. In addition, the molar ratios of repeating units derived from 1-naphthyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, dimethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (A-26) were 47.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, 10 mol% and 5 mol%, respectively.

[0132] The compositions of Synthesis Examples 1 to 26 are shown in Tables 1 to 4.

[0133] [Table 1]

[0134] [Table 2]

[0135] [Table 3]

[0136] [Table 4]

[0137] Example 1 Siloxane resin composition for forming a cured film (P-1) Under yellow light, 65.7 g of a polysiloxane (A-1) solution containing p-toluenesulfonic acid pyridine salt as an organic salt, 0.750 g of 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime) ("Irgacure" (registered trademark) OXE-01, manufactured by BASF Japan Ltd. (hereinafter referred to as "OXE-01")) as a photosensitizer (photopolymerization initiator), 0.250 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure" 819, manufactured by BASF Japan Ltd. (hereinafter referred to as "IC-819")), and 0.250 g of dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA, manufactured by Shin Nippon Pharmaceutical Co., Ltd. (hereinafter referred to as "DPHA") as a photopolymerizable compound were mixed. As an additive, 15.0 g of ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (“Irganox” (registered trademark) 1010, manufactured by BASF Japan Ltd. (hereinafter “IRGANOX1010”)) was used, and 0.150 g of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter “KBM-5103”)) was used, and 0.300 g of a 10 mass % diluted solution of an acrylic surfactant (“BYK” (registered trademark) 352, manufactured by BYK Japan Ltd. (hereinafter “BYK-352”)) in PGMEA (corresponding to a concentration of 300 ppm) was dissolved in 6.90 g of the solvent PGMEA and 10.0 g of DAA, and the mixture was stirred at room temperature. The resulting mixture was filtered through a 0.45 μm filter to obtain a cured film-forming siloxane resin composition (P-1).

[0138] Examples 2 to 6 Siloxane resin compositions for forming cured films (P-2) to (P-6) Siloxane resin compositions for forming cured films (P-2) to (P-6) were obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was replaced with a polysiloxane (A-2) solution to a polysiloxane (A-6) solution, respectively.

[0139] Example 7 Siloxane resin composition for forming a cured film (P-7) Under yellow light, 92.9 g of a polysiloxane (A-8) solution containing p-toluenesulfonic acid pyridine salt as an organic salt, 2.50 g of THP-17 (trade name, manufactured by Toyo Gosei 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 referred to as "KBM-303")), and 0.300 g (corresponding to a concentration of 300 ppm) of a 10 mass% diluted solution of an acrylic surfactant ("BYK" (registered trademark) 352, manufactured by BYK Japan K.K. (hereinafter referred to as "BYK-352")) in PGMEA were dissolved in 0.258 g of a solvent PGMEA and 3.00 g of DAA, and stirred at room temperature. The resulting mixture was filtered through a 0.45 μm filter to obtain a cured film-forming siloxane resin composition (P-7).

[0140] Example 8 Siloxane resin composition for forming a cured film (P-8) A siloxane resin composition for forming a cured film (P-8) was obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was changed to a polysiloxane (A-10) solution and 0.657 g of p-toluenesulfonic acid pyridine salt was added as an organic salt.

[0141] Examples 9 to 12 Siloxane resin compositions for forming cured films (P-9) to (P-12) Siloxane resin compositions for forming cured films (P-9) to (P-12) were obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was replaced with the polysiloxane (A-11) solution to the polysiloxane (A-14) solution, respectively.

[0142] Examples 13 to 19 Siloxane resin compositions for forming cured films (P-13) to (P-19) Siloxane resin compositions for forming cured films (P-13) to (P-19) were obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was replaced with the polysiloxane (A-15) solution to the polysiloxane (A-21) solution, respectively.

[0143] Example 20 Partition wall resin composition (P-20) 50.0 g of titanium dioxide white pigment (CR-97; manufactured by Ishihara Sangyo Kaisha, Ltd. (hereinafter referred to as "CR-97")) was mixed with 50.0 g of the polysiloxane (A-1) solution obtained in Synthesis Example 1, and then dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1). Next, under yellow light, 40.25g of the pigment dispersion (MW-1), 15.70g of polysiloxane (A-1) solution containing p-toluenesulfonic acid pyridine salt as organic salt, 0.755g of OXE-01 as photosensitizer (photopolymerization initiator), 0.252g of IC-819, 15.1g of DPHA as photopolymerizable compound, 0.151g of IRGANOX1010 as additive, 1.01g of KBM-5103, and 0.302g of PGMEA 10 mass% diluted solution of acrylic surfactant BYK-352 (corresponding to a concentration of 300 ppm) were dissolved in 17.02g of solvent PGMEA and 10.1g of DAA, and stirred at room temperature. The resulting mixture was filtered through a 5.0 μm filter to obtain a siloxane resin composition (P-20) for forming a cured film.

[0144] Example 21 Partition wall resin composition (P-21) 50.0 g of titanium dioxide white pigment CR-97 was mixed with 50.0 g of the polysiloxane (A-2) solution obtained in Synthesis Example 2, and then dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-2). A siloxane resin composition for forming a cured film (P-21) was obtained in the same manner as in Example 20, except that 40.25 g of the pigment dispersion (MW-1) was added instead of the pigment dispersion MW-1, and 15.70 g of the polysiloxane (A-2) solution containing methanesulfonic acid pyridine salt was added instead of the polysiloxane (A-1) solution.

[0145] Comparative Example 1 Siloxane resin composition for forming a cured film (P-22) A cured film-forming siloxane resin composition (P-22) was obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was changed to a polysiloxane (A-7) solution.

[0146] Comparative Example 2 Siloxane resin composition for forming a cured film (P-23) A siloxane resin composition for forming a cured film (P-23) was obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was changed to a polysiloxane (A-9) solution containing phosphoric acid.

[0147] Comparative Example 3: Siloxane resin composition for forming a cured film (P-24) A siloxane resin composition for forming a cured film (P-24) was obtained in the same manner as in Example 1, except that the polysiloxane (A-1) solution was changed to a polysiloxane (A-10) solution.

[0148] Comparative Example 4: Siloxane resin composition for forming a cured film (P-25) With reference to Patent Document 6, a phosphoric acid derivative compound 2-methacryloyloxyethyl acid phosphate (product name "P-1M", manufactured by Kyoeisha Chemical Co., Ltd.) was reacted with monoethanolamine in a mass ratio of 9.5:0.5 under yellow light to prepare a 20 mass% PGMEA solution of the reaction product. 2.47g of this solution, 65.0g of polysiloxane (A-1) solution, 0.742g of OXE-01 as a photosensitizer (photopolymerization initiator), 0.247g of IC-819, 14.8g of DPHA as a photopolymerizable compound, 0.148g of IRGANOX1010 as an additive, 0.990g of KBM-5103, and 0.300g of a 10% by mass diluted solution of BYK-352 in PGMEA (corresponding to a concentration of 300 ppm) were dissolved in 5.25g of solvent PGMEA and 10.0g of DAA, and stirred at room temperature. The resulting mixture was filtered through a 0.45μm filter to obtain a siloxane resin composition (P-25) for forming a cured film.

[0149] Comparative Examples 5 to 9: Siloxane resin compositions for forming cured films (P-26) to (P-30) Siloxane resin compositions for forming cured films (P-26) to (P-30) were obtained in the same manner as in Comparative Example 3, except that the polysiloxane (A-10) solution was replaced with the polysiloxane (A-22) solution to the polysiloxane (A-26) solution, respectively.

[0150] The compositions of Examples 1 to 21 and Comparative Examples 1 to 9 are shown in Tables 5 to 7.

[0151] [Table 5]

[0152] [Table 6]

[0153] [Table 7]

[0154] The evaluation methods in Examples 22 to 42 and Comparative Examples 10 to 18 are shown below.

[0155] <Storage stability> The viscosity (viscosity before storage) of the siloxane resin composition for forming a cured film obtained in each Example and Comparative Example was measured after preparation. The viscosity was measured at 23°C using an E-type rotational viscometer (VISCOMETER TV-25 (manufactured by TOKI SANGYO)). The siloxane resin composition for forming a cured film obtained in each Example and Comparative Example was placed in a sealed container, and the viscosity was measured in the same manner after storage at room temperature (23°C) for 7 days and after storage at room temperature (40°C) for 3 days. The storage stability was evaluated for each storage condition based on the viscosity change rate ({|viscosity after storage-viscosity before storage| / viscosity before storage}×100) according to the following criteria. A: Viscosity change rate less than 5% B: Viscosity change rate: 5% to less than 10% C: Viscosity change rate is 10% or more.

[0156] <Pattern processability> The siloxane resin compositions for forming cured films obtained in each of the Examples and Comparative Examples were spin-coated onto a bare glass substrate using a spin coater (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and pre-baked at 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film with a thickness of 10 μm.

[0157] The prepared film was exposed to light of 100 mJ / cm at a gap of 100 μm through a grayscale mask having line and space patterns of widths of 100 μm, 50 μm, 40 μm, 30 μm, 20 μm, and 10 μm using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as the light source. 2 Thereafter, using an automatic developing apparatus ("AD-1200 (trade name)" manufactured by Mikasa Co., Ltd.), shower development was performed with 2.38% by mass TMAH for 60 seconds, and then rinsing was performed with water for 30 seconds.

[0158] The minimum pattern size after exposure and development was taken as the resolution. The developed pattern was observed under a microscope adjusted to a magnification of 50 to 100 times, and the development residue was evaluated according to the degree of dissolution of the unexposed parts according to the following criteria. A: No residue is observed even on fine patterns of 50 μm or less. B: No residue is observed on patterns larger than 50 μm, but residue is observed on patterns smaller than 50 μm. C: Residue is observed on patterns larger than 50 μm.

[0159] <Solvent resistance> The siloxane resin compositions for forming cured films obtained in each of the Examples and Comparative Examples were spin-coated onto a bare glass substrate using a spin coater (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and pre-baked at 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film with a thickness of 11 μm.

[0160] The prepared film was exposed to light of 100 mJ / cm using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as the light source. 2The film was exposed under the following conditions. After that, the film was shower-developed with 2.38% by mass TMAH for 60 seconds using an automatic developing apparatus (Mikasa Co., Ltd.'s "AD-1200 (trade name)"), and then rinsed with water for 30 seconds. The developed film was cured in air at 180°C for 1 hour using an oven (trade name IHPS-222, Espec Co., Ltd.) to produce a cured film with a thickness of 10 μm.

[0161] The solvent for the solvent resistance test was selected as TOK106 (Tokyo Ohka Kogyo Co., Ltd.), a resist stripper, and the solvent resistance test was performed by immersing the cured film in this for 5 minutes at 70° C. The film thickness was measured before and after the solvent resistance test, and the solvent resistance was evaluated according to the following criteria from the film thickness change rate ({|film thickness after solvent resistance test-film thickness before solvent resistance test| / film thickness before solvent resistance test}×100). A: Film thickness change rate less than 1% B: Film thickness change rate: 1% to less than 5% C: Film thickness change rate is 5% or more.

[0162] <Transparency> A cured film was prepared in the same manner as in the evaluation of <substrate adhesion> using the siloxane resin composition for forming a cured film obtained in each Example and Comparative Example. The transmittance of ultraviolet light and visible light (300 nm to 800 nm) was measured for the glass substrate having the obtained cured film using a spectrophotometer (U-4100 (manufactured by Hitachi High-Tech Science Corporation)) with the glass substrate used as a reference. The transmittance of the cured film was evaluated according to the following criteria based on the transmittance value at a wavelength of 400 nm. A: Transmittance 90% or more B: Transmittance less than 90%.

[0163] <Refractive index> Using the siloxane resin compositions for forming cured films obtained in each of the examples and comparative examples, a cured film with a thickness of 2 μm was produced on a silicon wafer in the same manner as the evaluation of <substrate adhesion>. For the silicon wafer having the obtained cured film, using a prism coupler (PC-2000 manufactured by Metricon Co., Ltd.), light with a wavelength of 550 nm was irradiated from a direction perpendicular to the surface of the cured film under atmospheric pressure at 20 °C, and the refractive index was measured and rounded to the third decimal place. For Examples 41 and 42, since the cured film was white and the irradiated light was reflected and measurement could not be performed, it was described as "-" in the table.

[0164] <b* value> Using the siloxane resin compositions for forming cured films obtained in each of the examples and comparative examples, a cured film was produced in the same manner as the evaluation of <substrate adhesion>. For the glass substrate having the obtained cured film, using a spectrophotometer (trade name CM-2600d, manufactured by Konica Minolta, Inc.), the chromaticity (b* value) was measured in SCI mode from the cured film side. Note that the larger the b* value, the greater the yellowness of the cured film.

[0165] <SEM-EDX measurement> Using the siloxane resin compositions for forming cured films obtained in each of the examples and comparative examples, a cured film was produced in the same manner as the evaluation of <substrate adhesion> except that the curing temperature was 150 °C. For the obtained cured film, observation was performed with a scanning electron microscope, and EDX analysis was performed at an acceleration voltage of 15 kV. Semi-quantitative calculation was performed by ZAF correction calculation, and the atomic ratio of N to Si was N (mol%) / Si (mol%), the atomic ratio of S to Si was S (mol%) / Si (mol%), the atomic ratio of P to Si was P (mol%) / Si (mol%), and the atomic ratio of F to Si was F (mol%) / Si (mol%).

[0166] <Impurity analysis> The siloxane resin compositions for forming cured films obtained in each Example and Comparative Example were analyzed and quantified by gas chromatography / mass spectrometry (GC / MS) to determine the contents of benzene, toluene, xylene, aniline, styrene, and naphthalene in the resin compositions. As for the pretreatment method, the analysis of benzene, toluene, xylene, and styrene was performed according to the EPA5021A method specified by the US 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 of the German Federal Institute for Risk Assessment. The detection values ​​are summarized in the table. When the value was below the detection limit (1 ppm), it was written as "<1".

[0167] The evaluation results of each of the Examples and Comparative Examples are shown in Tables 8 and 9.

[0168] [Table 8-1]

[0169] [Table 8-2]

[0170] [Table 9-1]

[0171] [Table 9-2]

Claims

[Claim 1] A method for producing a polysiloxane solution using an alkoxysilane compound as a raw material and an organic salt as a catalyst for hydrolysis and thermal condensation, wherein the pH value of a 1.0 mass % aqueous solution of the organic salt is 3.0 to 5.5.